SECTION 1

PHYSICAL
CHEMISTRY
CHAPTER
ATOMS, MOLECULES AND
STOICHIOMETRY
1

Introduction
The English scientist John Dalton proposed the atomic theory in which he stated that matter is made
up of tiny repeating units known as atoms. The atomic theory has proved very useful in explaining the
chemical properties and behaviour of matter. For instance, chemical reactions involve rearrangement
of atoms. The atom itself consists of a nucleus, containing neutrons and protons, and energy levels
(shells) containing electrons. Arrangement of electrons in the outer shell of an atom, as well as the
distance of the electrons from the nucleus, affects the chemical properties of an atom. Chemical
reactions involve sharing or total transfer of electrons between atoms. The rearrangement or transfer
of electrons during chemical reactions depend on how tightly they are held to the atom, and this in
turn depends on the number of protons (nuclear charge) in thenucleus as well as distance of the
outer-most shell from the nucleus. A large number of protons in the nucleus implies that the outer
shell electrons are firmly held to the atom and so they may not easily be transferred during chemical
reactions. Take sodium and chlorine as examples. The sodium atom is large and it has a small number
of protons. The outer electrons are therefore weakly held to the atom. This explains why sodium
reacts by losing its outer most-shell electron. On the other hand, the chlorine atom is smaller and has
a larger nuclear charge. The outer- most electrons are therefore firmly held to the atom. It is difficult
for an atom of chlorine to lose an electron, but it can easily accept an electron because the incoming
electron is strongly attracted by the large number of electrons in the nucleus.
Many substances are made up of molecules. A molecule is a particle made up of two or more atoms
held together by a covalent bond. This type of bond involves sharing of electrons between atoms . If
the molecules of a substance contain the same type of atom, the substance is known as an element, for
example, oxygen. On the other hand arecompounds in which the molecules contain atoms of different
elements.
The particles encountered in chemistry, that is, the atoms, ions, electrons, molecules and protons, are
so tiny that chemists need a convenient method of counting them . Take hydrogen as an example. 4 g
of the gas contains a very large number of molecules, 12 x 1023. If we were to count these molecules,
say, in dozens, we would have an inconveniently large number, that is100 000 000 000 000 000
000 000(1 x 1023) dozens. To avoid such cumbersome numbers, chemists have come up with the
concept of the mole. One mole is the quantity that contains 6 x 1023 particles. 4g of hydrogen gas
therefore contains 0.167 moles of hydrogen molecules. The concept of the mole is particularly useful
in stoichiometric calculations. These are calculations of amounts of products or reactants involved
during chemical reactions. When substances react, they combine in definite proportions, known as
the stoichiometric ratio, to form products which are also in a definite ratio. It is therefore possible to
use a balanced equation to determine the amounts of products or reactants involved in chemical
reactions.

1.1 Relative masses of atoms and molecules

The masses of atoms and molecules are given relative to the 12C scale. On this scale, an atom of 12C atom
has a mass of 12 atomic mass units (a.m.u). This isotope of carbon was chosen because its atomic mass
could be determined accurately. Formally, the relative atomic mass, Ar, of an element is defined as

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝒕𝒉𝒆 𝒆𝒍𝒆𝒎𝒆𝒏𝒕

Ar = 𝟏
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝑪−𝟏𝟐
𝟏𝟐

Similarly, the relative molecular mass, Mr, of a compound is defined as

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒐𝒎𝒑𝒐𝒖𝒏𝒅

Mr = 𝟏
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝑪−𝟏𝟐
𝟏𝟐

The relative molecular mass of a compound is found by adding the Ar values for each atom in the mole-
cule of that compound. Ionic compounds such as sodium chloride do not contain molecules. They are
made up offormula units, for example , the formula unit for sodium chloride is NaCl. Instead of using the
term relative molecular mass for an ionic compound, the appropriate term is relative formula mass
(RFM). However, for convenience’s sake, chemists frequently use the term relative molecularmass for
both ionic and covalent compounds.

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒇𝒐𝒓𝒎𝒖𝒍𝒂 𝒖𝒏𝒊𝒕 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒐𝒎𝒑𝒐𝒖𝒏𝒅

Relative formula mass = 𝟏
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝑪−𝟏𝟐
𝟏𝟐

1.2Isotopes

Isotopes are atoms of the same element that contain different numbers of neutrons.

In a sample of an element, some atoms are heavier than the others. The heavier atoms contain more
neutrons. However, the number of protons and electrons is the same in all the atoms.
Isotopes differ from each other in:
 Number of neutrons.
 Mass.Isotopes are identified by their mass numbers, for example, the isotopes of iron are
represented by the nuclide notationbelow.
54 56 57
Fe Fe Fe
26 26 26
All the isotopes contain 26 electrons. The mass numbers 54, 56 and 57 distinguishes between
the isotopes (these numbers are also known as relative isotopic masses). Thus the isotopes
 can simply be shown as Fe-54, Fe-56 and Fe-57 (or 54Fe, 56Fe, 57Fe). The heaviest isotope has the
massnumber 57.

Recall the nuclide notation

 Speed of movement in an electric field. The
nucleon number or mass number
heavier isotopes (with more neutrons) move
= sum of protons and neutrons more slowly.
Isotopes are similar to each other in the following ways:
54  They have the same number of electrons
Fe  Since the electronic structure is the same, they
26
have similar chemical properties.
 They have the same number of protons.
atomic number = number
of protons(= number of electrons)

Isotopes of hydrogen
Hydrogen has three isotopes which all have the atomic number 1 (that is, each isotope contains 1 electron
and 1 proton). The number of neutrons in each isotope is calculated from nucleon number = n + p, where
n = neutron number and p = proton number.
Thus n = nucleon number – p

Isotope neutron number

nucleon number (nucleon number - atomic number)

1
1 H 0

atomic number 2
H 1
1
3 Table 1.0
H 2
1

The relative isotopic mass

This is defined as

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒂𝒏 𝒊𝒔𝒐𝒕𝒐𝒑𝒆 𝒐𝒇 𝒂𝒏 𝒆𝒍𝒆𝒎𝒆𝒏𝒕

Relative isotopic mass = 𝟏
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝑪−𝟏𝟐
𝟏𝟐

The relative isotopic mass coincides with the nucleon number (sum of protons and neutrons). This is
because a proton and a neutron each has a relative mass of 1. For example, an atom of 12C has 6 neutrons
and 6 protons. Its nucleon number = 12, which is equal to its relative isotopic mass.

1.3 Relative masses of atoms and molecules from mass spectra

The technique of mass spectrometry, which uses a machine known as a mass spectrometer, is used to
 Determine the structure of a molecular compound and its Mr
  Find the number of isotopes in an element, their relative isotopic masses and their relative
abundances.

Instrumentation
Fig 1.1 is a block diagram illustrating the main features of the mass spectrometer

Fig 1.0

1. The sample is introduced as a vapour.

2. In the ionization chamber, fast moving electrons bombard atoms or molecules of the sample,
knocking out electrons from them. This results in the formation of positively charged ions.
3. The positive ions are accelerated through an electric field. It is the potential difference across
the field that causes the electrons to accelerate.
4. The beam of moving cations is deflected by a magnetic field. If the sample is an atomic
element such as a metal or a noble gas, the case is straightforward. The heavier isotopes will
be deflected less than the lighter isotopes. The result is that the isotopes are separated on the
basis of their mass. They are collected separately, and at a computer terminal the masses of
the different isotopes as well as their abundances are computed. The computer will
display this information on a mass spectrum.
The mass spectrum of iron is shown in Fig 1.0.

 Number of peaks (vertical lines) = number of isotopes.

91.72% Thus iron has three isotopes.
abundance
(%)
 The x-axis shows the relative isotopic masses of these
isotopes. The lightest isotope of iron is 54Fe, with an
isotopic mass of 54 units. It has the least number of
neutrons (54 - 26 = 28). The heaviest isotope is 57Fe,
with an isotopic mass of 57. It has the largest number of
5.9% 2.1%
Fig 1.1 neutrons (57-26 = 31).
 The vertical axis gives the relative abundance of the
54 56 57
m/e isotopes. The height of a peak is directly proportional to
the abundance of an isotope.
 The most abundant isotope of iron is therefore 56Fe. We also conclude that it is the most stable
isotope. If it were not, it would be present in small amounts. The easiest way to understand these
isotopic abundances is this:
Consider a 100g sample of iron metal. Of this mass, 91.72g would be due to 56Fe, 5.9g to 54Fe. A
very small amount, 2.1g, would be due to 57Fe.

1.3.1 Determination of relative atomic mass of an atomic element from

its mass spectrum
When the isotopic masses of all of the isotopes of an element, and their respective relative abundances are
known, the relative atomic mass of an element can be calculated using the formula

( 𝐀𝐢 𝐱 𝐢𝐭𝐬 𝐚𝐛𝐮𝐧𝐝𝐚𝐧𝐜𝐞 ) + 𝐁𝐢 𝐱 𝐢𝐭𝐬 𝐚𝐛𝐮𝐧𝐝𝐚𝐧𝐜𝐞) +( 𝐂𝐢 𝐱 𝐢𝐭𝐬 𝐚𝐛𝐮𝐧𝐝𝐚𝐧𝐜𝐞)+ …

Ar =
𝟏𝟎𝟎

Where Ai means the relative isotopic mass of isotope A and Bi means the relative isotopic mass of isotope
B etc. For iron,

(54 x 5.9 )+ (56 x 91.72)+ (57 x 2.1)

Ar = = 55.74
100

1.3.2 Molecular elements and compounds

A molecule is a chemical entity made up of two or more atoms joined by a covalent bond. It is the
smallest unit of a compound or an element that preserves the chemical properties of that element or
compound. Some elements are molecular (made up of molecules), e.g. bromine, oxygen, phosphorous and
sulphur (Fig 1.2).

P sulphur atom

P P

P Fig 1.2Molecular
structure of phosphorous
a molecule of phosphorous( p )
4 and sulphur.
a molecule of sulphur (S )
8

Mass spectrometry of compounds and molecular elements

Mass spectrometry for a molecular element
We will use bromine as an example. Fragmentation of bromine molecules in the mass spectrometer
produces a mixture of positively charged ions. Ions of different masses are deflected to different extends,
so they can be collected separately. A computer terminal then calculates the relative abundances of these
ions. The relative abundances are expressed in terms of peak heights. The taller the peak, the larger the
number of ions giving rise to that peak.
Fragments of the same mass produces a single peak. Fragments are expected to differ in mass depending
on which isotope of bromine is present. In addition, there will be peaks caused by unfragmented bromine
molecules (molecular ions), Br2+. These are the molecular peaks.
How many peaks would be expected on the mass spectrum of bromineand what would be
Qratio of peak height( Bromine has two isotopes, 79Br and 81Br in the ratio 1:1).
the

A5 peaks in the ratio 1:1:2:1:1

The following ions are formed in the mass spectrometer from bromine molecules:
1.⁷⁹Br⁺2.81Br⁺3.⁷⁹Br-⁷⁹Br⁺
4.⁷⁹Br-81Br⁺5.81Br-⁷⁹Br⁺6.81Br-81Br⁺
Species 1 and 2 are atomic ions formed by the fragmentation of bromine molecules. Since they have
different masses (79 and 81 respectively),they are collectedseparately and they form different peaks. The
ratio of peak heights (abundances) for these two species is 1:1.
The rest of the species are molecular ions, that is, they are unfragmented molecules which bear a positive
charge. Species 3 is the lightest of the molecular ions. It produces a peak at m/e 158(79 + 79). Species4
and 5 have the same mass (160), and so they produce a single peak. Species 6 is the heaviest of all the
species produced in the mass spectrometer (mass 162).
Note that the peak due to species 4 and 5 at mass 160 is two times taller than the rest of the peaks. This is
because there are two contributing species for this peak. A total of five peaks are therefore observed.
These peaks are in two groups. The first group, with two peaks, is made up of the peaks produced by the
lightest species, ⁷⁹Br⁺ and 81Br⁺. The second group, with three peaks, is made up of the peaks produced by
the heavier molecular ions (Fig 1.3).

Mass spectrum of a compound

Fragmentation of molecules of a compound forms a
mixture of positive ions with different masses, which are
collected separately in the massspectrometer, giving rise
to a number of peaks. The different ions are formed by
the breaking of different bonds in the molecule.
Different fragments (with different formulae) will give
rise to the same peak if they have the same relative
Fig 1.3 The mass masses.Fig 1.4 shows the bonds that may break during
spectrum of bromine the fragmentation of ethanol in a mass spectrometer.
Different ions will be formed due to breaking of
different bonds as shown(Table 1.2).
1 2 The last species shown in the table is not a fragment. It
represents the whole unfragmented molecule (it is the
H H
molecular ion). Using the Table 1.2 , we would expect
H C C O H six peaks in the mass spectrum of ethanol.
H H The actual number of peaks depends on which bonds
Fig 1.4
4 actually break in the mass spectrometer.
3
Note that fragments 2 and 3 have the same mass and will therefore form only one peak. In the mass
spectrum in Fig 1.5, peak heights (intensities) have been assigned arbitrarily.
 The mass spectrum of ethanol (not to scale)

peak intensity
(abundance)

Fig 1.5 Mass spectrum

0 15 17 29 31 45 46 of ethanol
m/e

Bond broken fragment formed relative mass of fragment

CH3+ 15
1
CH2OH+ 31

2 CH3CHOH+ 45

3 CH2CH2OH+ 45

4 OH+ 17

CH3CH2+ 29
Table 1.2 Ions formed
+ during the fragmentation of
CH3CH2OH 46
ethanol

Of particular importance is the molecular ion peak at m/e 46. Since it represents the full molecule, its m/e
value is the same as the relative molecular mass of the compound being analyzed.

Example
An organic compound Q contains 40% C by mass and 53.3% O by mass. Its mass spectrum is shown
below.

peak
intensity
(height)

15 17 43 59 60
m/e
(a) Calculate the empirical formula of this compound.

(b) Suggest an identity for Q and write down the formulae of the species responsible for
each peak in the spectrum.

Working
Since it is an organic compound, Q must also contain hydrogen.

C O H
% 40 53.3 6.7

40 53.3 6.7
Divide by Ar
12 16 1
3.333 3.33 6.7
Simplest ratio 1 1 2

(a)Therefore the empirical formula is CH2O

From the mass spectrum, the compound has an Mr of 60.
(CH2O) n = 60
30n = 60
n = 2
Therefore the molecular formula of Q is C2H4O2.

b) Q could be ethanoic acid, CH₃COOH

H O
H C C
H O H

The molecule may fragment as shown, giving rise to the fragments whose masses are given in the table.

species relative mass

CH3+ 15
OH+ 17

CH3CO+ 43

CH3COO+ 59

CH3COOH+ 60
1.4 Chemical formulae
We have already used the empirical and the molecular formula in the foregoing calculation.
The empirical formula gives the simplest ratio of the different atoms present in the compound.
A molecular formula shows the actual number of the different atoms present in one molecule of a
compound.
Examples are given in Table 1.3.

compound molecular formula empirical formula

Ethanoic acid C2H4O2 CH2O

hydrogen peroxide H2O2 HO

butane C 4 H8 C2H4 Table 1.3 Molecular and empirical

formulae of some compounds
ethyne C 2 H2 CH

Thus we know, for instance, that butane contains twice as much hydrogen as carbon.

Determination of formulae
Empirical formulae can be found from % composition data as in the previous example.
We find the ratio of atoms in the compound in terms of moles, which makes sense because when we write
a formula, say as C₂H₄O₂, we mean that in one mole of this substance, there are 2 moles of C, 4 moles of H
and 2 mol of O.
As already discussed, the molecular formula of a compound can be found by mass spectrometry. The peak
with the largest m/e value corresponds to the unfragmented molecular ion. This m/e value therefore gives
the Mr of the compound being analyzed.
Another method of determining Mr is by combustion analysis. This method is particularly applicable in
finding the molecular formula of hydrocarbons.

Finding molecular formula of a hydrocarbon by combustion analysis

Assuming complete combustion of the hydrocarbon, the only products would be water and carbon
dioxide. Let the hydrocarbon be CX H Y.
Then its combustion will be represented by the general equation (memorize it!) :
y
CxHy + x + y O2 xCO2 + 2 H2O
4

The usefulness of this formula becomes quite obvious if the values of x and y are large.
Consider the complete combustion of candle wax, a C30 alkane.
2C30H62 + 91O2→ 60CO2 + 62H2O
62
Moles of oxygen are found by (x + y/4) = 30 + = 91/2.
4

Study the formula again:

CxHy + (x + y/4)O2 xCO2 + y/2H2O
1 mol of the hydrocarbon combines with (x + y/4) moles of oxygen to form x moles of carbon dioxide and
y/2 moles of water. Now, this molar ratio is the same as the volume ratios of the reacting gases (number
of moles is directly proportional to volume of gas).
Since combustion is a gas phase reaction, the stoichiometry of the reaction can be expressed in terms of
volume ratios, for example if we are using cm³ as the unit for volume:

CxHy + (x + y/4)O2 xCO2 + y/2H2O

1cm³: (x+ y/4) cm³ x cm³ : y/2cm³

Suppose that instead of burning 1cm³ of the hydrocarbon, we burn 10 cm³,then we have to multiply
throughout by 10 to maintain the ratio.
CxHy + (x + y/4)O2 xCO2 + y/2H2O
10 : 10 (x+ y/4) 10x : 10(y/2)

Example

10cm³ of a hydrocarbon were completely burnt in 100 cm³ of oxygen. At the end of the reaction,
80cm³ of residual gas were collected, of which 40cm³ were absorbed in sodium hydroxide solution.
Find the molecular formula of the hydrocarbon.

Working
Let the hydrocarbon be CX HY
CxHy + (x + y/4)O2 xCO2 + y/2H2O
10cm³ : 10 (x+ y/4) cm³ 10x : 10( y/2)
The residual gas is the gaseous mixture that remains at the end of the reaction. It contains carbon dioxide
and unreacted (excess) oxygen.
The 40cm³ of gas which were absorbed in aqueous sodium hydroxide are carbon dioxide.
(carbon dioxide is an acidic gas and so dissolves in(reacts with) aqueous sodium hydroxide).

Excess volume of oxygen = total residual gas – volume of carbon dioxide

= (80 – 40) cm³
= 40 cm³.
Volume of oxygen that reacted = initial volume of oxygen – volume of excess oxygen
= (100-40) cm3
= 60cm3
From the general equation of combustion,
Volume of CO2 produced = 10x = 40
∴ x = 4
Volume of oxygen used = 10 (x+y/4) = 60
But x =4: substituting and solving for y
60 = 10 (4+y/4) y=8
The molecular formula of the hydrocarbon is C₄H₈
1.5 Stoichiometry and the mole concept

1.5.1 The mole concept

The need to count things is part of our everyday lives. There are different units of counting, for example,
we often count bread and eggs in dozens.
Scientists usually deal with very large numbers of particles. For example, 2g of sodium metal contain a
very large number of sodium atoms. We need a convenient way of quoting such large figures. Towards this
end, chemists use a unit of counting known as the mole.

The mole is the amount of matter that contains the Avogadro number (L) of particles. The term
particle is general, for example, it could refer to atoms, molecules, ions or electrons.
The Avogadro number (constant) = 6 x 1023

Example

1(a) How many molecules are present in 0.35 mol of hydrogen gas?
(b) How many moles are 1013 molecules of hydrogen?

2(a) Why is the statement ‘two moles of oxygen’ misleading?

(b) How many moles of electrons are lost by half a mole of magnesium metal in forming the Mg 2+
ion?

Solutions
1(a) 1 mol → 6.0 x 1023molecules
0.35 mol → less
0.35mol
Number of molecules = x 6.0 x 1023
1mol
= 2.1 x 1023

(b) 1 mol → 6.0 x1023 molecules.

less ← 1013 molecules

1013 molecules
number of moles =
6.0 x 1023 molecules
= 1.67 x 10-11

2(a) The statement is ambiguous; it could refer to molecules of oxygen or to atoms of oxygen. For
example, 2moles of oxygen contain 2 moles of oxygen molecules and 4 moles of oxygen atoms.

(b) Mg → Mg2+ + 2e-

1 mol of magnesium loses 2 mol of electrons. Therefore ½ a mol of magnesium would lose 1 mol of
electrons.

Inter- converting mass and moles

 mass in grams For example, 2g of sodium expressed in moles is 2/23 =0.087.
moles = 0.3mol of hydrogen gas expressed in grams becomes Mr x
Ar (or Mr) mols = 2 x 0.3= 0.6g.
m Similarly, 1.0 mole of water = 1.0 x 18 = 18g.
that is , n =
From the last example, we make this general inference
Ar (or Mr)
thus One mole of a substance has a mass equal to its Ar or
its Mr
mass in grams = moles x molar mass

Check using CO2. The Mr of CO2 is 46. 1.0 mol of CO2 should therefore have a mass of 46g.
mass = mole x Mr
= 1.0 x 46 = 46g

1.5.2 The molar gas volume

The volume occupied by 1.0 mole of a gas is constant, irrespective of the identity of the gas, provided
temperature and pressure are kept constant.
This volume is known as the molar gas volume, Vm.

Vm = 22.4dm3 at standard temperature and pressure (s.t.p)

OR

Vm = 24dm3 at room temperature and pressure(r.t.p)

1.0dm3 = 1000 cm3

1.0cm3 = 10-3 dm3 = 10-6 m3

 Example

All measurements are done at s.t.p

(a) How many moles of gas are present in 15dm³ of hydrogen?

(b) What is the volume occupied by 0.13mol of ammonia gas?
(c) What is the mass of 22.4 dm³ of water vapour?
(d) How many atoms are present in 12 dm³ of oxygen gas?
(e) What is the volume occupied by 1012 atoms of neon gas?

Solutions
(a) mols = 15/22.4 = 0.670

(b)1 mol  22.4dm3

0.13mol  0.13mol x 22.4dm3mol-1
=2.91dm³
(c) 22.4dm³ = 1.0 mol of water
= 18g (the mass of 1.0 mol of a substance = to its Ar or Mr)
Parts (d) and (e) are left as an exercise to the reader.

1.5.3 Stoichiometry
During a chemical reaction, the ratio in which reactants combine and products form is always constant for
that particular reaction. For instance, in the formation of ammonia, nitrogen and hydrogen combines in
the ratio 1:3.
N2(g) + 3H2(g)  2NH3(g)
The same result is obtained no matter how many times the experiment is carried out, and irrespective of
how many different people carry out the experiment. The reaction ratio (stoichiometry) for a reaction can
be deduced from the balanced equation of the reaction.

2 moles of hydrogen gas are mixed with 2 moles of oxygen and the mixture is sparked so
that the two gases react to form water.Whichreactant is in excess and what would be the
molar composition of the residual gas?

Q 2H2(g) + O2(g)  2H2O(l)

According to the balanced equation, hydrogen and oxygen react in the ratio 2:1. In the given
situation, 2moles of hydrogen require 1 mole of oxygen. Oxygen is therefore present in excess
by 1 mole. The residual gas contains 1 mole of oxygen(water forms as a liquid).
A
In industrial processes, it is usually necessary to mix reactants in the exact ratio in which they react. This
minimizes wastage of raw materials and ensures that the product formed is not contaminated by excess
reactants. It would be time consuming, difficult and even expensive to separate the product from excess
reactants.

Reactions taking place in solution

Concentration
This is a measure of how much solute is dissolved in a given volume of solvent. In most reactions the
solvent is water. Concentration measures the extent of scattering of particles in a solution. If there is a
very large number of solute particles in a small volume of solution, then concentration of the solution is
high. Adding more solvent (dilution) will cause the particles to spread far, and so concentration is
reduced.
amount of solute
Concentration(C) =
volume of solvent
The amount of solute is usually given in moles (n), and the volume (V) in dm³.

C= n Often, concentration is expressed as mass m(in g) of solute dissolved in

V
a given volume of solvent (in dm3).
units = moles m
dm3 That is, C = , for which the units become gdm-3
V

= moldm-3

1 dm3 = 1000 cm3 = 1 litre

Example

1. Calculate the concentration of a 25.00 cm³ solution which contains 2g of sodium

hydroxide. Express your answer in moldm-3 and gdm-3.

2. What would be the final concentration when 25.00 cm³ of water are added to 100 cm³ of 0.5
mol/dm³ of sodium hydroxide solution?

Solutions

1. Convert cm³ to dm³ and g to moles.

Moles of NaOH = g/Mr (NaOH)
= 2/40
= 0.05
Vol of solution = 25/1000
= 0.025dm3
 Since n remains constant after dilution,
C = n/v
we equate I and II.
= 0.05/0.025 C₁V₁ = C2V2
= 2.0 moldm-3
0.5 x 0.1 = C2 x 0.125
Converting to g/dm-3
C = 2g/0.025dm³ 0.5x0.1
C2 =
0.125
= 80gdm-3
2.Before dilution: Concentration after dilution = 0.4 moldm-3
n
C1 = NB. The volumes were converted to dm³ because it is
V₁
a good habit to work in these units. The same answer
n = C1 x V1 … I
could have been obtained using volumes in cm³.Also
After dilution: note that the final concentration is smaller. Dilution
n always results in lowering of concentration.
C2 =
V2

n = C2 x V2 ... II

Acid base titrations

It is possible to find the concentration of a solution of an acid or base by titration, as illustrated in this
example:

Example
25.0 cm³ of 0.1 moldm-³ sulphuric acid were required to exactly neutralize 20.0 cm³ of sodium
hydroxide solution. Calculate the concentration of the sodium hydroxide solution.

Solution
H2SO₄ (aq) + 2NaOH → Na2SO4 (aq) + 2H2O(l)
Stoichiometry 1 : 2
= 0.0050
n(H2SO4) = C x V
= 0.1 x 0.025 C(NaOH) = mol/vol
= 0.0025 = 0.0050/0.020
n(NaOH) = 0.0025 x 2 = 0.0001 mol/dm³

Titration is a quantitative procedure, that is, it relies on the fact that reactants combine in a specific ratio
to form products. If any reagent is present in excess, only the amount required for reaction, as shown by
the balanced equation, will react, and the remainder will be present in a mixture with the products. Dur-
ing titration, one solution has a known concentration. This is the standard solution which is placed in a
burette. The aim is to find the volume of the standard solution that would exactly react with a known
volume of the reagent whose concentration is not known.
A known volume of the second solution is transferred to a conical flask using a pipette. Most titrations
require the addition of a few drops of indicator into the flask. The indicator will change color at the end of
reaction, that is, when molar quantities of the reactants have reacted as shown by the balanced equation.
Commonly used indicators in acid-base titrations are phenolphthalein and methyl orange. Phenolph-
thalein is pink in alkaline solution and colourless in acidic solution. The standard technique is to place the
base in the burette, though this is not a rule. The indicator is then added to the acid in the conical flask,
giving a colourless solution. The end point of the neutralization is when the first trace of pink appears.
Fig 1.0shows the titration set-up.

FUNNEL
Solution of known concentration
(titrant) Remov e soon after filling the
burette
0

1
0
BURET T E
2 Solution of know n concentration
0 (titrant) is placed here
3
0
4
0
5
0
BURET T E T AP
BURET T E ST AND
Check for leaks. Nev er use a leaking
It should hold the burette in a burette. Also check that the tap can be
v ertical position (not tilted) opened and closed without diffficulty

BURET T E T IP
placed just inside the burette

ANALY T E
This is the solution whose concentration is
to be determined. The analy te must hav e a
known v olume.
Fig 1.0 Set-up for a titration

Back titrations
During a back titration, the amount of a reactant (analyte) is determined indirectly by titrating the
product of a reaction with another reagent. Two reactions are therefore involved. The first reaction
converts reactants to a product. In the second reaction, the product reacts quantitatively with another
reagent. In this way it is possible to determine the amount of product formed in the first reraction (see
example 1).
Another form of back titration involves putting a reactant (known amount) in the reaction vessel. Only a
certain amount will react according to the stiochiometry of the reaction. Another reagent is now added
into the reaction vessel to react with the excess reactant. It is then possible to determine the amount of
reactant that actually reacted. There are several reasons for carrying out a back titration, including

 The analyte may be in solid form. In this case a liquid reactant is added in excess to react with the
solid. A back titration is then carried out to determine the amount of excess liquid that reacted. It
 then becomes possible to determine the amount of liquid reactant that reacted. By using the
stoichiometry of the reaction, the amount of solid that reacted can be determined.
 If the analyte is contaminated by impurities,these may interfere with direct titration.
 Direct(forward) titration may be too slow.
 The direct reaction is reversible and does not go to completion.
 The direct reaction does not have a clear end point.
Example
Cu2+(aq) reactswith iodine according to the following equation

2Cu2+(aq) + 4I-(aq)  I2(aq) + 2CuI(s) … (i)

In one experiment involving this reaction, the iodine produced reacted completely with 25.00 cm3
of 0.10 moldm-3 sodium thiosulphate according to the equation

I2(aq) + 2S2O32-(aq)  2I –(aq) + S4O62-(aq) … (ii)

(a)Calculate the number of moles of Cu2+ that reacted with iodide ions reaction (i).

(b) Suggest an advantage of this method in the determination of the amount of Cu 2+ that reacts
with iodide ions.

Solution
(a) First calculate the number of moles of iodine that reacted with thiosulphate ions in reaction (ii).
This is the same as the number of moles of iodine produced in the first step.
25
Moles ofS2O32- thatreacted = C x V = 0.1 x
1 000
= 0.0025
Moles of iodine (reaction (ii)) = ½ moles of S2O32-
= ½ x 0.0025
= 0.00125
Reaction (i) therefore forms 0.00125 moles of iodine. According to the stoichiometry of this
reaction, moles of Cu2+ used = ½ moles of iodine used. That is,
Moles of Cu2+ = ½ x 0.00125 = 0.000 625

(b) The reaction of iodine with Cu2+ is easier to follow because starch can be added before the
titration to act as an indicator. When the reaction is complete, the blue-black colour of the iodine-
starch mixture disappears.

Example 2
Group II metal carbonates decompose when heated, according to the equation
MCO3(s)  MO(s) + CO2(g)
4.08 g of a mixture of Bao and an unknown carbonate X was heated strongly. After heating, the
mass of the mixture decreased to 3.64 g. This residue was then dissolved in 100 cm 3 0f 1.0 moldm-3
HCl. The excess acid required 16 cm3 0f 2.5moldm-3 NaOH for complete neutralization. Determine
the identity of metal X.
 Solution
Moles of NaOH that reacted with excess acid MCO3(s)  MO(s) + CO2(g)
16
= C x V = 2.5 x According to the stoichiometry of
1 000
this reaction,
= 0.040
moles of MCO3 = moles of CO2 = 0.01
HCl and NaOH react in the ratio 1: 1, so moles
Also, moles of MO formed from decomposition
of HCl that reacted = 0.032. This is the amount
of MCO3 = moles of CO2 produced
of excess acid that was available to react with
= 0.01
NaOH (the rest of the acid had reacted with the
solid residue). MO reacts with acid according to the equation

moles of acid added to residue = C x V MO(s) + 2H+ M2+ + H2O(l)

100 Therefore moles of acid that react = 2 x moles of MO
= 1.0 x = 0.1
1000 = 2 x 0.01 = 0.02
moles of acid that actually reacted with residue But total number of moles of acid that reacted with
= amount added – excess residue = 0.060, so the remainder of the acid reacted
with BaO.
= 0.1 – 0.04 = 0.060
That is,
The acid reacts with the residue in a neutraliza-
moles of acid that reacted with BaO = 0.060 -0.020
tion reaction according to the equation
= 0.040
= moles of BaO + moles of MO from decompo-
sition of MCO3. BaO + 2H+ Ba2+ + H2O
Upon heating, mass of original mixture Moles of BaO = ½ moles of acid
decreased by = ½ x 0.040 = 0.020
( 4.08 – 3.64) g = 0.44 g
Mass of BaO that reacted = moles x Mr
This is the mass of CO2 lost from the metal
= 0.020 x 153 = 3.06 g
carbonate in the mixture.
m Mass of MO in the residue
Moles of CO2 lost = = 3.64 g - 3.06
Mr
0.44 = 0.58 g
= = 0.010
44 Now, mass of MO = moles x Mr, that is
The carbonate in the mixture is decomposed 0.58 = 0.01 x (M + 16),
by heat according to the equation where M is the Ar of the unknown metal.
Solving for M gives 42.
The metal M is therefore calcium.

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1. Themajorchemicalspresent in the mineral dolomite are MgCO3 and CaCO3. 2.75 g of a sample of
dolomite was dissolved in 80 cm3 of 1.0 mol dm-3 HCl . The resulting solution was then diluted to
250 cm3 with distilled water. 25 cm3 of the diluted solution required 20 cm3 of 0.1 moldm-3 NaOH
solution for complete neutralization. Determine the percentage of MgCO 3 in the dolomite.
2. 4 g of contaminated limestone, CaCO3, is reacted with 200 cm3 of 0.5 moldm -3 HCl. The
resulting solution containing excess HCl required 50 cm3 of 0.5 moldm-3 NaOH for complete
neutralization. Determine the mass of impurities in the sample of CaCO3.

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 Questions, solutions and discussions

1(a) Define the term relative atomic mass.

(b)Chlorine has two isotopes, Cl-35 and Cl- 37.The relative atomic mass of chlorine is 35.5.
Calculate the isotopic abundances of the two isotopes of chlorine.

Solutions
(a) This is the ratio of the mass of an atom of an element to 1/12th the mass of one atom of
12C.

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝒂𝒏 𝒆𝒍𝒆𝒎𝒆𝒏𝒕

Ar = 𝟏
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒂𝒕𝒐𝒎 𝒐𝒇 𝑪−𝟏𝟐
𝟏𝟐

( b)Let the isotopic abundance of Cl -35 be y. The abundance of Cl- 37 becomes 100-y.
Using formula
( 𝐢𝐬𝐨𝐭𝐨𝐩𝐢𝐜 𝐦𝐚𝐬𝐬 𝐨𝐟 𝐂𝐥−𝟑𝟓 𝐱 𝐢𝐭𝐬 𝐚𝐛𝐮𝐧𝐝𝐚𝐧𝐜𝐞 ) + (𝐢𝐬𝐨𝐭𝐨𝐩𝐢𝐜 𝐦𝐚𝐬𝐬 𝐨𝐟 𝐂𝐥−𝟑𝟕 𝐱 𝐢𝐭𝐬 𝐚𝐛𝐮𝐧𝐝𝐚𝐧𝐜𝐞)
Ar =
𝟏𝟎𝟎
35y +37(100−y)
35.5 =
100
y = 75
Therefore the abundance of Cl- 35 is 75% and that of Cl-37 is 25%

2 Boron has two isotopes, B-10 and B -11 in the ratio of 1:4. What is the relative atomic mass of boron?

Solution
Change the ratio to percentages.
B-10: % abundance = (1/5) x 100 = 20
B -11: % abundance = (4/5) x 100 =80.
By formula
(10x20) + (11x80)
Ar =
100
= 10.8
OR by using the ratio directly:

(𝟏x10) + ( 𝟒x11)
Ar =
𝟓
= 10.8 as before.
3The mass spectrum of C3H7OH is as shown.

% abundance

M M+2 m/e

What is the most likely reason for the appearance of the (M + 2) peak?
A presence of hydrogen bonds in the molecules
B different fragmentations of the molecule
C presence of oxygen isotopes
D gain of two hydrogen atoms by C3H7OH
9189/3/O/N/2005

Solution C
Oxygen has two isotopes, O-16 and O-18. The M peak is caused by molecular ions, C3H7OH+
that contain the lighter O-16 isotope. Molecular ions that contain the heavier isotope O-18
would be two units heavier, giving rise to the M+2 peak.

4 Using a mass spectrometer, it is possible to determine

1 the number of protons in an atom
2 the relative molecular mass of an organic compound
3 number of isotopes of an element
Which of the numbered statements are correct?
9189/3/O/N/2005

Solution
2 and 3 are correct.

Notes
 The relative molecular mass of a compound corresponds with the highest m/e value obtained on the mass
spectrum of the compound. This peak is generated by the molecular (unfragmented molecule) ion.
 The number of peaks generated on the mass spectrum of an element depends on the number of isotopes
present in that element.

5 The mass spectrum of an element X is as shown in the following diagram.

(a) Determine the formula of the element X.
(b) What are the values of p and y?
relative abundance 9 : 6:1

3 : 1

35 37 p y 74
m/e

(c) How manyisotopes does the element X contain? Write down the formulae of the isotopes.
(d)Deduce the identity of the species responsible for each peak on the spectrum.
(e)Deduce the identity of element X, showing your reasoning clearly.

Solutions
(a) X2 .The species at m/e = 74 has two times the mass of the species at m/e =37, suggesting
that the species at m/e = 74 has the formula 37X-37X.

(b) p = 70 and y = 72

(c) Two isotopes, 35Xand 37X.

(d)
m/e species (e) The element has two isotopes, X-35 and X-37 in the ratio
3:1 (first two peaks on the mass spectrum).
35
35 X+
(35 x 3)+ (37+1)
37 37
X+ Ar of the element =
4
35 35 +
70 X X = 142/4
37
72 X35X+
= 35.5, so the element is chlorine.
37
74 X37X+
[do not forget the positive charges on the ions]

6How many peaks due to the Cl2+ ion are expected in the mass spectrum of chlorine, and in
what ratio would the heights of the peaks be?

Solution
3 peaks(the last three peaks in the mass spectrum in question 5 above). These peaks
are due to the molecular ions shown in the following table.
 ion m/e relative abundance(peak height)

35
Cl35Cl 70 3/4 x 3/4 = 9/16 peak 1

35
Cl37Cl 72
[3/4 x 1/4] x 2 =*6/16 peak 2
37 35
Cl Cl 72

37
Cl37Cl 74 1/4 x 1/4 = 1/16 peak 3

[* multiplied by 2 because there are two contributing species, doubling the

probability of finding such a species.]
The three species are therefore in the ratio of 9:6:1

7 The relative atomic mass of magnesium is 24.3. Which is the mass spectrum of
magnesium?

A B
10 10
relative 8 8
relative
intensity
6 intensity 6
4 4

2 2
0 0
23 24 25 26 23 24 25 26

m/e m/e
C D
10 10
8 8
relative 6 relative 6
intensity 4 intensity 4

2 2
0 0
23 24 25 26 23 24 25 26
m/e m/e
9189/3/O/N/2006

Solution C
HINT: the most stable isotope of Mg is 24Mg (tallest peak).
Check by calculation

(24 x7)+(25 x 1)+(26 x1)

Ar = = 24.3
9
8 What can be deduced from the following mass spectrum of a diatomic molecule X 2showing the
X2+peak heights?

6
peak height
5
4
3
2
1
0
158 160 162 m/e
1 Atoms in X2 have isotopic masses 79 and 81.
2 Relative abundance of each isotopes of X is 50%.
3 The Ar or x.
9189/3/O/N/2006 .

Solution: 1, 2 and 3 are correct

Atoms in X2 have isotopic masses 79 and 81. This explains the presence of the peak at
m/e = 160(79 + 81).

Element X has two isotopes, X-79 and X-81. The peak at m/e = 158 is due to X2+ ions
containing X-79 atoms only(79 +79 = 158). The peak at m/e 162 is due to X2+ ions
containing X- 81 atoms only.

The two isotopes of element X are present in the ratio of 1:1, since the corresponding
peaks at 158 and 162 are equal in height. The Ar of element X can be
calculated using the formula

(Abundance of isotope A x its isotopic mass)+ (Abundance of B x its isotopic mass)

Ar =
sum of peak heights

(2 x 79)+ (2 x 81)
= =80
4

Element X is therefore Br2.

9What is the mass of NaCl contained in 25cm3 of a of 0.01moldm-3 solution?

Solution
25
moles of NaCl = C x V = 0.01 x1000
 = 2.5 x 10-4
mass of NaCl = moles x Mr(NaCl)
= 2.5 x 10-4 x 58.5
= 0.0146g

10 20cm3 of a 0.01 moldm-3 sodium sulphate are accidentally spilled from a 1dm 3 solution.
What mass of NaOH remains in the container?

Solution

Tip:In a question where you are given concentration and volume of solution, the first thing
that should come to mind is finding number of moles, even though you might not be sure about
the next step.
moles of Na2SO4 lost = C x V
20
= 0.01 x
1000
= 0.0002
mass of Na2SO4 lost = n x Mr
= 0.0002 x 142
= 0.0284g
moles of solute in the 1 dm3 solution = 0.01
mass of solute in 1dm3 solution = n x Mr
= 0.01 x 142
= 1.42g
mass of sodium sulphate left in the container = 1.4200g -0.0284g
= 1.39g

11Calculate the volume of water that must be added to 250cm3 of 0.1 mol/dm3 NaOH to
reduce its concentration by 25%?

Solution
After reducing the concentration by 25%, it becomes C2 where
25
C2 = 0.1 – 25% of 0.1 = 0.1 - x 0.1
100

= 0.075
 Using C1V1 = C2V2,
where V2, the new volume after dilution, is to be calculated.
V2 = (C1V1)/ C2
0.1 x 250
=
0.075

= 333.33 cm3
Volume of water that must be added = 333.33 – 250
= 83.33cm3

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1100cm3 of 0.2moldm-3 NaCl is diluted by adding 50cm3 of water. What is the new concentration
of the solution?

2Oxides of nitrogen are pollutant gases which are emitted from car exhausts. In urban traffic when
a car travels 1Km, it releases 0.23g of an oxide of nitrogen, NxOy, which occupies 120cm3. What
are the values of x and y?9701/1/O/N/2007

3The amount of calcium ions in a sample of natural water can be determined by using an
ion-exchange column.

water sample A 50 cm3 sample of water containing dissolved CaSO4

was passed through the ion- exchange resin. Each
calcium ion in the sample was exchanged for two H+ ions.
The resulting acidic solution collected in the flask
required 25cm3 of 1.0 x 10-2 mol/dm3 KOH for complete
neutralization.
What was the concentration of calcium sulphate in the
original sample ?9701/1/O/N/2006

ion - exchange column

4Wines are made by the fermentation of glucose, C6H12O6. Ethanol and carbon dioxide
are the only products. The chief acid in an unopened bottle of wine is tartaric acid.
COOH
50 cm3 of a wine were exactly neutralized by 26 cm3 of 0.010moldm-3
H C OH KOH.
What was the concentration of tartaric acid in the wine?
H C OH
tartaric
acid COOH

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CHAPTER
ATOMIC STRUCTURE
2

Introduction
The atom is the basic unit of matter. In chemistry, emphasis is mainly on chemical properties and
reactions of matter. Chemical reactions occur at the atomic level, involving new arrangements of the
atoms in reactants. The atom can be studied at two levels
 Electrons, found in shells around the nucleus, directly determine the chemical properties of
an atom. It is therefore important to understand how electrons are arranged in atoms.
 The nucleus (protons and neutrons) affect chemical properties of an atom in an indirect way.
Protons provide the attractive force which keeps electrons bound to the atom. The strength of
this force therefore affects the reactivity and other chemical properties of an atom .The effect
of proton number and distance of electrons from the nucleus is a recurring theme in
chemistry. It helps to explain the chemical behaviour of atoms.

2.1 The nucleus

The nucleus is made up of protons and neutrons. Both particles have a relative mass of 1. The proton has a
relative charge of +1 whilst the neutron has no charge.

 Protons affect chemical properties of an atom indirectly by attracting and holding electrons to the
atom.
 The mass of an atom is mainly due to the nucleus, that is, protons and neutrons. This is because
the mass of an electron is so small that its mass contribution is negligible.
 Isotopes are atoms of the elements which have the same number of protons (that is, same atomic
number) and electrons, but different numbers of neutrons. Isotopes have the same chemical
properties but they have different masses. The isotopes with more neutrons are heavier. Table 2.0
compares properties of the nuclear particles (protons and neutrons) to those of electrons.
Protons, neutrons and electrons are collectively known as the sub-atomic particles.

Particle Relative charge Relative mass Location

proton +1 1 nucleus

neutron 0 1 nucleus
shells around
electron -1 0.000 5 (1/1840) nucleus
Table 2.0 properties of the sub-atomic particles
 2.2 Electronic structure
Electrons are involved in chemical reactions, but protons and neutrons are not. The arrangement of
electrons (electronic configuration) of an atom is important in determining the chemical behaviour of that
atom. Of particular importance are

 Structure of the valence shell. The valence (outer-most shell) is the one which directly
participates in chemical reactions, either by gaining, losing or sharing electrons with other
atoms. The number of electrons in the outer-shell shell is important in determining the type of
reaction that the atom undergoes. Metals, with a very small number of electrons in the valence
shell, usually react by losing the valence electrons (oxidation). Non-metal atoms, with a large
number of valence electrons (close to, but not equal to eight) usually react by gaining a few
electrons into the valence shell (reduction).
 Number of shells. As the number of shells increases, so does atomic size (atomic
radius). The valence shell is then a large distance from the nucleus. Valence electrons in such an
atom are loosely held to the atom and so can easily be lost. In other words, when atoms become
large, they begin to show some metallic properties (tendency to lose
electrons). In fact, elements become more metal-like on going down the group. This behaviour is
well illustrated by the Group (IV) elements. Increasing number of shells also increases the
shielding effect. This is the situation whereby inner shells prevent the valence shell from feeling
the full attractive force of the nucleus. The valence shell electrons are therefore weakly held to the
nucleus, causing them to be lost easily in chemical reactions.

2.2.1 Arrangement of electrons in shells and orbitals

Electrons are found in orbitals. In turn, orbitals of the same energy level belong to the same shell. An
orbital is not an object with physical boundaries. It is simply a region of space in which the probability
of finding an electron is very close to 100%. Orbitals are designated with the letters s, p, d and f. In any
given shell, the energy of the orbitals increases in the order shown in Fig 2.0 below.
Note that this is a comparison of orbitals in the same shell.
s p d f A shell can be thought of as a discrete energy level, the level
being measured relative to the nucleus. One way to
least energy understand this is to think of the nucleus as the ground level.
m ost
energy The shell which is closest to the nucleus is like an object which
is closest to ground level.Such an object has the least
most stable least stable
Fig (potential) energy and it is the most stable. A shell which is
(closest to (furthest
2.0 nucleus) from farther from the nucleus is like an object well raised above
nucleus) ground level. Such an object has alarge potential energy and is
relatively unstable.
The principal quantum number (n = 1, 2, 3 e.t.c) describes the energy of a shell and its orbitals. The
energy of a shell and its orbitals increases as n increases, for example, the shell n= 3 is at a higher energy
level (farther from the nucleus) than the shell n=2.

A shell which is closer to the nucleus has less energy and is more stable than a shell which
is farther from the nucleus.

If an orbital is close to the nucleus its electrons are tightly held by the attractive force of the protons. Such
electrons are not easily removed or transferred during chemical reactions (they are stable). Shells which
are a large distance from the nucleus feel a small attractive force of the nucleus. Such electrons are easily
lost or transferred during reactions, that is, they are relatively unstable.
From this discussion, it can be deduced that it is the outer-most electrons (valence electrons) which
participate in chemical reactions. They are the farthest from the nucleus and the most weakly held to the
atom (least stable).

Nature of the orbitals

The s orbitals
The s orbitals are spherical. They have the least energy in any given shell. In other words, they are closest
to the nucleus and they are the most stable.
The designation 1s, 2s, 3s... is used to represent s orbitals in different shells (different energy levels).
The coefficients 1, 2, 3 e.t.c represent the principal quantum number, n which defines the shell
(energies level) in which the orbital is found. The larger the value of n, the higher in energy and the more
unstable the orbital. Even though the s orbitals are the closest to the nucleus in any given shell, they have
different energies depending on the value of n. For instance, the 2s orbital is higher in energy and more
unstable than the 1s.
Apart from affecting the relative energies of the orbitals, the principal quantum number n also determines
the size of the orbital. The smaller the value of n, the smaller the orbital. When n is small, the orbital is
close to the nucleus and so it is strongly pulled inwards by the attractive force of the protons, shrinking its
size.
For example, comparing the 1s and 2s orbitals(Fig 2.1), the 2s orbital is:
 larger
 higher in energy
 less stable
 further from the nucleus

The p orbitals
These dumb - bell shaped orbitals are higher in energy than
the s orbitals in any given shell.
The p sub-shell is made up of three orbitals, the px, the
pyand the pz. They have the same shape and same energy
(that is, they are degenerate) but they differ in orientation.
The px has lobes along the x - axis, the pz along the z - axis
and the py along the y- axis(Fig 2.2). Note the use of the term
Fig 2.1 The 1s and 2s orbitals have sub-
similar shapes (spherical) but differ shell.
in distance from the nucleus, energy Sub-shells are orbitals that share the same shell
and size.

The d orbitals
In a particular shell, the d - orbitals are higher in energy than the p - orbitals. There are five orbitals in the
d sub- shell, and in the neutral atom they are degenerate, that is, they are at the same energy level. These
five orbitals are designated
dxy, dxz, dzy, dz2and dx2- y2
The shapes and orientations of the d- orbitals are shown in Fig 2.3.
 Fig 2.1 Shapes and orientation of the p orbitals. (a) The direction convention used in
chemistry. (b), (c) and (d) Orientation of the pz, py and px orbitals. (e) Degenerate p orbitals
form the p sub - shell. These three orbitals are mutually perpendicular and their nodes coincide
with the nucleus. The nodal plane is a region in which the probability of finding an electron is
zero. The central position of the nodal plane is known as the node, and this
coincides with the nucleus.

Fig 2.2 Shapes of

the d-orbitals.
Which orbital is not
shown here?

Note the following about the d – orbitals:

 The first three havelobes between the axes, for example, the dxyorbital has lobes between the x
and the y-axes, as shown in Fig 2.3.You can easily remember the names of these three orbitals by
noticing that the names take all possible combinations of two letters from the letters x, y and z .
  The last two d-orbitals (dz2and dx2 – dy2 ) have
lobes along the axes. The dz2 has two lobes which
lie along the vertical (z) axis. The dx2 –y2orbital
has four lobes which lie along the x and y axis.
 Of the five d-orbitals, four have four lobes and
have the same general shape. The dz2 has a
unique shape. It has two lobes and a ring around
the nodal region (Fig 2.4).
Fig 2.3
Electrons can be found in lobes and the ring, but not at the node
(nucleus) and nodal plane.

An important note
The diagrams of orbitals given so far should be understood only as models. Real orbitals
do not have clearly cut boundaries as depicted in the diagrams. Further more, the
diagrams give the impression that orbitals are solid structures in which electrons reside.
This is misleading. An orbital has no structure but is simply the volume of space in
which electrons spend most of their time, that is, the probability of finding an electron
in that region is close to 100%. In advanced work, the orbitals are interpreted as
mathematical functions.
Consider the hydrogen atom which has only one electron. This electron has kinetic
Fig 2.4 The dz2 energy and is free to move within a volume of space whose boundaries are
orbital approximately spherical. Since the electron moves very fast, if we were able to see it, it
would appear as if it were everywhere at the same time, and it would appear like an
electron cloud occupying a roughly spherical volume.

An orbital is the volume of space in which an electron spends most of its time. The probability of
finding an electron within this volume of space is approximately 100%.

2.2.2 Electronic configurations: The Aufbau method

The term aufbau is a German word, meaning to “build up”. The Aufbau method gives rules about how
electrons enter the atom. These guidelines should be followed when writing electronic configurations for
atoms.
An electronic configuration shows how electrons are arranged in an atom.

Rules for filling electrons in an atom by the aufbau method

1. Electrons will enter the lowest energy orbital first.
The 1s orbital, which is closest to the nucleus, and which feels the greatest pull by the nucleus, will
always be filled first.
2. Hund’s rule of maximum multiplicity.
A maximum of only two electrons may occupy an orbital, and these two electrons must be spin paired.
3. Pauli’s exclusion principle
Electrons will first occupy orbitals singly, thereafter pairing may occur according to Hund’s rule.
Since there is only one orbital in the s sub-shell, according to rule 2, this sub shell can carry a maximum of
only two electrons. The p sub-shell has three orbitals, so it can contain a maximum of six electrons. The d
sub-shell, with five orbitals, will carry a maximum of ten electrons (Table 2.1).

Sub-shell Number of orbitals Maximum number of

in the sub-shell electrons that may enter each
sub-shell

s 1 2

p 3 6

d 5 10
Table 2.1
f 7 14

Consider the p sub - shell, with three degenerate orbitals. Also suppose that we wish to fill them with five
electrons. Rule 3 says we should first make sure that each orbital has a single electron; only then can we
start pairing them (Fig 2.5).

Fig 2.5

The concept of spin pairing

The electron is always spinning about an axis. When ever a charged particle moves, it generates a
magnetic field around it. When two electrons co-exist in the same orbital, they must spin in opposite
directions, that is, one should have a clockwise spin and the other should have an anticlockwise spin. By
spinning in opposite directions, the magnetic moments of the two electrons cancel each other (magnetic
moments are vector quantities, so they amplify or deplete each other depending on their size and the
directions in which they are operating). The canceling out of magnetic moments means that there is no
net magnetic field in the orbital and this tends to stabilize both electrons. The phenomenon in which two
electrons in an orbital spin in opposite directions is known as spin pairing.
By convention, the up half -arrow (↿) is used to represent the clockwise spin and the down arrow (⇂) the
anticlockwise spin.

The electronic structure framework

Electrons will enter orbitals in the order given below:

In so doing, electrons enter the lower energy orbitals first. The electronic configuration of a hydrogen
atom (atomic number 1) is the simplest, having only one electron to account for:
H: 1s1
The next atom, He, has two electrons, giving the electronic configuration
He: 1s2
With two electrons, the 1s orbital is now full. Any subsequent electrons will have to enter the next shell.
Helium, with an exactly filled shell, is very stable and is classified among the stable Group 0(noble)
elements. Table 2.2 below shows the electronic configurations of the rest of the elements up to Ca.

The reader should complete the table by filling in the last column (from Al to Ca).

Table 2.2

Points to note
1. Certain configurations are associated with stability. There is stability associated with an exactly half
filled or exactly filled sub-shell or shell. The p3 configuration (half filled), as in nitrogen, is relatively
stable.
This stability is explained in terms of the symmetric occupancy of orbitals that occurs when sub-
shells or shells are exactly half - filled or exactly filled.

2. Whenever the outer-most (valence) shell is filled with eight electrons (an octet), the element is very
stable and is classified as a noble element (Group 0). An exception to the octet rule is Helium. It is in
Group 0 even though it has two electrons (a duet) in the outer-most shell. However, the outer- most shell
in helium is exactly filled, so helium is as stable as the other noble gases.

The concept of shells

You may remember showing the electron arrangement in an atom (such as sodium) diagrammatically as
shown in Fig 2.6.
Na:proton (atomic) This diagram shows that the atom has three shells of electrons around the
number 11 nucleus. But what exactly is a shell? Can we deduce the number of shells from
the electronic configuration?
Study the electronic configuration of Na:
1s2 2s22p⁶ 3s1
Recall that the coefficients (principal quantum number) of each orbital
represent the energy of that orbital. The obvious conclusion is that orbitals
Fig 2.6 with the same principal quantum number have similar energies. Such orbitals
form a shell.

A shell is an energy level made up of orbitals (sub shells) with the same quantum number, and
hence with similar energies.
However, this generalization fails when the distance of the shells from the nucleus increases. In such
cases, it is found that a shell may contain sub-shells that have different principal quantum numbers.

Since there are three values of n in the configuration of sodium, that is, 1, 2 and 3, we conclude that a
sodium atom has 3 shells, the shell n=1 ( K shell), n=2(L Shell) and n=3(M shell).
The K shell always has one sub shell ( the 1s) . This shell is the lowest in energy. The L shell always has two
sub shells; the 2s and the 2p. The M shell always has two sub shells; the 3s and the 3p, as illustrated for
the sodium atom in Fig 2.7.
 The s orbital is always lower in energy (closer to the nucleus) than the p orbital, even when they
belong to the same shell (same principal quantum number n).
 The 1s orbital (K shell) is the nearest to the nucleus. It is therefore the most stable because it feels
the strongest attraction by the nucleus. It is also the smallest.
 The L shell has two sub-shells, the 2s and the 2p. The total number of electrons in the two sub-
shells (in this case, 6+2) gives the total number of electrons in the shell. The two sub - shells in
the L shell are equivalent (not equal) in energy; the 2s orbital is slightly lower. However, the
energy difference between the two sub- shells is very small. In fact, it is so small that the two sub-
shells behave as a single shell.
 As the value of n increases, the shells move outwards from the nucleus and become larger. The
largest value of n corresponds to the outer-most shell. Thus in Na the outer - most shell
is the 3s (n=3, M). The outer- most shell is also referred to as the valence shell. It is the least
stable. Being farthest from the nucleus, the electrons in the shell are relatively weakly held to the
atom. The electrons therefore easily participate in chemical reactions.
 Fig 2.3 The three shells
(energy levels)in an atom of
Na. Notice that the second
shell is made up of two sub-
shells, the 2s and the 2p, giving
a total of eight electrons.

Relative energies of the orbitals

Imagine stacking empty orbitals one above the other, starting with the least energy orbital. The order
obtained would be as shown in Fig 2.4 below.
Electrons enter the orbitals in the order shown on the left, up
to calcium. Calcium, with 20 electrons has the configuration.
1s22s22p63s23p64s2
The 3d-orbitals, though present, remain empty because they
are higher in energy than the 4s shell. The last shell (valence)
shell in Ca is therefore the 4s, which contains two electrons.
This explains why Ca achieves the +2 oxidation state in all of
its compounds, corresponding to loss of the 2 valence
electrons.
Fig 2.4 Energy level diagram Take note of the following:
for the empty orbitals up to the The energy levels of the 4s and the 3d are reversed when
3d. electrons start to enter the 3d orbitals, as shown in Fig 2.5

This is often a source of confusion among students. The order

given in Fig 2.4 is what we would expect if the 3d orbitals were
not occupied. However, as soon as electrons begin to enter the
3d orbitals, they repel electrons in the 4s orbital. The effect is
that the 4s electrons move farther from the nucleus, that is,
they become higher in energy than the 3d orbitals.
This is illustrated below for scandium, titanium and bromine.
21 Sc : 1s22s22p63s23p63d14s2
22 Ti : 1s22s22p63s23p63d24s2
Fig 2.5 The relative energies of
the 4s and the 3d orbitals are 35 Br : 1s22s22p63s23p63d104s24p5
reversed when electrons start
entering the 3d orbitals
 By writing these configurations in this way, it becomes clear that the valence shell in the transition
elements, in this case, Sc and Ti, is the 4s. We therefore expect the transition elements to lose electrons
from the 4s orbital first during chemical reactions. This is what is actually observed. The transition
elements have a +2 oxidation state, corresponding to the loss of the outer-most 4s electrons. However, in
some books these configurations are written so that the 4s comes before the 3d. This is misleading
because it gives the wrong impression that during reactions, transition elements lose electrons first from
the 3d sub-shell.
It should also be mentioned at this stage that
as distance from the nucleus increases (increasing values of n), the difference in energy between
consecutive shells becomes so small that they practically behave as one shell.

1 Thus the 3d and the 4s shells behave as one shell in the chemistry of the transition elements.
The 4s is slightly higher than the 3d, so electrons are lost from the 4s orbital first. However, electrons are
also lost from the 3d orbitals due to the closeness in energy to the 4s shell. This explains why transition
elements exhibit variable oxidation statesin their compounds. Different numbers of electrons can be lost
in addition to the two 2s electrons, thus giving rise to different oxidation states. Consider calcium and
managanese as examples. Ca, a non-transition element, has only one oxidation state in all of its
compounds, corresponding to the loss of the two valence electrons in the 4s shell. Mn, a first row
transition element, has oxidation states from +2 to +7 in its compounds. The +2 state corresponds to loss
of the two outer-most 4s electrons. The +3 to +7 states correspond to further loss of electrons from the 3d
orbitals.

2. The 4s, 3d and 4p sub-shells behave as a single shell, which can hold up to 18electrons.
Consider the electronic configuration of Br (atomic
Sub-shell maximum occupancy number 35)
35 Br : 1s22s22p63s23p63d104s24p5
3d 10
The outer-most shell is the shell n=4, made up of the
4s 2
4s and the 4p orbitals. This shell therefore contains 7
4p 6 electrons. However, the 3d shell is so close in
TOTAL 18 energy to the 4s and the 4p sub-shells that it
behaves as if it were part of the valence shell.This
explains why the fourth shell in Br is said to have 17
electrons (10 from 3d, 2 from 4s and 5 from 4p). The configuration for Br can be written in terms of shell
occupancy as 2.8.8.17 (Fig 2.6).
Fig 2.6 Electronic structure of a bromine atom.
There are four shells, which is equal to period number. The fourth
shell, containing 17 electrons, is made up of the 3d, 4s and 4p sub
shells. When electrons are lost from the bromine atom, they come
from the outer-most sub shells first, the 4s and the 4p, which
contain a total of seven electrons. Similarly, when a bromine atom
gains an electron, it enters the highest sub shell, which is the 4p.
This gives the bromide ion the stable 2.8.8.18 configuration of
argon.

The next element after bromine is Ar, which has a total of 36 electrons. The fourth shell in Ar is exactly
filled with 18 electrons, explaining its position inGroup 0.
Ar:2.8.8.18
If we decide to treat the valence shell in Ar as being made up of the 4s and the 4p sub shells only, as is
often the case, then the number of valence electrons would be 8.

2.2.3 Relating electronic structure to the Periodic Table

 The number of shells in an atom of an element is equal to the period number for that element.
 The highest value of n in the electronic configuration corresponds to the outer-most shell, which
is the highest in energy. This is the first shell to participate in chemical reactions.
 The number of electrons in the outer-most shell corresponds to the group number for that
element.
 As shells move further and further from the nucleus, their energies become similar, and they may
be regarded as a single shell. This explains why the fourth shell and the fifth shells are said to take
a maximum of 18 electrons. Fig 2.7 shows at a glance the relationship between electronic
structure and position of an element in the periodic table.

Fig 2.7

 Fig 2.7 also emphasizes the fact that across a period, electrons enter the same shell, and for the
first three periods, the term same shell actually means same principal quantum number n.
However, from the fourth shell onwards, we see that the same shell can have sub-shells with
different principal quantum numbers.
 Going down groups, new shells are opened, represented by larger values of n. The opening of new
shells has the effect of increasing the size of atoms. For instance, the potassium atom, with four
shells, is larger than the sodium atom which has three shells. We also infer that potassium is more
reactive than sodium. Because of its large size, the outer-most electron in potassium is a large
distance from the nucleus. Consequently it is relatively weakly attracted to the nucleus. The
electron is therefore quite easily lost during reactions.
2.2 .4 The transition elements
The elements after calcium, that is scandium to zinc, form the first row of transition elements. Across this
row, electrons enter the d sub-shell.Here is the electronic configuration of calcium, which just precedes
scandium.
Ca (atomic number 20): 1s2 2s2 2p6 3s2 3p6 4s2
It has already been mentioned that in the transition elements, the 4s sub-shell is higher in energy than the
3d sub-shell. In the transition elements, electrons therefore enter a lower energy (penultimate) 3d sub-
shell. Thus in writing the electronic configurations of the transition elements, we show the 3d sub-shell
before the 4s sub-shell (Fig 2.8).

By the time electrons enter the 3d sub shell, the 4s sub shell is already
occupied. As electrons enter the 3d sub shell, they repel electrons in the
4s sub shell, causing it to rise in energy. The 4s therefore becomes the
outer most sub shell, as shown in the diagram. However, the 4s and the
Fig 2.8 3d are so close in energy that in chemical reactions, they behave as one
shell.

Table 2.3 gives the electronic configurations of the elements Sc to Zn.


In the transition elements, electrons enter the
3d sub-shell. We might have expected them
to enter the 4p sub- shell. However, the 4p
sub-shell is higher in energy and will only be
occupied after the 3d sub-shell is fully
occupied by 10 electrons.
 There are five orbitals in the d sub-shell.
These five orbitals, designated dxy , dxz , dzy ,
dz2 and dx2-y2areat the same energy level in
the neutral atom ( that is, they are
degenerate).
 According to the rules of electron filling up,
these five d orbitals are filled singly first up to
manganese. At manganese the d sub-shell is
now exactly half filled. There is an extra
stability associated with an exactly half filled
sub-shell; this stability is a result of
thesymmetric distribution of charge
(electrons).
 After manganese, that is, from iron and
onwards, electron pairing begins until the
Table 2.3Electronic configurations of the orbitals are fully occupied at copper and zinc.
transition elements from Sc to Zn There is also extra stability associated with a
fully occupied sub-shell.
 The configurations of chromium and copper are unexpected. We would have expected the
following configuration for copper(atomic number 29)
1s22s22p63s23p63d94s2.
 What actually happens is that an electron is unpaired from the 4s sub-shell and enters the 3d sub-
shell. This results in the formation of an exactly filled d sub-shell (with 10 electrons), which is a
stable configuration. The same thing happens at chromium, atomic number 24. The expected
configuration for Cr is 1s22s22p63s23p63d44s2.The actual configuration is 1s22s22p63s23p63d54s1
As in copper, an electron leaves the 4s sub-shell and enters the 3d sub-shell. This creates
an electronic configuration in which the d sub- shell is exactly half filled. Such a configuration is
relatively stable.

The d4 and d9 configurations, expected in Cr and Cu respectively, do not exist. They are replaced by the
relatively stable d5 and d10 configurations respectively. The 4s sub shell in Cr and Cu is therefore occupied
by a single electron. The rest of the first row transition elements have the general configuration 4s 23dn.

2.2.5 The short-hand notation

The electronic configuration of an element can be abbreviated as shown below.

The rest of the

configuration ( the noble elements)
do not have this part.

Core: noble gas

configuration

The table 2.4 shows the short-hand notation for some elements.

element number of full configuration abbreviated configuration

electrons
Li 3 1s22s1 He 2s1

Be 4 1s22s2 He 2s2

B 5 1s22s22p1 He 2s22p1

Na 11 1s22s22p63s1 Ne 3s1

P 15 1s22s22p63s2 3p3 Ne 3s2 3p3

K 19 1s22s22p63s2 3p64s1 Ar 4s1

Ca 20 1s22s22p63s2 3p64s2 Ar 4s2

1 2
Sc 21 1s22s22p63s2 3p63d14s2 Ar 3d 4s

V 23 1s22s22p63s2 3p63d34s2 Ar 3d34s2

Cr 21 1s22s22p63s2 3p63d54s1 Ar 3d54s1 Table 2.3 Short hand

configuration for some
9 1
Cu 21 1s22s22p63s2 3p63d94s1 Ar 3d 4s elements
Summary

 Electrons enter the orbitals starting with those of the lowest energy. Only two electrons may enter
an orbital and they must be spin paired. The orbitals in any shell are filled in the order s, p, d, f.
 The electronic configuration framework gives the order in which electrons enter the atom: 1s 2s
2p 3s 3p 4s 3d 4p 5s …
 The coefficients in this framework represent the energies of the orbitals. The coefficient is known
as the principal quantum number. Orbitals of the same principal quantum number belong to
the same shell. However, as distance of the shells from the nucleus increases, the shells become
closer and closer to each other in energy, so that they may behave as a single shell.
 A notation like s or p shows an orbital. If the notation includes a principal quantum number, e.g.
1s and 2p, it represents an energy level or a sub-shell.
 In noble elements the outer most p sub-shell is exactly filled with the maximum possible number
of electrons, that is, 6. All in all, the valence shell (ns, np) has a total of 8 electrons (an octet). This
octet configuration renders stability to the noble gases.
 In the transition elements, electrons enter the penultimate 3d sub-shell. Penultimate here means
‘underlying’, because in terms of energy, this shell is lower in energy than the occupied 4s sub-
shell. This is only true when the d-orbitals are occupied. When the d-orbitals are unoccupied, they
are higher in energy than the 4s, for example in Ca.

2.2.6 Evidence for electronic configurations

1. Formation of ions
Consider the elements in Period 3, Na to Cl. The first three elements, Na to Al are clearly metallic in
nature. In their reactions, they tend to form positiveions (cations) by losing valence electrons. But why is
it that sodium will form +1 and not + 2 ions, and magnesium will form + 2 ions, not +3 ions?
It is only the valence electrons that participate in chemical reactions. Being the farthest from the nucleus,
they are the least stable. They feel only a weak attraction by the nucleus and so they are easily lost.
Consider the configuration of a sodium atom
1s22s22p63s1
There is only one electron in the valence 3s shell. When sodium reacts, it loses this electron to form a
positive ion with a charge of +1. Note that formation of the ion exposes a shell filled with eight electrons
(stable octet). The cation formed therefore has the same stability observed in the noble gases. There is no
further tendency to lose an electron from the stable outer shell of the ion (Fig 2.9).

Na (Z=11)
electron lost
from valence shell

Na atom with one

Na+ion with a full
electron in valence
shell(unstable) octet in the outer-most Fig 2.9 Formation of
shell(stable) the Na+ ion.

Similarly, from the configurations of Mg and Al we deduce that only two and three electrons will be lost
respectively, forming the same stable core as in sodium (Fig 2.10).
 Na 1s22s22p63s1 los
es
1e-

Mg 1s22s22p63s2 loses 2 e -
n+
- 1s22s22p6
3e
2 2 6 2 1 loses stable neon core formed.
Al 1s 2s 2p 3s 3p
Fig 2.10
n= 1,2,3 respectively.

Note that the Na⁺, Mg2+ and Al3+ ions contain the same number of electrons ( they are isoelectronic).

2. Change in atomic radii across a period and down a group.

Atoms tend to shrink in size across the Periodic Table, but they increase in size down groups. Once more,
these observations can be explained by studying the pattern in electronic configurations down groups and
across periods.
Going across the periodic table, electrons enter the same shell. No new shells are opened, and so there is
no increase in the shielding effect. However, the number of protons in the nucleus increases across a
period. This increases the ability of the nucleus to attract shells inwards towards itself, resulting in a
decrease in atomic radii. Thus the sodium atom is much larger than the chlorine atom which is in the
same period. The change in atomic radii also influences the chemical properties of the elements. The
sodium atom, being large in size, will react by losing electrons because the outer-most shell, apart from
being sparsely populated, feels a weak attraction by the nucleus. On the other hand, chlorine, and indeed,
non metals, tend to react by gaining electrons, because the atoms are small so that the outer shell is closer
to the nucleus. Electrons in the outer-most shell feel a strong attraction by the nucleus. It is therefore
difficult to lose an electron from the outer shell. However, it is easy to gain an electron or electrons in the
outer shell because the incoming electron(s) feel a strong attraction by the nucleus.
Down the group, atomic radii tend to increase. This is because in moving from one element to the next
down a group, an additional shell is opened. The consequence of increasing atomic radii includes
 the tendency for elements to become more metallic down the group. It becomes easier for the
atoms to lose the valence electrons, which is what characterizes metals. A very good illustration of
this observation is found in the Group IV elements. Carbon is a non metal. Silicon and germa-
nium are metalloids, tin and leads are metals.
 Increasing reactivity of the metals down their respective groups. Metals react by losing valence
electrons. A metallic atom becomes more reactive as its size increases. This is because the valence
electrons are then a large distance from the nucleus and so they are only weakly held to the atom
by the attractive influence of the nucleus. T
 Increasing of the shielding effect down the Groups. The electrons in an atom are preveneted
from leaving the atom by the attractive influence of the ncuclues. Inner shells have a tendency of
preventing outer shell electrons from feeling the full attractive influence of the nucleus. This phe-
nomenon is known as shielding. Going down a group, the number of shells increases, and so does
the shielding effect. The valence shell electrons are therefore more weakly held to the atom as the
group is descended.

3. Ionization energies.
A formal definition of ionization energy will be given later on. For the time being, we will define it as a
measure of the amount of energy needed to knock out a valence electron from the atom of an element.
 In general, ionization energy increases across the periodic table. This is because proton number
is increasing and yet electrons are entering the same shell. The increase in proton number implies
that the outer shell electrons feel an increasing attractive force of the nucleus. The electrons
become more and more firmly held to the atom because the increase in the shielding effect is
 verysmall when electrons enter the same shell. Increasing amounts of energy are therefore
required to remove an electron from an atom as proton number increases across the period.
 However, the increase in ionization energy across the periods is not so straightforward. There are
some anomalies (irregularities) in this general trend, as illustrated for Period 3 in Fig 2.11.

Ar
Cl
I.E1 P
Si
Mg S
Al
Na

Ar
Trend in first ionisation energy , IE1 across the periodic table. IE1 Fig 2.11 Trend in first
is a measure of the energy required to remove an electron from ionization energy across
the outer - shell of an atom. Period 3.

(i) The ionization energies of aluminium and sulphur are lower than expected. These anomalies can be
explained in terms of the electronic configurations of the elements.
Mg 1s22s22p63s2
Al 1s22s22p63s23p1
In Al, the electron to be removed comes from a p sub-shell which is higher in energy (farther from the
nucleus) than the 3s sub-shell from which an electron would be removed fromP. It is therefore easier to
remove an electron from Al than from Mg, that is, Al has the lower ionization energy. Now compare the
electronic configurations of phosphorous and sulphur.
P 1s22s22p63s23p3
S 1s22s22p63s23p4
In sulphur, the electron to be removed comes from a p-orbital which is occupied by two electrons. The two
electrons in this orbital repel each other so that it becomes relatively easy to remove any one of them.
Compare with nitrogen, in which all 3p orbitals are singly occupied. Further more, the exactly half filled
3p sub-shell in a phosphorous atom leads to stability of the sub-shell, so that it is not so easy to lose an
electron from it. Sulphur therefore has a lower ionization energy than nitrogen.
Ionization energy decreases down a group. As additional shells are opened, the outer shell electrons
become further and further from the nucleus. They feel a decreasing attractive force of the nucleus and so
can more easily be removed.
 Ionization energy decreases down a group. As already explained, atomic sizes increases down a
group due to increasing number of shells. This has two effects which both lead to a reduction in
ionization energy.
(i) As the number of shells increases, the valence electrons experience more shielding from
the inner shells. The valence electrons therefore feel a weaker attraction from the nucleus.
(ii) As the atom becomes larger, so does the distance of the valence electrons from the
nucleus. Once more, the valence electrons feel a weaker attraction from the nucleus. It is
therefore easier to remove an electron from the outer most shell as a group is descended.
The graphic in Fig 2.11 illustrates the fact that ionization energies increase across a period but decrease
down a group (or increase up a group).
 Fig 2.11 Trend in ionization
energyacross periods and down
groups.

Successive ionization energies

Removal of an electron from an atom results in the formation of a +1 cation. The energy required for this
conversion is measured by the first ionization energy(IE1). If a second electron is removed from the +1
ion, a +2 ion is formed. The energy required to convert a +1 ion into a +2 ion is measured by the second
ionization energy (IE2) for that element. Similarly, the energy required to convert a +2 ion into a +3 ion is
the third ionization energy (IE3). IE1, IE2, IE₃ e.t.c are known as successive ionization energies for the
element under consideration. It is possible to deduce the position of an element in the Periodic Table by
studying its consecutive ionization energies.

Example 1
The successive ionization energies of an element Q are given below. Deduce, as far as possible, the
position of the element in the periodic table.

1st 2nd 3rd 4th 5th 6th 7th 8th

Ionization energy/ Kjmol-1 736 1450 7740 10 500 13 600 18 000 21 700 25 600

Solution and discussion

First notice that successive ionization energies have an increasing trend. This is expected. Suppose that an
atom X loses an electron to form the ion X⁺. It is going to be harder for the ion to lose another electron
to form the +2 ion.
X⁺→ X2+ + e
This is because the second electron to be lost must come from a positively charged particle to which it is
naturally attracted. An electron naturally resists being removed from a centre of positive charge. For this
reason, the second ionization energy of an element is higher than the first.
 Similarly, the third, fourth (e.tc.) ionization energies increase in that order because as the size of the
positive charge on the ion Xn+ increases, the electron to be lost becomes more and more strongly held to
the ion. For example, the third
ionization energy involves the process
X2+ →x3+ + e
and a very large amount of energy is required to knock out an electron from the +2 ion.
However, if you study the values given in the table above, you will find that there are sudden ‘jumps’ in the
ionization energies at some points. These sudden increases in energy can not be explained simply in terms
of an electron finding it harder to leave an ion with a large positive charge.
A change of the shell from which the electron is removed causes such abrupt changes in energy.
Successive ionization energies can therefore be used to deduce the energy levels (shells and sub-shells) in
an atom, and in turn this information can be used to deduce the position of the element in the periodic
table. In the given table, the sudden increase in energy is at the third ionization energy.This means that
the first two electrons removed came from the valence shell, but the third came from a new shell, which is
closer to the nucleus. Since the element has two valence electrons, we conclude that it is in group II.

If the first sudden increase in ionization energy is at the nth ionization energy, then the element
must be in Group (n-1).

In the given example, the first sudden increase in ionization energy was at the 3 rd ionization energy, so the
element must be in group (3-1) =2.
The element can not be Beryllium due to the fact that Be has too few electrons compared to the number of
electrons lost from the atom Q.

Example 2
Successive ionization energies are given below for an element M. Deduce, as far as possible, the
position of the element in the periodic table.

1st 2nd 3rd4th 5th 6th 7th 8th

Ionization energy/ Kjmol -1 1310 3390 5320 7450 11 000 13 300 71 000 84 100

Solution and discussion

The first large ‘jump’ in ionization energy is at the 7th value. The element must Be in group VI. However,
there is evidence of the existence of sub-shells. The fifth ionization energy shows a relatively large jump
compared to the values preceding it.However, it is not large enough to lead us to a conclusion that the 5 th
electron is coming from a new shell. Assuming that the element is indeed in Group VI, and that it has six
electrons in the outer- most shell, then four of these six valence electrons must be in the p sub-shell.
When all these four electrons have been lost, the next two electrons must come from a new sub- shell (the
s), as shown by the relatively large jump in the fifth ionization energy. However, the fifth and sixth
electrons are still coming from the valence shell (a different sub shell of the same shell), so the change in
ionization energy is not too high.
 [Type a quote from the document or the summary of an interesting point. You can position the text
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1 Sir James Jeans, who was a great populariser of science, once described an atom of carbonas being
like six bees buzzing around a space the size of a football stadium.
(a) (i) Suggest what were represented by the six bees in this description.
(ii) Explain (in terms of an atom of carbon) what stopped the bees from flying awayfrom the
space of the football stadium.
(iii) What is missing from Jeans’ description when applied to an atom of carbon?
(b) The diagram below represents the energy levels of the orbitals in atoms of the secondperiod,
lithium to neon.

(i) Label the energy levels to indicate the principal quantum number and the type oforbital at
each energy level.
(ii) In the space below, sketch the shapes of the two types of orbital.
(iii) Complete the electron configurations of nitrogen and oxygen on the energy leveldiagrams
below, using arrows to represent electrons.
(iv) Explain, with reference to your answer to (iii), the relative values of the first ionization
energies of nitrogen and oxygen. The values are given in the DataBooklet and should be
quoted in your answer.
(c) (i) State the formulae of the negatively charged ions formed by these elements insimple binary
compounds (nitrides and oxides).
(ii) Why do nitrogen and oxygen form negative ions, but not positive ions, in simplebinary
compounds?
9701/04/M/J/07

2Which isotope of an element in the third period of the Periodic Table contains the same
number ofneutrons as S?
ANaBMgCSiD P

3The successive ionisation energies, in kJ mol–1, of an element X are given below.

870 1800 3000 3600 5800 7000 13 200
What is X?
A33AsB40ZrC 52Te D 53I

4Unnilpentium is an artificial element. One of its isotopes is 105Unp262

Which of the following statements is correct?
A 105Unp262 has a nucleon number of 105.
BThe atom 105Unp260 is an isotope of 105Unp262.
CThere are 262 neutrons in105Unp262.
DThe proton number of 105Unp262 is 262.

5The table gives the successive ionisation energies for an element X.

What could be the formula of the chloride of X?

AXCl B XCl2C XCl3DXCl4

6What is the order of increasing energy of the listed orbitals in the atom of titanium?
A 3s 3p 3d 4sB 3s 3p 4s 3dC3s 4s 3p 3dD4s 3s 3p 3d

7 Which of the following particles would, on losing an electron, have a half-filled set of p orbitals?
AC–BNCN–DO+9701/04/O/N/2003

8Use of the Data Booklet is relevant to this question.

It is now thought that where an element exists as several isotopes, the stable ones usually
contain a ‘magic number’ of neutrons. One of these magic numbers is 126.
Which isotope is unstable?
A209Bi B208Pb C210Po D208Tl9701/04/O/N/2003
9An atom has eight electrons.Which diagram shows the electronic configuration of this atom in
its lowest energy state?

9701/04/O/N/2005
10 The first six ionisation energies of four elements, Ato D, are given.
Which element is most likely to be in Group IV of the Periodic Table?

9701/04/M/J/2005

11What is the electronic configuration of an element with a second ionisation energy higher than
that of each of its neighbours in the Periodic Table?
A1s22s22p63s2B1s22s22p63s23p1C1s22s22p63s23p2D1s22s22p63s23p3
9701/04/O/N/2005

12Gallium nitride, GaN, could revolutionise the design of electric light bulbs because only a small
length used as a filament gives excellent light at low cost.Gallium nitride is an ionic compound
containing the Ga3+ion.
What is the electron arrangement of the nitrogen ion in gallium nitride?
A1s22s2B1s22s22p3C1s22s22p4D1s22s22p69701/04/M/J/2006

13Use of the Data Booklet is relevant to this question.

The electronic structures of calcium, krypton, phosphorus and an element Xare shown.
Which electronic structure is that of element X?
A1s22s22p63s23p3B1s22s22p63s23p64s2
C1s22s22p63s23p63d64s2D1s22s22p63s23p63d104s24p6 9701/04/O/N/2006

14The graph shows the first thirteen ionisation energies for element X.
What can be deduced about element Xfrom the graph?
AIt is in the second period (Li to Ne) of the Periodic Table.
BIt is a d-block element.
CIt is in Group II of the Periodic Table.
DIt is in Group III of the Periodic Table.9701/04/O/N/2007

15 The first seven ionisation energies of an element between lithium and neon in the Periodic Table
are as follows.
1310 3390 5320 7450 11 000 13 300 71 000 kJ mol–1
What is the outer electronic configuration of the element?
A2s2B2s22p1C 2s22p4D2s22p6 9701/04/M/J/2009

16 Use of the Data Booklet is relevant to this question.

The elements radon (Rn), francium (Fr) and radium (Ra) have consecutive proton numbers in
thePeriodic Table.
What is the order of their first ionisation energies?

9701/04/M/J/2009

17 A simple ion X+contains eight protons.

What is the electronic configuration of X+?
A1s22s12p6B1s22s22p3C1s22s22p5D1s22s22p7
9701/04/O/N/2010

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box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
CHAPTER

CHEMICAL BONDING
3

Introduction
We live in a very stable universe. Matter does not just start falling apart around us. From this
observation alone we might begin to suspect that particles of matter are held together by strong
forces which prevent them from falling away from each other.
Indeed, these forces exist, and they are known as chemical bonds. The concept of chemical bonding in
chemistry is important as it helps to predict the relative stability, and hence reactivity, of matter. If
the atoms of a substance are held together by very strong chemical bonds, the substance is relatively
stable and is not easily converted to other substances.
There are three ways in which atoms may bond to each other.
(i) Covalent bonding
(ii) Ionic (electrovalent) bonding
(iii) Metallic bonding
A recurring concept in this topic is this:

All bonding (not just ionic) is electrostatic in nature

Type of bonding Nature of electrostatic

attraction

Covalent Attraction between electrons

located between two atoms of
a bond and the nuclei of both
atoms of that bond.

Metallic Attraction between a sea

of delocialised electrons and
positive metal atoms.

Ionic Attraction between positively

and negatively charged ions.
3.1 Covalent bonding
A covalent bond is formed by sharing of one or more electron pairs between two atoms. The simplest
example we can study is bonding in the hydrogen molecule (Fig 3.1). For a covalent bond to form between
two atoms, the appropriate orbitals from both atoms must approach each other and overlap. The electron
pair(s) contained in the overlap region is the covalent bond.

Why bonding occurs

By bonding, atoms achieve stability. For instance, a hydrogen atom is very unstable and does not have an
independent existence because of the single electron present in the outer shell. By bonding with another
atom, two things are achieved:
 The electron is paired up with another. Electrons tend to be more stable when they are paired,
because by pairing their magnetic moments cancel each other out (remember that when electrons
pair up they do so with opposite spins).
 Each atom then has the stable configuration of a noble gas in its outer-most shell. Inhydrogen,
each atom now has two electrons (a duplet) in the outer shell, just as in helium. In other
molecules, each atom of a bond strives to achieve an octet configuration in its outer-most shell, as
illustrated for the chlorine molecule in fig 3.2.

Bonding in hydrogen
Hydrogen has a single electron in an s orbital. The s orbitals of two atoms approach each other and
continue to do so until they have sufficiently overlapped, as illustrated in Fig 3.1 below. This results in the
formation of a σ bond.

Fig 3.1 sigma bonding

in the hydrogen
molecule
Bonding in the chlorine molecule
Each chlorine atom has seven electrons in the valence shell and is very unstable. As in hydrogen, a
chlorine atom has no stable independent existence. It tends to pair up with another chlorine atom,
forming a diatomic molecule, Cl2.

..
.. .
XX  The valence shell configuration of each Cl atom is 3s23p5, giving
X X a total of 7 valence electrons. Each atom therefore has an odd (un
..
X
paired) electron.
XX
 When the Cl-Cl bond forms, the odd electrons are paired up.
Cl [ 3s23p5] Cl [ 3s23p5] Each atom now contains a stable octet of electrons in the outer-
most shell.
 In the Cl2 molecule, each atom has three non-bonding pairs of

. ..
electrons (lone pairs). The two electrons shared between the two
XX atoms is known as a bonding pair.

.. .
X X
X Fig 3.2Sigma bonding in
XX chlorine

The following account explains the bonding in Cl 2 in terms of the valence shell electronic configuration of
each atom of the bond.

3.2 Sigma (σ) and pi (π) bonding

Formation of a covalent bond involves overlap of atomic orbitals. There are two possible orientations of
overlap.
 In sigma(𝜎)bonding, orbitals over-lap head-on.
 In pi(𝜋)bonding, orbitals overlap side-ways.
Sigma overlap has already been illustrated above for chlorine. Fig 3.3 illustrates some orbital
combinations that may lead to the formation of σ and π bonds.

 bonding is possible between ...

nucleus

...two px orbitals, ...or between a p orbital

(px, Py , pz) and an s orbital.

 bonding is possible between ...

...two pz orbitals ... or between two p y orbitals.

Fig 3.3 Formation of pi and sigma bonds

Bonding in oxygen (O2)

O : 1s22s22p4

The 2s and the 2p sub-shells make up the valence shell. There are 6 electrons in this shell, two short of an
octet. Each atom therefore needs two more electrons in its valence shell, and this can be achieved through
the sharing of two valence electrons between the two atoms. In each O atom, there are two p orbitals
which are singly occupied. It is these orbitals which overlap, forming a double bond between the atoms.
Two orbitals overlap sideways (π) whilst the other two overlap head-on (σ) as illustrated in Fig 3.4(a) and
(b).

Fig 3.4 (a)

 Fig 3.4 (b)

The bond between the two oxygen atoms therefore contains four electrons. It is a double bond, in which
one bond is σ and the other is π. Fig 3.4 below illustrates formation of a π bond by the overlap of two pz
orbitals.

Fig 3.4 The formation of a π bond in O2 by the overlap of twopz orbitals

How does a π bond differ from a σ bond?

On average, and for any given bond, π electrons are a greater distance from the nucleus than σ electrons.
π electrons are therefore diffuse(spread out) and relatively weakly held to the nucleus. The π bond is
therefore weaker, longer and is more easily broken than the σ bond. When a double bond is subjected to a
strain strong enough to cause bond breaking, it will always be the π bond that breaks first.
Organic compounds which contain the carbon to carbon double bond (alkenes) are quite reactive due to
the presence of the π electrons. The diffuse nature of the π bond and the fact that the π bond is relatively
weakly held by the nucleus makes the C=C bond an electron rich centre. Such a centre reacts by attracting
electron deficient species known as electrophiles.Because it is relatively weak, a π bond can not form a
single bond. Consider a chlorine molecule which contains a single bond. This bond can not be π; it would
be weak and will cause the molecule to be unstable.

All single bonds are sigma

Bonding in nitrogen(N2)
N: 1s22s22p3
In N, there are 5 valence electrons, contained in the 2s and the 2p sub-shells. The electrons in the 2s sub-
shell are already paired up, so they will not be involved in bonding. They will remain as a non
bonding(lone)pair of electrons. Each of the three 2p orbitals is singly occupied. Thus all three will overlap
and share their single electron with the corresponding orbital on another atom. That is, the p x of one atom
overlaps with the px of the other atom (σ), the py of one atom overlaps with a pyof the other atom (π). The
pz orbitals will do the same(π). The result is that each atom shares three electrons with the other atom,
forming three shared pairs of electrons, that is, a triple bond (Fig 3.5).

Fig 3.5 bonding in

nitrogen, N2

Important points to remember about π and σ bond formation

 If a bond is single, as in Cl2, then it is sigma.
 In a multiple bond (double or triple), only one of the bonds can be sigma. The rest are π.

3.3 The concept of hybridization

The methane molecule is drawn showing four covalent bonds around the C atom:

H
H C H
H
However, this does not agree with what we would expect from the electronic configuration of C:
C: 1s22s22p2
The configuration shows that the valence shell of C has two sub-shells, the 2s and the 2p. The 2s, being
fully occupied, may not participate in bonding. This leaves the 2p orbitals. But there are only two occupied
p orbitals which may participate in bonding, so we would expect C to form only two covalent bonds in its
compounds, for example, CH2 would be formed instead of CH4. The concept of hybridization has been
used to explain why carbon forms four covalent bonds in its compounds, not two.
3.3.1 Hybridization in methane
Here is the ground state configuration of a C atom:

Before hybridization occurs, an electron is excitedfrom the filled 2s sub-shell to the vacant 2pz orbital.
This creates four singly occupied orbitals, which may participate in bonding.

But before they overlap with orbitals from other atoms during bond formation, these four singly occupied
orbitals mix mathematically to form four equivalent hybrid orbitals. The hybrid orbitals have shapes
which ensure maximum overlap. The hybrids formed here are known as sp³ hybrid orbitals because they
are formed from the mixing of one s orbital and three p orbitals. Each hybrid orbital is occupied by a
single electron (Fig 3.6).

In methane, each hybrid orbital on the C atom overlaps

head-on with the 1s orbital of a hydrogen atom. Since
there are four hybrid orbitals, the carbon atom is able to
bond with four hydrogen atoms. Hybridization moulds
the hybrid orbitals so that they can overlap efficiently
with the 1s orbital of hydrogen, forming four sigma
bonds around the C atom.

Fig 3.6

Why hybridization occurs

Hybridization is the mathematical combination of orbitals to form hybrid orbitals. Before this happens,
an electron must be excited from the 2s to the the pz orbital. This requires an expenditure of energy since
the 2s sub-shell is lower in energy than the 2p sub-shell. However, the energy used is small since the 2s
and the 2p sub-shells belong to the same shell (energy level) and have similar energies. The energy used is
more than compensated for by the formation of a larger number of covalent bonds, for example, in CH4.
Bond formation has the tendency of stabilizing molecules, so the more bonds that can be formed, the
more stable the compound becomes. Thus methane is more stable than the compound CH 2 that would be
formed if hybridization did not take place. Hybridization also modifies orbitals, creating hybrids whose
shape, energy and orientation allows efficient overlap with orbitals on other atoms.
NB The compound CH2(methylene) does exist as an intermediate in certain types of reactions, but it is very unstable.
Its structure is shown below.

H
C
H

3.3.2 The bonding in ethene

A molecule of ethene is usually displayed as shown below.
Once more, we have to reconcile this structure with the electronic configuration of
a C atom. In ethene,there is a carbon to carbon double bond, made up of a π bond
and a σ bond (recall that in a multiple bond, there is always one σ bond). When C
forms four sigma bonds as in methane, it requires the use of four hybrid orbitals.
To form three sigma bonds as in ethene, three hybrid orbitals are required.

This implies that each carbon atom must use three bonding orbitals to make these hybrid orbitals. (Num-
ber of hybrid orbitals used by an atom in bonding is equal to number of atomic orbitals that mix to form
the hybrid orbitals). In ethene, each of the two carbon atoms is hybridized as shown below.

Formation of ethene in terms of orbital overlap takes place in this way:

 Each carbon atom has three sp2 hybrid orbitals and an unhybridized pz orbitals for use in bond-
ing. A hybrid orbital on one C atom overlaps head-on with a hybrid orbital on the other C, form-
ing a C to C sigma bond.
 A second hybrid orbital on each carbon atom overlaps head-on with the 1s orbital of H, forming a
C to H sigma bond.
 The third hybrid orbital on each C overlaps head-on with the 1s orbital of another H forming
another C to H sigma bond. The three hybrid orbitals on each carbon atom are therefore used in σ
 bond formation, resulting in the formation of a σ skeleton. The sigma skeleton only shows sigma
bonds (Fig 3.7).

H 1s H 1s
sigma skeleton

2 H
sp2 sp2 sp 1200 H
C 2 C C C
sp H
2
sp 2 sp H

H 1s H 1s
The three hybrid orbitals on each ...resulting in the formation of a
carbon atom overlap in sigma bond sigma skeleton. The three sigma
formation ... covalent bonds are spaced out at an
angle of 1200 relative to each other Fig 3.7Formation of
to minimize repulsion between C-C and C-H sigma bonds
them. in ethene.

 The pz orbital on the carbon atom is unhybridized and perpendicular to the pz orbital on the other
carbon atom. The two pz orbitals therefore overlap sideways to form a C to C π bond. The C to C
double bond in ethene therefore contains one sigma and one pi bond, as illustrated in Fig 3.8.

Fig 3.5 pi bond formation in ethene

3.3.3 Bonding in ethyne, C2H2

Ethyne has the structure shown below.
H C C H
It contains a C to C triple bond. In this multiple bond, only one is sigma. The other two are pi bonds. In
methane, carbon forms four sigma bonds and it is sp3 hybridized. In ethene, carbon forms three sigma
bonds and it is sp2 hybridized. We can guess that in ethyne, where each carbon atom forms only one sigma
bond, there is sp hybridization as illustrated below.



H  C C H

3.3.4 Bonding in carbon dioxide
Carbon has the valence structure:
… 2s22p2,
whilst oxygen has
… 2s22p4
There are therefore two singly occupied p orbitals in oxygen which can be used in bonding.
The two electrons in the 2s orbital of carbon are paired and can not participate in bonding unless they are
separated. The separation does happen, followed by hybridization, as explained before. There is sp
hybridization, as in ethyne. This results in the formation of two hybrid orbitals, leaving two orbitals on C
unhybridized (the py and the pz). The two unhybridized orbitals are at right angles to each other. There are
therefore a total of 4 orbitals to be used in bonding by the carbon atom, two sp hybrids and two
unhybridized orbitals.

 One hybrid orbital overlaps head-on with a bonding p-orbital on one oxygen atom, forming a C-O
sigma bond.
 The other hybrid orbital overlaps head - on with a p - orbital on the second oxygen atom,
forming the second C-O sigma bond. All hybrid orbitals on carbon are thus accounted for. This
leaves the two unhybridized py and pz orbitals.
 One unhybridized orbital, the pz, overlaps sideways with the remaining bonding p-orbital on an
oxygen atom, forming a π bond.
 The second unhybridized orbital on carbon overlaps sideways with the remaining p-orbital on the
second oxygen atom, forming another π bond. Each of the two C to O bonds therefore contains a
π and a σ bond (Fig 3.5).

Fig 3.5Bonding
in CO2

3.4 Dot and cross diagrams

We have described the bonding in some simple covalent molecules, including their dot and cross
diagrams. From now and onwards we put emphasis on the dot and cross diagrams, and hope that you can
 work out and describe the bonding in terms of the overlap of appropriate
atomic orbitals.
 deduce the numbers and nature of bonds (single ,multiple, dative) present in a molecule.
 determine the total number of electrons used by atoms in a molecule for bonding.

Guidelines for drawing dot and cross diagrams

1. Identify the central atom, for example, in methane, CH₄, there is a single atom of C. Thisbecomes the
central atom.
2.Deduce the number of valence electrons for the central atom.

The number of valence electrons is equal to group number

for example, C in group (IV) has 4 valence electrons.

3. Not all of the valence electrons on the central atom may be used in bonding. You have to decide how
many electrons will be used for bonding. To do this, you need to find out how much short the valence shell
is of an octet, for example, carbon, with a valence of 4 electrons, is short by four electrons.
4. Repeat steps 2 and 3 for the other atoms present in the molecule. Consider the carbon dioxide
molecule. The central atom, C, will use all four of its electrons in bonding, as already explained. O (group
VI) has six valence electrons, two short of an octet. It will therefore use two of its valence electrons for
bonding. This will leave out four electrons unused on O. Thesefour electrons will form two pairs of non
bonding electrons, also known as lone pairs.
5. Draw the dot and cross diagram, making sure each atom is using the correct number of electrons to pair
with electrons on the central atom, as worked out in 2 and 3 above.
You may need to do some ‘electron book-keeping’ to make sure you have used the correct number of
electrons. The total number of electrons shown in the dot and cross diagram should be equal to the sum of
the valence electrons of all the atoms used in bonding.For example, book-keeping for methane:

number of Check: there should be a total of 8 electrons in the dot and

valence electrons cross diagram for methane.
C 4 ‘Electron book-keeping’ becomes particularly useful when drawing
the dot and cross structures for ions.
H 1x4 = 4

Total 8 Book-keeping for methane

Important exceptions to the guidelines given so far

1. Some elements do not have enough valence electrons to satisfy an octet in their valence shell, even
when they share their valence electrons with other atoms in the formation of covalent bonds. Common
elements in this category are Be, B and Al. With only three valence electrons, the maximum number of
bonds that Al can form is three, as in AlCl3, which gives a sextet (set of six electrons) around the central
atom.
2. Some non- metallic elements can form more than four bonds around the central atom, that is, they are
able to exceed or expand the octet. Examples in this category include P, S, Cl, Br and I. Note that all
of them are in period 3 or beyond. Elements in periods 1 and 2 do not have the ability to exceed an octet,
as explained later on.
3. In odd electron systems it is not possible to pair up all electrons without leaving a single unpaired
(odd) electron in the outer most shell. An example is NO which has a total of 11 valence electrons.
Examples: dot and cross diagrams

1. CH4 (methane)
 Central atom is C. It has 4 valence electrons and will use them all in bonding.
 Hydrogen has one valence electron. It does not have to satisfy an octet. It only has to satisfy a
duet of electrons in its outer shell, because this will give it a stable Helium- like structure.
Hydrogen therefore uses the one available 1s electron, sharing it with an electron from C.
 The structure therefore has four single C-H (sigma) bonds.
H
X  Similar compounds formed by the group IV elements (such as
SiCl4) will have the same structure, because all of them, like C,
H X C XH
have 4 valence electrons.
X
H

2. H2O

O The oxygen atomneeds two electrons more to compete an octet. It will therefore
XH use two valence electrons for bonding. The water molecule has two bond pairs and
X
H two lone pairs (non-bonding pairs) of electrons.

Note
If asked in an exam to draw the dot and cross diagram of a molecule, you should not leave out lone
pairs, if any.

3. NH3 (ammonia)
 N, in group five, has five valence electrons. It needs three more electrons.

 Therefore it uses 3 of the valence electrons, sharing each of them with an

XH electron on H. This leaves a lone pair of electrons on the N atom.
N
XH  The molecule PH3 is analogous to NH3. They are both group V hydrides.
X
H

4. AlCl3
 Aluminium, in group (III), has 3 valence electrons. It needs five more electrons to satisfy an octet,
but there is no way it can obtain 5 electrons from 3 Cl atoms.
Al therefore uses all three valence electrons, each being paired with an electron
.. .
..Cl
..
from Cl. Chlorine, in group (VII), is one electron short of an octet. It will
x .. therefore use one electron for bonding, pairing it with an electron on Al.
Al x.Cl..
..Cl.x ..
.. .. NB In the following examples we will omit lone pairs (non-bonding pairs)
but remember that they should always be included in dot and cross dia-
grams.
 This leaves six electrons (3 lone pairs) unused on each Cl. Three Covalent bonds are formed
around Al. This means that even after forming covalent bonds, Al still has not satisfied an octet. It
lacks two electrons to fill an octet.
 AlCl3 is an example of an electron deficient molecule. This case is peculiar to molecules formed
by the group (III) elements, for example, boron triflouride (BF3) is also electron
deficient.
 AlF3 is the halide analogue of AlCl3. However, it is predominantly ionic, so it is outside the scope
of our current discussion on covalent bonding.

5. BeCl2
 Being in group two, Be needs 6 electrons to satisfy an octet. It therefore must share 6 electrons,
which is clearly impossible, since it has only two valence electrons. All it can do is form the
maximum possible number of bonds (two), by sharing each of its valence electrons with an
electron from Cl.
 Beryllium chloride therefore has two bonds, that is, four electrons around beryllium, four short of
a valence. This is another example of an electron deficient molecule.
Cl X Be X Cl

6. Sulphur hexafluoride (SF6)

 Sulphur, like O, is in Group VI. It is therefore expected to use only two electrons for bonding,
pairing each of them with a fluorine atom. If this was the case, then the compound formed will be
SF2. In practice, S is able to use all of its 6 valence electrons for bonding. F, in group 7, needs one
more electron to satisfy an octet. Each of the six F atoms will therefore provide an electron to
share with each of the six valence electrons of S. This forms 6 bonds, or a total of 12 electrons
around S. This does happen because S is able to expand the octet.It has accessible d
orbitalswhich it can use to accommodate some of the excess electron density.
The term ‘accessible’ means that the vacant d orbitals are close in energy to the
F occupied valence shell of Sulphur, so it is possible to involve them in bonding.
X
FX XF Electrons can be promoted into the d orbitals with a little expenditure of
S
FX X energy. In fact the energy used to promote electrons to the 3d orbitals is so
X
F
F small that it is more than compensated for by the extra stability attained by the
formation of extra bonds.
 Ability to expand the octet starts from P in Period 3. Other non- metal elements after P can also
expand the octet, e.g. in the molecule ICl6.
 Expansion of an octet results in the formation of more bonds than would be possible if an octet
was satisfied. The formation of extra bonds gives extra stability to a molecule. Remember that it is
the bonds that hold atoms together in a substance. The more bonds there are, the more stable the
substance.
 The earlier members of the periodic table, that is, the non- metals in Period I and II can not
expand the octet because the d orbitals are not accessible to accommodate extra electron density.

7 PCl3
 Phosphorous, in group five, needs three more electrons to fill the octet. P will therefore use three
of its valence electrons, leaving out two electrons, that is, one lone pair, unused. Cl needs one
more electron, so each chlorine atom will pair with an electron from S.
 The molecule nitrogen trichloride (NCl3) is analogous to PCl3. Both are the trichlorides of a group
V element.

P X N X
X Cl X
Cl X Cl Cl
X
Cl Cl

An octet is satisfied for both the P and the Cl atoms.

8. PCl₅ (Phosphorous pentachloride)

Cl As already explained, P and the latter non- metallic members of the

Cl
X X periodic table can expand the octet .This occurs, for example, in PCl₅. In
PX
Cl X X Cl forming an octet, the phosporous atom uses all of its valence electrons so
Cl that no lone pair is left on it.

3.4.1 Odd electrons and dative bonding

X
XNX O Consider the dot and cross diagram for NO2 shown on the left.
OX X
The total number of electrons to be accounted for is 17.
In compound formation, electrons always seek to be paired, because
valence electrons this makes them stable. However, if the total number of valence
N 5 electrons in the molecule is odd, as in NO2, one electron in the
O 6x2 12 molecule is bound to be left unpaired. Such an electron is known as
17 an odd electron. In NO2, the odd electron is on the nitrogen atom,
since it is the one which contributes an odd number of valence electrons.

A chemical species which bears an unpaired (odd) electron is known as a

free radical.

Nitrogen monoxide (NO) and halogen atoms are other examples of free radicals. Check that the total
number of valence electrons is odd in each species.
In all the examples given so far, it has been assumed that the covalent bond is formed by an equal
contribution by both atoms of the bond, that is, each contributes an electron to the bond. In NO 2, we see
an exception. In one of the N-O bonds, both electrons are contributed by one atom, that is, N. A bond
formed in this way is said to be dative orco-ordinateand its presence can be emphasized using the
notation →. The direction of the arrow shows which atom has contributed the electrons of the bond.

dative bond odd electron The dative bond avoids having to include a second
N to O double bond. The following structure (I),
X
O N XO N O containing two double bonds and no dative bond,
O could have been drawn for NO2.

The structure might look appealing at first sight because it agrees with ‘electron book-
keeping’ considerations. 17 electrons are used as before. More-over, there are two
double bonds, so the structure is likely to be stable, since double bonds are stronger
than single bonds.
 X
XNX O
O X X
However, notice that the structure can not be correct because now nitrogen has too many electrons
around it. By including two double bonds, nitrogen has exceeded its octet, which is not possible for
elements in periods 1 and 2. To avoid this, one of the bonds should be dative.

Draw the dot and cross diagram for the CO molecule

Q

Carbon monoxide presents a rare example of a multiple bond containing a dative bond.
Remember that a dative bond is a way of preventing the exceeding of an octet by Period 2 elements. In
CO, oxygen donates a pair of electrons into a vacant p orbital on the carbon atom to form a dative bond.
This involves overlap of a fully occupied orbital (that is, containing two electrons) on the oxygen atom
with the vacant orbital on C.

Important note
Once formed, the dative bond becomes indistinguishable from all the other covalent bonds in a molecule;
it has no special properties, and so in many cases when we write down the structures of molecules, we do
not need to show dative bonds, but you need to be aware of their existence.

Consequence of an odd electron in a chemical species

An unpaired electron is highly unstable and it will strive to achieve stability by pairing up with another
electron from a suitable reagent. This makes free radicals quite reactive.

The dimerization of NO2

Dimerization is a chemical reaction in which two identical molecules join chemically to form
one molecule whose Mr is twice the Mr of each reactant molecule.

An NO2 molecule tends to dimer with another, because in so doing, the odd electron on the nitrogen atom
of both molecules becomes paired up, forming a more stable compound (Fig 3.6). Thermodynamic data
show that the product of this reaction, dinitrogen tetraoxide, is more stable than NO2.

O O O O
N + N N N
O O O O
Fig 3.6 dimerization
2NO2 N2O4 of NO2
Free radicals such as theoxides of nitrogen have been largely blamed for the atmospheric reactions that
lead to the depletion of ozone. Another important free radical in the dynamic processes that destroy the
ozone layer is the chlorine atom. Since chlorine has an odd number of electrons in its outer-most shell, it
contains an odd electron in the valence shell.

Isoelectronic molecules
Molecules are said to be isoelectronic if they have the same total number of electrons.
Examples are N2 and CO. Both contain a total of 14 electrons. Isoelectronic molecules also contain the
same total number of valence electrons. Note that both CO and N2 contain a total of 10 valence electrons.
It is therefore not surprising that the bonding in isoelectronic molecules often shows some similarities.
Compare the bonding in N2 with that in CO and note that both contain a triple bond. However, there is no
dative bond in the nitrogen molecule.

3.4.2 Consequence of multiple bonds

Multiple bonds are stronger than single bonds, as illustrated in the Table 3.1.

Bond energy is a measure of the amount of energy

Bond bond energy/Kj mol-1
required to break a bond. In other words, it gives
C C 348 information about the strength of the bond. The larger
C C 612 the bond energy, the stronger the bond.
C C 837 Table 3.1

Use Table 3.1 above to estimate the bond energy of the π bond in the C to Cdouble bond.
Q
Since the single C to C bond energy is 348Kj/mol. We would expect the C to C double
A bond to have a bond energy of 348 x 2 = 969Kj/mol, assuming that the σ bond and the π
bond have equal bond energies. The actual value of the C to C double bond is smaller,
showing that the π bond has a smaller bond energy than the σ bond. The actual value of
the C to C double bond is smaller than the expected value by 696-612 = 84Kj. The π
bond is therefore weaker than the σ bond by 84Kj/mol, that is, it has a bond energy of
348 – 84 = 264Kj/mol.

The calculation above shows that a π bond is weaker than the corresponding σ bond. This is expected.
Sideways overlap (π) is not as efficient as head-on overlap. Consequently, π electrons are, on average, a
larger distance from the nucleus than σ electrons. This implies that electrons of the π bond are relatively
weakly attracted to the nuclei of both atoms of the bond. This makes the bond relatively weak. When a
multiple bond participates in a reaction in which bond breaking has to take place, it is always a π bond
that breaks first. This happens, for example, in the reaction between bromine and ethene.

This reaction, known as electrophilic addition, involves breaking of the C to C π bond.

3.4.3 Dative bonding in addition compounds
An addition compound is one formed by the combination of two molecules to form only one product. If
the two molecules are identical, the addition reaction is known as dimerization. The dimerization of two
molecules of NO2 to form N2O4 has already been discussed. Here we look at two more compounds that are
formed via an addition reaction and that contain dative bonds.

BF3.NH3
As the formula suggests, this compound is an addition product between BF3 (boron triflouride) and NH3.
It is completely different from either of the reactants, having no chemical or physical resemblance to
them. In the previous discussion it was shown that NH 3 has a non- bonding pair of electrons (lone pair)
on the nitrogen atom. Ammonia can therefore act as a good electron donor. On the other hand, BF3 is
electron deficient, having six electrons only in the valence shell of boron. A dative bond can therefore
form between the B atom in BF3 and the N atom in NH3:

pz Fig 3.6 illustrates the formation of a dative bond in

BF3.NH3. The 2s orbital on N of the ammonia
molecule, containing a lone pair of electrons,
F dative bond overlaps (σ) with a vacant pz orbital on the boron
F
B atom of BF3.The dative bond, when formed, may be
shown as below (a). However it should be
BF3 NH3
remembered that once formed, the dative bond
F (BF 3.NH 3 - white solid) becomes indistinguishable from any other covalent
bond (b):

..
N
H
H
H
Fig 3.6 formation of a dative bond in
BF3.NH3.

Al2Cl6
This compound is an addition product (dimer) of two molecules of AlCl 3.
2AlCl3 →Al2Cl6
The dimerization also involves dative bonding. The structure of Al2Cl6 is shown below
In this case, two dative bonds are formed. The reaction occurs because AlCl 3
is an electron deficient molecule. By pairing up with another molecule
through dative bonding, each Al atom achieves an octet and the dimer
would be more stable than the individual molecules .

3.5 Molecular geometry

The shape (geometry) of a molecule is important, for example in determining how it packs with other
molecules, how it forms molecular interactions, and in predicting polarity.
To determine the shape of a molecule, we use a method known as the Valence Shell
ElectronPairRepulsion (VSEPAR) theory. This theory has two important statements.

1. Electron pairs around the central atom in a molecule repel and reposition themselves as far
from each other as possible to minimize any further repulsion.

2.Lone pair-lone pair repulsion is greater than bond pair-lone pair repulsion which in turn is
greater than bond pair- bond pair repulsion.

Types of electron pairs in a molecule

Consider a hypothetical molecule XP2 that contains two lone pairs and two bond pairs.

Steps in determining the shape of a molecule

1. Draw a dot and cross diagram for the molecule.
2. Determine, from the dot and cross structure, the total number of electron groups/pairs around the
central atom.
3. Determine the best way to arrange these electron groups so that they are as far from each other as
possible. At this stage it is not necessary to distinguish between lone pairs and bond pairs.
4. To obtain the final shape, ignore the lone pairs. If lone pairs are present, they would have been used in
stage 3 to determine the best possible geometry for all the electron groups present. To obtain the final
bond angle, you have to take into consideration repulsions involving lone-pairs, if any.

The shape of a molecule refers to the geometry of its bonds (bond pairs), but the bond angle is deter-
mined by the electron pair geometry – both bond pairs and lone pairs.

3.5.1 Shapes of neutral molecules

Note: The dot and cross diagrams for all molecules in these examples will be reproduced from the
previous discussions. Make sure you can draw them on your own.

Important note
There is a strong temptation among students to simply memorize the shapes and bond angles from text-
books without being able to work them out. This is risky because examiners are rarely limited to the
examples given in text books, neither are they limited to the molecules and ions specified in the syllabus.
The following examples show you how to work out the shapes and bond angles in molecules and ions.

1. BeCl2
i.Dot and cross diagram:
Notice that lone-pairs around peripheral atoms (chlorine in this case)
Cl X Be X Cl
are not relevant in determination of shape, so they have been ignored.
Emphasis is on electron groups around the central atom, which is Beryllium in this case.
ii.There are two electron groups (pairs) around the central atom. Both are bonding pairs.
iii.What is the best way to position two electrongroups around the central atom so that they are as far
from each other as possible? Placing them at 1800 with respect to each other is the best way to minimize
repulsion between them.
1800 So the two covalent bonds of this molecule are at 1800 from each other. The shape is linear,
Be Cl with a bond angle of 1800.
Cl

2. CO2
There are two electron groups around the central atom, giving a bond angle of 1800, as in
O XXC XX O BeCl2. The shape is linear.
O C O

3.AlCl3

There are three bond pairs around Al. The best geometry to minimize repulsion between these bond
pairs is to place them in a triangular plane; at an angle of 1200 to each other. The shape is therefore
360
trigonal planar, bond angle 1200 (𝑡ℎ𝑎𝑡 𝑖𝑠, )
3

4. CH4
There are four bond pairs around the carbon atom. They should be placed at the corners of a regular
tetrahedron, giving a bond angle of 109.50. This is the optimum angle needed to ensure minimum
repulsion among four bonding pairs of electrons.
The tetrahedron is a three dimensional shape. The perfect tetrahedral bond angle is 109.50. CCl4 and
CH3Cl are further examples of molecules which show the tetrahedral geometry. However, in CH 3Cl, the
tetrahedron is distorted since the peripheral atoms are different.

5. SF6
There are sixbonding pairs around S. This gives an octahedral geometry (a 3 dimensional shape with 8
faces). We may visualize an octahedron by noticing that it is in fact a squarebipyramid, that is, a
bipyramid whose two apices are symmetrically situated opposite a central square plane. In a perfect
octahedron, as in SF₆, all bond angles are equal to 900(of course this is not apparent on paper). The reader
is advised to use solid models to get a clearer picture of the three dimensional shapes discussed so far
(tetrahedron, triangular bipyramid, octahedron).

All the examples we have considered so far included only bond pairs around the central atom of the
molecule. The following examples include one or more lone pairs around the central atom.

6. NH3
 The best way to arrange the four pairs of electrons around the N atom so that they are as far from each as
possible is to place them at the corners of a regular tetrahedron, as already discussed in the previous
example (at this stage we do not need to distinguish between lone pairsand bond pairs). The final shape
is of course not tetrahedral, but it is worked out from the tetrahedral geometry. The final bond angle will
also be estimated from the perfect tetrahedral angle of 109.50.

To obtain the correct shape, remember that the shape of a molecule refers to the spatial arrangement of
bonds around the central atom. Since a lone-pair is not a bond, we ignore it. Imagine ignoring the apical
lone pair in the diagram above. The shape becomes trigonal pyramidal, as shown below.

Notice that the bond angle has been reduced from the initial angle of 109.5 0, which is what we would have
expected had there been no lone pair on the nitrogen atom. The effect of the lone pair is to repel the bond
pairs, pushing them closer, so that the angle between them becomes smaller.
Analogous compounds of elements in the same group of the periodic table will have the same geometry.
This is because the elements have the same number of valence electrons, for example, PH3 is analogous to
NH3. Both are the hydrides of group V elements and they share the same geometry.

7. H2O
Shape : bent/v-shaped/angular
Bond angle : 104.50
The shape of the water molecule is worked out in Fig 3.7.

CH4, NH3 and H2O illustrate the VSEPAR theory well. Study the table below.

Molecule shape bond angle.

CH4 tetrahedral 109.50
NH3 trigonal pyramidal 107.50
H2 O bent/angular/ v- shaped 104.50

 The bond angles in the three molecules are close to each other because they are all derived from
the arrangement of four electron groups (lone pairs and bond pairs) around the central atom.
This arrangement is tetrahedral, with a bond angle of 109.50
 NH3 and water show a reduction in bond angle from the tetrahedral angle. CH 4 has a perfect
tetrahedral angle. To explain the reduction in bond angles in H 2O and NH3, we invoke the
VSEPAR theory. The reduction is smaller in NH3 because there is only one lone pair which repels
the bond pairs. The bond angle in water is smallest due to significant repulsion between two lone
pairs on the oxygen atom.

Fig 3.7 The electron pair geometry in water is tetrahedral, but the shape of the molecule (bond
pair geometry), after ignoring the lone pairs is angular, with a bond angle of 104.50.

Predict the shape and bond angle in H2S.

Q
 H2S is the hydride analogue of water. The two molecules have the same shape
A(V shaped) and bond angle (1040/104.50).

QPredict the shape of the NO2 molecule.

The molecule is V-shaped, as in water, but the bond angle is different. Any value slightly
Agreater than 1200 is a good estimation for the bond angle in NO2.

The dot and cross diagram for the nitrogen dioxide molecule was given in a previous discussion.
X
XNX O
O X X
There are three electron groups around the central N atom. These three groups, which include an odd
electron, are arranged in a trigonal geometry, at an angle of 1200 relative to each other. In the final
analysis, we ignore the odd electron on nitrogen, and we consider its repulsive action on the two N-O
bonds. At this moment we can say that the bond angle is close to 120 0. The odd electron does not cause
any significant repulsion to the bond pairs (compare with the effect of a lone pair). The two N to O bonds
are therefore able to space out until the bond angle is greater than 1200. The actual bond angle is quoted
in chemical literature as being approximately equal to 1340. The shape, after ignoring the odd electron, is
angular.

Important note
It is possible for two molecules to have the same shape but have different bond angles. This is illustrated by H 2O and
NO2. The two molecules have the same shape (angular) and yet they have completely different bond angles. The bond
angle for water is estimated from a tetrahedral angle of 109.50 whereas that of NO2 is estimated from a trigonal planar
angle of 1200.
The shape of a molecule refers to the geometry of its bonds (bond pairs), but the bond angle is determined by the
electron pair geometry – both bond pairs and lone pairs, around the central atom.
Water and NO2 have the same shape because they have the same number of bond pairs. They have different bond
angles because they have different numbers and nature of electron pairs around the central atom.

3.5.2 Shapes of ions

‘Electron book-keeping’ is very important in the determination of shapes and bond angles in ions. This
will be illustrated using the following ions.
Nitronium(NO2⁺) , nitrite(NO2⁻) and nitrate (NO3-)

1. The nitronium ion (NO2⁺)

This ion is so unstable that it has no independence existence. It is generated insitu from nitric acid during
some reactions, for example, the nitration of benzene (conversion of benzene to nitrobenzene). This is an
important step during the synthesis of explosives.
The first step in the determination of the shape of an ion is to find out how many (valence) electrons
should be used in the dot and cross diagram. For the nitronium ion:
 The dot and cross diagram should use 16 electrons. Notice that one electron had to be deducted during
the electron book-keeping. Being positively charged by one unit, the species has one less electron.

Notice that in the dot and cross diagram above, nitrogen is using a valency of four, not five, as would have
been expected. This is because the dot and cross structure has one less electron. The electron is removed
from the nitrogen atom, because it would have been the fifth and odd electron. An odd electron renders a
molecule unstable, and if the molecule is to form an ion by losing an electron, then it would be the odd
electron that is lost.

2. The nitrite ion (NO2⁻)

You will notice that in the dot and cross diagram of the nitrite ion, nitrogen has six electrons, instead of
the expected 5. This is because the book-keeping shows one more electron due to the presence of the -1
charge. The extra electron is placed on N, because this would make the total number of electrons around it
even. That is, there is no odd electron on the nitrogen atom, which would otherwise cause instability.
3. The nitrate ion (NO3-)
The dot and cross diagram should make use of 24 electrons. Remember that though double bonds
stabilize a molecule, too many double bonds around the nitrogen atom results in too many electrons
around it (nitrogen can not exceed the octet). To avoid exceeding the octet around nitrogen, remember to
include a dative bond.
You will have noticed that one of the oxygen atoms has
seven electrons around. You might not have expected
this because oxygen has six valence electrons, not
seven. The electron book-keeping shows that there is
an extra electron from the charge on the ion. The ques-
tion is where to put this extra electron, on the nitrogen
atom or on the oxygen atom. The electron is
accommodated on the oxygen atom because oxygen is
able to accept and stabilize a negative charge.

You may recall several other species in which an oxygen atom bears a negative charge, including the
hydroxide ion (- OH) and the carboxylate ion (COO⁻). In the NO3⁻ ion, the extra electron is on an oxygen
atom, and it has been shown as a small triangle. It is this electron that gives a charge of -1 to the ion.

Further examples: the importance of intuition and common sense

What is the shape and bond angle in nitric acid, HNO3? Here is where common sense and intuition
becomes an asset. A question which comes to mind is
‘Where is the hydrogen atom bonded, to the central nitrogen atom or to an oxygen atom?’
To answer the question we have to remember the behaviour of an acid such as nitric acid in water:
 It releases a proton (a hydrogen ion).
That means the hydrogen in nitric acid is bonded to an oxygen atom. If it were bonded to a nitrogen atom,
it could not be released in solution (think of ammonia, NH3, in which hydrogen atoms are directly bonded
to a nitrogen atom. None of these hydrogen atoms are ionizable in aqueous solution).
The dot and cross diagram and shape of the nitric acid molecule is shown in Fig 3.8. Of course, the nitrate
ion would have the same geometry. It is formed by loss of the hydrogen atom. This does not change the
shape, but it leaves an extra electron (shown as a small triangle) on the oxygen atom which bore the
hydrogen atom. This electron is responsible for the -1 charge on the nitrate ion. Thus in the nitrate ion,
one oxygen atom will appear to have contributed seven electrons to the structure, not the expected six.
The same type of reasoning can be used to deduce the
structures of other oxyacids, for example, sulphuric acid,
H2SO4, shown below.

Fig 3.8

H2SO4 is diprotic, that is, an acid which is capable of liberating two protons into solution. From this it can
be deduced that both hydrogen atoms on sulphuric acid are bonded to oxygen atoms. The HSO 4⁻ and SO4⁻
ions, which are formed when sulphuric acid loses one and two protons respectively, have the same
geometry.
The electron book-keeping for the sulphate ion and the corresponding geometry is shown below.

State the change in shape and bond angle that occurs in the following conversions.
Q
Illustrate your answer with suitable diagrams.

(i) CO2 to CO3- (ii) H2O to H3O+ (oxonium) (iii) NH3 to NH4+

A(i) Please see main text.

(ii) From angular to trigonal pyramidal (as in ammonia). Bond angle changes from 104.50 to
1070.
(When you draw the structure of H3O+ , note that it contains an O-H dative bond and one
lone pair).
 (iii) Left as an exerciser to the reader. Note that the amminoium ion, NH 4+contains a N-H
dativebond.

3.6Features of the covalent bond

Two important features of the covalent bond are bond strength and bond polarity. Bond strength is
purely a thermodynamic concept, so it will be discussed in detail under the relevant topic.

3.6.1 Bond polarity

Electrons that make up the covalent bond are under the attractive influence of the nuclei of two atoms.
But will the two atoms attract the electron pair to the same extend, or one of the atoms will have a greater
pull on the electrons? It all depends on the relative electronegativitiesof the atoms that make up that
bond.

Electronegativity

This is a measure of the relative tendency of an atom to withdraw electrons of a bond to-
wards itself.

Linus Pauling invented an arbitrary scale of relative electronegativities which we use today. The scale
ranges between 0 and 4.Thelarger the Pauling value, the more electronegative an atom is. An extract of
the scale is shown in fig 3.9.

Fig 3.9 The Linus scale of electronegativities

 Electronegativity increases across a period and up a group.

The most electronegative elements are therefore situated at the top of the far right side of the
Periodic Table. The three most electronegative elements are N, O and F. The most electronegative
element is fluorine.
 The noble elements have zero electronegativity.
This is because they do not have a tendency to form covalent bonds, at least in most of the
situations. A discussion of electronegativities is therefore irrelevant for the noble elements.
Explaining the trend in electronegativities
The trend in electronegativity across a period and down a group is expected.
Going across the period, the number of protons in the nucleus (nuclear charge) increases. The attractive
power of the nucleus for the bonding electrons therefore becomes stronger.
Going down a group, additional shells are opened. The effect is to increase the size of the atom, and to
hide the nucleus deeper and deeper inside the atom. The distance of the nucleus from the shared pair of
electrons between the two atoms increases, and attraction for these electrons becomes correspondingly
weak, that is, electronegativity decreases.

Polar bonds
If the two atoms of a bond have different electronegativities, they will attract electrons of the bond to
different extends.
The result is that the electron cloud of shared electrons is skewed towards the more electronegative atom.
This atom therefore becomes relatively negatively charged and the less electronegative atom becomes
relatively positively charged. The less electronegative atom will have a smaller electron density around it.
The electron rich side of the bond is represented by δ-and the electron deficient side by δ+.
This notation shows that the molecule now has two poles as far as electron distribution is concerned; an
electron rich pole and an electron deficient pole. Such a bond is therefore said to be polar. It is also said to
possess a dipole.

What exactly should be the difference in electronegativity of the two atoms for a bond to be regarded as
being polar?
 An electronegativity difference of zero implies that there is perfect sharing of the bonding
electrons. The bond is therefore perfectly non-polar.
 If the difference in electronegativity is greater than zero, but is vey small, the bond is regarded as
being approximatelynon-polar. This is because neither of the two atoms has the ability to strongly
 attract the bonding electrons to itself. However, it should be noted that such bonds do contain a
degree of polarity. The C-H bond is a good example. The difference in electronegativity between C
and H is 0.4 (refer to Fig 3.9). This is a very small difference, and so the bond is said to be
approximately non-polar.
 Bonds in which the difference in electronegativity is greater than 0.4 should be considered as
being polar. However, if the difference in electronegativity exceeds about 1.7, the bond becomes
ionic, that is, one atom will pull electrons of the bond (almost)completely to itself. It then becomes
a negative ion and the other atom becomes a positive ion. In LiF, the difference is
4.0-1.0 = 3, making the compound predominantly ionic.

Covalent or ionic?
It must be clear from the foregoing discussion that it is not always easy to put a clear cut boundary
between an ionic and a covalent bond. It is easy to say that the Cl-Cl bond is purely covalent because the
difference in electronegativity between the two atoms is zero. But what about a compound such as AlCl 3?
One might expect it to be ionic from a consideration of what is taught in juniour chemistry: a bond
between a metal and a non-metal is ionic. This statement is not always true. In fact, AlCl3 is a covalent
substance. The difference in electronegativity between the Al and the Cl atom is 1.5, which is very close to
the threshold value of about 1.7 required to make a bond ionic. We therefore describe AlCl 3 as being
covalent but witha significant degree of ionic character. In fact, according to the calculations done by
Linus Pauling, AlCl3 has about 43% ionic character and about 57% covalent character.
Also consider magnesium chloride, MgCl2. The difference in electronegativity between Mg and Cl is 1.8.
This is greater than the threshold value of 1.7. MgCl2 is therefore ionic. However, the difference in electro-
negativity between Mg and Cl is very close to 1.7, and so we should expect a high degree of covalent
character in MgCl2. The chemical properties of MgCl2 show that it is ionic with a high degree ofcovalent
character. Using Pauling’s method, MgCl2 would have about 55% ionic character and 46% covalent
character.

The reader is advised to use Pauling’s values with great care. They only give a qualitative method of esti-
mating covalent and ionic character. It is not always possible to classify a bond as being ionic or being
covalent simply by carrying out calculations using Pauling’s values. For example, one might expect HF to
be ionic with a high degree of covalent character. In fact, it is covalent with a high degree of ionic
character.

3.6.2 Interaction of dipole moments

The forgoing discussion on bond polarity was concerned with an isolated bond.
But what happens if two or morepolar bonds are present in a molecule?The polarity of a bond is
measured by a quantity known as the dipole moment, µ .The Debye, D, is used as a unit for this physical
quantity. The dipole moment is actually a vector quantity, that is, it is defined by its size and by its
direction. For instance, we may show the dipole moment of the HF bond as a vector quantity, in the
following way.

Now, if there is more than one polar bond in the

molecule, the dipole moments will add up in the
same way as vectors do. The result is that there may
be one large net (resultant) dipole moment working
in a specific direction.
In this case, the dipole moments have amplified each other. Another situation arises when the dipole
moments are oriented in such a way that they diminish each other. In fact, if the molecule is symmetric,
the dipole moments cancel each other out and the molecule will have no net dipole moment, even though
it contains polar bonds. For a molecule to be symmetric
 it must have a shape which has a centre of symmetry.
 all bonds must be identical, or if there are different bonds, they should be in the
ratio of 1:1, and they should be positioned so that the molecule has a centre of symmetry.
There are therefore two reasons why a molecule might be non- polar:
(i) either it has no polar bonds at all(for example chlorine),
(ii)or it has two or more polar bonds whose dipole moments cancel each other out by reason of the
molecule being symmetric.

Examples
The following molecules all contain polar bonds, but they are non-polar because, being symmetric, the
dipole moments cancel each other out.

1. AlCl3
The geometry of the molecule (triangular planar) is symmetric.

2. CO2

In the two examples above, all bonds are identical, so the dipole moments are equal to each other. CCl4,
with four identical bonds and a perfect tetrahedral shape, falls into the same category. It is non-polar.

3. 3,4-dinitrobenezene
4. [Pt(NH3)2Cl2]
This molecule has a square planar geometry. There are two possible isomers, shown below.

In each isomer, there are four polar bonds, two Pt-N bonds
and two Pt-Cl bonds. There are different bonds, but in the
ratio of 1:1. In trans-platin, identical bonds are
symmetrically arranged relative to each other, so their
dipole moments cancel out and the molecule is overally
non-polar.

In cis- platin, identical bonds are asymmetrically arranged relative to each other, so their dipole moments
do not cancel each out.
Cis-platin is a well known anti-cancer drug but Trans-platin has no medicinal value. Because of its
polarity, cis- platin is able to bind to the polar DNA molecules in cancerous cells. This prevents the DNA
from multiplying. When DNA of cancerous cells fails to multiply, the cells are not able to reproduce
themselves.

The following molecules are not symmetrical, and they have a net dipole moment, that is, they are polar.

5. CHCl3 (trichloromethane)
In this molecule, there are four bond pairs around the central carbon atom. The shape is therefore
tetrahedral as in CCl4 (tetrachloromethane).

However, CCl4 is non-polar, whereas CHCl3 is polar. This is because in CHCl3, there are two types of
bonds, the C-Cl and the C-H bonds. The shape is therefore a distorted tetrahedron, which is asymmetric.
The dipole moments cancel out to some extent, but they do not completely nullify each other.

6. 1,3 - dinitrobenzene
In 1,3-dinitrobenzene , the two polar bonds are asymmetrically
arranged with respect to each other. Consequently, their dipole
moments do not cancel each other. Rather, they add up, to give a net
dipole moment operating in the shown direction.
3.7Intermolecular forces
Forces of attraction exist betweenthe molecules of a substance. These are termed intermolecular forcesto
distinguish them from intramolecular forces (Fig 3.9), which are the covalent bonds holding atoms
together. It should be mentioned here that the term intermolecular force applies as well to substances
which do not contain molecules, for example neon. ‘Intermolecular’ forces of attraction exist between the
individual neon atoms.

Fig 3.9

Intermolecular forces are much weaker than covalent bonds. When a substance is heated, it is always the
intermolecular forces that break first. Covalent bonds, being stronger, will only start to break at higher
temperatures.
Breaking of intermolecular forces does not change the chemical identity of a substance. It simply pulls the
molecules apart; since no covalent bonds are broken, the molecules remain with the same formula as
before. Breaking of intermolecular forces, for example, during boiling, is therefore a physical process.
However, breaking of covalent bonds is a chemical process because it changes the identity of the
substance.
Intermolecular forces are important in explaining the physical properties of compounds, such as boiling
points, volatility, melting points, densities, colour etc.

Boiling points and melting points

When a substance boils, its molecules are separated from each other and escape into the gaseous state.
Separation of these particles requires the breaking of intermolecular forces that existbetween the
molecules. Different substances have different boiling points, reflecting the different strength of the
intermolecular forces present in them. The stronger the intermolecular forces, the more energy required
to separate the molecules. The boiling point of the substance would be correspondingly high.
Similarly, when a substance melts, intermolecular forces between particles of a solid are broken. The
molecules therefore spread and are able to flow, that is, the liquid state is formed.

Volatility
This is a measure of the ease with which a substance can turn to a vapour. A substance does not
necessarily have to be heated to its boiling point for its particles to evaporate. Try asking this question to a
number of people,
‘At what temperature does waterevaporate?’
You will be surprised by the number of people who think that water evaporates at 100⁰C. The fact is that
liquid water can evaporate at any temperature. However, at low temperatures, say 20⁰C, the rate of
evaporation of the water molecules is very small. This shows that the forces of attraction between water
molecules are relatively strong. A relatively large amount of heat energy is required to separate the
molecules from each other. In other words, water is involatile. Now take a substance like ether, CH3OCH3.
The forces of attraction between its molecules are so weak that at a relatively low temperature, say 20 0C, a
large number of the particles escape and enter the vapour state. Ether is therefore said to be a volatile
liquid.

Density
Density is a quantity which gives an idea of how tightly or loosely packed the particles are in asubstance.
If the particles are tightly packed, then the substance has a high density. Intermolecular forces tend to
hold together molecules of a substance. If the intermolecular forces are relatively strong, then the
particles are held relatively tightly to each other. Density would be correspondingly high.

Types of intermolecular forces

Intermolecular forces have been classified as:
 permanent dipole - dipole attractions
 Van der Waals forces
 hydrogen bonds

3.7.1 Permanent dipole - dipole attractions

These arise between molecules which bear a permanent dipole.

Consider the HCl molecule, which is permanently polar

 
H Cl
In a container of HCl, the molecules attract each other electrostatically; the Cl δ¯ end of one molecule will
attract the Hδ+ end of a neighbouring molecule.
    The same forces of attraction are also present in molecules which
H Cl H Cl contain more than one polar bonds. However, the molecules must be
asymmetric; otherwise the dipole moments will cancel each other
permanent
out, making the molecule non-polar.
dipole-dipole attraction.
The following compounds have permanent dipole - dipole attractions between their molecules because the
molecules have polar bonds and do not have a centre of symmetry.

 Trichloromethane, CHCl3(there are three polar C-Cl bonds which are asymmetrically arranged).
 Chloromethane, CH3Cl.
δ+ δ- δ+ δ-
CH3 Cl CH3 Cl

Q
Explain the difference in the boiling points of the two isomers below.
 NO2 NO2

NO2
NO2
1,3 - dinitrobenzene 1,4 - dinitrobenzene

A first isomer has the higher boiling point because it has a net dipole moment (it is
The
asymmetric). The net dipole moment acts in the direction shown by the arrow in the
diagram below.
NO2

NO2
1,3 - dinitrobenzene
The 1, 4-isomer is non-polar. Even though it has two polar bonds, their dipole moments
cancel out because the molecule is symmetric. Being non-polar, there are only weak
forces of attraction between the molecules. In the 1, 3- isomer, relatively strong
permanent dipole-dipole forces exist between the molecules. More energy is required to
break these forces, that is, the isomer has a higher boiling point.

3.7.2Van der Waals forces (temporary dipole-induced dipole attractions)

This type of intermolecular force arises between non polar molecules or atoms.

Examples are methane (containing molecules) and neon (containing atoms). The C-H bond in methane is
non- polar because the difference in the electronegativities of C and H is very small.
The fact that in a non-polar substance there are forces of attraction between the molecules is
demonstrated by the observation that such substances can be liquefied or frozen. During these processes,
the molecules or atoms get closer together and they become less mobile. This allows the intermolecular
forces to become stronger and more stable.

The origin of Van der Waals forces

Features of Van der Waals forces
 They are very weak, much weaker than permanent dipole - dipole attractions.
 They are extremely short lived (temporary). The Van der Waals attraction between any two given
molecules is instantaneous. However, since there will be a large number of molecules in the
container , on average, there is always some forces present between some molecules.
 The strength of Van der Waals forces increases with increasing number of electrons
(increasing Mr). The more electrons there are, the greater the distortion of molecular
orbitals and the stronger the Van der Waals forces.
 Van der Waals forces are found in all molecular or atomic substances. However, they are only
important in the absence of stronger intermolecular forces (hydrogen bonds or permanent
dipole-dipole attractions). Consider a molecule such as HCl. There are two types of
intermolecular forces between the molecules, that is, Van der Waals and permanent dipole-
dipole attractions. However, the latter forces are much stronger and they make the Van der
Waals forces insignificant.

The effect of number of electrons on strength of Van der Waals forces is clearly illustrated by the group
VII elements. Chlorine is a pale greenish-yellow gas, bromine is a red-brown liquid and iodine is a shiny
black solid at room temperature. How can this trend in physical properties be explained?
As the number of electrons increases down the group, so does the strength of the Van der Waals forces.
More energy is required to break these forces. In chlorine the forces are so weak that they can not hold the
molecules together at room temperature. In bromine the forces are strong enough to hold the molecules
loosely together in the liquid state. The forces are strongest in iodine. They are strong enough to hold the
molecules closely and tightly in the solid state.
The same observation is made for the hydrocarbons. Low Mr hydrocarbons such as methane and ethane
tend to be gaseous at room temperature. Higher Mr hydrocarbons such as pentane are volatile liquids. At
even higher Mr values the alkanes become solid, e.g. candle wax, which has, on average, 30 carbons per
molecule.

3.7.3 Hydrogen bonds

These are the strongest of the intermolecular forces. A hydrogen bond is a special type of a permanent
dipole-dipole attraction. It is formed between molecules which contain the N-H, O-H or F- H bonds.
N, O and F are the three most electronegative atoms. On the other hand, the hydrogen atom has no
intervening electrons between the nucleus and the valence shell. The nucleus of the hydrogen atom can
therefore easily be exposed when the hydrogen atom is bonded to N, O or F. The proton in the nucleus of
the hydrogen atom becomes available for the formation of hydrogen bonds.

The origin of hydrogen bonds

Consider a hydrogen atom bonded to one of the three most electronegative atoms, N, O and F. We will use
HF for our illustration.

The illustration given above applies not only to the H-F bond, but to the H-O and H-N bonds as well.

Requirements for a hydrogen bond

 A hydrogen atom bonded to one of the three most electronegative atoms, N, O and F
 A lone pair of electrons on the more electronegative atom (N, O, F). It so happens that in their
compounds, these atoms possess one or more lone pairs. A hydrogen bond specificallyinvolves
attraction between a lone pair on N, O or F and an electron deficient hydrogen atom,as illustrated
for HF.

The fact that a hydrogen bond is always directed towards a lone pair implies
  
 that hydrogen bonds are directional, that is, they operate in a specific
H F H F
direction. Consequently, orientation is very important for their formation. Two
hydrogen bond molecules must be oriented favourably with respect to each other for a
hydrogen bond to be formed between them.
The same directionality exists for permanent dipole- dipole attractions. Compare with Van der Waals
forces which are non- directional. Orientation factors are therefore not important in the formation of Van
der Waals forces.

Hydrogen bonding in water

Water contains O-H bonds, so hydrogen bonding is possible between its molecules.
 One question which immediately comes to mind is this,
“How many lone pairs does each oxygen atom use to form
hydrogen bonds, and how many hydrogen atoms does each
water molecule use?”

The answer to this question depends on whether we are discussing liquid or solid water (ice). In liquid
water, the molecules are always moving around. Consequently, there is a continuous process of hydrogen
bond formation and hydrogen bond breaking. A water molecule may use one or both lone pairs for hydro-
gen bonding, or no lone-pair is used at all. All that can be said is that on average, the probability of there
being a hydrogen bond between two water molecules is high. This probability decreases with increasing
temperature. Hydrogen bonds, though the strongest of the intermolecular forces, are still many times
weaker than covalent bonds. They are therefore easily broken when temperature and kinetic energy of the
molecules increase. Conversely, the probability of a water molecule forming one or more hydrogen bonds
with neighbouring water molecules increases with decreasing temperature. As temperature drops, mole-
cules lose kinetic energy and come closer together. This favours the formation of hydrogen bonds. Each
water molecule has the capacity to hydrogen bond with four other water molecules. The two lone pairs on
the oxygen atom form hydrogen bonds with two neighbouring water molecules. The two hydrogen atoms
make hydrogen bonds with two other neighbouring water molecules. All four possible hydrogen bonds are
formed (per molecule of water) in ice and this has important consequences on its properties.

Hydrogen bonding in ammonia

Ammonia, which contains N-H bonds, is also capable of forming hydrogen bonds(Fig 3.10). Once more,
the extent of hydrogen bonding depends on the temperature.

Hydrogen bonding in a mixture of water and ammo-

nia
Ammonia dissolves well in water, and there are two reasons for this
observation.
 Water and ammonia molecules are capable of associating
through hydrogen bonds (Fig 3.11).This allows the two sub-
stances to form a single phase mixture (solution).
 Some ammonia molecules react with water, to form a mix-
ture containing NH4+ and OH- ions, in addition to unreacted
Fig 3.10hydrogen bonding water and ammonia molecules.
in pure ammonia

Fig 3.11hydrogen
bonding in a mixture of
ammonia and water.
Intermolecular versus intramolecular hydrogen bonds
CompoundsA and B below are isomers. Isomer Ahas the higher boiling. How can this observation be
explained?
Isomer B has a hydrogen bond between the NH2 and the OH group
because of the close proximity of these two groups to each other.

This type of hydrogen bond, formed between groups on the same molecule, is known as an
intramolecular hydrogen bond. By forming this bond, the molecule uses up its capacity to hydrogen bond
with neighbouring molecules. Only weak Van der Waals forces are left to operate between the molecules.
Because of their separation in space, the NH 2 and the OH groups on isomer Acan not form intramolecular
hydrogen bonds. Intermolecular hydrogen bonds can therefore form between neighbouring molecules
(Fig 3.12).More energy is required to break the hydrogen bonds between neighbouring molecules. Thus
the first isomer has the higher boiling point.

Fig 3.12

Properties of hydrogen bonds

 They are the strongest of the intermolecular forces. However, they are much weaker than covalent
bonds.They are highly directional. A hydrogen bond acts only in a certain direction. It is always
from a H atom on one molecule to a lone pair of electrons on N, O or F on the other molecule.
 They are a special type of permanent dipole - permanent attractions.

Consequences of hydrogen bonding

 Anomalous behavior of water.
 Anomalous boiling points.
 Viscosity.
 Anomalous Mr values.
 Solubility.

Anomalous behaviour of water

Water expandsas it cools, so its solid state, ice, is less dense and tends to float on the liquid state. This is
quite unexpected. The general observation is that when matter cools it contracts, and the solid state
therefore becomes denser than the liquid state, that is, the solid state should sink into the liquid state.
This anomalous behaviour of water can be explained in terms of hydrogen bonding. As water is cooled, its
particles lose kinetic energy and come closer together. This allows more and more hydrogen bonds to
form. Each water molecule can form a maximum of four hydrogen bonds to four neighbouring water
molecules; two hydrogen bonds via its two lone pairs and two hydrogen bonds via its hydrogen atoms. In
liquid water, not all four hydrogen bonds may form because of the high kinetic energy of the molecules
which tends to interfere with formation of hydrogen bonds. In ice, all four hydrogen bonds are formed for
each water molecule. To minimize inter-electronic repulsions between these four water molecules, they
must be spaced out in a tetrahedral geometry. This spacing out implies an increase in volume, as it forms
a very open structure. In other words, water tends to expand as it freezes. This explains why a bottle of
water put in a fridge will burst when the water freezes. Fig 3.13 below illustrates hydrogen bonding in ice.

Fig 3.13 Hydrogen

bonding in ice.

Suppose that we freeze a fixed mass of water. In ice, the volume has increased, but mass has
remained the same. Using the relationship
D = m/V,
we can see that an increase in volume at constant mass results in a decrease in density, that is, density
and volume are inversely related. The decrease in density causes ice to float on liquid water. Most of us
will remember the story of the Titanic, the luxury ocean liner which collided with an iceberg on its maiden
voyage on Sunday, the 14th of April, 1912. An iceberg can be as big as a huge mountain. What causes it to
float is that its volume is much greater than its mass, giving it a lower density than liquid water.
Floating of ice on water causes lakes to freeze from the top. The layer of ice so formed then insulates the
liquid water underneath, keeping it relatively warm and unfrozen. This allows aquatic creatures to survive
at the bottom of frozen lakes.

Anomalous boiling points

The boiling point of water is much higher than expected from its Mr. Water is a relatively small molecule
(small number of electrons), and yet it has a higher boiling point than many molecules which are heavier
than it. This is well illustrated by the group six hydrides, of which water is a member. The Group (VI)
hydrides are, from the top of the group, H 2O, H2S, H2Se and H2Te. Going down the group, the number of
electrons in the molecules increases, and so does the strength of the Van der Waals forces. Consequently,
boiling points are expected to increase as more and more energy is required to break the Van der Waals
forces. This trend is indeed observed, except for water, which is clearly out of trend. Instead of having the
lowest boiling point by virtue of it having the least number of electrons (Mr), it has the highest boiling
point. This anomalous boiling point of water is explained by the presence of hydrogen bonds in water and
their absence in its analogues. Hydrogen bonds are much stronger than the Van der Waals forces present
in the other Group (VI) hydrides. A large amount of heat is required to break these forces and separate the
water molecules into the gaseous state.
It is important to note that Van Der Waals forces are present in all molecules. However, in hydrogen
bonded substances the important force is the hydrogen bond. In the absence of a stronger intermolecular
force such as the hydrogen bond and the permanent dipole-dipole attractions, Van der Waals forces
become the important force of attraction.
The same trend discussed for the Group (VI) hydrides is found among the Group (V) and (VII)
hydrides. In each case, the first member can form hydrogen bonds between its molecules, and so its
boiling pointer is much higher than expected. Compare with the group (IV) hydrides in which all
members can not form hydrogen bonds. Consequently, the first member, methane, which contains the
least number of electrons, has the lowest boiling point, as expected (Fig 3.14).

Fig 3.14 Trends in the boiling points of the hydrides of the Group(V), (VI) and (IV)
hydrides.

Viscosity
This is a measure of the ability of a liquid to resist flowing. Viscosity gives an idea of the size and strength
of intermolecular forces acting in a substance. Some substances are viscuous and so do not flow easily, for
example, honey, which is a rich mixture of concentrated glucose and fructose. Both glucose and fructose
have a large number of OH groups which can participate in hydrogen bonding. The molecules of water,
fructose and glucose are therefore closely associated to each other by hydrogen bonds and can not move
freely.

Anomalous Mr values
The apparent Mr of ethanoic acid in a solvent such as benzene is 120. The expected value is 60. This
observation can be explained in terms of hydrogen bonding. In benzene, molecules of ethanoic acid
associate to form dimers through hydrogen bonding, thus doubling the Mr(Fig 3.15).
In water, the dimerization does not take place because
the ethanoic acid molecules are more likely to form
hydrogen bonds to water molecules than to each
other. Dimerization of the ethanoic acid molecules
therefore occurs in a solvent, such as benzene, which
has no capacity to form hydrogen bonds with the
Fig 3.15Dimerization in ethanoic acid ethanoic acid molecules.

The same observation is made for HF, whose apparent Mr in some solvents like benzene is also double the
expected value.

Solubility
The solubility of some substances in water can be explained in terms of hydrogen bonding. For example,
methane and ammonia have similar Mr values (16 and 17 respectively). Ammonia is soluble in water but
methane is not. Ammonia can form hydrogen bonds with water. In this way the water and ammonia
molecules can mix homogeneously. Similarly, alcohols such as methanol and ethanol dissolve in water
through hydrogen bond formation as shown in the following illustration.

hydrogen bond

.
.O..
H
H H
..O..
Water and methanol (CH3OH) are miscible
C
H

H in each other through formation of

H hydrogen bonds
.. .O.

..O..
H

H H

3.7.4 Consequences of intermolecular forces

Intermolecular forces do not affect the chemical properties of a substance. However, they are responsible
for the physical properties of substances, e.g. boiling points, melting points and colour. A discussion of
physical properties should centre on intermolecular forces, with one important exception:
The melting and boiling of giant covalent substances such as silicon dioxide and diamond requires the
breaking of covalent bonds.

Boiling and melting points

Boiling and melting requires the pulling apart of molecules. During melting, the particles are pulled apart
from the solid so that they become more loosely associated in the liquid state. Boiling requires a further
pulling apart of liquid particles so that they become free of each other in the gaseous state.
The boiling and melting point of a substance depends on the type and strength of intermolecular forces
present. It also depends on the number or extent of such forces. A comparison of boiling points of pairs of
substances is given below to illustrate this point.

1. Ammonia and methane

Ammonia has a higher boiling point. There are hydrogen bonds holding the molecules of ammonia
together. These require a relatively large amount of heat to break. In methane there are only weak Van der
Waals forces, which require a small amount of energy to break. Note that the two molecules have similar
Mr values, so the difference in boiling point can not be explained in terms of strength of Van der Waals
forces.

2. CHCl3 and CCl4

CCl4 has a higher boiling point (76.80C) than CHCl3 (61.20C). CCl4 contains a larger number of electrons
(larger Mr), so there are relatively strong Van der Waals forces operating between its molecules.

3. CH3OHand CH3CH2OH
Both compounds have hydrogen bonds between their molecules, so the difference in boiling points must
be due to the difference in number of electrons. Ethanol (CH3CH2OH), with the larger number of
electrons, has stronger Van der Waals forces between its molecules.

4. Ne and Ar
In both substances,there are weak Van der Waals forces between the atoms. However, argon has the
larger number of electrons. It therefore has stronger Van Der Waals forces. The boiling point is
correspondingly higher.
5. AlCl3 and AlF3
AlF3 has the higher boiling point because it is predominantly ionic, whereas, AlCl3 is predominantly
covalent.
NB Aluminiumchloride does not boil but sublimes.

6. n-pentane and 2,2- dimethylpropane

The structures of these two compounds, which are isomeric to each other (same Mr), are shown in
Fig 3.16.

n-pentane has the higher boiling point because each molecule has a large surface area over which Van der
Waals forces can operate with a neighbouring molecule. The second compound has a roughly spherical
conformation. The contact area between two molecules is therefore much smaller (Fig 3.17). Since Van
der Waals forces act over a small area in 2,2-dimethylpropane, they are weaker and more easily broken.

Fig 3.17

Summary: intermolecular forces

 There are three types of intermolecular forces; permanent dipole-dipoleattractions, Van der
Waals forces and hydrogen bonds.
 These forces are too weak to affect the chemical properties of substances, but they are responsible
for physical properties, such as boiling points, melting points, color, etc.
  Hydrogen bonds are the strongest, followed by permanent dipole-dipole attractions. Van der
Waals forces are the weakest (of course, we have to compare compounds of similar Mr values.)
 Van der Waals forces are the predominant forces in non- polar substances such as the noble gases
and the diatomic elements such as O2.
 Permanent dipole-dipole attractions occur in compounds which contain bonds with permanent
dipoles. However, if the molecule is symmetrical the dipole moments cancel out, and overally the
compound would be non-polar, e.g. AlCl3.
 Hydrogen bonds occur if:
(i)a bond is made up of H bonded to one of the three most electronegative atoms, N, O or F.
(ii)A N , O or F atom is present in the neighbouring molecule to use its lone pair for forming the
hydrogen bond.

3.8Ionic bonding
An ionic bond is a strong electrostatic attraction between a positively charged ion (cation) and a
negatively charged ion (anion).

Ionic bonding between a metal and a non-metal

When a metal reacts with a non- metal, an ionic compound is formed in which the metal exists as a cation
and the non-metal as an anion.There are exceptions to this generalization; for instance, AlCl 3 has already
been discussed under covalent substances, even though it is formed between a metal and a non-metal.
It has been noted in the previous discussion on covalent bonding that electronegativity of the elements
increases across the periodic table. Thus metals have very low electronegativities, that is, a metal atom
has very little tendency to accept electrons of a bond towards itself. In fact, the opposite is true for metals;
they have a strong tendency to lose their valence electrons. We say they are electropositive.

Electropositivity is a measure of the tendency of an atom to lose an electron or electrons from the
valence shell in chemical reactions.

Electropositivity decreases across a period, that is, in any period; the metals are the most electropositive.
They have the greatest tendency to lose electrons.
This behavior of metals is expected. In any period, the metals have larger atoms than their non-metal
counterparts. Atomic radii decrease across a period. This has already been explained in terms of
increasing effective nuclear charge. Going across a period, the number of protons in the nucleus increases
and yet electrons are entering the same shell. The outermost electrons feel an increasing attractive force of
the nucleus (effective nuclear charge). The outermost shell is therefore pulled closer and closer to the
nucleus, resulting in a shrinking of atomic volume.
In metals, because of the large size of the atoms, the outermost electrons are weakly held to the atom.
These electrons are therefore easily lost. Further more, a loss of valence electrons exposes the underlying
shell, which has a compete octet of electrons. A metal therefore tends to be stabilized by the formation of
positive ions. On the other hand, to fill an octet in the outer most shell, a non-metal atom needs to accept
just a few electrons. Also, because of the small atomic size, the outer shell is closer to the nucleus, and it is
capable of accepting electrons, because the incoming electron(s) would be stabilized effectively by the
attractive force of the nucleus. Non- metals tend to be stabilized by accepting electrons to form negative
ions.
Consider what happens when chlorine and sodium are mixed. A sodium atom loses its valence electron,
forming a sodium ion, Na+. This ion is more stable than a sodium atom because it now has an outer shell
with a full octet of electrons. The electron lost by a sodium atom is gained by a chlorine atom. By
accepting this electron into its valence shell, Cl now has a full octet of electrons in the outer shell. The
chloride ion is therefore more stable than the chlorine atom.
The positive sodium ion and the negative chloride ion then attract to form sodium chloride, NaCl. It is this
attraction between a positive ion and a negative ion which is termed an ionic bond.

The bonding in sodium chloride is illustratedin Fig 3.18.

Fig 3.18Ionic bonding in sodium chloride

Use of dot and cross diagrams

In a strict sense, an ionic compound does not have a dot and cross diagram. Dot and cross diagrams are
mainly used to distinguish between shared electrons of a covalent bond because we need to know the
origin of each electron of the bond. In ionic compounds, there is no electron sharing, so it may not be
necessary to distinguish between electrons. However, examiners often ask candidates to draw the dot and
cross diagram for an ionic compound. The dot and cross diagram for NaCl is shown in Fig 3.19 below
(only the valence shells have been shown).

Fig 3.19

The formulae of ionic compounds

The formula of an ionic compound is written so that the total of positive charges balances with the total of
negative charges. An ionic compound, and indeed, all compounds, should be electrically neutral. It is
hoped that at this stage the reader has no difficulties in writing the formulae of ionic compounds. The
reader may do self-check exercise 3.1below.

Exercise 3.1

Write down the formulae of the following compounds

1. Magnesium chloride. 6. Aluminium sulphate

2. Iron (III) chloride. 7. Lithium oxide
3. Aluminium oxide 8. Ammonium sulphate
4. Sodium nitride. 9. Sodium nitrite
5. Magnesium nitride 10. Barium sulphite

The lattice structure of ionic compounds

One important property of an ionic bond is that it is highly directional, that is, it will only operate in a
fixed direction. It therefore tends to be localized. This means that ions and anions can only be held
together in a specific way, that is, the ions are not randomly organized. This results in a regular three
dimensional lattice of ions, with well defined layers. Such a regular three dimensional arrangement of
particles in space is known as a crystal or lattice. This can be illustrated using sodium chloride(Fig 3.20).
The co-ordination number in the NaCl crystal is six. This means that each ion is surrounded by six ions of
opposite charge.

Cl-
Fig 3.20 The crystalline
Na+ nature of NaCl

Properties of ionic compounds

1. High melting and boiling points
The electrostatic attractions between positive and negative ions are very strong. A large amount of heat
energy is required to pull the ions apart and breakdown the crystal into a molten state. Because of their
high melting points, some ionic compounds are frequently used as refractory substances. These are
substances whose use depends on their ability to resist heat, for example, MgO which is used as a furnace
lining.

2. They are hard

The particles of the lattice (cations and anions) are held in fixed positions by strong directional
electrostatic attractions. It is difficult to displace the particles with respect to each other.

3. Non conductors of electricity in solid state.

There are no free ions or electrons to carry electric charge.

4. Conducts electricity when molten or in aqueous solution

In the liquid (molten) state or aqueous solution, there are mobile ions (cations and anions) to carry
electric charge.

5. Brittle.
Under strain, ionic compounds snap without bending first. A force may displace layers and align them in
such a way that positive ions are directly in line with positive ions, and negative ions are directly in line
with negative ions. This causes sudden repulsion between layers, causing a smart cleavage to occur. The
cleavage is clean (not jagged), because it occurs along layers.

6. Soluble in polar solvents butinsoluble in non-polar solvents

The δ- end of a polar molecule such as water is attracted to the positive ions of the ionic compound. The
δ+ end of the solvent molecule is attracted to the negative ions of the solid lattice. This results in ions of
the crystal being pulled apart. This is illustrated for the dissolution of NaCl in water in Fig 3.21.

Fig 3.21

This pulling apart of ions by solvent molecules uses energy. However, the energy used is more than
compensated for by the formation of solvated ions. Formation of ion-solvent electrostatic attractions
releases energy. It is this energy which drives further dissolution of the solid.
An ionic compound will not dissolve in a non-polar solvent such as benzene. Solvent- ion attractions
would be very weak, that is, very little energy would be produced by solvation to compensate for the
energy that is used to pull the ions apart from the solid crystal.
Ionic or covalent?
In discussions on bonding, an impression is sometimes created that there is a clear cut boundary between
covalent and ionic bonding. It should be mentioned here that in most of the cases, a covalent bond has
some ionic character, and an ionic bond has some covalent character. When we say a bond is covalent, we
mean that the percentage of ionic character is much smaller than its covalent character, and most of its
properties are those of a covalent substance.
However, we do have cases where, in a covalent compound, the ionic character is so high that it has an
important effect on the properties of the substance. Similarly, some ionic compounds have considerable
covalent character. A good example is magnesium chloride. We usually expect an ionic compound to form
a neutral solution when it dissolves in water. When MgCl 2 dissolves in water, the solution formed is not
neutral, but is acidic. This shows that MgCl2 has significant covalent character.

3.8Metallic bonding
The bonding in metals is known as metallic bonding. It arises like this:
 Metal atoms give up their valence electrons and contribute them into a common pool.
 The metal atoms then become positively charged. These positive atomiccores are more stable
than the atoms, because by giving up the valence electrons they expose an underlying octet. The
term positive ion is sometimes used, but this is misleading because it gives the wrong impression
that the metal atoms completely lose their valence electrons. The metal atoms do not lose
electrons; they simply contribute them into a common pool. The term cation should particularly
be avoided.
 The electrons then form a delocalized sea. The term ‘delocalized’ emphasizes that the electrons
are not fixed (localized) in one place as in a covalent bond. They are mobile and no single electron
belongs to any single atom. The term ‘sea’ emphasizes that all electrons form a common pool. It is
not possible to distinguish between the electrons and tell where each electron came from.
 The positive atoms and the sea of delocalized electrons then attract electrostatically. This
attraction is very strong, and it is termed a metallicbond.

Metallic bonds are electrostatic attractions between positive metal atoms and a sea of delocalized
electrons.

Structure of metals
The bonding in metals is illustrated in Fig 3.22below.
The bonding in metals is giant metallic. There are strong forces of attraction permeating throughout the
structure in all directions. The solid state is crystalline, that is, it is characterized by a regular three
dimensional array of particles, just as in ionic compounds.

Properties of metals
As in covalent and ionic compounds, the properties of metals are closely related to the nature of bonding.

1.Most metals havehigh boiling and melting points

The metallic bond is very strong. The electrostatic attraction between the positive atomic cores and the
sea of delocalized electrons is so strong that a large amount of energy is needed to pull atoms apart and
break down the crystal into its molten state.

Important note
The statement ‘metals have high melting points’ is a useful generalization but it has exceptions, for
example, sodium metal begins to melt at only 980C!

2. Malleable and ductile

Metals can be drawn into wires (they are ductile) and they can be moulded into different shapes
(they are malleable). The layers of atoms in metals are regularly arranged. It becomes possible for one
layer to slip over another. As the slipping occurs, the layers remain held together by the strong forces of
attraction between the positive atomic cores and the sea of delocalized electrons. This metallic attraction
is non-directional. It works in all directions and is therefore not broken when layers and atoms change
positions. The slipping of layers causes an increase in length and a decrease in width, and if this continues
the metal becomes a wire.
When a metal is hammered, the strain displaces and spreads out the atoms, but the structure does not
easily crumble because whatever new positions the atoms take, they are still held by the strong metallic
forces.

3. Good conductors of electricity

When a potential difference is applied between the ends of a metallic object, the mobile electrons in the
sea of delocalization are induced to move in one direction, thus allowing the transmission of electricity.

4. Can be alloyed
Alloying involves doping a metal with a small quantity of another metal, or other metals.
Metallic bonds are non-specific. If a different metal atom is introduced, it loses its valence electrons and it
is then attracted to the sea of delocalized electrons like any other atom in the structure. It is therefore the
non- specific attraction between electrons and positive atomic cores that allow atoms of other metals to be
integrated into the structure. There are several reasons for alloying metals, including:

(i) Increasing strength

The foreign atoms may introduce irregularities in the structure, especially if they have very different
atomic sizes to those of the metal being alloyed. Irregularity hinders the slip of layers and atoms when a
stress is applied. The metal is then stronger and it can not easily be deformed.

(ii) Increasing electrical conductivity

The added atoms may be able to lose a larger number of electrons into the lattice. This is particularly true
if the added metal is a transition element. There will be more electrons to carry charge than in the un-al-
loyed metal.

(iii) Increasing resistance to corrosion

Stainless steel is an alloy of iron. It is well known for its resistance to rusting. The presence of other ele-
ments such as chromium helps to prevent corrosion. For example, when Cr atoms react with atmospheric
oxygen, a tough layer of impermeable chromium (III) oxide is formed, which prevents further entry of
oxygen and water.
(iv)Enhancing magnetic properties
A metal is magnetic if it has unpaired electrons in its valence shell. The more unpaired electrons there
are, the stronger the magnetic properties of the metal. An un-paired electron behaves as a tiny magnet.
This is a property of every charged particle; when it moves, it becomes a tiny magnet, whose strength can
be measured in terms of the magnetic moment. If electrons are paired, their magnetic moments cancel
each other. This is because paired electrons spin in opposite directions. Their magnetic moments will have
the same magnitude, but they will be oriented in opposite directions, so they cancel each other out. Mag-
netism is a property of the transition elements. Most of them have unpaired electrons in the outer-shell.
Alloying a non-magnetic metal with a transition element may give it magnetic properties.

5. Lustre in metals
Metals are lustrous (shiny). When electrons in the delocalized sea absorb quanta of light energy, they are
promoted to higher energy bands. They will not stay long in these unstable bands. They have a tendency
to fall back to their original energy levels. As they do so, they dissipate the same quanta of energy they had
gained. It is this emitted light that is picked by the eye as lustre.

A final note on bonding

Bonding occurs to stabilize matter. What actually needs to be stabilized is the valence shell of atoms,
because they are the ones which are involved in chemical reactions. If the valence shell has an unstable
electronic configuration, it will tend to participate in reactions that ensure stabilization of the outer shell.
It is usually noticed that the valence shell becomes stable if it acquires the octet number of electrons. In
covalent substances, this happens by sharing of electrons between two atoms.
In ionic compounds, the metal atom achieves stability by shedding the unstable valence shell. This ex-
poses the underlying shell which has a full octet of electrons. The non-metallic atom attains stability by
gaining a few electrons into the valence shell. This gaining of electrons fills an octet and stabilizes the ion
formed.
In metals, the metal atom also achieves an octet in the outer shell by shedding the unstable valence shell,
exposing the underlying shell, which has an octet of electrons.
Exercise 3.2

1 The elements of Group IV all form tetrachlorides with the general formula MCl4.
(a) Draw a diagram of a molecule of SiCl4, stating bond angles.
(b) Describe and explain how the volatilities of the Group IV chlorides vary down the group.
9701/04/M/J/2008

2The molecule dichlorocarbene, CCl2, can be produced under certain conditions. It ishighly unstable,
reacting with water to produce carbon monoxide and a strongly acidicsolution.
Suggest the electron arrangement in CCl2 and draw a dot-and-cross diagramshowing this. Predict the
shape of the molecule.
9701/04/M/J/2010

3 The oxides of the third period include the following:

Na2O; MgO; Al2O3; SO2; SO3.
Showing outer electrons only, draw a dot-and-cross electron diagram for magnesium
oxide, MgO.

9701/02/O/N/2002

4(a) Salt, sodium chloride, forms transparent colourless crystals. Describe the bonding insodium
chloride crystals, give the formula of each particle and sketch part of the crystalstructure.
(b) Explain why crystals of sodium chloride do not conduct electricity, but molten sodium
chloride does.
9701/02/O/N/2003

5 Hydrogen sulphide, H2S, is a foul-smelling compound found in the gases from volcanoes.
Hydrogen sulphide is covalent, melting at –85 °C and boiling at –60 °C.
(i) Draw a ‘dot-and-cross’ diagram to show the structure of the H2S molecule.
(ii) Predict the shape of the H2S molecule.
(iii) Oxygen and sulphur are both in Group VI of the Periodic Table.
Suggest why the melting and boiling points of water, H 2O, are much higher thanthose of H2S.
9701/02/M/J/2005

6 Carbon disulphide, CS2, is a volatile, stinking liquid which is used to manufacture viscose, rayon
and cellophane.
(a) The carbon atom is in the centre of the CS2 molecule.
Draw a ‘dot-and-cross’ diagram of the carbon disulphide molecule.Show outer electrons only.

(b) Suggest the shape of the molecule and give its bond angle and shape
9701/02/O/N/2002

7Ethyne is a linear molecule with a triple bond, C≡C, between the two carbon atoms.
Draw a ‘dot-and-cross’ diagram of an ethyne molecule. 9701/02/M/J/2006

8When separate samples of copper or iodine are heated to 50 °C, the copper remains asa solid while
the iodine turns into a vapour.
(i) Explain, in terms of the forces present in the solid structure, why copper remains asolid at
50°C.
(ii) Explain, in terms of the forces present in the solid structure, why iodine turns into avapour
when heated to 50°C. 9701/02/O/N/2006

9. Ethene, C2H4, and hydrazine, N2H4, are hydrides of elements which are adjacent in thePeriodic
Table. Data about ethene and hydrazine are given in the table below.

(a) Ethene and hydrazine have a similar

arrangement of atoms but differently shaped
molecules.
(i) What is the H-C-H bond angle in ethene?
(ii) Draw a ‘dot-and-cross’ diagram for
hydrazine.
(iii)What is the H-N-H bond angle in
hydrazine?

(b) The melting and boiling points of hydrazine are much higher than those of ethene.
Suggest reasons for these differences in terms of the intermolecular forces eachcompound
possesses.
9701/02/M/J/2007

10 This question is about the bonding of covalent compounds.

(a) Sketch the shapes of a 1s, a 2s, and a 2px orbital.
(b) Covalent bonding occurs when two atoms share a pair of electrons. Covalent bondingmay also be
described in terms of orbital overlap with the formation of σ bonds.
(i) How are the two atoms in a covalent bond held together? In your answer, state whichparticles
are attracted to one another and the nature of the force of attraction.
(ii) Draw sketches to show orbital overlap that produces the σ bonding in the H2and
HCl molecules.
(c) The bond in the HCl molecule is said to be ‘polar’.
(i) What is meant by the term bond polarity?
(ii)Explain why the HCl molecule is polar.
9701/04/O/N/2007

11The structural formulae of water, methanol and methoxymethane, CH3OCH3, are givenbelow.

(a) (i) How many lone pairs of electrons are there around the oxygen atom inmethoxymethane?
(ii) Suggest the size of the C–O–C bond angle in methoxymethane.

The physical properties of a covalent compound, such as its melting point, boiling point,vapour
pressure, or solubility, are related to the strength of attractive forces between themolecules of that
compound.
These relatively weak attractive forces are called intermolecular forces. They differ in theirstrength
and include the following.

A interactions involving permanent dipoles

B interactions involving temporary or induced dipoles
C hydrogen bonds

(b) By using the letters A, B, or C, state the strongest intermolecular force present in each
of the following compounds.
ethanal CH3CHO
ethanol CH3CH2OH
methoxymethane CH3OCH3
2-methylpropane (CH3)2CHCH3
9701/02/M/J/2008

12(a) Methanol and water are completely soluble in each other.

(i) Which intermolecular force exists between methanol molecules and water moleculesthat
makes these two liquids soluble in each other?
(ii) Draw a diagram that clearly shows this intermolecular force. Your diagram shouldshow any
lone pairs or dipoles present on either molecule that you consider to beimportant.
(b) When equal volumes of ethoxyethane, C2H5OC2H5, and water are mixed, shaken, andthen
allowed to stand, two layers are formed.
Suggest why ethoxyethane does not fully dissolve in water. Explain your answer.
9701/02/M/J/2008

13 Ketene, C2H2O, is a member of a class of unsaturated organic compounds that is widelyused in

pharmaceutical research for the synthesis of organic compounds.

CH2=C=O
ketene
Suggest values for the H-C-H and C=C=O bond angles in ketene.9701/02/O/N/2008

14At low temperatures, aluminium chloride vapour has the formula Al2Cl6.
Draw a ‘dot-and-cross’ diagram to show the bonding in Al2Cl6.Show outer electrons only.
9701/02/M/J/2009

15Elements and compounds which have small molecules usually exist as gases or liquids.
(a) Chlorine, Cl2, is a gas at room temperature whereas bromine, Br2, is a liquid under the
same conditions.
Explain these observations.
(b) The gases nitrogen, N2, and carbon monoxide, CO, are isoelectronic, that is they havethe
same number of electrons in their molecules.
Suggest why N2 has a lower boiling point than CO.
(c) A ‘dot-and-cross’ diagram of a CO molecule is shown below. Only electrons from outershells
are represented.

In the table below, there are three copies of this structure.

On the structures, draw a circle round a pair of electrons that is associated with each ofthe
following.
(i) a co-ordinate bond (ii) a covalent bond (iii) a lone pair
9701/02/M/J/2010

16 Which statements are a true about the following molecules

HCN CO N2

1. They are isoelectronic

3. They all have a strong triple bond
 2.N2 is the least reactive of the three compounds
CHAPTER

STATES OF MATTER
4

Introduction
There are three states of matter, namely solids, liquids and gases. These states mainly differ in
 regularity in the packing of particles
 how loosely or tightly the particles are packed
 the kinetic energy of the particles
 shape
Bonding and structure in a substance is important in explaining the state at room temperature of that
substance, as well as its physical properties, such as melting points and boiling points. If particles of a
substance are held by very strong forces of attraction, then the substance is likely to be solid at room
temperature. At this temperature, there is no sufficient energy to pull apart the particles from each
other and form the liquid or gaseous state. Thus ionic solids and metals are solids at room
temperature because of the very strong electrostatic attractions that hold particles together.
However, even covalent substances which contain Van der Waals forces can be solid at room
temperature if these forces are strong enough. A good example is candle wax, in which the Van der
Waals forces are strong enough to hold alkane molecules together in the solid state. This is a result of
the presence of a large number of electrons in each molecule of candle wax.
Some substances exist as gases at room temperature. This shows that the intermolecular forces in the
substance are so weak that even at room temperature; there is enough energy to break the forces and
keep the molecules apart in the gaseous state. It is possible to liquefy and solidify any gaseous
substance, for example, neon and nitrogen. This can be achieved by lowering temperature, increasing
pressure, or both. The effect is to bring the molecules closer, reduce their kinetic energy and allow
stronger intermolecular forces to form.

4.1 The gaseous state

Gases are characterized by
 the random and loose ordering of particles. The particles are not arranged in any definite order,
and they are always rapidly shifting positions in an unpredictable way.
 high kinetic energy. The particles are in a state of random and rapid movement, frequently
colliding with each other and with the walls of the container.
 lack of shape. A gas has no particular shape because the gas particles always spread to fill he
available space.

4.1.1 Ideal versus real gas: What properties should a gas have?
If a gas meets all of the following criteria, then it is acting as expected of a gas. We say it is behaving as an
ideal gas. These criteria are referred to as the assumptions of an ideal gas.

Assumptions of an ideal gas

1.The assumption of zero volume
Each particle of a gas (it could be an atom as in the noble gases or a molecule as in oxygen) has a
negligible volume relative to the volume of the container. The ratio
Volume of molecule
Volume of container

is so small that it can be rounded off to zero.

Common error
Students commonly report that an ideal gas has no volume. This is not true. The gas as a whole
certainly has a volume. However, the volume of an individual particle is negligible.

2.Collisions are perfectly elastic

When particles collide, they bounce back without loss of energy. Thus collisions do not reduce the kinetic
energy of particles. Such collisions are said to be perfectly elastic.

3. There are no forces of attraction between particles

The gas particles are therefore able to move independently of each other because they are not associated
through intermolecular forces.

4.An ideal gas obeys the ideal gas equation perfectly.

This equation is

PV = nRT
4.1.2 Validity of the assumptions
To what extend are the assumptions given above valid?
1. The assumption of zero volume.
It does not make sense to assign zero volume to a particle. If it exists, then it has a volume. Anything
which can be shown to exist is matter, and matter is that which occupies space, that is, has a volume. Each
particle of a gas has a volume. However, the volume is so small that for practical purposes, it may be
rounded off to zero.

2. Collisions are perfectly elastic

This is not practical. Whenever two particles collide, energy is lost as heat due to friction. However, the
loss of energy is very small owing to the small size of the particles.

3. There are no forces of attraction between particles

Electrostatic attractions between particles are inevitable. They will always exist. However, in gases, the
forces are very weak because of the large distance between particles. Further still, the particles are always
moving rapidly and randomly. This causes a continuous disruption of the intermolecular forces.

4. Ideal gases obey the ideal gas law.

The ideal gas equation is derived from assumptions 1, 2 and 3. Since these assumptions have their own
limitations, the fourth assumption is also limited. Real gases do not obey the ideal gas equation perfectly.

4.1.3 Real gases

In practice, ideal gases do not exist. Instead, we have real gases which approach (but will never
quiteattain)the ideal state under certain conditions.
In a real gas
 each particle has a volume
 When particles collide, they lose some energy
 There are forces of attraction between particles
Because of these properties, a real gas does not perfectly obey the ideal gas equation.

Under what conditions does a real gas approach ideal gas behavior?
 At high temperature
 At low pressure
At high temperature, the particles gain kinetic energy and spread away from each other, that is, the gas
expands. The volume of a particle then becomes negligible compared to the volume of the container. Also,
intermolecular forces become almost non-existent as distance between particles increases.
The reverse happens when a gas is cooled. The particles come closer and intermolecular forces begin to
form between the particles. The volume of a particle relative to the total volume occupied by the gas also
becomes important as the particles get closer and closer together. That is, a real gas deviates most from
ideal gas behavior at low temperatures.
At low pressure a gas is close to being ideal. When pressure is reduced, a gas expands (assuming constant
number of moles). The particles spread away and this favours the ideal behaviour. At high pressure a gas
deviates from ideality by forcing the particles into a smaller volume.

4.2 The ideal gas equation

The following observations (for a fixed mass of gas) lead to the ideal gas equation:
1. Volume varies directly as temperature, provided pressure is kept constant (Fig 4.1)
V ∝ T, V = k1T … I

Increasing temperature causes a gas to

expand. The volume increases
proportionally with increasing
temperature. The reverse happens when
the gas is cooled.

Fig 4.1
2. Volume varies inversely as pressure, provided temperature is constant (Fig 4.2).

𝟏
V ∝ , V = k2/P
𝐩

Increasing pressure results in compression of

the gas, that is, volume decreases, but of
course, it can not become zero, hence the
inverse nature of the graph.

Fig 4.2

3.Pressure varies directly as the number of moles of gas (Fig 4.3)

P ∝ n, P = k3n … III

Increasing the number of moles of a gas results in a propor-

tional increase in pressure, provided temperature and
pressure are kept constant.

Fig 4.3

4. Pressure varies directly as temperature (Fig 4.4)

P = k4T... (IV)
Pressure of a gas is a measure of the frequency with which
gas particles strike the walls of the container. When
temperature increases, so does the kinetic energy of the
particles. They strike the walls of the container more
frequently, that is, pressure increases.
 Fig 4.4

Combining the relationships (I) to (IV) gives the ideal gas equation
PV = nRT
Examiners frequently set questions that require use of the ideal gas equation. The problem students
usually face is in using the correct units.

Important derivations from the ideal gas equation

(i) Determination of Mr of an ideal
gas or a volatile liquid
PV = nRT ... (i)
Rearranging gives
m
But n = , where m = mass in grams
Mr 𝐦𝐑𝐓
Mr =
substituting n in equation (i) gives 𝐏𝐕

m This form of the general gas equation is useful in the

PV = RT determination of the Mr of a gas or a volatile liquid (the
Mr
liquid must be vapourised first).

(ii) Determination of density of an

ideal gas
That is, m = D x V ... (ii)
m
PV = RT Equating equation(i) and equation(ii)
Mr
PV x Mr
Rearranging gives mass m in grams DxV=
RT
and dividing both sides by V
𝐏 𝐱 𝐌𝐫
D=
𝐑𝐓
 PV x Mr
m= ... (i)
RT
m
Now, D = , Where D = density
V

(iii) Pressure of a combined system

In Fig4.5, two flasks A and B are arranged so that they can be combined into one system by opening the
tap. V1 and V2 represent the capacities, in m3 of the two flasks respectively. Before connection, the
pressure in flask A is P1 and that in Flask B is P2.
What would be the total pressure, PT in the combined arrangement after connection?

Fig 4.5

From PV = nRT,
we find n1 and n2, the number of moles of gas in flask A and B respectively.

P1V1
n1 =
RT

P2 V 2
and n2 =
RT

Total number of moles, nT is given by

nT = n1 + n2

P1V1 P2 V 2 PTVT
= + =
RT RT RT

factorizing LHS (P1V1 + P2V2) = PTVT

RT RT

multiplying both sides by RT gives P1 V 1 + P 2 V 2 = PTVT

P1V1 + P2V2 Where VT is the combined volume

rearranging gives PT =
VT
(iv) The relationship P1V1 = P2V2
Forn moles of an ideal gas at a pressure P1and volume V1, the ideal gas equation is given by
P1V1 = nRT ... (i)
Now suppose that pressure and volume are increased to P2 and V2 respectively at constant temperature.
The ideal gas equation becomes
P2V2 = nRT ... (ii)
Since the right hand-sides of equations (i) and (ii) are equal, it follows that the left hand sides are also
equal, that is,

P1V1 = P2V2.
This relationship is only true for an ideal gas at a constant temperature and constant number of moles.

A gas occupies 87 cm3 at a pressure of87.5 KPa. What pressure is required to reduce the
Q volume of the gas by 2% ?

Volume
A decreases by 87 cm3x 2/100 = 1.74 cm3. The new volume (V2) is therefore
87.00 - 1.74 = 85.26 cm3. Let the new pressure be P2
P1V1 = P2V2
P₁V₁ 87.5 x 87
P2 = =
V₂ 85.26

=89.29 KPa

4.2.1 Deviations from ideality

You now know that a gas deviates the most from ideal behaviour when pressure is high and when temper-
ature is low. Look again at the ideal gas equation, PV = nRT.
When temperature and number of moles are kept constant, we may write
PV = constant ... (i)(since R is also constant).
This outcome can be shown graphically. Suppose that volume is increased, that is, the gas expands (Fig
4.6(a)). This increase is countered by a proportional decrease in pressure, so the product PV remains con-
stant. Similarly, when pressure is increased (Fig 4.6(b)), that is, the gas is compressed, volume decreases
proportionally, so the product PV also remains constant.

PV PV Fig 4.6 For an ideal gas, the product PV

remains constant when pressure or
PV = constant PV = constant volume is altered, provided temperature
(a) (b)
and amount of gas (moles) is kept
constant.
V P

In practice, a plot of PV against V or P is not constant but becomes approximately constant at high
temperature and pressure (the gas approaches ideality under these conditions). In other words, for a real
gase, the graph of PV against P or V deviates from the horizontal line shown in Fig 4.6 above. This is
llustarted in Fig 4.7 below.
At low pressures (less than P2), a real gas shows negative deviation from ideal gas behaviour (the curve is
below the line for an ideal gas).
A real gas shows positive deviation from ideal gas behaviour when pressure is sufficiently high. The curve
is then above that of a real gas.

Fig 4.7 deviation of a real gas

from ideality

Which of the following gases deviates the most from ideal gas behaviour. Explain your
Q
answer.
A. NH3 B. HCl C. O2 D. N2

A3. Intermolecular forces are strongest in ammonia, where there is hydrogen bonding. The
NH
assumption that an ideal gas possesses no forces of attraction between molecules is therefore the
least valid for ammonia.

Fig 4.8 below shows the relative deviations of four gases NH3, HCl, O2 and H2 from ideality.

Fig 4.8

 NH3 contains relatively strong hydrogen bonds, so it deviates the most from ideal gas behaviour.
 Comparing HCl, O2 and H2, HCl has the strongest intermolecular forces (permanent dipole-
dipoleattractions), so it shows the greatest deviation.
 Both H2 and O2 contain relatively weak Van der Waals forces. However, these forces are stronger
in oxygen which has the larger number of electrons. Oxygen therefore deviates more from ideal
gas behaviour.
 In hydrogen, intermolecular forces are a very weak. Deviation from ideality is the smallest and it
is positive. Of all gaseous elements, hydrogen (Ar = 2) resembles an ideal gas the most, followed
by helium (Ar = 4). Note that each particle of hydrogen and helium contains two electrons.
However, helium atoms are heavier, so at any given temperature, they have the smaller kinetic
energy. This favours establishment of intermolecular forces.
Worked examples Answer D
m
Using PV = RT
1 .Use of the Data Booklet is relevant to this question. Mr
mRT
Which expression gives the pressure exerted by Mr =
PV
1.6 x 10–3mol of N2in a container of volume3.0 dm3at
273oC? Remember to convert temperature to K and volume to m3
83.1
1.6 x 10¯3 x 8.31 x 273 (83.1 cm3 = m3 = 83.1 x 10-6 m3)
10⁶
A. Pa
3.0 x 10¯⁶

1.6 x 10¯3 x 8.31 x (273+273) 3.When an evacuated glass bulb of volume 63.8 cm3 is
B. Pa
3.0 x 10¯⁶ filled with a gas at 24 °C and99.5 kPa, the mass increases
by 0.103 g. Deduce whether the gas is ammonia,
1.6 x 10¯3 x 8.31 x 273 nitrogen or argon.9701/02/M/J/2004
C. Pa
3.0 x 10¯³

1.6 x 10¯3 x 8.31 x (273+273)

D. Pa
3.0 x 10¯³ Solution
mRT 0.103 x 8.31 x (24 + 273)
9701/01/O/N/2004 Mr = =
PV 99.5 x 1000 x 63.8 x 10¯⁶
= 40.0
Answer D The gas is therefore argon.
using PV = nRT
nRT
P=
V
... (i) 4.A small spacecraft of capacity 10m3 is connected to
another of capacity 30m3. Before connection, the pressure
First convert volume to m3 and temperature to K:
inside the smaller craft is 50KPa and that inside the larger
3 is 100KPa. If all measurements are made at the same
3.0 dm3 = m3 = 3.0 x 10-3 m3
10³ temperature, what is the pressure in the combined
2730C = (273 + 273)K arrangement after connection?
9701/01/O/N/1990
R is the ideal gas constant = 8.31 JK-1mol-1 (Data
Booklet)
then substitute in equation (i) above. Solution
𝐏₁𝐕₁ + 𝐏₂𝐕₂
Use PT =
𝐕𝐓
2.Use of the Data Booklet is relevant to this question.
50 (10)+ 100(30)
In an experiment using a gas syringe, 0.10 g of a gas is =
30+10
found to occupy 83.1 cm3, measured at standard pressure
= 87.5 KPa
(1.0 x 105Pa) and 27°C.
What is the relative molecular mass of the gas?

0.10 x 8.31 x 27 0.10 x 8.31 x 300 5.When a 0.150g sample of substance X was vapourized
A. B.
1.0 x 105 x 83.1 1.0 x 105 x 83.1 at 600C, the vapour occupied a volume of 70.0 cm3 at a
pressure of 101KPa. Calculate the Mr of X
0.10 x 8.31 x 27 0.10 x 8.31 x 300
C. D.
1.0 x 105 x 83.1 x 10¯⁶ 1.0 x 105 x 83.1 x 10¯⁶
 [Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
Exercise4.1
text box.]

1.When an evacuated glass bulb of volume 63.8 cm3 is filled with a gas at 24°C and 99.5 kPa, the mass
increases by 0.103 g. Deduce the density of the gas.

Hint
𝐏 𝐱 𝐌𝐫
D= (First find Mr of the gas)
𝐑𝐓

2.The density of ice is 1.00 g cm–3.

What is the volume of steam produced when 1.00 cm3of ice is heated to 323 °C (596 K) at a pressure
of one atmosphere (101 kPa)?

[1 mol of a gas occupies 24.0 dm3at 25 °C (298 K) and one atmosphere.]

A 0.267 dm3B 1.33 dm3C 2.67 dm3D 48.0 dm39701/01/M/J/2008

Hint
Since D = m/V, you can find the mass(m) of ice . This will also be the mass of steam. Then use the formula
𝐦
PV = RT
𝐌𝐫

3.When used for cutting or welding, ethyne is transported in cylinders which contain the gas under
pressure. A typical cylinder has a volume of 76 dm3 and contains ethyne gas at 1 515 kPa pressure at
a temperature of 25 °C.Use the general gas equation, pV = nRT, to calculate the amount, in moles,
of ethyne in this cylinder.
9701/02/M/J/2006

4.Flask X contains 1dm3 of helium at 2 kPa pressure and flask Y contains 2dm3 of neon at 1 kPa
pressure.If the flasks are connected at constant temperature, what is the final pressure?

1 1 2
A 1 kPa B 1 kPa C 1 kPa D 2kPa
3 2 3
9701/01/M/J/2002

5.A 2 g sample of hydrogen at temperature T and of volume V exerts a pressure p.

Deuterium, ≾H, is an isotope of hydrogen.

Which of the following would also exert a pressure p at the same temperature T ?
A 2g of deuterium of volume V
B 4g of deuterium of volume
C a mixture of 1 g of hydrogen and 2 g of deuterium of total volume V
D a mixture of 2 g of hydrogen and 1 g of deuterium of total volume
9701/01/O/N/2002
4.3 The solid state
Crystalline versus amorphous solids
It is common for science students to refer to solids as having a regular arrangement of solid particles. This
is not always the case.
Solids with a regular three dimensional arrangement of particles are said to be crystalline. The system of
regularly repeating particles is known as a lattice. Some solids have particles which are irregularly ar-
ranged. Such solids are said to be amorphous(non-crystalline). Examples of amorphous solids include
glass and coal (a very impure form of carbon).

Crystalline solids
A crystalline solid can be a covalent, ionic or metallic substance. Ionic compounds are crystalline in
nature. These have already been discussed in Chapter 3, using NaCl as an example. Metals also have a
crystalline form.
When most elements and compounds turn to solid, they form a regular array of particles. Some
substances are gaseous or liquid at room temperature. When we discuss their solid states, we are referring
to what we would get after freezing the substance.
To describe the solid crystalline state of a given substance, reference should be made to:
1. Type of chemical bonding present
This should be described as simple or as giant. The bonding in metals is giant metallic. Bonding in ionic
solids is giant ionic. In covalent compounds there could be giant covalentbonding, as in silicon dioxide,
graphite and diamond, or simple covalent bonding, as in carbon dioxide, iodine and argon. In substances
with giant bonding, the bonding repeats and extends throughout the structure in all directions, without
breaks.
2. Nature of the lattice particles
These are the particles which build up the solid. Lattice particles can be positive and negativeions (ionic
compounds), positive atomic cores (metals), atoms (noble gases) or molecules as in ice and iodine.
3. Forces holding the lattice particles together.
These are intermolecular forces in simple covalent substances: Van der Waals forces, permanent dipole-
dipole attractions, or hydrogen bonds.
In ionic compounds these are ionic bonds (electrostatic attractions). In metals, the lattice particles are
held together by metallic bonds (electrostatic attractions)

4.3.1 Ionic solids

 There is giant ionic bonding.
 Lattice particles are positive ions (cations) and negative ions (anions).
 These ions are held together by strong electrostatic attractions extending throughout the struc-
ture in all directions. Being directional, these forces hold the ions in a regular three dimensional
array.
 NaCl has already been used to illustrate these points.
The properties of ionic compounds should be explained in terms of the structure and bonding present
(see Chapter 3).
4.3.2 Metallic solids
 The bonding in metals is giantmetallic bonding.
 The lattice particles present are positive metal atoms(not cations)
 These atoms are held together by the electrostatic attractions between them and a sea of deloca-
lized electrons (Fig 4.6). These forces of attraction work in all directions (non-directional) and
they hold the atoms in a regular three dimensional array. The forces of attraction extend in all
directions throughout the structure without breaks.
 The properties of metals are closely related to the structure and nature of bonding(See section 3).

Copper and aluminium

Aluminium
 Aluminium has a high mass to strength ratio,
that is, it is very strong and yet very light. This
makes it useful in situations were lightness and
strength should be present together. For this
reason, it is used to make aircraft bodies.
 Aluminium is also resistant to corrosion. This is
because it forms a thin superficial (on the
surface) layer of Al2O3. This layer is tough and
impermeable, so it protects the underlying
metal from further reaction with oxygen and
Fig 4.6 water. This, plus its excellent ability to conduct
heat, makes it useful in making cooking pots.
 Aluminium is an excellent electrical conductor and is used to make electrical cables. However, it
is not used extensively for this purpose because it is expensive.

Copper
 The uses of copper depend onits malleability and ductility. Whilst it is true that all metals are
generally ductile and malleable, some metals are more ductile and malleable than others.
 it is an excellent conductor of heat and electricity.
 it is inert and so resists attack by atmospheric agents( corrosion)
 it can be alloyed with many other metals ability .
Copper is thus used to make electrical cables and components, car radiators (it conducts heat from
the engine rapidly and loses it to the environment easily, it also resists corrosion) and in water pipes
(resistant to corrosion). Pure copper tends to be too soft and weak for some uses. Alloying produces
metals which are stronger and harder.

Bronze (reddish-brown) is an alloy of copper and tin. Bronze has greater tensile strength than copper. It
can also be cast into moulds more easily. For this reason, it is used to make sculptures, such as the one
shown in Fig 4.7.
 Other uses of bronze include :
1. For electrical connectors (it is a better conductor than most steels)
2. Boat and ship propellers (It is resistant to corrosion)

Brass (muted yellow, but duller than gold) is an alloy of copper with zinc. It
is harder and stronger than copper. Its colour makes it decorative. The uses of
brass include
1. Making musical instruments (brass has excellent acoustic properties)
2. In ornaments.

Fig 4.7 A bronze statue

4.3.3 Simple covalent solids

 The bonding present is simple covalent bonding.
 The lattice particles are molecules such as iodine and carbon dioxide. They can also be atoms e.g.
argon.
 The particles are held together by weak intermolecular forces, e. g Van der Waals forces in solid
iodine, and hydrogen bonds in ice. However, in solids, these forces are strong enough to hold the
particles in fixed positions, forming a regular three dimensional structure.

The lattice structure of solid iodine

Fig 4.2 above is a sketch showing the lattice structure of iodine.

The lattice particles are iodine molecules (I2), which are held
together by weak Van der Waals forces.
 This explains why iodine easily sublimes to gas. A small
amount of heat energy is required to break the Van der
Waals forces between the molecules.
 Iodine is poorly soluble in water. For iodine molecules to
dissolve in water, the relatively strong hydrogen bonds
between water molecules must be broken first. When
new Iodine - water interactions form (Van Der Waals
Fig 4.8
forces),they are much weaker than the hydrogen bonds
found in pure water. Such a process in which stronger forces are replaced by weaker forces is not
energetically favourable.

The lattice structure of ice
The lattice particles are water molecules, held together by hydrogen bonds. A peculiar property of ice is
that it is less dense that liquid water, and so tends to float on the surface of the liquid. This property is due
to the open structure of ice (Fig 4.9). Each water molecule is tetrahedrally bonded to four others through
hydrogen bonds. This geometry spaces out the water molecules, resulting in an open structure whose
volume is much higher than its mass, that is, water tends to expand as it freezes. This lowers its density.
 4.3.4 Giant covalent substances
In giant covalent substances, there are a large
number of strong covalent bonds extending
throughout the structure in all directions.
The lattice particles are molecules or atoms, but
these are connected to each other by strong cova-
lent bonds without breaks, forming a giant
structure. Examples are silicon dioxide, diamond
and graphite.

Bonding in graphite
Graphite is an allotrope of carbon. Carbon has
Fig 4.9The lattice structure of ice
two other known allotropes, diamond and
buckminsterfullerenes.
The electronic configuration of C is 1s 2s 2p . With this configuration, C can form two bonds only,
2 2 2

because it has two singly occupied p orbitals.An electron is excited from the 2s sub-shell to a vacant p
orbital. This creates four singly occupied orbitals. There are now four orbitals which can be used for
bonding. However, these orbitals have to be hybridized first to make them equivalent to each other, and
to ensure that they have the correct shapes for overlap. sp2 hybridization takes place, that is, one s orbital
mixes with two p orbitals to form three hybrid orbitals (Fig 4.10). This leaves the pz orbital occupied but
unhybridized. When we discuss the bonding in graphite we should account for how each carbon atom uses
its three singly occupied hybrid orbitals, and its unhybridized p z orbital.

Fig 4.10

Each carbon atom in graphite uses the three hybrid orbitals to overlap head-on with corresponding hybrid
orbitals from three neighbouring carbon atoms. This forms threesigma bonds around each carbon atom.
The geometry around each carbon atom is therefore trigonal planar. This overlap results in one carbon
atom being bonded to three other carbon atoms, which must therefore be spaced out at 1200 relative to
each other to minimize repulsion between the three bond pairs of electrons.

Fig 4.11
The perpendicular unhybridized pz orbitals on the carbon atoms overlap sideways to form a pi bond which
stretches throughout the layer (Fig 4.12).

Fig 4.12

Each carbon atom therefore contributes one electron to the pi bond. These electrons are delocalized
throughout the layers. In graphite, there are a large number of such layers, held together by Van der
Waals forces. Fig 4.13 shows the key features of graphite.
The C-C bond length in graphite is intermediate between a single C to C bond and a C to C double bond.
This shows that the covalent bond is reinforced to some extend by pi bonding. The bonds are therefore
stronger than C to C single bonds. This accounts for the high melting point of graphite (3 730° C). A very
large amount of heat energy is required to break the strong covalent bonds and separate the carbon atoms
from each other.
The uses of graphite are closely related to its structure and the nature of bonding present (table4.2).
Three properties of graphite which makes it a very useful substance are
 It is slippery
 It is a good electrical conductor along layers (it does not conduct across layers, that is, at right
angles to the layers)
 It has a very high melting point

Fig 4.13 Key features of graphite

Table 4.2 Uses of graphite in relation to its properties.

Use Explanation in terms of structure and bonding

Dry lubricant Slippery due to the presence of weak Van der Waals forces between layers.
Being weak, these forces easily break, allowing layers to slide against each
other.
Graphite is very useful as a lubricant in industrial processes which involve
very high temperatures. It is not easily decomposed by heat because of its
very high melting point.

Electrodes in electrolytic It is a good conductor of electricity along layers due to the presence of
processes. delocalized π electrons.

NB Graphite does not conduct across layers.

Heat resistant crucibles for It has a very high melting point.

molten metals

Bonding in diamond
As in graphite, the lattice particles in diamond are C atoms. These are also connected by strong covalent
bonds that extend in all directions throughout the structure. The atoms are arranged in a regular three
dimensional array, that is, diamond is a crystalline solid. Like graphite, diamond has a giant covalent
structure.

In diamond there is sp³ hybridization. Excitation of an

electron from the 2s sub-shell to the vacant 2pz of a carbon
atom creates four singly occupied orbitals. All four of them mix
to form four hybrid orbitals. Each hybrid orbital is occupied
by a single electron. This is sp³ hybridization (as in methane),
because one s orbital mixes with three p orbitals. These four
hybrid orbitals are arranged tetrahedrally (bond angle=
109.50) around the C atom (Fig 4.14). This is the geometry
Fig 4.14 which minimizes inter-electronic repulsion between the hybrid
orbitals.
Each carbon atom bonds tetrahedrally to four others by sigma overlap. This forms C to C sigma bonds
that extend throughout the structure (Fig 4.15).
 Properties and uses of diamond
1.Diamond is one of the hardest substances
known.
Its hardness is due to the presence of a large
number of very strong covalent bonds extending
in all directions.
Because of its hardness, it is used to make the
tips of drilling instrument, for example, in
mining equipment. Diamond tipped electrical
saws arealso used to cut diamonds.
Fig 4.15 Structure of diamond (Diamondcuts diamond).

2.Diamonds have a large refractive index. Refraction of light by diamonds gives them a sparkle. Theyare
therefore used in jewelry.

Table 4.3 gives a comparison of the two allotropes of carbon, diamond and graphite.

Silicon dioxide
Silicon dioxide is a giant covalent substance with a diamond like structure (Fig 4.16).
The simplest repeating unit (lattice particle) is SiO2. Each Si atom is
tetrahedrally bonded to four O atoms, so the bond angle, as in diamond,
is 109.50. Each O atom is in turn bonded to a Si atom. This network of
Si-O covalent bonds extends throughout the structure in all
directions.The properties of silicon dioxide are similar to those of
diamond. It has a very high melting point because to melt it a large
number of very strong covalent bonds must be broken to form discrete
SiO2 molecules.
The presence of a large number of very strong covalent bonds also makes
Fig 4.16 it hard and rigid.

4.3.5 Ceramics
Ceramics are ionic or giant covalent materials whose uses depend on their strength, resistance to heat,
chemical inertness and insulating properties.
These properties are a result of strong and numerous bonds that stretch throughout the structure. The
bonds hold atoms rigidly in space and this explains their hardness. Ceramics with an ionic nature, for
example, magnesium oxide and aluminium oxide, find widespread use because of their very high melting
points. Magnesium oxide is used to line furnaces and as electrical insulators in equipment which are likely
to become very hot.
Aluminosilicates are clays based on the SiO2 structure. They have a sheet structure in which some silicon
atoms are replaced by Al atoms. When the clay is fired, water is driven from between the sheets and a
three dimensional network of bonds is established. Fired clay is used to make a wide range of useful
products, including china, bricks and crockery. The main disadvantage of ceramics is that they are brittle.
Table 4.3Comparison of graphite and diamond

Question and answer section: states of matter

Q1. Which substance has a diamond-like solid structure?

A. SiO2B. Graphite C. Ice D. Copper

A. SiO2

Q2. Which substance does not contain delocalized electrons

A. Silicon B. Graphite C. Copper D. Aluminium

A. Silicon.

Q3. Which gas deviates the least from ideal gas behaviour under the same conditions of temperature and pressure ?

A. Hydrogen B. Helium C. Carbon dioxide D. Neon

A. Hydrogen

Q4. Which substance(s) contain two types of chemical bonds?

(i) Ice (ii) graphite (iii) diamond

A.(i) and (ii) are correct. Both substances contain strong covalent bonds and weak Van der Waals forces.
Q5. What happens when water freezes?

(i) Its volume decreases (ii) Its density decreases (iii) Its molecules spread apart

A.(ii) and (iii) are correct.

Q6. Which relationship(s) are correct for an ideal gas

(i) Vm α P (ii) P α T (iii) PV α T

A. (ii) and (iii) are correct. PV = nRT, but for any given ideal gas, nR is constant, so PV = kT where K = nR.
that is, PV α T. When temperature increases, both P and V increases , so the product PV also increases.

Q7.Which of the following solids has a simple molecular lattice?

A . magnesium oxide B. sodium C. silicon(IV) oxide D. sulphur

A.Sulphur. It exists as S8molecules

Q8.For an ideal gas, the plot of pV against p is a straight line. For a real gas, such a plot shows adeviation from
ideal behaviour. The plots of pV against p for three real gases are shown below. The gases represented are
ammonia, hydrogen and nitrogen.

What are the identities of the gases X, Y and Z?

X Y Z
A ammonia nitrogen hydrogen
B hydrogen nitrogen ammonia
C nitrogen ammonia hyrogen
D nitrogen hydrogen ammonia

A.D

Q9.Which diagram correctly describes the behaviour of a fixed mass of an ideal gas? (T is measured
in K.)

9701/01/M/J/2008
 A.D. Graph in A should be inverse, not linear. Recall that for an idea gas at constant temperature,
PV = constant. The graphs in B and C should therefore straight lines that are parallel to the x - axis.
APTER
5
CHEMICAL ENERGETICS

Chemistry is concerned, among other things, with studying the changes that matter may undergo. These
changes can be chemical (involvingthe formation of new substances) for example, the conversion of hy-
drogen and nitrogen to ammonia, or they can be physical, for example, the sublimation of iodine.
Chemical energetics (thermodynamics) is concerned with answering the question

‘Is the process feasible (possible) or not, and why?’

For example,

Is the conversion of graphite to diamond feasible (graphite and diamond are allotropes of carbon)?

Note the use of the term ‘feasible’. If a process is feasible, it means it is possible though in practice it may
not happen. For example, it is possible (feasible) for a boulder at the top of a hill to roll down, but
whether this actually happens or not depends on other factors. Chemical energetics simply tries to pre-
dict the feasibility of a process. Whether in practice the process actually takes place or not is beyond the
scope of energetics, but is addressed by another branch of chemistry, known as reaction kinetics. For
instance, the conversion of graphite to diamond is energetically feasible. From an energetic point of
view, it is possible to convert the graphite (‘lead’) in your pencil to diamonds! In practice, this does not
take place, or takes place under conditions which are so stringent that the whole process is uneconomic.
Chemical energetics and reaction kinetics therefore represent two points of view in chemistry. A process
might be feasible from an energetic point of view, but from a kinetic point of view, it might not take
place.
In this topic we explore why chemical processes occur and we get an idea of how to predict feasibility of
a reaction. We make this analysis by studying the transfer ofheat energy during reactions.

5.1 Absorption and release of energy during chemical reactions

Chemical energetics (thermodynamics) is the branch of chemistry that studies the flow of heat energy
during chemical processes.

In a chemical reaction, this flow of energy is in two parts

 Absorption of energy when bonds break. For a chemical reaction to take place, bonds in
reactants must first break, and this requires energy.
 Release of energy when new bonds are formed. The second process involved in a chemical
reaction is bond formation. This occurs when atoms of reactants rearrange and bond in new ways.
Bond breaking is said to be an endothermic process, that is, one which absorbs or requires heat
energy in order to take place. Bond formation is an exothermic process, that is, heat energy is released
when a bond is formed.

5.2 Energy content

Chemical reactions are usually accompanied by a change of energy content of the reacting substances.
This change in energy content manifests as a loss or gain of heat energy during the reaction. The energy
content of products and reactants can therefore be conveniently expressed in terms of heat energy,
referred to as enthalpy, H. Although it is impossible to actually determine the absolute energy con-
tent(enthalpy) of reactants and products, it is possible to determine the energy difference between them.
This energy difference, known as an enthalpy change, ΔH, manifests as net absorption or net release
of heat energy during the reaction.
You are probably familiar with reactions which give out heat energy. Such reactions are said to be
exothermic. In such reactions, the temperature of the contents of the reaction vessel increases. On the
other hand,endothermic reactions, which absorb energy, are accompanied by a decrease in temperature
of the products.

Understanding exothermic and endothermic reactions

Recall that a chemical reaction involves two processes, bond breaking (endothermic) and bond
formation(exothermic).In terms of energy flow, these two processes oppose each other. Bond breaking
absorbs (uses) energy whereas bond formation releases energy. The net energy flow during the reaction
(net absorption or net release) depends on which process has a numerically greater energy (enthalpy)
term.
An endothermic process is assigned a positive enthalpy value. This is because the reactants gain
(absorb) energy which is then transferred to products during the reaction. In other words, the products
are now at a higher energy level than the reactants. In other words, the energy content of the products in-
creases.
An exothermic process is assigned a negative enthalpy value. The negative sign denotes net loss of
energy to the environment. The energy content of the products therefore decreases.
We may represent an endothermic process with an arrow pointing up, showing an increase in energy
content of the products. An exothermic process may then be represented by an arrow pointing downward,
showing a net loss of energy.

Consider a hypothetical reaction in which 500Kj of energy are absorbed to break bonds and 800 Kj are
released when new bonds are formed in the products (Fig 5.1).The net flow of energy, ∆H, is obtained by
adding the two enthalpy terms. Thus

ΔH = 500 + (-800) = - 300Kj

The negative sign indicates that there is a net release of heat energy. In words, we say

‘The enthalpy change of the reaction is -300Kj’or “the process releases 300Kj of heat energy’.
 Fig 5.1 Energy
‘transactions’ of a chemical
reaction

Note that it is not proper to say ‘the process releases -300Kj of energy’, because the use of the term
‘releases’ denotes a negative enthalpy.
The enthalpy change of the process can be shown on an energy level diagram (Fig 5.2).

In this reaction, more heat energy is given out when new

bonds in products form than is used when bonds in
reactants break. On the other hand, if a reaction is
endothermic, the process of bond breaking uses up more
energy than is released by the process of bond formation.
The net effect is therefore absorption of energy (Fig 5.3).

An example of an endothermic process: the

dissolution of ammonium nitrate in water

Fig 5.2 Energy level diagram of an

thermometer
exothermic reaction which gives
out 300Kj of energy
ammonium
nitrate
Fig 5.4
Ammonium
nitatre dissolving
in water

In this process, the thermometer registers a decrease in

temperature. The walls of the beaker will also feel cooler.
This is a property of an endothermic reaction: temperature
Fig 5.3 In an endothermic reaction drops during the process.
there is a net absorption of energy, so the
products are higher in energy.
Some readers may see a contradiction here and expect temperature to increase since heat energy is being
absorbed. As an example, consider an endothermic reaction which takes place in solution. There is a net
flow (absorption) of heat energy from thesolution into the bonds of the products. Because heat energy has
moved from the solution to bonds of the product, it can be said that the solution has lost heat energy, not
to the environment, but to the bonds of the products, so its temperature should drop. During an
endothermic process, there is therefore a net transfer of energy to the bonds of the products. This energy
is not kept in the bonds as heat energy, but as chemical energy, otherwise the temperature would not
change. An endothermic process is therefore accompanied by an increase in the energy content (potential
energy) of the products, but temperature of the system drops.
A well known example of an endothermic reaction is photosynthesis. During this reaction, light energy is
absorbed and stored in the bonds of the product (carbohydrate) as chemical potential energy.

Now consider an exothermic process

Neutralization of a strong monoprotic acid by a strong base such as NaOH releases about 57Kj of energy
per mole of the acid used (that is, ∆H = -57Kjmol-1). This is an exothermic process in which bond
formation in the products releases more energy than is used to break bonds in the reactants. The excess
energy enters the solution as heat, so a thermometer would record an increase in temperature.
Energy content of the products therefore decreases due to the conversion of potential chemical energy to
heat, but the temperature of the system increases because it has gained heat.

An important note on the +, - notation in chemical energetics

Which enthalpy change is greater, -100Kj and -200Kj? Students need to be careful here. From a
consideration of directed numbers in mathematics, students might say that -100Kj is greater than -2ooKj, butthis is
wrong. From a point of view of chemical energetics, -200Kj is the larger number. It is important to realize that the
signs + and – are only symbolic, they simply tell us whether a process releases energy (-) or absorbs energy (+). A
process with an enthalpy change of -200Kj gives out 200Kj of energy, but a process with an enthalpy change of -100Kj
gives out only 100Kj. The second process clearly has the smaller enthalpy change (Fig 5.4). It is often more useful to
use the terms more exothermic/ lessexothermic, for example, the process whose ∆H value is -200 Kjmol-1 is more
exothermic than the one with a value of -100Kjmol-1.

Fig 5.4 Process A has the greater enthalpy, disregarding the sign of
the value, since the sign is only symbolic.
5.3 Enthalpy of reaction and stability

The sign of the enthalpy change of a reaction, that is, whether it is positive or negative, helps in predicting
relative stability of products and reactants.
If a reaction is exothermic, there is a net loss of energy from the bonds of reactants, so the products
should be at a lower energy level. Since the products have less potential chemical energy, they are more
stable, relative to the reactants. From an energetic point of view, such a reaction is feasible (Fig 5.5).

The relative stability of the products can be explained in

terms of formation of bonds that are stronger than those that
are broken in the reactants. As you now know, bond
formation releases energy. Formation of a strong bond is
accompanied by the release of large amounts of heat energy.
Combustion of a fuel such as methane is exothermic because
a product (CO2)of the reaction has bonds that are stronger
than those in the reactant molecules. On the other hand, if a
reaction is endothermic, energy is absorbed and so the
products are higher in energy. The products are therefore
Fig 5.5 If a reaction is less stable than the reactants. Such a reaction is not
exothermic, the products are energetically favourable. It is possible that it might not take
lower in energy, and therefore
place, but a large number of endothermic processes actually
more stable than the reactants.
take place.

 If the magnitude of the enthalpy change is relatively small, enough energy might be found in the
immediate surroundings to drive the reaction.

 To explain why some endothermic reactions take place, we use the concept of entropy, that is, the
tendency of a system to achieve disorder. If a process is accompanied by an increase in entropy
(disorder), then it may take place, because by attaining disorder, stability is also achieved. This
explains why some endothermic processes take place, for example, the dispersing of ions of
NH4NO3 in water leads to an increase in entropy. This, with the fact that the enthalpy change of
the process is a small positive number, explains why NH4NO3 dissolves in water even though the
process is endothermic.

From this discussion, it can be concluded that exothermic reactions are feasible, because from an
energetic point of view, they are favourable: the products formed are relatively stable. But this does not
necessarily mean that the reaction will take place. A good example is the reaction between oxygen and a
fuel such as petrol. The reaction is feasible, as it is accompanied by release of energy, implying that the
products would be lower in energy than the reactants. However, in practice, mixing oxygen and petrol
does not result in a reaction, until a spark or strong heating is applied. Such a reaction is said to be
feasible but non-spontaneous. It will not occur under ordinary conditions of temperature and pressure.
Some exothermic reactions are spontaneous. Such reactions occur under ordinary conditions of
temperature and pressure; as soon as the reactants are mixed, they react. An example is the reaction
between AgNO3 and BaCl2 solutions. As soon as the two substances are mixed, a white precipitate of AgCl
is immediately formed. Whether an exothermic reaction will occur spontaneously or not is beyond the
scope of energetics. This issue is best discussed under a separate topic, reaction kinetics.
Consider the conversion of graphite to diamond.
C (graphite) C (diamond), ΔH = +5Kj/mol
Why does this conversion not take place? The answer is not ‘because the reaction isendothermic’. Since
the enthalpy change of reaction is a small positive number, from an energetic point of view, the
conversion might be feasible. The reason why graphite can not be converted to diamond is the high
activation energy associated with the conversion. Activation energy is a purely kinetic term, and it will be
discussed under reaction kinetics.

5.4 Reversible processes

Consider the reversible conversion of hydrogen and nitrogen into ammonia during the Haber process.
N2(g) + 3H2(g) Ý 2NH3(g) ∆H = -92.4Kj
The enthalpy value of -92.4Kj refers the forward reaction. This reaction is exothermic, that is, the
formation of ammonia in the Haber process is accompanied by release of heat energy. The enthalpy of the
reverse reaction has the same magnitude but opposite sign. The decomposition of ammonia to form
hydrogen and nitrogen is therefore an endothermic process, with an enthalpy change of +92.4Kj.

5.5 Zero enthalpy reactions

In some reactions, the enthalpy change is zero. In such reactions, the energy used to break bonds in the
reactants is exactly equal to the energy released when new bonds are formed. The reactants and the
products are therefore at the same energy level (Fig 5.6).

Fig 5.6 Energy level diagram of a zero enthalpy

reaction

Standard conditions for thermochemical measurements

In order to make meaningful comparison of thermochemical results, it is essential that measurements be
taken under standard conditions, and that the conditions of the system are the same before and after the
reaction.
 The standard conditions of temperature and pressure for thermochemical
measurements are 298K ( 250) and 1 atmosphere.

An enthalpy change measured under these conditions is said to be standard and it is given the symbol
∆Hθ, where the superscript ‘θ’ means ‘under standard conditions’.

5.7 Enthalpy terms

There are different enthalpy terms, each relating to a particular type of chemical or physical change. It is
of extreme importance that these terms be defined concisely and exactly to avoid ambiguity. More often
than not, errors in calculations come from a wrong or roughly accurate definition of one or more enthalpy
terms.By the time you are through with this section you should be able to define the following terms as
completely and as precisely as possible.

1. Enthalpy change of reaction 6. Electron affinity

2. Enthalpy change of formation 7. Ionization enthalpy (ionization energy)

3. Enthalpy change of combustion 8. Enthalpy change of hydration

4. Bond enthalpy (bond energy) 9. Enthalpy change of solution

5. Enthalpy change of atomization 10. Enthalpy change of neutralization

5.7. 1Enthalpy change of reaction

Consider the balanced equation:

CuO(s) + Al(s)  Cu(s) + Al2O3(s)... ∆Hθr

This is a balanced equation for the formation of the given products from the given reactants at 1 atm and
298K. The energy change for this reaction under these conditions is known as the standardenthalpy
change of reaction, ∆Hθr.

The standard enthalpy change of a reaction (∆Hr) is the heatabsorbed or

evolved(given out) when reactants combine to form products according to the balanced
equation, all measurements being taken under standard conditions of 1 atm and 298K.

For example
3O2(g) + 4NH3(g) 6H2O(l) + 2N2(g) ∆Hθr = -1 258Kj
This definition emphasizes that the reaction should be balanced. From the definition, we also learn that
the enthalpy change of reaction can be positive (energy absorbed) or negative (energy evolved), that is,
the reaction could be endothermic or exothermic.

5.7.2Enthalpy change of formation

The standard enthalpy change of formation (∆Hθf) of a substance is theheat

evolved or absorbed when 1 mole of the substance is formed from its elements in their
normal states under standard conditions of temperature (298K) and pressure (1 atm).

For example, the standard enthalpy change of formation of MgO refers to the energy
change for the reaction:

1
Mg(s) + O2 (g)  MgO(s) ∆H = -602Kjmol-1
2

Important points to note in this definition:

1.∆Hθfrefers to the formation of 1 mole of a substance. If the balanced equation does not produce 1 mole,
then it should be rewritten in such a way that one mole of product is formed. Consider the balanced
equation for the formation of MgO from its elements:

Mg(s) + O2 (g)  2MgO(s)

Written in this way, the equation does not represent the enthalpy change of formation ofMgO. It
represents the enthalpy change of reaction for the written equation. We divide the equation by 2 so that 1
mol of product is formed.The units of ∆Hθfare always given per mole of substance formed.

2. ∆Hθfcan be positive or negative. It all depends on the reaction being studied. Defining ∆H θf as ‘...the
energy absorbed...’ or ‘...the energy released ...’ is wrong as it gives the impression that ∆H fθ is always
endothermic(energy absorbed) or is always exothermic(energy released). The correct way to define ∆H θf
should be ‘It is the energy change ...’ or ‘ It is the energy released or absorbed...’

3.State symbols are an important part of the definition, because all substances must be in their normal
states under standard conditions. Whenever an equation is written to illustrate ∆H θf, the correct state
symbols should be shown.

4. ∆Hθfrefers to the formation of a substance from its elements. The reactant side of the equation should
therefore always show elements. The presence of compounds or radicals such as the Cl atom on the left
hand side of the equation renders the equation wrong if it is meant to illustrate ∆Hθf.

5. It is clear from the given definition that the standard enthalpy formation of an element iszero, that is,
there is no heat change when an element is formed from itself.
Significance of enthalpies of formation
 A negative enthalpy change of formation (exothermic) indicates that a substance is stable relative
to its elements. For instance, the enthalpy change of formation for MgO is -602Kjmol-1, indicating
that MgO is stable relative to elemental oxygen and magnesium metal. It will not easily
decompose to form oxygen and magnesium. Rather, Mg and O 2 can combine to form MgO, since
this results in the formation of a more stable product.

Consider the interesting case of hydrogen peroxide, H2O2. Its enthalpy change of formation is
-133Kjmol-1. Is the statement, ‘Hydrogen peroxide stable’ correct? The answer is no. It is well
known that hydrogen peroxide is unstable with respect to decomposition to form water and
oxygen. For this reason, it is always stored in dark bottles (to minimize exposure to light) and in a
cool place (to slow the decomposition process). The negative value of -133Kjmol-1 simply shows us
that hydrogen peroxide is stable relative to its elements, which are oxygen and hydrogen. It will
not easily decompose to form these gases, however, it can be unstable in other ways, for example,
it decomposes fairly easily to form water and oxygen.

 Some substances have a positive enthalpy change of formation. Such substances are unstable
relative to their elements. An example is chlorine dioxide, whose enthalpy of formation is
+103Kjmol-1. Chlorine dioxide easily decomposes to chlorine and oxygen when warmed, because
the elements formed are relatively more stable.

5.7.3 Hess’ Law

There are certain cases where the enthalpy change of a process can not be found directly. Indirect
methods can then be used, which depend on Hess’ Law of constant heat summation.

Hess’ Law states that:

The energy change of a reaction is the same irrespective of the reaction route taken, provided
that all measurements are made under the same conditions.

Hess’ law can be used in conjuction with enthalpies of formation or combustion to determine enthalpy
changes that can not be found using direct methods.

Consider a reaction in which substances A and B react to form product C.

A+B  C

This is the direct route. Now suppose that the reaction can be carried out indirectly by first producing an
intermediate X, then converting the intermediate to the desired product C.
The alternative route has two steps, each with its own enthalpy change, ∆H2 and ∆H3. Hess Law says that
the total enthalpy for the alternative route (∆H3 + ∆H2) is equal to the enthalpy of the direct route, ∆H1:

Enthalpy change of route 1 = enthalpy change of route 2

∆H1 = ∆H2 + ∆H3
 The alternative route can be used to find the enthalpy of reaction, ∆H 1 if it
is impossible or difficult to find the enthalpy directly.
Hess’ Law is a direct consequence of the conservation of energy; energy
can neither be created nor be destroyed by changing the route of a reaction.
The example below shows how Hess’ Law can be used to find the enthalpy
of a reaction indirectly using the enthalpies of formation of the substances
involved in the reaction.
Fig 5.7 Energy cycle
for a hypothetical
reaction

Example
Methylhydrazine and dinitrogen tetraoxide burn spontaneously upon mixing. The reaction produces
large quantities of heat energy. This mixture can therefore be used as rocket fuel. How much energy
is released by the reaction?

5 N2O4 (l) + 4CH3NHNH2 (l)  4CO2 (g) + 12H2O (l) + 9N2 (g) ∆Hr =? ... I

Data
∆Hθf (CH3NHNH2 (l)) = +53kjmol-1
∆Hθf (N2O4) = -20kjmol-1
∆Hθf (CO2 (g)) = -393 kjmol-1
∆Hθf (H2O (l)) = - 286kjmol-1

If we know the enthalpies of formation of each substance in the equation, then we can construct an
alternative route involving these enthalpies. If we add them up, the sum will be equal to the enthalpy of
reactionI. Fig 5.4 shows the energy cycle that can be used to calculate the enthalpy of reaction I using
Hess’ Law. The energy cycle shows the direct reaction route and the indirect route (involving enthalpies of
formation).

Fig 5.8 Energy cycle for calculating enthalpy of reaction using Hess’
Law.
To find the required enthalpy change of reaction, ∆H r, we add enthalpies of formation ∆H1 to ∆H5. In this
case, the summation is anticlockwise as shown by the curved arrow. Remember that whatever the
direction of the arrow, it should always start at the reactants and end at theproducts. Drawing an arrow
from the starting point (reactants) to the ending point (products) may be useful in determining which is
route 1 and which route 2 is. It is also helpful in identifying which enthalpies ought to have their signs
reversed. Moving along the route arrow(in this case, the arrow labeled route 2), if we find that we are
going against the direction of a reaction arrow, we reverse the sign of ∆H. For example, at the position
labeled A on route 2, we are going against the reaction arrows labeled ∆H1 and ∆H2, so the sign of these
enthalpy terms must be reversed. The direction of route 2 is the same as the direction for the reactions
labeled ∆H3, ∆H4 and ∆H5. The signs of these enthalpy terms remain positive, that is, they should not be
reversed.
It is advisable to write a general equation in terms of ∆H before substituting any figures:
Enthalpy of Route 1(direct route) = Enthalpy of route 2(indirect route)
that is, ∆Hr = -5∆H1 + (- 4∆H2) + 4∆H3 + 12∆H4 + 0 …II

 ∆H1and ∆H2: signs have been reversed to - as already explained.

 ∆H5has been replaced by 0. The enthalpy change of formation of an element is zero.
 Each enthalpy of formation is multiplied by the appropriate coefficient to agree with the
definition of enthalpy of formation, for example, the enthalpy change of formation of N 2O4 refers
to formation of one mole of the compound. In the cycle, five moles are formed, so we multiply the
given value(∆H1) by 5.
 NB: If a substance contains carbon (for example, CO 2 in Fig 5.4), the enthalpy of its formation
refers to formation of the compound from graphite, which is the more stable allotrope of carbon.

Substituting the given data into equation II:

∆Hr = [-5(-20) -4(53) + 4(-393) + 12(-286)] Kjmol-1= -5 116 Kjmol-1
The reaction therefore produces a very large amount of energy. This explains its use in rocket fuel.

Example 2
The standard enthalpy changes of two reactions are given by the following equations

2Fe(s) + 3/2 O2(g)  Fe2O3(s) ∆Hθ = -822Kjmol-1

C(s) + ½ O2(g)  CO(g) ∆Hθ = -110Kjmol-1

What is the standard enthalpy change for the reaction?

Fe2O3(s) + 3C(s)  2Fe(s) + 3CO(g)

Solution
∆Hr = -∆H1 + ∆H2(Fig 5.8.1)
= -(-822) + 3(-110)
= +492 Kjmol-1
 Fig 5.8.1

Δ Hr
Fe2O 3 (s) + 3C(s) 2Fe(s) + 3CO(g)

Δ H1 = -822 Δ H2 = 3(-110)

[2Fe(s) + 1/2O 2(g)] + [ 3C(s) + 3/2O 2(g)]

Measuring standard enthalpy of formation

Some enthalpies of formation can be measured directly using a bomb calorimeter. The enthalpies of
formation of carbon dioxide, magnesium oxide and many other oxides have been measured in this way
because they can conveniently be formed from the combustion of their respective elements. However,
there are many substances for which direct determination of enthalpy change of formation is impossible
because the compound can not be formed directly from its elements. An example is hydrogen peroxide. It
can not be synthesized directly from the combination of hydrogen and oxygen.
One indirect method involves using enthalpies of combustion.

5.7.4Standard enthalpy change of combustion, ∆Hθc

The standard enthalpy change of combustion (∆Hθc) of a substance is the amount

of heat evolved when 1 mole of the substance burns completely in oxygen, the meas-
urement of heat released being adjusted to standard conditions of temperature and
pressure.

For example, the enthalpy change of combustion of hydrogen refers to the equation:

H2 (g) + 1/2O2 (g)  H2O (l)

Important points to note in this definition:

1. ∆Hθc refers to the combustion of one mole of a substance (of course it applies only to combustible
substances). If more than one mole of a substance is shown in the balanced equation, the equation should
be adjusted appropriately to show 1 mole of a substance being burnt, for example, the enthalpy change of
combustion of magnesium refers to the equation

Mg(s) +1/2O2 (g)  MgO(s) not 2Mg(s) + O2(g)  2 MgO(s)

Note that in this case, the equation for the enthalpy change of combustion is the same as that for the
enthalpy change of formation.
2. It is important that oxygen be present in excess so that there is complete combustion. Thisis
particularly important when organic substances burn. In a limited amount of oxygen, incomplete
combustion tales place. A mixture of products is formed and the amount of heat evolved is less than what
would be evolved if there was complete combustion.

3. The definition specifies that ∆Hc is the energy released; it does not generalize it as ‘... energy change...’.
This generalization may be used for a process that can be exothermic or endothermic. Combustion is
always exothermic .

Determination of enthalpy of combustion

A bomb calorimeter can be used for this purpose (Fig 5.9)

Fig 5.9 Automated bomb calorimeter

The apparatus is designed to minimize loss of heat to the surroundings. A sample of known mass is burnt
completely in the bomb calorimeter and the increase in temperature of a known volume of water
surrounding the bomb is noted. The equation below can then be used to calculate the enthalpy change of
combustion:

Heat produced = mc∆θ

m is the mass of water( 1g ≈ 1cm³)
c is the specific heat capacity of water = 4.2JK-1g-1
∆θ is the increase in temperature of water, in Kelvins or in degrees celcius.
Sample Data:
Volume of water in calorimeter = 400cm³
Initial temperature of water = 100C
Final temperature of water = 200C
Mass of ethanol burnt = 0.90g

We wish to calculate the enthalpy change of combustion of ethanol.

The heat evolved when ethanol burns is given by:

∆H = mc∆θ
= 400 x 4.2 x 10
= 16 800J

Note:
 We use mass of water in this part of the calculation, not mass of the substance being burnt.
 The units are in joules since the value of c is given in these units.

Moles of ethanol used = m/Mr = 0.90/46

= 0.01957
∴ 0.01957 moles of ethanol produce 16 800J of energy when burnt.

By definition, the enthalpy change of combustion is given in terms of one mole of a substance burnt.
That is, 1 mole of ethanol produces

16 800/0.01957 = 858 456.8217 J

Therefore the enthalpy change of combustion of ethanol is 858.5Kjmol-1

This value can save as a rough guide to the heat energy evolved per mole when ethanol is completely
burnt. Limitations of the experiment include:

1. Heat loss to the environment.

2. Absorption of heat by the calorimeter and the thermometer.
3. Incomplete combustion is inevitable unless a large excess of pure oxygen is used

The value is therefore less than the actual value, which has been accurately determined to be
-1 371 Kjmol-1. Refined calorimeters are available, which are very accurate (and very expensive). These
apparatus are also calibrated to compensate for heat losses.

Enthalpy of combustion and molecular structure

The enthalpies of combustion of the first four alkanes are given in Fig 5.10.
 ∆Hθc/Kjmol-1
Methane 890
Ethane 1560
Propane 2220
Butane 2877

There is a clear trend in these values which is associated with molecular structure:

Fig 5.10 Enthalpy changes of combustion of the first four alkanes

There is an increase of about 670 KJmol-1 from one hydrocarbon to the next. This shows that each addi-
tional CH2 group is contributing about 670 KJ mol -1. We conclude that the energies associated with a
certain type of bond is constant. The more bonds we have in the hydrocarbon, the more energy is released.
This is not surprising. Hydrocarbons store chemical energy in their bonds. The more bonds there are, the
greater the energy released per mole of the hydrocarbon. We therefore expect the higher Mr hydrocarbons
to be better fuels.However, the selection of fuels is not as easy as that. Consider the equations for the
combustion of the hydrocarbons:

CxHy+ (x + y/4) O2  xCO2 +(y/2) O2

1. CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l)

2. C2H6 (g) + 7/2O2 (g)  2CO2 (g) + 3H2O (l)

3. C3H8 (g) + 5O2 (g)  3CO2 (g) + 4H2O (l)

4. C4H10 (g) + 13/2O2 (g)  4CO2 (g) + 5H2O (l)

It can be seen that even though more energy is released for longer chain alkanes, the demand for oxygen
also increases. For instance, 1 mole of methane will need only 1 mole of oxygen for complete combustion,
but 1 mole of butane will need 6.5 moles. The increase in demand for oxygen implies that there is more
incomplete combustion, that is, less heat energy would be produced than expected. Not only that; there
will also be wastage of the fuel since some of it will escape unburnt in the form of soot(carbon), carbon
monoxide and unburnt hydrocarbon molecules. Pollution therefore increases with increasing Mr of chain
alkanes. Fig 5.5 shows the expected trend in heat of combustion when the alkanes are burnt, and the trend
that is actually obtained if combustion takes place in a limited supply of air.

Fig 5.11 The effect of number of carbon atoms on the heat

yield when the alkanes are burnt in a fixed volume of air.

A compromise must therefore be reached, and the fuel chosen must be able to burn almost completely in
air. Short chain alkanes such as methane burn efficiently with little pollution. However these fuels tend to
be gaseous or volatile liquids and pose a storage problem and fire risk. Longer chain fuels are liquid. They
are more convenient to handle, but as already noted, they demand a larger amount of oxygen, which
might not be present since air contains only 21% oxygen. The internal combustion engine is perhaps one
of the most inefficient devices invented by man. The petrol engine burns C8 hydrocarbons, but to a large
extend the combustion is incomplete because of the limited supply of air in the engine. It has been
estimated that only about 20% of the energy in the fuel is actually converted to the energy that drives the
vehicle.

Significance of enthalpies of combustion

The burning of fuels produce heat energy. This is an exothermic process in which the products are lower
in energy, and therefore more stable than the reactants.
Bond formation produces heat energy (it is exothermic), and bond breaking uses up heat energy (it is
endothermic). During combustion, more heat is produced by forming new bonds in products than is used
in breaking bonds in reactants. This implies that stronger bonds are formed in the products (CO2,
produced when a hydrocarbon burns, has two double bonds, which are very strong). Stronger bonds
means the products are more stable than the reactants.
Using enthalpies of combustion to find enthalpy
of formation of a compound

The use of Hess’ Lawin conjuction with enthalpy changes of formation to find the enthalpy change of a
reaction indirectly has already been discussed. Enthalpies of combustion can also be used in this way to
find the enthalpy of formation of a substance. This is particularly useful if the substance can not be
formed directly from its elements, for example, ethanol can not be formed directly by combining carbon,
hydrogen and oxygen.

Example 1
Calculate the enthalpy change of formation of ethanol given the following combustion data:

∆Hθc/ Kjmol-1

C (graphite) -393.5

H2 (g) - 285.8

C2H5OH (l) - 1371.0

Solution

Let the direct route be the formation of ethanol from its elements. From this route we create another
route involving the combustion of each substance in the equation,that is if it can be burnt.

∆H1, ∆H2 and ∆H3 are the standard enthalpies of combustion of the substances involved in the formation
of ethanol.

By Hess’ Law

Enthalpy of route 1 = enthalpy of route 2

∆Hθf = 2∆H1 + 3∆H2-∆H3 … (i)

 = [2(-393.5) + 3(-285.8) - (-1371)] Kjmol-1

= -273.4 KJmol-1

Notice the coefficients in equation 1. Enthalpy of combustion is defined per mole of substance burnt,
therefore if x moles are burnt, the total energy of combustion becomes x∆H. Also note the use of the +,-
signs; this is frequently a source of confusion among students. To avoid a mix up in signs, it is strongly
advised that you start by a writing a general algebraic expression such as equation (i) above, before you
substitute any figures.

Example 2
The standard enthalpy change of formation of CO2 and and H2O are -394 Kjmol-1 and -286 Kjmol-1
respectively. If the standard enthalpy change of combustion of propyne, C 3H4, is -1 938 Kjmol-1,
what is its standard enthalpy change of formation?
9189/1/O/N/2010

Solution

ΔH1
C3H4(g) + 4O 2(g) 3CO 2(g) + 2H2O(l)

x ΔH2 ΔH3

[C(s) + 2H2(g)] + [3C(s) + 3O 2(g)] + [2H2(g) + O2(g)]

Let the standard enthalpy change of formation of propyne be x. By Hess’ Law

∆H1 = -x + ∆H2 + ∆H3

-1938 = -x + 3(-394) + 2(-286)
x = 184
The standard enthalpy change of formation of propyne is +184 Kjmol-1.

5.7.5 Lattice Energy, ∆HL.E

We have discussed the relative stability of compounds with reference to enthalpies of formation.
The relative stability of ionic compounds is best explained in terms of their lattice energies.
 Lattice Energy is the amount of heat energy evolved when 1.0 mole of a solid ionic
crystal is formed from its respective gaseous ions under standard conditions of
1.0atm and 298K.

For example, the lattice energy of MgO is represented by the equation

Mg2+ (g) + O 2-(g)  MgO(s)

Important:
1. Lattice energies are always negative (exothermic). Energy is released whenever an ionic compound is
formed from its ions.
2. Lattice energy refers only to ionic compounds.
3. Lattice energy is defined per mole of crystal formed.
4. State symbols are important in the definition of lattice energy. Omitting then renders the
equation for lattice energy wrong.

Determination of lattice Energy

Direct determination of lattice energy is not possible. An indirect method which combines several
enthalpy terms is used. Suppose that we wish to form MgO. One method would be to form it from its
elements in their normal states at 298K and 1.0 atm:

Mg(s) + 1/2O2 (g)  MgO(s) ∆Hθ = standard enthalpy change

of formation of MgO.

An indirect method involves the following processes which ultimately converts the elements to their
respective gaseous ions. The energy released when these ions combine to form one mole of an ionic crystal
is referred to as lattice energy.

I. The elements are converted to gaseous atoms. The energy needed (absorbed) for this conversion is the
enthalpy change of atomization.

5.7.6 Standard Enthalpy Change of Atomization

The Standard Enthalpy Change of Atomization of an element refers to the

energy absorbed in forming 1.0 mole of gaseous atoms from that element in its
natural state under standard conditions of 1.0 atm and 298K.

For example, the standard enthalpy of atomization of chlorine refers to the process
1/2Cl2(g)  Cl (g)
Note that the given equation shows the formation of 1 moleofchlorine atoms, not one atom. Enthalpies of
atomization are always endothermic because energy is required to pull atoms from each other and
disperse them into a gaseous state (recall that bond breaking is endothermic. During atomization, there is
bond breaking only and no bond formation). The term atomization also applies to metals, for example,
the standard enthalpy change of atomization of sodium metal refers to the energy released when the metal
is converted to 1 mole of gaseous sodium atoms, under standard conditions.

Na(s)  Na (g)

The energy change is also referred to as the enthalpy of sublimation of the metal because there is a direct
change of state from solid to gas. The process absorbs energy, which is used to overcome the electrostatic
attractions between positive metal atoms and a sea of delocalized electrons in the metal lattice.

II. The second step in the indirect formation of an ionic compound involves changing the gaseous metal
atoms to unipositive gaseous atoms. The energy needed for this conversion is the first ionization energy
of that metal.

5.7.7 Ionization Energy, ∆HIE

The First Ionization Energy of an element refers to the energy required(absorbed)

to knock out 1 mole of electrons from 1 mole ofgaseous atoms to form 1 mole of
gaseous +1 ions, under standard conditions of 1.0 atm and 298K.

For example, the first ionization energy of magnesium refers to the process

Mg (g)  Mg+ (g) + e

Note that the term ionization energy applies to both metals and non-metals. However, the formation of
an ionic compound involves ionization of metals, so the following discussion will put emphasis on
conversion of gaseous metal atoms to ions.

 Ionization energies are always positive. Electrons are naturally held to the atom by attraction to
the nucleus. Therefore energy is required to remove them.
 Ionization Energies increase across a Period in response to increasing nuclear charge (number of
protons). A nucleus with a larger number of protons has a stronger attraction for the outer-shell
electrons. Consequently, a larger amount of energy would be required to remove an electron from
this shell.
 Ionization Energies decrease down a group, even though nuclear charge increases. This is
because down a group, additional shells are opened. This increases the size of the atoms and the
distance of the outer-shell electrons from the nucleus. Consequently, the valence shell electrons
feel a weaker attraction from the nucleus. Increase in atomic radii down a group has a greater
effect than the increase in proton number.

III. If the ionic compound to be formed consists of +2 ions, for example, magnesium oxide,then the +1
gaseous metal ions must be changed to gaseous +2 ions. The energy neededfor this conversion is the
second ionization energy of that metal.
 The Second Ionization Energy of an element refers to the energy required to knock
out 1.0 mole of electrons from 1.0 mole of gaseous +1 ions to form 1.0mole of gaseous +2
ions, under standard conditions of 1.0 atm and 298K.

For example, the second ionization energy of magnesium refers to the process

Mg+ (g)  Mg2+ (g) + e

The second ionization energy of an element is always higher than the first because the electron being
removed is now attracted to the atom by both the nucleus and the positive charge on the +1 ion. More
energy is therefore required to pull out the second electron.

IV. If the ionic compound to be formed consists of +3 ions, for example, aluminium oxide, then it is
necessary to convert the +2 metal ions to +3 ions. The energy absorbed in this conversion is known as the
third ionization energy for that metal.

The Third Ionization Energy of an element refers to the energy required to knock
out 1.0 mole of electrons from 1.0 mole of gaseous +2 ions to form 1.0 mole of gaseous
+3 ions, under standard conditions.

For example, the third ionization energy of aluminium refers to the process

Al2+(g)  Al3+(g) + e

The third ionization energy of an element is higher than the first and second ionization energies. This
time, the electron to be removed is under strong attraction by the +2 charge on the ion from which it is
being removed.

V. The next step in the formation of an ionic compound would be changing the gaseous non-metal
atoms(formed by the process of atomization) to gaseous -1 ions. The energy released by this conversion
is the first electron affinity of that element.

5.7.8 Electron Affinity

The First Electron Affinity of an element refers to the energy released when
1.0 mole of gaseous atoms accept 1.0 mole of electrons to form 1.0 mole of -
1gaseous ions, under standard conditions.

For example, the first electron affinity of oxygen is represented by the equation

O(g) + e- O-(g)

The first electron affinity affinity is exothermic. This shows that the process is favourable in terms of
energy. The incoming electron is stabilized by being attracted to the protons in the nucleus.

VI. If the ionic compound contains -2 ions, for example, O2-in MgO, then the -1 ions haveto be converted
to -2 ions. This process absorbs energy and is known as the secondelectron affinity for that element.

The second electron affinity of an element refers to the energy absorbed to force
1.0 mole of electrons into the outer shell of 1.0 mole of gaseous -1 ions to form
1.0mole of gaseous - 2 ions.

For example, the second electron affinity of oxygen refers to the process

O- (g) + e- O2-(g)

The second electron affinity is endothermic because the incoming electron is being forced to enter the
outer shell of a negatively charged particle. There is repulsion between the atom and the incoming
electron, and so energy must be supplied to force the process.

VII. If the ionic compound contains an anion of -3 charge, for example, the nitride ion inmagnesium
nitride, Mg3N2, then the -2 ions must be converted to the -3 state. This endothermic process is known as
the third electron affinity for that element.

The third electron affinity of an element refers to the energy required to force
1.0mole of electrons into the outer shell of 1.0 mole of gaseous -2 ions to form
1.0mole of gaseous - 3 ions.

For example, the third electron affinity of nitrogen refers to the process

N-2(g) + e- N3-(g)

The third electron affinity of an element is more positive (more endothermic) than the second electron
affinity. This is because the third electron has to enter the shell of an atom (ion) which already bears a
large negative charge (-2). The incoming electron experiences great repulsion from the charge on the ion
so a large amount of energy is required to force process to take place.

VIII. The last step in the formation of the ionic compound is combining the gaseous positive ions from
the metal and the negative gaseous ions from the non-metal to form an ionic crystal. The energy released
by this process is theLatticeEnergy of that ionic compound, which has already been defined.

Lattice energy, atomization, ionization and electron affinity are combined together with the enthalpy of
formation of the ionic compound, in an energy cycle known as the Born-Haber cycle. Using Hess’ Law,
any enthalpy term in the Born-Haber cycle can then be determined. This method can be used to
determine lattice enthalpies since they can not be determined directly.
The Born-Haber cycle for the formation of NaCl
We wish to find the lattice energy of NaCl. Let this be the direct route in Fig 5.12.This diagram has been
drawn so that the direction of the arrows is informative. An arrow pointing upwards denotes an endo-
thermic process, and an arrow pointing downwards an exothermic process.

Fig 5.12 Born-Haber cycle for the formation of NaCl

∆H1 = Standard enthalpy change of formation of NaCl (exothermic) = -411Kj/mol

∆H2 = Standard enthalpy change of atomization of Na metal (endothermic) = +109Kj/mol
∆H3 = First ionization enthalpy of Na (endothermic) = +494Kj/mol
∆H4= Standard enthalpy change of atomization of chlorine (endothermic) = +121Kj/mol
∆H5 = First electron affinity of chlorine (exothermic) = -367Kj/mol
∆HL.E= lattice enthalpy of NaCl (exothermic) =?

By Hess’ law: Energy of direct route (∆HL.E) = Energy of indirect route

∆HL.E = -∆H5 - ∆H4 - ∆H3 - ∆H2 + ∆H1

Substituting: ∆HL.E = -(-367)-(+121)-(+494)-(+109)+(-411)

= -768 Kj/mol
Note that lattice energies are always negative.

Next, we have to construct Born-Haber cycles for ionic compounds in which charges on the cation or
anion (or both) are greater than 1. However, before doing that, let us study another enthalpy term which
always appears in a Born-Haber cycle (even the one for NaCl discussed above) but is often overlooked.
This enthalpy term is known as bond enthalpy (that is, bond energy).

5.7.9 Bond Enthalpy

Bond enthalpy is the average energy needed to break one mole of a specific
covalent bond in the gaseous phase, to form separate gaseous atoms.

For example, the bond energy of chlorine refers to the energy required to break one
mole of the Cl-Cl bond.

Cl-Cl(g)  2Cl-(g)

The Born-Haber cycle drawn for NaCl (Fig 5.12) involved the conversion

½Cl-Cl(g)  Cl(g) ... (i)

This has been defined as the atomization of chlorine. Now, notice that this process involves the breaking
of a covalent bond, so it can also be expressed in terms of bond energy.

Enthalpy change of atomization of chlorine = ½(Cl-Cl) bond energy

The co-efficient ½ is a direct consequence of the definition of bond energy. Bond enthalpies are quoted
per mole of covalent bond broken. Now, in equation (i) above, only half a mole of the bond is being
broken. The atomization of a covalent bond and bond energy differ mainly in that atomization refers to
the formation (product side) of 1 mole of gaseous atoms, as in (i) above, but bond energy emphasizes the
breaking of one mole of a covalent bond(reactant side).

From the data booklet, the bond enthalpy of chlorine is +242Kj/mol. The enthalpy change of
atomization of chlorine is therefore ½(242) = +121Kj/mol. In your exams you may notice that the Data
Booklets that are provided do not contain the enthalpies of atomization of covalent bonds such as the
Cl-Cl bond. The reader should be able to determine these enthalpies of atomization from relevant bond
energies, usually given in the Data Booklet.

Factors that affect the magnitude of bond enthalpies

Bond enthalpies are a direct measure of the strength of a covalent bond. You will notice that bond
enthalpies are always positive (endothermic), that is, energy is required to separate the two atoms of a
bond. The pair or pairs of electrons shared between the two atoms of the bond experience attraction from
the nuclei of both atoms of that bond. It is this electrostatic attractionthat holds the two atoms of the
bond together. The stronger the electrostatic attraction, the stronger the bond and the greater the energy
required to break it (that is, the more endothermic the bond enthalpy). One very important factor that
affects bond enthalpy, and hence, bond strength, is atomic size.
Consider the bond enthalpies of the hydrogen halides (HX) given in Table 5.1.

The trend is clear; the H-X bond becomes weaker(less

Bond Bond energy/Kjmol -1 energy is required to break it) as the radius of the halogen
atom increases. When one or both atoms of a covalent
H-Cl 431 bond increase in size, overlap of atomic orbitals during
bond formation becomes poor. As a result, the bond pair of
H-Br 366
electrons is a large distance from the nuclei of both atoms
H-I 299 of the bond. Electrostatic attraction between the bond pair
and the nuclei therefore becomes weak.
Table 5.1 Energies of the H-X bond

Q
Explain why the atomic radii of Cl, Br and I increases in that order.

A Going down the Group, a new shell is opened form one element to the next. Increase in number of
shells results in an increase in atomic size.

Another important factor that affects bond energy is nature of the bond. Multiple bonds (double and
triple) are shorter and stronger than single bonds.

5.7.10 More Born-Haber cycles

The following Born-Haber cycles involve formation of ions whose magnitude is greater than 1. Once more,
the direction of arrows has been meant to inform the reader whether the process involved is exothermic or
endothermic.

The Born-Haber cycle for the formation of MgO (Fig 5.13)

Data: ∆H1 = ∆Hθf(MgO) = -602Kjmol-1 Calculation

The aim is to determine the Lattice Energy of
∆H2 = ∆Hatomization(Mg) = +150Kjmol-1
MgO
∆H3 = ∆HI.E1(Mg) = +736Kjmol-1
∆H4 = ∆HI.E2(Mg) = +1 450Kjmol-1 By Hess Law
∆H6 = e.a1 (O) = -142Kjmol-1 Enthalpy of route 1 = enthalpy of route 2

∆H7 = e.a2 (O) = +844Kjmol-1 L.E = -∆H7-∆H6-∆H5-∆H4-∆H3-∆H2+∆H1

= - (+844)-(-142)-(+248)-(+1450)-(+736)
More information
- (+150) + (-602)
The O=O bondenergy is 496Kj/mol.
= -3 888Kjmol-1
 2- 2+
O (g) + Mg (g)
2+
Mg (g) + O (g)

H7
H6
H4 H5 2+ -
Mg (g) + O (g)
Mg (g) + 1/2O2(g)

direct
H3 route

Mg(g) + 1/2O2(g)
lattice energy

H2

Mg(s) + 1/2O2(g)
H1

Fig 5.13 Born - Haber cycle for the formation of MgO

 ∆H5 is the enthalpy change of atomization of oxygen, which is equal to ½ the bond energy of the
O=O bond.
 The terms ∆H2 to ∆H7 are against the arrow for route 2. The signs of these terms are reversed
accordingly. ∆H1 is in the same direction as the arrow for route 2, so the sign for ∆H 1 remains +.

Born – Haber cycle for Al2O3

Fig 5.14 is a Born-Haber cycle for the formation of Al2O3.

Data : ∆H1 = ∆Hθf(Al2O3) = -1669Kjmol-1 Calculation

∆H2 = ∆Hatomization(Al) = 314Kjmol-1 Enthalpy of route 1 = enthalpy of route 2
∆H3 = ∆HI.E1(Al) = 577Kjmol-1 L.E= -3∆H8-3∆H7-∆H6-2∆H5-2∆H4-2∆H3
∆H4 = ∆HI.E2(Al) = 1820Kjmol-1 -2∆H2+∆H1 ... (i)
∆H5 =∆HI.E3(Al) = 2740 = - 3(+844)-3(-142)-(+744)-2(+2 740)
∆H7 = e.a1 (O) = -142Kjmol-1 - 2(+1 820)- 2(+577) - 2(314) +(-1 669)
∆H8= e.a2 (O) = +844Kjmol-1 = -15 421Kjmol-1

More information
The O=O bondenergy is 496Kj/mol.
 Fig 5.14 Born - Haber cycle for the formation of Al2O3

Notice the use of co-efficients in equation (i). This is a direct consequence of the way the enthalpy terms
are defined. For example, ∆H2 represents the enthalpy of atomization of Al metal, which is the energy
required to produce 1.0 mole of gaseous atoms of Al. Now, in Fig 5.14, two moles of Al atoms are produced
during the atomization process, so the value of ∆H θatomization must be multiplied by 2 to obtain the total
energy absorbed in that step.
Also notice how ∆H6, the total enthalpy change of atomization of oxygen has been obtained.
(∆Hatomization = 3/2 x Bond Energy = 3/2 x 496 = +744Kj)

A Born-Haber cycle can be used to find the value of any other enthalpy term involved in it, if the rest of
the enthalpy terms are known.
 Q
Explain why lattice enthalpies are always negative.

A formation is exothermic. During the formation of an ionic crystal from its respective
Bond
gaseous ions, there are no bonds broken (no energy is absorbed).There is only bond formation in
which strong ionic bonds are formed and this is accompanied by evolution of large amounts of
heat energy.

Significance of lattice energy

The magnitude of lattice energy is a measure of the strength of an ionic bond. The more negative the value
of lattice energy, the lower in energy the ionic compound and the more stable it is. We thus have a way of
comparing the relative stabilities of ionic compounds.

What factors affect the magnitude of lattice energy?

The lattice enthalpies of four ionic compounds are given in Table 5.2.

NB Lattice Enthalpies are often given in

Data Booklets without the negative sign. The
reader should always remember that Lattice
Enthalpies are negative.

The following factors affect the magnitude of

Lattice Energy
Table 5.2 Lattice energies of some
ionic compounds  Size of ions(compare NaCl, NaBr and
NaI in Table 5.2, in which size of the
halide ionchanges)

 Size of charge on ions(compare NaCl and MgCl2 in the table above, in which charge on the metal
ion changes)

Lattice energy varies inversely as the size of an ion, that is, the larger the ion, the smaller the lattice
energy and vice-versa. We thus expect, for instance, the lattice energy of NaCl to be smaller(less
exothermic/less negative) than that of LiCl because the sodium ion is larger than the lithium ion.
Compare the lattice enthalpies of NaCl, NaBr and NaI in Table 5.2 above. The values become smaller in
that order due to an increase in the radius of the halide ion.

When comparing lattice energies, always remember that the more negative value represents the larger
lattice energy, that is, the more negative the value, the more exothermic is theformation of the com-
pound from its ions. To prevent confusion we may refer to the magnitude of the lattice energy, disre-
garding the sign as in table 5.2 above.
Why do ionic radii affect the magnitude of lattice energy?
1. Distance of nucleus from outer shell
Compare The Lattice Enthalpies of LiCl and NaCl, which are -846 and -771Kjmol-1 respectively. LiCl has
the larger Lattice Enthalpy because the Li+ ion is smaller than the Na+ ion in NaCl.
Being larger, the nucleus of the Na+ ion is a greater distance from the outermost shell of the ion. This
nucleus therefore has a weaker attraction of the anion, Cl-. The Li+ ion is smaller and its nucleus is closer
to the electrons in the outer-shell of the Cl- ion. The attraction between cation and anion is therefore
stronger in LiCl. When LiCl is formed, very strong ionic attractions are formed, accompanied by the
release of large amounts of heat energy. The ionic attractions in NaCl are weaker, and less energy is
released when this compound is formed from its ions.

2. The effect of charge density

We may think of charge density as the ‘concentration’ of a charge, that is, how much charge is distributed
in a given volume. The Li+ and the Na+ ion have the same size of charge. However, being larger, the
sodium ion has the smaller charge density, that is, its charge is dispersed over a larger volume. Such an
ion is not very effective at attracting an anion. The ionic bond in NaCl is therefore weaker than in LiCl. As
already mentioned, a relatively weak ionic bond is accompanied by the release of a relatively small
amount of energy (smaller value of lattice energy).

How size of charge affects Lattice Energy

Table 5.2 shows that MgCl2 has a larger Lattice Energy than NaCl.The larger charge on the Mg 2+ ion
results in a stronger electrostatic attraction with the Cl - ion. That is, the ionic bonds in MgCl2 are stronger
and more heat energy is produced when the bonds are formed.
The concept of charge density is also relevant in explaining the differences in lattice enthalpies of NaCl
and MgCl2. The Mg2+ ion has a larger charge, and yet its ionic radius is smaller. It therefore has the larger
charge density, that is, it has a large charge spread in a small volume. Such an ion has a relatively strong
attraction for an anion.

Quantifying Lattice Energy

In words
Product of charges on cation and anion  Lattice Enthalpy is directly pro-
Lattice Energy α
sum of radii of cation and anion portional to size of charge. The
larger the charge on one or both
5.7.11 More on Bond Energies of the ions, the greater the lattice
That is energy.
q+that
q- the strength
Where  Lattice Enthalpy is inversely pro-
We have seen of qionic
+ = charge
bonds on
in cation
ionic compounds can be measured in terms of Lattice
LE  portional to ionic radius. The lar-
Energy of ther ++ r-
compound. q- = charge on anion
ger the radius of one or both ions,
In covalent substances, we use bondrenthalpies
+ = radius of
tocation
compare the strength of covalent bonds
the smaller and the
the lattice relative
energy.
r = radius of anion
stabilities of covalent substances. Bond energy is defined as the amount of energy required to break one
-

5.7.11More on bond energies

We have already defined bond energy as the amount of energy required to break one mole of a gaseous
bond to form separate gaseous atoms. For example, the bond energy of the C-H bond refers to the process
C-H(g) C(s) + H(g)

Bond energies are always positive, that is, energy is required to break bonds. The larger the bond energy
(the more endothermic it is), the stronger the bond. A substance with strong covalent bonds is stable and
so resists undergoing chemical changes.

Average bond energies

The bond energies given in Data Booklets are averages. This means that a particular bond energy is
obtained by averaging the bond enthalpies for that bond in different compounds. Consider the O-H bond.
Its bond energy differs depending on where it is found, for example, the O-H bonds in water and ethanol
have slightly different bond energies. The O-H bond energy given in Data Booklets is therefore an average.

Determination of the average C-H bond energy in methane

Methane is atomized into its constituent gaseous atoms. This involves breaking four C-H bonds:

H C H 4C - H(g) ...(i)

We may find the energy change of process (i) indirectly by using the standard enthalpy change of
formation of methane and the standard enthalpy change of atomization of carbon and hydrogen. These
enthalpies are linked by an energy cycle in Fig 5.15.

∆Hr is the energy required to break all four C-H

bonds in methane

By Hess’ Law,

∆Hr = - ∆Hθ1 + ∆Hθ2 + 4∆Hθ3 ... (ii)

Where ∆Hθ1 = standard enthalpy change of forma-

tion of methane = -75 Kjmol-1
∆Hθ2 = standard enthalpy change of atomi-
Fig 5.15 An energy cycle for the
determination of the C-H zation of carbon = +715Kjmol-1
bond energy
∆Hθ3 = standard enthalpy change of atomi-

Substituting and evaluating equation 1: zation of hydrogen = +218Kjmol-1

∆Hθr = - (-75) + 715 + 4(218)

= + 1 662kJ

Therefore 1 662 Kj of energy are required to break four C-H bonds in methane. The average C-H bond
1 662
energy is therefore = +415.5Kjmol-1
4
That is, breaking 1 mole of gaseous C-H bonds in methane would require 415.5 Kj of energy.

The strength of the C-H bond in other compounds can be found in a similar way. It is found that in most
cases, the values agree, showing that a definite quantity of energy (the bond energy) is associated with a
particular type of bond. However, in some cases there is a significant difference in the value of the bond
energy because of the particular environment of the C-H bond. So what is the C-H bond energy,
disregarding the compound in which it is found? The answer has been found by averaging the C-H bond
energies in different compounds. The value recorded in data booklets is 412 KJmol -1.

The C-C bond energy

We may use ethane to compute a value for the C-C bond energy.

H H
H C C H

ethane H H

First we calculate the total energy required to break all the bonds in ethane (six C-H bonds and one C-C
bond).

∆Hr, the energy needed to atomize ethane by

breaking all bonds, is found by Hess’ Law:

∆Hr = -∆H2 + 2∆H3+ 6∆H4 ... (iii)

Data:

∆H2 = enthalpy change of formation of

ethane = -85KJ/mol
∆H3= enthalpy change of atomization of
Fig 5.16 Energy cycle for determination carbon = +715KJ/mol
of the C-C bond energy in ethane ∆H4= enthalpy change of atomization of
hydrogen = + 218KJ/mol

Substituting these values in equation (iii)

∆Hr = - (-85) + 2(715) + 6(218) = +2 823Kj

This is the enthalpy change of atomization of ethane, that is, the energy needed to break six C-H bonds
and one C-C bond.

E(C-C) + 6E(C-H) = 2 823,

where E(C-C) means ‘energy of the C-C bond’ and E(C-H) means ‘energy of the C-H bond’.

The energy of the C-H bond is 412Kjmol-1, so

E(C-C) + 6(412) = 2 823

E(C-C) = 2 823 – 2472

= +351Kjmol-1

We would expect all C-C bonds to have this energy, irrespective of the molecule in which the bond is
found. In most cases the values obtained are similar. In a few cases, the special environment in which the
C-C bond is found leads to a significantly different value. The C-C bond energy recorded in data booklets
is an average of the C-C bond energies in a wide range of compounds. This value is 348Kj/mol.

Uses of Bond Energies

Bond energies are useful in the following ways:
 Comparing the strength of bonds
 Understanding reaction mechanisms, that is, how reactions take place.
 Estimating enthalpy changes of reactions

Comparing the strength of bonds using Bone Energies

Table 5.3 compares some Bond Energies.

As seen in this table, some bonds are relatively stronger than

others. A substance which contains strong bonds is relatively
inert, that is, it won’t react easily. This is the case with the
nitrogen molecule which has a bond energy of +944Kj/mol.
Compare this with the Cl-Cl bond energy, which is only +242
Kj/mol. This partly explains why chlorine is more reactive
than nitrogen. It is easier to break the Cl-Cl bond energy
during chemical reactions than it is to break the N to N bond
in the nitrogen molecule.
However, there are other factors apart from bond energies,
which affect the reactivity and stability of substances.
Table 5.3 A comparison of
some bond energies

Factors affecting the relative strength of a bond

 Multiple bonds are stronger than single bonds. Compare the energies of the N-N and NɼN bonds
in Table 5.3.
 Bond strength is also affected bybond length. In general, shorter bonds are stronger than longer
ones. Bond length is itself related to the size of the atoms that make up that bond. The bond
strengths of the halogens show a trend:

Bond length increases down the group. Going down the

Halogen bond
length/nm group from one element to the next, an additional shell is
opened. This increases the size of the halogen atom,
Cl-Cl0.199 leading to poor overlap of orbitals during bond forma-
tion.This poor overlap of orbitals results in a longer bond,
Br-Br0.228 because the atomic orbitals can not approach each other
I-I 0.267 as closely as they would if the orbitals were small.

The bond energies of the halogens are expected to decrease down the group, due to increasing bond
length. Indeed, this is observed:

Halogen bond energy/ The bonds become weaker down the group. But does this
Kj mol-1 make the halogens more reactive? This question must be
answered with care. It all depends on the type of reaction we
Cl-Cl 242 are discussing. In a large number of their reactions, the
halogens act as oxidizing agents. In the process, they are
Br-Br 193
reduced, that is they gain electrons. Whether the halogen is
I-I 151 relatively more or less reactive therefore depends on its
willingness to accept electrons.
The smaller the halogen atom, the more willing it is to gain an electron, and the more reactive it is. In this
sense, chlorine is the most reactive of the three halogens given above. The chlorine atoms in Cl2 are quite
small, and they have a few shells intervening between the nucleus and the outer shell. An electron is
therefore easily attracted and stabilized in the outer shell because it will be close to the nucleus to which it
feels a strong attraction.

Using bond energies to estimate the enthalpy change of a reaction

The standard enthalpy change of a reaction, ∆Hθr has already been defined as the energyabsorbed or re-
leased when a chemical reaction takes place according to the written balancedequation. Bond energies
can be used to determine the value of ∆Hr.
This method depends on the fact that bond breaking is endothermic (absorbs energy) and bond breaking
is exothermic (gives out heat energy). For instance, the O to O double bond has an energy of 497 Kj/mol.
This means that 497 Kj of energy are absorbed when one mole of the bond breaks, and that 497Kj of
energy are released when 1 mole of the bond forms.
A chemical reaction therefore involves two opposing processes, one that absorbs heat energy (bond
breaking) and another that releases heat energy (bond formation). The enthalpy change of a reaction is
then found by

∆Hr = (Total energy used to break bonds in reactants) + (Total energy released when
bonds form in products)

Example 1

Estimate the enthalpy change, ∆Hr, for the reaction below.

CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)

Solution
Calculating the total energy absorbed:
This is the energy needed to break four moles of C-H bonds and two moles of O=O bonds (reactant
side).
 H Energy absorbed = 4E(C-H) + 2(O=O)
H C H + 2(O = O) Data (from Data Booklet)
C-H bond energy = 412Kjmol-1
H
O=O bond energy = 496Kjmol-1
(4C-H bonds and 2O=O bond)
∴Energy absorbed = (4 x 412) + 2(496) =+2 640 Kj
Calculating the total energy released:
This is the energy released when 2 moles of C=O bonds and four moles of O-H bonds are formed:

O= C =O + 2 O Total energy released = 2E(C=O) + 4E (O-H)

H H = 2(743) + 4(463) (using the Data Booklet)
= - 3 338 Kj
2C=O bonds and 4O-H bonds
Note that this value is negative since it represents energy released.

Enthalpy of reaction = Enthalpy of bond breaking (positive) + Enthalpy of bond formation (negative)
= 2 640 + (-3 338)
= -698 Kj

For practice

A mixture of hydrazine and fluorine is a potential fuel for rockets. How much energy would be released
when the two substances react?

N2H4 (g) + 2F2 (g)  N2 (g) + 4HF (g)

Data

Bond Energy/Kjmol-1
N-H 388
O=O 496
NɼN 944
H-F 562
N-N 163

Answer
Extra information
-962Kj
Hydrazine contains 1 N-N bond and 4 N-H bonds.
We now look at enthalpies associated with processes that take place in aqueous solution, namely,
dissolution of ionic compounds and acid- base reactions.

5.7.12 Enthalpy change of solution

The standard enthalpy change of solution, ∆Hθsol, is the energy released

orabsorbed when 1.0 mole of a substance dissolves in a large volume of water to
form an infinitely dilute solution under standard conditions.

For example, the standard enthalpy change of solution for NaCl refers to the
process:

NaCl(s)  Na+ (aq) + Cl-(aq), ∆Hθsol = +3.9 Kj mol-1

 Standard enthalpies of solution are quoted per mole of substance that dissolves in a solvent. In
most cases, the solvent refers towater.
 The term standard enthalpy of solution refers to both ionic and covalent substances.
 ∆Hθsol can be endothermic or exothermic; it all depends on which substance is involved.
 Enthalpies of solution refer to the formation of infinitely dilute solutions.
An solution is said to be ‘infinitely dilute’ if there is a sufficiently large excess of water so that
adding any more doesn't cause any further heat to be absorbed or evolved.

Dissolution of an ionic solid in water

When sodium hydroxide dissolves in water, heat energy is evolved and the solution becomes warmer.
When ammonium chloride dissolves in water, heat energy is absorbed and the solution becomes cooler.
Why are some dissolution processes endothermic and others exothermic?
To understand enthalpies of solution of ionic compounds, we divide the dissolution process into two
stages:

 1 mole of the solid ionic crystal is dissociated into its respective gaseous ions. This process isthe
reverse of lattice energy. The process is therefore endothermic (lattice energy is exothermic).
Energy is obviously needed to force oppositely charged particles apart.
 The gaseous ions are then dissolved in a large volume of water to make an infinitely dilute
solution. The energy evolved by this step is known as the enthalpy change of hydration, ∆Hθhyd.

Standard enthalpy change of hydration is the energy evolved when 1.0 mole of a gaseous ion
(cation or anion) dissolves in a large volume of water to form an infinitely dilute solution, under standard
conditions.

For example, the enthalpy change of hydration of the Na+ ion refers to the process

Na+ (g) + H2O  Na+ (aq) ∆Hθhyd. = -390KJ/mol.

  ∆Hθhyd is always exothermicbecause it results in the formation electrostatic attractions between
the ions and the water molecules. These attractions are actually relatively weak bonds. The
formation of bonds is always accompanied by release of energy.
 Different ions produce different amounts of heat energy when they dissolve in water.

Table 5.4 below compares the enthalpies of hydration of some ions.

Factors that affect the magnitude of

Cations Anions
hydration energy
Ion -∆Hθhydration / Ion -∆Hθhydration/
Kjmol-1 Kjmol-1 It is clear from the Table 5.3 that the magnitude of
hydration energy depends on
H+ 1 090 F- 506  the size of charge on the ion
 the size of the ion( ionic radius)
Li+ 519 Cl- 364
 number of protons in the nucleus.
Na+ 406 Br- 336
The first two factors above contribute to the charge
density of the ion.
K+ 322

Rb+ 301 Size of charge

The larger the charge on the ion, the more
Mg2+ 1 917 negative the hydration energy. Compare the
enthalpies of hydration of Na+, Mg2+ and Al³+,
Ca2+ 1 650
which become more negative in that order.
Al3+ 4 690 When an ion has a large charge, it can form strong
electrostatic attractions with water. Strong bonds
Table 5.4 Hydration Enthalpies of selected are formed, accompanied by the release of large
ions. All values are negative and
amounts of heat energy.
are in Kjmol-1.

Ionic radius
Enthalpy change of hydration is inversely proportional to ionic radius. The larger the ion, the smaller the
Enthalpy of hydration. Compare the enthalpies of hydration of the ions of Groups (I) and (II). Going down
each group, additional shells are opened and the ions become larger. The nucleus is then a large distance
from the surface of the ion. Attraction of water molecules by the nucleus of the ion is therefore smaller,
that is, enthalpy change of hydration decreases (becomes less negative).

Number of protons in the nucleus of the ion (nuclear charge)

Going along a period, for example from Na to Mg and Al, the number of protons in the nucleus increases.
The nucleus’ attraction for solvent molecules therefore increases, that is, the hydration energy of the ions
increases. The increase in hydration energy from Na+ to Al3+ can also be explained in terms of increase in
charge density as the ionic radii decreases due to increasing proton number.
Charge density
An ion with a relatively large charge and a relatively small ionic radius (for example, Al3+) has a large
charge density. Such an ion has a very powerful attraction for water molecules, resulting in the release of
large amounts of heat energy. The hydration energies of Na+, Mg2+ and Al3+ increases in that order due the
increase in charge density of the ions

The Hydration Enthalpies of Na+, Mg2+ and Al3+ (Period 3) increases in that order due to

 increase in ionic charge

 increase in nuclear charge (proton number)
 decrease in ionic radii
 increase in charge density

The Hydration Enthalpies of Groups (I) and (II) ions decrease down the group due to
 Increase in ionic radii
 decrease in charge density

Finding enthalpy of solution by Hess’ Law

As an example, consider the dissolution of NaCl in water. The energy change associated with this process
is the enthalpy change of solution, ∆H sln. This value can be determined from an energy cycle (Fig 5.17).

By Hess’ Law:
Enthalpy of Route 1 = Enthalpy of Route
∆HθSln = - ∆H1+ ∆H2+ ∆H3
= - LE (NaCl) + ∆Hθhyd (Na+) + ∆Hθhyd (Cl-) … (i)
The Lattice Energy of NaCl is - 771 Kjmol-1.
∴ ∆HθSln = - (-776) + (- 390) + (-381)
= +5Kjmol-1

The dissolution of NaCl in water is therefore an endo-

thermic process.
Fig 5.17Energy cycle for the determination of
the enthalpy change of solution of an ionic
compound
5.7.13 Standard Enthalpy Change of Neutralization, ∆Hneut
This is the energy released when an acid and a base completely neutralize each other in aqueous
solution to form 1.0 mole of water, under standard conditions.

For example, the Standard Enthalpy Change of Neutralization for the reaction between sulphuric
acid and sodium hydroxide pertains to the equation

½ H2SO4 (aq) + NaOH (aq)  ½ NaCl (aq) + H2O (l)

 The assumption is that the reaction takes place in a volume of water large enough to form an
infinitely dilute solution.
 ∆Hθneut is exothermic. This is because strong bonds are formed (in water) resulting in the release
of energy.
 The units are Kj per mol (of water produced).

Table 5.5 below shows enthalpies of neutralization for some acid, base pairs. All values are negative and
have units of Kjmol-1.

 The neutralization of a strong acid by a strong base

Acid Base -H neut
always produces about 57Kj per mole of water
HCl KOH 57.1 formed. This is expected since the same overall
reaction takes place :
HCl NaOH 57.2
H+(aq) + OH-(aq)  H2O(l) (after cancelling out
HNO3 NaOH 57.3 spectator ions)

HNO3 1/2Ba(OH)2 58.1

This explains why the definition is made in terms of
HCl NH3 52.2 amount of water formed. Even for dibasic acids and
alkalis such as sulphuric acid and barium hydroxide,
CH3COOH NaOH 55.2 the value is the same because we define the enthalpy
change of neutralization per mole of water. If two or
HCN NH3 5.3
more moles of water are shown in the balanced
HF NaOH 68.6
chemical equation, then we should divide throughout
by the appropriate number so that we remain with
one mole of water on the product side.
Table 5.5 Enthalpies of neutralization

 If either the acid or the base is weak, the enthalpy of neutralization would be less exothermic than
-57Kjmol-1. Let us use HF and NaOH as an example. HF is a weak acid. Its ionization in water to
produce the H+ ion is not so energetically favorable because the H-F bond is quite strong. The
neutralization of NaOH by HF is therefore more endothermic that -57 Kjmol-1.
 The Enthalpy Change of Neutralization is even smaller if both the acid and the alkali are weak, for
example, the enthalpy change of neutralization of NH3 (weak base) by HCN (weak acid) is only
-5.3 Kjmol-1.

Experimental determination of enthalpy of neutralization

Calorimetric measurements can be used to find the enthalpies of neutralization of an acid by a base. The
important thing in this determination is to make sure that loss of heat to the environment is negligible
and that the solution is stirred well to evenly distribute heat, otherwise pockets of heat energy are created
(water is a poor conductor of heat) and the thermometer will record a wrong temperature. Another issue
is loss of heat energy to the calorimeter and the thermometer. Advanced calorimeters are calibrated to
cater for loss of heat to the environment and to the apparatus. This gives very accurate values of
enthalpies of neutralization.

Q
Equal volumes of 2.0 moldm-3 NaOH and 2.0 moldm-3 HCl solutions are mixed in a plastic
cup and thetemperature of the mixture changes from 200C to 250C. Explain how this
information can be used to determine a value for the enthalpy change of neutralization per
mole of the acid.

The recorded increase in temperature when the two solutions are mixed is smaller
than the actual value due to loss of heat to the environment. Suggest how a more accurate
value of the temperature change can be obtained without modifying the experimental
set up.

Let volume of NaOH = ycm3= volume of HCl

A
Total volume after mixing = 2y
Heat , Q, produced by reaction = mc∆θ,
where m = mass of solution = total volume in cm3 = 2y
c = specific heat capacity of water = 4.2 Jg-1K-1
∆θ = increase in temperature = 5
Q = 2y x 4.2 x 5 = 42y joules
2 moles of acid produce 42y joules. 1 mole of the acid therefore produces 21y joules

The value of temperature change can be corrected graphically. Mark on an appropriately

scaled graph paper the initial temperature and the highest temperature attained. Now allow
the solution to cool, recording the drop in temperature at regular time intervals. On the graph
paper draw the ‘cooling curve’ and extraplate it backwards to the y (temperature ) axis, as
illustrated below.

extrapolation of
cooling curve x = initial temperature

y cooling curve y = maximum temperature recorded

z
z = new maximum after extrapolation

The corrected temperature change is (z-x)which is slightly larger than the uncorrected value
 (y - x)

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5: Miscelleneous problems

1. Use the following data to calculate the standard enthalpy change of reaction (i) below
4NH3(g) + 5O2(g) Ý 4NO(g) + 6H2O(g) ... (i)
Data:

Compound ∆Hθf / Kjmol-1

NH3(g) -46.1

NO(g) +90.

H2O(g) -241.8

9701/11/O/N/2009

2. Heats of combustion of ethane, acetylene and hydrogen are -1 393Kjmol-1, -1 310Kjmol-1 and
-285 Kjmol-1 respectively.
What is the enthalpy change for the hydrogenation of acetylene?
C2H2 + 2H2 C2H6

9189/3/O/N/2008

3. (a) State Hess’ Law

(b) (i) Write an equation to define the lattice energy of calcium oxide.
(ii) Construct a Born-Haber cycle for the formation of calcium oxide.
(iii) Use the cycle to calculate the lattice energy from the following information, and any
relevant data from the Data Booklet.

∆H atomization of calcium = +178Kjmol-1

∆H formation of calcium oxide = -635Kjmol-1
∆H electron affinity (1st and 2nd) for oxygen = +657Kjmol-1

(iv)Explain how and why the lattice energy of calcium oxide is different from that of
strontium oxide.
(c) An ice pack is used as a simple treatment for minor strains and sprains. It consists of a thick
plastic bag containing ammonium nitrate powder, and a second thinner plastic bag full of water.
If the bag is given a sharp blow, the thinner bag bursts and the ammonium nitrate dissolves
endothermically. The drop in temperature depends on the mass of the ammonium nitrate used
and the volume of water.

Given that ∆Hθ solution for ammonium nitrate is +26Kjmol-1 and the specific heat capacity of
the resultant solution is 4.2 JgK-1, calculate the mass of ammonium nitrate that would decrease
the temperature of 500cm3 of water by 250C.
9189/1/O/N/2011

4(a) Write an equation to represent the lattice energy of sodium oxide, Na 2O.
(b) The Born-Haber cycle shown may be used to calculate the lattice energy of sodium
oxide.

(i) Identify the species A and B in the cycle, including theappropriate state symbols.

(ii) Identify the enthalpy changes labelled by the numbers 1 to 4 in the cycle.

(c) Use your cycle, the following data, and further data from the Data Booklet to calculate avalue for
the lattice energy of sodium oxide.
Data:
enthalpy change of atomisation for Na(s) +107 kJ mol–1
first electron affinity of oxygen –141 kJ mol–1
second electron affinity of oxygen +798 kJ mol–1
enthalpy change of formation of Na2O(s) –414 kJ mol–1
enthalpy change of atomization for oxygen = half the bond energy for O2.

(d) (i) How would you expect the magnitude of lattice energy of magnesium oxide to
compare with that of sodium oxide? Explain your reasoning.

(ii) State a use of magnesium oxide, and explain how the use relates to your answer in
part (d) (i).
9701/4/O/N/2002

5. Use the following data, together with relevant data from the Data Booklet, to construct aBorn-Haber
cycle and calculate a value for the lattice energy of zinc chloride.

standard enthalpy change of formation of ZnCl2–415 kJ mol–1

standard enthalpy change of atomisation of Zn(s) +131 kJ mol–1
electron affinity per mole of chlorine atoms –349 kJ mol–1

9701/4/M/J/2007

7. From an appropriately drawn and labelled Born-Haber cycle of CaF2, write down an expression to
find the second electron affinity of oxygen. Calculate this value using the following information as
well as any other relevant data from the Data Booklet.

∆Hθ atomization of Ca = +193 Kjmol-1

First electron affinity of oxygen = -142 Kjmol-1
∆Hθ formation of calcium fluoride = -1 214 Kjmol-1
Lattice energy of calcium fluoride = -2 602 Kjmol-1

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A similar experiment can be simulated in the lab using a plastic cup (plastic is a good insulator) as the
reaction vessel, but the value obtained is only an estimate because loss of heat to the environment and to
Glossary Sheet
the apparatus can not be avoided.
Examiners frequently demand precise definitions of enthalpy terms. Even if they do not,calculations in energetics
frequently depend on how certain enthalpy terms are defined. If your definitions and understanding of these
terms is hazy, even the simplest problems in Chemical Energetics will prove to be a real challenge. For this reason,
we have brought together the definitions of all the enthalpy terms discussed in this chapter. Memorize them, and
more importantly understand them.

1. The Standard Enthalpy Change of Reaction (∆Hr) is the heatabsorbed or evolved when reactants
combine to form products according to the balanced equation, all measurements being taken under standard
conditions of 1 atm and 298K.

For example
3O2 (g) + 4NH3 (g) 6H2O (l) + 2N2 (g) ∆Hθr = -1 258Kj

2. The Standard Enthalpy Change of Formation (∆Hθf) of a substance is theheat evolved or absorbed
when 1 mole of the substance is formed from its elements in their normal states under standard conditions of
temperature (298K) and pressure (1 atm).

For example, the standard enthalpy change of formation of MgO refers to the energy change for the reaction:
1
Mg(s) + O2 (g)  MgO(s) ∆H = -602Kjmol-1
2

3. The Standard Enthalpy Change of Combustion (∆HCθ) of a substance is the amount of heat evolved
when 1 mole of the substance burns completely in oxygen, the measurement of heat released being adjusted to
standard conditions of temperature and pressure.

For example, the enthalpy change of combustion of hydrogen refers to the equation:

H2 (g) + 1/2O2 (g)  H2O (l)

4. Lattice Energy is the amount of energy evolved when 1.0 mole of a solid ionic crystal is formed from its
respective gaseous ions under standard conditions of 1.0atm and 298K.

For example, the lattice energy of MgO is represented by the equation

Mg2+(g) + O 2-(g)  MgO(s)

5. The Standard Enthalpy Change of Atomization of an element refers to the energy absorbed in
forming 1.0 mole of gaseous atoms from that element in its natural state under standard conditions of 1.0 atm and
298K.

For example, the standard enthalpy of atomization of chlorine refers to the process

1/2Cl2(g)  Cl (g)

6. The First Ionization Energy of an element refers to the energy required to knock out 1 mole of electrons
from 1 mole of gaseous atoms to form 1 mole of gaseous +1 ions, under standard conditions of 1.0 atm and 298K.

For example, the first ionization energy of magnesium refers to the process
 Mg (g)  Mg+ (g) + e-

7. The Second Ionization Energy of an element refers to the energy required to knock out 1.0 mole of
electrons from 1.0 mole of gaseous +1 ions to form 1.0 mole of gaseous +2 ions, under standard conditions of 1.0
atm and 298K.

For example, the second ionization energy of magnesium refers to the process

Mg+ (g)  Mg2+ (g) + e-

8. The Third Ionization Energy of an element refers to the energy required to knock out 1.0 mole of electrons
from 1.0 mole of gaseous +2 ions to form 1.0 mole of gaseous +3 ions, under standard conditions.

For example, the third ionization energy of aluminium refers to the process

Al2+(g)  Al3+(g) + e-

9. The First Electron Affinity of an element refers to the energy released when 1.0 moleof gaseous atoms
accept 1.0 mole of electrons to form one mole of gaseous -1 ions, under standard conditions.

For example, the first electron affinity of oxygen is represented by the equation

O(g) + e- O -(g)

10. The second electron affinity of an element refers to the energy absorbed to force 1.0 mole of electrons
into the outer shell of 1.0 mole of gaseous -1ions to form 1.0 mole of gaseous - 2 ions.

For example, the second electron affinity of oxygen refers to the process

O –(g) + e- O 2-(g)

11. The third electron affinity of an element refers to the energy required to force 1.0 mole of electrons into
the outer shell of 1.0 mole of gaseous -2 ions to form 1.0 mole of gaseous - 3 ions.

For example, the third electron affinity of nitrogen refers to the process

N-2(g) + e- N3-(g)

12. Bond enthalpy is the average energy needed to break one mole of a specific covalent bond in the gaseous
phase, to form separate gaseous atoms.

For example, the bond energy of chlorine refers to the energy required to break one mole of the Cl-Cl bond.

Cl-Cl (g)  2Cl-(g)

13. The standard enthalpy change of solution, ∆Hθsol, is the energy releasedor absorbed when 1.0 mole of
a substance dissolves in a large volume of water to form an infinitely dilute solution under standard conditions.

For example, the standard enthalpy change of solution for NaCl refers to the process:

NaCl(s)  Na+ (aq) + Cl-(aq), ∆Hθsol = +3.9 KJ /mol

14. Standard enthalpy change of hydration is the energy evolved when 1.0 moleof a gaseous ion (cation or
anion) dissolves in a large volume of water to form an infinitely dilute solution, under standard conditions.

For example, the enthalpy change of hydration of the Na+ ion refers to the process

Na+ (g)  Na+ (aq) ∆Hθhyd. = -3.90Kj/mol.

15. Standard Enthalpy Change of Neutralization is the energy released when an acid and a base completely
neutralize each other in aqueous solution to form 1.0 mole of water, under standard conditions.

For example, the Standard Enthalpy Change of Neutralization for the reaction between sulphuric acid and
sodium hydroxide pertains to the equation

½ H2SO4 (aq) + NaOH (aq)  ½ NaCl (aq) + H2O (l)

 Electrochemistry
CHAPTER
6

In Chapter 2 we discussed the composition of an atom in terms of sub-atomic particles. It was

mentioned that electrons have a direct effect on the chemical properties of substances. Chemical
reactions result in a rearrangement of atoms and electrons in the outer-shells of these atoms. This
rearrangement of electrons determines, to a large extend, the stability of the products of a reaction
relative to the reactants.
There are certain reactions which involve a total transfer of electrons between reactants. Such reac-
tions are known as redox reactions (that is, reduction-oxidation reactions).
Electrochemistry is concerned with the study of redox processes. By the time you are through with this
chapter, you should be able to

 decide whether a given reaction is redox or not, on the basis of oxidation numbers
 determine the number of electrons that are transferred during redox reactions
 identify the oxidizing and the reducing agent in a redox reaction
 predict the energetic feasibility of a redox reaction in terms of Electrode Potentials
 construct electronically and stoichiometrically balanced redox equations
 describe the key concepts involved in electrochemical cells, and predict the voltage out-put of a
simple cell
 explain the principle of electrolysis, and predict the products of a given electrolytic process
 Calculate quantities involved during electrolytic processes, for example, mass of metal deposited
and volume of gas produced.

6.1 Oxidation and Reduction

Two processes, known as reduction and oxidation, are involved in a redox reaction. These terms may be
defined in terms of transfer of oxygen /hydrogen atoms, or transfer of electrons (Table 6.1). In
electrochemistry, emphasis is on the transfer (loss or gain) of electrons. A large number of redox
reactions do not involve the transfer of oxygen or hydrogen atoms. However, for most organic redox
reactions, gain or loss of hydrogen or oxygen is more apparent than transfer of electrons.
 Oxidation is Reduction is Useful Mnemonic

Loss of electrons Gain of electrons O I LeH R I GHe

Gain of oxygen Loss of oxygen Oxidation Is Loss (of
electrons or hydrogen)
Loss of hydrogen Gain of hydrogen

An increase in oxidation A decrease in oxidation Reduction Is Gain (of

number number electrons or hydrogen)

Table 6.1 Definitions of reduction and oxidation

6.2 The concept of oxidation numbers

Oxidation numbers help in the determination of number of electrons transferred in redox reactions, and
in determining whether a reaction is redox or not.
The oxidation number (oxidationstate) of an atom is the charge it would have if it existed as a stable ion.
The oxidation number therefore describes the relative state of oxidation or reduction of the atom of an
element. For example, in nitrogen monoxide, nitrogen has an oxidation state of -2. It is in a relatively
reduced state, because it is possible for nitrogen to attain higher oxidation states, for example, the +5
state in HNO3.

Panel 1Guidelines for assigning oxidation numbers

1. An element or neutral atom is assigned an oxidation 6. The oxidation state of hydrogen is always equal to +1,
number of zero. except in hydrides where it is -1.The oxidation state of
2. The oxidation number for a monatomic ion is the oxygen in all of its compounds is always equal to -2,
charge on that ion, e.g. for Na+, the except in the peroxides (where it is -1) and in OF2
oxidation state of sodium is +1 (the + sign should be (where it is +2). The oxidation state of halogens in a
written.) large number of their compounds is -1, for example, the
3. In a polyatomic ion, the sum of oxidation numbers of oxidation state of Cl in NaCl is -1. However, there are
the different elements present is equal to the charge many exceptions to this generalization.
on the ion, e.g. in the SO42- ion , the sum of the 7. The oxidation state of metals in their compounds is
oxidation state of S and four O atoms is equal to -2. always positive. In their stable compounds, this
4. In neutral molecules, the algebraic sum of the oxidation oxidation number is equal to group number, e.g the
numbers of the different elements present is equal to oxidation sate of Al in Al2O3 is +3, since Al is in Group
zero. (III). The transition metals exhibit variable oxidation
5. In any compound made up of two elements, the more states in their compounds.
electronegative atom will have a negative oxidation
number and the lesselectronegative will have a
positive oxidation number.
 Examples Solutions 5. Mn O42-

Determine the oxidation number 1. -2 (Guideline 6) x -2

of the indicated element in each 2. Let oxidation state of N be x. x + -2(4) = -2

of the following compounds. The oxidation states of H and O x =6

are +1 and -2 respectively. The oxidation state of Mn in
H N O3 inMnO42- is +6.
1.O in H2O
+1 x -2 7.K2 Cr2O7
2.N in HNO3 Using Guideline 4, +1 x -2
1 + x -2(3) = 0 +1(2) + 2x -2(7) = 0
3. S in H2S
x=5 2x = 12
4.Cl in ClO- The oxidation state of N in x=6

5. Mn in MnO42- HNO3 is +5. The oxidation state of Cr in

3. Let the oxidation state of S K2 Cr2O7 is +6.
6.Mn in MnO4- be x.
7. Cr in K2Cr2O7 ( potassium H2S The rest of the problems
dichromate) +1 x are left as an exercise to
+1(2) + x = 0 the reader.
8. Cr in K2CrO4 (potassium
chromate) x = -2
The oxidation state of S in
9. V inVO2+and inVO2+
H2S is -2
4. Cl O-
x -2
x - 2 = -1(Guideline 3)
x=1
The oxidation state of
Cl in ClO-is +1.

Identifying redox reactions using oxidation numbers

One limitation of defining redox reactions in terms of gain or loss of hydrogen or oxygen is that a large
number of redox reactions do not involve hydrogen or oxygen at all. If we define a redox reaction in terms
of electron transfer we have an easy way of identifying redox reaction. Since reduction is gain of electrons,
it must be accompanied by a decrease in oxidation number of the atom which is being reduced (the atom
gains negative charge). Oxidation is loss of electrons. It is therefore accompanied by an increase in the
oxidation number of the atom which is being oxidized since the atom loses negative charge.

Q of the following conversions are redox?

Which
(i) CaCO3 CaO + CO2
(ii) K2Cr2O7 K2CrO4
(iii) VO2+ + Zn + 2H+ V3+ + Zn2+ + H2O

(i) and (ii) are not redox reactions. All atoms have the same oxidation state on both sides of the
A
equation. (iii) is redox because the oxidation state of Vanadium changes from +4 in VO 2+ to +3
in V3+.

NB. It is usually not necessary to calculate the oxidation state of every atom in the equation. For example,
in reaction (iii), check using vanadium only. Being a transition element, it is the one whose oxidation
state is likely to change.

Let us analyze reaction 3 further and determine

 The substance which is reduced
 The substance which is oxidized
 the reducing agent and the oxidizing agent
 the number of electrons transferred in the reaction

VO2+ is reduced because V experiences a decrease in oxidation number. Zn is oxidized because its
oxidation state increases (from 0 to +2). It loses two electrons, so its oxidation number increases by 2. It
gives these electrons to VO2+. In other words, Zn causes VO2+ to be reduced (to gain electrons). Zn is
therefore the reducing agent, but in carrying out its function it is oxidized. We may also say VO2+ takes
electrons from Zn, that is, it causes Zn to undergo oxidation. VO 2+ is therefore the oxidizing agent, and in
the process, it is reduced.

 An oxidizing agent causes another substance to be oxidized (to lose electrons). A reducing
agent causes another substance to be reduced (to gain electrons).
 An oxidizing agent is the species which is reduced in the reaction. The reducing agent is the
species which is oxidized in the reaction.
 Reduction and oxidation always happen together. If we identify one substance which is
oxidized in a reaction, there must be another substance which is being reduced.

We also need to know the number of electrons that are transferred in the reaction.

VO2+(aq) + Zn(s) +2H+(aq)  V³+(aq) + Zn2+(aq) + H2O(l)

Zn loses two electrons and becomes Zn2+, but VO2+ needs only one electron to be reduced from the +4
state to the + 3 state. Two moles of VO 2+ are therefore needed per mole of Zn. Thus, though the equation
above looks balanced, it in fact is not, because it does not account for the other electron from Zn. Where
does it go? The correct(balanced) equation is shown below:

2VO2+ (aq) + Zn(s) +4H+ (aq)  2 V³+ (aq) + Zn2+ (aq) + 2H2O (l) ... (i)

The reaction involves the transfer of two moles of electrons from one mole of Zn to two moles of VO2+.
It should also be noted that there is a relationship between the stoichiometry of the reaction and the
number of electrons transferred. The following equation generalizes this relationship.
 In a redox reaction,

𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐫𝐞𝐝𝐮𝐜𝐞𝐝 𝐬𝐩𝐞𝐜𝐢𝐞𝐬 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬 𝐥𝐨𝐬𝐭 𝐛𝐲 𝐨𝐱𝐢𝐝𝐢𝐳𝐞𝐝 𝐬𝐩𝐞𝐜𝐢𝐞𝐬

= ...(I)
𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐱𝐢𝐝𝐢𝐳𝐞𝐝 𝐬𝐩𝐞𝐜𝐢𝐞𝐬 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬 𝐠𝐚𝐢𝐧𝐞𝐝 𝐛𝐲 𝐫𝐞𝐝𝐮𝐜𝐞𝐝 𝐬𝐩𝐞𝐜𝐢𝐞𝐬

Example

In an experiment, 3.0 moles of Zn were required to reduce 2.0 moles of an aqueous ion (X) of
Vanadium to VÆÄ (aq). What is the oxidation state of V in the ion X?

Solution
The reduced species is X andthe oxidized species is Zn
Moles of electrons lost by oxidized species = 2(Zn is always oxidized from 0 to +2 state)
Let the oxidation state of V in ion X be p. Since X is reduced to +2 state, the number of electrons
gained by X = p-2(the oxidation number of V changes from a higher value, p, to a lower number, +2).

Using formula (I) above:

Further information
2 2
= p−2 Species X, in which vanadium
3
has an oxidation number of +5
could be the vanadate ion, VO3-
Solving for p yields:
(stable in alkaline medium) or
the vanadic ionVO2+, which is
p= 5, which is the oxidation number of V in species X. stable in acidic medium.

Balancing redox equations

Half equations
It has already been mentioned that in a redox reaction, there is simultaneous oxidation and reduction. It
is therefore possible to resolve the redox reaction into two equations; one showing what is happening to
the oxidized species, and the other showing what is happening to the reduced species.
These equations are known as the oxidation half equation and the reduction half equation respectively.
They are known as half equations because in practice they can not happen on their own. They only occur
in a full reaction which can be obtained by adding together the two half equations.
Example 1
Construct balanced half equations for the reduction of VO2+ by Zn to V3+in aqueous solution. Hence
construct a balanced equation for the reaction.

Solution
In VO2+ , vanadium has an oxidation number of +5. For this species to become V3+, it must gain 5-3 = 2
electrons.
VO2+ + 2e V3+

Next, balance oxygen atoms by adding two water molecules to the right hand side (RHS) of the equation.
VO2+ + 2e  V3+ + 2H2O
Next balance hydrogen atoms by adding 4H+ ions to the left hand side (LHS) of the equation
4H+ + VO2+ + 2e  V3+ + 2H2O ... (i)
In general, if O atoms are short on the product side, balance by adding the correct number of H2O
molecules on that side. This necessitates the addition of the correct number of H + ions to the reactant
side.
Reaction (i) is the reduction half-equation (it involves gain of electrons). This reduction requires an
acidic medium (H+ ions). The role of the hydrogen ions is to combine with O atoms in VO 2+ to form
water.

The oxidation half equation is straight forward. Zn loses two electrons and becomes Zn2+.

Zn  Zn2++ 2e ... (ii)

Bring the reduction and oxidation half equations together and add them vertically. This gives the net
equation for the reaction between Zn and VO 2+ in the presence of an acid. Notice that the number of
electrons in the two half-equations must be equal, so they cancel out. This shows that all the electrons
produced by the reducing agent are taken up by the oxidizing agent.

4H+ + VO2+ + 2e- V3+ + 2H2O ... (i) reduction half-equation

Zn  Zn2++ 2e-... (ii) oxidation half-equation

Net equation 4H+ + VO2+ + Zn  V3+ + Zn2++ 2H2O ... (iii)

NB A redox reaction must be both stoichiometrically and electronically balanced. That is, it must be balanced both
in numbers of atoms present on the two sides of the reaction and in the number of electrons involved in the
reduction and the oxidation half-equations.

Example 2
Construct a balanced equation for the oxidation of iron (II) chloride to iron (III) chloride by
potassium permanganate in aqueous solution. The permanganate is reduced to manganese (II)
chloride.
 Solution

The chloride ion is a spectator ion in this reaction and can be ignored for convenience.
The reduction half-equation involves the reduction of MnO4- to Mn+2. The oxidation number of Mn in
MnO4- is +7. To form Mn+2, MnO4- must therefore gain 7-2 = 5electrons.
MnO4- + 5e Mn+2
Balance O by adding 4H2O to the RHS then balance H by adding 8H+ to the LHS.
8H++ MnO4-+ 5e  Mn2+ + 4H2O ... ( i) reduction half equation
The oxidation half equation is the conversion of Fe2+ to Fe3+. In this process, Fe2+ loses one electron:

Fe2+  Fe3+ + e ... (ii) oxidation half equation

Fe2+ loses one electron and yet MnO4- needs five to be reduced to Mn2+. We therefore multiply equation
(ii) by 5 to balance the number of electrons. Equation (i) and (ii) are now added up vertically to get the
overall equation:

8H++ MnO4-+ 5e Mn2+ + 4H2O

5Fe2+ 5Fe3+ + 5e

Net equation8H++ 5Fe2+ + MnO4- Mn2+ + 5Fe3+ + 4H2O

The equation shows that an acidified solution of potassium permanganate oxidizes iron (II) chloride to
iron (III) chloride. The purple color of potassium permanganate disappears and the mixture turns
yellowish brown due to the formation of Fe(III )chloride.

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text box.]
Balance the following redox reactions

(a) Cr2O72- + Fe2+ Cr3+ + Fe3+

(b) VO2+ + Sn2+ V3+ + Sn4+
(c) Fe3+ + I- Fe2+ + I2
(d) Cr2O72- + SO2  Cr3+ + H+ + SO42-

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6.3 Electrode potentials

Consider a metal electrode M in contact with a solution of its ions (For example, a copper rod immersed in
copper (II) sulphate solution).
 Two opposing processes take place:
 Oxidation of the metal to its ions
M(s)  Mn+ (aq) + ne-
reduction of the metal ions back to the metal.
Mn+ (aq) + ne-  M(s)
In other words, the following equilibrium is established
Fig 6.1 A half cell containing Mn+ (aq) + ne- Ý M(s)
an electrode M in contact with
a solution of its ions. There is a therefore a flow of electrons between the electrode and its ions,
the metal loses electrons, which are transferred to the ions in solution.

The process reaches dynamic equilibrium in which the rate of the forward reaction is equal to the rate of
the reverse reaction. There is therefore no net change to the metal or to the solution.
The set up in Fig 6.1 is a half cell because only one electrode is involved. It is possible to connect this cell
to another half cell and provide a complete circuit for the flow of electrons between the two cells. A
voltmeter can then be connected to the external circuit to measure the potential difference between the
electrodes in the two half cells.
We may need to compare the potentials due to different electrodes. To do this, we connect a half cell of the
electrode M to a standard reference cell. By using different electrodes, it is possible to compare the
potential differences of the half-cell relative to the reference cell. The standard reference cell used is a half
cell known as the standard hydrogen electrode, S.H.E(Fig 6.2);so called because the ‘electrode’ is
hydrogen gas in contact with its ions, H+. The potential difference recorded between the electrode M and
the SHE is known as the electrode potential (or reduction potential) of electrode M. In this set up, it is
necessary to make sure that standard conditions are employed. The electrode potentials obtained under
these conditions are said to be standard. This makes the comparison of electrode potentials of different
electrodes meaningful. The standard conditions used are

Temperature: 298K (250C)

Pressure: 1.0 atm
All concentrations are 1.0 moldm-3

In the SHE, hydrogen gas dissociates into its ions

H2 (g)  2H+(aq) + 2e-

The Pt metal provides an inert surface for this reaction, and also acts as a catalyst, since hydrogen on its
own does not easily dissociate into hydrogen ions. Pt is particularly selected on the basis of its inertness
and catalytic ability. It does not ionize in the acidic medium in which it is immersed; otherwise it would
generate its own voltage.
The hydrogen ions in solution accept electrons provided by
hydrogen gas. The ions are thus reduced to H2 (g).
2H+ (aq) + 2e H2 (g)
An equilibrium is therefore established on the platinum
electrode
2H+ (aq) + 2e Ý H2 (g)
This equilibrium involves movement of electrons between the Pt electrode and the solution of H + ions. At
equilibrium there is a potential difference between the electrode and the solution.
 By convention, the SHE is assigned a voltage of zero. The value
recorded by the voltmeter when the SHE is connected to an
electrode M is therefore attributed to the electrode. This value is
known as the electrode potential of the electrode M.

The standard electrode potential, Eθ, of an electrode is the

potential difference between a half cell made up of that
electrode and its ions, and a standard hydrogen electrode,
under standard conditions.

Standard Electrode Potentials are measured in Volts (V).

Fig 6.3 illustrates how the electrode potential of Zinc can be

determined by linking a Zn(s)/Zn2+(aq) half cell to the SHE. The
arrows indicate the direction of flow of electrons.
There are two half cells involved in this set-up. One cell is
Fig 6. 2 The standard hydrogen
electrode
Zn(s)⃒Zn2+(aq), read as ‘Zinc electrode in contact with its
ions’. The other half cell isthe SHE, Pt(s)⃒H2(g),H+(aq),read
as ‘hydrogen gas in contact with its ions over a platinum
electrode’.

Fig 6.3 Set-up for the determination of the electrode potential of Zn

metal

In the Zn(s)⃒Zn2+(aq) half cell zinc is oxidized to Zn2+ ions

Zn(s) ÝZn2+(aq) + 2e- ...(i)
In the SHE, a similar process takes place, in which hydrogen is oxidized H+ ions.
H2 (g) Ý 2H+ + 2e- ... (ii)

Notice that each atom in H2 (g) provides an electron during dissociation, so a total of two electrons are
produced per molecule of hydrogen gas.Both half cells therefore produce electrons, and which ever of the
two cells is more negative in terms of these electrons will supply electrons in the external circuit.
  In this case, zinc metal provides electrons in the external circuit. This is because zinc metal has a
greater tendency to lose electrons (to be oxidized) compared with hydrogen gas. The Zinc
electrode is therefore relatively negative, whilst the Pt electrode on the SHE side is relatively
positive. We say there is a potential difference between the two electrodes. It is this potential
difference (Voltage) that forces a flow of electrons (current) in the external circuit. Notice the use
of the word relative. Neither electrode (Zn or Pt) has a full positive or negative charge. Instead,
one electrode (Zn) ionizes more readily so it becomes richer in electrons than the Pt electrode.

 The voltmeter measures the potential difference between the Zn and the Pt electrode. The direc-
tion in which the needle of the voltmeter moves shows that electrons flow from Zn to Pt. In this
case, the needle of the voltmeter moves to the negative side of the zero mark. The electrode
potential of zinc is therefore negative.

 By convention (that is, not by measurement), the SHE electrode is assigned a voltage of zero, so
the voltage reading is the standard electrode potential of Zinc. This method of assigning a zero
value to the SHE half-cell is valid because the aim is to compare the electrode potentials of
different electrodes. The comparison is legitimate as long as the voltage of the SHE is taken as a
constant(the constant zero is used for its convinience)

 Notice the presence of a salt bridge in Fig 6.3. Its function is to complete the circuit between the
two half cells so that current can flow. The salt bridge contains an aqueous salt such as KNO 3.
Flow of current in the salt bridge is in the form of movement of ions, not electrons. Another
important function of the salt bridge is to maintain electroneutrality. This will be explained later.

 In Fig 6.3, the voltmeter records a negative value of -0.76V. The negative sign indicates that the
needle of the voltmeter sweeps to the negative side of zero. It shows that electrons flow from zinc
to the Pt electrode. The value -0.76 is the standard electrode potential of Zincand it pertains to
forward reaction of the equilibrium
Zn2+(aq) + 2e-Ý Zn(s)
Electrode potentials are also known as reduction potentials because they refer (by convention) to the
reduction half equations.

An important note on the +, - notation

The sign of the electrode potential (+ or -) indicates the direction of flow of electrons. A negative sign shows that
electrons flow from the electrode M to the SHE, that is, the electrode M has the greater tendency to release electrons
than hydrogen gas. A positive value shows that electrons flow from the SHE to the electrode M, that is, hydrogen gas
has the greater tendency to release electrons than the electrode M.

An example of a positive electrode potential is that of Ag. This value is +0.80V, and it refers to the forward
reaction of the equilibrium
Ag+(aq) + e-Ý Ag(s)
The electrode here is Ag metal immersed in its ions, Ag +.The positive value shows that hydrogen (in SHE)
ionizes more readily than silver metal. The Pt surface in SHE therefore becomes richer in electrons
(supplied by the dissociation of H2) than the Ag electrode. Electrons therefore flow from the SHE to the
Ag(s)⃒Ag+(aq) half cell. The needle of the voltmeter deflects to the positive side of zero, that is, a positive
value is recorded.
Table 6.2 gives the electrode potentials for some elements. The table includes non-metallic elements.
The measurement of the electrode potentials of such electrodes will be discussed later.

The significance of electrode potentials

First the reader should recall that electrode potentials are given in terms of reduction (gain of
electrons). For example, the electrode potential of zinc metal, -0.76, refers to the forward reduction
reaction in the equilibrium
Zn2+(aq) + 2e-Ý Zn(s) ... (i)

Reading the equilibrium in reverse gives

Electrode Equilibrium Standard Zn(s) Ý Zn2+(aq) + 2e-...(ii)
Electrode
Potential/ for which the potential is +0.76V. The positive
V value after reversingequation (i)indicates that Zn
metal readily loses electrons, compared to hydrogen
Mg Mg2+(aq)+ 2e-Ý Mg(s) -2.38 gas. Thus, as already explained, electrons will flow
from Zinc to SHE.
Al Al3+ + 3e-Ý Al(s) -1.66
But why did we reverse the equilibrium?
Zn(s - 0.76 The electrode here is a metal, and metals usually
Zn2+(aq) + 2e-Ý Zn(s)
undergo oxidation in their reactions. We have
therefore reversed the equilibrium to show the oxi-
Pb(s) Pb2+(aq)+ 2e-Ý Mg(s) -0.13
dation of zinc. The sign of the electrode potential
after reversing the reduction half equation helps in
H2 H+(aq) + e-Ý ½ H2(g) 0.00
assessing the ease with which a metal can be
oxidized. If the reduction potential is negative before
Cu Cu2+(aq) + 2e-Ý Cu(s) +0.34
reversing, as is the case with most metals, it becomes
positive after reversing. The positive value shows
Ag Ag+(aq) + e-Ý Ag(s) +0.80
that under standard conditions, the metal can easily
be oxidized to its ions, that is, it is quite reactive. The
I2 I2(g) + 2e-Ý 2I-(aq) +0.54
more positive the potential after reversing, the more
reactive the metal.

Cl2 Cl2(g) + 2e-Ý 2Cl-(aq) +1.36

For metals, it is recommended that the reader develops
the habit of reading the redox potentials in reverse. This is
because the reverse reactions show oxidation, which is the
Table 6.2 Standard Electrode Potentials, reaction likely to be undergone by metals. A positive
measured at 298K and for 1.0 moldm-3 solutions. potential after the reversal shows that the metal is
For gases such as chlorine, the reaction takes relatively easily oxidized to its ions.
place on the surface of an inert metal,
particularly platinum.
By referring to Table 6.2, you can see that both magnesium and aluminium are expected to be very
reactive metals.Magnesium is indeed very reactive, but aluminium shows an inertness which is due to
kinetic factors to be explained later.
It possible to arrange metals in order of reactivity by comparing theirreduction potentials. The more
negative the electrode potential before reversing, or the more positive the value after reversing,
the more reactive the metal. Some metals have a positive reduction potential, for example, copper whose
electrode potential is +0.34V. That means the reverse oxidation reaction
Cu(s) Ý Cu2+(aq) + 2e-
has a negative reduction potential of -0.34V. The negative sign shows that the oxidation of copper metal
to Cu2+ is not energetically favourable. In other words, copper is a relatively unreactive metal. In Table
6.1, silver has the most positive electrode potential, so it is the least reactive (most stable) of the metals in
this table. All metals with positive electrode potentials are below hydrogen in the reactivity series. When
connected to a SHE, electrons flow from the SHE to the metal electrode, showing that hydrogen is
oxidized instead of the metal.

Q
Arrange the metals in Table 6.2 above in order of decreasing reactivity(that is, from the
most reactive to the least reactive)

AMg, Al, Zn, Pb, Cu, Ag

6.4 The electrochemical series

This is an arrangement of the metals in order of their standard electrode potentials, starting with the most
negative (that is, the most positive if the electrode potentials are considered in reverse). Part of the
electrochemical series is shown in Fig 6.4 (Hydrogen is included in this list as a reference).
A metal which is high in the reactivity series(large and negative electrode potential), for example, Mg
shows the following properties

 it readily gives up electrons to form ions, for example, Mg(s) Mg2+ + 2e-. These electrons are
gained by another substance in a redox reaction. This other substance is therefore reduced. In
other words, a metal with a large and negative electrode potential (high up the electrochemical
series) is a good reducing agent.
 it is very reactive

On the other hand, a metal which is at the bottom of the electrochemical series

 does not readily give up electrons. Instead, its ions readily gain electrons(for example, from a
metal higher in the series) to form the neutral metal, e.g

Ag+(aq) + e- Ag(s)

Note that the electrode potential for this reaction is positive (= +0.80V. See Table 6.2). This
shows that the conversion of the ions to the metal is energetically feasible. However, the reverse
 reaction in which Ag is oxidized to its ions is negative. This shows that the oxidation of Ag metal
to its ions is energetically unfavourable. In other words, Ag metal is relatively inert.

Metal Reaction Standard

Electrode Most
Potential/ V
most negative
reactive Mg Mg2+(aq)+ 2e-Ý Mg(s) -2.38 Eθ

Al Al3+ + 3e-Ý Al(s) -1.66

Zn Zn2+(aq) + 2e-Ý Zn(s) - 0.76

Pb Pb2+(aq)+ 2e-Ý Mg(s) -0.13

H2 H+(aq) + e-Ý ½ H2(g) 0.00

Cu Cu2+(aq) + 2e-Ý Cu(s) +0.34

Ag Ag+(aq) + e-Ý Ag(s) +0.80

Most
least Fig 6.4 Shortened form of the electrochemical series positive
reactive of metals
Eθ

6.5 Standard Electrode potentials for non metals

The standard electrode potential of chlorine is +1.36V and it refers to forward reaction of the equilibrium
Cl2 (g) + 2e-Ý 2Cl-(aq) ... (i)
Fig 6.5shows the set up for the determination of the electrode potential of a gas such as Cl 2. The design of
the cell is necessitated by the fact that a gas can not be dipped into a solution of its ions as is the case with
metal electrodes. Instead, it gets into contact with its ions, in this case, Cl- ions, over a platinum metal
surface.

Understanding the electrode potentials of the halogens

The electrode potentials of metals can be understood by reversing the relevant equilibrium so that the
reaction shows oxidation of the metal. For the Group (VII) elements, it is not necessary to do this reversal,
because the halogens usually undergo reduction, in which they gain electrons to form the halide ions.
The halogens all have positive electrode potentials which shows that the reduction of the gas to its ions is
energetically favourable. The halogens are therefore good at accepting electrons. In so doing, they act as
oxidizing agents. The more positive the value of the reduction potential, the easier it is for the halogen to
be reduced (to accept electrons, for example, from a metal).
Compare the Standard electrode potentials of Cl2, Br2 and I2 given in Fig 6.6. The decrease in the reduc-
tion potentials of the halogens down the group explains why they become less reactive as the group is
descended.
 Fig 6.5 The set up for the determination of the electrode
potential of chlorine gas

 Chlorine, with the most positive electrode potential, has the greatest ability to accept electrons. In
other words, it easily causes other substances, for examples, metals, to lose electrons. Chlorine is
therefore a powerful oxidizing agent.

 Iodine, with the smallest electrode potential, has the least ability to accept electrons. It is
therefore the weakest oxidizing agent of the three halogens.

 The halogens therefore become weaker oxidizing agents down they group, as they become less
willing to accept electrons. This trend can be explained in terms of atomic radii. Going down the
group, atoms of the halogen become larger due to the opening of new shells. Large atoms are not
so good at accepting electrons in their outer shell. This is because the outer shell is a large
distance from the nucleus, so the incoming electron feels only a weak attraction from the nucleus.
This weak attraction implies that the electron is not effectively stabilized, so its incorporation into
the outer shell of the atom is not so favourable.

most Eθ/V most

reactive positive Eθ
Cl2(g) + 2e-Ý 2Cl-(aq) +1.36
Cl2

Br2(g) + 2e-Ý 2Br-(aq) +1.07

Br2
Fig 6.6 The Standard Electrode Potentials of least positive
least Ithe
2 Ihalogens - become
2(g) + 2e Ý 2I-(aq) less positive +0.54
down the group. The reactivity of the Eθ
reactive
elements decrease in that order.
Electrode potentials for a redox couple that involves ions
The Data Booklet gives the standard electrode potential of the Fe3+(aq)/Fe2+(aq) couple as +0.77V. This
corresponds to the equilibrium
Fe3+(aq) + e-Ý Fe2+(aq)

Fe3+, having the larger oxidation number, is the one that is gaining electrons, that is, it is being reduced to
Fe2+(reduction is accompanied by a decrease in oxidation number). The value of the electrode potential
for this redox couple is found by setting up a half cell shown in Fig 6.7and connecting it to the SHE.

Fig 6.7 A half cell for the determination of the

Fe3+/Fe2+ electrode potential

6.6 Using Standard Electrode Potentials to predict redox reactions

Eθvalues can be used to determine the feasibility of a redox reaction. If a reaction has a net cell potential
which is positive, it is energetically feasible and can take place under standard conditions. In terms of
thermodynamics, the reaction has a negative enthalpy of reaction, that is, the products are lower in
energy and more stable than the reactants.
A negative cell potential corresponds with a positive enthalpy of reaction. Such a reaction is not energeti-
cally favourable.

Example 1
Predict if an aqueous solution of Fe (II) can convert aqueous potassium permanganate to Mn 2+.

Solution
If a reaction occurs between these two substances, Fe (II) will be the reducing agent and will be oxidized
to Fe (III). MnO4- would be the oxidizing agent and would be reduced to Mn 2+(Mn in MnO4- is in a high
oxidation state (+7) so it is likely to be converted to a lower oxidation state.
Fe (II) is in a lower oxidation state so it is likely to be converted to a higher oxidation state).
A balanced equation can then be constructed by combining the reduction half equation and the oxidation
half equation. The relevant reduction potentials are shown below.

Eθ/V
MnO4-(aq) + 8H+ (aq) + 5e-Ý Mn2+ + 4H2O +1.52... (i)

Fe3+ + e-Ý Fe2++0.77 ... (ii)

These two half equations have been taken as they are in the Data Booklet, that is, in terms of reduction.
The electrode potential of MnO4-/Mn2+ is more positive, which means that MnO4-is the one which is more
likely to undergo reduction, that is, it is likely to behave as an oxidizing agent. Next we reverse reaction
(ii), together with the sign of its electrode potential. We do this for two reasons. First, we intend to bring
Fe2+ to the same reactant side as MnO4- so that the two substances can react. Secondly, we need to show
the oxidation of Fe2+ to Fe3+. Since MnO4- undergoes reduction, Fe2+ must undergo oxidation. We now
have a reduction half equation and an oxidation half equation.
Notice that equation (ii) must be multiplied by 5 to balance the number of electrons with those shown in
equation (i). The net equation is obtained by adding the two equations vertically. The electrode potentials
are also added vertically to obtain the cellpotential, Eθ.

Eθ/V
MnO4-(aq) + 8H+ (aq) + 5e-Ý Mn2+ + 4H2O +1.52 (i)
5Fe2+ Ý 5Fe3+ + 5e--0.77 (ii)

Cell reaction MnO4-(aq) + 8H+ (aq) + 5Fe2+ Ý Mn2+ + 5Fe3++ 4H2O +0.75(iii)

Since the net cell potential of the reaction is positive, we conclude that the reaction is indeed feasible
under standard conditions. MnO4- ions oxidize Fe2+ ions to Fe3+. Meanwhile, MnO4-is reduced to Mn2+,
resulting in the decolourization of the purple solution.

The following working order is useful in the determination of the feasibility and outcome of a redox reaction.

 The first step is to select the correct half equations from the Data Booklet. First, write down these equilibria as
they are in the Data Booklet, that is, in terms of reduction.
 Next, consider which of the two equations has the more positive electrode potential. This gives you the species
which is likely to undergo reduction (This species is on the right hand side of the equation). This equation is
therefore your reduction half equation.
 Now reverse the second equation, that is, the one with the less positive (or, more negative) electrode potential.
This gives you the oxidation half equation, and also brings reactants to the same side. Do not forget that when
you reverse an equation, you reverse the sign of its electrode potential as well.
  Balance the number of electrons and add the two half equations vertically. The electrode potentials are also
added vertically, but take care that you have reversed the less positive electrode potential before adding. Also
check that you have the correct reactants on the reactant side(For example, MnO4-(aq) + 5Fe2+ (aq), not MnO4-
(aq) + 5Fe3+).
 The value you obtain after adding the two electrode potentials is the cell potential. If it is positive, then the
reaction is feasible under standard conditions. If the value is negative, then the reaction is not energetically
feasible under standard conditions. However, the reaction might still take place if reaction conditions are
altered, for example by heating or using concentrated solutions, rather than 1.omoldm-3 solutions.

Example 2
Predict if an aqueous solution of Fe (II) can convert aqueous potassium dichromate to Cr 3+(aq).

Solution
Reduction potentials as extracted from the Data Booklet:

Eθ/V
Cr2O72-(aq) + 14H+ (aq) + 6e-Ý 2Cr3+ + 7H2O (l) +1.33
Fe3+ (aq) + e-Ý Fe2+(aq) +0.77

Reverse the (second) equation with the less positive electrode potential and the sign of the electrode poten-
tial, balance electrons and then add the two equations vertically:

Cr2O72-(aq) + 14H+ (aq) + 6e-Ý 2Cr3+ + 7H2O (l) +1.33

6Fe2+ (aq) Ý 6Fe3+ (aq) + 6e--0.77

Net reactionCr2O72-(aq) + 14H+ (aq) + 6Fe2+ (aq) Ý 2Cr3+ + 7H2O (l) + 6Fe3+ (aq) +0.56V

Since the net cell potential is positive, the reaction does take place. Potassium dichromate, just like KMnO 4,
oxidizes light green Fe2+ (aq) to yellowish brown Fe3+ (aq). Meanwhile, the orange dichromate is reduced to
dark green Cr3+ (aq).

Oxidizing power of the oxoanions

MnO4-, Cr2O72-, ClO3- and VO3- are example of oxoanions. They are all rich in oxygen and contain an
element in a high oxidation state, which can therefore be reduced to lower oxidation states by suitable
reducing agents. The oxoanions are therefore good oxidizing agents; for example, both KMnO 4 and
k2Cr2O7 can oxidize Fe2+ to Fe3+ in aqueous solution. As oxidizing agents, the oxoanions usually require an
acidic medium. The role of the acid is to remove the oxygen atoms from the oxidizing agent, converting
them to water. In other words, the oxidizing agent loses oxygen, that is, it is reduced. Reduction of the
oxoanion therefore involves both the loss of oxygen and the gain of electrons by an element in the
oxoanion. For example, when Cr2O72- is reduced to Cr3+, each Cr atom in Cr2O72- gains 3 electrons, since
the oxidation number of Cr changes from +6 to +3. 1 mole of Cr2O72- therefore gains 6moles of electrons.
You can arrange oxidizing agents in order of their strength by comparing their reduction potentials. A
powerful oxidizing agent has a large and positive reduction potential. A less positive (more negative)
reduction potential shows that the substance is a weaker oxidizing agent. We can therefore conclude that
the permanganate ion, MnO4- , whose reduction potential is +1.52, is a stronger oxidizing agent than the
dichromate ion, Cr2O72-, whose reduction potential is +1.33V.

The issue of spectator ions

Consider the reaction that occurs between dichromate and iron (II) ions.

Cr2O72-(aq) + 14H+ (aq) + 6Fe2+ (aq) Ý 2Cr3+ + 7H2O (l) + 6Fe3+ (aq)

Notice that this is an ionic equation in which spectator ions have been ignored. The full equation may be
written depending on which spectator ions are present.

Construct a balanced full equation for the aqueous reaction between K2Cr2O7 andiron (II)
Q
sulphate in the presence of sulphuric acid.

Redox titrations
A redox titration involves a redox reaction which takes place in aqueous solution. This procedure can be
used to determine the amount (moles, mass or concentration) of a reducing or oxidizing agent involved in
a redox reaction. Some redox titrations are self indicating, that is, they involve clear colour changes at the
end point. An indicator is not necessary in such titrations.

Example

During a titration, 25 cm3 of 0.1 moldm-3KMnO4-were required to exactly neutralize 20.00 cm3 of an
aqueous solution containing Fe2+.

(a) Which reagent was placed in the burette?

(b) Determine the concentration of Fe2+ in the solution

(c) Explain why it is possible to determine the end point of the reaction without using an indicator.

Solution
(a)KMnO4. The reagent whose concentration is known is always placed in the burette.
(b) MnO4- (aq) + 8H+ (aq) + 5Fe2+ Ý Mn2+ + 5Fe3++ 4H2O ... (i)
25
moles of MnO4-that reacted = C x V = 0.1 x = 0.0025
1000
 MnO4-: Fe2+ = 1 : 5 (equation (i))

∴moles of Fe2+ that reacted = 0.0025 x 5 = 0.0125

Concentration of Fe2+ = n/V = 0.0125/0.020 = 0.625 moldm-3
(c) The reaction involves decolourization of potassium permanganate. The end point is reached when one
last drop of KMnO4 from the burette causes the colour of the titration mixture to change to pale pink
(colour of very dilute KMnO4)

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text box.]
Predict whether the following pairs of substances can react in a redox reaction. Where a reaction takes
place,
 construct a balanced equation and calculate the cell potential.
 identify the oxidizing and the reducing agent

1. KMnO4 and HCl (that is, MnO4- and Cl-)2. KMnO4 and HBr-3. K2Cr2O7 and HCl4. VO2+ and Zn5.
Cu2+ and Mg6. Cu2+ and Ag
7. Cl2 and Fe2+8. Br2 and Fe2+9. I2 and Fe2+
10. Na2S2O3 and I2

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6.7 The redox series

This is an arrangement of electrode potentials, starting with the most positive and ending with the most
negative. A short form of the redox series is shown in Table 6.3.

Electrode reaction Eθ/V

F2 + 2e-Ý 2F- +2.87

S2O82- + 2e-Ý 2SO42- +2.01

H2O2 + 2H+ + 2e-Ý 2H2O +1.77

MnO4- + 8H+ + 5e-Ý Mn2+ + 4H2O +1.52

PbO2 + 4H+ + 2e-Ý Pb2+ + 2H2O +1.47

Cl2 + 2e-Ý 2Cl- +1.36

 Cr2O72- + 14H+ + 6e-Ý 2Cr3+ + 7H2O +1.33

Br2 + 2e-Ý 2Br- +1.07

Ag+ + e-Ý Ag +0.80

Fe3+ + e-Ý Fe2+ +0.77

I2 + 2e-Ý 2I- +0.54

O2 + 2H2O + 4e- Ý 4OH- +o.40

Cu2+ + 2e-Ý Cu +0.34

Sn4+ + 2e-Ý Sn2+ +0.15

2H+ + 2e-Ý H2 +0.00

Pb2+ + 2e-Ý Pb -0.13

Sn2+ + 2e-Ý Sn -0.14

Fe2+ + 2e-Ý Fe -0.44

Zn2+ + 2e-Ý Zn -0.76

Mg2+ + 2e- Ý Mg -2.38

Ca2+ + 2e- Ý Ca -2.87

K+ + e-Ý K -2.92

Table 6.3 The redox series

Interpretation of the redox series

A large positive electrode potential shows that the species on the left hand side of the equation is a good
oxidizing agent. For example, the electrode reaction
F2 + 2e Ý 2F-
has an electrode potential of +2.87V. The large and positive value of Eθ shows that the forward reaction is
very energetically feasible. Thus, a large number of substances are able to convert fluorine to its ions. In
these reactions, F2 is reduced and it therefore acts as an oxidizing agent.
Less positive values of Eθ shows that the species on the left hand side is a weaker oxidizing agent. For
example, the electrode potentials of the halogens become less positive down the group, showing that their
oxidizing power decreases down the group.
A large negative electrode potential shows that the species on the right hand side is a good reducing
agent. This is the case for the groups (I) and (II) metals, for example,
Mg2+ + 2e-Ý Mg, Eθ/V = -2.38
If you read the electrode reaction in reverse, you have the oxidation reaction
Mg Ý Mg2+ + 2e-, Eθ/V = +2.38
The large and positive electrode potential shows that indeed, the oxidation of Mg is very likely. Mg reacts
with a large number of oxidizing agents, to form Mg 2+ compounds. Whilst Mg metal is being oxidized, it
acts as a reducing agent.

Predicting redox reactions using the redox series

Consider the two electrode equations below

Eθ/V
Cl2 + 2e-Ý 2Cl-+1.36
Br2 + 2e-Ý 2Br- + 1.07

Both electrode potentials are positive, showing that the species on the left hand side are good oxidizing
agents. However, the first electrode potential is more positive and the second is more negative. This
means that chlorine is a better oxidizing agent than Br2. It also means that Br- is a better reducing agent
than Cl-. We would therefore expect a reaction to take place if we mixed Cl 2 and Br-ions. Chlorine would
act as an oxidizing agent and Br- would act as a reducing agent. In the reaction, chlorine would be reduced
to Cl- but Br- would be oxidized to Br2.

Eθ/V
Cl2 + 2e-Ý 2Cl-+1.36
2Br- Ý Br2 + 2e-- 1.07

Cl2 + 2Br- Br2 + 2Cl-+0.29

Note that the reduction equation involving bromine has been reversed to show the oxidation of Br-.The
net reaction has a positive Eθcell value, showing that the reaction is feasible. This is an example of a
redoxdisplacement reaction. A halogen higher up in the redox series (higher up in the periodic table) will
displace the one below it from its solution. In the reaction above, chlorine displaces Br2 from Br-(aq). Br-
ions are thus removed from solution, and are replaced by Cl- ions.
Similarly, we would expect Br2 to convert I-(aq) to iodine. Meanwhile, Br2 is reduced to Br-(aq)

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Ex 6.3
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1.A part of the redox series involving transition metals is given below

Use the information in the table to predict if a reaction is possible

Electrode Eθ/V
under standard conditions between the following pairs of substances.
reaction
+0.77 Where a reaction occurs, construct a balanced equation and identify
Fe3+ + e-Ý Fe2+
the oxidizing and reducing agent.
Cu2+ + 2e Ý Cu +0.34
Cu2+ + e-Ý Cu+ +0.15 (a) Cu+ and Cu+(b) CuSO4(aq) and Fe (c) Cu+ and Fe
Fe2+ + 2e-Ý Fe -0.44

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Limitations of electrode potentials
(i) Effect of concentration
Standard electrode potentials refer to standard conditions of 298K, 1atm and 1.0moldm -3
solutions. Any predictions made using these conditions might differ from what is actually observed,
depending on the conditions employed. For example, if a reaction is predicted to be feasible because it has
a positive Eθcell value, in practice the reaction might not take place if very dilute solutions are used.
Consider the reaction between Cr2O72- and Fe2+. The two half equations and the net reaction are shown
below. The Eθcell shows that the reaction is feasible under standard conditions.

Eθ/V
Cr2O72-(aq) + 14H+ (aq) + 6e-Ý 2Cr3+ + 7H2O (l) +1.33
6Fe2+ (aq) Ý 6Fe3+ (aq) + 6e--0.77

Cr2O72-(aq) + 14H+ (aq) + 6Fe2+ (aq) Ý 2Cr3+ + 7H2O (l) + 6Fe3+ (aq) +0.56

Suppose that a very dilute solution of Cr2O72- is used. The decrease in the concentration of Cr2O72- results
in the electrode potential of the first reaction being reduced from +1.33V. Suppose that the new value of
the electrode potential is 1.00V.
The Eθcell for the reaction then becomes 1.00 +(-0.77) = +0.23V
Note that the Ecell is now less positive than +0.56V, which would be the E θcell under standard conditions. A
less positive cell potential implies that the reaction becomes less feasible. In fact, the reaction will not take
place if the dilution reduces the cell potential to a negative value.
Now consider what would happen if the concentration of Fe2+ was reduced from 1.0moldm-3. Reducing
the concentration of Fe2+ would make the electrode potential of the reversed reaction Fe2+ (aq) Ý Fe3+
(aq) + e-more negative than -0.77V, for example, it may become -0.80V. In other words, the oxidation of
Fe2+ to Fe3+ becomes less likely . The cell potential for the reaction between Fe 2+ and Cr2O72- becomes
1.33+ (-0.80) = +0.53V. Once more, the cell potential becomes less positive (that is, more negative) and
the reaction becomes less likely.

In some cases, electrode potentials tell us that a reaction will not take place, but you should remember
that the reaction might in fact take place if non standard conditions are used. Consider the reaction
between MnO2 and chloride ions. The relevant half equations are shown below.

Eθ/V
MnO2+ 4H+ + 2e-Ý Mn2+ + 2H2O +1.23
½ Cl2 + e-Ý Cl- +1.36

If MnO2 is to react with Cl- ions, then the second equation must be reversed to bring the reactants to the
same side.

Eθ/V
MnO2+ 4H+ + 2e-Ý Mn2+ + 2H2O +1.23
2Cl-Ý Cl2 + 2e--1.36

MnO2+ 4H+ + 2Cl-Ý Mn2+ + 2H2O + Cl2 -0.13V

Since the cell potential is negative, we do not expect MnO 2 to oxidize chloride ions under standard
conditions. Now, consider what happens when concentrated HCl is used. The concentration of chloride
ions is then greater than 1.0moldm-3 and this makes the electrode potential of the reaction
2Cl-Ý Cl2 + 2e-
more positive than -1.36V, that is, the reaction becomes more feasible. Suppose that the new electrode
potential changes from -1.36V to -1.30V. Similarly, an increase in the concentration of hydrogen ions
would make the electrode potential of the first reaction more positive than +1.23V, for example, it may
become +1.40V. The cell potential for the reaction between MnO 2 and Cl- then becomes 1.40-1.30
= +0.10V. The positive value shows that under these conditions, MnO 2 converts Cl- ions to chlorine. In
fact, this is the method used to synthesize chlorine in the lab.

(ii) Electrode potentials and reaction rates

One limitation of electrode potentials is that they fail to predict the speed of a redox reaction. Consider the
reaction between peroxodisulphate(S2O82-) ions and iodide ions.
The relevant electrode potentials are given below.

Eθ/V
S2O82-+ 2e–Ý2SO42–+2.01
I2 + 2e–Ý 2I–+0.54

Reversing the second electrode potential and combining the two half equations gives

S2O82-+ I2 Ý2SO42–+ 2I-Eθcell = +1.47 V

The large and positive Eθcellvalue shows that the reaction is energetically feasible. Peroxodisulphate ions
are expected to oxidize iodide ions to iodine. Meanwhile, the peroxodisulphate ions are reduced to
sulphate ions. In practice, this reaction is so slow that for practical considerations we may say it does not
take place at all. The reaction has a very high activation energy due to the fact that the reacting ions have
the same charge, so they naturally repel.
Electrode potentials often predict that a reaction is feasible, but they do not tell us if in practice the
reaction can actually takes place.

6.8 Electrochemical cells

An electrochemical cell is a device that contains chemicals which react through reduction and oxidation to
produce a voltage. This voltage can be used to induce a flow of electrons (current) in the external circuit. A
simple electrochemical cell can easily be set up by connecting two half cells by means of a salt bridge and
an external circuit. A wet cell consists of solid electrodes immersed in a liquid. Fig 6.8 shows a wet cell
made up of a Zn(s)/Zn2+ (aq) half cell and a Cu(s)/Cu2+ half cell. This cell, known as the Danielli Cell, uses
Cu and Zn electrodes.
The relevant reduction potentials are

Eθ/V
Cu2+ (aq) + 2e-Ý Cu(s) +0.34 (i)
Zn2+ (aq) + 2e-Ý Zn(s) -0.76(ii)
Since copper has the more positive electrode potentialwe expect Cu 2+ ions to be reduced to Cu metal.
Reaction (i) is therefore the reduction half equation. Reversing reaction(ii) gives us the oxidation half
equation
Zn(s) Ý Zn2+ (aq) + 2e +0.76V

 Zinc is therefore the one which loses electrons, that is, it undergoes oxidation.

The metal with the more negative reduction potential (before reversing) undergoes oxidation.
This is because after reversing the equation, the oxidation reaction becomes more positive, that
is, more feasible.

 Zinc is therefore the source of electrons in this cell. The electrons travel in the external circuit in
the direction shown by the arrows in Fig 6.8.The electrons are conducted into the Cu2+ solution,
leading to reduction of the Cu2+ ions to copper atoms.

Cu2+ (aq) + 2e-Ý Cu(s) Eθ/V = +0.34.

 The zinc electrode thus dissolves as it releases Zn2+ ions into solution. Meanwhile, the copper
electrode gains mass as atoms of copper formed from Cu 2+ stick on it.The overall cell reaction
and the cell potential can be worked out.
E /V
θ

reduction half equation Cu2+ (aq) + 2e-Ý Cu(s) +0.34 (i)

oxidation half equation Zn(s) Ý Zn2+ (aq) + 2e-+0.76(ii)

Cu2+ (aq) + Zn(s)  Cu(s) + Zn2+ (aq) +1.10 (iii)

Fig 6.8 A Danielli cell

 The net equation (iii) shows the reduction of Cu2+ to Cu metal by zinc. Meanwhile, the zinc
metal dissolves as it is oxidized to Zn2+. The cell potential of the electrochemical cell is +1.1oV.
 This voltage pushes electrons into the external circuit. This flow of electrons (from Zn to Cu),
known as a currentcan be put to use, for example, to light an electric lamp.

 All electrochemical cells work using the same principle. There are two half cells. In one half cell,
an electrode undergoes oxidation and in the process provides electrons, which flow to the other
half cell. In the other half cell, the electrons from the oxidized electrode cause a reduction
reaction to take place. A net redox reaction occurs, involving a reducing agent and an oxidizing
agent. In the Cu/Zn cell above, the reducing agent is Zn metal and the oxidizing agent is Cu 2+.

Electrochemical cells and the reactivity series

You probably recall that a metal higher up in the reactivity series has a large and negative reduction
potential. Such a metal is easily oxidized, that is, it is a good reducing agent. It will easily reduce the ions
of a metal lower than it in the electrochemical series. If you study reaction (iii) you will notice that Zinc,
which is higher than Cu in the electrochemical series, reduces Cu 2+ ions to Cu metal. This is an example of
a redox displacement reaction. Cu2+ ions are displaced from solution (as cu metal) by Zn. At the end of
the reaction, Zn2+ ions have taken the place of Cu2+ ions in solution.
The reader should realize that such a redox displacement reaction can easily be carried out in the lab
without setting up an electrochemical cell. For example, when a Zn rod is dipped into a solution of CuSO 4,
a reaction occurs between zinc metal and Cu2+ions. The following observations are made:
 the zinc rod dissolves and is soon coated pink
 the blue colour of CuSO4 fades

Zinc metal reduces Cu2+ ions to copper atoms, which stick onto the Zn rod, forming a pink coat. Mean-
while, Zn metal is oxidized to Zn2+. There is a transfer of electrons from the zinc metal to the Cu 2+ ions. In
an electrochemical cell, the reducing agent (Zn) is separated from the oxidizing agent (Cu2+) by half cells.
This allows electrons from the reducing agent to flow in an external circuit to the oxidizing agent. These
electrons can be employed to do useful work, for example, lighting a bulb, before they reach the oxidizing
agent.

Predict if a redox displacement is possible when the following substances are

Q
mixed.Where a reaction occurs

(i) Construct a balanced equation

(ii)Calculate the Eθcell
(iii)State the oxidizing agent and the reducing agent.

(a) Cu2+(aq) and Mg(s)

(b) Cu2+(aq) and Ag(s)
(c) Zn2+(aq) and Mg(s)

A A metal higher up in the electrochemical series will displace the ions of a metal which is
lower from its solution.

(a)Mg, being higher than copper in the electrochemical series, will displace Cu 2+ ions
 from solution. In other words, Mg is more reactive than Cu, and Mg2+ ions are more
stable than Mg metal, so the conversion Mg Mg2+ is favourable. On the other hand,
Cu metal is more stable than Cu2+. In the presence of Mg metal, Cu2+ ions are
converted (reduced) to Cu metal.

Cu2+ (aq)+ Mg(s)  Cu2+(s) + Mg2+ (aq) Eθcell =+1.10V

The positive value of the cell potential shows that the reaction is energetically feasible
under standard conditions.

Questions (b) and (c) are left as an exercise to the reader.

Anode and cathode in an electrochemical cell

In Fig 6.8, zinc metal undergoes oxidation, so it becomes the source of electrons. Copper metal, being less
willing to release electrons, becomes relatively positively charged. Electrons therefore flow from the zinc
electrode to the relatively positive copper electrode. Which then is the anode and cathode in this
electrochemical cell? There is a strong temptation to say that zinc is the cathode (since it is relatively
negatively charged compared with Cu) and Cu is the anode. This is incorrect.
Zinc is the anode and copper is the cathode. The confusion for some students comes from the way they
define the terms ‘cathode’ and ‘anode’. It is frequently taught in juniour chemistry that an anode is
positively charged and a cathode is negatively charged. Although this definition appears to work well in
juniour chemistry, it presents students with unnecessary difficulties at ‘A’ level. Here is the proper
definition of the terms ‘cathode’ and ‘anode’.

An anode is an electrode where oxidation takes place. In electrochemical cells, the anode
is the negative electrode.

A cathode is an electrode where reduction takes place. In an electrochemical cell, the

cathode is the positive electrode.

In an electrochemical cell, the metal with the more negative reduction potential (as taken from the Data
Booklet) undergoes oxidation. It is the anode. The electrode with the more positive reduction potential
provides a surface where reduction takes place. It is the cathode.

More about the salt bridge

It was mentioned in an earlier discussion that the salt bridge has two functions; completing the circuit
between two half cells and maintaining electroneutrality (preventing a build up of charges which would
cause the electrochemical cell to stop working).
The salt bridge contains an aqueous solution of a salt, for example, KNO 3. Consider what happens when
the Zn/Cu cell (Fig 6.8) is working. At the anode, Zinc metal dissolves, increasing the concentration of
Zn2+ ions in solution. A build up of positive ions will eventually prevent the zinc from dissolving any fur-
ther. That means the zinc stops supplying electrons, and the cell stops working. The salt bridge supplies
negative ions (NO3-) to neutralize the excess positive charge from Zn2+ ions. NO3- ions therefore move
from the salt bridge to the Zn2+ solution. At the cathode, Cu2+ ions are removed from solution as they form
copper metal. Removal of positive charges makes the solution relatively negatively charged due to the
presence of an excess of SO42- ions. The build up of negative charge reduces the tendency of electrons,
which are also negatively charged, to enter the solution in this half cell. This stops the reduction reaction
at the cathode. The salt bridge provides positive ions (K +) that counter the excess negative charge. K+ ions
and NO3- ions therefore move in opposite directions in the salt bridge, and this movement transports
electric charge, thus completing the circuit between the two half cells.

The shorthand notation for describing electrochemical cells

The Danielli cell is made up of two half cells. The Zn/Zn2+ and the Cu/Cu2+ half cells.
The full cell can be shown using a shorthand notation.

Zn(s) ⃒ Zn2+(aq) ⃒⃒ Cu2+(aq) ⃒ Cu(s)

 The electrodes, in this case Zn and Cu, are written on the far right and far left of the notation.
 A single vertical line (⃒ ) represents the junction between an electrode and its ions.
 Double lines, broken or full, ( ⃒⃒ ) represent the salt bridge.
 The electrode with the more negative electrode potential, that is, the anode, is written at the left
hand - side cell. The one with the more positive electrode potential (cathode) is shown on the
right hand side.

Consider the electrochemical cell whose cell notation is

Al(s) ⃒ Al3+(aq) ⃒⃒ Pb2+(aq) ⃒ Pb(s)

The anode is Al whilst the cathode is Pb. The electrode on the left loses and supplies electrons in the
external circuit, that is, it is oxidized

Al(s)  Al3+(aq) + 3e- Eθ = +1.66V ...(i)

(after reversing the reduction potential)

Reduction occurs at the cathode

Pb2+(aq) + 2e  Pb(s) Eθ = -0.13V...(ii)

Multiplying (i) by 2 and equation (ii) by 3 to balance the electrons, and then adding the two equations
together gives the net reaction

2Al(s) + 3Pb2+(aq)  2Al3+(aq) + 3Pb(s) ...(iii)

For this reaction, Eθcell = +1.66 +(-0.13) = +1.53V

The relationship Eθcell = EθR - EθL

The cell potential of an electrochemical cell can be obtained by using the formula
Eθcell = EθR - EθL,
where EθRis thereduction potential of the right hand side cell and EθL is the reduction potential of the left
hand side cell.For example, the cell potential for reaction (iii) above is -0.13 -(-1.66) = +1.53
This is a useful relationship, but it may cause unnecessary difficulties if the following points are over-
looked.
  This relationship is only valid in assessing feasibility of the reaction if the anode (more negative
reduction potential, as given inthe Data Booklet) is on the left hand side and the cathode is on the
right hand side. This is the case with the cell

Al(s) ⃒ Al3+(aq) ⃒⃒ Pb2+(aq) ⃒ Pb(s)

 When using this formula, both reduction potentials are taken as they are in the Data Booklet, that
is, no reduction potential should be reversed. For the cell above, the reduction potential for the
left cell (Al/Al3+)is -1.66V and that of the right cell (Pb/Pb2+) is -0.34.
 This relationship is often used to predict the direction of electron flow, not necessarily feasibility.
Consider the following problem from a past paper

Chlorine gas and iron (II) ions react together in aqueous solution as follows.

Cl2 + 2Fe2+ 2Cl– + 2Fe3+

The following diagram shows the apparatus needed to measure the E cell for the above
reaction.

Use the Data Booklet to calculate the Eθcell for this reaction, and hence decide which
direction (left to right, or right to left) electrons would flow through the voltmeter V
when switch S is closed.
[UCLES 9701/J2008 paper 4 .q1]

The relevant reduction potentials from the Data Booklet are

Eθ/V
 Cl2 + 2e-Ý 2Cl-+1.36
Fe3+ + e-Ý Fe2++0.77

If we use the convention ‘left cell is the more negative and right cell is the more positive’, then

Eθcell = EθR - EθL = 1.36 - 0.77 = +o.59V

Whilst this value indicates that the reaction is feasible, this is not the answer examiners expected. The
question clearly required students to interpret the diagram as drawn, that is, the left cell is Cl2/Cl-(more
positive) and the right one is Pt/Fe2+, Fe3+.

The Eθcell is therefore 0.77-1.36 = -0.59V.

The negative cell potential in this case does not mean the reaction is not feasible. It is simply a result of
which cell is on the right and which one is on the left. The first value (+0.59V) indicates that the reaction
is feasible and that electrons flow from the anode (oxidation) to the cathode (reduction). The negative
value -0.59V indicates that the convention ‘left cell is the more negative and right cell is the more
positive’ has not been used since in the diagram the anode (more negative) is the right cell. Electrons
therefore flow from the right to the left.

Do not forget
 that the anode has the more negative(less positive) cell potential. Oxidation takes placehere, re-
leasing electrons.
 Consequently, electrons will always flow from the anode to the cathode. The actualdirection in
which electrons flow in an electrochemical cell depends on which side , right or left, the anode is.

An electrochemical cell can be set up in which the overall reaction is

Q
Mg(s) + Cl2 (g)  Mg2+ (aq) + 2Cl-(aq) ... (I)

(a) By means of a Data Booklet, write down two equations that can be used to construct
equation (I).

(b) Hence
(i) Construct a fully labelled diagram of the electrochemical cell represented by
equation (I)
(ii) Show the short-hand notation of the cell and calculate the cell potential of
equation (I)

A(a) Eθ/V
Cl2(g) + 2e-Ý 2Cl-(aq)+1.36
Mg2+ + 2e-Ý Mg(s)-2.38

(b)(i) One half cell (oxidation) should contain magnesium metal dipped in an aqueous
solution of Mg2+(for example, MgSO4(aq) ). The other half cell (reduction) should have
 chlorine gas passing over a platinum electrode in a solution containing Cl - ions. The
two half cells are connected by an external circuit and a salt bridge.

(ii) Mg(s) ⃒ Mg2+ (aq) ‖ Cl-(aq), Cl2(g)⃒ Pt(s)

Eθcell = EθR - EθL = 1.36 -(-2.38) = +3.74V

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1.Construct a fully labelled diagram for the electrochemical cell represented by the short-hand
notation

Mg(s) ⃒ Mg2+(aq) ⃒⃒ Ag+(aq) ⃒Ag(s)

(a) Indicate by means of arrows on the diagram the direction of electron flow.
(b) Construct a net equation for the cell reaction and by means of a Data Booklet calculate the
cell potential

2. An electrochemical cell is set up to determine the voltage of an electrochemical cell that involves
chlorine gas and magnesium metal (Fig 6.4.1 ).

(a) Labell the diagram as completely as possible.

(b) Show the short-hand notation for this cell.
(b) Construct a net equation for the cell reaction and calculate the
cell potential

Fig 6.4.1

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6.8.1 Practical electrochemical cells
text box.]
The Danielli cell is quite useful in demonstrating the principles behind an electrochemical cell. Its major
disadvantage is its cumbersome nature which limits its portability.
Commercial electrochemical cells, known as batteries, have been designed to be a convenient source of
energy. These include the dry cell, the lead-acid battery and the fuel cell.

1 The dry cell

The most common dry cell is the Zinc-Carbon cell. The cell is said to be dry because it does not contain
liquids. Fig 6.9 shows a typical dry cell.

Fig 6.9 A Zinc - Carbon

dry cell

At the anode, oxidation of zinc metal takes place

Zn(s)  Zn2+ (aq) + 2e-Eθ/V = +0.76V... (i)

At the cathode, NH4+ions are reduced to ammonia and hydrogen.

NH4+ (aq) + 2e- 2NH3 (aq) + H2 (g) Eθ/V = +0.74... (ii)
The net reaction is therefore
Zn(s) + NH4+ (aq)  Zn2+ (aq) + 2NH3 (aq) + H2 (g) Eθcell = 1.50V

 Zn acts as a reducing agent. It reduces NH4+ ions to NH3.

 NH4+ has a nitrogen atom in a high oxidation state (+4). NH 4+ can therefore act as an oxidizing
agent. In this reaction it oxidizes Zn metal to Zn2+.
 As the cell works, the zinc casing becomes thinner as zinc metal is dissolved to Zn2+. This explains
why dry cells may eventually start to leak.
 Reaction (ii) produces hydrogenwhich prevents further conversion of NH4+ ions to NH3 (Le
Chatelier’s principle). This inhibition of reaction (ii) causes the dry cell to stop working (the cell
is said to be polarized). To prevent this polarization, MnO2 is included in the cell. It oxidizes the
hydrogen to water. This explains why dry cells often ooze a liquid after they have been working for
a long time.
 The dry cell produces a maximum voltage of 1.5V. Dry cells can be combined to give batteries with
the desired size of voltage, for example, connecting 3 cells in series gives a maximum voltage of
4.5V. Dry cells are not rechargeable. This is because reaction (ii) can not be reversed, since
hydrogen is lost from this reaction as water. The cells soon stop working, that is, they become flat.
 Dry cells find widespread use because they are light and compact. They are used, for example, in
transistor radios and torches.

Effect of size of the dry cell

Size of a dry cell does not affect the voltage out put, provided the chemical composition is the same. This
is because the reactions involved are the same, and these reactions take place under the same conditions.
However, smaller cells contain a smaller mass of reactants, so they become flat more quickly.

2. The lead-acid battery

This is a well known example of asecondary (rechargeable)battery. The anode (negative electrode) is a
plate of lead metal and the cathode is lead (IV) oxide, PbO2,present as a coat on a lead metal plate. Both
the anode and the cathode are immersed in an electrolyte of moderately concentrated sulphuric acid (Fig
6.10)

During discharge
At the cathode (positive terminal) PbO2 is reduced to Pb2+ by electrodes coming from the anode. The Pb2+
ions immediately combine with SO42- ions from H2SO4 to from white and insoluble PbSO4.
At the anode (negative terminal), the lead plates are oxidized to Pb2+. Once more, the Pb2+ ions combine
with SO42- ions to form PbSO4. The two half equations are shown below

Eθ/V
cathode reduction half reaction PbO2(s) + 4H+ + 2e-Ý Pb2+ + 2H2O +1.87 ...(i)
anode oxidation half reaction Pb(s) Ý Pb2+ + 2e +0.13 ...(ii)

PbO2(s) + 4H+ + Pb(s) Ý2Pb2+ + 2H2O +2.00... (iii)

Note that the reduction potential for equation (i) is more positive than the one quoted in the Data Booklet
(+1.47V). This is because the acid (H+) used in the battery is fairly concentrated and this drives the
equilibrium to the right, that is, the reaction becomes more favourable in the forward direction.

 Under standard conditions, one cell in the lead-acid battery would produce a voltage of +1.34V. In
practice, each cell produces a maximum of 2V. This is because the conditions used are not
standard. Fairly concentrated sulphuric acid is used, and this makes the reduction potential for
reaction (i) more positive than +1.47V.

 In practice, the lead-acid battery usually contains six cells, each producing a maximum voltage of
2.00V. The maximum voltage that the battery can produce is therefore 12.00V.

 The net cell reaction (reaction (iii)) shows PbO 2 acting as an oxidizing agent and Pb metal as a
reducing agent. This reaction is expected, and does not take place only in the lead-acid battery. It
can be carried out in the lab by mixing PbO 2, Pb and H2SO4. Compounds of lead are more stable
in their +2 oxidation states. Lead (IV) compounds are unstable relative to the +2 state. Thus PbO 2
is easily reduced to Pb2+. Meanwhile, it acts as an oxidizing agent. In this case, it oxidizes Pb
(which, like most metals,is a reducing agent) to Pb2+. The Pb2+ ions immediately combine with
sulphate ions from H2SO4 to form a white precipitate of PbSO4.
 Fig 6.10 The lead - acid accumulator (‘car’ battery)

During charging
The major advantage of the lead-acid battery is that it can be recharged. This is done by passing an
electric current from an external source into the battery. In vehicles, the charging process is automated.
As the engine runs, it drives a dynamo or alternator, which in turn generates an electric current. This
current is then passed into the battery. The flow of electrons in to the battery essentially reverses the
anode and cathode half reactions. Half of the Pb 2+ produced in reaction (iii)are reduced to Pb metal,
which is deposited on the negative (anode) lead metal plate. The rest of the Pb 2+ are oxidized to PbO2(s)
which forms a deposit on the positive (cathode) lead metal plate.

Eθ/V
Pb2+ + 2e Ý Pb(s) -0.13
Pb2+ + 2H2O Ý PbO2(s) + 4H+ + 2e--1.87

These reactions have negative potentials and so will not take place under normal conditions. The
processes are actually driven by electrical energy from an external source.
 The lead-acid battery: key facts at a Charging
glance Pb2+ is converted to PbO2 (cathode) and to Pb
metal (anode)
Anode (negative terminal): Zinc plate
Cathode (positive terminal): PbO2(s) Cell Notation
coated on lead plates Pb(s)⃒ Pb2+(aq) ⃒⃒ Pb2+(aq) ⃒PbO2(s)
Electrolyte: H2SO4
The anode and cathode are shown in bold.
Discharge reaction:
Cathode reaction (reduction) : PbO2 reduced Advantage: rechargeable.
to Pb2+
Anode reaction (oxidation) : Pb oxidized to Disadvantages :
Pb2+ (i) Heavy due to the presence of lead
Cell potential: +2.00V. Total for 6 cells and sulphuric acid.
= 12.00V (ii) Needs careful disposal because lead
compounds are poisonous.

3. The fuel cell

A fuel cell generates electrical energy from the net redox reaction between oxygen and hydrogen
gases

2H₂ (g) + O₂ (g) → 2H₂O (l) Eθ = +1.23V... (i)

The hydrogen and oxygen gases are fed into the cell through different outlets from an external source (Fig
6.11).In this reaction, hydrogen is used as a fuel. Notice that this reaction is comparable to the exothermic
combustion of hydrogen in oxygen. The key fact is that in an electrochemical cell, the aim is not to
produce heat energy but electrical energy.

Use of an electrolyte
An alkalior an acid can be used as an electrolyte. Fig 6.11 shows an alkaline fuel cell.

graphite

graphite

Fig 6.11 An alkaline hydrogen fuel cell

The half equations
Equation (i), like all redox reactions, can be resolved into a reduction half equation and an oxidation half
equation. At the anode, catalytic oxidation of hydrogen gas occurs to produce H + ions.
H₂ (g) ⇌ 2H⁺ + 2e⁻(ii)
The anode (negative electrode) is made of porous graphite which is coated with a catalyst of nickel and
nickel (II) oxide. The graphite electrode provides an inert surface on which hydrogen is oxidized,
catalyzed by nickel and nickel (II) oxide.
Apart from acting as an electrolyte, the alkali supplies OH⁻ ions which remove the H⁺ ions produced in
reaction (ii).
2OH⁻ (aq) + 2H⁺ (aq) → 2H₂O ... (iii)
This speeds up the anode reaction by pushing equilibrium(ii) to the right, that is, more hydrogen gas
molecules are oxidized to replace the OH⁻ ions that are lost from the equilibrium as water (Le Chatelier’s
principle).
By combining equations (ii) and (iii) we obtain the half equation for the oxidation of hydrogen gas at the
anode in the presence of an alkali (OH⁻ ions). Note that this oxidation half equation actually involves two
types of reactions.

H₂ (g) ⇌ 2H⁺ + 2e⁻ ... (ii) [oxidation]

2OH⁻(aq) + 2H⁺ (aq) → H₂O ... (iii) [neutralization]

Anode half equation: H₂ (g) + 2OH⁻ (aq)→ 2H₂O (l) + 2eEθ = +0.83V ... (iv)

Note that the oxidation of hydrogen gas in the absence of OH⁻ ions (reaction ii) would give an Eθ value of
zero. The presence of OH⁻ ions therefore makes the Eθ value more positive, and the oxidation half
reaction more feasible.
The anode reaction produces electrons which then travel in the external circuit towards the cathode. This
flow of electrons can be used to operate a device (the load).

The reduction half equation (cathode)

An O atom is reduced by gaining two electrons which come from the anode via an external circuit.
O + 2e → O2⁻
Since there are two oxygen atoms in a molecule of oxygen, a total of four electrons would be gained per
molecule of oxygen
O₂+ 4e⁻⇌ 2O2⁻ ... (v)
The oxide ions are too unstable to have an independentexistence. They rapidly react with water, to
produce OH⁻ ions. This reaction can be understood in this way: the negatively charged oxide ion (a strong
base) is attracted to a relatively positively charged hydrogen atom in water (water behaves as an acid). It
then extracts this hydrogen atom, resulting in the formation of two OH⁻ions.

O2⁻ + H₂O → 2OH⁻ ... (vi)

δ-
δ+
δ+ 2OH-
By combining equations (v) and (vi), we obtain the reduction (cathode)half equation.

O₂ + 4e⁻⇌ 2O2⁻
2O2⁻ + 2H₂O Ý4OH⁻

Reduction half equation: O₂ (g) + 4e⁻ + 2H₂O (l) → 4OH⁻ (aq) Eθ = +0.40V ... (vii)

The cathode is porous graphite coated with nickel which catalyzes the reduction of oxygen.
The OH⁻ ions generated at the cathode continuously diffuse through the cell to the anode, where they aid
the oxidation of hydrogen .

We now combine equation (iv) (anode half reaction) and equation (vii) (cathode half reaction) to obtain
the cell reaction that takes place in the fuel cell (Equation (iv) is multiplied by 2 to balance the number of
electrons).

Eθ/V
anode 2H₂ (g) + 4OH⁻ (aq) Ý4H₂O (l) + 4e +0.83 ... (iv)
cathode O₂ (g) + 4e⁻ + 2H₂O (l) Ý4OH⁻ (aq)+0.40 ... (vii)

Net: 2H₂ (g) + O₂ (g) Ý2H₂O (l) +1.23

Notice that the same amount of OH- ions that are used at the negative electrode are produced at the
positive electrode. The concentration of electrolyte is therefore expected to remain constant. However,
concentration of NaOH is reduced due to the formation of water. To reduce the dilution problem, water is
drained out of the cell as soon as it is formed.

Use of an acid electrolyte

It is possible to use an acid as an electrolyte. At the anode, hydrogen is oxidized

H₂ (g) ⇌ 2H⁺ (aq) + 2e⁻ ... Eθ/V = +0. 00V ... (viii)
At the cathode, oxygen is reduced
O₂ (g) + 4H⁺ (g) +4e⁻⇌ 2H2O (l) Eθ/V = +1.23V ... (ix)
Notice that in acidic solution we have selected those half equations which involve hydrogen ions.Similarly,
for an alkaline electrolyte, we used those half equations which involve hydroxyl ions. Combining
equations (viii) and (ix), we obtain the overall equation for the fuel cell

Eθ/V
2H₂ (g) ⇌4H⁺ (aq) + 4e⁻0. 00V
O₂ (g) + 4H⁺ (g) +4e⁻⇌ 2H₂O (l) +1.23V

Net equation: 2H₂ (g) + O₂ (g) →2H₂O (l) +1.23V

We obtain the same equation as before. The Eθ cell is not changed by changing the electrolyte. Overally,
hydrogen ions consumed at the cathode are generated at the anode. Concentration of electrolyte therefore
remains constant. In view of this, it is safe to assume that alkali or acid acts as a catalyst. It speeds up the
reaction between oxygen and hydrogen, it is regenerated at the end of the reaction, it does not change
nature of the product, and it does not change the Eθcell of the reaction.

Question and answer section : The fuel cell

Q. Why is a fuel cell known by this name?

A. The overall reaction in the fuel cell is 2H₂ (g) + O₂ (g) →2H₂O. From this reaction, hydrogen acts like a fuel
because it is oxidized by oxygen to produce (electrical) energy.

Q. A fuel cell may use NaOH or KOH solutions as the electrolyte. What is the advantage of KOH over NaOH?

A.In both cases, there is a carbonate problem in which OH⁻ ions neutralize acidic CO₂from the atmosphere to
form a carbonate.
OH⁻ (aq) + CO₂ (g) → H⁺ (aq) + CO₃2-(aq)

This results in the precipitation of carbonates, for example, Na2CO3 if NaOH is used. These carbonates may
poison the nickel catalyst and clog the cell. KOH is preferred as the electrolyte because potassium carbonate has
a better solubility than sodium carbonate.

Q.The voltage obtained by using an acid and an alkaline electrolyte is the same. Why then is an alkali preferred as
the electrolyte?

A. An alkaline electrolyte has more advantages than an acid catalyst.

 It allows for a wide choice of catalysts.

 Alkaline systems work well at room temperature.
 The cell and electrodes can be built from low cost carbon and plastics.

Q. What are the possible advantages and disadvantages of the hydrogen fuel cell?

A. The advantages include

 It can supply a continuous current, which is suitable in devices which require a steady and reliable source
of current, for example, in a spaceship.
 It is one of the greenest sources of energy to be developed. There is no pollution associated with it, since
the sole product of the reaction is water.

The main disadvantages include

 The development of a fuel cell is rather expensive. This has limited the widespread use of fuel cells.
 The storage of hydrogen still presents a problem because of its explosive nature. Effective methods of
storing hydrogen before it is fed into the fuel cell have been found, but more research is still needed to
improve them and make their use widespread.
 The fuel cell is large and cumbersome. Once more, this prevents it from being a versatile source of
electrical energy.
 The source of hydrogen gas is still a challenge since it is not found in air. Producing hydrogen by the
electrolysis of water is not a solution to the energy problem since the process consumes huge quantities of
electrical energy. A method has been developed for producing hydrogen gas from methane, but the
demands of the process makes its application limited.
6.9 Electrolysis

Electrolysis is a process whereby an electric current is used to decompose a compound into one or more
elements. An electrolytic cell is essentially the reverse of an electrochemical cell, as illustrated in Table
6.4.Electrolytic cells differ in design and complexity, but they have the same basic components.

 An external source of current, for example a battery

 Electrodes. These provide surfaces on which reduction and oxidation reactions take place. The
positive electrode, connected to the positive terminal of the power source, is known as the
anode.This is where oxidation takes place, just as in electrochemical cells.The negative electrode
is connected to the negative terminal of the power source and is known as the cathode.This is
where reduction takes place. The anode is so named because it attracts anions (negative ions).
Similarly, the cathode attracts cations (positive ions).
 Anelectrolyte. This is a liquid conductor which allows current to flow between the anode and
the cathode.

Electrolytic cell Electrochemical cell

Takes in electric current from an external Produces a current in an external circuit

source

Current from an external source drives Chemical reactions in the cell produce an
chemical reactions in the cell electric current.

The anode is the positive electrode and The anode is the negative electrode and the
the cathode is the negative electrode cathode is the positive electrode

Table 6.4 Comparison of electrolytic and electrochemical cell

6.9.1 Electrolysis of water

Fig 6.12 shows a simple set up for the electrolysis of water. During this process, water is decomposed into
its elements, that is H2 and O2.

 The water is acidified with a little sulphuric acid to improve its conductivity. It is also possible to
improve conductivity of water by adding a salt such as sodium sulphate.
 A suitable indicator, for example, litmus, can be added to the water to demonstrate the changes in
pH that take place at each electrode during the electrolysis. However, for the indicator to give
reliable results, an acid or alkali should not be added to the water. Instead, a salt such as sodium
sulphate can be added to improve the conductivity of water. The advantage of sodium sulphate is
that it has no ions which can be discharged during the electrolysis process.
 Any suitable material, for example graphite, can be used as the anode and the cathode. This
material must be chemically inert and it must be a good conductor of electricity.

At the anode
Water is oxidized to oxygen. Therelevant equation for the oxidation of acidified water can be extracted
from the Data Booklet.
2H2O  O2 + 4H++ 4e-Eθ cell = -1.23... (i)
Here we have selected an equation involving H + ions, since the water has been acidified. The hydrogen
ions produced at the anode are attracted to the negatively charged cathode.

At the cathode
H+ ions are reduced to hydrogen gas.
2H+ + 2e- H2Eθ cell = 0.00V... (ii)
The net equation for the electrolysis of water is obtained by combining equations (i) and (ii).

Eθ/V
2H2O  O2 + 4H+ + 4e--1.23V... (i)
4H+ + 4e- 2H20.00V... (ii)

2H2O  O2 (g) + 2H2 (g) -1.23... (iii)

The negative value indicates that the reaction is not

likely to take place spontaneously. It is not energeti-
cally feasible, and energy must be supplied to drive it.
In this case, the reaction is driven by electrical energy
from an external source.
It is also possible to carry out the electrolysis in an
alkaline environment. Once more, the role of the alkali
is to improve the conductivity of water. The relevant
half equations for an alkaline environment are
Cathode (reduction): 4H2O + 4e−  H2 + 4OH-
Anode (oxidation):4OH-  O2+ 2 H2O+ 4e-
At the cathode, electrons from an external source
reduce water to form OH- ions which then drift to the
anode where they are oxidized. The net equation is
obtained by adding the two equations together and
subtracting 2H2O from both sides

Fig 6.12 Apparatus used to demonstrate

the electrolysis of water

Cathode (reduction) 4H2O + 4e−  2H2 + 4OH-

Anode (oxidation) 4OH-  O2+ 2 H2O+ 4e-

2H2O  O2 + 2H2

Explain why during the electrolysis of water, hydrogen and oxygen are produced in the
Q of 2: 1
ratio

The formula of water shows that each molecule contains two hydrogen atoms and one oxygen
A
 atom. Consequently, hydrogen and oxygen are produced in the ratio of 2:1 when water undergoes
electrolysis.

The electrolysis of aqueous sodium sulphate is essentially the electrolysis of pure water. The role of the
sodium sulphate is simply to improve the conductivity of water. The ions in sodium sulphate are not
discharged. Since the solution is neutral, the electrode reactions involve OH - and H+ ions from the auto-
dissociation of water.
H2O Ý 2H+ + OH-
The H+ ions are attracted to the cathode whey they are reduced to hydrogen.
2H+ + 2e- H2 ... (iii)

The removal of H+ ions from the solution around the cathode results in an accumulation of OH - ions. If
red litmus indicator had been added to the water, it will change to blue, showing that pH around
thecathode increases.
At the anode, OH- ions are oxidized.
4OH– O2 + 2H2O + 4e-... (iv)
The removal of OH- around the anode increases concentration of H + ions, so if litmus indicator had been
added to the solution, it would turn red around the anode.
The net equation for the electrolysis of sodium sulphate solution is obtained by combining equations (iii)
and (iv)(after balancing number of electreons)
4H+ + 4OH–  2H2 + O2 + 2H2O
The left hand side of the reaction involves 4OH- and 4H+ ions, which is essentially 4H2O, so the reaction
can be rewritten as
4H2O 2H2 + O2 + 2H2O
and subtracting 2H2O from both sides gives
2H2O 2H2 + O2
The same net equation is obtained, irrespective of which electrolyte is used.

The industrial importance of the electrolysis of water

Electrolysis of water is a method that is used in many countries to produce hydrogen and oxygen gases.
The importance of the process comes from the fact that hydrogen can not be obtained from the fractional
distillation of air (there is very little hydrogen in the atmosphere).
The uses of oxygen include
 In hospitals for patience in ICU(Intensive Care Unit)
 Mixed with acetylene (ethyne) for use in oxyacetylene torches. These are very hot flames used for
welding.
 Used in hospitals to destroy bacteria that cause gangrene. These bacteria thrive in anoxic (oxygen
deficient) environments and are killed by oxygen.
 Rockets use liquid oxygen to burn fuel and generate lift.

The uses of hydrogen include

 in the manufacture of ammonia by the Haber-process.
 In the manufacture of margarine.
  In the manufacture of hydrochloric acid.
 In the reduction of some metal ores.

Many countries are considering finding other sources of hydrogen. This is because the electrolysis of
water on an industrial scale consumes large quantities of electricity, which makes the process expensive.
In some countries, hydrogen is now being obtained from methane.

6.9.2 Electrolysis of aqueous salt solutions

The products of the electrolysis of a salt solution depend on
 the concentration of the solution
 the electrode potential of the ions involved

Consider the electrolysis of NaCl (aq). The ions present in the solution are shown in Table 6.5.
The cations (H+ and Na+) are attracted to the cathode. The large and negative value of the electrode
potential for Na shows that it can not be discharged in water. In other words, Na metal is so reactive that
if it were to be produced in water, it would instantly react with water to form NaOH. So at the cathode,
hydrogen is preferentially discharged.
2H+ + e-Ý H2
If the electrode potential of a metal is negative, the metal can not be formed from its ions in aqueous
solution by electrolysis

Cations Electrode Potentials/V Anions Electrode Potentials/V

Na+ Na+ + e-Ý Na-2.71 Cl- Cl2 + 2e-Ý 2Cl-(aq)+1.36

Table H+ OH-
2H+ + 2e-Ý H2-0.00 O2 + 2H2O + 4e-Ý4OH-+0.40
6.5

NB: OH- and H+ ions come from the auto-dissociation of water.

The anions (Cl- and OH-) are attracted to the anode. The discharge (oxidation) reactions for these ions are
the reverse of the reduction potentials given in the Data Booklet.

Eθ/V
2Cl-(aq) Cl2 + 2e--1.36 ... (i)
4OH-O2 + 2H2O + 4e--0.40 ... (ii)

Both processes have negative electrode potentials, showing that they are not likely to take place, unless if
energy is supplied, for example, in the form of an electric current. However, the electrode potential for the
second reaction is more positive, so we would expect O2 to be discharged in preference to Cl2. This is what
actually happens if the NaCl solution is dilute. However, if a concentrated solution of NaCl is used, chlo-
rine will be discharged instead of oxygen. Increasing the concentration of Cl - ions makes the electrode
potential of reaction (i) more positive than -1.36V. At a certain concentration of Cl - ions, the electrode
potential becomes more positive than the one for the discharge of O2. In that case, chlorine will be
discharged in preference to O2.
In the electrolysis of a dilute solution of NaCl, oxygen is discharged at the anode in preference to
chlorine. This is expected from a comparison of the relevant electrode potentials. However, when the
solution is concentrated, the deviation from standard conditions implies that chlorine can be discharged
instead of oxygen. Note that to easily understand the discharge of anions, you need to read their
reduction potentials in reverse.

The production of chlorine by the electrolysis of

concentrated aqueous NaCl (Brine)

Fig 6.13 shows the electrolytic cell for the manufacture of chlorine by the electrolysis of brine.
At the cathode, hydrogen gas is produced due to the reduction of H + ions from water. The anode attracts
OH- and Cl- ions, but in this case, it is Cl- ions that are discharged, as already explained.

 This method of producing Chlorine is known as the Chlor-alkali process, because itproduces chlo-
rine as well as an alkali. The other product is hydrogen.
 The cell used is known as the diaphragm cell because it makes use of a porous diaphragm to
separate the anode compartment from the cathode compartment. This is important in ensuring
that chlorine produced at the anode does not mix with NaOH which accumulates in the cathode
compartment.

Fig 6.13 Diaphragm cell for the electrolysis of brine

 At the anode, Cl- ions are discharged in preference to OH- ions.

2Cl-  Cl2 + 2e-
This leaves behind OH- ions, which then drift through the diaphragm to the cathode
compartment. The diaphragm is made up of a porous substance to ensure that solution rich in
NaOH can pass through it.
  The level of liquid is higher in the anode compartment, ensuring that solution can only flow in
one direction, that is, from anode to cathode. This ensures thatNaOH in the cathode compart-
ment does not mix with chlorine produced at the anode.
 At the cathode, H+ ions are discharged in preference to Na+ ions. Na+ ions therefore accumulate in
the cathode compartment and they attract OH - ions from the anode compartment. The solution in
the cathode compartment therefore gradually becomes richer in NaOH. This solution is drained
out and the NaCl present in it is removed by crystallization.
The electrolysis of brine therefore produces three products; hydrogen, chlorine and NaOH. The net
equation for the electrolytic process is
2NaCl (aq) + 2H2O (l)  Cl2 (aq) + 2NaOH (aq) + H2 (g)
This equation is useful in determining the ratio in which the three products are produced. The ratio of Cl 2:
NaOH: H2 is 1: 2: 1. However, this reaction is an oversimplification and is misleading. It gives the wrong
impression that NaCl has a reaction with water. NaCl does not react with water. It simply dissolves in it.
The three products of the Chlor-alkali process have very important industrial uses, as shown Table 6.6.

Sodium hydroxide Chlorine Hydrogen

Used in the manufacture of Used in the manufacture of Used in the production of

 soap and  organic solvents  ammonia

detergents  household bleaches  margarine
 rayon fibres  swimming pool  metals from their
 paper cleaning chemicals ores

Table 6.6 Uses of the products of the Chlor-alkali process

A fourth product, sodium chlorate, is produced when the contents of the anode and cathode compart-
ments are allowed to mix. This is done by removing the diaphragm and stirring the contents of the cell.
This allows chlorine and NaOH to mix and react according to the equation.

Cl2 (g) + 2NaOH (aq)  NaClO(aq) + NaCl (aq) + H2O (l)

The uses of sodium chlorate, NaClO, include the manufacture of water treatment chemicals.

Preferential discharge of aqueous cations during electrolysis

Discharge of cations during electrolysis takes place at the cathode by reduction.
Mn+ (aq) + ne-Ý M(s) ... (i)
For metal cations, the order in which discharge takes place in aqueous solution can be deduced from the
electrochemicalseries. It is very difficult to discharge ions at the top of the series. In fact, if the reduction
potential for reaction (i)is negative, it is impossible to discharge the ions as a metal. A negative electrode
potential implies that the formation of the metal in aqueous solution is not energetically favourable. In
other words, if the metal were to be produced, it would immediately react with water to produce the ions
once more. Examples of metals which can not be discharged in aqueous solution include K, Naand Mg.
Metals that are below hydrogen in the electrochemical series, for example Ag and Cu have positive
reduction potentials. This shows that reduction of the metal ions is possible in aqueous solution, forming
a metal. Table 6.7 is an arrangement of metal cations according to the ease with which they can be
discharged at the cathode.

Q
During the electrolysis of an aqueous solution containing equal numbers of
moles of Cu2+, Ag+ and Mg2+ ions, state and explain the order in which the
ions would be discharged.

Ag+ ions are discharged first, since the Ag+/Ag electrode potential is the most positive. When
A
discharged, Ag metal would be the most stable. The next iron to be discharged is Cu 2+. Mg2+, with
a negative reduction potential, can not discharged in aqueous solution.

Preferential discharge of anions during electrolysis

Discharge of anions takes place at the anode by oxidation. During this process, the anions lose their
negative charge (electrons) . Consider the discharge of Cl- ions during electrolysis.
Cl2 + 2e-Ý 2Cl-Eθ = +1.36V

This reduction equation must be read in reverse inorder to show oxidation of the anion to form chlorine
gas.
2Cl-Ý Cl2 + 2e-Eθ/V = -1.36V ... (i)

Compare with the equation for the discharge of OH- ions as oxygen gas
4OH-Ý2H2O+ O2 + 4e-Eθ/V = -0.40 (after reversing) ... (ii)
Since the oxidation process for OH- has a more positive Eθ value, it implies that in the electrolysis of a
dilute solution containing OH- and Cl- ions, OH- ions would be preferentially. Table 6.7is an arrangement
of anions according to their ease of discharge during electrolysis.

Cation Electrode potential Eθ/V

Most difficult
Cl- Cl2 + 2e-Ý 2Cl- +1.36 to discharge

Br- Br2 + 2e-Ý 2Br- +1.07

I- I2 + 2e-Ý 2I- +0.54

OH- 2H2O + O2 + 4e-Ý +0.40 Easiest to

4OH- to discharge
Table 6.7 Preferential discharge of anions
  The anion with the most positive reduction potential is the most difficult to discharge during elec-
trolysis. When read in reverse, this process has the most negative potential, so it is the least likely
to take place.
 The anion with the least positive reduction potential is the easiest to discharge.
 Polyatomic ions such as SO 42- are the most difficult to discharge. In fact, they are usually not
discharged during electrolysis.
 The predictions given above apply only under standard conditions, that is, the assumption made
is that the ions have a concentration of 1.0moldm -3 and that the electrolysis is carried out at 298K.
Changing concentration affects the identity of the substance discharged. For example, during the
electrolysis of concentrated NaCl, Cl 2 and not O2 is produced at the anode.

Electrolytic purification of copper

Impure copper is purified by making it the anode in an electrolytic cell containing copper (II) sulphate
solution. The cathode is made of pure copper (Fig 6.14).
The copper anodes dissolve through oxidation, releasing Cu2+ ions, which then migrate to the cathode
Cu(s)  Cu2+ + 2e-
At the cathode, Cu2+ ions are reduced, forming copper metal, which sticks onto the cathode.
Cu2+ + 2e- Cu(s)
The anodes therefore get thinner whilst the cathodes gain mass and become thicker. At the end of the
process, the cathodes, containing pure copper, are removed from the electrolytic cell. The purification
process removes certain impurities, particularly zinc, gold and silver.We can use electrode potentials to
explain how these impurities are removed from the impure copper.

Fig 6.14 Electrolytic purification of copper

  The conversion of zinc metal to Zn2+ has a
Equation Reduction
positive reduction potential (reverse of
potential/ V
equation (i)), that is, at the anode, any zinc
(i) Zn2+(aq) + 2e-Ý Zn(s) -0.76 in the copper easily turns to Zn2+ ions. On
the other hand , the reduction of Zn2+ ions
(ii) Cu2+(aq) + 2e-Ý Cu(s) +0.34 to zinc metal has a negative reduction po-
tential, that is, the reduction of Zn2+ ions to
(iii) Ag+ (aq) + e-Ý Ag(s) +0.80 zinc metal is not likely in aqueous solution.
The ions therefore stay in solution.
Table 6.8 Preferential discharge of ions  The reduction potentials of silver and
involved in the purification of copper by goldare more positive than that of copper
electrolysis.
(they are more stable). These two impurities
do not easily dissolve at the anode.
Instead, they remain in their solid metallic state and drop to the bottom of the cell as the impure copper
anode dissolves.
6.9.3 Electrolysis of molten salts
The electrolysis of molten (liquid) salts is a good method for producing reactive metals such as sodium
and magnesium. These metals can not be produced by electrolysis of the aqueous salt solution, as already
explained. The major disadvantage of this method is that huge amounts of heat energy are required to
melt most salts and keep them liquid during the electrolytic process.
The heat energy is required to overcome the electrostatic attractions between anions and cations in the
ionic crystal. This causes breakdown of the lattice, and makes the ions mobile. The molten solution can
therefore conduct electricity because the ions carry electric charge when they move from one point to
another.
The electrolysis of a pure molten salt is straightforward because there are no other ions to consider except
those that came from the ionic compound.
Fig 6.15 below shows a set up for the electrolysis of molten lead (II) bromide in the lab.

Fig 6.15 Electrolysis of molten lead (II) bromide

PbBr2is decomposed by heat according to the equation

PbBr2Ý Pb2+ + 2Br-
Pb2+ ions migrate to the cathode where they are reduced to lead metal.
Pb2+ + 2e- Pb (l)
Meanwhile, Br- ions drift to the anode whey they are oxidized to Br 2.
2Br-  Br2(g)+ 2e-

Extraction of Al by the electrolysis of molten aluminium (III) oxide

The major ore of aluminium is bauxite, which is impure Al2O3. Fig 6.16 shows the electrolytic cell for the
extraction of Al from molten Al2O3 by the Hall-Héroult process.
Since the melting point of bauxite is very high (about 2 000 0C), a fluxing agent is added. This is a
substance which lowers the melting point of another. In this case, cryolite, Na3AlF6, is used. Its presence
lowers the melting point of bauxite to about 950 0C.This saves energy and makes it easy to keep the ore
molten. Cryolite also acts as an electrolyte to improve conductivity of the cell.

Fig 6.16 Electrolytic cell for the extraction of aluminium by the Hall - Héroult process.

Al2O3 is decomposed by heat according to the equation

Al2O3 2Al3+ + 3O2-
At the anode, oxide ions are oxidized
O2- O2 + 4e-
At the cathode, Al3+ ions are reduced to Al.
Al3+ + 3e- Al
The molten aluminium drains out of the cell from the bottom.

Anodization of Aluminium
The large and negative reduction potential for Al shows that it is a very reactive metal, that is, it is very
unstable relative to its ions, Al3+.
Al3+ + 3e-Ý Al(s) Eθ = -1.66V
Reading in reverse gives
Al(s)  Al3+ + 3e-Eθ = +1.66V

The large and positive value of this reaction indicates that the oxidation of aluminium to Al3+ is
energetically favourable.However, in practice, aluminium is an unreactive metal. In fact, some of its uses
depend on this property (for example, it is used to make cooking pots). The inertness of Al metal is due to
kinetic factors. In air, freshly prepared aluminium rapidly undergoes a superficial (surface) reaction with
oxygen, forming a thin, tough and impermeable layer of Al 2O3. This oxide layer is tenacious, that is, it
sticks to the metal surface so tightly that it is not easily removed. Being impermeable to air and water, the
oxide layer protects the metal underneath from further corrosion.
The aluminium oxide layer on aluminium objects can be made thicker by anodizing. This is achieved by
making the aluminium object the anode in the electrolysis of dilute sulphuric acid.
Oxygen is discharged at the anode
4OH- O2 + 2H2O + 4e-...(i)
The oxygen then reacts with the aluminium object to form Al2O3
Al(s) + O2(g)  Al2O3(s)

Question and answer section: electrolysis of molten Al2O3

Q. In the early nineteenth century, attempts were made to extract aluminium from Al2O3 using sodium
metal.

a) Explain the chemical principles underlying this method of extraction, supporting your answer with an
equation.
b) What are the major disadvantages of this method?

A. a) Na metal is higher in the electrochemical cell than aluminium and is therefore a more powerful reducing
agent(than Al itself). Na is therefore able to reduce Al2O3 by removing oxygen atoms.

Al2O3 + 6Na  2Al + 3Na2O

b) Na metal is difficult to handle because of its very reactive nature, for example, it can easily burn in air.
The production of Na itself (by electrolysis) is an expensive process.

Q. Explain the use of graphite anodes in the electrolytic cell for the extraction of aluminium.

A. Graphite has a very high melting point, so it is not decomposed by the high temperature used in the
process. Graphite also has the advantage of being relatively cheap.

Q.Explain why the anodes must continuously be replaced during the extraction of aluminium.
A. Oxygen produced at the anode oxidizes carbon in graphite to CO2. This reaction is promoted by the high
operating temperature of the cell. The anodes are therefore gradually consumed and must be replaced
continuously.

Q. Construct a balanced net equation for the production of Al by electrolysis of Al2O3.

A. Anode reaction 3[2O2- O2 + 4e-]

Cathode reaction 4[Al3+ + 3e- Al]

Net reaction 6O2- + 4Al3+ 3O2 + 4Al

Combining the ions on the left side gives the net reaction as
2Al2O3 3O2 + 4Al

Q The net reaction for the electrolysis of Al2O3 using the Hall-Héroult process is sometimes given as

2Al2O3 + 3C  4Al + 3CO2

What is the justification for writing the net equation like this? Explain why this equation is an
oversimplification of the electrolytic process.

A. 2Al2O3 3O2 + 4Al ... (i)

The oxygen produced at the anode oxidizes graphite to CO2
3O2 + 3C  3CO2 ... (ii)
Combining equations (i) and (ii) gives the net equation
2Al2O3 + 3C  4Al + 3CO2

This equation is an oversimplification because it gives the wrong impression that Al2O3 is reduced by
carbon to Al metal. The conversion of Al2O3 to Al in this process is not achieved by the use of a
reducing agent, but by the use of an electric current (as a reducing agent, carbon is too weak to reduce
Al2O3 ). Moreover, the equation wrongly shows a one step reduction, not an electrolytic process which
is followed by the reaction of graphite with oxygen.

Q. Explain the need to keep current high and voltage low in the electrolytic production of Al by the Hall-
Héroult process.

A High current helps to keep temperature high so that the ore remains molten. Low voltage minimizes the
discharge of fluoride ions at the anode as the poisonous fluorine gas. The fluoride ions come from the
electrolyte, Na3AlF6.

Q State two uses of cryolite in the extraction of Al.

A -Electrolyte
-Lowers melting point of bauxite
 Q. In table form, give three uses of aluminium in relation to its properties.

A.

Use Property

Making cooking pots  Resists corrosion

 Good conductor of heat

 Light
Overhead power cables  Resistant to corrosion
 Good conductor of
Electricity (it is a better
conductor than Cu).

Aircraft bodies  Light

6.10Quantitative electrolysis

It is possible to calculate the amount of substance produced during electrolysis, for example, the amount
of metal deposited at the cathode and the volume of gas produced at the anode.

6.10.1 Electric charge and the Faraday constant

The quantity of electricity passed during electrolysis is measured in coulombs (C).This quantity, also
known as electric charge, Q, depends on the duration (time) of the process and also on the size of current.

that is , Q = I x t

Where I = current in amperes

t = time in seconds

Since 1 electron has a charge of -1.60 × 10–19 C,one mole of electrons has a charge of
–1.60 × 10–19 C x (6, 022 x 1022) = 96 352C
This figure, often rounded off to 96 500C/mol, is known as the Faraday constant, F.

The Faraday constant, F is the size of charge on 1 mole of electrons

F ≈ 96 500 C
This value is obtained by multiplying the Avogadro number L and the charge e on an
electron, that is

F = Le = 96 500 C
6.10.2Amount of metal deposited at the cathode during electrolysis
A metal is deposited by the reduction of its ions at the cathode
Mn+ (aq)+ ne-Ý M(s)
Consider the discharge of copper during the electrolysis of CuSO 4 (aq).
Cu2+ (aq)+ 2e-Ý Cu(s)
2 moles of electrons are required to discharge 1 mole of Cu. The number of electrons transferred during
the process depends on the charge on the ion. For a +1 ion such as Ag+, the number of electrons trans-
ferred would be 1 mole.
Ag+ (aq) + e- Ý Ag(s)

The number of moles of electrons required to discharge 1 mole of a metal from its ions is equal to
the charge on the ions.

For copper, the size of electric charge required to discharge 1 mole of metal
= 2 moles of electrons x charge on one mole of electrons
= 2F ( = 2 x 96 500C)

The charge required to discharge 1 mole of a metal from its ions is given by
Q = zF,
where z is the size of charge on the ionand F is the Faraday constant.

𝐐
Since a charge of zF discharges 1 mole of metal, a charge Q would discharge moles of metal.
𝐳𝐱𝐅

The number of moles, n of metal discharged during electrolysis is given by

𝐐
n= where Q = It ... (i)
𝐳𝐱𝐅

The mass, m of metal deposited is given by n x Ar, where n is as given in equation (i) above.

The mass m of metal deposited during electrolysis is given by

𝐐
m= x Ar ... (ii)
𝐳𝐱𝐅
You may use equations (i) and (ii) in exams without proof, but it is certainly helpful to know how the
equations are derived.

Further analysis of equation (ii)

Rearranging equation (ii) gives

𝐀𝐫
m= x Q ... (iii)
𝐳𝐱𝐅
For a particular metal ion,Ar, z and F are constant, so equation(iii) can be expressed in terms of Q as

m= 𝐊xQ ... (iv)

𝐀𝐫
where K is a constant equal to
𝐳𝐱𝐅

Now equation (iv) is that of a straight line, showing direct variation between mass of metal deposited and
the size of charge that passes during the period of electrolysis.

Mass, m of metal deposited during electrolysis is directly proportional to charge,Q

m αQ

That is, increasing charge results in a proportional increase in mass of metal deposited. Charge, Q can be
increased by increasing either the current, or the duration of electrolysis (time) or both, since Q =It.
Fig 6.17 is a graph showing the mathematical relationship between mass of metal deposited and size of
charge.

mass of metal
deposited
y

x Fig 6.17 Graph showing

direct variation between
charge and mass of metal
Charge Q = It
deposited during electrolysis.

Such a graph can be drawn from a series of experimentally obtained values for m and Q.(see
𝐀𝐫
exercise6.5).The slope, m1 of this line is equal to the constant (refer to equations (iii) and (iv))
𝐳𝐱𝐅

𝐀𝐫
slope =m1 = ... (v)
𝐳𝐱𝐅

This outcome can be used to determine Ar, z or F experimentally, as illustrated in a later example.
Example 1

A constant current of 20.0A was passed through an electrolytic cell containing CuSO4(aq). The
anode in this cell was made of impure copper, and the cathode was made from pure copper. After 10
hours it was found that 225g of pure copper had been deposited on the cathode.

(i) Calculate the following, using appropriate data from the Data Booklet.

 number of moles of copper produced at the cathode

 number of moles of electrons needed to produce this copper
 number of moles of electrons that passed through the cell.

(ii) Hence calculate the percentage of the current through the cell that was actually used to
discharge the copper metal at the cathode. Explain why your answer is not 100%.

[Adapted from UCLES 9701/ON/2010/41]

Solutions
(i)
 Moles of Cu = m/Ar = 225/63.5 = 3.543
 amount of electrons needed = chargex molesproduced

= 2 x 3.543
= 7.087 moles

 Number of coulombs = I x t
= 20 x 10 x 60 x 60
= 720 000C

Number of moles of electrons passed through the cell

Total charge
=
charge on 1 mole of electrons,F

720 000
=
96 500

= 7.461

(ii) Of the 7.461 moles of electrons that passed through the cell, only 7.087 were used to form copper.
The percentage of the current used to produce the copper is therefore
7.087/7.461 = 95%
The value is not 100% because a small percentage (in this case, 5%) of the current
is used in dissolving the impurities at the anode.
Example 2

Describe a method suitable for the determination of the Avogadro constant, L by an electrolytic
procedure. Explain how the results from your experiment can be used to calculate a value for L.

Solution
A suitable method involves an electrolytic cell using copper electrodes as shown in Fig 6.18
 Both the anode and cathode are made of copper metal of known masses.
 As soon as the circuit is closed, the time is noted and the current, I, is read off from the ammeter.
The rheostat is adjusted when necessary to ensure that a steady current passes through the cell.

During the electrolytic process, the anode dissolves and loses mass. Meanwhile, copper is deposited at the
cathode, so it gains mass. After some time t, the switch is opened; the anode and cathode are removed,
washed and then reweighed. The aim is to note the gain in mass of the cathode, or the loss in mass of the
anode (the loss in mass by the anode should be equal to the gain in mass by the cathode). Let this mass be
m grams.

Processing results
Amount of electricity passed = charge = I(in amps) x t (in seconds)

m
Moles of Cu deposited =
63.5

m
moles of copper are deposited by It
63.5
Coulombs . Therefore 1 mole of copper would
63.5 x It
be deposited by a charge of
m
This is equivalent to the charge on two moles of
electrons, according to the reduction equation
Cu2+ (aq) + 2e- Ý Cu(s)
63.5 x It
That is 2 x e x L = ... (i)
Fig m
6.18 The expression on the left hand side represents
the charge on two moles of electrons (e is the

charge on one electron and L is the Avogadro constant)

Rearranging equation (i) gives
63.5 x It
L=
2 x m x (1.60 x 10-19)

1.98 x 1020 x It
L = ...(ii)
m
Example 3

When a constant current of 10A was passed through copper(II) sulphate solution for 7
minutes, 1.38g of copper was discharged at the cathode. Use this information to calculate a
value for

(a) the Avogadro constant, L

(b) the Faraday constant, F

Solution
(a) Using equation (ii) in example 2 and substituting the given data

1.98 x 1020 x It
L =
m

1.98 x 1020 x 10 x 7 x 60
L = .
1.38

= 6.026 x 1023

The actual value of the Avogadro constant is 6.022 x 1023. One possible source of error in this method
is the difficulty in maintaining a constant current.

(b) F = L.e
= 6.026 x 1023 x 1.60 x 10-19
= 96 417Cmol-1
The Faraday constant is commonly given as 96 500Cmol-1

Example 4

A current of 12A is passed for 150 minutes through aqueous sodium sulphate using inert electrodes.
What is the volume of gas liberated at the cathode at s.t.p?

A 0.1 dm3 B 2.5dm3 C 3.1dm3 D 6.3dm3

Solution D
OH- ions migrate to the anode where they are discharged as O2 (g) by oxidation
4OH-(aq)  2H2O + O2 (g) + 4e- … (i)
From equation (i),4 mol e- discharges  1mol O2
Charge on 4 moles of electrons = 4F since 1 mole of e- has a charge given by the Faraday constant, F
= 4 x 96 500Cmol-1
= 386 000C
Charge that flowed during the process = Ixt
= 12 x 150 x 60
= 108 000 C

If 386 000 coulombs discharge one mole of oxygen, 108 000 coulombs will
discharge

108 000
moles = 0.27979 moles of oxygen, which gives a volume of
386 000

0.279797x 22.4dm3 = 6.267dm3

~6.3dm3

Example 5
30g of a metal X was discharged by electrolysis, according to the equation

X3+(aq) + 3e- X(s

Given that the electrolysis was done for 24 125 seconds with a constant current of 2.4A, deduce the
identity of metal X

Solution
𝐐
m= 𝐳𝐱𝐅
x Ar(where Q = I(A) x t(s) = 24 125 x 2.4 = 57 9ooC)

m
Ar = x zF
Q

30 x 3 x 96 500
=
57 900

= 150

Element X is therefore Samarium, Sm.

Example 6
An electrolytic cell was set up invoving copper and silver electrodes immersed in solutions of their
ions. At the end of the process, it was found that 4g of silver metal had been deposited. Calcullate the
mass of copper that was deposited in the same time interval.
Solution
Ag is deposited at the cathode in cell B, whilst in cell A, Cu is deposited
4
Number of moles of Ag metal deposited =
108
Ag+(aq) + e- Ag(s) ...(i)
½ Cu2+(aq) + e- ½ Cu(s) ...(ii) (that is, Cu2+(aq) + 2e- Cu(s))

From equation (ii), it can be seen that the same number of electrons (charge) produces
Ag and Cu metals in the ratio of 1 mole Ag: ½ mole Cu.

Moles of Cu produced is therefore = ½ moles of Ag

4 1
= x
108 2

Mass of copper produced = moles x Ar

4 1
=
108
x 2
x 63.5

= 1.18g
 [Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 6.5in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

A student decided to verify the value of the Faraday constant using an electrolytic method.
(Fig 6.19)

Method
• The cathode is cleaned and weighed before being placed in the copper(II) sulphatesolution.
• The circuit is completed and the current set at 0.3 A by adjusting the variable resistor.
• The current is maintained at 0.3 A for exactly 40 minutes at which point the circuit is
broken.
• The cathode is removed from the solution and carefully washed with distilled water to
remove any copper(II) sulphate solution.
• Distilled water is removed from the cathode by rinsing it with propanone in which the
water dissolves.
• The cathode is finally dried by allowing the propanone to evaporate from its surface.
• The cathode is reweighed and placed back in the solution.
• A constant current of 0.3 A is passed for a further 40 minutes when the rinsing, drying
and weighing are repeated.
• This procedure is repeated a further 8 times.

The results of the experiment are recorded in Table 6.9.

(a) Use the additional columns of the

Table 6.9 to record the charge
passed and the mass ofcopper
deposited on the cathode.

You may use some or all of the

columns. Label the columns you
use, including the unit and an
equation to show how the value is
calculated.

(b) Present the data calculated in (a)

in graphical form. Draw the line of
best-fit.

Fig 6.19
 A B C D E F

time mass of
/minutes cathode
/g

0 115.74

40 115.97

80 116.22

120 116.46

160 116.70

200 116.94

240 117.19

280 117.49

320 117.67

360 117.92

400 118.14
Table 6.9

(c) Draw construction lines on the graph to derive relevant values and use them to calculate
a numerical value for the Faraday constant.

HINT: See section 9.6.2 on how to tackle this problem

[Adapted from UCLES 9701/ON/2008/5]

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
CHAPTER

CHEMICAL EQUILIBRIUM
7

Introduction
When ethanol is mixed with ethanoic acid in a ratio of 1:1 and heated in the presence of a strong acid,
a fruity smell is soon detected due to the formation of an ester. When the contents of the reaction
vessel are analyzed after, say 24 hours, it is found that the product is mixed with unconverted
reactants. This indicates that the reaction has not gone to completion. Even if the vessel is analyzed a
few days later, it is found that some reactant molecules still remain. It is also found that the amounts
of reactants and products remain the same, provided temperature is kept constant. This is an
example of a reversiblereaction, in which the products, once formed, are able to react in the reverse
direction to regenerate the reactants.

CH3CH2OH + CH3COOH Ý CH3COOCH2CH3+ H2O

ethanol ethanoic acid ethylethanoate(ester)

Now consider what happens when a small piece of sodium metal is placed in water. A reaction occurs
rapidly and all the sodium is soon used up. This is an example of an irreversible reaction, in which the
products can not react backwards to form the reactants.

2Na(s) + 2H2O (l) 2NaOH (aq) + H2 (g)

In this section, Chemical Equilibrium, we explore reversible reactions and try to answer the questions

How far does the reaction go? Does it go to completion, for example the reaction between water
and sodium, or is it reversible, for example, the reaction between ethanol and ethanoic acid? If
the reaction is reversible, how far does it go in terms of converting reactants to products?

These are important questions to an industrial chemist. Irreversible reactions result in all reactants
being converted to products. This reduces wastage of raw materials and saves time and costs related
to separation of products from reactants. However, a large number of reactions are reversible, for
example, the Haber process for the manufacture of ammonia. Even so, it is still possible to find ways of
ensuring that as much of the reactants as possible react, and that the yield of the reaction is close to
100%.

7.1 Chemical equilibria

This chapter mainly focuses on reversible reactions. Consider a simple reversible reaction
A + B⇌C + D
 There are two opposing reactions, a forward reaction and a reverse reaction. The forward
reaction results in some reactant molecules being converted to products. The reverse reaction re-
sults in some product molecules being converted back to reactants.
 A 100% yield of product is not possible because some products are continuously being converted
back to the reactants.
 All substances shown in the equation co-exist in the same reaction vessel as a mixture.At
dynamic equilibrium, the concentration of reactants and products remains constant.

Compare with irreversible reactions in which there is 100% yield of product and at the end of the reaction
concentration of one or all reactants drop to zero (if a reactant is present in excess, its concentration does
not decrease to zero).

An important note

In practice most reactions have a degree of reversibility. When we say a reaction goes to completion as shown below
A+B→C
We simply mean that at the end of the reaction, a negligibly small amount of reactant molecules remain, and the yield
of the product is very close to 100%, say 99, 99%.

The diagrams below are concentration-time graphs for a reversible and for a non-reversible reaction.

Fig 7.1 Concentration - time graphs for a reversible and non-reversible

reaction.

Notice that for an irreversible reaction, concentration of reactant drops to zero, that is, the graph touches
the x-axis. For a reversible reaction, concentration of reactant drops, but it will not become zero. At
equilibrium, a fixed amount of reactant molecules remain unreacted, giving a fixed equilibrium reactant
concentration, [A]eq.
The graphs below show how the concentrations of product changes with time for a reversible and for a
non-reversible reaction.

Notice that for an irreversible reaction, there is

concentration (almost) 100% yield of product. For a reversible
of product reaction, the yield of product is less than 100%.

7.1.1 Dynamic equilibrium

Consider the reversible reaction between
hydrogen and iodine to form
H₂ (g) + I₂ (g) ⇌ 2HI (g)
time
Suppose that we start by mixing 1 mole of iodine
Fig 7.2 Concentration time graph for a and 1 mole of hydrogen gases in a closed flask.
reversible and for an irreversible reaction At the beginning, the forward reaction is faster
than the reverse reaction.
This is in accordance with the collision theory of reaction kinetics which states that reactant molecules
must first collide before they react. Since the concentration of reactants is still high, frequency ofcollisions
between reactant molecules is high and the forward reaction is accordingly fast. At the very beginning,
reactant concentration therefore drops rapidly, as shown by the steep part of the graph in Fig 7.3. As the
reaction proceeds, the concentration of the product increases. The reverse reaction therefore becomes
more important as the frequency of collisions between product molecules (to form reactants) increases.
The reactant concentration does not drop to zero, and the yield of the product does not increase to100%.
There comes a time when concentration of reactants stops decreasing and concentration of products stops
increasing. At this point, the concentration of reactants and products become constant and the speed of
the forward and reverse reactions are equal. We say the system has achieved dynamic equilibrium.

Dynamic equilibrium refers to the situation in a reversible reaction in which the rate of the
forward reaction is equal to the rate of the reverse reaction, and concentration of products and
reactants has stopped changing.

Important note

The term dynamichelps to clear a misconception which is likely to arise from the definition given above. The fact
that the concentration of the product and reactant stops increasing may mislead some students into thinking that the
forward and reverse reactions have come to a stop. If a reaction is reversible, it can not come to a stop. There is
continuous conversion of reactants to products and vice versa. At equilibrium, this inter-conversion continues (it is
dynamic), but the rates of the forward and reverse reactions are now equal, so that there is no further decrease in the
concentration of reactants or increase in the concentration of products. The term dynamic equilibrium is appropriate
because it emphasizes that at equilibrium, there is continuous activity among reactant and product molecules.

Fig 7.3 below refers to a situation in which equilibrium is achieved after time T eq. At this point, the
concentration of product and reactant becomes constant.

The equilibrium concentration of the reactants

and products are R and P respectively.
The shapes of the graphs do not always have to
be as in Fig 5.3. Here we have shown a situation
in which the equilibrium concentration of the
reactant is much smaller than that of the
product. In other words, the equilibrium lies in
favour of the product. This is not always the case.
 concentration

time
Fig 7.3 When equilibrium has been achieved,
concentration of reactant and product becomes
constant

concentration

time
Fig 7.4 A reversible reaction in which
there are more reactants than products
at equilibrium

At equilibrium, it is found that concentrations of reactants A and B have decreased to certain fixed values
and the concentrations of the products C and D have increased to certain fixed values. The ratio

[C]c[D]d is therefore found to be constant, at a given

temperature. This constant is known as the
[A]a[B]b equilibrium constant, Kc .
therefore becomes constant at equilibrium. This ratio is referred to as the equilibrium constant, Kc, that
is,

[C]c[D]d
Kc =
[A]a[B]b

The square bracket [ ] is a notation which means ‘concentration of...’ . The equilibrium constant Kc is
convenient for reactions that take place in solution, but it can also be used for gas phase reactions.
 Example
An equilibrium mixture was found to contain 1 mole of hydrogen gas, 2 moles of iodine gas and 10
moles of hydrogen iodide gas. Calculate the value of the equilibrium constant K c for the reaction

2HI(g) Ý H2(g) + I2(g)

Solution
Concentrations at equilibrium: Note

[H2] = 1/v , [I2] = 2/V, [HI] = 10/V  In this case, it was not necessary to specify volume.
1 2
This is because the volume cancels out when the
[H₂][ I₂] ( )( ) expression for Kc is simplified. This is not always the
V V
Kc = = 10
[HI]² ( )² case. In some equilibria, volume does not cancel out
V
and so it must be specified.
2
( 2)  The value of Kc in this case has no units, since units in
V
= 10 = 0.2 the denominator and numerator cancel out.
( 2)
V

7.1.3 Equilibrium constant, Kp

The equilibrium constant Kc applies to both reactions that take place in solution and in gaseous phase.
However, for gaseous phase equilibria, it is more convenient to use the equilibrium constant in terms of
pressure, Kp. This is because for gases it is easier to measure pressure than concentration.
The expression for Kp is written in a similar way to Kc, but this time instead of using concentrations ([ ])
we use partial pressures (P), for example, the partial pressure of gas A is written PA. The square of the
partial pressure of A is written as PA2. Thus for reaction (II)below

A(g) + B(g) Ý C(g) + D(g) ... (II)

we may write an expression for the equilibrium constant in terms of partial pressures as

PCcPDd
Kp =
PAaPBb

Take note of the following

 Equilibrium constants (Kp and Kc ) apply only to a system that is at equilibrium.
 The units of Kp and Kcvary depending on the specific equilibrium being studied.

Recall the following about partial pressures

(see section 4: states of matter)

 The partial pressure of a particular gas in a gaseous mixture is the pressure the gas would exert if it
existed alone in the container.
 The partial pressure, PA , of gas A in a gaseous mixture is given by
 PA = mole fraction of A x Total pressure  The total pressure, PT, of a gaseous
= ηA x PT mixture is equal to the sum of the partial
pressures of all the gases present, for
The mole fraction, ηA, of gas A is given example, if the container contains gases
A, B and C, the total pressure in the
moles of gas 𝐀 container is given by
ηA =
Total number of moles of all gases
PT = PA + PB + PC
𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐠𝐚𝐬 𝐀
∴PA = x PT
𝐓𝐨𝐭𝐚𝐥 𝐧𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐚𝐥𝐥 𝐠𝐚𝐬𝐞𝐬

Example 1
Sulphur trioxide was heated in a flask, causing it to decompose to form sulphur dioxide and
oxygen. The equilibrium mixture was to found to contain 360g of sulphur trioxide, 3.80 g of oxygen
and 32g of SO2. Given that the total pressure in the flask was 40KPa, calculate the partial pressure
of each gas in the equilibrium mixture. Hence calculate the value of Kp for the equilibrium and
determine the units.

Solution
0.5
moles of each substance present at equilibrium: PSO2 = x 40KPa = 0.0977 = 3.908
5.119
moles of SO3 = 360/Mr = 360/80
2SO3(g) Ý 2SO2(g) + O2(g)
= 4.50
.
moles of O2 = 3.80/32 = 0.119 Po₂ .P²so2
Kp =
P²so3
moles of SO2 = 32/64 = 0.5
Total number of moles of gas at equilibrium 0.928 .3.908²
=
= 4.50 + 0.119 + 0.50 = 5.119 35.2²

moles of SO₃ =0.0112

PSO3 = x PT
Total moles present
The units of Kpare
4.50
= x 40 KPa = 35.2 KPa KPa.KPa²
5.119 = = KPa
KPa²
0.119
PO2 = x 40 KPa = 0.928 KPa
5.119
Example 2
Dinitrogen tetraoxide decomposes to form nitrogen dioxide according to the equation
N2O4 (g)Ý 2NO2(g)
When 2 moles of N2O4 were put in a sealed 500 cm3 flask and allowed to reach equilibrium with
NO2, it was found that at equilibrium only x moles of N2O4 had decomposed and the total pressure
in the flask was P atm. Write an expression for Kp in terms of x and P. What are the units?

Solution

N2O4 (g)Ý 2NO2(g) (2−x)

= xP
initial moles 2 0 (2+x)
equilibrium moles 2-x 2x 2x
PNO₂ = xP
(2+x)
(Since the stoichiometry of the reaction
is 1N2O4 : 2NO2, if x moles of N2O4 P²NO₂
Kp =
decompose, 2x moles of NO 2 are formed) PN₂O₄

2x
Total moles of gas at equilibrium = (2-x) + 2x ={ x P}2
(2+x)
= (2 + x) (2−x)
xP
(2+x)
Equilibrium partial pressures :
2x
moles of N₂O₄ = P
2−x
PN₂O₄ = x Total pressure
total moles

=
Example 3
At high temperatures, steam decomposes into its elements according to the following equation

2H2O(g)Ý2H2(g) + O2(g)

In one experiment at 1 atm pressure, it was found that 20 % of the steam had been converted into
hydrogen and oxygen.
What are the values of the equilibrium partial pressures, in atm, of𝟐𝐱the components of this
equilibrium? = P
𝟐−𝐱
9701/1/O/N/2004

Solution
2H2O (g) Ý 2H2 (g) + O2 (g)
eqlm moles 0.8 0.2 0.1

Total moles at equilibrium = 0.8 + 0.2 + 0.1 = 1.1

 0.8
PH₂O = x 1 atm = 0.730 atm
1.1
0.2
PH₂= x 1 atm = 0.180 atm
1.1

0.1
PO₂= x 1 atm = 0.091
1.1

 moles of steam which dissociated = 20 % = 0.2

∴ moles of steam remaining at equilibrium = 80% = 0.8
 Since stoichiometry of reaction is 2 H2O : 2 H2 : 1 O2, moles of hydrogen at equilibrium = moles
of steam that dissociated = 0.2 and moles of oxygen at equilibrium = ½ moles of hydrogen = 0.1

Equilibrium constant of the reverse [A][B]

so[C] = ... (ii)
reaction K̍′ c

Consider the equilibrium Equating the right hand sides of equations (i) and (ii)
gives
A+BÝC
[A][B]
The value of the equilibrium constant, Kc, for the Kc x [A][B] =
K′ c
forward reaction is given by
Dividingboth sides by [A][B] gives

Kc =
[C] Kc = 1/K′c or
[A][B]
𝟏
K′c =
𝐊𝐜
so[C] = Kc x [A][B] ... (i)
𝟏
The equilibrium constant, K′c for the reverse Similarly, it can be shown that K′p=
𝐊𝐩
reaction In other words, the value of the equilibrium constant
of the reverse reaction is the inverse of the equilibrium
C Ý A + B is given by constant for the forward reaction (see the example
[A][B] below).
K′c=
[C]

Example
The ester ethylethanoate undergoes hydrolysis in water to form ethanoic acid and ethanol.
CH3COOCH2CH3 (aq) + H2O (l) Ý CH3CH2OH(aq) + CH3COOH(aq) ... (i)

The equilibrium constant for this reaction is 0.25 at 298K. In an experiment, 2 moles of ethanoic
acid were mixed with 2 moles of ethanol in a 250 cm3 flask. The mixture was topped up with
distilled water to the 250 cm3 markand allowed to reach equilibrium. Calculate the concentrations
of ethanol, ethanoic acid and ethyl ethanoate present at equilibrium.
 Solution

CH3CH2OH(aq) + CH3COOH(aq) Ý CH3COOCH2CH3 (aq) + H2O(l) ... (ii)

Initial moles 2 2 0 0
eqlm moles 2-x2-xx x

(since stoichiometry of the reaction is 1 : 1: 1: 1, moles of ethanol which react = moles of ethanoic acid
which react = moles of each product formed)
Kc for reaction (ii) is the inverse of the Kc for reaction (i) = 1/0.25 = 4 (the reactions occur in opposite
directions)

[H₂O][CH₃COOCH₂CH₃]
Kc = equilibrium concentrations:
[CH₃CH₂OH][CH₃COOH]
[CH3COOCH2CH3] = moles / volume
x x
( )( ) x²
4 = V V = x/0.25 dm3 = 1.33/0.25
[(2−x).(2−x)] =(2−x)²
𝑉 𝑉 = 5.32 moldm-3
(in this case, volume cancels out) [CH3COOH] = [CH3CH2OH]

4=
x² = (2-x)/0.25
4−4x+x²
(2-1.33)/0.25 = 2.68 moldm-3
solving for x using the quadratic
formula gives x = 1.33

7.1.4 Open and closed systems

Consider what happens when CaCO₃ is strongly heated in an open vessel.
CaCO₃(s)  CaO(s) + CO₂ (g)
The reaction fails to be reversible because the carbon dioxide formed immediately escapes. No equili-
brium is achieved and the CaCO₃ will continue to decompose until none of it is left.
However, when a small amount of CaCO₃ is heated in a closed vessel, say at 800⁰ C, it is found that only a
certain amount of the carbonate will decompose. Thereafter no further decomposition occurs; no matter
how long the solid is heated (provided the temperature is kept constant). Similarly, the partial pressure of
CO₂ reaches a certain level (about 25KPa) and will not increase beyond that unless if temperature is
increased. This example serves to illustrate an important point; dynamic equilibrium is only achievable in
a closed system. In fact, many reactions would be reversible if they were carried out in closed vessels (sys-
tems).

A closed system is defined as one in which no transfer of matter occurs between the system and the
environment.

7.1.5 Achieving equilibrium from the opposite direction

In a closed vessel, the decomposition of calcium carbonate soon reaches equilibrium in which it co-exists
with the products of decomposition
CaCO₃(s) ⇌ CaO(s) + CO₂ (g)
Equilibrium at 800⁰C is achieved when the partial pressure of CO₂ has increased to a constant value of
25 KPa. Since the reaction is reversible, we should get the same result if we start with a certain mass of
CaO and CO₂, say at 50KPa. These two substances (they are now the reactants) are placed in a closed
vessel and heated at a constant temperature, say of 800⁰C. A reaction occurs to form calcium carbonate.
The result is that the partial pressure of CO₂ and mass of CaO begins to decrease and some calcium
carbonate begins to form. However, CaCO₃ soon starts to decompose back to CaO and CO₂.
CaO(s) + CO₂(g) ⇌ CaCO₃(s)
Thedecomposition of CaCO3 causes the partial pressure of CO₂to increase until it has reached an
equilibrium value of 25KPa. Similarly, the masses of CaO and CaCO3 change until they reach constant
equilibrium values (Fig 7.5).

50Kpa
25KPa
PCO2

A initial pressure of CO2

mass of CaO
B equilibrium pressure of CO2

C initial mass of CaO

mass of CaCO 3
D equilibrium mass of CaO
o time
O initial mass of CaCO3
Fig 7.5 When carbon dioxide and CaO
are heated at 8000C in a closed vessel, E equilibrium mass of CaCO3
equilibrium is soon achieved in which
the reactants and product are present
in fixed amounts.

7.1.6 Homogeneous versus heterogeneous equilibria

An equilibrium process is said to behomogeneousif all the substances in the equilibrium are in the same
phase, for example
HI (g) ⇌ H₂ (g) + I₂ (g)
If an equilibrium contains mixed phases it is said to be heterogeneous. An example is the decomposition
of CaCO₃.
CaCO₃(s) ⇌ CaO(s) + CO₂ (g)
The two phases present are solid and gas. We may wish to express the equilibrium constant of this
reaction in terms of partial pressures, since we can easily measure the pressure of CO₂.
Suppose that we write the expression for the equilibrium constant as

Pco₂ .Pcao
Keq =
Pcaco₃

Taking the partial pressures of the solids CaO and CaCO3 to be constant, the expression for the
equilibrium constant may then be written as
Keq = K1PCO₂
Dividing both sides by the constant K1 gives
Keq
= K1PCO₂
K1
The term on the left hand side is the constantKp, the equilibrium constant in terms of partial pressure.
Kp = PCO₂

 For heterogeneous equilibria, epressions for Kc or Kp do not include solids.

 If a liquid in the equilibrium mainly saves as a solvent, it may also not be shown in the
equilibrium expression.

Consider the dissolution of carbon dioxide in water to form a solution containing hydrogen ions and
carbonate ions.
CO₂ (g) + H₂O (l) ⇌ H⁺ (aq) + HCO3⁻ (aq) ... (i)
Only a very small amount of water molecules react with carbon dioxide. Water mainly acts as a solvent
that absorbs and hydrates carbon dioxide
CO2(g)  CO2(aq)
We may treat water as a pure liquid in equilibrium (i), its concentration remains almost constant and so it
may not appear in the expression for the equilibrium constant, that is

[H+ ][HCO₃¯]
Kc =
[CO2 ]

The reader should not conclude that water is always not shown in expressions of equilibrium constants.
One has to consider each situation separately and judge whether water should or should not appear in the
expression of the equilibrium constant. Consider the hydrolysis of an ester in water
CH₃COOCH₂CH₃ + H₂O (l) ⇌ CH₃COOH (aq) + CH₃CH₂OH (aq)
If this was a simple case of a solute dissolving in water, we would ignore the concentration of water in the
expression for Kc. Now, this reaction involves hydrolysis, a reaction in which water is not simply a solvent,
but is a reactant. The concentration of watertherefore appears in the expression for the equilibrium
constant.

[CH₃COOH][CH₃CH₂OH]
Kc =
[H₂O][CH₃COOCH₂CH₃]

However, in this reaction water also serves as a solvent so it is present in very large amounts and
[H 2O] remains almost constant , so as an approximation, the expression for Kc can be written without
water.

[CH₃COOH][CH₃CH₂OH]
Kc ≈
[CH₃COOCH₂CH₃]
Mathematical interpretation of equilibrium constants
Equilibrium constants provide a mathematical way of quantifying the extent to which a reaction goes to
completion. First, consider a reaction A Bwhich goes to completion.
Suppose that we treat this equation as if it were reversible, and we write the expression for the equili-
brium constant as
[𝐵]
Kc = ... I
[𝐴]

At the end of the reaction, concentration of the reactant, [A] drops to zero, so we have
[𝐵]
Kc= =∞
0
In other words, if a reaction is irreversible, the value for the equilibrium constant is infinitely larger
than 1. The equilibrium constant is written so that the concentrations of products (raised to their respec-
tive powers) are in the numerator and the concentrations of reactants are in the denominator. For the
value of Kcor Kpto be greater than zero, the numerator must be larger than the denominator, that is, the
proportion of products at equilibrium is relatively high. The greater the numerator, the higher the value of
Kc or Kp, and the greater the proportion of products at equilibrium. We therefore conclude that a very
large value of Kcor Kp implies that the reaction is, to a large extent, irreversible, that is, the tendency of
products to react back to form reactants is relatively small. If the equilibrium constant is greater than
1010, the reaction is regarded as going to completion(irreversible).
Now consider a reaction whose equilibrium constant is avery small number less than 1, say 10⁻⁵. To get
such a small value, the numerator (representing products) in the expression for K c or Kp must be much
smaller than the denominator (representing concentration of reactants). In this case, the tendency of the
reaction to go to completion is very small. The products, to a large extent, react back to form the
reactants, so that at equilibrium a very small amount of productsand a very large amount of reactants is
present. Reactions with an equilibrium constant which is less than 10-10 are regarded as not taking place
at all.
Consider the equilibrium
H₂ (g) + I₂ (g) ⇌ 2HI (g)
At 731K, the value of the equilibrium constant, K c, is approximately 47. This value shows that there is a
significant amount of HI present at equilibrium. We may not say straight away how much of the HI is
present, but clearly it is not a negligible amount. It would be different if the value of K c was very small, say
1.0 x 10⁻⁵. In that case we would conclude that the amount of product at equilibrium is very small, that is,
the tendency of the reaction to go to completion is very small.
The equilibrium constant therefore gives a measure of the composition of the equilibrium mixture. Are
there more products than reactants, more reactants than products, or are there comparable amounts of
each?

More worked examples

[H
Kc =
[CH

0
=
Q1A and B react to form product C
according the equation
A (aq)+ B(aq) Ý C (aq)

500 cm3 of the equilibrium mixture is

found to contain 0.2 moles of A, 0.2
moles of B and 0.4 moles of C at 298K.

Calculate the equilibrium constant,

Kc, of the reaction, and state its
units.

A Concentrations at equilibrium :
[C] = 0.4 moles / 0.5 dm3 = 0.8 moldm-3
[A] = [B] = 0.2/0.5 = 0.4
[𝐜]
Kc =
[𝐀][𝐁]

0.8
=
0.4 x 0.4

=5 mol-1 dm3

Q2Ethanoic acid and ethanol reacts in

aqueous solution and in the presence of an
acid catalyst to form an ester and water. This
reaction is reversible so that at equilibrium
ethanol, ethanoic acid, ethylethanoate and
water are present in the same reaction vessel.
One equilibrium mixture was found to contain
0.117 moles of ethanoic acid, 0.017 moles of
ethanol, 0.083 moles of ethylethanoate and
0.083 moles of water.

Calculate the value of the equilibrium constant

Kc for this reaction.

A The equilibrium is:

CH₃COOH + CH₃CH₂OH ⇌ CH₃COOCH₂CH₃ + H₂O

Q5When 1 mol each of ethanol and ethanoic Total pressure

acid are allowed to reach equilibrium at 600C,
what is the number of moles of That is, PT
ethyl ethanoate formed?
1
C2H5OH + CH3COOH Ý CH3CO2C2H5 + H2O
x

PN2O4 = x/2
ethyl ethanoate
Kc = 4 at 600C

A
C2H5OH + CH3COOH Ý CH3CO2C2H5 + H2O
initial 1 1 0 0
moles
eqlm 1-x 1-x x x
moles

[ CH₃CO₂C₂H₅][ H₂O ]
Kc =
[ C₂H₅OH ][ CH₃COOH ]

x x
( )( )
V V
4 = 1−x 1−x
.
V V

where V is the volume of the container. Upon

simplification, V cancels out and the equation
simplifies to
3x2 -8x + 4 = 0
solving gives x = 2/3 = moles of ethylethanoate
formed.

Q6At 600C and a total pressure of 1 atm,

N2O4 is 50 % dissociated.
N2O4(g) Ý 2NO(g)

Calculate Kp at this temperature

A N2O4(g) Ý 2NO(g)

stoichiometry 1 : 2
initial partial x0 atm
pressures
eqlm partialx/2 x
pressures

(b)

CH3COOH + CH3CH2OH Ý CH3COOCH2CH+ H2O

initial moles 0.10.10.50.5
eqlm moles 0.1 -x 0.1 -x0.5 + x0.5 + x
Construct an expression for Kc using the equilibrium
moles (divide the moles by V to convert them to
concentrations, but note that in this case V cancels
out). Equate your expression to 4, which is the
equilibrium constant of the reaction obtained in part
(a). Solve for x using the quadratic formula. You
should get x = 0.1. You can now find the moles of
each substance present at equilibrium.

8 A sample of 1 mole of sulphur dioxide was mixed

with 1 mole of oxygen in a 1 dm3 flask and allowed to
reach equilibrium according to the equation
2SO2(g) + O2(g) Ý 2 SO2(g)

At equilibrium, x moles of oxygen had reacted. What

is the value of the equilibrium constant, Kc, at this
temperature.

A
2SO2(g) + O2(g) Ý 2SO3(g)
stoichiometry 2 : 1 : 2
initial moles 10 0
eqlm moles1- 2x1-x 2x

If x moles of O2 react, then 2x moles of SO2 react since

the stoichiometry of the reaction is 1O2 : 2SO2.
Similary, 2x moles of SO3 are formed since O2 : SO3 =
1:2.
The equilibrium moles shown are equal to equilibrium
concentrations since the reaction vessel is 1 dm3.

[ SO₃ ]2 (2x)²
Kc = =
[O2 ][SO2 ]² (1−x)(1−2x)²

Which statement about this equilibrium reaction is correct?

4. The key reaction during the Contact process for
A Decreasing the temperature decreases the value of manufacturing sulphuric acid is as follows
Exercise 7.1
the equilibrium constant.
2SO2(g) + O2(g) Ý 2SO3(g) , ∆H = - 197 Kjmol-1
1. 0.20 mol of hydrogen gas and 0.14 mol of iodine gas
were heated at a certain temperature and allowed to When a 2:1 ratio of sulphur dioxide and oxygen at
reach equilibrium. a total initial pressure of 3 atm is passed over a
catalyst at 4300C, the partial pressure of sulphur
H2(g) + I2(g)Ý 2HI(g) trioxide at equilibrium is found to be 1.9 atm

The equilibrium mixture was found to contain 0.26 mol (i) Calculate the partial pressures of SO2 and O2
B Decreasing the temperature increases the rate of
this reaction.

C Increasing the pressure increases the value of the

equilibrium constant.

D The reaction is exothermic in the forward direction.

9701/1/M/J/2004

3. Acetals are compounds formed when aldehydes are reacted

with an alchol and an acid catalyst. The reactionbetween
ethanal and methanol was studied in the inert solvent
dioxan.

H+
CH3CHO + 2CH3OH Ý CH3CH(OCH3)2 + H2O
ethanal methanol acetal A

The equilibrium concentration of the acetal product was

measured. The result is included in the following table.

[CH3CHO] [CH3OH] [H+] [acetal A] [H2O]/

/moldm-3 /moldm-3 /moldm-3 / moldm-3 moldm-3

at 0.20 0.10 0.05 0.00 0.00

start
at
equili- (o.20 -x) x
brium
at
equili- 0.025
brium

(i) Complete the second rowof thetable in terms of x,

the concentration of acetal A at equilibrium.

(ii) Using the [acetal A] as given, 0.025 moldm-3, calculate

theequilibrium concentrations of the other reactants and
products and write them in the third row of the table.

(iii) Write the expression for the equilibrium constant for this
reaction, Kc, stating its units.

(iv) Use your values in the third row of the table to calculate
the value of Kc 9701/42/O/N/2011, adapted

7.2 Factors affecting chemical equilibria

Position of equilibrium
For a system at equilibrium (constant temperature), the value of the equilibrium constantremains the
same, despite changes in factors such as concentration, and pressure. However, the position of the
equilibrium is affected andshifts when these factors are changed.

Factors that affect position of equilibrium without changing the equilibrium constant are
 pressure (gases)
 concentration ( solutions or gases)

What about temperature and presence of a catalyst?

 Temperature affects both position of the equilibrium and the size of the equilibrium constant.
 A catalyst does not have any effect on the position of equilibrium. This is because it speeds up
both the reverse and the forward reactions to the same extent. Consequently, size of the
equilibrium constant does not change.

The term ‘position of equilibrium’ refers to the relative rates of reaction for the forward and for the
reverse reaction. When we say the position of the equilibrium shifts to the right, it means that the forward
reaction becomes faster than the reverse reaction and so the proportion of products increases. Of course,
whilst this is happening, the system is temporarily in disequilibrium and the term equilibrium constant
becomes temporarily irrelevant. However, shifting of the position of equilibrium adjusts quantities of
reactants and products in the equilibrium so that equilibrium is achieved under the new conditions. When
this happens, it is found that the relative amounts of reactants and products at equilibrium have changed
but the equilibrium constant of the reaction has not changed (assuming temperature has remained con-
stant). A very important concept known as Le Chatelier’s principle is useful in explaining how changing
conditions may affect position of equilibrium.

Le Chatelier’s principle

Le Chatelier’s principle states that:

When a constraint (disturbance) is imposed upon a system at equilibrium, the position of
the equilibrium will shift in that direction which nullifies the constraint and re-establish
equilibrium under the new conditions.

7.2.1 Effect of pressure

The position of a gaseousphase equilibrium may be affected by changing pressure. To predict the direction
in which the equilibrium shifts, it is necessary to construct a balanced equation and assess which side has
the greater or the smaller number of moles of gas.

Effect of increasing or decreasing pressure

Suppose that a system is at equilibrium and we impose a constraint by increasing pressure, e.g. by
compressing the gaseous mixture in a syringe . According to Le Chatelier’s principle, the position of the
equilibrium will shift in that direction which will nullify the constraint, that is, reduce pressure.
The position of the equilibrium therefore shifts to that side which forms the smaller number of gas moles,
because a reduction in the number of moles results in a reduction in pressure.
(Pressure is directly proportional to number of moles of gas. The fewer the number of moles, the smaller
the pressure and vice versa).

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 248
Consider the reversible dimerization of NO₂.
2NO₂ (g) ⇌N₂O₄ (g)
red-brown colourless

What will be the effect of increasing pressure on this equilibrium? The forward reaction has the smaller
number of moles. Increasing pressure will therefore favour the forward reaction. Reduction in the
number of moles implies a reduction in pressure, so that the constraint initially imposed on the system is
removed.
Here we need to explain again the term ‘.. willfavour... the forward reaction.’ Sometimes chemistry
employs terms which are normally used to describe human actions, choices and feelings (For instance, we
may talk about the size of attractive force which an electron in an atom feels from the nucleus). These
terms are perfectly acceptable, but we should understand exactly what they mean in the context of
chemistry.When we say a condition will favour the forward reaction, we simply mean that the forward
reaction becomes temporarily faster, resulting in the formation of more products. After some time, the
rates of the forward and reverse reactions become equal once more. We say the reversible reaction has
settled to a new equilibrium under the new condition imposed, e.g. a higher pressure. In the NO₂/N₂O₄
equilibrium, the formation of more N₂O₄ is accompanied by the fading of the red brown colour of NO₂,
showing that more of the NO₂ is reacting to form more of the colourless product, N₂O₄(Fig 7.6). If
pressure continues to increase, the brown colour continues to fade. If pressure is now maintained at a
high value, we have a new equilibrium situation, comprising of more N₂O₄ than NO₂.

Fig 7.6 A syringe can be used to

investigate the effect of changing
pressure on the
NO2/N2O4equilibrium

Now suppose that pressure is reduced, for example, by gradually allowing the compressed gas to expand.
It is found that the brown colour of NO₂ begins to appear. This brown colour becomes denser as the
pressure continues to decrease. In this case, lowering of pressure is now favouring the reverse reaction,
which has the greater number of moles. By forming more moles of gas, pressure of the system increases so
that the constraint of reducing pressure is nullified.
A question which may also arise is this:
What is the effect of increasing or decreasing pressure on the value of the equilibrium constant?
The answer is that there is no effect. The value of the equilibrium constant is not affected by changing
pressure. This is because the system responds in such a way that removes the constraint and maintains
the value of the equilibrium constant.

Predict the effect of increasing pressure on the equilibrium

Q
2HI(g)Ý H2(g) + I2(g)

A
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Changing pressure has no effect on the equilibrium. This is because the number of moles of gas
is the same on both sides of the equilibrium.

7.2.2 Effect of concentration

Consider the generalized equilibrium
A(aq) +B(aq)Ý C(aq) + D(aq)

 Increasing the concentration of a reactant, say A, will cause the equilibrium to shift to the right.
By immediately reacting to form a product (forward reaction), concentration of the reactant A is
reduced, that is, the constraint imposed on the equilibrium is removed.
 Similarly, increasing the concentration of a product such as D will cause the equilibrium to shift
to the left so that the added molecules are removed by participating in the reverse reaction.

Q
A reaction A + B Ý C is carried out with an initial concentration of 0.1 moldm-3 of A.
Equilibrium is achieved when the mass of product C has increased to x g.

Within the same axes, draw a graph showing the nature of the product curve when
the experiment is repeated with 2.0 moldm-3 A.

AThe equilibrium mass of C increases.Increasing concentration of a reactant causes the

equilibrium to shift to the right , so that more product is formed.

The dichromate - chromate equilibrium

The Cr₂O₇2- (aq)/ CrO₄2⁻ (aq) system can be used to illustrate how changing concentration of a substance
affects the position of an equilibrium. The dichromate ion, which is orange in colour, coexists in an
equilibrium mixture with the yellow chromate ion:

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Cr2O72-(aq) Ý 2CrO42-(aq)
orange yellow

First consider the dichromate to chromate reaction (forward reaction). This is a hydrolysis reaction in
which a water molecule, acting as a reactant, is split.

2- 2-
O O O

Cr Cr + H 2O 2 Cr + 2H +
O O
O O O
O O O

dichromate- orange chromate- yellow

In the reverse reaction, hydrogen ions cause two chromate ions to link through an oxygen bridge,
resulting in the formation of water.

2- 2-
O O O

2H+ + Cr Cr Cr + H 2O
O O
O O O
O O O

The dichromate - chromate equilibrium is therefore written in full as

Cr₂O₇2-(aq) + H₂O (l) ⇌ 2CrO₄2- (aq) + 2H⁺(aq)
When solid potassium dichromate is dissolved in water, the solution is mainly orange, showing that in
this equilibrium the predominant species is the dichromate ion. In other words, the equilibrium lies in
favour of dichromate. When NaOH (aq) is gradually added, the solution begins to turn yellow. The OH⁻
ions react with hydrogen ions in the equilibrium to form water. Lowering of the concentration of a
product, in this case hydrogen ions, causes the equilibrium to shift to the right, to replace the hydrogen
ions and remove the disturbance caused by addition of alkali.

Cr₂O₇2-(aq) + H₂O (l) ⇌ 2CrO₄2- (aq) + 2H⁺ (aq)

Orange Yellow
2OH-

2H2O
When an excess of NaOH has been added, the solution turns completely yellow, showing that chromate
ions are now the predominant species under alkaline conditions. When the alkaline solution is acidified
gradually, e.g. using HCl (aq), the solution remains yellow for some time as the acid neutralizes the excess
alkali. Continued addition of an acid will increase the concentration of hydrogen ions on the product side
of equilibrium 1. This causes the equilibrium to shift to the left, so that the excess hydrogen ions are

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removed. This causes the solution to become orange once more.
Even though the dichromate and the chromate ions coexist at equilibrium in aqueous solutions, the rela-
tive stabilities, and hence amounts of each substance present at equilibrium depends on pH of the
solution. A low pH (acidic) favours the orange dichromate ion. A high pH (alkaline) favours the yellow
chromate ion.

7.2.3 Effect of temperature

To predict the effect of temperature on equilibrium, we need to know which side is endothermic (absorbs
heat energy) and which one is exothermic (releases heat energy)

Increasing temperature (heating) favours the side which is endothermic. This side absorbs the excess
heat applied, thus reducing the constraint of heat.
Decreasing temperature (cooling) favours the side which is exothermic. This side releases heat energy
to counter the constraint of cooling.

If the enthalpy change of reaction is zero, then a change in temperature will not have any effect on the
position of the equilibrium. The equilibrium composition remains unchanged.
We refer once more to the NO₂/N₂O₄ equilibrium.

NO₂ (g) ⇌ N₂O₄ (g) ... ∆Hr < 0

Red browncolourless

The enthalpy change of the forward reaction is exothermic (∆H <0).

An experiment to investigate the effect of temperature on this equilibrium can be carried out using the
apparatus shown in Fig 7.7.Increasing temperature favours the reverse reaction. This reaction, being
endothermic, removes the constraint of increasing temperature by absorbing the extra heat.
 The proportion of NO2 in the mixture increases whilst that of N₂O₄ decreases.
 The colour of the mixture intensifies as more of the red brown NO 2 is formed(tube 2)

Lowering temperature favours the forward reaction. This reaction, being

exothermic, releases heat energy and this nullifies the constraint of cooling.
 The proportion of N2O4 in the mixture increases whilst that of
NO2decreases.
 The brown colour of the mixture fades as more of the red brown NO 2
is consumed and more of the colourless N2O4 is formed (tube 1)

Fig 7.7 A set up to show

the effect of changing
temperature on the
NO2/N2O4equilibrium.

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 Effect of temperature on the equilibrium constant
Increasing or decreasing temperature causes the value of the equilibrium constant
to change. Consider a gas phase reaction A(g) + B (g) Ý C (g) which is endothermic
in the forward direction and whose equilibrium constant is K p. Increasing
temperature (T) favours the forward reaction, causing the proportion of products
to increase. In other words, the equilibrium constant K p of the forward reaction
increases whilst that of the reverse reaction decreases (Fig 7.8). Note that
increasing temperature also increases the total pressure in the reaction vessel. The
reaction vessel therefore has a larger proportion of the product C at higher
temperature and pressure.
Fig 7.8Effect of
temperature on the
value of the 7.2.4 Effect of catalyst
equilibrium constant A catalyst does not affect the position of equilibrium. Neither does it change the
value of theequilibrium constant.
This is because it speeds up both the forward and reverse reactions to the same extent. A catalyst can
notincrease yield of a product.What then is the use of a catalyst in equilibrium processes such as the
Haber process for the manufacture of ammonia? A catalyst reduces the time required to achieve
equilibrium, that is, it makes both the forward and the reverse reactions fast. Suppose thatwithout a
catalyst it takes 24 hours for an equilibrium product yield of x g to be achieved. In the presence of
catalyst, the same x g of product will be produced but in a shorter time, say a few sconds.

7.2.5Le Chatelier’s principle and electrode potentials

You probably recall that standard electrode potentials are quoted under standard conditions
 concentrations of aqueous reagents = 1 moldm-3
 pressure of gases = 1 atm
 temperature = 298K

Standard reduction potentials are equilibria in which the forward reaction is reduction and the reverse
reaction is oxidation, for example
Cu2+(aq) + 2e-Ý Cu(s) Eθ = +0.34V

The reduction potential of +0.34V strictly refers to 298K and 1 moldm -3 Cu2+(aq). If the concentration of
Cu2+ is increased above 1 moldm-3, the reduction potential becomes more positive than +0.34V. This
observation can be explained in terms of Le Chatelier’s principle. Increasing concentration of Cu 2+ pushes
the equilibrium to the right to remove the excess Cu2+ and restore equilibrium. In other, words, the
forward reaction becomes faster and the electrode potential becomes more positive.
Consider the anode and cathode half reactions in a fuel cell

anode (oxidation):H2(g) + 2OH–(aq)Ý2H2O(l) + 2e–Eθ = +0.83V...(i)

cathode (reduction):O2(g) + 2H2O(l) + 4e–Ý4OH–(aq)Eθ = +0.40V ... (ii)

 The anode supplies electrons (reaction (i)) and so it is the negative electrode. Increasing
concentration of OH- ions pushes equilibrium (i) to the right, thus releasing more electrons. In
other words, the surface of theelectrode becomes more negative. In terms of electrode potentials,
the Eθ value of reaction (i) becomes more positive, that is, the reaction becomes more feasible.
However, note that reaction (i) is an oxidation process which is the reverse of the reduction

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 reaction given in the Data Booklet. So if you were to think in terms of reduction potentials, you
would say that the electrode potential of reaction (i) becomes more negative.
 The cathode receives electrons from the anode (reaction (ii)). In other words, the cathode is
deficient in electrons relative to the anode. This deficiency in electrons makes the cathode
relatively positive.Increasing concentration of OH- ions pushes equilibrium (ii) to the left so that
the excess OH- ions are removed. The reverse reaction becomes more important and since this
reaction produces electrons, it implies that negative charge begins to accumulate on the cathode.
The surface of the cathode therefore becomes more negative. In terms of electrode potentials, the
Eθ value of reaction (ii) also becomes more negative, that is, the forward reduction reaction
becomes less feasible.
 The overall reaction taking place in the fuel cell is obtained by combining equations (i) and (ii).
The net cell potential is not affected by increasing concentration of OH - ions. This is because the
increase in [OH-] makes reaction (i) more feasible and reaction (ii) less feasible to the same
extend. The two effects therefore cancel out (Note that after balancing the number of electrons,
both equations contain 4OH- but on opposite sides of the equations. In that case it is easy to see
that increasing or decreasing concentration of OH - ions should not have any effect on the overall
cell potential).

Now consider the redox processes that take place in the lead-acid battery (‘car’ battery).

anode: Pb(s) ÝPb2+(aq) + 2e- ... (i)

cathode: PbO2(s) + 4H+(aq) + 2e–Ý Pb2+(aq) + 2H2O(l)...(ii)

The electrodes are lead metal (anode) and lead (IV) oxide (cathode) immersed in aqueous sulphuric acid.
Apart from acting as an electrolyte, sulphuric acid also facilitates reactions (i) and (ii) by combining with
Pb2+ ions to form insoluble lead (II) sulphate. Removal of Pb 2+ ions from equilibrium (i) pushes the equi-
librium to the right, resulting in the release of more electrons. As a result, the surface of the lead anode
becomes more negative. The forward oxidation reaction becomes more feasible and the reverse reduction
reaction less feasible. If you think in terms of reduction potentials, you can say that the potential for reac-
tion (i) becomes more negative.Similarly, removal of Pb2+ ions from equilibrium (ii) forces it to the right
and the reduction potential becomes more positive.
Since both reactions (i) and (ii) are favoured by the removal of Pb2+ ions (these ions are on the same
sideof the reactions) we can predict that the overal effect is to make the net cellpotentialmore positive,
that is, the net reaction, obtained by combining equations (i) and (ii) becomes more feasible.

Exercise 7.2

(1) (a)State Le Chatelier’s principle.

(b) The key reaction in the Haber process for the manufacture of ammonia is
N2(g) + 3H2(g) Ý 2NH3(g), ∆H < 0
(i) Explain which conditions of temperature and pressure (low or high) would favour a high
yield of ammonia.

In practice, a temperature of about 4500C is used, together with a catalyst of finely divided
iron.

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 (ii) Explain whether or not this temperature agrees with your prediction in (b)(i) above.
(iii) Justify the need of a catalyst in the Haber process.

(2) A key reaction in the Contact process for the manufacture of sulphuric acid is

SO2(g) + O2(g) Ý SO3(g), ∆H =-197 Kjmol-1

(a) Predict which conditions of pressure and temperature (high or low) would favour a high yield of
sulphur trioxide.

(b) In practice, the reaction is carried out at about 450 0C and 1 atm, in the presence of vanadium
(V) oxide as catalyst.
Suggest why a very low pressure is used

(3) In relation to the following equilibria

Equilibrium I: H2O (g) + C(s) Ý H2 (g) + CO(g); ∆H = +131Kj

Equilibrium II: 2CrO42-(aq) + 2H+ (aq) Ý Cr2O72-(aq) + H2O (l)

use Le Chatelier’s principle to predict and explain the effect of

(i) increasing the pressure on equilibrium I

(ii) increasing the temperatsingure on equilibrium I
(iii) increasing [H+] on equilibrium II

7.3 Ionic equilibria

We now focus on those equilibrium processes which involve participation of ions in aqueous solution

7.3.1 Acid - Base equilibria

Defining acids and bases

There are different ways of defining the terms acid and base. The most widely used definition is
theBrønsted-Lowry theory.

According totheBrønsted-Lowry theory, an acid is a proton (hydrogen ion) donor and a base is a proton
acceptor.

All Brønsted-Lowry bases bear one or more lone pairs of electrons which are used to accept one or more
protons from an acid.Most neutralization reactions can be described using the Brønsted-Lowry theory.
Consider the reaction between HCl and NH3 to form ammonium chloride.

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NH₃ (g) + HCl (g) → NH₄Cl(s)
HCl donates a proton to ammonia, thereby acting as an acid. NH₃ uses its lone pair of electrons to accept
a proton from HCl. NH₃ therefore acts as a base. One advantage of the Brønsted-Lowry definition of acids
and bases is that it is not confined to aqueous solutions. For example, in the reaction above, both
ammonia and HCl are gases. A white ‘smoke’ of ammonium chloride is formed. This substance is a solid,
but owing to the very small size of its particles, it will appear as fumes which can settle as a white powder.
The Brønsted-Lowry definition includes substances which are usually not considered to be acids or bases.
Consider the reversible reaction between ammonia and water.
NH₃ (aq) + H₂O (l) ⇌ NH₄⁺ (aq) + OH⁻ (aq) ... (i)
A water molecule donates a proton to an ammonia molecule. Water therefore acts as a Brønsted acid, and
ammonia as a Brønsted base. In most cases we would not consider water to be an acid.

Conjugate acid base pairs

A reversible Brønsted neutralization frequently contains an acid and a base on either sides of the
equilibrium. On the left hand side of equation (i) above, ammonia is a base and water is an acid. On the
right hand side, an ammonium ion donates a proton to the OH⁻ ion, thus promoting the reverse reaction.
The ammonium ion therefore acts as a Brønsted acid and the hydroxide ion as a Brønsted base.
NH₃ and its ion, NH₄⁺, form one conjugate acid-base pair. H₂O and its ion, OH⁻ forms the second
conjugate acid-base pair.

forward reaction: am m onia is base and water is acid

.. -
OH

reverse reaction : am m onium is acid and OH- is base

.... ..
-

The conjugate acid-base pairs involved are shown in Fig 7.9.

Another example of a Brønsted-Lowry

conjugate acid-base pair
neutralization reaction is the reaction between
water molecules (Fig 7.10).
B A A B
H₂O + H₂O ⇌ H₃O⁺ + OH⁻
NH3 + H2O NH 4 + OH -
+

Prepublication manuscript © L. MWANAWENYU 2011. Please This reaction,

do not which
photocopy is the autodissociation
or reproduce Page 256of
A acid water, is sometimes simplified as
conjugate acid-base pair
B base H₂O ⇌ H⁺ + OH⁻... I
But the proton, being very reactive, will quickly
 Fig 7.9

Combining equations I and II gives the overall equation

H₂O + H₂O ⇌ H₃O⁺ + OH⁻
In this reaction, one water molecule acts as a Brønsted acid, and the other as a Brønsted base. Also notice
the presence of conjugate acid base pairs.

conjugate acid-base pair

What are the two statements of the valence shell
A B B A Q
electron pair repulsion theory? What changes in
H2 O + H 2O OH - + H3 O + shape and bond angle occur when H₂O is
converted to the oxonium ion?
conjugate acid-base pair

Fig 7.10

Acidity of the ammonium ion

Study again the reversible reaction between water and ammonia
H₂O (l) + NH₃ (aq) ⇌ NH₄+(aq) + OH⁻ (aq)
We have seen that the ammonium ion is a Brønsted acid (it is the conjugate acid of ammonia). What this
means is that if we start with a solution of ammonium ions in water, they should show an acidic character.
Indeed, it is found that when ammonium chloride is dissolved in waterthe resulting solution is not
neutral (as might have been expected for a salt) but it is slightly acidic .
NH₄Cl (s) → NH₄+(aq) + Cl⁻ (aq) pH < 7
The ammonium ion is a stronger acid than water, so it donates a proton to a water molecule, that is, water
acts as a base. A Brønsted-Lowry neutralization takes place as shown in Fig 7.11.

The concept of pH and pOH

conjugate acid-base pair
pH is defined as the negative logarithm of hydrogenion
concentration.
A B B A
NH4+ + H2O NH3 + H3O+ pH = - log10[H⁺]

(In subsequent discussions, we will ignore the subscript

conjugate acid-base pair (base) 10 and simply assume its presence.)
Fig 7.11 acidity of the ammonium ion

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It is therefore possible to calculate the hydrogen ion concentration when pH of the solution is known.
[H+] = 10-pH
pH is a measure of how acidic or alkaline a solution is. The concept of pH was developed using the
assumption that acidity is caused by hydrogen ions and alkalinityby hydroxide ions.
The pH scale runs from 0 to 14. On this scale, a substance with a pH of 7 is neutral. In such a solution, the
concentration of hydroxide ions is equal to the concentration of hydrogen ions.
pOH is defined as the negative logarithm of hydroxide ion concentration.

pOH = -log [OH⁻]

The concentration of OH-ions in a solution can therefore be calculated.

[OH-] = 10-pH

Note
The letter p can be interpreted as ‘...negative logarithm of...’. Thus pE means -log E (where E is the electrode
potential)

An important relationship between pH and pOH is

pH + pOH = 14(at 298K)

Example 1

Calculate
(a) The pH of 0.01 moldm-3 HCl
(b) The hydrogen ion concentration that gives a pH of 0
(c) The pOH of a solution whose pH is 4
(d) The hydroxide ion concentration in a solution in which [H+] = 3.0 x 10-6moldm-3
(e) The hydrogen ion concentration in a solution whose pOH is 11.

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 Solutions

(a) HCl  H+ + Cl- (d) [H+] = 3.0 x 10-6

0.01 0.01 0.01
pH = -log(3.0 x 10-6) = 5.5
Since HCl fully dissociates in water, pOH = 14 – 5.52 = 8.48
[HCl] = [H+ (aq)] = 0.01 [OH-] = 10-POH
pH = -log[H+] = 10-8.48
= -log 0.01 = 3 x 10-9 moldm-3
=2
(e) pOH = 11, so pH = 3
(b) pH = -log [H+] [H+] = 10-3
[H+] = 10-pH
= 100
= 1 moldm-3

(c) pH + pOH = 14
pOH = 14 - pH
= 14 - 4
= 10

Important note
Consider a solution whose pH = 1. This solution has a large concentration of H + ions and is therefore strongly acidic.
However, this does not mean that there are no hydroxide ions. When we say a solution is acidic, we simply mean that
the concentration of hydrogen ions is greater than the concentration of hydroxide ions. Similarly, in an alkaline
solution, the concentration of OH- ions is greater than that of hydrogen ions. In a neutral solution, [OH-] = [H+].

7.3.2 The ionic product of water

Water slightly autodissociates according to the equation
H₂O (l) Ý H⁺ (aq) + OH⁻ (aq) ... I

We may write the equilibrium constant for this autodissociation as

[𝐻 + ][𝑂𝐻 − ]
Keq =
[𝐻₂𝑂]

Since water is weakly dissociated, equilibrium I lies much to the left, that is, a very small amount of
water is ionized and its concentration therefore remains fairly constant. We may therefore write
[𝐻 + ][𝑂𝐻 − ]
Keq =
𝐾
Where K = [H2O] = constant. This simplifies to
KeqK = [OH⁻][H⁺]

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The product of the two constants on the left hand side is another constant, known as the ionic product
ofwater, Kw.

Kw = [OH⁻][H⁺] = 1.0 x 10-14 at 298K

From this expression we can work out the units for Kw.
Units: moldm⁻3 x moldm⁻3 = mol2dm⁻6

Kw, like any other equilibrium constant, is affected by temperature. At 298K (25⁰C), the value of
Kw is 1.0 x 10 ⁻14 mol2dm⁻6.How does Kwchange when temperature is increased or decreased? The
enthalpy change for the reaction
H₂O (l) ⇌ H⁺ (aq) + OH⁻ (aq)
is endothermic. By Le Chatelier’s principle, the value of K w is expected to increase as temperature
increases, that is, the extent of dissociation of water increases with increasing temperature. This is
supported by the following data.

Temp/0C 0 5 10 15 100

Kw 0.114 0.186 0.293 0.452 51.3

x 10-14

Table 7.1 The effect of temperature on the

ionic product of water

Q that the pH of pure water is 7 at 298K.

Show

x= 10-14mol2dm-6
H₂O (l) ⇌ H⁺ (aq) + OH⁻ (aq)
= [H+] = 10-7
A Let [H+] = x = [OH-]
pH = -log[H+]
Kw = [OH⁻][H⁺] = 1.0 x 10-1
= -log (10-7)
1.0 x 10-14 = x2
=7

If you try to calculate the pH of pure water at 100 0C (refer to Table 7.1), you will find that it is 6.1. The
statement, ‘the pH of pure water is 7’is therefore not necessarily true, because the pH of water depends on
its temperature.
Can we therefore conclude that water is more acidic at 10o 0C than at 250C? By no means! A solution
would be acidic if it had a greater concentration of hydrogen ions than hydroxide ions. No matter what the
temperature of water is, the concentration of hydrogen ions is always equal to the concentration of
hydroxide ions, that is, pure water is always neutral. When temperature increases, the degree of
dissociation of water increases. The concentration of H + and OH- increase by the same amount. Since both
[H+] and [OH-] increases, the value of Kw also increases.

The relationship between pH, pOH and Kw

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 We know that But ‘-log’ is denoted by p, so
kw = [OH⁻][H⁺]
pKw = pOH + pH
Taking the logarithms of both sides:
But Kw = 10-14 at 298K, so
LogKw = log [OH⁻] + log [H⁺]
-log (10-14) = pH + pOH
Multiplying throughout by -1 gives
Simplifying the left hand side gives
- LogKw = -log [OH⁻] - log [H⁺]
14 = pH + pOH

A problem with the pH scale

It is taught in junior school that the pH scale runs from 0 to 14. However, when you try to work out pH using some
values of [H⁺], you get unexpected answers. For example, let us calculate the pH of a solution whose [H⁺] is 2.0
moldm⁻3.

pH = -log2 = -0.30
Here we have obtained a negative answer, which does not fit into the pH scale. However, notice that mathematically
the answer makes sense. If a number is greater than 1, then the negative of itslogarithm would be a negative
number. Can we therefore conclude that the definition of the pH scale is wrong? To clear this paradox, we need to
take a brief look at the history of the pH scale.
In 1909, Soren Sorenson, a Danish scientist working for the Carlsberg beer manufacturing company, devised a
method that would allow him to work conveniently with very small concentrations of hydrogen ions. The
concentrations which Sorenson was working with where so small (for example, 0.000000035) that they were
tedious when used in calculations. He invented the pH scale in which he took the logarithm of the hydrogen ion
concentration and multiplied it by -1. For instance, instead of working with a hydrogen ion concentration of 10⁻⁵
mol/dm3 he took the logarithm of the number, which gave -5. Multiplying the answer by -1 made the number
positive. Since he was working with very small concentrations of hydrogen ions, his method always gave him
positive numbers between 0 and 14. These became the limits of his pH scale.
When we use the pH scale, we should therefore know that it applies to very small concentrations which are not
greater than 1. In routine calculations we may encounter hydrogen ion concentrations which are greater than 1.
Taking the negative logarithm of such numbers will give a negative pH value.

7.3.3 Acid strength

The strength of an acid refers to the extent to which it dissociates in water.
 A strong acid is one which fully ionizes in water, that is, once it forms ions, the ions can not
recombine in the reverse reaction to reform the acid.
 A weak acid is one whose dissociation in water is partial. Equilibrium is established between
 the acid and its ions.
Let the notation HA represent a weak acid.
HA ⇌H⁺ + A⁻

At equilibrium, there are three species present; H⁺ ions, the anion A⁻and undissociated acid molecules
HA.
An example of a weak acid is ethanoic acid, which undergoes partial dissociation in water according
to the equation

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 CH₃COOH (aq) ⇌ CH₃COO⁻(aq) + H⁺(aq)
ethanoate ion

The acid dissociation constant, Ka

A common misconception
The acid dissociation constant, Ka This is a measure of the strength of an acid.
Ask several people this question: The strength of an acid is determined by its Ka value, and not
Which one is the stronger of the two acids A by its pH.Consider the weak acid HA, partially dissociating in
and B given below?
water
Acid pH HA Ý H⁺ + A⁻
We may write the equilibrium constant Ka as
A2
[𝑯+ ][𝑶𝑯− ]
Ka =
B 4 [𝑯𝑨]

Ka is the acid dissociation constant of the acid, measured in

moldm-3 . If an acid is fully ionized, e.g. HCl, then at
Chances are that most people will think that
acid A is the stronger acid because it has the equilibrium [HA] = 0 and the value of Ka is infinitely large.
lower pH. In fact, this is what is often taught in The larger thevalue of Ka, the stronger the acid. Strong acids
junior science courses. The answer to the above have large Ka values which are well over 1, for example, the Ka
question is that we can not know which of the for nitric acid is 40. However, the fact that there isa numerical
two is stronger, unless if we know the acid value for the Kaof nitric acid implies that it is not exactly fully
dissociation constants of both acids. pH is not ionised; there is a degree of reversibility to the reaction. On
a measure of acid strength. It is simply a meas- the other hand, HCl is infinitely dissociated in water, so no K a
ure of the concentration of hydrogen ions in
value can be assigned for it.
the solution. If the concentration of hydrogen
Table 7.2shows the Ka values of some acids. The acids have
ions is very small, the pH of the solution will be
quite high. For instance, the pH of 1.0 x 10- been arranged inorder of decreasing acid strength. As the
5moldm-3HCl is 5. This is a relatively high pH, acids become weaker, the Ka values become smaller, but the
even though HCl is a strong acid. pKa ( = -log Ka) values become larger.

Dissociation of polyprotic (polybasic) acids

A polyprotic acid, also known as a polybasic acid, is capable of releasing more than 1 protons in solution,
for example, a diprotic acid such as H2SO4 is capable of releasing two protons (Table 7.3)

 A polyprotic acid dissociates in steps, for example, sulphuric acid , which is diprotic, dissociates in
two steps.

H2SO4 HSO4- + H+
HSO4-Ý H+ + SO42-
Each step has its own dissociation constant. The dissociation constant for the first step is the first
dissociation constant, Ka₁, and that for the second step is the second dissociationconstant, Ka₂.

 Ka₁, Ka₂, K₃ (e.t.c) decrease in that order. Also

note that the second, third (etc) dissociations
of a strong acid
Prepublication are reversible.
manuscript Take sulphuric 2011. Please do not photocopy or reproduce
© L. MWANAWENYU Page 262
acid as an example. The second dissociation step,
HSO4-Ý SO42- + H+ is reversible, showing that
HSO4-(hydrogen sulphate) is a weak acid.
 Acid K a/ pKa
moldm-3

HNO3 40 -1.60

H2SO3 (sulphrous 1.6 x 10-2 1.80

acid)

CH2ClCOOH 1.3 x 10-3 2.89

CHCl2COOH 3.29

HNO2 (nitrous 4.7 x 10-4 3.33

acid)

HCOOH(methanoic 1.78 x 10-4 3.75

acid)

C6H5COOH(benzoic 6.31 x 10-5 4.20

acid)

CH3COOH 1.74 x 10-5 4.76

NH4+ 5.62 x 10-10 9.25

Table 7.2 Acid dissociation constants
for some acids

Table 7.3 Dissociation nature

of some acids

Determination of Ka values
The Kavalue of an acid (at a certain temperature ) can be worked out if both pH and concentration of the
acid are known. At 298K, 0.1moldm-3 methanoic acid has a pH of 2.4. The acid dissociation constant can
be calculated as shown below.

HCOOH Ý HCOO- + H+ Assuming a volume of 1dm3,

moles atbeginning 0.1 00 concentration of HCOOH at the
moles at eqlm 0.1 - xx x beginning of the experiment is
equal to number of molespresent.
Let x be the number of moles of
[HCOO-][H+] HCOOH that dissociate. Since the
Ka = reaction is 1:1:1, x moles of H+ and
[HCOOH] x moles of HCOO- are produced.

x2
= ...(i)
0.1 - x

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 (3.98 x 10¯3 )² (3.98 x 10¯3 )²
≈
but x = [H+ ] = 10-pH 0.1−(3.98 x 10¯3 ) 0.1

= 10-2.4 = 3.98 x 10-3 (since 3.98 x 10-3 ≈ 0)

Substituting in equation (i) gives Ka≈1.58404 x 10-4 moldm-3

Q
Calculate the pH of

(i) 0.1 moldm-3 HCl

(ii) 0.1 moldm-3 CH3COOH (Pka = 4.76)
Explain why your answers to part (i) and (ii) are different.

A (i)HCl  H+ + Cl- ... (i)

[ ] after dissociation0 0.1 0.1

pH = -log [H+]
= -log 0.1
=1

CH3COOH Ý CH3COO- + H+ ... (ii)

(ii)
initial moles 0.1 0 0
in 1 dm 3

moles at eqlm 0.1 -xx x

[H+ ][CH₃COO¯]
Ka = (where Ka =10-Pka = 10-4.76 = 1.74 x 10-5)
[CH₃COOH]

x²
1.74 x 10-5 =
0.1−x

Since Kais very small, x ≈ 0, so 0.1 - x ≈ 0.1, that is

x²
1.74 x 10-5 = x =√1.74 𝑥 10¯5 𝑥 0.1
0.1
= 1.32 x 10-3 = [H+]
pH = -log [H+]

= - log (1.32 x 10-3)

= 2.88

The pH of 0.1 moldm-3 HCl is lower than that of 0.1 moldm-3 CH3COOH. This is because CH3COOH is
a weak acid whereas HCl is strong. Equation (i) shows that HCl undergoes full dissociation, releasing
the maximum possible number of moles of H+ ions in solution. Equation (ii) shows that CH3COOH
dissociates only partially, so the concentration of H + in solution is smaller. Consequently, pH would

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 264
 be higher.

(a) Apple juice has a pH of 3.5.

Q Calculate the molar concentration of H+ in apple juice

(b) A 25.00 cm3 sample of apple juice was exactly neutralized by 27.50 cm3 of 0.10
moldm-3 NaOH using phenolphthalein indicator.
Assuming that a single monobasic acid is present, calculate the molar concentration
of the acid in the juice.

(c) (i) How can you explain the difference between the results in (a) and in (b)?
(ii) What constant can be determined from these results?
(iii) Calculate the numerical value for this constant.
9701/2/M/J/1990

(a) pH = -log [H+] = 3.5 Conc of acid = moles / volume

A
[H+] = 10-pH = 10-3.5 0.00275
= 25
=3.16 x 10-4 moldm-3 1000

= 0.11 moldm-3

(b) moles of OH- = moles of acid

0.10 x 27.5
=
1000
= 0.00275

(c)(i) Apple juce is a weak acid, that is, it only partially dissociates so the concentration of of H +
ions is small. During neutralization, the acid dissociates completetly, so a larger
concentration of H+ is obtained.

[H+ ][A¯]
(ii/iii) Ka =
[HA]

but [H+] = [A-] since acid is monobasic

(3.16 x 10¯4 )²
so Ka = [HA]eqlm ≈ 0.11 since the acid is weak.
0.11

= 9.07 x 10-7 moldm-3

Q1.0 moldm-3 of a monoprotic acid HA has a pH of 1. Which of the following statements are
trueabout the acid ?

1. It is a strong acid
2. The acid dissociates completely in water whose pH is greater than 7
3. The acid only partially dissociates in water whose pH is 7

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 265
 A2 and 3 are correct.
1. The acid is not strong. If it were strong, it would dissociate fully in water and its pH would be
-log 1.0 = 0. The fact that the pH of the acid is higher shows that it does not dissociate fully in
water, that is, it is a weak acid.

2. Presence of alkali (pH >7) causes the acid to dissociate fully. In pure water (pH =7), the acid
partially dissociates
HA Ý H+ + A-

In the presence of an alkali, H+ ions are removed from the right hand side of the equilibrium as
water. By Le Chatelier’s principle, this causes more of the acid HA to dissociate to replace the H +
ions.

Degree of ionization of acids, α

The degree of ionization (dissociation) of an acid, α is given by
amount ionized
α= ... (i)
initial amount

This can be converted to % by multiplying by 100.

For a strong acid initial amount ≈ amount ionized, so α ≈ 1 (≈ 100%). For a weak acid,
initial amount > amount ionized, so α is a fraction less than 1 (0< α<1).

Q
A weak acid HA dissociates in water according to the equation
HA(aq)ÝH+(aq) + A-(aq)

2 moles of the acid were dissolved in water and allowed to reach equilibrium with its ions.
If the acid is only 60% dissociated, calculate the acid dissociation constant of the acid.

A HA Ý H+ + A- [H+ ][A¯] x²
initial moles 2 0 0 Ka = =
[HA] 2−x
eqlm moles 2-x x x
1.2²
amount ionized 60 =
α= = 100 2−1.2
initial amount
= 1.8
x 60
= 100solving gives x = 1.2
2

7.3.4 Weak bases

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A weak base is one which only partially dissociates in water. Ammonia is a typical weak base. When added
to water, a reversible reaction takes place.

NH₃ (aq) + H₂O (l) ⇌ NH₄⁺ (aq) + OH⁻ (aq)

The equilibrium mixture contains a large concentration of unreacted ammonia molecules. Compare with a
strong base such as NaOH. In water it dissociates completely and the concentration of NaOH drops to
zero.
NaOH(s) → Na⁺ (aq) + OH⁻ (aq)
Compare the pH of 0.1moldm⁻3 ammonia and 0.1 moldm⁻3sodium hydroxide. For NaOH, the calculation
is straightforward

NaOH(s) → Na⁺(aq) + OH⁻(aq)

initial moles0.10 0
moles at end00.10.1
At the end, all the NaOH has dissociated, and the concentration of OH⁻ ions is equal to 0.1.
pOH = -log[OH⁻]
= -log 0.1 = 1.
pH = 14-pOH = 14 – 1 = 13.

For ammonia

NH₃ + H₂O⇌ NH₄⁺ + OH⁻

initial moles0.100
equilibrium moles0.1-x xx

In this case [OH-] at equilibrium is not equal toinitial [NH 3] because not all of the ammonia dissociates.
For us to calculate the pH of the solution, we need to know the value of x, that is, the amount of ammonia
molecules that actually dissociate in water, which is equal to the amount of OH - present at equilibrium.
We can not possibly know the value of x unless we know the extent to which the ammonia dissociates,
which is given by the base dissociation constant.

The base dissociation constant, Kb

The base dissociation constant, Kb, gives a measure of the extent to which a base dissociates in water. In
other words, it is a measure of base strength. The larger the value of Kb, the stronger the base. A strong
base such as NaOH has an infinitely large Kb.
Consider the weak base ammonia
NH₃ + H₂O ⇌ NH₄⁺ + OH⁻for which the equilibrium constant Kc is given by
[NH4+][OH-]
Kc = ...(I)
[NH3][H2O]
But the concentration of water remains fairly constant since a very small amount reacts with ammonia.
Treating [H₂O] as a constant and transferring it to the left hand side of equation I, we get a new constant
on this side, which is the base dissociation constant, Kb.

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 [NH4+][OH-]
Kb =
[NH3]

Kb is sometimes converted to pKb, just for convenience.

pKb = -log Kb
When you use pKb you must remember that the larger the value of pKb, the weaker the base.
Weak bases such as ammonia have very small Kb values. This implies that at equilibrium, a large amount
of the base remains undissociated. The Kb value for ammonia is 1.67 x 10⁻⁵ moldm⁻3. Its pKb value is given
by -log (1.67 x 10⁻⁵) = 4.78.

Example
Calculate the pH of 0.1 moldm-3 ammonia.

Solution

NH₃ + H₂O ⇌ NH₄⁺ + OH⁻

Start 0.1 0 0 moles
Equilibrium 0.1-x x x x = moles of ammonia that dissociate
= moles of NH4+ and OH- that are formed
[NH4+][OH-]
Kb =
[NH3]

1.67 x 10⁻⁵ = x2/0.1-x

≈ x2/0.1 judging by the very small value of Kb, x is very small
so that 0.1 -x ≈ 0.1

x = √ (1.67 x 10⁻⁵ x 0.1) = [OH⁻]

that is[OH⁻] = 1.29 x 10-3
pOH = -log[OH-] = - log (1.29 x 10-3)
= 2.89
pH = 14-pOH = 14-2.89
= 11.11

The relationship between Ka, Kb and Kw

In any aqueous solution, the product of [H+ ] and [OH-] is constant at a particular temperature and is
known as the ionic product of water.

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Kw = [H+ ] [OH-]
It can be shown that Ka x Kb = [H+] [OH-] That is,

Ka x K b = Kw

Example
Given that pKa(NH4+) = 9.25 at 298K, calculate the value of Kb for ammonia.

Solution

ka(NH4+) = 10-9.25 5.62 x 10-10 x Kb(NH3) = 10-14

= 5.62 x 10-10 10-14

Kb(NH3) =
ka(NH4+) x Kb (NH3) = Kw 5.62 x 10-10
= 1.78 x 10-5moldm-3

7.3.5 Buffer solutions

A buffer is a solution which resists change in pH when a little acid or base is added. Buffers are designed
to keep pH nearly constant in some processes which are sensitive to changes in pH.

Acidic versus alkaline buffers

An acidic buffer is designed to maintain an acidic pH, that is, pH < 7. It consists of a weak acid and its
soluble salt in aqueous solution.
pH of the buffer depends on the exact proportion of acid to salt.

An alkaline buffer is designed to maintain an alkaline pH, that is, pH > 7. It consists of a weak base, such
as NH3, and its soluble salt, for example,NH4Cl, in aqueous solution.
pH of the buffer depends on the exact proportion of base to salt

The pH of an acidic buffer

Consider the buffer made up of the weak acid HA and its salt Na+A-. Since the Na⁺ ions will exist as
spectator ions, we ignore them and take the anion A⁻ to represent the salt.
The weak acid dissociates partially
HA ⇌ H⁺ + A⁻
[𝐻 + ][𝐴⁻]
Now, Ka =
[𝐻𝐴]

Making [H⁺] subject of the formula

[𝐻𝐴]
[H⁺] = Ka
[𝐴− ]

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Taking the logarithms of both sides

[𝐻𝐴]
log [H⁺] = log{ Ka }
[𝐴− ]

[𝐻𝐴]
log [H⁺] = logKa + log and multiplying throughout by -1.
[𝐴− ]

[𝐻𝐴]
- log[H⁺] = - logKa - log and using the definitionp = -log...
[𝐴− ]

[𝐻𝐴]
pH = pKa - log
[𝐴− ]

[𝐴𝑐𝑖𝑑]
That is, pH = pKa - log ... I
[𝑆𝑎𝑙𝑡]

[𝐴⁻]
OR pH= pKa+ log
[𝐻𝐴]

[𝑆𝑎𝑙𝑻] The highlighted characters are meant to provide a

That is, pH = pKa +log ... II mnemonic. When you use equation (II), which has a
[𝐴𝑐𝑖𝑑]
+sign, then the salt should be in the numerator.

Equations I and II are different mathematical versions of the same formula, known as the
Henderson – Hasselbachequation. You may use either of the formulae to calculate the pH of a buffer
when the ratio of salt concentration, [A⁻] to acid concentration [HA] is known. The concentrations [Salt]
and [Acid] can be expressed either in moldm-3 or as gdm-3.

Example 1
What should be the ratio of ethanoic acid to sodium ethanoate in a buffer whose pH is to be
maintained at 6? (pka of ethanoic acid = 4.73)

Solution
You may quote the Henderson - Hasselbach equation without further proof.

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 [𝑆𝑎𝑙𝑡] [𝑆𝑎𝑙𝑡]
PH = pKa +log Let be x
[𝐴𝑐𝑖𝑑] [𝐴𝑐𝑖𝑑]

[𝑆𝑎𝑙𝑡] 1.24 = log₁₀x

That is , pH -pka = log
[𝐴𝑐𝑖𝑑]
x = 101.24 = 17
But pH = 6 and pka of ethanoic acid is 4.76
[𝑆𝑎𝑙𝑡]
[𝑆𝑎𝑙𝑡]
= 17
[𝐴𝑐𝑖𝑑]
6 - 4.76 = log
[𝐴𝑐𝑖𝑑]
That is, [Acid]: [Salt] = 1:17

Example 2
A buffer solution is prepared as follows :

53.5 g of NH4Cl are dissolved in 400 cm3 of 15.0 moldm-3 NH3 and the mixture is diluted to 1.00 dm-3.
(a) Calculate

(i) [NH4+(aq)] (ii) [NH3(aq)] of the prepared buffer solution.

(b) Use one of the following values to calculate the pH of the prepared buffer solutin :
NH4+ , Ka = 6.00 x 10-10 moldm-3
NH3(aq) , Kb = 1.67 x 10-5
9701/3/M/J/1995

Solution
53.5 15 x 400
(a)(i) moles of NH4Cl = m/Mr = (ii) moles of NH3 = C x V =
53.5 1 000

= 1.oo = 6.00 moles

∴ [NH4+] = 1.00 moldm-3 ∴ [NH3] = 6 .00 moldm-3

(b) Using NH4+ : rearranging

The ammonium ion behaves as an acid [NH₄⁺]
according to the equation [H+] = Ka x
[NH₃]
+
NH4 Ý NH3 + H+ 1
= 6 x 1o-10 x
6
[NH₃][H+ ]
Ka = = 10-10
[NH₄]⁺
pH = -log (10-10) = 10

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 Alternatively
Using NH3 : [NH₃]
[OH-] = Kb x
[NH₄⁺]
Aqueous ammonia contains the base
ammonium hydroxide
1
= 1.67 x 10-5 x
6
NH3(aq) + H2O(l) Ý NH4OH(aq)
= 1.002 x 10-4
NH4OH(aq) Ý NH4+(aq) + OH-(aq)
pOH = -log (1.002 x 1o-4) = 4
[NH₄⁺][OH¯] but pH + pOH = 14,
Kb = (NH3 = NH4OH])
[NH₃] so pH = 14 - 4 = 10

Example 3

Calculate the pH of a buffer solution prepared by mixing 500cm3 of an aqueous solution containing
34g of sodium ethanoate and 500cm3 of a solution containing 2g of ethanoic acid (pKa = 4.76).

Solution
When the two solutions are mixed, volume is doubled
Moles of salt (CH3COO-Na+) and so concentration of acid and salt are
= m/Mr halved, that is
= 34/82
[salt] = 0.830/2 = 0.415
= 0.415
[acid] = 0.0667/2 = 0.03335
0.415
[salt] = [salt]
0.5 pH = pKa+log
[acid]
= 0.830
[0.415]
Moles of acid (CH3COOH) pH = 4.76 +log
[0.03335]
= 2/60
= 5.85
= 0.0333
= 4.76 + log 12.45
0.0333
[acid] = = 5.86
0.5
= 0.0667 The buffer is acicid so its pH should be less than 7.

Example 4

Calculate the pH of a solution whose concentration with respect to ethanoic acid and with respect
to sodium ethanoate is 0.40 moldm-3 and 0.20 moldm-3 respectively.

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 Solution

Ratio of salt to acid is 0.2 : 0.4 = 1:2.

Substituting into the Henderson-Hasselbach equation,
pH = 4.76 + log(1/2) = 4.46

How does an acidic buffer work?

A buffer resists changes in pH when a little acid or base is added to it. The mode of action of an acidic
buffer can be illustrated by the CH₃COOH/CH₃COO⁻Na⁺ system.
The first step is to write the equations of the processes which exist in the buffer before an acid or an alkali
is added.
Ethanoic acid is partially dissociated, and the salt, sodium ethanoate fully ionizes.

CH₃COOH (aq) ⇌ CH₃COO⁻ (aq)+ H⁺ (aq) ... I

CH₃COONa → CH₃COO⁻ (aq) + Na⁺ (aq) ... II
When the concentration of hydrogen ions increases (that is, when a little acid is added), the ethanoate
ions in reaction II remove the excess hydrogen ions.
CH₃COO⁻ (aq) + H⁺ (aq) → CH₃COOH ... III
The salt CH₃COONa is the important source of ethanoate ions since it fully ionizes in solution. There are
also ethanoate ions from equation I, but they are present in very small amounts (ethanoic acid dissociates
weakly) and are therefore not significant in removing the hydrogen ions. Reaction III is a buffering reac-
tion. Such a reaction should not readily regenerate the species it has removed from solution. In this case,
the removed species is H⁺ ions. They are not readily returned to the solution because the ethanoic acid
formed is a weak acid; it does not readily release a proton. Hydrogen ions are thus effectively removed
from the solution and this prevents the pH of the solution from decreasing.

When pH of the solution starts to increase (that is, upon addition of a little alkali), the excess hydroxide
ions are removed by the protons in reaction I, to form water.
H⁺ (aq) + OH⁻ (aq) → H₂O (l)
This is an effective buffering equation because the water formed only slightly dissociates and so does not
readily give back the hydroxide ions to the solution. pH of the solution is thus prevented from increasing.

Alkaline buffers
The mode of action of an alkaline buffer can be illustrated using the NH₃/NH₄Cl buffer system.
The reactions which exist in the buffer are
NH₃ (aq) + H₂O (l) ⇌ NH₄⁺ (aq) + OH⁻ (aq) ... I
NH₄Cl (aq) → NH₄⁺ (aq) + Cl⁻ (aq) ... II
When excess hydrogen ions are introduced into the system, they are neutralized by the OH⁻ ions present
in reaction I.
H⁺ (aq) + OH⁻ (aq) → H₂O (l)
When excess hydroxide ions are introduced into the system, they are removed by the ammonium ions in
equation II.

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NH₄⁺ (aq) + OH⁻ (aq) → NH₃ (aq) + H₂O (l)

Applications and uses of buffers

Some chemical processes are sensitive to changes in pH. Such reactions should therefore take place in a
buffered environment to reduce wide fluctuations in pH.

 Citric acid and a little NaOH are added to some mixtures to produce a ‘pH adjuster’.
The NaOH partially neutralizes the citric acid to produce the salt sodium citrate. A buffer is thus
formed, containing a weak acid (citric acid), and its salt, sodium citrate. The structure of citric
acid and its salt are shown below. On average, only one –COOH group is neutralized (not
necessarily the one shown) since NaOH is added in very small amounts.

CH2COOH CH2COOH

HO C COOH HO C COO-Na+

CH2COOH CH2COOH

citric acid sodium citrate

 Baby lotions are buffered to prevent or minimize nappy rash. This skin condition arises when
bacteria present in faeces and urine convert some chemicals, for example urea in urine, to
ammonia.
CO(NH2)2(aq) + H2O(l)  2NH3(aq) + CO2(aq)
It is the ammonia produced in this reaction that irritates the skin, causing a rash to appear. The
production of ammonia increases pH on the surface of the skin, which causes the bacteria to
proliferate, since they grow well in a slightly alkaline environment. Baby lotion is buffered at
around pH 6, which kills the bacteria or prevents them from multiplying.

 HCO3-in the form of soluble salts such as NaHCO3 , plays a vital role in the buffering of blood.
This salt actually works with its corresponding weak acid, carbonic acid, H 2CO3.

NaHCO3 Na+(aq) + HCO3-...(I)

H2CO3Ý H+(aq) + HCO3-(aq) ...(II)

When the concentration of H+ ions begin to increase, for example in rapidly respiring tissues,
HCO3-helps to prevent lowering of pH by removing the excess hydrogen ions.

HCO3-+ H+ H2CO3

This prevents poisoning of tissues by acid (acidosis).

When pH becomes too alkaline , the excess OH- ions are removed by the hydrogen ions in
equilibrium (II).

7.4 Acid - Base titrations

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The technique of titration can be used to find the quantity or concentration of acid or base that reacts
during neutralization .

7.4.1 Acid – base indicators

Acid-base indicators are substances which change colour according to the pH of the solution in which they
are. They are frequently used to identify the end point in acid -base titrations.
Most indicators are weak organic acids in which the dissociated form (anion) and the undissociated form
have different colours. For example, methyl orange is red in its undissociated form and yellow in its
dissociated form.

undissociated form of methyl orange (red) dissociated form (yellow)

Fig 7.12The dissociated and undissociated forms of methyl orange

We will represent the undissociated form as HMe and the dissociated form as Me⁻.In solution, the fol-
lowing equilibrium exists:

HMe ⇌H⁺ + Me⁻ ... (I)

red yellow

When the pH is low (high [H⁺]), the reverse reaction is favoured (Le Chatelier’s principle) and so the
solution would be red due to the presence of HMe. This is the colour of methyl orange in an acicic
environment. Now suppose that an acidic solution containing methyl orange is titrated with an alkali such
as NaOH. Some hydrogen ions are removed from the right side of the equilibrium (I). This causes the
equilibrium to shift to the right, resulting in the production of more of the dissociated form of methyl
orange. At the equivalence point, the colour of the indicator is halfway between the red undissociated
form and the yellow dissociated form, that is [HMe] = [Me⁻]. The colour at the equivalence point is
therefore orange (mixture of red and yellow).When one more drop of NaOH is added beyond the
equivalence point, the solution in the titration flask becomes alkaline and the yellow form becomes
predominant. For an indicator to be useful, it must give a rapid colour changewhen one more drop
oftitrant(from burette) is added to the analyte (in titration flask) past the equivalence point. Methyl
orange, phenolphthalein and bromothymol blue are frequently used as acid- base indicators because they
give sharp colour changes at the end-point of the titration.

Q
What is the ratio of [Me⁻] to [HMe] in solution at a pH of 2 (pKa for methyl orange
is 3.7)?

[In− ]
ALet the undissociated form of the indictor 2 = 3.7 + log
[HA]
[In− ]
log do not=photocopy
Prepublication manuscript © L. MWANAWENYU 2011. Please[HA]
2 – 3.7 = -1.7
or reproduce Page 275
[𝐈𝐧− ]
= 10-1.7
[𝐇𝐀]
 be HIn.
HIn (aq) Ý H+ (aq)+ In-(aq)
Using the Henderson-Hasselbach
equation
[In¯]
pH = pKa + log ...(I)
[HIn]

This calculation confirms that for methyl orange, the ratio of the dissociated form, In⁻ to the un-
dissociated form, HMe, is very small in acidic medium. In other words, at equilibrium, there is a very
small amount of the dissociated form and more of the undissociated acid. Thus at low pH, methyl orange
would be red in colour, since the red form, HMe, is more predominant.

Q
At what pH does methyl orange change colour during an acid-base titration? (Pka for
methyl orange is 3.7)

A Colour change takes place approximately at the equivalence point. At this point, [HA] =
[In− ]
[A-]. The ratio is therefore equal to 1 at the equivalence point.
[HA]

Using the Henderson-Hasselbach equation,

[In¯]
pH = pKa + log
[HIn]

pH = Pka + log 1
pH = pKa = 3.7

In other words, the pH at which an indicator changes colour is given by the pKa value for that indicator.

Range of an indicator
The calculation above shows that methyl orange will change colour from the red form to the yellow form,
or vice versa, when the pH of the solution is 3.7. In fact, 3.7 is the mid-point of the range of pH over which
methyl orange will change colour.

The range of an indicator is the range of pH over which it will change colour.

The three common indicators mentioned above have a pH range of about two units. That is, as a rule of
thumb, the visible colour change takes place about 1 pH unit on either side of the Pka value. For methyl
orange we calculated that the mid point of its range is 3.7(=pKa). pH therefore starts to change at a pH of
about 3.7 -1 = 2.7, and will continue to change until the pH is about (3.7 +1) = 4.7. The range for methyl
orange is therefore approximately 2.7 – 4.7. The actual range is shown in Table 7.4. Since we know the
pKa values for the other indicators, we can estimate their ranges.
For the indicator to be useful in an acid-base titration, its pH range must be in the vertical region of sharp
pH change on the titration curve. The indicator must also be able to change colour rapidly at the end -

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point. Different indicators have different ranges of pH because they have different acid-dissociation
constants. However, different indicators may be suitable for the same titration if they both have ranges
within the region of sharp pH change of the titration curve.

An important note

Some readers may suppose that all indicators change colour when the pH of the solution is 7. This is not true. Of the
indicators given in Table 7.4, only bromothymol blue changes colour at around pH 7. Methylorange changes colour at
a pH well below 7 and phenolphthalein changes colour at a pH well above 7.

Colour change
Indicator pKa Range(from pKa-1
to pKa + 1) Acid Alkali

Methyl orange 3.7 3.1-4.4 Red Yellow

Bromothymol blue 7.0 6.0-8.0 Yellow Blue

Phenolphthalein 9.0 8.0-10.0 Colourless Red

Table 7.4 The ranges and colours of three common indicators. Note that
the colourless form of phenolphthalein persists even when the solution
becomes alkaline; it will only start to change at a pH of about 8 and is
completely changed to red when pH becomes 10.

7.4.2 Titration curves

Titration curves help to visualize what exactly happens during the course of an acid-base titration. A
titration curve is obtained from a plot of pH of solution in flask (analyte) against volume of titrant from
burette. As the titrant is gradually added to the conical flask, neutralization takes place between the titrant
and the analyte, and this causes a change in pH of the solution in the flask. The exact trend of this change
in pH gives a titration curve. The shape of the titration curve depends on the relative strength of the acid
and the base used in the titration, but all titration curves generally have a sigmoid shape (roughly S-
shaped).
At the equivalence point of the titration, the two forms of the indicator are present in equal amounts,
giving a composite colour, for example, orange for methyl orange and green for bromothymol blue.

In all of the titrations below, an alkali is added from the burette to a flask containing an acid. The titration
curve therefore starts at a low pH but gradually rises until it is above pH 7.
During the titration, it is essential that the rapid change in colour be caused by a single drop of titrant;
otherwise the end point would be overshot. For example, at the end point using phenolphthalein, the
colour should be faint pink and not red. A red colour shows that too much alkali has been added from the
burette.
There are four types of acid-base titrations.

Type I : Strong acid against strong base

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Titrant: 0.1 moldm-3 NaOH (aq)
Analyte: 50 cm3 of 0.1 moldm-3 HCl (Fig 7.13)

Fig 7.13Titration set up used to obtain a titration curve

The initial pH
This is found using concentration of HCl before the titration is carried out.
pH = - log[H⁺] = -log 0.1 = 1
The titration curve will therefore begin at a pH of 1 (Fig 7.14). Titration curves are usually drawn so that
they start from a low pH and increase towards alkaline pH values. This is the reason why an acid, and not
an alkali, was put into the flask. However, there is nothing wrong with doing the titration the other way
round, that is, placing the acid in the burette and the alkali in the titration flask. Of course, this will invert
the shape of the titration curve; it now starts at a high pH above 7 and decreases as acid is added to the
flask.

During the titration: Before the equivalence point is reached

The alkali is added gradually to the acid in the conical flask. A neutralization reaction occurs, to form
water and salt.
NaOH (aq) + HCl (aq) → NaCl (aq) + H₂O (l)
When spectator ions are ignored, the reaction is found to be simply
OH⁻ (aq) + H⁺ (aq) → H₂O (l)
We therefore expect pH to remain fairly constant during this stage of the titration, because the sole
product of the reaction, H2O, is neutral.
At the equivalence point
The number of moles of HCl in the flask is given by
C x V = 0.1 x 50/1000 = 0.005

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 Since the reaction is 1:1 with respect to the acid and the base, the equivalence point is when
exactly 0.005 moles of HCl have reacted with exactly 0.005 moles of NaOH.
The volume of NaOH discharged from the burette to achieve this equivalence point is given by
V = n/C = 0.005/0.1
= 0.05 dm3 = 50cm3
At the equivalence point, the solution in the flask is the neutral salt NaCl, in which [OH⁻] = [H⁺]. At this
point, pH is equal to 7. However, one or two more drops from the burette beyond 50cm 3 will suddenly
cause the concentration of hydroxide ions to be higher than the concentration of hydrogen ions. This will
cause the indicator to change colour rapidly as the pH increases sharply. This sharp increase in pH cor-
responds to the steep part of the titration curve (Fig 7.10). The final volume of titrant which causes a
sudden colour change of the indicator is the end point volume. This volume is slightly larger than the
equivalence volume because it is achieved by adding one or two drops of titrant past the equivalence
point. The end point volume is therefore a good approximation of the volume of the titrant required for
complete reaction to take place.
The end point pH is found from the mid point of the region of sharp pH change on the titration curve.

Continued addition of titrant

This will make the solution even more alkaline so that pH continues to increase. However, the increase in
pH beyond the equivalence point is only gradual because addition of the titrant to the flask also causes
dilution of the solution. Dilution implies that the increase in the concentration of OH⁻ ions is very small
and so pH should remain fairly constant.

pH when 55.00cm3 of NaOH has been added

The alkalinity of the solution at this point is due to the 5.00cm3 of NaOH that has been added beyond the
end point volume of 50.00cm3. The number of moles of NaOH present in these 5.00cm 3 of solution is
given by C x V = 0.1 x 0.005dm3 = 0.000 5
The total volume of solution at this stage (volume of NaOH + volume of HCl) is now 55 cm 3 + 50cm3
= 105 cm3 = 0.105dm3. The concentration of OH⁻ ions is then given by
C = n/V = 0.000 5/ 0.105
= 4.762 x 10⁻3

Calculating pOH at this point of the titration:

pOH = -log[OH⁻] = -log (4.762 x 10-3)
= 2.32
Thus pH = 14-2.32 = 11.67

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 Fig 7.14 Titration curve for the titration of 50cm3 of 0.1 moldm -3HCl and 0.1 moldm-3NaOH.
Take note of key points which are discussed in the main text; theequivalence volume, the
end-point pH and the pH when 55cm3 of titrant have been added.

When we calculate the pH at higher volumes, say at 70.00 cm3 and 80.00 cm3, we find that the pH is only
slightly higher than 11.67. This is shown by the leveling out of the graph in Fig 7.10
The pH should gradually approach the pH typical of the solution of a strong base, NaOH.
However, as mentioned, the graph does not really reach pH 14 with practical volumes of titrant, because
of continued dilution of the solution in the flask.

Choice of indicator
Any indicator which changes colour within the region of sharp pH change can be used. Methyl orange,
bromothymol blue and phenolphthalein all have pH ranges within this region, so any one of them may be
used.

Type II : Strong acid against weak alkali

Suppose that we start with 50.00 cm3 of 0.1moldm-3 HCl in the flask and titrate it with 0.1moldm-3
ammonia (a weak alkali). The titration curve obtained is similar to the one above, but there are important
differences (Fig 7.15)
The reaction that takes place before the equivalence point has been reached is
NH₃ (aq) + HCl (aq) → NH₄⁺ (aq) + Cl⁻ (aq)

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The end point volume of NaOH (aq) is 50.00cm⁻3 as before. There are two important differences of the
titration curve to the one obtained for a strong acid and a strong base.
The highest pH achieved is lower and the region of sharp pH change is shorter. After the end point an
excess of a weak base, ammonia, is being added to the titration flask. The highest pH that can be achieved
is therefore lower than what would be obtained with a strong base. The decrease in the height of the
region of sharp pH change has two important consequences.

 Phenolphthalein, whose pH range is now outside the region of sharp pH change, becomes useless
as an indicator. This is because it will not start to change colour until about pH 8.
 The pH of the solution at the equivalence point is now slightly less than 7 because the NH₄Cl
solution present at this point is slightly acidic. The ammonium ion, being the conjugate of a weak
base (NH₃), is slightly acidic in nature, as shown by the equation below.
NH₄⁺ (aq) + H₂O (aq) → NH₃ (aq) + H₃O⁺
It is the presence of the oxonium ions (H₃O⁺) that causes the solution to be acidic.

Choice of indicator
You have noticed that the decrease in the height of the region of rapid pH change puts phenolphthalein
out of range and therefore renders it useless. If you check with Fig 7.15, you will notice that methyl orange
and bromothymol blue are still in the region of sharp pH change, so they can be used as indicators in the
titration of a strong acid with a weak base.

Fig 7.15Titration curve for a strong acid - weak base titration

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Type III: weak acid against strong base.
The titration curve in Fig 7.16 below was obtained when 50.00cm3 of 0.1 moldm⁻3 ethanoic acid (weak
acid) was titrated with 0.1 moldm⁻3 NaOH.

Fig 7.16Titration curve for a weak acid and strong base

Calculating the initial pH

The following equilibrium exists in the flaskbefore the base is added.
CH3COOH (aq) Ý CH3COO-(aq) + H+ (aq)
At equilibrium, a certain amount of the acid, say, x, moles, has dissociated. The amount of the acid
present at equilibrium is therefore 0.1-x. The amount of ethanoate and hydrogen ions on the product side
at equilibrium is each equal to x. Thus

Ka = x2/ (0.1-x)
1.7 x 10⁻⁵ = x2/(0.1-x)
The very small value of Ka shows that the acid is very weak and x is approximately equal to zero, that is,
0.1-x ≈ 0.1.
∴1.7 x 10⁻⁵ ≈ x2/0.1
solving gives x ≈ 1.30384 = [H⁺]

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pH = -log 1.30384
= 2.88
Notice that the initial pH is higher than in the two previous cases where the acid used was strong.

During the titration

The reaction taking place is
CH₃COOH (aq) + NaOH (aq) → CH₃COO⁻Na+ (aq) + H₂O(l)
As soon as the alkali hits the acid in the flask, it is neutralized to form the salt sodium ethanoate and
water. Before the equivalence point, pH increases only slightly because of the bufferingeffect of a mixture
of ethanoic acid and sodium ethanoate.
The titration curve obtained would be similar to the one obtained for titration of a strong acid against a
strong base. The key difference is that the lower limit of the curve has been raised and the height of the
region of sharp pH change has been reduced. This causes methyl orange to go out of range so that it is
useless as an indicator. It would change colour well before the equivalence point has been reached. Also
notice that the end point pH is now above 7. That is, the solution present at the end point is slightly alka-
line. Ethanoate ions which are present at the equivalence point are slightly alkaline, giving a pH greater
than 7 in solution. The phenomenon which causes a solution of the salt sodium ethanoate to be
acidic is known as salt hydrolysis. The ethanoate is a conjugate of a weak acid, so it has significant
alkalinity due to the hydrolysis reaction
CH₃COO⁻ (aq) + H₂O (l) → CH₃COOH (aq) + OH⁻ (aq)
It is the presence of hydroxyl ions that causes the solution to be slightly alkaline.

The final pH
Beyond the equivalence point, there is an excess of the strong base, sodium hydroxide in the flask, so the
final pH would be high, but it will not increase to 14 because of dilution.

Choice of indicators
The fact that the minimum pH of the curve is raised renders methyl orange useless. However, both
phenolphthalein and bromothymol blue have pH ranges within the vertical region of sharp pH change.
Any one of these may be used.

Hint
Just remember the titration curve for a strong acid and a strong base. In this case, all three indicators work, the order
from the bottom (lower pH) is methyl orange, bromothymol blue, and phenolphthalein. When titrating a strong acid
with a weak base, the maximum pH that can be attained is reduced. The graph is lowered and phenolphthalein
becomes useless whilst the other two remain effective. When titrating a weak acid with a strong base, the starting pH
is raised, so that methyl orange becomes useless, whilst the other two remain effective.

Determination of Ka
When exactly half of the weak acid in the titration flask has been neutralized, the flask now contains
equimolar amounts of the acid, CH3COOH and its salt, CH3COO-Na+. This happens at ½ of the
equivalence volume (= 25 cm3). The mixture in the flask is therefore a buffer and it causes pH to change
only gradually when a small volume of alkali is added from the burette. The K a value of the weak acid can
be found using the Henderson-Hasselbach equation

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 [Salt]
pH = pKa +log
[Acid]
[Salt]
But at ½ of the equivalence point [Salt] = [Acid], so =1
[Acid]
∴pH = pKa
The value of Ka can therefore be found from the pH at this point.
pH = -logKa
and Ka = 10-pH

Type IV: Weak acid against weak base

Let us use the titration curve of a strong acid with a strong base as a reference point. The initial pH
would be very low because the acid, being strong, dissociates fully, supplying the maximum possible
amount of hydrogen ions to the solution in the flask. Similarly, the final pH is high because the base,
which is now in excess, is strong and is able to dissociate fully, supplying a large amount of hydroxide ions
to the solution. Since the vertical region of sharp pH change spans values of pH from very lowto very
high, all three indicators have their ranges included in this vertical region, and any one of them can be
used.
When the acid is weak and base strong, the initial pH is higher, and this has the effect of reducing the
height of the region of sharp pH change. We have already seen that methyl orange then becomes useless
as an indicator.
When the base is weak and the acid strong, the maximum pH is lowered and this also causes the region of
sharp pH change to be shorter. This renders phenolphthalein useless.

Now consider what happens when both the acid and the base are weak. The initial pH is raised, while the
final pH is lowered. Height of the vertical region of the curve is therefore much reduced. In fact, it is so
reduced that none of the three indicators is effective because an indicator requires a vertical portion of the
curve which is at least two pH units to give a sharp colour change.
The titration curve in Fig 7.17 was obtained for 0.1 mol/dm3 ammonia and 50 cm3of 0.1 mol/dm3.
ethanoic acid.The reaction taking place before the equivalence point is
CH₃COOH (aq) + NH₃ (aq) → CH₃COO⁻ (aq) + NH4⁺ (aq)
The pH at the end point is approximately 7. This is because the two ions present, CH₃COO⁻ and NH₄⁺
have opposite effects which almost cancel each other out. CH₃COO⁻ hydrolyses in water, producing OH⁻
ions. NH₄⁺ ions hydrolyze in water producing oxonium ions. The oxonium ions and hydroxide ions then
neutralize each other so that overally, the solution is neutral.
H₃O⁺(aq) + OH⁻(aq) → 2H₂O(aq)

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 Fig 7.17Titration curve obtained for a weak base and a weak acid

7.4.3 Titrations involving polybasic acids

A polybasic acid can yield more than one hydrogen ions in solution. In pure water, only the first proton
can easily be released. Subsequent protons find it difficult to dissociate from the acid and enter solution
because they are attracted to the negative charge that now resides on the partially dissociated acid after
loss of the first proton.Consider the dissociation of H2SO4. The first proton is released according to the
equation
H2SO4 HSO4- + H+
The second proton is released according to the equation
HSO4-Ý SO4 2- + H+ ... (i)
This process is difficult because it requires loss of a positively charged particle (H+) from a negatively
charged ion (HSO4-). However, in the presence of an alkali such as NaOH, the OH -ions neutralize H+ ions
and remove them from the right hand side of equilibrium (i) as water. This promotes further dissociation
until the acid loses all of its hydrogen atoms. There is therefore step wise neutralization of the acid by the
base, and this causes the titration curve to have more than one regions of sharp pH change. The number
of such regions is equal to the number of dissociable hydrogen atoms on the acid. For sulphuric acid, there
are two regions of sharp pH change, and for phosphoric acid, H3PO4, there are three. For phosphonic acid,
H3PO3, there are only two regions of sharp pH change, because the third hydrogen atom is not bonded to
oxygen but to phosphorous (H3PO3 is diprotic) .This hydrogen atom can not be neutralized.

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Consider what happens when 50cm3 of 0.1 moldm-3 phosphoric acid, H3PO4 is titrated with 0.1 moldm-3
NaOH (aq). This acid has three acidic protons, so the titration curve has three distinct regions of sharp
pH change, corresponding to three separate neutralization reactions (Fig 7.18). These reactions are
labeled (i),(ii) and (iii) in the following discussion.
The first hydrogen atom is neutralized according to the equation
H3PO4(aq) + OH-(aq)  H2PO4-(aq) + H2O(l) ...(i)
The reaction is 1:1, so
moles of NaOH required to reach end-point = moles of acid that react
= Cacid x Vacid

50
= 0.1 x = 0.005
1000

moles of NaOH
End point volume=
concentration of NaOH

0.005
=
0.1
= 50 cm3
When 50cm3 of NaOH have been added, end point of reaction (i) is reached and the titration curve rises
sharply. The end point pH for reaction (i) is acidic because the product formed in the flask (H2PO4-) is
still acidic. Methyl orange, whose pH range is on the acidic side of the pH scale, would be suitable as an
indicator for the first step of the neutralization.
After the first end point, H3PO4 (aq) has been used up and only H2PO4-(aq) remains. A second
neutralization reaction begins, according to the equation
H2PO4-(aq) + OH-(aq)  HPO42-(aq) + H2O (l) ... (ii)
The end point volume for reaction (ii) is also 50 cm3. By the time the second end point is reached, 100cm3
of NaOH would have been added to the titration flask. The end point of this second step is alkaline
because the product formed, HPO42-(aq) undergoes salt hydrolysis, producing OH- ions.
HPO42- + H2O  H2PO4 - + OH-
Phenolphthalein, whose pH range is between 8 and 10, is a suitable indicator for the second neutralization
reaction (The two indicators, methyl orange and phenolphthalein, are put together in the titration flask
before the titration). Note that the region of sharp pH change associated with the second step is shorter,
because the acid that is reacting, H2PO4-, is weak.
At the end of the second reaction, the product that remains in the flask is HPO42-. This is also acidic, so it
reacts with more alkali according to the equation
HPO42-(aq) + OH-(aq)  PO43- + H2O (l) ... (iii)
A further 50cm3 of alkali is required to reach end point. The third region of sharp pH change on the
titration curve is very short and not so well defined because the acid being neutralized, HPO42-, is very
weak. No indicator is suitable here. After reaction (iii) is complete, the graph levels out because the final
product, PO43-, has no further reaction with NaOH. Addition of more NaOH from the burette does not
cause any significant increase in pH because of dilution.

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 (i)First end point pH.
Methylorange turns from red to orange

(ii)Second end point pH.

Phenolphthalein changes from colourless to light pink.

(iii) Third end point is not well pronounced. No

indicator is suitable for this stage of the titraton

Fig 7.18Titration of
a triprotic acid
with a strong acid

Q
The pHof 0.200 mol dm-3 NH3 is 11.3. 20.0 cm3 of this solution was titrated with 0.100
moldm-3 HCl. Sketch a graph to show how the pH changes during the titration. Mark clearly
the key points of your graph.

The initial pH (11.3) is that of the

A solution in the titration flask
(ammonia). Recall that the solution
whose concentration is known (HCl)
is put in the burette. The pH in the
flask gradually decreases due to
addition of an acid.

The end point pH is slightly less than

7 because the ammonium ion present
at the end point is slightly acidic due
to salt hydrolysis.

Note that there is enough information

in the question to allow calculation of
the end point volume (shown by the
broken vertical line).

7.5 Solubility and solubility product

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7.5.1 Solubility product
We may wish to assess the extent to which an ionic compound dissolves in water. Consider a generalized
ionic compound AxBy dissolving in water reversibly to give its ions, A n⁺ and Bp⁻
AxBy (s) ⇌ xAn⁺ + yBp⁻
We may write the equilibrium constant, Keq, as

[An+]x [Bp-]y
Keq = but [AxBy(s)] is constant
[AxBy(s)]

[An+]x [Bp-]y
Keq =
K

Taking the constant K to the left hand side, we see that this side now has two constants multiplying each
other. This gives another constant, which we call the solubility product, Ksp.
Ksp = [An+]x [ Bp-]y
For instance, the solubility product of Al₂O₃ refers to the equilibrium
Al₂O₃ (s) ⇌ 2Al3⁺(aq)+ 3O2-(aq)

Ksp = [Al3⁺]2[O2-]3 ... I

The solubility product, Ksp, is a measure of the extent to which an ionic compound dissolves in water. Ksp
is a true equilibrium constant and it is valid only for a system in which equilibrium has been achieved,
that is, when rate of dissolution of the salt is equal to the rate at which the ions combine to form the salt.

 The larger the value of Ksp, the greater the concentration of ions of the salt present in solution at
equilibrium and the more soluble the salt.
 Ksp is constant for a particular salt at a specified temperature. The value of Ksp changes when
temperature changes.
 The units of Ksp depend on the salt which is being studied. For Al₂O₃ above, the units may be
worked out from equation I above:
units: (moldm⁻3)2(moldm⁻3)3 = mol5dm⁻15

 The value of Ksp depends on temperature. In most cases, the solubility product increases as
temperature increases. In other words, most partially soluble salts become more soluble when
temperature is increased. This is because the dissolution of most partially soluble salts is endo-
thermic, and so is favoured by an increase in temperature(Le Chatelier’s principle)

Table 7.5shows the solubility products, Ksp, of some compounds at 298K.

Suggest reasons for the differences in the solubilities

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the following or reproduce
pairs of substances . Page 288

(a) BaSO4 and CaSO4

(b) Ca(OH)2 and Mg(OH)2
Compound Solubility
product
Q
BaSO4 1.3 x 10-10

CaSO4 2.4 x 10-5

Ca(OH)2 5.5 x 10-6

Mg(OH)2 1.1 x 10-11

AgCl 1.8 x 10-10

Q
AgBr 7.7 x 10-13

Table 7.5 Solubility products of

some compounds A

Ksp for PbI₂ is 7.0 x 10⁻⁹mol3dm-9at 25⁰C. This very small value shows that PbI₂ is almost insoluble in
water at 25⁰C. In other words, there are very few ions in solution formed from the dissolution of the lead
iodide.

Determination of solubility product

This involves finding the concentration of the ions of the salt present at equilibrium, as illustrated in the
example below.

Example

A 20.0 cm3 sample of saturated, aqueous Ca (OH)2 required 18.0cm3 of 0.050moldm-3 HCl for
complete neutralization. Calculate

(a) The pH of the saturated solution

(b) The solubility product of calcium hydroxide, stating the units .

Solution
Being saturated, the solution may be treated
as being at equilibrium.
Ca (OH) 2(s)Ý Ca2+ (aq) + 2OH-(aq)... (I)

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 (a)Moles of HCl used = C x V Kw 10¯¯¹⁴
[H+] = =
18 [OH¯] 0.0450
= 0.05 x
1000
= 2.222 x 10-13
= 9.0 x 10-4
pH = -log[H+]
Since HCl reacts with OH- in = -log (2.222 x 10-13)
the ratio of 1:1,
= 12.65
moles of OH- = moles of HCl

= 9.0 x 10-4
(b) From equation (I)
[OH-] = n/V [Ca2+] = ½ [OH-]
9 x 10¯⁴
= = ½ x 0.0450
20/1000
= 0.0225 moldm-3
= 0.0450
Ksp = [Ca2+][OH-]2
These are the moles of OH- ions
present in thesaturated solution. = 0.0225 x (0.0450)2

Now Kw = [OH-][H+] = 10-14 = 4.56 x 10-5 mol3 dm-9

Q
State a use of calcium hydroxide which depends on its solubility in water .

7.5.2 Solubility
Solubility is defined as the amount of solute that dissolves in 1dm3 of solvent, usually water, at a given
temperature. Suppose that for a particular solute, only 2g can dissolve in 1 dm3ofwater at 298K. The
solubility of the salt at this temperature is therefore 2gdm -3. Alternatively, the solubility can be given in
moldm-3. It does not matter how much of the solute is added to 1dm3 of water, only 2g will dissolve,
provided the temperature is the same. The amount of solute that can dissolve in a solvent is affected by
the volume of solvent used, for example, more sugar will dissolve in 1 dm3 of water than in 50 cm3. This is
why it is important to define solubility with reference to a fixed volume of solvent. The following are
important factors that affect solubility (for a fixed volume of solvent).

Temperature
For most partially soluble salts, solubility increases with increasing temperature. Of course, this also
increases the solubility product by increasing the number of moles of ions present in solution.

Presence of ions in common with the salt

Consider PbI2 as an example. It will dissolve better in pure water than in a solution that already contains
some Pb2+or some I- ions. The decrease in solubility of PbI2 in the presence of Pb2+ or I- is an example of
the common ion effect.

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7.5.3 The Common Ion Effect
This is the observation that the solubility of an ionic compound in a solvent is reduced by the presence of
ions which are common to that ionic compound.
Consider again the dissolution of PbI2 in water
PbI2(s) Ý Pb2+ (aq) + 2I-(aq) ... (I)
Now suppose that the water already contains I- ions. Presence of these ions will, by Le Chatelier’s
principle, cause equilibrium (I) to shift to the left, thus removing the extra iodide ions which were already
present in solution. In this way, the solubility of PbI2 is reduced and the equilibrium constant, that is, Ksp,
is kept constant.

Example

Calculate the solubility of AgCl in

(a) pure water

(b) in 0.1 moldm-3 NaCl(aq) [Ksp(AgCl) = 1.8 x 10-10)
Explain why the value you obtained in (b) is different from that obtained in (a).

Solution

AgCl(s) Ý Ag+ (aq) + Cl-(aq)

Ksp = [Ag+][Cl-]
Initial moles/dm31 0 0
1.8 x 10-10 = (x) (x+0.1) ... (I)
Eqlm moles 1-xx x
(x are moles of AgCl that dissolve) 1.8 x 10-10 = x2 + 0.1x

x2 + 0.1x - 1.8 x 10-10 = 0

(a) Ksp = [Ag+][Cl-]
Solving for x using the quadratic formula
Let [Ag+] = x = [Cl-] at equilibrium
−𝑏±√𝑏 2 −4𝑎𝑐
x =
1.8 x 10-10 = x2 2𝑎

−0.1± √(−0.1)2 −[4 𝑥(−1.8 𝑥 10¯10 )]

x = √( 1.8 x 10-10) = 1.34 x 10 -5 =
2

Solubility = 1.34 x 10-5 moldm-3 = 3.6 x 10-9

(Since x is moles of AgCl that dissolve) Solubility = 3.6 x 10-9mol2dm-6

(b)AgCl(s) Ý Ag+(aq) + Cl-(aq)

Initial moles/dm31 0 0.1
Eqlm moles 1-xx x+0.1

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 Alternatively 1.8 x 10-10 = (x)(0.1)
x = (1.8 x 10-10)/ 0.1
(b)AgCl(s) Ý Ag+(aq) + Cl-(aq)
= 1.8 x 10-9 = solubility of AgCl
Initial moles1 00
/dm3 This is a good and acceptable estimation
of x(= solubility of AgCl).
Eqlm moles 1-xx x+0.1

Ksp = [Ag+][Cl-] The solubility of AgCl in 0.1 moldm-3HCl is

therefore many times smaller than the
1.8 x 10-10 = (x) (x + 0.1) solubility in pure water. This is caused by the
Since the Ksp of AgCl is very small, the value of x is common ion effect
very small, so small that (x + 0.1) is approximately
equal to 0.1, that is

7.5.4 Saturated solutions and precipitation processes

A saturated solution is one that has dissolved so much solute that it can not dissolve any more. You have
probably used limewater to test for the presence of carbon dioxide. Limewater is in fact a saturated
solution of Ca(OH)2. This solution is not capable of dissolving any more Ca(OH)2. In this solution, the
product of ions [Ca2+][OH-]2 is exactly equal to Ksp.
Ca(OH)2(s) Ý Ca2+(aq) + 2OH-(aq) ...(I)

Ksp = [Ca2+][OH-] 2 = 5.5 x 10-5 mol3 dm-9

Suppose that some Ca2+ ions are added to the saturated solution. The product [Ca 2+][OH-] 2 is now greater
than Ksp. This causes the equilibrium (I) to shift to the left, removing the excess Ca2+ ions and resulting in
the formation of a precipitate of Ca(OH)2. In this way Ksp remains constant.

Precipitation of an ionic compound occurs if the product of its ions in solution, raised to their
respective powers, exceeds the value of Ksp .

Example

Equal volumes of 0.001moldm-3 Pb(NO3)2 and 0.002 moldm-3 KI are mixed. Predict whether or
not a precipitate would be formed (Ksp of PbI2 = 1.0 x 10-9).

Solution
PbI2 is the solid expected to form. When the two volumes are mixed, concentration of both Pb(NO 3)2 and
KI are halved.

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 0.01 [Pb2+] [I-]2 = 0.0050 x 0.01 = 5.0 x 1o-5
[Pb2+] = = 0.0050
2
Since [Pb2+] [I-]2> Ksp, a precipitate will be
0.02 formed)
[I-] = = 0.01
2 Formation of a precipitate reduces the concentration
of ions on the left side of equilibrium (i), thus
PbI2(s) Ý Pb2+ (aq) + 2I-(aq) ... (i) keeping Ksp constant.

Ksp (PbI2) = [Pb2+][I-]2

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
Exercise
text box.] 7.3 solubility and solubility product

1. The solubility of barium hydroxide, Ba(OH)2 , at 250C is 0.24gdm-3.

(a) (i) Calculate the molar concentration of the aqueous solution

(ii) If the solute is completely ionized, calculate the hydroxide ion concentration of the
solution.

(iii) Calculate the pH of the saturated aqueous barium hydroxide

(b) (i) Write an expression for the solubility product of barium hydroxide.
(ii) Calculate the solubility product of Ba(OH)2, stating its units

(c) Bottles containing aqueous barium hydroxide need to be kept firmly stoppered or a white
deposit forms on the surface.

(i) Name the white deposit.

(ii) Write an equation to show how the white deposit is formed.
9189/2/M/J/2011

2(a)Barium ions are poisonous. Patients with digestive tract problems are sometimes given
an X-ray after they have swallowed a ‘barium meal’, consisting of a suspension ofBaSO 4 in
water. The [Ba2+(aq)] in a saturated solution of BaSO4 is too low to causeproblems of toxicity.

(i)Write an expression for the solubility product, Ksp, for BaSO4, including its units.

(ii)The numerical value of Ksp is 1.30 × 10–10. Calculate [Ba2+(aq)] in a saturated

solution of BaSO4.

(iii)The numerical value of Ksp for BaCO3 (5 × 10–10) is not significantly higher thanthat for
BaSO4, but barium carbonate is very poisonous if ingested. Suggest areason why this

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might be so.

(b)A useful commercial source of magnesium is sea water, where [Mg2+(aq)] is0.054
moldm–3. The magnesium is precipitated from solution by adding calciumhydroxide.

Mg2+(aq) + Ca(OH)2(s)Ca2+(aq) + Mg(OH)2(s)

(i) Write an expression for the Ksp of Mg(OH)2, including its units.

(ii)The numerical value for Ksp is 2.00 x 10–11. Calculate [Mg2+(aq)] in a saturated
solution ofMg(OH)2.

(iii) Hence calculate the maximum percentage of the original magnesium in theseawater
that this method can extract.
9701/04/M/J/2003

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

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CHAPTER
8 Reaction Kinetics

Introduction
The central question in Reaction Kinetics is
How fast...?
In this topic we study reaction rates and the factors that affect them. We also study quantitative
methods of determining reaction rates. In Chapter 5 we discussed the energetic point of view of
chemical processes, in which the key question is ‘Is the reaction feasible?’
In this chapter we look at another point of view, the kinetic point of view. A reaction is said to be
energetically feasible if it has a negative enthalpy change, ∆H. Whether or not the reaction actually
takes place is beyond the scope of chemical energetics; this is a kinetic issue. Think of a boulder
resting on top of a hill. Is it energetically feasible for the rock to roll downward? The answer is clearly,
yes. But how many boulders do we see rolling down hills? In practice the event might not take place
because of the presence of an energy barrier. For example, the boulder might be stuck to the ground,
and to initiate the rolling movement, a certain amount of energy must be applied first to loosen the
rock. Similarly, a reaction might be energetically feasible but in practice it may fail to take place, or
will take place very slowly, because of the presence of a kinetic barrier. The minimum energy
required to overcome this kinetic barrier and initiate the reaction is known as activation energy.
The concept of activation energy is very important in chemistry and its applications. If a reaction has
a very high activation energy, then a large amount of energy is required to force it to take place. In
industry, this implies large consumptions of energy, therefore increasing production costs. The use of
high temperatures might also weaken equipment such as pipes, leading to high maintanance costs
and increased risks of explosions or leakages. The use of large amounts of heat to drive reactions can
be avoided by using catalysts, which work by lowering the activation energy of a reaction.

8.1Rate of reaction
This is the decrease in reactant concentrationor the increase in product concentration in a given time. The
term ‘time’ is essential in this definition. Rate is always how much a certain quantity changes in a given
time.
The unit of rate of reaction is moldm-3s-1.

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 𝐝𝐞𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐦𝐨𝐥𝐝𝐦¯³
Rate of reaction = = = moldm-3s-1
𝐭𝐢𝐦𝐞 𝐬

OR

𝐢𝐧𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐦𝐨𝐥𝐝𝐦¯³

Rate of reaction = = = moldm- 3s-1
𝐭𝐢𝐦𝐞 𝐬

8.1.1 concentration/time graphs

Fig 8.1 below shows the nature of a concentration/time graph. Graph (a) is for the consumption of a
reactant during the reaction, and graph (b) is for the formation of a product.

Fig 8.1 Graphs showing how concentration of reactant decreases and how
concentration of product increases with time.

 Concentration of reactant decreases with time as the reactant is being consumed. The slope of the
graph is therefore negative, that is, the graph is down-sloping. However, note that the decrease in
concentration is not linear, but curvilinear. The slope of the curve, which gives the rate of
reaction, is not constant. Rate of reaction depends on concentration of reactant.
At the beginning of the reaction, reactant concentration is high, and so the reaction is fast and
concentration of reactant drops rapidly. This explains why the slope of the curve is initially steep.
As the reaction progresses, concentration of reactant drops and this makes the reaction slower.
Conversion of reactants to products becomes slower and the slope of the curve becomes less
steep. Eventually, the concentration of reactant approaches zero, provided the reaction is
irreversible. A large number of reactions have a degree of reversibility if carried out in a closed
system. In such reactions, concentration of reactant does not drop to zero.
 Concentration of product increases during the reaction. Again, the curve is not linear. The slope of
the curve represents the rate of reaction. The steeper the slope, the faster the reaction. At the
beginning, the reaction is fast since the concentration of reactants is high. Products are thus
rapidly formed. This explains why the first part of the graph is steep. As the reaction progresses,
rate of reaction becomes slow as reactants are used. The curve therefore begins to level out.

Zeroth order reactions

In a zeroth order reaction, rate of reaction is not affected by changes in reactant concentration. In
other words, rate remains constant when concentration of reactant is increased or decreased. The
slope of the concentration time/graph is therefore constant, that is, the graph is linear, as shown in
Figure 8.2.

Graphical determination of rate of reaction

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The rate of a reaction can be determined from a suitably
drawn concentration/time graph. However, for most
reactions, rate of reaction changes with time, as already
explained, so we talk about the instantaneous rate of
 concentration
of reactant

time

Fig 8.2 Concentration / time graph

for a zeroth order reaction

concentration Rate of reaction at time, t

of reactant
= slope of tangent at that time
x 𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐲
=
y 𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐱
change in reactant concentration
t time =
change in time
Fig 8.3 Finding rate of reaction at
time t using a concentration/time.

Alternatively, the rate can be obtained from a product concentration/ time graph.

8.1.2 Rate / time graph

The shapes of the graphs above have been explained in terms of the decrease in rate of reaction with time.
For any reaction, the rate/time graph is therefore as shown in Fig 8.4.

rate Initially the rate of reaction is high since the concentration of reactants is
still high. Rate of reaction depends on how frequently reactant particles
collide. When concentration of reactants is high, frequency of collisions is
also high and the reaction is correspondingly fast. The rate of reaction
decreases with time, that is, the rate/time graph is down sloping. This is a
result of the decrease in reactant concentration. However, this decrease is
not uniform, so the graph is not a straight line but is curvilinear. The
time consumption of reactants is rapid at the beginning of the reaction, so at
approximately time zero, thecurve is very steep. The curve becomes less
Fig 8.4rate/time
steep with time because the speed at which reactant molecules are
graph
consumed decreases.
The inverse (concave) nature of the graph also illustrates an important point. Rate of reaction is inversely
related to time. The larger the time it takes for the reaction to take place, the slower the
reaction. Conversely, a reaction which occurs within a very small amount of time is fast, that is
1
Rate α
t
Suppose that reaction A occurs in 10 seconds and reaction B in 40 seconds, then

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 1 1
Rate of reaction A α = 0.1 Rate of reaction B α = 0.025
10 40

Reaction A is therefore four times faster than reaction B.

8.2Factors that affect rate of a reaction

When we discuss factors that affect the speed of a reaction, we should make a clear distinction between
one chemical reaction carried out under different conditions and two different chemical reactions.
Different reactions proceed at different speeds, even when the reaction conditions are the same. This
observation can be explained in terms of the different activation activation energies of the reactions.
A specified reaction will proceed slowly or rapidly, depending on the following factors:

 Concentration of reactant or pressure of a gaseous reactant

 Temperature
 reactant particle size(surface area)
 Presence or absence of a catalyst
 Light(for some reactions)

A concept known as the collision theory is useful in explaining these factors.

8.2.1 The collision theory

The collision theory sates that for reactant molecules to react, they must first collide with sufficient
energy and with the correct orientation.

For a reaction to take place, reactant particles must first collide, but the collisions must be energetic
enough to overcome the activation energy of the reaction and form a product. A collision which actually
results in a product being formed is known as an effective collision. The speed of reaction depends on the
frequency of effective collisions. The more frequent they are, the faster the reaction.

The orientation factor is also important. This is about the direction in which reactant particles
approach each other. Orientation factors are more significant if the reactant molecules are large. Such
molecules may have certain reactive centres which must approach each other if the collision is to be
successful. Consider the condensation reaction between two amino acids, which are the building blocks in
all proteins. For the reaction to take place, the –COOH group on one amino acid must collide with the
–NH2 group on the second amino acid. This is the orientation that favours a reaction (see case 1 below)
Case 2 is an example of how the two amino acids may collide with a wrong orientation. In this case, the
two amino acids actually repel each other because of the lone pair of electrons on each N atom.

.. ..

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 .. ..

Effect of temperature
The speed of most reactions increases as temperature increases.
The effect of temperature can be explained in terms of the collision theory. Increasing temperature results
in an increase in the kinetic energy of the reactant particles, and this increases the frequency of effective
collisions.

Effect of concentration and pressure

Increasing the concentration of a reactant will also increase the speed of reaction. The higher the
concentration, the greater are the chances of effective collisions. Increasing pressure of reactant in a gas
phase reaction also increases rate of reaction. When pressure of the gas is high, particles are close and
they collide frequently. Note that increasing concentration or pressure does not make collisions effective;
it simply increases the chances of collisions. For the collisions to be effective, temperature must be
increased to make the collisions more energetic.

Effect of particle size

Reducing the particle size of a reactant exposes a greater total surface area for reaction. This increases the
speed of reaction. A well known example are explosions which were often reported in flour mills. The very
fine nature of the flour particles greatly increased the speed of combustion reactions (An explosion is a
very rapid reaction which results in a sudden increase in the volume of gaseous products). If reactant
particles are course or large, only particles on the surface can react. In other words, the total surface area
of the reactant is reduced.

8.3The concept of activation energy

The collision theory says that for reactant particles to react they must possess enough energy.

Activation energy is the minimum energy which reactant particles must possess in order
to collideand form a product.

When particles collide, they must do so with energy greater than or equal to the activation energy,
otherwise the reaction will not take place.
Activation energy may be visualized as an energy barrier to a reaction. The higher the activation energy of
the reaction, the higher the energy barrier, and the slower the reaction.

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Energy profile diagrams
An energy profile shows both energetic and kinetic information about a chemical reaction. Energetic
information is shown in terms of relative energy levels of reactants, and kinetic data is shown in terms of
the magnitude of the activation energy, Ea. Contrast with an energy leveldiagram which shows only
energetic data.Fig 8.5 shows an energy profile for an exothermic and for an endothermic reaction.

energy The concept of activation energy helps to explain

why some reactions are very slow or do not take
place at all, despite being energetically feasible. An
example is the reaction of peroxodisulphate ions
Ea with iodide ions.
reactants S₂O₈²⁻ (aq) + 2I⁻ (aq) → SO₄2-(aq) + I₂ (aq)
 H(negativ e) Despite being energetically feasible, the reaction is
products so slow that a mixture of the two ions can stay for a
very long time without showing any appreciable
progress of reaction reaction. This is due to the high activation energy
of the reaction. It is so high that very few particles
energy can achieve it. As a result, the number of particles
that have sufficient energy for reaction at any given
time is very small. The high activation energy of
Ea products this reaction is expected sincethe two reactants are
both negatively charged and so they naturally
H(positiv e) repel. A very large amount of energy is
reactants
required to force the ions to collide and react.

progress of reaction
Fig 8.5 Energy profile for (a) an exothermic
reaction (b) an endothermic reaction

8.4The Maxwell-Boltzmann curve

The distribution of molecular speeds in a gaseous reactant can be shown by the Maxwell-Boltzmann
curve (Fig 8.6). In the sample, the particles possess a range of kinetic energies, from lowest to highest.
Only molecules whose energy is greater than or equal to activation energy are able to form products.
These are the particles whose collisions are energetic enough. In fig 8.6, Ea2 is the activation energy for a
relatively slow reaction. Since the activation energy is relatively high, very few particles, represented by
area y, can afford the energy required to react. For a faster reaction, the activation energy is smaller.
Consequently, more particles, represented by the area (x + y), can achieve the energy required for
reaction.
The highest point on the curve corresponds to the most probable (mean) energy of the particles, labeled A
on the diagram. The Boltzmann curve can be used to explain the effect of temperature and a catalyst on
the speed of a reaction.

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 Effect of temperature
Fig 8.7shows the effect of increasing temperature
proportion of
particles (from T1 to T2) on the position and shape of the
Boltzmann curve.
x  Increasing temperature lowers the maximum
point of the curve and shifts it to the right. As
y a result, the average energy of the particles
increases from A1 to A2 but the proportion of
particles that can achieve this energy de-
A Ea 1 E a2 creases from n1 to n2.
Energy
 The activation energy of the reaction is not
Fig 8.6 The Boltzmann curve showing affected by changing temperature. At the
the distribution of molecular energies lower temperature T1, the proportion of par-
in a gaseous reactant. ticles with sufficient energy to react is x.
a gas sample
proportion of
When temperature is increased to T2, the
of particles proportion of particles whose energy is equal
T1 to or greater than Ea increases to (x+y).
More particles therefore have sufficient
n1 (T2 > T1)
T2 energy to react, and the speed of reaction in-
n2
creases.
y
Increasing temperature increases rate of reaction by
x increasing frequency of collisions and also by in-
creasing the number of particles that have energy
A1 A2 E
a energy equal to or greater than activation energy.
Fig 8.7 The effect of changing tempera-
ture on the distribution of molecular
energies in a gaseous sample.

8.5Catalysts and catalysis

A catalyst is a substance that speeds up a reaction by providing an alternative

reaction route with lower activation energy, but is recovered unchanged in nature or in
quantity at the end of the reaction.

Catalysisis the speeding up of a chemical reaction by a catalyst.

The Boltzmann curve (Fig 8.8) can be used to explain the effect of a catalyst on the speed of a reaction.
 A catalyst does not alter the kinetic energies of the molecules. The shape of the curve is therefore
not altered.
 Activation energy for the unanalyzed reaction is Ea2. At this higher activation energy, fewer
particles can achieve the energy required for effective collisions. The Region marked x represents
the particles whose energy is greater than or equal to E a2. These are the particles that can react
whenactivation energy = Ea2.
 A catalyst creates an alternative route with lower activation energy (Ea1). More particles can
therefore achieve the energy required for effective collisions. Note that the proportion of particles

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 that can react increases from x to (x + y) and so the reaction becomes faster at the lower
activation energy.

proportion of  A catalyst is the only factor that alters the

particles magnitude of activation energy. Other
factors such as temperature and concen-
tration do not affect the size of the
x activation energy. They simply change
the frequency or energy, or both, of
y collisions.
The effect of a catalyst can further be explained
using an energy profile (Fig 7.9). This diagram
Ea1 Ea2 Energy shows the lowering of activation energy by a cat-
Fig 8.8 A catalyst lowers activation alyst.
energy and increases the proportion of
particles that can react. Properties of catalyst
 Generally increases speed of a reaction.
 Creates a new reaction route (mechan-
ism) whose activation energy is lower
than for the uncatalyzed reaction.
 Does not change the enthalpy of reac-
tion. This is expected from Hess’ law.
The enthalpy change of reaction
remains the same when the route of a
reaction is changed, provided that the
relative energy levels of reactants and
products are the same.
 A catalyst does not make an impossible
reaction possible. It simply makes a
feasible reaction faster.
Fig 8.9 Energy profile showing the  A catalyst takes an active role during a
lowering of activation energy by a chemical reaction. An erroneous defini-
catalyst tion is often made by students in which
they claim that a catalyst is a substance
that does not take part in a chemical reaction. For it to speed up a reaction, a catalyst must play
an active role. In fact, a catalyst undergoes a temporary chemical change during a reaction.
However, it is regenerated in its original chemical form, and in its original quantity, at the end of
the reaction.
 In a reversible reaction, a catalyst speeds up the forward and the reverse reaction to the same ex-
tent. In other words, a catalyst does not alter the position of equilibrium, but simply allows the
equilibrium to be achieved faster. The value of the equilibrium constant is therefore not altered
by the presence of a catalyst.

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During the Haber process for the manufacture of ammonia, hydrogen and nitrogen
Q combines according to the equation
3H2(g) + N2(g) Ý2NH3(g) ∆H = -93 Kjmol-1

Which statements are true about this process?

1. The rate of the reaction is increased by lowering temperature

2. The yield of ammonia is increased by lowering temperature
3. The rate of reaction increases when temperature is increased

2 and 3 are correct.

A1 and 2.
Since the reaction is exothermic, lowering temperature favours the formation of ammonia
(Le Chatelier’s principle). In other words, the percentage of ammonia in the equilibrium
mixture increases. However, the rate of reaction decreases, that is, it takes a longer time for
the maximum yield of ammonia to be achieved. For this reason, very low temperatures are
avoided in the Haber process

3.Increasing temperature increasesrate of reaction, that is, equilibrium is rapidly achieved.

However, the percentage of ammonia in the equilibrium mixture decreases because the
equilibrium now lies more to the left. For this reason, very high temperatures are avoided in
the Haber process. The actual temperature used (about 4500C) is a compromise between
low temperature (which favourshigh yield of ammonia but reduces rate of reaction) and
high temperature (which increases rate of reaction but decreases the yield of ammonia).

8.5.1 Homogeneous versus heterogeneous catalysis

Homogeneous catalysis is the speeding up of a reaction by a catalyst which is in the same phase as the
reactants, e.g. both catalyst and reactants could be in solution.
Heterogenous catalysis is when the catalyst and reactant are in different phases. Well known
examples of heterogeneous catalysis include the use of solid iron in the Haber process for the manufacture
of ammonia, and the hydrogenation of unsaturated oils during the manufacture of margarine.

Example of homogenous catalysis: The catalysis of the reaction between peroxodi-

sulphate and iodide ions

Peroxodisulphate can be reduced to sulphate by iodide ions. Meanwhile, the iodide ions are oxidized to
iodine.

S₂O₈²⁻ (aq) + 2I⁻ (aq) → 2SO₄²⁻ (aq) + I₂ (aq) … (i)

This is a redox reaction because the oxidation number of sulphur in peroxodisulphate decreases, whilst
that of iodine increases. We may wish to assess the energetic feasibility of this reaction. A large and
positive Eθ value implies a feasible reaction. Reaction 1 above can be resolved into its half equations,
either by inspection or by using the data booklet.

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 Eθ/V
Reduction half equation : S₂O₈²⁻ (aq) + 2e⁻→2SO₄²⁻(aq) +2.01 ...(ii)
Oxidation half equation : 2I⁻(aq) →I₂(aq) + 2e⁻-0.54 ...(iii)
net equation S₂O₈²⁻(aq) +2I⁻(aq) 2SO₄²⁻(aq) + I₂(aq) +1.47
Since the Eθcell of reaction (i)is large and positive, it can be concluded that the reaction is energetically
feasible. Now, a clear distinction has to be made between energetic and kinetic feasibility. If a reaction is
energetically feasible (large and positive Eθcell value or negative enthalpy change) it does not
necessarily mean that it will happen spontaneously. If the reaction has a very high activation energy, it
may not take place. It is said to be kinetically unfeasible. Such a reaction can be made to take place by
using harsh conditions (high temperature, high pressure/concentration) or by using a catalyst.
The reaction between peroxodisulphate and iodide has a very high activation energy since the ions
participating in the reaction have like charges and so they repel each other.A very large amount of energy
is required to force the reacting ions to collide.
Introducing a catalyst such as Fe2+(aq) or Fe3+(aq) speeds up the reaction by creating an alternative
reaction mechanism with a lower activation energy.

Eθ/V
S₂O₈²⁻ (aq) + 2e⁻→2SO4²⁻ (aq) +2.01 … (ii)
Fe²⁺ (aq) → Fe³⁺ (aq) + e⁻ - 0.77 … (iv)
2I⁻ (aq) →I₂(aq) + 2e⁻ -0.54 …(iii)

If Fe²⁺ is used as the catalyst, it will reduce peroxodisulphate to sulphate, a role which is played by iodide
ions in the uncatalyzed reaction. In turn, Fe2+ is oxidized to Fe3+. By combining equations (ii) and (iv):

S₂O₈²⁻ (aq) + Fe²⁺ (aq) → 2SO₄²⁻ (aq) + Fe³⁺ (aq) … (v)

Eθ = 2.01 + (- 0.77) = +1.24V
This reaction is energetically feasible since it has a positive Eθ value. It is also kineticallypossible since it
involves ions of opposite charge which naturally attract each other. The activation energy of this reaction
is thereforevery low, and so it is very fast. However, at this stage, we can not conclude that iron (II) has
acted as a catalyst. We can only make this conclusion after the Fe(II) has been successfully recovered from
Fe(III). In reaction (vi) below, the Fe (III) formed in reaction (v) is reduced back to Fe (II) by iodide ions.
Meanwhile the iodide ions are oxidized to iodine. Note that in this reaction, Fe3+ replaces S2O82- as the
oxidizing agent in the conversion of iodide to iodine. Reaction (vi) is obtained by combining equations
(iii) and (iv) above.

2I⁻ (aq) +Fe³⁺ (aq) →Fe²⁺ (aq) + I₂ (aq) ... (vi)

Eθ = 0.77 + (-0.54) = +0.23V
Combining equations (v) and (vi) gives the original reaction (i). The Eθcell for reaction (i) is also
obtained by adding the Eθcell values for reactions (v) and (vi).

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 Eθ/V
S₂O₈²⁻ (aq) + Fe²⁺ (aq)→ 2SO₄²⁻ (aq) + Fe³⁺ (aq) +1.24 ...(v)
2I⁻ (aq) +Fe³⁺ (aq)→Fe²⁺ (aq) + I₂ (aq) +0.23 ... (vi)

S₂O₈²⁻ (aq) + 2I⁻ (aq) 2SO₄²⁻ (aq) + I₂ (aq) +1.47 as before

 Fe2+ has acted as a homogeneous catalyst. It created a new reaction mechanism in which the
reacting particles have opposite charges which naturally attract (equations (v) and (vi)). A very
small amount of energy is therefore needed to bring about energetic collisions, that is, the
activation energy is very small. The reaction is very fast since the attraction between ions of
opposite charge is rapid.
 The mechanism described above emphasizes the fact that a catalyst takes an active role in the
reaction and often undergoes temporary chemical changes during the reaction.
 It is also possible to use Fe3+ instead of Fe2+ as the catalyst. First, Fe3+ oxidizes I- to I2. Meanwhile,
the Fe3+ is reduced to Fe2+. The catalyst is regenerated when Fe2+ reduces S₂O₈²⁻ to SO42-.
Meanwhile, Fe2+ is oxidized back to Fe3+.
 Transition elements and their ions or compounds often act as catalysts because they have the
ability to change their oxidation states during the catalysis, for example, iron can easily change
form the +2 to the +3 state and back.

Heterogeneous catalysis
Well known cases of heterogeneous catalysis involve a solid catalyst and gaseous reactants. It is believed
that the catalyst adsorbs reactant particles on its surface, bringing them together in the correct
orientation required for a reaction to take place. The catalyst must be able to bind the reactant particles by
forming weak bonds. This usually requires the catalyst to have available orbitals to accept electrons from
the reactant particles when the weak bonds are formed between the catalyst and the reactant particles.
This explains the ability of transition metals and their compounds to participate in catalysis. They have
vacancies in the d-orbitals to accommodate electrons from the reactant molecules. Formation of weak
bonds between the catalyst and reactants weakens bonds in the reactant molecules. The activation energy
of the reaction is therefore lowered since only a small amount of energy is required to break bonds in the
reactants.
A large number of industrial processes involve heterogeneous catalysis. Examples are the use of iron in
the manufacture of NH3 from H2 and N2 (Haber process) and the use of vanadium (V) oxide in the
Contact process for the manufacture of sulphuric acid.

A heterogeneous catalyst usually works by bringing reactant molecules closer together with the correct
orientation, and by weakening bonds in reactant molecules.

Some cases of heterogeneous catalysis involve a liquid reactant and a solid catalyst. A well known example
is the decomposition of hydrogen peroxide in the presence of solid manganese dioxide. On its own,
hydrogen peroxide decomposes very slowly to form water and oxygen. When a little MnO 2 (black powder)
is added, a vigorous reaction takes place and there is brisk effervescence as oxygen gas is rapidly released.
This catalysed decomposition of hydrogen peroxide is a convenient way of preparing oxygen in the lab.

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8.5.2 Enzymes
These are biological catalysts which speed up biochemical reactions. Like inorganic catalysts, enzymes
work by providing an alternative reaction pathway with a lower activation energy. However, enzymes have
certain properties which make them unique (Seesection11.1for further details). Enzymes allow biological
processes to take place under relatively mild conditions of temperature, pressure and pH. In the absence
of enzymes, most biochemical reactions would require stringent conditions, for example, high tempera-
ture. Such conditions would destroy cells and kill the organism.

8.5.3 Autocatalysis
This is a phenomenon in which a product of a reaction speeds up the reaction.

A well known example is the hydrolysis of ethyl ethanoate to form

ethanoic acid and ethanol. This reaction requires H+ as a catalyst.
rate of
reaction When the reaction is carried out in the absence of an acid, itis
very slow at the beginning, but after some time the rate of reac-
tion suddenly increases (Fig 7.10).
Fig 8.10 At the beginning, the reaction is very slow because of the absence
of a catalyst. Ethanoic acid, which is produced during the reac-
time
tion, acts as a catalyst by providing H+ ions.
This explains the increase in the rate of reaction. After some time, the rate of formation of products begins
to decrease again and soon levels out. This is because the hydrolysis of ethyl ethanoate is reversible.
CH3COOCH2CH3(aq) + H2O(l) Ý CH3COOH(aq) + CH3CH2OH(aq)
When the concentration of the products, ethanoic acid and ethanol, begins to increase the reverse reaction
becomes more significant and this reduces the rate of formation of products.

8.6Quantitative kinetics

8.6.1 The rate law

You now know that altering concentration of a reactant causes the rate of reaction to change. It is
important to be able to quantify the effect of changing reactant concentration on the rate of reaction.

The rate law, also known as the rate equation, is an experimentallydetermined equation linking
the rate of reaction to the concentration of reactants.

 The rate law gives a quantitative description of the effect of changing concentration on the rate of
reaction. For example, the rate law may tell us that doubling concentration of a reactant causes
the rate of reaction to double as well.
 The rate law can only be established experimentally. It is not possible to determine the rate
equation by simply inspecting the stoichiometrically balanced equation.

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Order of reaction
The order of reaction with respect to a particular reactant is the power to which the concentra-
tion of that reactant is raised in the rate law.

The overall order of reaction refers to the sum of the orders of the different reactants shown in
the rate law.

Consider the reaction

aA + bB →cC + dD
The rate law may be written as
R = k [A]m[B]n
m is the order of reaction with respect to reactant A. n is the order of reaction with respect to reactant B.
The overall order of reaction is (m+ n).
K is the constant of proportionality (rate constant) between the rate of reaction and the concentration
terms in the equation.

8.6.2 First order reactions

If the reactionaA + bB →cC + dD is first order with respect to reactant A, the rate law is
R = k[A]
This is clearly a linear equation of the form Y =mX; the graph of R against [A]is a straight line passing
through the origin (Fig 8.11).

-3 This graph shows that when the concentration of A is

Rate/moldm
changed, the rate of reaction changes proportionally, for
example, doubling concentration also causes the rate of
reaction to double.
The slope of this line gives the value of the rate constant,K
Fig 8.11
Change in rate of reaction
[A]/moldm
-3 K = = slope of line
change in concentration

This is the same result that could have been obtained by making k subject of the formula in the rate law
R = k[A].

8.6.3 The concept of half life

The half life of a reaction refers to the time it takes for the concentration of reactant to be reduced to half
of an initial value.

The half life of a first order reaction is constant, as illustrated in Fig 8.12.Let the initial concentration be
[A]0. The time required for this concentration to be halved to ½ [A] 0 is the first t1/2. The time needed for
further halving of the concentration to ¼[A]0 is the second t1/2. Further halving of the concentration
reduces it to 1/8[A]0, giving the third t1/2.
For a first order reaction, the first, second, third (etc) half lives are constant. In the graph below,
t1/21 = t1/22 = t1/23 . This is a good method of recognizing a first order reaction.

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 Determination of t1/2
concentration For a first order reaction, t1/2can be determined
[A]0 graphically, as shown in Fig 7.12, or by formula

𝐥𝐧 𝟐
t1/2= where K is the rate constant
1 𝐊
2 [A]0
1
4 [A] 0 Fig 8.12
The half life of a first order
1 2 3 reaction is constant
t t 1 /2 t 1 /2 time
1 /2

The rate/concentration graph of the reaction A  B is shown below

Q
(a) Deduce the order of the reaction with respect to
reactant A.

(b) Determine the half-life of the reaction (assume

the units of rate are moldm-3s-1)

(a) The order = 1(since the graph of rate/[A] is linear, that is, it has a constant slope)
A
(b) K =slope of rate/[A] graph = 2 units
𝐥𝐧 𝟐 𝐥𝐧 𝟐
t1/2= =
𝐊 𝟐
= 0.35 seconds

8.6.4 Second order reactions

If the reaction aA + bB →cC + dD is second order, say, with respect to reactant B, the rate law in terms
of B is written as
R= k [B] 2
This is a quadratic expression of the form Y = mX2. The graph of R against [B] is therefore the positive
half of a parabola whose minimum point is at the origin (Fig 8.13(a)).The graph can be linearized for
easier analysis:
R= k[B]2
Let [B]2 be X, then
R= kX
A linear graph is then plotted for R against X, as shown in Fig 7.13(b).The slope of this linear graph gives
the value of K, the rate constant.

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 Rate Concentration - time graph for a second order reaction
The graph has the same shape as that of a first order reaction, and for the
same reason (Fig 8.14). Concentration of reactant decreases with time,
so the graph is down-sloping, but the rate of decrease of concentration is
not uniform, so the slope of the curve becomes less and less steep with
time, that is, the curve has an inverse shape.
[B]
concentration
[B] 0
R

Fig 8.14
X( = [B]2) 1 2
Fig 8.13 t 1 /2 t 1 /2
time

What distinguishes between the graph of a second order and that of a first order reaction is the half life.
For a first order reaction, the graph has a constant t1/2. For a second order reaction, the t 1/2 successively
becomes larger with time, for example, in Fig 8.14 above,t1/22 >t1/21 .

8.6.5 Zeroth order reactions

It sometimes happens that the rate of reaction is unaffected by changing the concentration of a reactant.
The reaction is said to be of zeroth order with respect to that reactant. If a reaction is zeroth order with
respect to reactant A, we may write
R = k[A]0
Which simplifies to R=k, that is, rate of reaction remains constant when concentration of the reactant is
altered. The graph of R against [A] is shown in Fig 8.15(a). The corresponding concentration/time graph
is shown in Fig 8.15(b). Since the rate of reaction is constant, the rate of decrease of [A] is also constant,
that is, the concentration/time graph is linear.

Rate

[A]
Fig 8.15

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8.6.6 Finding orders of reaction by the initial rates method.
Rate of reaction has already been defined as the rate of decrease of the concentration of a reactant, that is
decrease in concentration of reactant
Rate =
Time
The rate of reaction at a particular time, that is, the instantaneous rate of reaction, can be found by taking
the slope at the appropriate time on the concentration /time graph. When the slope is taken at time zero,
the rate obtained is known as the initial rate of reaction (Fig 8.16).
The initial rate of reaction therefore refers to the rate of reaction when an infinitesimally small amount
of reactant has reacted, that is, it is the rate of reaction at approximately time zero.

concentration
of reactant
Tangent drawn at time zero . Slope of this tangent gives the
initial rate of reaction.

0 time
Fig 8.16 Finding the initial rate of
reaction by graphical means

Consider the reaction aA + bB → cC + dD. Suppose that we wish to find the order of reaction with
respect to reactant A. The concentration of A is varied in several experiments (runs), whilst that of B is
held constant. The initial rate of reaction at each new concentration of A is then determined. Similarly, to
find order of reaction with respect to reactant B, the concentration of B must be varied whilst that of A is
held constant. The initial rate when B is varied is then recorded.
Consider a simple reaction A + B  C. Suppose that when the reaction is carried out using an initial
concentration [A]0the corresponding rate of reaction is R1.
The rate law can then be written as
R1 = K [A]1m ...(i)
The experiment is now repeated using a higher concentration of A, [A] 2. Let the corresponding rate of
reaction be R2.
The rate law then becomes
R2 = K [A]2m ...(ii)
Note that changing concentration changes rate of reaction, but does not change the order of reaction.
Dividing equation (ii) by (i) (or vice-versa).
m
R2 [A]2
= m
R1 [A]1
m
R2 [A]2
=
R1 [A]1

The value of m, which is the order of reaction with respect to reactant A can then be calculated.

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 Example 1

At 7000C, nitrogen monoxide and hydrogen reacts as follows.

2NO(g) + 2H2(g)  N2(g) + 2H2O
The results of some investigations of this reaction are shown below.

Experiment Initial concentration Initial Initial rate

of NO/moldm-3 concentration of H2 of reaction
/moldm-3 /moldm-3s-1

1 0.0020 0.012 0.0033

2 0.0040 0.012 0.013

3 0.0060 0.012 0.030

4 0.012 0.0020 0.020

5 0.012 0.0040 0.040

6 0.012 0.0060 0.060

Use the data given in the table to deduce the rate law for the reaction between nitrogen monoxide
and hydrogen gas. Hence deduce the value for the rate constant, including its units.
9701/3/M/J/1993, adapted.

Solution
The rate equation will have the general form
R = K [NO]m[H2]n
First, the orders of reaction m and n must be found
Finding m
Using lines 1 and 2
The concentration of NO is doubled, but that of H 2 remains constant. Any change in rate of
reaction is therefore due to the change in concentration of NO. Using the formula

R2 [A] 2
=
R1 [A] 1

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 m The rate law is therefore
0 .0 1 3 0 .0 0 4 0
= R = K [NO]2[H2]
0 .0 0 3 3 0 .0 0 2 0
Overally, the reaction is third order (recall that
4 = 2
m overall order is the sum of the orders of all the
4= 2m⇒m = 2 reactants shown in the rate law). Such a reaction
is said to be termolecular. It requires the collision
Therefore order of reaction with respect to NO is 2 of three molecules to occur, which is quite unusual.
(In other words, doubling the concentration of The rate constant K is found by making it subject
NO causes the rate of reaction to increase fourfold). of the formula, then substituting values
from any run, for example, run 6.
Finding n
R
Using any lines in which [H2] changes but [NO] K=
remains constant, for example, [NO]2[H2]
runs 4 and 5
0.060
= = 6 9444
n 0.0122 x 0.0060
0.040 0.0040
=
0.020 0.0020 The units are

2 = 2n moldm-3s-1
= mol-2dm6s-1
⇒n = 1 (moldm-3)2(moldm-3)
Order of reaction with respect to hydrogen is 1.

Example 2

Ethylethanoate slowly hydrolyzes in water, according to the equation

CH3COOC2H5 + H2O  CH3COOH + C2H5OH

HCl

The reaction is catalyzed by a strong mineral acid such as HCl. The reaction was followed twice with
two different concentrations of HCl. The results obtained are recorded in Table 8.1.

Use a graphical method to deduce the rate law. Hence calculate the value of the rate constant, giving
its units.

Why is it not possible to determine the order of reaction with respect to water in this experiment.

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 Time/min With[ HCl] = 0.1moldm-3 With [ HCl] = 0.2 moldm-3
[ethylethanoate]/moldm-3 [ethylethanoate]/moldm-3

0 0.200 0.200

25 0.152 0.115

50 0.115 0.067

75 0.088 0.038

100 0.067 0.022

125 0.051 0.013

9701/1/O/N/1999, adapted

Solution
The aim here is to find the rate of reaction with respect to ethylethanoate and HCl. This can be done
graphically. The two graphs are shown in Fig 8.17.
The initial rate of reaction is given by the slope of the tangent at time zero. For graph A (where [HCl =
0.1], the initial rate is

(0.200−0.130)
=
30

= 2.3 x 10-3

Graph B is the graph of concentration of ethylethanoate against time, with a doubled concentration of
HCl. Notice that the curve is steeper, showing that the reaction is faster.
From this graph, the initial rate of reaction

(0.2−0.1)
=
25

= 4.0 x 10-3

Both graphs have a constant half-life (check), showing that the reaction is first order with respect to
ethylethanoate.
The rate law may be written as
R = K[ethylethanoate][HCl]m
To find order with respect to HCl, use the relationship
m

R2 [A] 2
=
R1 [A] 1

Where R2 is theinitialrate of reaction when [HCl] = 0.2 moldm-3, R1 = initial rate of

reaction when [HCl] = 0.1 moldm-3, and A = HCl.

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 Fig 8.17

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 m
4.0x10-3 0.2 Order with respect to HCl = 1
=
2.3 x 10-3 0.1 The rate law is therefore
R = K [ethyl ethanoate][HCl]
1.74 = 2m
In this reaction, it is not possible to determine the
log 1.74 order of reaction with respect to water. This is
m= ≈1 because water is manly present as a solvent and so
log 2
its concentration remains fairly constant.

Notes
 The rate law includes the catalyst, HCl, indicating that the catalyst participates in the slower (rate
determining ) step of the hydrolysis mechanism. The rate law is always written using the slower or the
slowest step in the mechanism. If a catalyst appears in the rate law, the reaction rate is affected by altering
the concentration of the catalyst. In this case, the reaction is first order with respect to the catalyst.
Increasing or decreasing concentration of the acid therefore results in a proportional increase or decrease in
the rate of reaction, for example, doubling the concentration of HCl doubles the rate of reaction.

 If a catalyst does not appear in the rate law, it is because it participates in a faster (non rate determining)
step. In such a situation, changing concentration of the catalyst has no effect on the rate of reaction. The
reaction is said to be zeroth order with respect to the catalyst.

 A catalyst, whether it appears in the rate law or not, usually alters the rate law by changing the orders of
reaction. This is because the catalyst creates an alternative pathway which is has a different rate law. The
value of the rate constant Kin the new rate law increases, indicating that the reaction becomes faster.

 t1/2 is a good measure of reaction rate, especially where the purpose is to compare the speeds of two
reactions. Graph B above has a steeper slope and its half-life is half of that in graph A (check). This means
that the reaction is two times faster when the concentration of HCl is doubled.

8.7Reaction mechanisms
Reactions are usually written in the format aA + bB → cC + dD. This gives the impression that the
reaction is a single step process. In practice, reactions rarely proceed in a single step, but involve one or
more steps. The sequence of small steps leading from reactants to products is known as the mechanism
of the reaction.
Consider a reaction
A→C
Suppose that the reaction proceeds in two steps, first by forming an intermediate X, which reacts further
to form the product C. Also assume that the first step is the slower step.
The mechanism of the reaction can then be shown as

I. A→ X slower
II. X→C faster

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The overall reaction can be obtained by vertical summation of reactions I and II. Note that the interme-
diate X cancels out in this summation. If summation of all steps of the mechanism does not give the ex-
pected equation, then the mechanism is wrong (or the equations in the mechanism are not balanced).
However, if summation of the steps gives the expected equation, it can not be concluded straightaway that
the mechanism is correct. All we can say at this stage is that the mechanism is sensible. The actual
mechanism can only be determined experimentally.

I. A→X
II.X→C
AC

A complete energy profile for such a reaction can be shown as in Fig 8.18 below.

energy

Ea2 activ ation energy of the first step

Ea 2 X E a1 E a1 activ ation energy of the second step

A

H
B

progress of reaction
Fig 8.18 Energy profile of an exothermic two step reaction

 The profile has two ‘humps’; the first hump represents the activation energy of the first step, and
the second hump represents the activation energy of the second step. If the reaction had, say,
three steps, the energy profile would also have three humps.
 This profile has been drawn on the assumption that the reaction is overally exothermic, so the
final product Bis at a lower energy level than the reactantA.
 The first step is endothermic since it results in the formation of an unstable intermediate. In
other words, the intermediate X is higher in energy than the reactantA. The instability of the
intermediate allows it to react rapidly to form the product. However, the intermediate can also
react in the reverse direction to form the reactant once again. From an energetic point of view,
both the forward reaction (forming the product B) and the reverse reaction in which the
intermediate reforms the reactants are feasible.
A ÝXB

This is because the reactant and the product are both stable relative to the intermediate.
 The highest point in the energy profile gives the activation energy of the overall reaction. This has
been labeled Ea2in the diagram above. Note that the activation energy of the second step (E a1)is
smaller. This is because the intermediate has weak bonds, making it unstable. A relatively small
amount of energy is required to break these bonds and convert the intermediate into a product.
The step with the smaller activation energy is the faster. Note that the product(X = intermediate)
of the first step is the reactant of the second step. The activation of step II is therefore measured
relative to its reactant, X.

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  The rate of reaction is determined by the slower or slowest step. In the mechanism above,
reaction I has been arbitrarily made the slower reaction, so it is the one from which we may write
the rate law:
R=k[A]m
We may not know the actual value of m until we carry out an experiment to determine it.
 Energy profiles are not always as shown in Fig 8.19. The exact shape of the profile depends on the
mechanism of the reaction and on whether the reaction is overally exothermic or endothermic.
Fig 8.19 below shows the energy profile of a two step reaction which is overally endothermic.

energy

Ea 1
E a2 products
H
reactants Fig 8.19 Energy profile
for a two step endothermic
reaction

progress of reaction

 Some mechanisms are said to be concerted. In such a reaction, the intermediate is so unstable
that its existence is extremely brief. Such a reaction can therefore be considered as taking place in
one step. The energy profile of such a reaction is usually drawn with only one hump. The
activation energy (hump) of the step involving the intermediate is so small that it is close to zero.
This hump is therefore omitted on the energy profile. An example of a reaction which has a
concerted mechanism is the reaction of chloroethane with NaOH (aq).
CH3CH2Cl + OH-(aq) CH3CH2OH + Cl-

CASE 1
The alkaline hydrolysis of a chloroethane: A concerted reaction.
Halogenoalkanes are organic compounds which contain the C-Hal bond, where Hal represents a halogen
atom. In alkaline hydrolysis of halogenoalkanes, the Hal atom is replaced by an OH group from a strong
base, forming an alcohol. There are two different mechanisms involved, depending on the nature of the
halogenoalkane. These mechanisms have been termed SN1 or SN2 depending on the nature of the haloge-
noalkane.
Hydrolysis of chloroethane proceeds by SN2 (nucleophilic substitution bimolecular- seesection3.2 :
mechanisms of organic reactions)
The overall equation is
CH3CH2Cl + OH-(aq) CH3CH2OH + Cl-
The reaction can be understood by splitting it into two steps.
I. CH3CH2Cl + OH-(aq) [CH3CH2 (OH) Cl]‡ slower
II. [CH3CH2 (OH) Cl]‡ CH3CH2OH + Cl-faster
NB The symbol ‡shows a transition state, which is less stable than an intermediate.
The first step is an addition reaction, in which the reactants combine to form a single product. This is the

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rate determining step. So we may write the rate law as
R = k[CH₃CH₂Cl]m[OH⁻]n
It has been found experimentally that the values of m and n are both 1, that is, the rate of reaction is first
order with respect to each reactant. So the rate law is
R = k[CH₃CH₂Cl][OH⁻]
The reaction is first order with respect to both reactants. Changing the concentration of either reactant
will cause the rate of reaction to change proportionally, as illustrated in Fig 8.19below.

Rate Rate

-
[OH ] [CH 3CH2Cl]

Fig 8.19The reaction between chloroethane and NaOH(aq) is first order with respect
to both reactants.

Overally, the order of reaction is 2, so the mechanism of this reaction is termed SN2. The
number 2 represents the order of reaction, that is, the rate determining step involves the collision of two
reactant particles. SNstands for nucleophilic substitution. If you look carefully at the reaction, you will see
that it is a substitution reaction in which the OH⁻ group replaces the Cl group. A nucleophile is an electron
rich species (in this case, OH-) which participates in some types of organic reactions.
The energy profile of the reaction has only one hump (Fig 8.20) because step II is very rapid. The
intermediate, CH3CH2 (OH) Cl, which should be more properly termed a transition state, is very unstable.
Its conversion to the products has a very low activation. In practice, the reaction can therefore be
considered to take place in one step. This is an example of a concerted mechanism. The structure of the
transition stateis shown in Fig 8.20. It is very unstable because one of the carbon atoms has too many
bonds around it (five instead of four)

H H
The transition state occupies the
CH 3 C highest energy level on the energy
energy Cl
profile diagram.
OH

CH3CH2Cl

CH 3CH 2OH
Fig 8.20 Energy profile for the
reaction between chloroethane
and aqueous sodium hydroxide

progress of reaction

CASE 2

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The alkaline hydrolysis of 2-chloro-2-methylpropane: a non-concerted mechanism
2-chloro-2-methylpropane, (CH₃)₃CCl is also a halogenoalkane. It is attacked by the OH⁻ ion in a
nucleophilic substitution reaction, but the mechanism is different.
I.(CH3)3CCl  (CH3)3C+ + Cl-slow
II. (CH3)3C+ + OH- (CH3)3COH fast
The rate determining step is the first step, so we may write
R= K[(CH₃)₃CCl]m
The value of m has been experimentally determined to be 1, so the order of reaction is 1 and the mechan-
ism is appropriately named SN1 (nucleophilic substitution first order). Note that if the rate law is written
to include OH⁻, then [OH-] would be raised to power zero, since OH - ions are involved in a
non - rate determining step:
R= K[(CH₃)₃CCl][OH⁻]0
he reaction is therefore zeroth order with respect to OH⁻ ions. Increasing or decreasing the concentration
of NaOH has no effect on the rate of reaction. The graphs in Fig 8.21 illustrate the kinetics of this
reaction.

Rate/concentration tim e graphs

Rate Rate

First order

zeroth order

[NaOH] (CH 3)3CCl

concentration/time graphs

[(CH 3)3CCl]
[NaOH]
graph is linear, that is slope = rate of
reaction is constant

time time

Fig 8.21 Graphs illustrating the kinetics of the reaction between [(CH₃)₃CCl and
NaOH.

The intermediate in this reaction is a carbocation, (CH3)3C+. This carbocation is relatively stable and it
exists for some time in the reaction vessel before it is converted to the product. The mechanism therefore
has two distinct steps, that is, it is non-concerted. The energy profile has two humps, (Fig 8.22)

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energy

(CH 3)3C

(CH 3)3CCl
(CH 3)3COH

progress of reaction
Fig 8.22 Energy profile for the reaction between (CH3)3CCl and NaOH

Orders of reactants in multistep reactions

In a multistep mechanism, the faster steps are reversible, wheras the slowest step in the mechanism can
be regarded to be irreversible. This can be explained in this way:
 The rapid steps involve unstable intermediates, which can therefore react in both directions, that
is, some intermediate species react in the forward direction to form products,whilst some react in
the reverse direction to form reactants. This outcome is expected since both the products and the
reactants are lower in energy than the intermediates. Conversion of the intermediate to both
reactants and products is therefore energetically feasible.
 The slowest step involves conversion of an unstable intermediate to a stable product. The reaction
therefore tends to be unidirectional, that is, it proceeds only in the direction reactant  product.

Q
The Esson - Harcourt reaction involves the reaction between hydrogen peroxide and iodide
ions in the presence of an acid
H2O2 + 2I– + 2H+ Ý 2H2O + I2
This reaction is considered to proceed by the following steps.
step (i) H2O2 + I– IO– + H2O
step (ii) IO– + H+ HOI
step (iii) HOI + H+ + I–I2 + H2O
The general form of the rate equation is
rate = k[H2O2]a[I–]b[H+]c

(a) Show that the mechanism is consistent with the given reaction

(b) Determine values for the orders a, b and c in the rate equation for a case in which the
second step is the slowest.

(a) Intermediates that are on opposite sides

ofA
Kf [H₂O₂][I¯]
equations cancel out. In steps (i) and [IO–] =
Kb [H₂O]
(ii), IO-cancels. In equations (ii) and (iii),
Substituting this expression for [IO–] in
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not photocopy reproduce givesPage 320
(I) andorsimplifying

Kf [H₂O₂][I¯]
R = K{ }[H+] ... (V)
Kb [H₂O]
HOI cancels out. Combining the three
equations after cancelling out the two
intermediates gives the expected overall
equation.

(b)Being slowest,the secondstep is the rate

determining step, that is
rate = K[IO–][H+] ... (I)
We will treat the first step (i), which is
fast, as being reversible
H2O2 + I– ÝIO– + H2O

Rate equation for the forward reaction:

Rf = Kf [H2O2][I-] ... (II)
Rate equation for the reversereaction:
Rr = Kr [IO–][H2O] ... (III)
Step (i) should attain dynamic equilibrium
since step (ii) is much slower and does not
easily remove the products of the first step.
When step (i) achieves dynamic equilibrium,
rate of forward reaction equals rate of the
reverse reaction, that is
Kf [H2O2][I-] = Kr [IO–][H2O] ... (IV)
Comparing equations (I) and (IV), we notice
that[IO–] is a common factor. Making this
factor subject of equation (IV) gives

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 Another worked example

QA dilute solution of hydrogen peroxide can be used to bleach

hair. It decomposes slowly in aqueous solution according to the
following equation:
2H2O2 (aq)  2H2O(l) + O2(g)
A solution with an original concentration of 3.0 moldm-3 was
placed in a bottle contaminated with transition metal ions,
which act as catalysts for the decomposition. The rate of Fig
decomposition was measured by withdrawing 10 cm3 portions at 8.23
various times and titrating with acidified 0.1 moldm-3
KMnO4(aq) (5 moles of peroxide react with 2 moles of KMnO4 ). From the graph, t1/2 ≈ 14 minutes
The following results were obtained. ln 2 ln 2
Rate constant, K = =
t1/2 14
Time/min Volume of 0.1 moldm-3
= 4.95 x 10-2
KMnO4 (aq)/cm3
0 30.0 (c) We need to find the concentration, C of H2O2
5 23.4 when the first 10 cm3sample is withdrawn .
10 18.3 moles of H2O2 = conc x V = C x 10/1000
15 14.2
20 11.1 = 0.01C
25 8.7 moles of KMnO4 = conc x V = 0.1 x 30/1000
30 6.8
= 0.003
(a) Confirm that the reaction is first order with respect to the (The first sample of H2O2 is titrated with 30.00
peroxide. cm3 of KMnO4)
moles of H₂O₂ 5
(b) Write an expression for the rate equation and calculate the = (refer to question)
moles of KMnO₄ 2
rate constant and half life
0.01C 5
(c) Calculate the concentration of the hydrogen peroxide at the
= ⇒C = 0.75 moldm-3
0.003 2
time the first portion was withdrawn. Hence estimate how
The original concentration of the peroxide was
long the solution had been in the contaminated bottle.
3.0 moldm-3. When the titration with KMnO4
was peformed, [H2O2] had dropped to 0.75
(d) Suggest a method whereby the shelf life of hydrogen
moldm-3. There are two half-lives between 3.0
peroxide colud be increased.
moldm-3 and 0.75 moldm-3.
9701/03/O/N/1991
From 3.0 to 3/2 = 1.5 first half-life
from 1.5 t0 1.5/2 = 0.75second half life
A The concentration of hydrogen peroxide is directly
proportional to the volume of KMnO4 used, that is, the greater Since each half-life is 14 minutes, two half-lives
the concentration of hydrogen peroxide, the greater the volume give 28 minutes. This is the time the peroxide
of hydrogen peroxide required for reaction. Voume of KMnO4 has been in the bottle.
can therefore be used to represent concentration of hydrogen
peroxide (Fig 8.23) (d) Possible methods include
 Using dark coloured bottles to reduce
(a) The graph has a constant half-life. This shows that the exposure of the peroxide to light.
reaction is first order with respect to peroxide.  Keeping the peroxide in a cool place.
 Adding chelating agents such as EDTA4-
(b) R = k[H2O2]

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 to trap transition metal ions which catalyse the relative initial
expt [(CH3)2CO] [H+] [CN-] rate /moldm-3
decomposition.
sec-1
1 0.020 0.060 0.060 1.00
2 0.020 0.050 0.050 0.833
Exercise 8.1 3 0.020 0.050 0.060 1.00
4 0.025 0.050 0.050 1.042
1 Acetals are compounds formed when aldehydes react with
(ii) Hence write a rate equation for this reaction.
an alcohol and an acid catalyst. The reaction between ethanal
and methanol was studied in the inert solvent dioxan.
Two different mechanisms have been suggested
for this reaction
H+
CH3CHO + 2CH3OH Ý CH3CH(OCH3)2 + H2O
Mechanism A:
When the initial rate of this reaction was measured at various (CH3)2C=O + H+(CH3)2COH+
starting concentrations of the three reactants, the following (CH3)2COH+ + CN– (CH3)2C(OH)CN
results were obtained.
Mechanism B:
experiment [CH3CHO] [CH3OH]/ [H+] Relative (CH3)2C=O + CN– (CH3)2C(O–)CN
/moldm-3 moldm-3 /moldm-3 rate (CH3)2C(O–)CN + H+(CH3)2C(OH)CN
1 0.20 0.10 0.05 1.00
2 0.25 0.10 0.05 1.25
3 0.25 0.16 0.05 2.00 (iii) Which mechanism is consistent with the rate
4 0.20 0.16 0.10 3.20 equation you deduced in (ii), andwhich step in
this mechanism is the slower (rate determining)
(i) Use the data in the table to determine the order with step? Explain your answer.
respect to each reactant. 9701/04/M/J/2005

(ii) Use your resullts from part (i) to write the rate equation for
the reaction.
3In the late 19th century the two pioneers of the
study of reaction kinetics, Vernon Harcourt
(iii) State the units of the rate constant in the rate equation.
and William Esson, studied the rate of the
reaction between hydrogen peroxide and iodide
(iv) Calculate the relative rate rate of reaction for a mixture in
ions in acidic solution.
which all three reactants are 0.2o moldm-3
9701/04/O/N/2011 H2O2 + 2I– + 2H+ 2H2O + I2

This reaction is considered to go by the following

2 (a) What do you understand by the term order of reaction? steps.

(b) Cyanohydrins can be made by reacting ketones with an step 1H2O2 + I–IO– + H2O
acidified solution of sodium cyanide. step 2IO– + H+HOI

(CH3)2C=O + H+ + CN–(CH3)2C(OH)CN step 3HOI + H+ + I–I2 + H2O

The general form of the rate equation is as
In a series of experiments, the reaction was carried out follows.
with different concentrations of the three reagents, and
the following relative initial rates were obtained. rate = k[H2O2]a[I–]b[H+]c

(i) Use the data in the table to deduce the order of (a) Suggest how the appearance of the solution
the reaction with respect to propanone, hydrogen might change as the reaction takes place.
ions andcyanide ions

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(b) Suggest values for the orders a, b and c in the rate equation for each of the following cases.

numerical value
Case
a b c

step 1 is the slowest overall

step 2 is the slowest overall

step 3 is the slowest overall

8.8 methods of determining reaction rates

8.8.1 Titrimetric analysis

This method is only possible for a quantitative reaction that takes place in solution.
Samplesare withdrawn from the reaction container at timed intervals and analyzed, for example, by
volumetric analysis (titration) to ascertain how much of the reactant has been consumed. It is then
possible to find rate of reaction, that is,how fast the concentration of reactant decreases. One major source
of inaccuracy of this method is that when the sample has been withdrawn, the reaction continues in the
sample, and this will affect the time factor in the analysis of reaction rate. One method of preventing this
error is quenching. A substance is added to the withdrawn sample to stop the reaction. Such a substance
is known as a quenching agent. An example is the iodination of propanone, which is
acid catalyzed as shown
CH₃COCH₃ (aq) + I₂ (aq) → CH₂ICOCH₃ (aq) + HI (aq)
H⁺
To follow the rate of reaction by titrimetric analysis, a sample is withdrawn from the reaction vessel and
pipetted into a solution of sodium hydrogen carbonate, which neutralizes the acid catalyst, thus
quenching the reaction. This prevents further changes in concentration before the titration is carried out.
The quenched mixture can be analyzed by titrating the unreacted iodine against a standard solution of
sodium thiosulphate.
I2 + 2S2O32-(aq)  2I-(aq) + S4O62-

8.8.2 Monitoring rate of decrease of mass of reactant

The reaction vessel can be placed on a scale and the decrease in mass over time is noted. The decrease in
mass is caused by the reactant being used up. This particularly applies when gaseous products are formed
and escape from the reaction vessel. The rate of decrease in mass of the container is equal to the rate of
disappearance of reactant, which in turn is equal to the rate of reaction. Particular care should be taken
that no reactant molecules are lost, for example through evaporation and liquid sprays.

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8.8.3Monitoring rate of increase in volume or pressure of a gaseous
product.
If the reaction produces a gaseous product, rate of reaction can be conveniently found by measuring the
increase in volume of the product over regular time intervals, for example, the gas can be trapped in a
syringe. Similarly, the reaction vessel can be connected to a pressure gauge. The rate of reaction is them
measured in terms of how fast pressure of the product increases. This method can also be used for
reactions in which a gaseous reactant is used up. In this case, the pressure gauge can be used to measure
the rate of decrease of pressure of the reactant.

8.8.4Colorimetric analysis
(From the word ‘color’ – students often confuse between the terms calorimetry [energetics] and colori-
metry.)
This method is useful and convenient for a reaction which is accompanied by a change in colour, for
example, the reaction of iodine with propanone. The analysis involves measuring colour intensity at timed
intervals. From these measurements, concentration of the coloured substance can be calculated at
different times. Fig 8.24 below shows a photoelectric colorimeter. The mode of operation of this
colorimeter is explained in Fig 8.25.

Fig 8.24 A
colorimeter

light in filtered light light

source of
light

photocell
Filter sam ple m eter

Fig 8.25 A schematic diagram illustrating how a photoelectric colorimeter

works.

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This method depends on measuring the intensity of light that is transmitted through the reaction mixture,
which must be in solution form. First the light is passed through a filter that will select the most appropri-
ate wavelength. The intensity of light transmitted by the solution depends on the depth of colour of the
solution. If at the start of the reaction, the solution is colourless, then a large amount of light is transmit-
ted through the solution. This light strikes a photoelectric cell which converts light energy to electrical
energy. The greater the intensity of light passing through the solution, the larger the electric signal gener-
ated. A meter records the amount of current and relates it to the concentration of the solution. Suppose
that a coloured product is produced during the reaction. As the concentration of the product increases, the
depth of colour of the reaction mixture increases and less light is transmitted through the solution. As a
result, a smaller current is generated. The rate of reaction is given by the rate at which the electric signal
diminishes in strength. In turn, this is proportional to the rate of formation of the coloured product.

8.8.5Conductrimetric analysis
This is appropriate for a reaction which involves ions. The electrical conductivity of the solution decreases
when ions are being used up and increases when ions are produced. The rate of change of conductivity is
proportional to the rate of reaction.

All the methods discussed above do not give the rate of reaction directly. Instead they give concentra-
tion/time data which can then be plotted on a graph. The Rate of reaction at a particular time is
obtained by taking the slope of the curve at that time.

8.8.6UV –Vis spectroscopy

This technique makes use of the absorption of ultraviolet and visible radiation by some types of
compounds, for example, complexes of transition elements. See section 9.5for details.

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7.3 miscellaneous problems

1 (a) What do you understand by the terms (i)order of reaction (ii) rate constant?
(b) Explain with the aid of suitable diagrams, why a relatively small increase in temperature causes a
large increase in the rate of a chemical reaction.

(c) The kinetics of the acid-catalyzed reaction of propanone with iodine

CH3COCH3(aq) + I2(aq)  CH2ICOCH3(aq) + HI(aq)
can be investigated experimentally by varying the concentrations of the three substances involved
and detrmining thetime for the colour of iodine to disappear. In this method the rate of reaction
is measured in terms of the rate at which the iodine concentration changes,that is,

volume of aqueous iodine used

rate of reaction α time for colour of iodine to disappear

The following results were obtained in such an experiment.

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Deduce the order of the reaction with respect to (i) propanone (ii) iodine (iii) hydrogen ions.
Write a rate equation for the reaction.
What conclusions about the mechanism can you draw from the rate equation?

Relative time for

Volume of Volume of Volume of Volume of colour of iodine to
propanone/cm3 iodine/cm3 sulphuric acid/cm3 water/cm3 disappear.
8 4 8 0 1
8 4 4 4 2
4 4 8 4 2
8 2 8 2 0.5

2 Zinc is an essential element for plant and animal life. It is often administered in the form
of a chelate, which is a complex between a metal ion and a polydentate ligand.
The rate of the reaction between zinc ions and the ligand 4-(2-pyridylazo)resorcinol,PAR, has
beenstudied.

Both PAR and its zinc complex absorb radiation in the UV-visible region. Figure 8.26shows
their absorption spectra.

Devise a suitable experimental technique for studying

how the rate of this reactionvaries with [Zn2+(aq)].

9701/04/M/J/07

Fig 8.26

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3 The ester 4-nitrophenyl ethanoate hydrolyses in alkaline solution according to the following
equation.

(a) Suggest, and briefly describe, a suitable experimental technique for studying the rateof this
reaction.

(b) The reaction rate was studied using two solutions of different hydroxide ion concentrations.

run A: [OH–] = 0.20 mol dm–3

run B: [OH–] = 0.40 mol dm–3

The following graphs show how the concentration of the ester, 4-nitrophenyl ethanoate,
varied over time in the two runs.

(i) By drawing tangents on the graphs, measure and calculate the initial rates ofreaction during
the two runs. Give the units in each case.

(ii) By using your results, calculate the overall order of reaction with respect to [OH –].

(iii) From the curve of run B, determine the order of reaction with respect to [ester].

(iv) Explain how you arrived at you answer in (iii).

(v) Write a rate equation for the reaction.

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(vi) Use your rate equation and the initial rates to calculate a value for the rateconstant,
including units.
9701/04/M/J/02

4(a) What do you understand by the term rate of reaction?

(b) The mechanism of a reaction is as shown below

H2O2 + I-H2O + IO-slow

H+ + IO- HIOFast

HIO + H+ + I- H2O + I2 fast

(i) Deduce the overall equation for the reaction and give its rate expression.

(ii) Give the overall order of the reaction

(c) The following data was obtained onstudying the decomposition of a gas X.

time/s 0 300 600 900 1 200

pressure of
gasX/atm 0.367 0.208 0.130 0.072 0.043

(i) Plot a graph of pressure of X against time

(ii) Given that pressure of X is directly proportional to the concentration of gas X, show that
the order of the reaction with respect to X is one.

(iii) Calculate the rate constant for the reaction.

(d) The following reaction is slow and has a high activation energy. It can be catalysed by Fe 2+
ions.
S2O82- + 2I- 2SO42- + I2

(i) Suggest a reason for the high activation energy of the uncatalysed reaction.

(ii) Show by means of equations how Fe2+ can catalyze the reaction.

(iii) What property of Fe2+ makes it a suitable catalyst for the reaction?
9189/01/O/N/2004

5(a) Define the term order of reaction.

(b) Hydrogen peroxide reacts with iodide ions in acidic conditions according to the following
equation.

H2O2 (aq) + 2I-(aq) + 2H+(aq)  I2(aq) + 2H2O(l)

The rate of this reaction can be determined by mixing known amounts of the three reactants,
periodically sampling the mixture and immediately adding manganese (IV) oxide, MnO 2 before

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titrating with sodium thiosulphate.

Why would adition of AgNO3 instead of MnO2 not be appropriate for this reaction?

(c) Experiments to determine the order of the reaction gave the following results

experiment Initial Initial Initial Initial rate/

[I-]/moldm-3 [H+] /moldm-3 [H2O2]/moldm-3 mol dm-3s-1
1 0.01 0.1 0.005 0.083
2 0.01 0.1 0.010 0.166
3 0.01 0.2 0.005 0.332
4 0.03 0.1 0.005 0.249

(i) Deduce the order of the reaction with respect to each of the three reactants.

(ii) Calculate the rate constant, stating its units

9189/01/O/N/2010

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Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 331
9THE PERIODIC TABLE AND
PERIODIC TRENDS

9.1 CHEMICAL PERIODICITY: PERIOD

3 ELEMENTS

Introduction
Periods of the Periodic Table show well defined trends in chemical and physical properties.
Properties which are observed in one period apply to the other periods. This recurrence of physical
and chemical properties is known as periodicity. The discovery of periodic patterns has greatly
simplified the study of inorganic chemistry.
In this section we study the trends in chemical and physical properties of the Period 3 elements and
apply the knowledge to other periods. As you go through this section, make sure you see how these
trends link with the concepts you learnt in physical chemistry. In fact, if your understanding of
physical chemistry is good, you will find inorganic chemistry easy and straightforward. For, example,
when we discuss the trends in melting points of the Period 3 elements, you will notice the importance
of understanding the concepts of bonding learnt in section 4.

9.1.1Periodicity of physical properties

Na Mg Al Si P S Cl Ar
Atomic
number 11 12 13 14 15 16 17 18

Metallic bonding Giant Simple covalent bonding

(relatively strong) covalent (relatively weak )
bonding
(very
strong)

metals metalloid non metal

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1.1.1 Periodicity in bonding and structure
There is a change from metallic to non-metallic character across the period. Na, Mg and Al are metals. Si
is a semi-metal. The remaining elements are non-metals.

Explanation
Metallic nature is favoured by large atoms with a relatively small number of protons, or atoms that have a
large number of shells. Elements to the left hand side of the periodic table, that is, Na, Mg and Al, have
large atoms with a small number of protons in the nucleus. The electrons in the valence shell are therefore
weakly held to the atom. They are quite easily detached and contributed into a common pool which
characterizes metals. Going towards the right hand side of the periodic table, atoms shrink in size due to
increasing nuclear charge. The valence shell electrons are therefore closer to the nucleus. These electrons
are more strongly held to the atom since they are close to the nucleus and since the nucleus has more
positive charges. These valence electrons are not easily detached and contributed into a common pool.
The non– metallic elements therefore tend to exist as covalently bonded substances.
The gradation in bonding and structure across the period has a profound effect on physical properties of
the elements, such as boiling points and densities.

1.1.2 Boiling and melting points

Na Mg Al Si P S Cl Ar

Mpt/0C 98 650 660 1407 44 119 -101 -189.2

Bpt/0C 890 11o7 2467 2357 280 445 -35 -185.6

Table 9.2 Melting points and boiling points of Period 3 elements.

The trend in melting points along Period3 elements is shown in Fig 9.1 below.

Fig 9.1 Trend in the melting points of the Period 3 elements

 The metals, Na, Mg and Al have high melting and boiling points because of their metallic nature.
The bonds in these elements are strong electrostatic attractions between positive metal cores and
a sea of delocalized electrons. Atoms are therefore strongly held to the structure and it is difficult

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 to pull them from each other during melting or boiling. A large amount of energy is needed to
bring about boiling and melting.
 The melting and boiling points of Na, Mg and Al increase in that order. This shows increasing
strength of the metallic bonds. The increase in size of positive charge on the metallic core (from 1
in Na , 2 in Mg and 3 in Al) and the increase in the number of electrons delocalized in the lattice
results in stronger electrostatic attractions between the positive metal cores and the delocalized
sea of electrons. The fact that nuclear charge increases and atomic size decreases also implies that
there are stronger attractions between the nucleus and the sea of delocalized electrons. All these
factors help to hold the atoms firmly to the lattice.
 Si has the highest melting point in Period 3. This can be explained in terms of the type of bonding
present. Silicon has a giant molecular structure, similar to that in diamond. A very large amount
of energy is required to break the Si to Si bonds, which are very strong and numerous.
 P, S, Cl and Ar are all simple covalent substances with weak Van der Waals forces between the
molecules. Only a small amount of energy would be required to break these forces during melting
and boiling. The differences in the boiling points of these elements are a result of differing
strength of VDW forces. Sulphur, which exists with S₈ molecules, has the largest number of
electrons per molecule, and hence the highest melting point. The melting point of sulphur is
higher than that of phosphorous because phosphorous exists as P 4 molecules. Each P4 molecule
has less electrons than an S8 molecule (compare Mr values). Van der Waals forces are therefore
stronger in sulphur than in phosphorous.

Bond angle in P4 is approximately 1070, as in NH3 (3 bond pairs and one lone pair around each P atom).
In S8, the bond angle is approximately 1040, as in water. Notice that there are 2 bond pairs and 2 lone
pairs around each sulphur atom.

Reference point: Chemical bonding

The type of bonding present in a substance affects its physical properties such as melting and boiling points. Melting
and boiling are physical processes. They do not change the chemical identity of a substance. When a substance melts
or boils, lattice forces holding atoms or molecules together are broken, separating the atoms or molecules from each
other. The size of melting or boiling point depends on the strength of these lattice forces. In metals, the lattice forces
are strong, so metals generally have high melting and boiling points. When simple covalent substances such as
phosphorous and chlorine melt or boil, it is only weak intermolecular forces, not covalent bonds, that are broken.
Simple covalent substances therefore have relatively low melting and boiling points. The stronger the intermolecular
forces, the higher the melting or boiling point. However, note that in giant covalent substances such as silicon
Melting or boiling require the breaking of very strong covalent bonds. Giant covalent substances therefore have very
high melting and boiling points, which are often higher than that of most metals.

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Important note
It is often said that metals have high melting points. Note that this is not true for the soft Group (I)
metals. K and Na have low boiling points, even lower than some covalent substances such as Sulphur.

1.1.3 Atomic radius

The atoms become smaller going across the period (Table 9.3). Nuclear charge increases across the
period, and this implies that the outer shell is pulled more strongly towards the nucleus. The atoms thus
shrink in size. Fig 9.2 below shows that the decrease in atomic radius is sharp at the beginning of the
period, but towards the end it becomes only gradual. This is because the increase in number of electrons
in the outer shell offsets to some extent the effect of increasing proton number.

Na Mg Al Si P S Cl Ar

Atomic 0.156 0.136 0.125 0.117 0.110 0.104 0.099 -

radius/nm

Table 9.1.4 Atomic radii of Period 3 elements

Ionic radii
The variation in ionic radii of the Period 3 elements is shown in table 9.1.5
and Fig 9.1.3.

Element Na Mg Al Si P S Cl Ar

Ion Na+ Mg2+ Al3+ - P3- S2- Cl- -

Atomic
radius/nm 0.095 0.065 0.050 - 0.212 0.184 0.181 -
Fig 9.1.2 Trend in atomic
radii across Period 3 Table 9.1.5 Trend in ionic radii across Period 3

 The Period 3 cations have the same electronic configuration, 1s22s22p6. This corresponds to loss of
all valence electrons. The cations are therefore smaller than the neutral metal atoms because of
the loss of a shell. Moreover, the ions have fewer electrons which therefore feel a stronger
attractive pull from the nucleus.
 The ionic radii of the ions Na+, Mg2+, Al3+ decrease in that order. This is because the number of
electrons remains constant, and yet number of protons in the nucleus increases. This increase in
nuclear charge implies that the nucleus has a greater pull on the outer most shell, causing the ions
to shrink in size.
 The anions of Period 3 are larger than the cations, and they all have the same electronic
configuration, 1s22s22p63s23p6. The anions are larger than the cations because they have one more
shell than the cations.

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  The ionic radii of the anions P3-, S2-, Cl- decrease in that
order due to increasing nuclear charge. Meanwhile, the
number of electronsremains constant.

Fig 9.1.3 Trend in ionic radii of

the Period 3 elements

1.1.4 Variation in first ionization energy

In general, ionization energy increases across a period (Fig 9.3).
The increase in ionization energy is due to the increase in nuclear charge. The number of protons in the
nucleus increases, and yet electrons enter the same shell where they cannot effectively shield each other
from the attractive influence of the nucleus. We sayeffective nuclearcharge increases across the period.
The effective nuclear charge refers to the strength of the attraction by the nucleus which an electron feels.
As the effective nuclear charge increases, the outer most electrons are bound more firmly to the atom and
more energy would be required to remove an electron from this shell.

A direct result of the increase in nuclear charge is that shells

are drawn more strongly towards the nucleus, resulting in a
decrease in atomic radii across the period. This shrinkage in
atomic size also contributes to the increase in IE across the
period. As the atoms become smaller, the outer most
electrons become closer to the nucleus, so they are held
more strongly to the atom.
Anomalies are found at S and Al. These two elements have
lower ionization energies than would have been expected
from their positions in Period 3. The electronic
configurations of P and S are shown below to help explain
this anomaly:

2 9.1.3 In sulphur, the electron to be removed is paired with another

S: [Ne] 3sFig Trend in ionization
3pacross
energy x 3p
3pPeriod 3z in a 3p orbital. This electron is already experiencing
y
repulsion and so it is more easily removed than in
phosphorous. In P, The 3p sub shell is also exactly half -
P: [Ne] 3s2
3px 3py 3pz filled, so its electrons are relatively stable. More energy is
required to remove an electron from P than in S.

The electronic configurations of Al and Mg are shown in the following diagrams to help explain why the
first ionization energy of Al is lower than that of Mg.

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Mg: [Mg] 3s22 For Al, the electron to be removed is in a p sub shell. In Mg, the electron is in
Mg: [Mg] 3s an s sub shell. Since the p sub shell is higher in energy(that is, it is further
from the nucleus), the electron in Al is more easily removed than the one in
3p Mg, that is, less energy is required to knock out an electron from the outer
Al: [Ne] 3s22 3p
Al: [Ne] 3s most shell of Al.

1.1.5 Electronegativities
Electronegativity increase across a period.
Electronegativity measures the ability of an atom to attract electrons of a bond towards itself. Going
across the period, nuclear charge increases and atomic size decreases (an atom with a large number of
protons pulls shells strongly towards itself). The atom is then able to attract electron density of a bond
more effectively because the electron density is closer to the nucleus.

1.1.6 Electropositivity
This is the tendency of an atom to give away valence electrons during chemical reactions. Elec-
tropositivity decreases across the period. The metals have the higher electropositivity.

 They have large atoms whose valence electrons are a large distance from the nucleus. The
electrons are therefore weakly held to the atom and they are easily lost.
 The number of protons in the metal atom is relatively small. The nucleus therefore has a weak
attraction for the valence shell electrons.
 There are only a few electrons in the valence shell. The energy expenditure on removing the
electrons, as measured by ionization energies, is therefore small.
 By losing the few valence electrons, a stable octet of electrons is exposed. The resulting cation has
a high stability and this more than compensates for the energy used to remove the electrons.

The electropositivity for Na, Mg and Al decreases in that order in response to an increase in nuclear
charge, a decrease in atomic size and an increase in the number of valence electrons to be removed.

1.1.7 Electrical conductivity

The electrical conductivities of the period (III) elements are shown in Table 9.4.

Element Na Mg Al Si P S Cl Ar

Conductivity 0.218 0.224 0.382 2 x 10-7 10-17 10-23 - -

x 10-8 / Ω
Table 9.4

The metals are good electrical conductors because of the presence of a sea of delocalized electrons. These
mobile electrons are responsible for conducting electric charge. The non-metals are very poor conductors,
or do not conduct at all. Electrons in these covalent substances are localized in covalent bonds. They
cannot move, so electric charge cannot be conducted through the substance.

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9.1.2 Chemical periodicity
The change from metallic to non metallic character results in a noticeable change in chemical properties
across the periodic table.

1.2.1. Redox properties

The metals act as reducing agents. This is expected. Because of the large size of their atoms and the
relatively small number of electrons in the nucleus, metals readily lose the valence electrons. By so doing
they are oxidized (oxidation is a loss of electrons) and in the process they act as reducing agents (reducing
agents are electron donors). Standard Reduction Potentials are given below for Na, Mg and Al.

The electrode potentials are negative, showing

Reduction equation Eθ/V
that the metals are good reducing agents. The
Na -2.71 value of E⁰ becomes less negative from Na to Al,
Na+ + e-Ý Na
indicating decreasing reducing power. This is
Mg -2.38 because nuclear charge increases and outer
Mg2+ + 2e-Ý Mg
electrons become more firmly held to the
Al -1.66 atom.It becomes harder to remove these
Al3+ + 3e-Ý Al
electrons during reactions.
Typical reactions in which the metals act as reducing agents include reaction with water, oxygen and
acids.

1.2.2 Reaction with oxygen

Na and Mg burns rapidly in air, forming their respective oxides:
4Na(s) + O₂ (g) →2Na₂O(s)
2Mg(s) + O₂(s) → 2MgO(s)
These reactions are very exothermic, showing that the products being formed are very stable. Freshly
prepared Al reacts rapidly with oxygen on its surface to form a thin layer of aluminium oxide.
2Al(s) +3/2 O₂ (g) → Al₂O₃(s)
Any further reaction of the metal is prevented by the thin layer of oxide formed, since it is tenacious
(sticks firmly to the metal) and impervious to oxygen and water (the oxide layer is insoluble in water). It is
the presence of this layer of oxide which gives Aluminium its kinetic inertness to oxygen, water and
dilutes acids.
Silicon resists direct combination with oxygen because of the large number of very strong covalent bonds
present.

White phosphorous burns readily in air with a white flame, forming a white solid, P₄O₆ (limited oxygen)
or P₄O₁0 (excess oxygen).

2P₄(s) + 5O₂ (g) → P₄O₁0(s)

When writing this equation, always remember that white phosphorous exists as P₄. In this
reaction, phosphorous attains the highest possible oxidation state (+5) in the oxide. In P4O6, the oxidation
number of P is +3, showing incomplete oxidation. P 4O6 is therefore easily oxidized by oxygen to form
P₄O₁0.

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Note
 P₄O₁0 is often written as P2O5. Note that in both formulae, the oxidation number of P is +5.
 In the reaction with oxygen, P is oxidized, that is, it acts as reducing agent.

Sulphur burns steadily in oxygen with a blue flame, forming a colourless and choking gas.
S(g) + O₂(g) → SO₂(g)
In this reaction, sulphur does not attain the highest possible oxidation state of +6, showing that it is a
relatively weak reducing agent. Further oxidation of SO₂ to sulphur trioxide, SO₃, is possible
under industrial conditions, e.g. in the contact process for the manufacture of sulphuric acid. The reaction
is reversible and requires heating and the use of a catalyst. Again, this shows that S is relatively weak as a

reducing agent.
Chlorine is too weak a reducing agent to combine directly with oxygen.

Formula of the Oxides of Period 3 elements

Element Na Mg Al Si P S Cl Ar

Oxide Na2O MgO Al2O3 SiO2 P4O10 SO2 Unstable, -

P 4 O6 SO3 includes
Cl2O,
Cl2O7 and
ClO2

Oxidation +1 +2 +3 +4 +5 +4 +1
Number +3 +6 +7
+4
Table 9.5The oxides of Period 3 elements

NB The highlighted oxides cannot be formed by direct combination of the element with oxygen under
ordinary conditions.
Note that the oxidation numbers of the elements in the oxides increases across the periodic table, in
response to an increase in the number of valence electrons. This is because the valence electrons are the
ones that participate in chemical reactions.

1.2.3 Reaction of the elements with water

Na and Mg are powerful enough as reducing agents to reduce water to hydrogen.Na reacts violently in
cold water in a very exothermic reaction, forming a strongly alkaline
solution of NaOH, and liberating hydrogen gas.
Na(s) + H₂O (l) → NaOH (aq) + H₂ (g)
Because of its low density, a piece of sodium metal floats in water, so that a reaction takes place on the
surface of water. The increase in the kinetic energy of water molecules on the surface due to an increase in
temperature causes the metal to spin around on the surface. The part of the sodium metal exposed to the
air can also catch fire.
Magnesium is a weaker reducing agent than sodium. It has no appreciable reaction with cold water.

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However, it reacts rapidly with steam, forming a white or yellow ash of magnesium oxide and hydrogen
Mg(s) + H₂O (g) → MgO(s) + H₂ (g)
Aluminium has no reaction with water. From an energetic point of view, we would have expected a
reaction to take place. The inertness of Al is kinetic; the metal is protected by a tough and impervious
layer of Al2O3, as already explained.
The rest of the elements in Period 3 are rather weak as reducing agents. However, chlorine reacts slowly
and reversibly with water, to form a weakly acidic solution of HClO.

Cl2(g) + H2O (l) H+(aq) + ClO-(aq) + Cl-(aq)

This is in fact a disproportionation reaction in which chlorine is both oxidized to ClO - (oxidation number
increases from 0 to +1) and reduced to the -1 state in Cl-.

1.2.4. Reaction of the elements with chlorine

All period 3 elements except argon, combine directly with chlorine to form chlorides. The metals Na, Mg
and Al combine readily with chlorine to form ionic chlorides, for example, sodium metal burns vigorously
in chlorine.
2Na(s) + Cl2 (g)  2NaCl(s)
The reactions of Na, Mg and Al become less vigorous in that order, indicating a decrease in reducing
power of the metal. Fig 9.4 shows how AlCl3 could be prepared in the lab by the reaction
Al(s) + Cl2 (g)  Al2Cl6(s)
Heating is required to overcome activation energy associated with the tough impermeable oxide layer on
the surface of Al.The non metals, except Ar, also combine with chlorine, forming simple covalent
chlorides, for example,
P4(s) + 10Cl2 (g)  4PCl5(s)
The reaction of the Period 3 elements with chlorine involves oxidation of the element, and reduction of
chlorine. The vigour of the reaction and chemical stability of the chloride decreases across the period due
to
 decreasing reducing power of the element
 decreasing difference in electronegativity between the element and chlorine.
The oxidation number of the element in its chloride increases across the periodic table, in response to in-
creasing number of valence electrons. The total number of bonds that can be formed also increases (Table
9.6).

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 Element Na Mg Al Si P S Cl

Chloride NaCl MgCl2 Al2Cl6 SiCl4 PCl5 S2Cl2

PCl3 unstable - -

Oxidation +1 +2 +3 +4 +5 +2
Number +3
Ionic with Covalent
Bonding some covalent with S i m p l e
Ionic character significant
ionic C o v a l e n t
character
Behaviour No Dissolves
in water reaction. with slight Undergoes hydrolys i s
Dissolves to hydrolysis.
give pH of pH ≈ 3 pH ≈ 2 pH ≈ 2 pH ≈ 2
solution of solution is
pH 7 about 6

State at rtp White solid White solid White solid Volatile PCl3 is a Orange
colourless volatile volatile
liquid colourless liquid
liquid.PCl5 is
a pale yellow
solid
Lattice forces Mixed vdw
I O N I C and ionic V D W
Table 9.1.6 Chlorides of Period 3 elements

The exact method of preparation of the chloride depends on its nature. Fig 9.1.4 shows how AlCl3 can be
prepared in the lab.

Fig 9.1.4Lab preparation of AlCl3.

1. Chlorine gas is produced by a suitable reaction. Can
you suggest such a reaction?
2. Aluminium metal is heated strongly with chlorine gas
passing over it. At the high temperature of the
reaction, gaseous AlCl3 is formed.
3. AlCl3 cools down and dimers to form Al2Cl6.
4. Unreacted chlorine is vented out.

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9.2.3Compounds of Period 3 elements

2.3.1 The chlorides

The formula and nature of the chlorides of Period 3 elements are given in Table 9.6.
There is gradation in the bonding of the chlorides from giant ionic to simple covalent. This
corresponds to a change in the elements from metallic to non- metallic. The change in bonding from ionic
to simple covalent can be explained in terms of the increase in the electronegativity and the decrease in
electropositivity of the elements across the period. The tendency of the element to lose valence electrons
(electropositivity) and form an ionic compound decreases, and at the same time the tendency of the
element to stabilize a shared pair of electrons (covalent bond) by attracting it increases. The change in
type of bonding affects physical properties such as state at room temperature and melting points. NaCl
and MgCl2 have giant ionic bonding, and so at room temperature they are solids with high melting points.
The rest of the Period 3 chlorides are either volatile liquids or are solids with low melting points. In these
covalently bonded substances, there are weak Van der Waals operating between molecules. A small
amount of heat energy is required break these forces and separate the molecules from each other.

Shapes of the simple covalent chlorides

AlCl3 PCl5
Cl
Cl 900 Cl PCl3
1200
P Cl P P
Cl Cl
120 0 Cl Cl
Cl Cl
trigonal planar
trigonal trigonal bipyramidal
bipyramidal

SiCl4 Cl
1090

Si tetrahedral
Cl
Cl
Cl

In PCl₅, phosphorous has more than an octet of electrons around it. This is because it has accessible d
orbitals which it can use to accommodate some of the excess electron density. We say P has the ability to
expand its octet. This ability is shown by the non- metallic elements from P (period III) onwards.

Reactions of the chlorides with water

Going across Period 3 there is an increasing tendency for the chlorides to hydrolyze in water. This
coincides with increasing covalent character across the period.
NaCl is ionic and has no reaction with water. It simply dissolves, forming a neutral solution.
NaCl(s) → Na⁺ (aq) + Cl⁻ (aq)
The enthalpy change of solution for this reaction is +3Kj/mol. The dissolution of NaCl in water is
endothermic, that is, more energy is used to break the strong electrostatic attractions between the Na⁺ and
Cl⁻ ions than is released when these ions form electrostatic attractions with water. This observation can be
tracked down to the large size of the Na⁺ ion. It can form only weak attractions with water molecules, so

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weak that the energy released is not enough to compensate for the energy used in breaking down the
lattice of NaCl.

MgCl₂ is ionic, so it dissolves in water to form Mg² ⁺ and Cl⁻ ions. However, the solution formed is not
neutral. Rather, it is slightly acidic (pH= 6.5). This shows that there is a degree of covalent character in
MgCl₂. Strictly speaking, MgCl₂ dissolves in water with slight hydrolysis.
MgCl₂(s) → Mg²⁺(aq) + 2Cl⁻ (aq)
Hydrolysis is a reaction in which a water molecule is split, forming the OH⁻ and H⁺ ions. It is the presence
of H⁺ ions from water that lowers the pH from 7. The Mg²⁺ ion is quite small compared to its charge. The
effect of small ionic size and large charge is to increase the charge density of the cation. A cation with a
high charge density has a large charge confined in a small volume. Such an ion is good at attracting a lone
pair in water, leading to hydrolysis.

H
Mg2+ O Mg2+ + OH- + H+
H

The OH⁻ ions produced form a co-ordination complex with Mg²⁺ and water, so they cannot recombine
with H⁺ ions.
Mg2+ (aq) + OH-(aq) + 5H2O (l)  [Mg(H2O)5OH]+(aq)
However, a much larger amount of Mg²⁺ ions will remain as hydrated ions, that is, Mg 2+ions surrounded
by shells of water molecules.

Aluminium chloride, being covalent, hydrolyses in water more readily than does MgCl ₂. The solution
formed is also more acidic (pH ≈ 3).

AlCl3(s) + 6H2O (aq)  [Al (H2O)5OH]2+(aq) + H+(aq) + 3Cl-(aq)

When a small amount of cold water is added to a sample of solid aluminium chloride (which exists as
Al2Cl3 at low temperatures), a vigorous reaction takes place, producing copious fumes of HCl. The heat
produced during the reaction drives out the volatile HCl from solution. If a large amount of cold water is
used, little or no fumes are produced. This is because there is not enough heat to drive out the HCl.
The behaviour of AlCl₃ in water can be explained in two ways.
 Al in AlCl₃ has in incomplete octet around it (it has a sextet of electrons). AlCl₃ is therefore elec-
tron deficient at the Al atom. The Al atom can therefore attract a water molecule through a lone
pair of electrons on the oxygen. This is the initial step in the hydrolysis reaction.
 Since aluminium chloride has a high degree of ionic character, we can imagine some of the mole-
cules dissociating in water to form Al³⁺ and Cl⁻ ions. The Al³⁺ ion has a very small radius and a
large charge. Because of its very high charge density, it easily hydrolyses water molecules, forming
an acidic solution

A clear distinction should be made between dissolution and hydrolysis. Dissolution is aphysical process,
which results in the formation of a mixture (solution). Components of the mixture can easily be separated
e.g by evaporation (At junior levels it is often erroneously taught that physical changes such as dissolution
are not accompanied by heat energy changes. This is clearly wrong. Most dissolution processes absorb or
give out heat energy, known as the enthalpy ofsolution),
Hydrolysis is a chemical reaction which involves splitting of a water molecule. New products are formed
and this process is not as easy to reverse as is the case with dissolution.

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SiCl₄ and PCl₃/PCl₅ hydrolyze in water much more readily than AlCl₃. A larger number of H⁺ ions are
produced in solution, so the solution formed is even more acidic.SiCl 4 and PCl3 are colourless liquids
which fume in moist air. This is a result of the reaction between the chloride and water in the atmosphere,
to produce fumes of HCl. PCl5 is a pale yellow solid which hydrolyses rapidly in water.
The behavior of these chlorides in water is typical of covalent chlorides with accessible d orbitals. These d
orbitals are used to accommodate a lone pair of electrons from water during the first step of hydrolysis.
Note that hydrolysis is not accompanied by a change in oxidation number, since it is not a redox reaction.

SiCl₄(l) + 2H₂O (l) → SiO₂(s) + 4H⁺ (aq) + 4Cl⁻ (aq) (= SiO₂ + 4HCl)

PCl₃(l) + 3H₂O (l) → H₃PO₃ (aq) + 3HCl (aq) (phosphonic acid + hydrochloric acid)

PCl₅ (l) + 4H₂O (l)→ H₃PO₄ (aq) (aq) +5HCl (aq) (phosphoric acid + hydrochloric acid)

A note on phosphonic and phosphoric acids

Phosphonic acid, H3PO3 is the reduced form of phosphoric acid, H3PO4. It is produced from the hydrolysis of PCl3,
whereas H3PO4 is produced from the hydrolysis of PCl5. Note that PCl3 is also the reduced form of PCl5. (In the
presence of excess Cl2, PCl3 is oxidized to PCl5). A common error among students is to treat both H3PO3 and H3PO4
as tribasic acids. Only H3PO4 is tribasic. All its hydrogen atoms are bonded to oxygen, so they can be
dissociated in solution.
H3PO4  PO42- + 3H+
H3PO3 is dibasic. Two hydrogen atoms are bonded to oxygen. These can be dissociated in solution. The third
hydrogen atom is bonded to P and so cannot be dissociated in solution.

O O
phosphoric acid phosphonic acid
P P
OH H
OH OH
OH OH

More information on PCl5

Written as PCl5, the formula of this compound is misleading. At room temperature it is actually made up of
[PCl4]+ and [PCl6] - ions, that is, it exists as the ionic compound
[PCl4]+ [PCl6]-. What happens is that one PCl5 donates a chloride ion to another PCl5 molecule. The donating
molecule therefore
Disulphur becomesS₂Cl₂
dichloride, [PCl4]is+ whilst the receiving molecule becomes[PCl6]-. The structures of these two ions
an unstable orange liquid which readily reacts with water in a
are shown below.
disproportionation reaction.
2S₂Cl₂ (l) + 2H₂O (l) → 3/8S₈(s) + SO₂ (g) + 4H⁺ (aq) + Cl + + SO₂ + 4HCl)
4Cl⁻ (aq) (= 3S
Cl
Notice that the oxidation state of sulphur decreasesClfrom +1 in S₂Cl₂
Cl to 0 in sulphur and
increases to +4 Pin SO₂. This shows that the reaction P involves disproportionation. This reaction is an
oversimplification.
Cl In practice, the reaction is complex and produces several other sulphur containing
Cl
Cl Cl
Cl
products. The observations made include turbidity (cloudiness) due to the formation of solid sulphur and
a pungent smell due to the production of sulphur dioxide. Cl

tetrahedral (bond angle 1090) octahedral ( bond angle 900)

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More information on S2Cl2

Disulphur dichloride is an unstable orange -yellow liquid which fumes in air due to reaction with water vapour. The
white fumes formed are HCl. The structure of S2Cl2 is analogous to that of hydrogen peroxide, H2O2.

Note that three of the atoms are within the same plane. The fourth atom (Cl) occupies a different plane. The EU has
classified S2Cl2 as a corrosive, toxic and environmentally unfriendly chemical.

2.3.2 The oxides of Period 3 elements

Element Na Mg Al Si P S Cl

P4O10 Cl2O7
Oxide Na2O MgO Al2O3 SiO2 P4O6 SO2 (Cl2O)

State at 200C S o l i d Gas Liquid

(Gas)

Bonding G i a n t i o n i c Giant Simple molecular

covalent

Behaviour Reacts, Reacts,

in water forming forming No reaction. No Hydrolyzes, forming
NaOH Mg(OH)2 Insoluble reaction. strongly acidic solution.
Insoluble pH≈2
Alkaline Weakly
pH≈13 alkaline
pH≈9

Acid/base Basic Basic amphoteric A c i d i c

nature

m.p/0C 1275° 2 900 2 040 1 610 580 -10

sublimes 24

Table 9.1.7 The chemical and physical properties of the Period 3 elements. Note that
there is considerable discrepancy on the melting/sublimation point of Na 2O reported in
different sources.

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Bonding and structure
The bonding in the oxides change from ionic to covalent across the period. This coincides with the change
in the elements from metallic to non- metallic. Na₂O and MgO have giant ionic structures. Al₂O₃ has a
giant ionic structure, but there is also a high degree of covalent character. SiO₂ has a giant covalent
structure, similar to that of diamond. The rest of the period three oxides are simple covalent.
The melting points of the elements depend on the bonding and structure. Na 2O and MgO have very high
melting points since they have giant ionic structures. The melting point of MgO is much higher than that
of Na2O. This is because of the doubly charged Mg 2+ ion in MgO. This results in very strong ionic
attractions between the Mg2+ and O2- ions. A very large amount of heat energy is required to break down
the lattice and pull the ions from each other.
The melting point of Al2O3 is lower than that of MgO, something we mightnot have expected, given that
the Al3+ ion has the larger charge and so electrostatic attractions would be greater in Al 2O3 than in MgO.
The relatively low melting point of Al2O3 can be explained in terms of the high polarizing power of the
Al3+ ion. Polarization is when a cation withdraws electrons from, and therefore distorts the electron cloud
of an anion. In this case, Al3+, with its high charge density, withdraws some electron density from the
oxide ion. Consequently, there is some shared electron density (covalency) between the two atoms. The
bonding in Al2O3 is therefore not purely ionic; the presence of covalent character weakens the bonding
present, and consequently the melting point is relatively low. However, the melting point is not reduced
by a large value. This is because the oxide ion is relatively small and offers considerable resistance to
being polarized.

Reactions of the oxides with water

Na₂O reacts readily with water in an exothermic reaction to form a strongly alkaline solution of NaOH
(pH is about 13)
Na₂O(s) + H₂O (l) → 2NaOH (aq)
MgO is sparingly soluble in water, hence the solution formed is weakly alkaline. The poor solubility of
MgO in water can be explained in terms of its high lattice energy. A large amount of energy is required to
break down the lattice of MgO since the electrostatic attractions between Mg 2+ and O2- ions are very
strong.
MgO(s) + H₂O (l) → Mg²⁺ (aq) + 2OH⁻ (aq)
Al₂O₃is insoluble in water. The lattice energy of the oxide is high and water molecules are not able to
break it down. Also, Al2O3 has a complex structure which is not purely ionic. This structure is insoluble in
water.

An important note

The chemistry of aluminum compounds is heavily influenced by the very high charge density of the Al³⁺ ion. For instance,
one would expect AlCl₃ to be ionic, not covalent, since it is formed between a reactive metal and a reactive non-metal.
AlCl₃ is in fact mainly covalent, though it has a high degree of ionic character. Because of its high charge density, the Al³⁺
in AlCl₃ withdraws electrons from the chloride ion, resulting in a shared electron density between the two atoms. This
shared density of electrons is significantly stabilized through mutual attraction by the nuclei of Al and Cl. Electron
density shared between two atoms is, of course, a covalent bond.
It is also observed that some compounds of Al are very unstable, for example, aluminum carbonate, Al 2 (CO3) 3. With its
high charge density, Al³⁺ readily polarizes the carbonate ion, and in the presence of water
or water vapour, carbon dioxide and aluminium (III) hydroxide are produced.
Al2 (CO3)3 + 3H2O → 2 Al (OH) 3 + 3CO2

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SiO₂is a giant covalent solid with a diamond like structure.It is insoluble in water. Water molecules are
not able to break the very strong and numerous Si –O bonds.
The oxides ofphosphorous are simple covalent solids, soluble in water through hydrolysis.
It should be noted that whereas metallic oxides react with water to form an alkaline solution, non-
metallic oxides, if they do dissolve, will hydrolyze to form acidic solutions.

P₄O₆(s) + 6H₂O (l) → 4H₃PO₃ (aq)

P₄O₁0 (s) + 6H₂O (l)→ 12H⁺ (aq) +4PO₄²⁻ (aq) (= 4H₃PO₄)

P₄O₆ forms phosphonic acid, H3PO3 whilst P₄O₁0 forms phosphoric acid.
SO₂ and SO₃are simple covalent gases. SO₂ is weakly soluble in water, forming a solution of sulphrous
acid. Notice that the oxidation state of S is +4 in both sulphrous acid (H₂SO₃) and SO₂. In fact, sulphrous
acid is sometimes written as SO₂ (aq).
SO₂ (g) + H₂O (l) ⇋2H⁺ (aq) + SO₃²⁻ (aq)
Sulphrous acid (H₂SO₃) is weakly acidic and is easily decomposed back to SO₂ and water. The acid has no
independent existence and it has a tendency to be oxidized in air, to form the more stable sulphuric acid.
H₂SO₃ (aq) + 1/2O₂ (g) → H₂SO₄ (aq)
In this reaction, the oxidation number of S changes from +4 to +6. This is the oxidation of aqueous SO₂ to
sulphuric acid. As such, aqueous SO₂ is a reducing agent, able, for instance, to reduce Cr2O72- (aq) to
Cr3+ (aq) . SO₃ is not naturally occurring. It is formed industrially by reacting SO₂ with oxygen in the
presence of a vanadium (V) oxide catalyst (Contact process).
SO₃ hydrolyzes readily and violently in water to form a mist of sulphuric acid.
SO₃ (g) + H₂O (l) → 2H⁺ (aq) + SO₄²⁻ (aq)
The oxidation state of S in both sulphuric acid and sulphur trioxide is +6. This is the highest possible
oxidation state for S.

Acid base nature of the oxides

The oxides of Period 3 change from basic through amphoteric to acidic.
Na₂O and MgO are ionic and basic. They are neutralized readily by cold dilute acids, forming their
respective salts and water, for example
Na₂O(s) + 2HCl (aq) → NaCl (aq) + H₂O (l) ... pH = 7
MgO(s) + H₂SO₄ (aq) → MgSO₄ (aq) + H₂O (l) (pH is slightly less than 7 because of
hydrolysis of Mg2+ ions ).
These reactions can be reduced to the ionic form
O²⁻ + 2H⁺→ H₂O
In the ionic oxides, neutralization occurs in this way because of the presence of the oxide ion in the
lattice. The reaction basically involves the combination of two unstable ions, forming a neutral and stable
product, H₂O.
Al₂O₃ is amphoteric, that is, it behaves both as an acid and as a base.It reacts with dilute acids in the
same way as MgO and Na₂O.
Al₂O₃(s) + 6H⁺ (aq) → 2Al³⁺ (aq) + 3H₂O (l) pH ≈ 3

The solution formed is acidic because the Al³⁺ ions hydrolyze in water:

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Al³⁺(aq) + 6H₂O(l) → [Al(H₂O)₆]³⁺(aq) →[ Al(H₂O)₅OH]²⁺(aq) + H⁺(aq)
Al₂O₃ reacts with a strong base such as NaOH, to form an aluminate
Al₂O₃ (s) + 2NaOH (aq) + 3H₂O (l) → 2Na [Al (OH)]
The product of this reaction, sodium aluminate, Na [Al (OH)], contains the aluminate ion, which is a
complex ion. The formation of complex ions is usually associated with transition elements. The ability of
Al3+ to form a complex ion can once more be explained in terms of the high charge density of the ion. It is
able to strongly attract four OH- ions, and form dative bonds with the ions by using a lone pair of electrons
on the O atom of each OH- ion.

OH Tetrahedral geometry in the aluminate ion. All of

the bonds (in bold) are dative. This is an example of
a complex ion.
Al3+ A complex ion is a covalent ion in which a central
metal cation is bonded datively to one or more
OH electron rich groups, known as ligands.
HO
HO

bond angle = 1090

In the reaction of Al₂O₃ with OH- ions , Al₂O₃ acts as an acidic oxide, forming an aluminate salt. The
amphoteric nature of Al₂O₃ shows that though the oxide is predominantly ionic, there is some degree of
covalent character. Once more, this is caused by the high charge density of the Al³⁺ ion.

The oxides of the non- metals are acidic

SiO₂is acidic, but it will not react with alkalis under normal conditions because of the very strong Si-O
bonds that must be broken in the reaction. SiO₂ does react with bases in a non- aqueous reaction and at
very high temperatures to form salts known as silicates. In the blast furnace for the extraction of iron,
SiO₂, present in sandy impurities, is neutralized by CaO to form calcium silicate, which is tapped out as a
slag.
SiO₂(s) + CaO(s) → CaSiO₃(l)
SiO2 also reacts with fused NaOH to form sodium silicate.

SiO₂(s) + 2NaOH  Na2SiO3

P₄O₆ and P₄O₁₀are acidic oxides that readily react with alkalis, forming strongly acidic solutions, e.g.
P₄O₆ (s) +8NaOH (aq) →4Na₂HPO₃ (aq) + 2H₂O (l)
To balance this equation, it is necessary to know that the salt being formed contains the hydrogen
phosphorous ion, HPO₃²⁻, and not PO₃³⁻ (The hydrogen atom in the hydrogen phosphorous ion is
bonded to the P atom and so it is not dissociated).

A hint on balancing the equation

Students often find this equation difficult to balance. It can be balanced in two steps. First, the oxide reacts with water
to form an acidic solution of phosphorous acid. The H⁺ ions from the diprotic phosphorous acid are then neutralized
by NaOH (aq). The two reactions are then added to obtain the net equation.

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1.P₄O₆ (s) +6H₂O (l) → 8H⁺ (aq) + 4HPO₃²⁻ (aq)
2. 8H⁺ (aq) + 8NaOH (aq) → 8H₂O (l) + 8Na⁺(aq)

Overall P₄O₆ (s) +8NaOH (aq)  4Na₂HPO₃ (aq) + 2H₂O (l)

Similar reactions can be balanced in the same way (that is, in reactions in which the oxide can react with both water
and a base such as sodium hydroxide)

P₄O₁₀reacts with an alkali to form phosphate.

P₄O₁₀(s) + 12NaOH (aq) → 12Na⁺ (aq) + 4PO₄³⁻(aq) + 6H₂O(l) ( = 4Na₃PO₄ + 6H₂O)
Sulphur has two stable oxides, SO₂ and SO₃ (only SO2 exists naturally). Both react with NaOH (aq) to
form sodium sulphite and sodium sulphate respectively.
The equations can also be balanced by the 2 step method used in the previous example. It should be noted
that SO₂ produces a sulphite (SO₃²⁻) and SO3 produces a sulphate (SO₄²⁻).
SO₂ (g) + 2NaOH (aq) → 2Na⁺ (aq) + SO₃²⁻ (aq) + H₂O (l) (= Na₂SO₃ + H₂O)
The products of the reaction are the same as those produced when sulphrous acid, H 2SO3, reacts with
NaOH. This is because an aqueous solution of SO2 is essentially a solution of sulphrous acid. The equation
above can therefore be obtained by combining two equations,

SO2 + H2O  H2SO3

H2SO3 + 2NaOH  Na2SO3 + 2H2O

Net equation SO2 + 2NaOH  Na2SO3 + H2O

Note that H2SO3 is dibasic, so it reacts with NaOH in the ratio 1:2, to produce two moles of water.
The reaction of SO₃ with NaOH (aq) is violent.
SO₃(l) + 2NaOH (aq) → 2Na⁺ (aq) + SO₄²⁻ (aq) + H₂O (l) (= Na₂SO₄ + H₂O)
The products of the reaction are the same as those produced when sulphuric acid reacts with NaOH. This
is because in water, SO3 is converted to H2SO4.

Chlorine formsunstableoxides, Cl₂O₇ and Cl₂O. Both are acidic and react readily with NaOH (aq) to
form chlorate (VII) and chlorate (I) acid respectively.
Cl₂O₇ (l) +2NaOH (aq) → 2NaClO₄ (aq) +H₂O (l)
The product formed is an aqueous solution of sodium chlorate (VII), which is also known as sodium
perchlorate and is the conjugate base of chloric (VII) acid, HClO₄, also known as perchloric acid. The
products of the reaction above are therefore the same as those formed when HClO₄ reacts with NaOH
(aq). The reaction of dichlorine oxide with NaOH is
Cl₂O (g) + 2NaOH (aq) → 2NaClO (aq) + H₂O (l)
This reaction forms sodium chlorate (I), which is the conjugate of chloric (I) acid, HClO.

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Notes for use in qualitative analysis
The reader should be familiar with the tests and chemistry of the following Period 3 ions.

Mg2+ Al3+ Cl-

Here we discuss only Al3+. The other ions will be discussed later under the Groups (II) and (VII) ions.

A summary of the reactions of Al3+ (aq)

NaOH(aq) xs NaOH(aq)
xs NH3(aq) NH3(aq)
Al(OH)3(s) Al3+ Al(OH)3(s) Al(OH) 4-(aq) + Na+(aq)
ppt insol 3 1 2
white ppt white ppt colourless solution
4
5 Na2CO3(aq)

Al(OH)3(s) + CO2 + H2O

Reactions 1 and 2
Al3+ forms a white gelatinous precipitate with NaOH (aq). This precipitate dissolves in excess NaOH to form a
colourless solution containing the aluminate complex ion, Al (OH)4-. Reaction 1 is precipitation, and reaction 2 is
complexation. If the reagent is not added slowly and carefully, the white precipitate might be missed, and only a
colourless solution is observed.

Reaction 3
A precipitation reaction occurs due to the presence of OH- ions in aqueous ammonia
NH3 + H2O Ý NH4+ (aq) + OH-(aq)

However, the precipitate formed does not dissolve in excess NH3 (aq) because the concentration of OH- ions in NH3
(aq) is very small.

Reaction 5
This reaction might appear strange at first sight. The chemistry behind this reaction can be explained in terms of
 the acidic nature of Al3+(aq).
 Le Chatelier’s principle.
Al3+ ions have a large charge density, and so hydrolyze in water, producing H+ ions.
Al3+ + 6H2O (l) Ý [Al (H2O) 5(OH)] 2+ (aq) + H+ (aq) ... (I)
The solution is acidic enough to react with carbonate ions, producing effervescence due to the production of CO2.
CO32-(aq) + H+ (aq)  CO2 (g) + H2O (l) ... (II)

However, effervescence may not occur, depending on the relative concentrations of Al3+ and CO32- ions. Instead,
HCO3-may be formed, not carbon dioxide.
The effect of reaction (II) is to remove the H+ ions from equilibrium (I). By Le Chateliers’ principle, this causes more
H2Omolecules in the complex [Al (H2O) 5(OH)] 2+ to hydrolyze, thus releasing more H+ ions.
[Al (H2O) 5(OH)] 2+Ý[Al (H2O) 4(OH) 2] 2++ H+

Continued removal of H+ ions from the equilibrium results in all H2O molecules in the complex
[Al (H2O) 5(OH)] 2+ being hydrolyzed to produce OH- ions. This results in the formation of the precipitate Al (OH) 3.

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 Questions, solutions and discussions

Q1The elements phosphorus, sulphur, and chlorine are regarded as having simple molecular
structures.

(a) What are the molecular formulae of each of these three elements?

(b) (i)Place the three elements in order of their melting points with the highest first.

(ii) Suggest an explanation for the order you have given in (i).

(c)Sulphur and chlorine can be reacted together to form disulphur dichloride, S 2Cl2.
Disulphur dichloride, S2Cl2, is decomposed by water forming sulphur and a mixture of
hydrochloric acid and sulphurous acid.When 2.7 g of S2Cl2 is reacted with an excess of water,
0.96 g of sulphur, S, isproduced.

(i) What is the amount, in moles, of S2Cl2 present in 2.7 g?

(ii) What is the amount, in moles, of S produced from 1.0 mol of S 2Cl2?

(iii) Construct a balanced equation for the reaction of S2Cl2 with water.

(d) The reaction between S2Cl2 and water is a redox reaction.

Which product has been formed by oxidation and which by reduction?

9701/02/O/N/07

Solutions

3 (a)P4, S8, Cl2

(b) (i)highest is S8, Cl2 is lowest

(ii) The number of electrons in the molecules decreases in the order S8, P4, Cl2. Therefore Van der
Waals forces become weaker.

(c)(i) and (ii) is for the reader

(iii) 2S2Cl2+ 3H2O →3S + H2SO3+ 4HCl

(d) Oxidation product is H2SO3 and reduction product is S

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Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 352
 Q2The Periodic Table we currently use is derived directly from that proposed by Mendeleev in 1869
after he had noticed patterns in the chemical properties of the elements he had studied.
The diagram below shows the first ionization energies of the first 18 elements of the Periodic
Table as we know it today.

(a) Give the equation, including state symbols, for the first ionization energy of fluorine.

(b) Explain why there is a general increase in first ionization energies from sodium to
argon.

(c) (i)Explain why the first ionization energy of aluminium is less than that of magnesium.

(ii) Explain why the first ionization energy of sulphur is less than that of phosphorus.

The table below refers to the elements sodium to sulphur and is incomplete.

(d) (i) Complete the ‘melting point’ row by using only the words ‘high’ or ‘low’.

(ii) Complete the ‘conductivity’ row by using only the words ‘high’, ‘moderate’ or ‘low’.

(e) When Mendeleev published his Periodic Table, the elements helium, neon and argon were not
included. Suggest a reason for this.
9701/02/M/J/08

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 (a)F(g) →F+(g) + e–

(b) From Na to Ar, electrons are added to the same shell where they shield each other only slightly.
At the same time, nuclear charge increases and so the valence electrons feel a stronger attraction

(c) (i) Outermost electron in Al is in 3p which is higher in energy/farther from the nucleus than the 3s
outer shell in Mg.

(ii) Phosphorous and sulphur :

For phosphorous the valence 3p sub-shell is singly filled/exactly half-filled. For S one 3p orbital
has paired electrons which repel each other.

(d) (i) and (ii)

Element Na Mg Al Si P S

Melting point low ……. high high low low

conductivity high ……. high moderate low low

(e) They had not been discovered yet

Q3Magnesium chloride, MgCl2, and silicon tetrachloride, SiCl4, each dissolve in or react with water.
Suggest the approximate pH of the solution formed in each case.Explain, with the aid of an
equation, the difference between the two values.
9701/02/O/N/2008

Solutions

MgCl2:6 to 7
SiCl4: 0 to 3
MgCl2has no reaction with water, it simply dissolves
SiCl4reacts with water/undergoes hydrolysis in water
SiCl4+ 2H2O →SiO2+ 4HCl or
SiCl4+ 4H2O →Si(OH)4+ 4HCl or
SiCl4+ 4H2O →SiO2.2H2O + 4HCl
NB MgCl2 actually undergoes slight hydrolysis in water

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 Q4Copper and titanium are each used with aluminium to make alloys which are light, strong
and resistant to corrosion.
Aluminium, Al, is in the third period of the Periodic Table; copper and titanium are both
transition elements.

(a) Write the electronic configuration of aluminium and of titanium, proton number 22.

Aluminium reacts with chlorine.

(b) (i)Outline how, starting from aluminium powder, this reaction could be carried out
in a school or college laboratory to give a small sample of aluminium chloride. A diagram
is not necessary.

(ii) Describe what you would see during this reaction.

(iii) At low temperatures, aluminium chloride vapour has the formula Al2Cl6.
Draw a ‘dot-and-cross’ diagram to show the bonding in Al2Cl6. Show outer electrons only.

Copper forms two chlorides, CuCl and CuCl2.

(c) When copper is reacted directly with chlorine, only CuCl2 is formed.
Suggest an explanation for this observation.

Titanium also reacts with chlorine.

(d) When an excess of chlorine was reacted with 0.72 g of titanium, 2.85 g of a chloride A
was formed.

(i) Calculate the amount, in moles, of titanium used.

(ii) Calculate the amount, in moles, of chlorine atoms that reacted.

(iii)Hence, determine the empirical formula of A.

(iv) Construct a balanced equation for the reaction between titanium and chlorine.

(e) At room temperature, the chloride of titanium, A, is a liquid which does not conduct
electricity. What does this information suggest about the bonding and structure in A?
9701/02/M/J/2009

Solution

1 (a) Left for the reader

(b) (i)Pass chlorine gas over heated aluminium

(ii) Aluminium glows and a whitesolid is formed . Colour of chlorine fades.

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 (iii) Left for the reader

(c) Chlorine is a powerful oxidizing agent

0.72
(d) (i) Moles of Ti = = 0.015
47.9
(2.85−0.72)
(ii) Moles of chlorine = = 0.06
35.5
(iii) Ti : Cl2 = 0.015 : 0.06 = 1:4
Therefore empirical formula of A is TiCl4
(e) Simple covalent.

Q5Magnesium will react on heating with chlorine, or oxygen, or nitrogen to give the chloride, or
oxide, or nitride respectively. Each of these compounds is ionic and in them magnesium has
the same +2 oxidation state.

(a) (i) Write an equation, with state symbols, for the second ionization energy of
magnesium.

(ii) Use the Data Booklet to calculate the enthalpy change that occurs when one mole
of gaseous magnesium ions, Mg2+, is formed from one mole of gaseous magnesium
atoms.

Include a sign in your answer.

(b) Separate samples of magnesium chloride and magnesium oxide are shaken with water.
In each case, describe what you would see when this is done, and state the approximate
pH of the water after the solid has been shaken with it.

(c) Magnesium burns in nitrogen to give magnesium nitride, a yellow solid which has the
formula Mg3N2.
Magnesium nitride reacts with water to give ammonia and magnesium hydroxide.

(i)Construct an equation for the reaction of magnesium nitride with water.

(ii) Does a redox reaction occur when magnesium nitride reacts with water?
Use the oxidation numbers of nitrogen to explain your answer.
9701/21/M/J/2009

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 Solutions

2 (a) (i) Mg+(g) →Mg2+(g) + e–

(ii)736 + 1450 = +2186 kJ mol–1(sum of first and second ionization energy)

(b) (i) MgCl2dissolves , giving a solution of pH 6 – 7

(ii)MgO is slightly soluble in water, giving a pH of 8-11

(c) (i) Mg3N2+ 6H2O →3Mg(OH)2+ 2NH3

(ii)In Mg3N2,N has oxidation state of –3. In NH3, N has oxidation state of –3. Therefore reaction is
not redox since N does not change its oxidation state.

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1.The elements of the third period of the Periodic Table form chlorides of general formula EClx.
where E represents the element. These chlorides show a variation in oxidation number from
sodium to sulfur.

(a) (i) Use the information given to complete the table below.

Formula of chloride NaCl MgCl2 AlCl3 SiCl4 PCl3 SCl2

Oxidation number of
element in the
chloride

(ii) By considering the electron configurations of the elements, explain the variation in
oxidation number in the chlorides from Na to Al and from Si to S.

Sodium hydride, NaH, is a colourless crystalline solid which melts at 800 °C and has the
same crystal structure as sodium chloride which has a melting point of 808 °C. When molten
sodium chloride is electrolyzed using graphite electrodes, a shiny deposit, D, forms on the
cathode and a greenish-yellow gas is evolved from the anode. When molten sodium hydride
is electrolysed, under suitable conditions using graphite electrodes, the same shiny deposit
D is formed on the cathode and a colourless gas, G, is evolved from the anode.

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(b) (i) Describe with the aid of a diagram the bonding in a sodium chloride crystal.

(ii) Suggest the type of bonding that is present in sodium hydride.

(iii) What is the oxidation number of hydrogen in sodium hydride?

(iv) Draw a ‘dot-and-cross’ diagram for sodium hydride. Show outer electrons only.

(v) The metals magnesium and aluminium form hydrides with formulae MgH2 and
AlH3. The non-metals phosphorus and sulfur form hydrides with formulae PH 3 and
H2S.
By considering their positions in the Periodic Table, suggest oxidation numbers for
these four elements in their hydrides.

At room temperature, the chlorides of sodium, magnesium and aluminium are all solids which
dissolve in water.
The hydrides of sodium, magnesium and aluminium are also solids which react with water
with the rapid evolution of the same colourless gas G in each case.

(c) (i) What is the pH of the solutions formed when separate samples of sodium chloride,
magnesium chloride, and aluminium chloride are dissolved in water?

(ii)Suggest an equation for the reaction between sodium hydride and water.

(iii) Suggest a value for the pH of the solution formed in (ii).

At room temperature, the chlorides of silicon, phosphorus and sulfur are all low melting point
solids or low boiling point liquids that can be seen to react with water.

(d) (i)Suggest what type of bonding is present in sulfur dichloride, SCl2.

(ii) Write a balanced equation for the reaction between the chloride of silicon, SiCl4,
and water.
9701/22/O/N/2009

2.The formulae and melting points of the fluorides of the elements in Period 3, Na to Cl, are
given in the table.

Formual of
fluoride NaF MgF2 AlF3 SiF4 PF5 SF6 ClF5

m.p. /K 1268 990 1017 183 189 223 170

(c) (i) Suggest the formulae of two fluorides that could possibly be ionic.

(ii) What is the shape of the SF6 molecule?

(iii)In the sequence of fluorides in the table, the oxidation number of the elements increases

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from NaF to SF6 and then falls at ClF5.
Attempts to make ClF7 have failed but IF7 has been prepared.
Suggest an explanation for the existence of IF7 and for the non-existence of ClF7
9701/22/M/J/2010

3(a) State the formulae, and describe the reactions with water, of the oxides of the elements in the
third period from sodium to sulphur. 9701/22/M/J/1992

4. It has often been stated that the elements of the Periodic Table show a general trend across a period
from metallic to non-metallic behaviour, coupled with an increase of oxidation number in their
compounds.

Illustrate this statement by describing and explaining the formula, the properties and the reactions
with water of the chlorides of the elements sodium to phosphorous. 9701/22/M/J/1992

5 (a) Describe the variations in melting points and conductivities of the elements sodium to argon, and
explain these variations in terms of their structures and bonding.

(b) Alloys of aluminium and magnesium are often used in aircraft manufacture because of their high
strength and low density.
A 1.00 g sample of one such alloy was reacted with an excess of aqueous sodium hydroxide and
the volume of hydrogen given off was measured : 1.00 dm3 of gas was produced at 250C and a
pressure of 1.01 x 105 Pa.
The aluminium containing product of this reaction is the same as that from the reaction between
aluminum oxide and sodium hydroxide. From your knowledge of the latter reaction, construct an
equation for the reaction between aluminium and sodium hydroxide, and hence calculate the
percentage of aluminium in the sample of alloy. 9701/22/M/J/1992

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9.2 GROUP (II) ELEMENTS: Mg To Ba

Introduction
Some generalizations can be made about elements in the same group.
They have the same number of valence electrons, and so they are expected to have similar chemical
properties. This is observed most of the times, but exceptions do exist, and reactivities tend to change
down the group. Also, the similarity in chemical properties is well defined in some groups, and not so
well in others. It is also noticed that the first member of a group usually has properties which are
atypical of the group, for example, Beryllium in Group (II) forms a covalent chloride, BeCl₂, but the
rest of the elements form ionic chlorides.

9.2.1Electronic structure of Group (II) elements

Valence shell configuration: ns²

The Group(II) elements therefore belong to the S block of the Periodic table(just as the Group(I) metals,
because only the s-sub shell is occupied in the valence shell. The value of n is equal to period number, for
instance, in Mg n=3(Period 3) and in Sr, n=5 (Period 5).
From the configuration of the valence shell, we learn the following
 The Group (II) metals react by losing two valence electrons. They therefore act as reducing agents.
 They form +2 ions in their reactions. All of their compounds only have the +2 oxidation state.
A question which immediately arises is why the +1 oxidation state, corresponding to loss of one of the
valence 2s electrons, is not formed. This can be answered in two ways.
 Electrons usually stabilize each other by pairing. A single electron in the 2s orbital is very
unstable, and so it is easily removed.
 If only one valence electron is lost, the resulting +1 ion would have an outer shell with only one
electron, which is very unstable. By losing both electrons, a full octet of electrons is exposed. The
+2 state is therefore more stable, and its formation is favoured to that of the +1 state.

9.2.2Structure and bonding

The elements of Group (II) are all metallic. However, metallic character increases down the group.
Beryllium, the first member of the group, is the least metallic. It has a high degree of non- metallic
character, for instance, it forms a covalent chloride, BeCl2. Going down the group, more shells are opened,
and atoms become bigger in size. Two factors come into play:
 The distance factor. The distance of the valence electrons from the nucleus increases. The
attraction they feel from the nucleus becomes weaker and weaker. Down the group, the outer
most electrons are easily detached and contributed into a common pool of delocalized electrons,
which characterizes metals.

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  The screening(shielding) effect increases. Each additional shell opened screens (shields) the
valence electrons from feeling the full attractive influence of the nucleus.
One might expect the effect of shielding to be compensated for by the increasing nuclear charge. That is,
as the number of protons increases down the group, the attraction of the nucleus for the valence electrons
would increase and shells would be pulled inwards, keeping the size of atoms small. This does happen to
some extent, but the shielding effect has a greater impact than the increase in nuclear charge.

9.2.3Physical properties

2.3.1 Atomic and ionic radius

Atomic Metallic Ionic radius of
number radius/nm M2+ ion/nm

Mg 12 0.160 0.065

Ca 20 0.197 0.094
Fig 9.2.1
Sr 38 0.215 0.110
Trend in atomic
Ba 56 0.211 0.134 and ionic radii
down Group (II)

Table 9.2.1 Trend in atomic and ionic radii

down Group (II)

 Atomic and ionic radii increase down the group. This is because additional shells are being
opened. The more shells an atom has, the larger it is. However, the increase in atomic radii from
one element to the next is not large because the increase in nuclear charge has a counteractive
effect: as proton number increases, the ability of the nucleus to pull shells towards itself increases,
keeping the atoms relatively small.
 The ions are smaller than the atoms from which they are formed. This is because each ion has one
less shell than the neutral atom.

2.3.2 Ionization energies

Ionization energy decreases down the group.
The outer most electrons become more and more loosely held to the atom for two reasons:
 Increasing size of the atoms (due to opening of new shells) implies that the distance of the valence
electrons from the nucleus increases.
 The opening of new shells implies that the valence electrons become more and more shielded
from feeling the full attractive influence of the nucleus.
These two factors work together so that valence electrons become loosely held to the atom down the
group, and less energy would be required to remove them

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2.3.3 Density

Table 9.2.2
Densities of Group
(II) elements

Density gives a measure of how much mass is packed in a given volume. A large mass packed in a small
volume results in high density. The trend in density is not so straightforward for two reasons
 Density is made up of two terms, mass and atomic volume, which has opposite effects to each
other. The larger the mass, the greater the density, but the larger the volume, the smaller the
density. Down the group, volume of the atoms increase, so density is expected to decrease (D is
inversely proportional to V). This observation is made only for the first three elements. Density
decreases from Be to Ca, but begins to increase from Sr to Ba.
The increase in density from Sr to Ba is a result of the sharp increase in mass. In Sr and Ba the
increase in mass is much greater than the increase in volume, so density increases.
 It should also be noted that the elements of Group (II) have different crystal structures and this
has an effect on the trend on densities.

2.3.4 Melting points and boiling points

The Group (II) elements generally have high melting points because of the presence of strong metallic
bonding. In the metallic lattice, metal atoms have a charge of +2, and so they form strong electrostatic
attractions with the sea of delocalized electrons.In general, melting points decrease down the group. As
the size of atoms increase, the charge density on the positive atomic cores decrease, and the electrostatic
attractions between the atoms and the sea of delocalized electrons become weaker, that, is less energy
would be required to separate the atoms from each other and break down the metal lattice during melting.
The increase in atomic size weakens attraction in another way. When the atoms are large, then the sea of
delocalized electrons is a large distance from the nuclei of the metal atoms. The sea of delocalized
electrons is therefore weakly attracted to the positive nuclei of the atoms.
Mg has an abnormally low melting point. This is a result of its specific crystal structure. The metals in
group (II) have different crystal structures, so that the trend in melting points is not as regular as would
have been expected from a consideration of atomic radii alone.

9.2.4Trends in chemical properties

The Group (II) elements are metals and so they show chemical properties usually associated with metals.
 They react by losing their valence electrons. Thus they are reducing agents as they tend to give
away the valence electrons to oxidizing agents such as oxygen, chlorine and dilute acids. The
Group (II) elements have a fixed oxidation number of + 2 in their compounds, corresponding to
loss of the two valence electrons.
 In general, reactivity increases down the group and reactions become more violent. As the size
of atoms increases, the tendency for the valence electrons to be lost during chemical reactions
increases as the electrons become weakly held to the atoms. This is supported by electrode
potential data for M2+(aq)/M(s) for the Group (II) metals. The values given below are for the
forward reduction half equation M2+(aq) + 2e-∏ M(s)

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 In general, the electrode potentials are large and
positive in the reverse (oxidation) direction. This
shows that the Group (II) metals are very
reactive and are easily oxidized to the +2 state.
The electrode potentials become more positive
Table 9.2.3 Reduction potentials
in the reverse direction, showing that the metals
(M2+ (aq) + 2e ⇋ M(s)) of the group (II) metals are more easily oxidized on going down the
group (they become more powerful reducing
agents), that is, the tendency to lose the valence electrons increases.
The increase in the reactivity of the metals is illustrated by their reaction with oxygen, water and dilutes
acids.

2.4.1 Reaction of the metals with oxygen

The metals reduce oxygen to O²⁻. Meanwhile the metal is oxidized to its +2 state. The vigourof reaction
increases down the group, as already explained. The reactions produce a basic metal oxide MO. The
reaction of the metal with oxygen can be generalized as
2M(s) + O2(g)  2MO(s)
Magnesium burns rapidly with a bright white flame to form a white ash of MgO, which may be tainted
gray by the formation of magnesium nitride.
2Mg(s) + O₂ (g) → 2MgO(s)
3Mg(s) + ½ N₂ (g) → Mg₃N(s)
Formation of Mg₃N does not occur readily because the reaction has a very high activation energy due to
the very strong triple bonds that must be broken in nitrogen molecules for the reaction to take place. If Mg
is burnt in a closed vessel, Mg₃N might be formed toward the end of the reaction when oxygen is almost
used up.
Mg might not burn easily because of the heat resistant layer of magnesium oxide that forms on the surface
of the metal. In that case, prolonged heating with a very hot Bunsen flame will be necessary. Alternatively,
the magnesium metal can be scraped first to remove the oxide layer.
MgOforms a weakly alkaline solution in water because of its poor solubility
Calcium burns faster and more readily than Mg. This particularly applies to the freshly cut metal which
is not coated with a surface layer of calcium oxide.
CaO dissolves in water more readily than MgO, forming an alkaline solution of Ca(OH)₂.
Sr and Ba burns explosively in air, forming their respective oxides, which dissolve appreciably in water
to form strongly alkaline solutions.
Ba also forms a peroxide with oxygen, in which the oxidation state of oxygen is -1.
Ba(s) + O2 (g) BaO2(s)
The anion present in this solid is the peroxide ion, O₂²⁻. This anion is large enough to be polarized by the
smaller metal cations at the top of the group. However, BaO₂ is stable. Because of its large size and low
charge density, Ba²⁺ is not able to polarize and destroy the peroxide ion.

The oxides of group (II) metals

The Group (II) oxides have giant ionic structures in which the lattice particles are the M²⁺ and the O²⁻
ions. The first member of Group (II), Be, forms an amphoteric oxide. This shows that although BeO is
ionic, it has a high degree of covalent character.

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The rest of the oxides are basic, and they react readily with dilute acids, forming their respective salts, for
example,
MgO(s) + H2SO4 (aq)  MgSO4(aq) + H2O(l)
The lattice energies of the Group (II) metal oxides become smaller (less negative) down the group.
This is a result of the increase in the ionic radius of the M²⁺ ion. Going down the group, additional shells
are opened and this results in an increase in the size of the ions. This weakens the electrostatic attractions
between the metal ion and the oxide ion in two ways.
 Charge density of the M2+ ion decreases down the group. An ion with a small charge density has a
relatively weak attraction for an anion.
 The distance between the nucleus of the metal ion and the anion increases. This weakens the
attraction between the protons in the cation and the negative charge on the anion.
MgO, at the top of the group, has a very high lattice energy, and for this reason it is used as a refractory
material for lining the walls of furnaces.

Solubility of the oxides

Solubility increases down the group.
BeO is insoluble in water, though it is dissolved by both dilute acids and alkalis. MgO is poorly soluble in
water, so it forms a weak alkaline solution of Mg (OH)₂
MgO(s) + H₂O(s) → Mg²⁺ (aq) + OH⁻(aq)
CaO dissolves much better than MgO. SrO and BaO dissolve well in water.
To dissolve in water, the electrostatic attractions between the metal cation and the oxide ion must be
broken. The stronger the forces, the harder it is for water to break down the solid lattice. The strength of
these attractions is measured in terms of the lattice energy of the oxide. The higher the lattice energy (that
is, the more negative it is), the stronger the forces of attraction. Lattice energies of the Group (II) oxides is
high for the members at the top, and it decreases down the group (Table 9.2.4). It is therefore harder to
break down the lattice structure of MgO, but going down the group, the forces holding the ions of the
lattice together become weaker, and it becomes easier for water molecules to separate the ions.

Cation Ionic radius Lattice energy of Table 9.24The lattice enthalpies

present of cation oxide/Kjmol-1 x -1
(theoretical) of the Period 2 metal
oxides. Note the inverse relationship
MgO Mg2+ 0.065 3 929
with ionic radii of the M2+ ions. As the
CaO Ca2+ 0.099 3 477 ionic size increases down the group,
the lattice enthalpy decreases, that is ,
SrO Sr2+ 0.113 3 205 it becomes less exothermic.

BaO Ba2+ 0.135 3 042

2.4.2 Reaction of the Group (II) metals with water

The metals become more reactive down the groupfor reasons that have already been explained.
M(s) + 2H₂O → M(OH)(s) + H₂ (g)
In these reactions, the metals act as reducing agents, reducing water to OH⁻. Water acts as an oxidizing
agent, oxidizing the metal to its +2 state. The readiness and vigour of reaction increases down the group.
Beryllium has no reaction with water. Mg metal has no appreciable reaction with cold water, but it
burns rapidly in steam, forming its oxide and liberating hydrogen.

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Mg(s) + H₂O (g) → MgO(s) + H₂(s)
The initial product of the reaction is actually Mg(OH)₂, but it is dehydrated because of the high
temperature, forming MgO.
Calcium reacts vigorously with cold water in a very exothermic reaction which may cause the water to
boil. The water is immediately clouded by calcium hydroxide.
Ca(s) + 2H₂O (l) → Ca(OH)(s) + H₂ (g)
Sr and Ba react explosively with cold water. The reaction of Ba is more violent. The suspension formed is
not as cloudy as that for Ca. This is because the hydroxides of Sr and Ba are more soluble in water.
The resistance of Beryllium to reaction with water can be explained in two ways
 The atoms are very small and therefore do not easily lose their outer shell electrons
during the reaction with water.
 The metal is protected by a thin, tough and impermeable layer of BeO, which protects the metal
underneath. This renders the metal kinetically stable with respect to its oxide.

Solubility of the group (II) hydroxides

The hydroxides dissolve reversibly in water to form a suspension. Solubility increases down thegroup.
M(OH)₂(s) ⇋M²⁺(aq) + 2OH⁻(aq) … (i)
Going down the group, the equilibrium lies more and more to the right and the suspension becomes less
cloudy as the amount of undissolved metal hydroxide decreases.
Mg(OH)₂ is poorly soluble in water. It therefore forms a weakly alkaline solution. For this reason, it is fre-
quently used as an antacid, for example in toothpaste and in milk of magnesia (for treating acid indiges-
tion). If it were very soluble in water, it would not be suitable as an antacid because the high concentration
of OH- ions would lead to poisoning.
The solubilities given in Table 9.25 show the increasing tendency of the hydroxides to dissolve in water
down the group.

The enthalpy change of this reaction (∆Hθsolution)

Solubility/moles per 100g of
water becomes more exothermic down the group, that
is, the dissolution becomes more energetically
Mg(OH)2 0.2 x 10-4 favourable. Reaction (i)might be thought of as
happening in two steps, as shown in the energy
Ca(OH)2 16 x 10-4 cycle in Fig 9.2.2below.
Solubilities are best explained in terms of
Sr(OH)2 330 x 10-4
energetics. The dissolution process involves
Ba(OH)2 240 x 10-4 dissociation of the solid lattice to form aqueous
ions.
Fig 9.25 Solubilities of the Group (II) metal
hydroxides. M(OH)₂(s) → M²⁺(aq) + OH⁻(aq) …. (i)
First the ionic crystal is broken down into its constituent gaseous ions. This is the reverse of lattice energy,
and it is an energy absorbing process (endothermic). The gaseous ions are then hydrated in water. This
process is exothermic. Whether the enthalpy of reaction (i) is relatively positive or negative therefore
depends on which of the two terms, lattice enthalpy and hydration enthalpy, has the greater numerical
value.

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 HOsol
M(OH)2(s) Mg 2+(aq) + 2OH-(aq) Fig 9.2.2 An energy cycle for the
determination of the enthalpy change of
solution for the dissolution of a Group (II)
L.E HOhydr metal hydroxide.

Mg2+(g) + 2OH-(g)

By Hess’ law,
∆Hθsol = - L.E + ∆Hθhydr ... (ii)
Here we consider only the hydration of the M2+ ions, since the hydration enthalpy of the OH - ion remains
constant. Going down the group, both LE of the metal oxides and the hydration enthalpy of the metal ion
decrease because of the increasing size of the M 2+ ion. However, the decrease in LE (the endothermic
component in equation (ii)) is faster than the decrease in hydration enthalpy (the exothermic component
in equation (ii)), that is, going down the group, ∆Hθsolbecomes more exothermic. The dissolution process
therefore becomes more energetically favourable.

An important note
The size of the anion is important in determining whether or not the fall in LE is faster that the fall in enthalpy of
hydration. When the size of the anion is small, such as the hydroxide ion, then the fall in LE is faster and the enthalpy
of solution becomes more negative, that is, solubility increases down the group. When the anion is a large species
such as the sulphate and the carbonate ions, the fall in LE is very slow,much slower than the fall in hydrationenthalpy.
In that case, enthalpy change of solution becomes more positive down the group and solubility decreases.

2.4.3 The Group (II) sulphates

The elements of Group (II) form stable sulphates, M(SO₄).
The solubilities of these sulphates decrease down the group, as shown in the Table 9.2.6 . For example,
from this table you can easily verify that MgSO4 is about 111 times more soluble than BaSO4.
This trend in solubilities can be explained in terms of
Solubility/moles per 100g of
chemical energetics. The dissolution process is
water
M(SO)4(s)  M2+(aq) + SO42-
MgSO4 3 600 x 10-4
The enthalpy change of solution, ∆Hθsol for this process
CaSO4 11 x 10-4 can be calculated from Hess’ Law and a suitable energy
cycle diagram (see Fig 9.2.2).
SrSO4 0.62 x 10-4 ∆Hθsol = -L.E + ∆Hθhydr... (i)
BaSO4 0.009 x 10-4 We consider only the enthalpy of hydration of the M2+
ion, since the hydration enthalpy of SO42- remains
Table 9.2.6 Solubilities of the
constant.
Group (II) sulphates

Whether the solid sulphate dissolves or not depends on whether the dissolving process is favourable
(relatively negative enthalpy change of solution = exothermic) or unfavourable (relatively positive
enthalpy change of solution = endothermic).
Both L.E and ∆Hθhydr decrease down the group (they become less exothermic due to the decrease in size
of the M2+ ion). However, the change in LE of the metal sulphate down the group is only slight, so that
enthalpy change of solution is to a large extend influenced by the change in the hydration enthalpies of

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the M2+ ions. In other words, the decrease in ∆Hθhydris much faster than the decrease in L.E. Going down
the group, the radius of the metal cation increases, and hydration of the ions become more endothermic,
since weaker attractions are formed with water. Enthalpy of solution therefore becomes more
endothermic down the group, and more exothermic up the group.
We can rewrite equation (i) as
∆Hθsol = constant + ∆Hθhydr... (ii)
since the change in L.E is very slight . Now, ∆Hθhydr becomes more positive down the group. Substituting
these more positive values in equation (ii) causes ∆Hθsol to become more positive as well. In other words,
∆Hθsol becomes more endothermic and thetendency of the metal sulphate to dissolve in water becomes
less energetically feasible.MgSO4 is soluble. CaSO4 is less soluble, but it does dissolve appreciably. SrSO 4
is sparingly soluble and BaSO4 can be considered as being insoluble.

Explain why lattice energy changes only slightly for the Group (II)sulphates?
Q

The change in lattice energy is slight because of the large size of the sulphate ion.
A
q₊q₋
L.E α
r+ + r₋

where q+ and q- are the charges on the positive and negative ion respectively and r+ and
r- are the radius of the positive and the negative ions respectively. Lattice energy varies
inversely as the sum of radii (r+ + r-) of the cation and anion. When (r+ + r-) increases,
lattice energy decreases. Now, since r-(radius of sulphate ion) is large, the change in the
sum (r+ + r-) remains fairly constant when the radius of the M2+ ion increases down the
group. Since (r+ + r-) remains almost constant, the change in L.E of the Group (II)
sulphates is small.

Note
The hydroxides of Group (II) elements show the reverse trend, that is, they become more soluble down the group.
This time lattice energy decreases faster than enthalpy of hydration. This is because the OH - ion is relatively small.
The increase in the radius of the M2+ ion down the Group results in a significant increase in the sum (r+ + r-), leading
to a decrease in lattice energy down the group.

2.4.4 The carbonates and nitrates of the Group (II) elements

The elements from Mg to Ba form stable carbonates and nitrates.
All of the Group (II) nitrates are soluble. The carbonates are rather insoluble, as shown in
Table9.2.7.In general, solubility of the carbonates decreases down the group just as is observed for the
sulphates, and for the same reason.

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 Solubility/moles per
Thermal stability of the group (II) nitrates and
100g of water carbonates

MgCO3 1.3 x 10-4 he nitrates and carbonates of the group (II) nitrates are
decomposed by heat. The decomposition of the nitrates can be
CaCO3 0.13 x 10-4 generalized by the equation

SrCO3 0.07 x 10-4 M(NO₃)₂(s)  MO(s) +2NO₂(g) + O₂(g)

𝟏
𝟐
BaCO3 0.09 x 10-4
When the decomposition takes place, red brown fumes of NO2
Fig 9.2.7 Solubilities of the are produced, together with a gas that relights a glowing splint
Group (II)
(oxygen). A white residue of metal oxide is left behind.
carbonates

MCO3(s)  MO(s) + CO2 (g) The carbonates decompose according to the equation
When the decomposition is complete, a white residue is left which dissolves in a strong acid such as HCl
without producing effervescence. This shows that the product is a metal oxide, and not a carbonate.
The ease of decomposition of the nitrates and carbonates by heat decreases down the group, that is, it
becomes more difficult to decompose them, and higher temperatures would be required. Another way of
putting it is that the stability of the carbonates and nitrates towards heat increases down the group. As an
example, consider the decomposition of magnesium and Barium nitrate. Mg(NO 3)2 decomposes fairly
easily when strongly heated in a Bunsen flame but Ba(NO3)2 resists decomposition and only starts to
decompose at much higher temperatures.

Explaining the trend in thermal stabilities of the Group (II) nitrates and
carbonates
The nitrate ion, being large, can be easily polarized by a cation. That is, some electron density from the
anion is attracted by the cation, resulting in the distortion of the electron cloud of the anion. This creates a
region of shared electron density between the metal cation and the N atom of the nitrate ion. This region
of electron density is shared between the cation and the anion. The result is that some covalent character
is introduced, and some ionic character is removed from the metal nitrate. This has the effect of
destabilizing the metal nitrate so that it can be decomposed fairly easily by heat.
At the top of the group, the metal ion, M²⁺, because of its small size, has the greatest charge density, and
hence is the most effective at polarizing the nitrate ion. Mg (NO₃) is therefore the least stable, and it is
easily decomposed by heat. Going down the group, the size of the cation increases and its charge density
decreases. The cation becomes less and less able to effectively polarize the anion. The metal nitrate
therefore becomes more thermally stable. Higher temperatures would be required to decompose the
nitrate. Ba (NO)₃, at the bottom of the group, has the largest ionic radius, and hence the smallest charge
density. Ba(NO₃)₂ is therefore thermally stable. A very high temperature is required to decompose it. The
same explanation applies for the metal carbonates.

The alternative explanation

Decomposition of the nitrates and carbonates result in the formation of metal oxides. The more stable the
oxide, the more favourable is its formation, and the easier it is to decompose the metal nitrate or
carbonate.
Stability of the oxide is best measured in terms of its lattice energy. The larger the magnitude of the
lattice energy, the more stables the oxide. Lattice energy of the metal oxide depends on the charge density

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of the cation. The higher the charge density, the stronger the attraction between the cation and the oxide
ion. This time a large charge density does not result in polarization and instability, since the oxide ion is
small and not easily polarized. The Mg²⁺ ion, being the smallest, has the highest charge density, so MgO
has the largest magnitude (most negative) lattice energy. The formation of MgO is therefore energetically
favourable and happens fairly easily at relatively low temperatures. Going down the group, the size of the
metal cation increases, its charge density decreases and its ability to attract the oxide ion decreases. The
magnitude of lattice energy of the oxide correspondingly decreases and the metal oxide becomes less
stable. The formation of the metal oxide becomes less favourable down the group, that is, decomposition
of the nitrate becomes less likely.

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 Group (II) elements: quick facts

Magnesium
Named from the ancient region Magnesia in Greece, from which the metal was discovered. This
silvery white metal is relatively strong and less dense than Al. Its alloy with Al, sometimes known as magnalium, is
prized for its relative lightness and it is accordingly used in applications where lightness and strength are
important, such as in aircraft bodies.
Magnesium is the 11th most abundant element by mass in the human body. It is required for the proper functioning
of many enzymes. Magnesium (II) is found at the centre of chlorophyll molecules. This explains the addition of
magnesium salts to fertilizers.
Magnesium compounds have a number of medical uses.
 As common laxatives (substances that induce bowel movement. They are also known as purgatives). A
well known example is Epsom salts in which the active ingredient is MgSO₄.7H₂O.
 Milk of magnesia is a suspension of magnesium hydroxide in water. This suspension is slightly alkaline
because of the poor solubility of Magnesium hydroxide in water. Milk of magnesia is used as an
antacidto treat acid indigestion.
Magnesium hydroxide is also the antacid found in many types of toothpastes. It neutralizes acids formed
by bacteria in the mouth, thus preventing corrosion of teeth.
 MgO is used as a refractory(heat resistant) lining in furnaces because it has a very high melting point.

Calcium
From Latin, calx, meaning ‘lime’.
Calcium was known as early as the first century when the ancient Romans prepared lime as calciumoxide. Ca is a
soft gray alkaline metal which can be cut with a knife. It is the fifth most abundant metal by mass in the human
body. It is required for teeth and bone formation (bone is essentially calcium phosphate). Ca (II) is also important
in the transmission of nerve impulses.
Limestone is a rock in which the major component is CaCO₃. This explains the chemical erosion of limestone
landscapes by acid rain. Limestone is mainly used as a source of CaO (quicklime) and slaked lime (calcium
hydroxide). CaO is made by heating CaCO₃ at high temperature:
CaCO₃(s) → CaO(s) + CO₂ (g)
CaO, formed insitu in the blast furnace for the extraction of iron, is used to remove sandy impurities by
neutralizing
silicon dioxide (silica), which is the major component of sand.
CaO(s) + SiO₂(s) → CaSiO₃(s)
The calcium silicate formed is then tapped out as a slag which is used for road surfacing.
CaO, as lime, is used in agriculture to neutralize acidic soils. Slaked lime (Ca(OH)2) is also used for the same
purpose. CaO and Ca(OH)2 are poorly soluble in water, producing a weakly alkaline solution. The advantages are
that
 They work for a long time, since they dissolve only gradually.
 They do not cause a sudden increase in soil pH (excessive alkalinity), since they have a poor solubility in
water.
CaO, obtained from the decomposition of limestone or marble, is also used in the manufacture of cement.

 Plaster of Paris is another important compound derived from calcium. The chief ingredient present is
calcium sulphate hemihydrate, CaSO₄.1/2H₂O. It is made by heating gypsum (CaSO₄.2H₂O) to about
150⁰C. Plaster of Paris is used, among other things, in plaster casts for broken limbs. This is because it
hardens when it absorbs water, due to the reaction

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 1
CaSO₄. H₂O + 3/2 H2O  CaSO₄.2H₂O
2

 Gypsum, CaSO4.2H2O, is used in a wide variety of applications:

1. As a fertilizer and soil conditioner
2. In Plaster of Paris, as already explained.
3. A component of Portland cement used to prevent flash setting of concrete.
4. In foot creams, shampoos and many other hair products.
A large deposit of gypsum at Montmartre in Paris is the source of the name ‘Plaster of Paris’.

Barium
From Greek ‘barys’ meaning ‘heavy’ (It is a heavy metal).
The uses of metallic Barium are limited and include as an ‘oxygen scavenger’. Being very reactive, it removes
oxygen from sealed glass tubes (oxygen can interfere, for example, with the operation of a vacuum tube). Barium
sulphate is used in X-ray studies of the gastrointestinal (GI) system. The GI system includes the stomach,
intestines, and associated organs. Prior to the examination, the patient swallows a barium ‘meal’ containing a
slurry of barium sulphate in water.The barium sulphate then coats the GI tract, for example, the lining of the small
intestines. A fluoroscope is then held over the patient’s abdomen. The fluoroscope produces x-rays which can easily
pass through tissues, but is blocked (absorbed) by BaSO4. The absorption pattern, as seen, for example, on an X-ray
film, can reveal some problems of the GI lining by highlighting abnormalities.
 The ability of BaSO4 to absorb X-rays is a result of its very low solubility in water.
 BaSO4 is insoluble so it does not release ions that would be absorbed into the blood stream, leading to
poisoning (Ba2+ ions are toxic).

Questions, solutions and discussions

Q1Magnesium is the eighth most common element in the Earth’s crust. The metal is widely used in
alloys which are light and strong. Some reactions of magnesium and its compounds are shown in
the following reaction scheme .

H2(g) + A (aq) Mg (s) dil. HCl B(aq) + H 2 (g)

heat in air
Na 2CO 3(aq) NaOH (aq)

heat
C (s) D (s) E (s)
heat

dil. HNO3
heat

ev aporate
F (s) F (aq)

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 (a) Identify, by name or formula, compounds A to F.

(b) (i) Construct balanced equations for the following reaction

magnesium to compound A
compound C to compound D
compound F to compound D

(ii)Suggest a balanced equation for the effect of heat on compound E.

9701/02/M/J/2005

Solution

(a) AMgSO4B MgCl2C MgCO3DMgOEMg(OH)2 FMg(NO3)2

(b) (i) Mg + H2SO4→MgSO4+ H2

MgCO3→MgO + CO2

2Mg(NO3)2→2MgO + 4NO2+ O2

(ii) Mg(OH)2→MgO + H2O

Q2This question is about the elements in Group II of the Periodic Table, magnesium to barium.
(a) Complete the following table to show the electronic configuration of calcium atoms and of
strontium ions.

1s 2s 2p 3s 3p 3d 4s 4p 4d

Ca 2 2 6

Sr2+ 2 2 6

(b) Explain the following observations.

(i) The atomic radii of Group II elements increase down the Group.

(ii)The strontium ion is smaller than the strontium atom.

(iii) The first ionization energies of the elements of Group II decrease with increasing
proton number.

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 (c)Samples of magnesium and calcium are placed separately in cold water and left for some time.
In each case, describe what you would see and write a balanced equation for each reaction.

(d) Strontium nitrate, Sr(NO3)2 undergoes thermal decomposition.

(i) State one observation you would make during this reaction.
(ii)Write a balanced equation for this reaction.
9701/02/M/J/07

Solutions

(a)Left for the reader

(b) (i) Number of shells increases down the group

(ii) outermost shell has been removed

(iii) Number of shells increases, so outermost electrons are further from nucleus/shielding of outer
electrons increases .

(c) (i) Mg reacts very slowly, bubbles of gas are slowly produced
Mg + 2H2O →Mg(OH)2+ H2

(ii)Ca reacts more vigorously reaction, forming a white suspension and rapidly evolving a gas/Calcium
is rapidly used up.
Ca + 2H2O →Ca(OH)2+ H2

(d) (i) Brown fumes are gas evolved

(ii) 2Sr(NO3)2→2SrO + 4NO2+ O2

Q3Agricultural lime is manufactured from limestone (calcium carbonate) by first heating the
rock to a high temperature in a lime kiln. The product is allowed to cool and a calculated
amount of water is added. A highly exothermic reaction takes place and a white powder
called ‘slaked lime’ is produced.

(a)Write balanced equations for these two reactions.

(b)Give two reasons why lime is used in agriculture.

(c)How does the temperature required to decompose the carbonates of Group II elements
vary down the group, and why is this so?

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 (d)The mineral dolomite is a double carbonate of magnesium and calcium, with the
formula CaMg(CO3)2. When 1.000 g of an impure sample of dolomite was completely
dissolved in an excess of hydrochloric acid, 0.450 g of carbon dioxide was given off.

(i)Write a balanced equation for the reaction.

(ii) Calculate the percentage purity of the dolomite.9701/04/SP2007

Solutions

(a) CaCO3 →CaO + CO2

CaO + H2O →Ca(OH)2

(b) To neutralize acidic soils

To precipitate clays , thereby improving soil quality.

(c) Increases
Going down the Group , the metal cation increases in size . The ability of the cation to polarize the
anion therefore decreases. This increases stability of the carbonate.

(d) (i) CaMg(CO3)2+ 4HCl →CaCl2+ MgCl2+ 2CO2+ 2H2O

(ii) Mr of dolomite = 40 + 24 + (2 x 60) = 184

184 g of dolomite ( 1 mole) should produce 2 moles of CO2 = 2 x 44 g of CO2
Hence 1 g of dolomite should give
88
= 0.478 g of CO2
184
% purity of the dolomite is
0.450
x 100
0.478

= 94.1%

Q4Calcium is the fifth most common element in the Earth’s crust. Calcium compounds occur in bones
and teeth and also in many minerals.
Some reactions of calcium and its compounds are shown in the following reaction scheme .

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 dilute HCl roast in air
U (aq) Ca (s) V (s)

H2O (l) dilute HNO3

H2O (l)

Na2CO3 (aq) X (s) W (aq)

dilute
H2SO4 reaction 1

Y (s) Z (s)

(a) State the formula of each of the calcium compounds U to Y.

(b)Compound Y may be converted into compound V.

Outline how this reaction would be carried out in a school or college laboratory using a
small sample of Y.

(c)(i) Construct balanced equations for the following reactions.

calcium to compound U

compound V to compound W

compound U to compound Y

(ii) Construct a balanced equation for the effect of heat on solid compound W.

(d) Suggest the formula of an aqueous reagent, other than an acid, for reaction 1.

(e)What would be observed when each of the following reactions is carried out in a testtube?

the formation of X from Ca(s)

the formation of X from V9701/21/M/J/11

Solutions

(a)UCaCl2 VCaO WCa(NO3)2 XCa(OH)2 Y CaCO3

(b) Heat strongly in a boiling tube

(c) (i) Ca + 2HCl →CaCl2+ H2

CaO + 2HNO3→Ca(NO3)2+ H2O

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 CaCl2+ Na2CO3→CaCO3+ 2NaCl

(ii) 2Ca(NO3)2→2CaO + 4NO2+ O2

(d) Any soluble salt, for example, Na2SO4(aq)/K2SO4(aq)

(e) (i) effervescence/bubbles /Ca dissolves/white suspension formed

(ii) Heat given out/vigorous reaction occurs/steam is formed

Q5The element magnesium is used in fireworks and warning flares.

(a) (i) Describe, with the aid of an equation, the reaction of magnesium which makes it suitable
for use in fireworks.

(ii) Draw the lattice structure of the product formed in part (a)(i) and explain why it is used in
furnace linings.

(b) The reaction between magnesium oxide and water is very slow and is reversible to form
magnesium hydroxide which is used in indigestion remedies and in toothpastes.

(i) Suggest two reasons for the partial solubility of magnesium oxide in water.

(ii) Comment on the use of magnesium hydroxide in toothpastes.

(c)(i) Explain why the solubilities of the Group (II) sulphates in water decrease down the group.

(ii) Describe a simple test for the sulphate ion9189/01/O/N/2010

solutions
(a)(i) Magnesium burns in air with a bright white flame
Mg(s) + O2 (s)  MgO (s)
(ii)
2+
Mg

2-
O

MgO is used in furnace linings because it has a very high melting point and so it is resistant to
heat.

(b) (i) Lattice energy of MgO is very high/ forces of attraction between Mg2+ and O2- are very strong -
water does not easily break down the crystal OR

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 Sum of hydration enthalpies of Mg2+ and O2- is less exothermic than the lattice energy of MgO.

(ii) Being partially soluble, Mg(OH)2 makes toothpaste slightly alkaline, thus neutralizing acids
produced by bacteria in the mouth. These acids are responsible for decay of teeth.

(c)(i) ΔHsolution = - L.E + ΔHhydration

Going down the group, ΔHhydration of the metal cations decrease rapidly (becomes more
endothermic) due to increase in ionic radii. However, L.E remains fairly constant (it decreases only
slightly) due to the large size of the SO42- ion. ΔHsolution therefore becomes more endothermic down
the group, that is, the dissolution of the Group (II) sulphate becomes less energetically feasible.

(ii) White precipitate formed with Ba 2+ (aq) or Pb2+ (aq)

Q5 A 5.00 g sample of an anhydrous Group (II) metal nitrate loses 3.29 g in mass on strong heating.
Which metal is present in the nitrate?

A. Mg B. Ca C. Sr D. Ba

Solution

2M(NO3)2 2MO + 4NO2 + O2 … (i)

mass 5.00
moles ofM(NO3)2 = = ( 124 is the ‘Mr’ of (NO3)2 )
Mr (Ar of M)+ 124

Mass of oxide MO formed = 5.00 - 3.29 = 1.71 g

1.71
Moles of MO =
Ar of M
From equation (i), moles of M(NO3)2 = moles of MO, that is
5.00 1.71
=
(Ar of M)+ 124 Ar of M

Let Ar of M be x, then

5.00 1.71
=
𝐱 + 124 𝐱+M

Solving for x gives 37, so the metal M is Ca (Ar = 40)

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 [Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 9.2in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

1(a)Describe the reactions, if any, of magnesium and calcium with cold water and write a balanced
equation for any reaction.

(b) Explain qualitatively why magnesium sulphate and calcium sulphate have different solubilities in
water.

(c) Give a commercial use of either magnesium sulphate or calcium sulphate (specify which).

(d) Magnesium reacts with nitrogen only at very high temperature, producing a yellow solid D. D
contains 72 % of magnesium , by mass.

(i) Suggest why a high temperature is required for this reaction.

(ii) Calculate the empirical formula of D.

(iii) When water is added to the yellow solid D, a white suspension forms and ammonia is
liberated. Identify the white suspension and write an equation for the action of water on D.
9701/02/O/N/1993

2(a)(i) Describe how the ease of thermal decomposition of the hydroxides and nitrates of the Group (II)
metals varies down the group. Write generalized balanced equations for the reactions.

(ii) Suggest an explanation for this trend.

(b) A Group (II) hydroxide exists as a hydrate M(OH)2. nH2O. On heating, 1.ooo g of this hydrate lost
0.542 g in the form of steam, as it was converted into the anhydrous M(OH)2. Subsequent heating to
constant mass produced a further mass loss of 0.068 g.
Calculate the value of n, and the Ar of the metal M. 9701/01/O/N/1996

3(a) When water is added to the solid remaining after barium nitrate has been heated, an alkaline
solution is produced. The addition of sulphuric acid to this solution produces a white precipitate.

Identify the products of these two reactions and write equations for them.

(b) When the procedure described in (a) is repeated using the solid left after magnesium nitrate has
been heated, several differences are observed.

Describe clearly what these differences are , and explain why they occur.

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(c) A 4.50 g sample of a carbonate of a Group (II) metal (known to be either calcium or strontium) lost
1.34 g in mass when heated strongly. Identify the metal, showing clearly your working.
9701/01/O/N/2000

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

9.3 GROUP (IV) ELEMENTS: CARBON TO

LEAD

Introduction
The Group (IV) elements are characterized by a change from metallic through metalloid, to metallic
structure. In fact, it is noticed in all groups that there is a tendency for metallic character to increase
down the group, but this observation is clearly noticeable in Group (IV). The similarity in the
structure and properties of elements which is obvious in Group (II) is not so apparent in Group (IV),
as shown in Table 9.3.1.

9.3.1 Brief overview of the elements

Carbon
There are two well known allotropes of carbon, namely, graphite and diamond.
Both graphite and diamond have crystalline giant covalent structures, characterized by a very large
number of C to C bonds extending throughout the structure. This explains the very high boiling and
melting points of these substances.

Silicon and germanium

These two elements have giant covalent structures, similar to that of diamond. However, in electronics,
they are referred to as metalloids because under some conditions they conduct electricity, thus behaving
as if they were metals.

Tin and lead

Tin has two forms, white tin and gray tin. White tin, which is metallic, is the more stable allotrope at
temperatures equal to or greater than room temperature. Its metallic nature is shown by its behavior as a
reducing agent, although it is a mild reagent. Gray tin has a giant covalent structure, and it is formed
when white tin is cooled well below room temperature. The conversion from white tin to gray tin by
cooling is a very slow process.

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Lead has a giant metallic structure. Metallic lead has a bluish - whitish colour after being cut, but it soon
tarnishes on exposure to air.It is therefore clear that metallic character increases down the group. This is
caused by the increase in atomic radii down the group. As the atoms get larger, overlap of atomic orbitals
become poor, and covalent bond formation becomes less likely. At the same time, the tendency of the
atoms to lose their outer most electrons and contribute them into a common pool of delocalization
increases, which is what characterizes metals. This tendency to lose electrons is a result of the increasing
distance of outer shell electrons from the nucleus. Moreover, as the number of shells increase, these outer
electrons experience greater shielding from the nucleus.

C Si Ge Sn Pb
Atomic
number 6 14 32 50 82
Outer shell
configuration 2s22p2 3s23p6 4s24p2 5s25p2 6s26p2
Atomic
radius/nm 0.077 0.117 0.122 0.141 0.154
3 730(d)
m.p/oC 1 410 937 232 327
(g)
4 830(d)
b.p/oC 2 680 2 830 2 270 1 730
(g)

Conductivity 1 x 106 2 x 106 8 x 106 5 x 106

Type of Giant Giant Giant Giant metallic Giant metallic
structure molecular molecular molecular

I.E1 1 090 786 762 707 833

Table 9.3.1 The properties of group (IV) elements ( d = diamond, g = graphite)

Electronic structure
The valence shell configuration of the Group (IV) elements is
... ns²np²
Where n is equal to period number, for example, for C in period 2, n=2 and for Si in period 3, n=3.

9.3.2Physical properties of the Group (IV) elements

Physical properties of the elements are influenced by the bonding and structure present. As the nature of
bonding changes down the group, so does the physical properties such as melting points and electrical
conductivities.

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3.2.1 Trend in melting points

In general, melting points decrease down the group. Notice

the unexpected melting point of lead.

Melting involves breaking forces which hold lattice particles

together. The stronger the forces, the higher the melting
point. Strength of these forces depends on the type of
bonding present, and on the specific crystal structure of the
solid.Carbon, silicon and germanium have giant covalent
structures. This explains their high melting points. A large
Fig 9.3.1Trend in melting amount of energy is required to break a large number of
points of the Group (IV) strong covalent bonds. However, the melting points of these
elements three elements decrease down the group, showing that the
covalent bonds become weaker with increasing atomic size.
As atomic size increases, overlap of atomic orbitals to form covalent bonds becomes less efficient.
Consequently the bonds become longer and weaker.

Tin and lead have giant metallic structures, so they have lower boiling points. In general, metallic bonds
are weaker than the covalent bonds in giant covalent structures, and less energy is required to break them.
The melting points of tin and lead depends on the strength of the metallic bonds.Lead has a highermelting
point, showing that it has the stronger metallic bonds. The nuclear charge of lead is much higher than that
of tin. As a result, the nucleus has a stronger attraction for electrons in the delocalized sea, despite the fact
that in Pb there are more shells (the change in nuclear charge from Sn to Pb is very large, and so has the
greater effect than that of increase in number of shells). The atoms of lead are therefore more firmly held
to the lattice and more energy is required to pull them from each other during melting.

3.2.2 Trend in atomic radii

The size of atoms increase down the group (Table 9.3.1)
Atomic radii increases down the group as new shells are opened. The increase in atomic size down a group
is not sharp because the increase in nuclear charge has a counterbalancing effect. As number of protons
increase, there is a greater pull of shells towards the nucleus and this prevents atomic size from increasing
rapidly.

3.2.3 Trend in ionization energies

Ionization energies follow the same trend as melting points (Table 9.3.1 and Fig 9.3.2).

Explaining the trend

Ionization energy is a measure of how firmly valence electrons are held to the atom. The more strongly
held the atoms, the higher the energy required to remove them.
In general, ionization energies fall down the group, showing that the valence shell electrons become more
weakly held.Down the group, atomic size increases due to the opening of new shells. The valence electrons
become weakly held to the atoms because of shielding by underlying shells and because of the increasing
distance of the valence electrons from the nucleus.

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 Lead has a higher first ionization energy than
expected. Once more, the explanation lies in the
nuclear charge of lead atoms. The largest jump in
proton number from one element to the next is found
at Sn and Pb. This sharp increase in proton number
implies that the valence shell electrons in lead are
more firmly held to the atom than in tin.

Fig 9.3.2 Trend in ionization

energy of the Group (IV)
elements
3.2.4 Electrical conductivity
In general, electrical conductivity increases down the group (Table 9.3.1)
Carbon’s two allotropes differ in their conductivities. Diamond is an insulator but graphite is a good con-
ductor of electricity along its layers.
Si and Ge are semi-conductors. The conductivity of Ge is twice that of Si. Sn and lead are better conduc-
tors than Ge and Si but note that the conductivity of Pb is slightly less than that of Sn.

Explaining the trend

The increase in conductivity down the group coincides with the increase in metallic character. Down the
group, atomic size increases and valence electrons become loosely held to the atoms. It becomes easier for
these valence electrons to be detached and contributed into a common sea. It is this sea of delocalized
electrons which gives metals their ability to conduct electricity. Pb has a slightly smaller conductivity than
tin. Once more, this is a result of the very high nuclear charge of lead. The large number of protons in the
nucleus has a greater attraction for electrons in the 4s sub shell than those in the 4p (this is because the 4s
is closer to the nucleus). As a result, for lead, it is easy to lose the 4p electrons, but the 4s remain tightly
held to the atom. For tin, the nuclear charge is relatively small and both the 4s and the 4p electrons are
delocalized in the metal lattice. The increased number of delocalized electrons results in greater conduc-
tivity.
Diamond is an insulator because there are no free delocalized electrons to carry charge. Instead, the
valence electrons in the atoms are localized in covalent bonds. The ability of graphite to conduct electricity
has nothing to do with size of atoms (the size of atoms is the same as in diamond), but with the bonding
present. Each carbon atom uses only three of its valence electrons to bond to other carbon atoms. The
fourth electron of each atom is then delocalized in the structure. This delocalized system of electrons is
responsible for the conductivity of graphite along the layers.

9.3.3Trends in chemical properties

The following observations will be important in explaining trends in chemical properties
 Atomic size increases down the group and this coincides with increasing metallic character
(valence electrons become more loosely held to the atom).
 Nuclear charge increases down the group (nuclear charge has an indirect effect on chemical
properties).

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3.3.1 Oxidation states
The valence shell of the Group (IV) elements has the configuration.
ns²np²
The +4 oxidation state is therefore common to all group four elements. The +2 state is also important in
all of the elements.
The group (IV) elements exhibit two stable oxidation states in their compounds, the +2 and the +4. This
differs from the Groups (I) and (II) elements which exhibit only one stable oxidation state, the +1 and the
+2 respectively.

Why two oxidation states?

The valence shell is made up of two sub-shells, the ns and the np. The +4 state corresponds to loss of all
the four valence electrons. However, it is also possible to lose only the two electrons in the np sub-shell,
which is higher in energy (less stable) than the ns sub-shell. When this happens, two electrons are left in
the 2s sub-shell. Since these remaining electrons are paired, they are quite stable, so formation of the +2
state is also energeticallyfavourable.

Relative stabilities of the +4 and the +2 oxidation states

The +4 oxidation state becomes more stable up the group. The +2 state becomes more stable down the
group.CO₂, in which C has the +4 state, is more stable than CO, in which carbon has the oxidation state of
+2. Similarly, SiO₂ is the stable oxidation state for Si. SiO does not exist.
It is difficult to reduce carbon dioxide to carbon monoxide. The reduction can take place, but the reaction
is endothermic and strong heating is required. On the other hand, carbon monoxide is easily oxidized to
carbon dioxide and the reaction is exothermic, that is, the product is more stable than the reactant.
The +4 state becomes less stable down the group, with respect to the +2 state. However, the +4
stateremains more stable than the +2 state in all elements up to tin. In lead, the +4 state becomes less
stable than the +2 state. Thus all of the group (IV) elements, except lead, react with oxygen to form the
dioxide. Lead forms the monoxide, PbO.This trend in the relative stabilities of the +4 and the + 2 states
can be explained in terms of the inert pair effect.
Redox data can be used to show the trend in the relative stabilities of the +4 and the +2 states.

Element Reduction equation Eθ/V

Ge Ge4+ + 2e- Ý Ge2+ -1.60

Sn Sn4+ + 2e- Ý Sn2+ +0.15

Table 9.3.2 The reduction potentials
of Group (IV) elements
Pb Pb4+ + 2e- Ý Pb2+ +1.80

The reduction potentials become more positive, showing that the formation of the X 2+ ion becomes more
feasible. In other words, stability of the +2 state increases whilst that of the +4 state decreases, as
illustrated in Fig 9.3.3.

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 The inert pair effect
Relative +4 The valence shell of the Group (IV) elements has
stability
the configuration ns²np². Down the group, the
two electrons in the ns sub-shell become more
+2 firmly held to the atom, that is, they become more
stable and their tendency to be used in chemical
reactions decreases. This observation has been
C Si Ge Sn Pb termed the ‘inert pair effect’.
The +2 state, corresponding to loss of the np
Fig 9.3.2 Change in the relative stabilities of
electrons, (which are higher in energy and therefore
the +4 and +2 oxidation states in the Group
less stable) becomes more important down the
(IV) elements. Note that in lead, the +2 state
is more stable than the +4 state. group. The increase in nuclear charge down the
group is a key factor in explaining the inert-pair
effect.
As the number of protons increase, the attraction for the valence electrons in the ns and np sub shells
increase. However, the ns electrons, being closer to the nucleus, feel a stronger attraction. It therefore
becomes harder to remove or unpair these electrons during reactions. Loss of the np electrons also help to
stabilize the ns electrons. Once the two electrons in the np sub-shell have been lost, the remaining
electrons feel a greater attraction by the nucleus since the attractive influence of the nucleus is now being
shared by fewer electrons. This stabilization of ns electrons by loss of np electrons becomes more
significant as nuclear charge increases down the group.

3.3. 2 Reactions of the group four elements

Reactions with oxygen

All of the Group (IV) elements combine directly with oxygen. In all cases, except lead, the dioxide is
formed.
X(s) + O₂ (g) → XO₂(s)
Lead reacts with oxygen to form the monoxide
Pb(s) +1/2 O₂ (g) → PbO(s)
This shows that in lead the +2 state is more stable than the +4 state. It is however possible to form the
unstable lead dioxide by other meansthan direct combination with oxygen.

Carbon
Graphite burns in oxygen to form carbon dioxide.
C(s) + O₂ (g) → CO₂ (g)
The reaction is very exothermic. The enthalpy change of formation of carbon dioxide, -394Kj/mol, shows
that carbon dioxide is more stable relative to its elements.
The enthalpy change for the formation of carbon monoxide is also negative (-111Kj/mol). This also shows
that carbon monoxide is relatively stable with respect to its elements, but the more negative value for car-
bon dioxide shows that carbon dioxide is more stable, hence in an excess supply of oxygen, carbon
dioxide will be formed instead of carbon monoxide.

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Diamond does not react with oxygen at temperatures that can easily be achieved. In fact, for practical
considerations, diamond can be considered as having no reaction with oxygen. However, it has been
possible to burn diamonds at extremely high temperatures, producing carbon dioxide as the only product.
This shows that diamond is indeed carbon. The inertness of diamond is due to kinetic factors. Diamond
contains a very large number of strong covalent bonds which must be broken to allow reaction with oxy-
gen. The reaction has a very high activation energy.

Silicon
Silicon does not react with oxygen at ordinary temperatures. Even at very high temperatures, the reaction
is very slow. The resistance to reaction with oxygen is, once more, kinetic. Silicon has the same crystal
structure as diamond.
The +4 state of silicon, as in silicon dioxide, is more stable than the +2 state. In fact the +2 state is too
unstable to exist. Silicon dioxide is abundant in nature in the form of quartz (sand is small fragments of
quartz).

Germanium
Germanium reacts with oxygen to form germanium dioxide. The fact that the +2 state is not formed shows
that the +4 state is more stable. GeO does exist under certain conditions, but it is unstable and is easily
oxidized to GeO₂. It cannot be formed by direct combination with oxygen but by reducing GeO₂ at
1000⁰C.

Tin
Tin reacts with oxygen at high temperatures to form tin (IV) oxide. Lead (II) oxide is not formed by this
direct combination with oxygen, since the +4 state is more stable. At normal temperatures, the reaction of
tin with oxygen is very slow. It is this inertness which makes tin useful in the manufacture of tin cans used
in the canning industry. Tin cans are not made of tin. They are made of steel and then coated with a very
thin layer of tin to protect the steel from rusting.

Lead
Lead combines directly with oxygen. This time, the +2 state is more stable so it is formed in favour of the
+4 state. Lead dioxide can be formed, but not by direct combination with oxygen. At normal
temperatures, the reaction of lead with oxygen occurs readily. However, formation of a tough layer of PbO
protects the metal from further attack, so that the reaction with air is only superficial (occurs on the
surface). This kinetic inertness explains why lead was at one time used to make water pipes. Lead is no
longer used for this purpose because it leads to poisoning by Pb 2+ ions formed by the slow dissolution of
lead in water.

3.3.3 The compounds of Group (IV) elements

3.3.1 The oxides

Table 9.3.2 shows the formulae and properties of the +4 oxides of Group (IV) elements.

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The dioxides(MO2) of Group (IV) elements : Oxidation state of the element M is +4

Oxide CO2 SiO2 GeO2 SnO2 PbO2

Preparation by No. Prepared by

direct Y E S oxidation of Pb2+
combination by the
with O2 electrolysis of a
Pb2+ solution.

Structure Simple Giant covalent, Mixed giant covalent and ionic

covalent diamond like
structure

B.p /OC -78 2 590 1 200 1 900 Decomposes

when heated

Acid/base A c i d i c A m p h o t e r i c
nature

Acid base Reacts with strong alkali, giving React with both acids and alkalis. With fused alkali,
reactions MO32- salts. MO32- salts are formed.

CO2 + 2OH-  CO32- + H2O e.g. SnO2 + 2OH- SnO32- + H2O

Carbonate stannate(IV)

SiO2 + 2OH- SiO32- + H2O Similarly, PbO2 forms PbO32- (plumbate (IV)) and GeO2
silicate forms GeO32-. Notice that this is analogous to the
reaction of CO2 and SiO2 with alkali.

With concentrated acids, +4 salts are formed.

e.g. PbO2 + 4HCl  PbCl4 + 2H2O.
(ionic: PbO2 + 4H+ Pb4+ + 2H2O)

Thermal Resists decomposition even at very high temperatures Decomposes on

stability warming, to
produce PbO
PbO2 PbO + ½
O2

Table 9.3.2 The oxides of Group (IV) elements in the +4 oxidation state

 Carbon dioxide has a very low boiling point and is a gas at room temperature. This is because the
bonding present is simple covalent, and so weak Van der Waals forces exist between the
CO2molecules. Compare with the other oxides, for example, SiO 2, in which there is giant covalent
bonding.
 SiO2, GeO2 and SnO2 are solids at room temperature, with vey high melting and boiling points.
This is a result of the nature of bonding present, which is giant covalent or giant covalent mixed

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 386
 with ionic character. A large amount of heat is required to break the large number of very strong
covalent bonds and decompose the structure during melting or boiling.
 PbO2 is a solid at room temperature but it is very sensitive to heat. It decomposes on warming to
form the +2 oxide, PbO, which is more stable. PbO2 is therefore a good oxidizing agent because

1. It has the ability to donate oxygen atoms during reactions.

2. Whilst it is being reduced to PbO, it gains electrons from another substance (reduction is gain
of electrons). This other substance therefore loses electrons, and is thus oxidized (oxidation is
loss of electrons).

PbO2 is powerful enough to oxidize an acidified solution of iodide ions to iodine.

EO/V
PbO2 + 4H+ + 2e- Ý Pb2+ + 2H2O +1.47
I2 + 2e- Ý 2I- +0.54

PbO2 + 4H+ + 2I- Ý Pb2+ + 2H2O + I2 + 0.93

Note that the second reduction equation and its electrode potential have been reversed
before adding up the two equations.
The reaction is energetically feasible because it has a positive Eθcell.
SnO2 is not able to oxidize iodide ions to iodine because this would reduce tin from a stable
oxidation state (+4) to a less stable oxidation state (+2). The very small electrode potential for
Sn4+/ Sn2+ shows that the conversion of Sn (IV) to Sn (II) is unlikely.
Sn4+ + 2e-Ý Sn2+ Eθ = +0.15V
Sn(II) is easily oxidized to the +4 state, which is the more stable state. In other words,Sn(II)
compounds are good reducing agents, for example, they can reduce Fe 3+ to Fe2+.

Construct a balanced equation for the reaction between SnCl2 (aq) and FeCl3 (aq)
Q and show that it is energetically feasible. Write down two observations that are
made in this reaction.

 SiO2 and CO2 are acidic, so they react with alkalis such as NaOH. Notice that the two reactions
are analogous. They both form a salt containing the ion MO32-. CO2 forms sodium carbonate
(Na2CO3) whilst SiO2 forms sodium silicate (Na2SiO3). The behaviour of SiO2 and CO2 towards
alkalis is expected. In general, covalent oxides are acidic whereas ionic oxides are basic.

 The rest of the Group (IV) oxides are amphoteric. This is because their structures are
intermediate between giant covalent and ionic. The reaction with bases is analogous to that of
SiO2 and CO2. The reaction with concentrated acid produces the +4 chloride, MCl 4. In dilute
solution, presence of a large amount of water causes the tetrachloride to decompose by
hydrolysis.

Table 9.3.3 summarizes the main properties of the +2 oxides of the group (IV) elements.

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 387
The monoxides(MO) of Group (IV) elements : Oxidation state of the element M is +2

Oxide CO SiO GeO SnO PbO

Preparation by No. Can be No. Exists only No. Can be No. Can be prepared by heating the
direct produced by the at very high produced by the corresponding hydroxide or nitrate.
combination of reduction of temperatures reduction of
the element CO2. GeO2 at 1000OC e.g. Pb(NO3)2 PbO + 2NO2 + ½ O2
with O2
Pb(OH)2 PbO + H2O

Structure Simple covalent Predominantly ionic, but have some

covalent character.

Acid/base Neutral A m p h o t e r i c
nature

Acid base No reaction with acids or bases React with both acids and alkalis to form +2 salts. With
reactions alkalis, salts of the formula M(OH)3- areformed.

e.g. SnO + OH- + H2O  Sn(OH)3- + H2O

With acids, +2 salts are also formed.

e.g. PbO + 2HCl  PbCl2 + H2O.

Thermal
stability When warmed or heated in air, they are easily oxidized to the +4 state, MO2. Stable

Table 9.3.3 Key properties of the Group (IV) oxides with the +2 oxidation state

 All of the monoxides are unstable, except PbO. These monoxides are therefore easily oxidized to
the +4 oxidation states, which are more stable. For lead, the +2 state is more stable, so it resists
being oxidized to the +4 state. This observation has already been explained in terms of the inert
pair effect.
 CO is a simple covalent substance that has weak Van der Waals between particles. It is therefore a
gas at room temperature.

3.3.2 The chlorides of Group (IV) elements

All Group (IV) elements form +4 chlorides of the general formula XCl 4. They are all oily liquids with
simple molecular structures. The shape of the tetrachlorides is tetrahedral.

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 Cl
1090 The tetrachlorides have simple covalent bonding with weak Van der Waals forces between
X
the molecules. They therefore have low melting and boiling points. However, the melting
and boiling points increase down the group as the strength of Van der Waals forces
Cl Cl increases in response to increasing number of electrons.
Cl

Preparation of the +4 chlorides

SiCl4, GeCl4 and SnCl4 are easily prepared by direct combination of the element with chlorine gas, for
example,

Si + 2Cl2 SiCl4
Preparation of CCl4 by direct combination with chlorine is difficult because the reaction has a very high
activation energy due to the large C-C bond energy. These bonds must break first to allow combination
with chlorine. As bond energies in the elements decrease down the group, (Table 9.24) activation energy
decreases, and so it becomes possible for Si, Ge and Sn to combine directly with chlorine to form the
tetrachloride.

This decrease in bond enthalpy is expected. Going down

Bond Average bond
Energy/Kjmol-1 the group, atomic size increases and overlap of atomic
orbitals to form the X-X bond becomes poor. As a result,
PbCl can notofbethe
the 4distance prepared
bond pairby of
theelectrons
direct combination
from the nucleiof
C-C 348 lead withatoms
of both chlorine. PbCl2 The
increases. is formed instead,
bond pair sincefeels
therefore the only
+2
state of lead
a weak is more from
attraction stablethe
than the +4
nuclei of state.
both PbCl
atoms4 can
of be
the
Si-Si 226 prepared
bond. The byresult
the reaction of PbO
is that the withbecomes
X-X 2bond cold concentrated
longer and
HCl. The down
weaker reaction
themixture
group. should be cold to prevent
Ge-Ge 188

Sn-Sn 151
Table 9.2.4 Bond energies in the
Group (IV) elements

Thermal stability of the tetrachlorides

The tetrachlorides become less stable down the group as a result of the increasing size of the atom of the
element, X. As the size of X increases, overlap of its valence orbitals with that of chlorine becomes less
efficient. As a result, the X-Cl bond becomes longer and weaker.
CCl4, SiCl4 , GeCl4and SnCl4 are thermally stable and resist decomposition by heat.
PbCl4 decomposes readily on warming to produce PbCl 2 and Cl2. Even without warming, PbCl4 undergoes
gradual decomposition.

PbCl4  PbCl2 + Cl2(g)

Yellow liquid white solid

This reaction occurs for two reasons.

 The bonds in PbCl4 are weak and so easily break, as already explained.
 The product formed is more stable since the +2 oxidation state of lead is more stable relative to
the +4 state.

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Hydrolysis of the tetrachlorides
All Group (IV) tetrachlorides undergo hydrolysis in water, except CCl4, for example
SiCl4 + 4H2O  SiO2.2H2O + 4HCl
A strongly acidic solution of pH ≈2 is formed. The product SiO 2.2H2O is sometimes written as Si(OH)4.
GeCl4 also hydrolyzes rapidly in water, forming GeO 2. The hydrolysis of SnCl4 and PbCl4 to SnO2 and PbO2
is only partial. CCl4 resists hydrolysis in water because of the absence of d-orbitals in C to accept the
electron rich water molecules during the first step of the reaction. The rest of the chlorides hydrolyze in
water because there are energetically accessible (low energy) d-orbitals to form bonds with water, as
illustrated for silicon in Fig 9.3.3.

vacant and energetically

accessible d - orbitals
3d
3p
3s
Si in SiCl4 dative bond
O
H
H

Fig 9.3.3 The use of d-orbitals in the initial step of the

hydrolysis of SiCl4

The +2 chlorides, XCl2

Only tin and lead form stable +2 chlorides, either by direct combination with chlorine or by
decomposition of XCl4. In tin, the +4 chloride is more stable than the +2. SnCl₄is therefore not
decomposed to SnCl₂ by warming, but by strong heating. For lead, the +2 chloride is more stable. PbCl₄ is
therefore easily decomposed by warming to form lead (II) chloride and chlorine gas.
C, Si and Ge do not form the +2 chlorides for two reasons
 the +2 state is unstable compared to the +4 oxidation state.
 Excitation of an electron from the ns sub shell to the np sub shell of the element occurs before
bonding, accompanied by sp3 hybridization. This creates four hybrid orbitals that are equivalent
in terms of shape and energy. Thus the element can form four bonds, not two, by sigma overlap
of the four hybrid orbitals with four chlorine atoms.

The tendency of Sn and Pb to form their respective +2 chlorides by direct combination with chlorine can
be explained in this way
 The inert pair effect: As already explained, going down Group (IV), the two ns electrons become
inert due to the strong attraction they feel from the nucleus. The formation of PbCl 2 and SnCl2
involves the loss of the two np electrons, which are relatively loosely held in Pb and Sn.
 Pb cannot form PbCl4 when it reacts with chlorine. This is because in Pb, the +2 state is more
stable than the +4 state.

The bonding in PbCl2 and SnCl2 is ionic. These compounds are therefore crystalline solids.

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 Some uses of Group (IV) elements and their compounds

The allotropes of carbon have a wide variety of uses

Graphite
 Inert electrodes in electrolytic processes
 Dry lubricant in machines which are likely to generate large
amounts of heat(oil based lubricants decompose)
 Mixed with clay for use in ‘lead’ pencils
CARBON
 Moderator in nuclear reactors. It slows neutrons by absorbing
Them.

Diamond
 Tips in drilling tools (It is very hard)
 jewelry(It has a high refractive index, which gives it an attractive
sparkle)

Buckminsterfullerene (C60)
 Trapping and protecting reactive atoms
 plugs in nano test tubes

Organic and inorganic compounds of C also have many uses. Some of the
useful inorganic compounds include carbon dioxide, which is used
 to produce effervescence in fizzy drinks
 in fire extinguishers
 as a dry ice refrigerant. Its advantage in this sense is that it leaves
no residues when it sublimes, and it is relatively environmentally
friendly.
 as a solvent. The use of supercritical carbon dioxide in
extractions is fairly modern. Substances which can be extracted
in this way include caffeine and limonene which is found in the
peels of citrus fruits

The use of CO2 in fizzy drinks

Carbon dioxide reacts reversibly with water
CO2(g) + H2O(l) Ý H2CO3(aq) Ý HCO3-(aq) + H+(aq) ...(i)

Equilibrium (i) lies well to the left, that is, the dissolution of
carbon dioxide in water is only slight. To increase the amount of carbon
dioxide that dissolves the gas is pumped under high pressure into the
liquid. Increasing pressure forces the equilibrium to the right, thus
producing more hydrogen ions and hydrogen carbonate ions (Le
Chatelier’s principle). The hydrogen ions produced are mainly
responsible for the acidic taste of Coca-cola.
Some American consumer lobby groups are known to have filed against
the Coca-cola company on claims that the level of acidity of the beverage is
toxic. These claims were rejected in American courts (home of the Coca-
cola company) as baseless.

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 In fact, the pH of coca-cola, which is approximately 5, is about 1000 times
less acidic than the contents of the stomach, whose pH is about 2 (due to
hydrochloric acid which is secreted by the walls of the stomach).
Furthermore, carbonic acid, which is the chief acid in coke, is immediately
destroyed when a bottle or can of Coke is opened (the fizzing sound is
caused by CO₂ escaping under pressure). The production of bubbles and
fizzing that occurs when a bottle of Coca-Cola is opened can be explained
using Le Chatelier’s principle. Before the bottle is opened, pressure inside
the bottle is high due to undissolved carbon dioxide. When the bottle is
opened, the undissolved gas escapes, thus lowering pressure. By Le
Chatelier’s principle, equilibrium (i) above shifts to the left, thus
producing more carbon dioxide to replace the gas which is escaping. This
results in the decomposition of carbonic acid, producing bubbles of carbon
dioxide. This explains why an opened bottle of Coca–Cola soon goes ‘flat’.
The acidic taste is lost as carbonic acid is converted to carbon dioxide and
water. Once it gets in the stomach, this loss of carbonic acid continues so
that the pH of the stomach is not altered to any significant extent. Some
people have also reported that Coke is acidic enough to corrode an iron
nail. This is not correct. To dissolve an iron nail, the reaction below should
take place:
H₂CO₃(aq) + Fe(s) → FeCO₃(s) + H₂(g)
This reaction does not take place. Carbonic acid is too weak an acid to
corrode metals.

Silicon is the most abundant element on Earth, after oxygen. It is the major
component of sand, sandstone and silicates found in clay.
Ultrapure silicon and germanium are used in the manufacture of
SILICON AND transistors. These are electronic components found, for example, in
GERMANIUM computer chips. Silicon dioxide is found in a large number of ceramics.
This is because silicon dioxide has a very high melting point and is
therefore heat resistant.

Tin is used to coat steel cans (by electroplating) which are used for packing
foods. The tin metal reacts with oxygen to form a thin, tough, impermeable
TIN and insoluble layer of tin (II) oxide. This oxide layer protects the steel from
rusting. Other uses of tin include
 making useful alloys such as bronze (tin and copper)
 the chloride (SnCl2.H2O) is used as a reducing agent and as a
mordant in calico printing. A mordant is a substance that is used
to set dyes on fabrics by forming a co-ordination complex with the
dye.

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 LEAD  Lead metal and PbO2 are used as electrodes in storage batteries
such as the car battery.
 Tetraethylead (Pb(C2H5)4 is used as an antiknock in petrol
engines therefore allowing smooth running of the engine. Petrol
that contains this compound is known as leaded petrol. Health
concerns related to the toxic nature of Pb2+ has resulted in a
decrease in the use of leaded petrol.
 Lead metal is used as a shield to absorb harmful radiation
around X-ray equipment and nuclear reactors.
 PbCrO4, a bright yellow substance of very low solubility , is used
to make road marks.

Notes for use in qualitative analysis

Reactions involving Pb2+ and lead compounds

Three oxides of lead are known

Oxide colour Oxidation state

of lead

PbO yellow +2

PbO2 black +4

Pb3O4 red +2 and +4

 Heating PbO2 on a Bunsen flame results in a change of colour from black to yellow. A colourless gas is
given off which relights a glowing splint.
PbO2(s)  PbO(s) + 1/2O2
This decomposition is accompanied by reduction of Pb(IV) in PbO 2 to Pb(II) in PbO. This
proves that the +2 state of lead is more stable than the +4 state.

 Red lead oxide (Pb3O4) is in fact a double oxide, containing PbO and PbO2. The formula of Pb3O4 can
be written as 2PbO.PbO2. PbO, which is more stable, has the greater proportion. Red lead oxide
behaves in its chemical reactions as if it were a mixture of PbO 2 and PbO.

Action of heat on read lead oxide

When Pb3O4 is heated, the PbO2 in it decomposes to PbO and oxygen is evolved. The PbO component is not
altered.

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2PbO.PbO2 (s)  3PbO(s) + ½ O2
There is a change of colour from red to yellow as PbO is formed.

Action of dilute HNO3 on red lead oxide

PbO is ionic and is therefore basic (In fact, it is amphoteric). PbO2 is less basic because it contains a degree of covalent
character. When dilute HNO3 is added to red lead oxide, the PbO in it is neutralized to form Lead (II) nitrate. PbO2 is not
affected and remains as a black residue.

Pb3O4(s) + 4HNO3 (aq) 2Pb (NO3)2(aq) + 2H2O (l) + PbO2(s)

red solid colourless solution black solid

Q Predict the effect of adding the following to red lead oxide

a) concentrated HCl followed by heating
b) NaOH(aq)

Reactions of and tests for Pb2+

PbCrO4 bright yellow ppt

dil HNO3 dil HNO3

Na2CrO4(aq)
10
1
Heat HCl(aq) 2+ NaOH(aq) xs NaOH(aq)
PbCl42- PbCl2 Pb Pb(OH)2(s) PbO22-(aq)
9
colourless white ppt 2
6 NH3(aq)
white ppt (Pb(OH)42-)
solution KI(aq) 7
8 5 heat colourless solution
H2SO4(aq)
Pb(OH)2(s) 3
PbI2 H2O2
PbSO4
yellow ppt
white ppt NH3(aq) PbO 4
Pb(OH)2
heat
cool heat dark brown ppt

differently coloured solutions ,

depending on temperature

Reactions 1, 2 and 6
Pb2+ is precipitated by both NaOH (aq) and ammonia as Pb (OH)2. Now, this product is amphoteric, so it reacts further
with strong alkali, in this case, NaOH, producing a soluble complex, Pb (OH)42-. The white precipitate of Pb(OH)2 dissolves
in the process (reaction 2). However, Pb(OH)2 does not react with a weak base such as ammonia. The precipitate formed in
reaction 6 is therefore insoluble in excess ammonia.
Reactions 1 and 2 can be reversed by carefully adding a dilute acid. In this case, HNO3 acid is used because using H2SO4
and HCl would result in the formation of a precipitate
.
Reactions 3 and 4
Pb(OH)42- formed in reaction 2 has lead in the +2 state. This is the stable state of Pb. Oxidation of Pb2+ to Pb(IV) would
require a good oxidizing agent such as H2O2. This is what happens in reaction 3. The Pb(OH)2 formed is unstable. Heating
it results in the formation of PbO2, which then decomposes to PbO, releasing, O2. Lead (IV) is thus converted back to lead
(IV) (reaction 4.)

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Note that PbO is also obtained by heating Pb (OH)2 (reaction 5)

Reactions 7, 8, 9 and 10
Pb2+ ions form precipitates with Cl- ions (reaction 9), iodide ions (reaction 8), sulphate ions (reaction 7) and chromate
ions (reaction 10). Note that PbI2 and PbCrO4 are yellow solids whereas PbCl2 and PbSO4 are white. Also note that
PbCl2 and PbI2 are insoluble in cold water but dissolves when heated due to complex ion formation.

Questions, solutions and discussions

Q1 (a) (i) Sketch the variation in melting points of the elements in Group (IV).

(ii)Explain how this variation in melting point is related to the structure and bonding of
the elements.

(b) CCl4 and SiCl4 behave differently with water.

(i) Describe the reaction (if any) of CCl4 with water.

(ii)Describe the reaction (if any) of SiCl4 with water.

(iii)Write equations for any reactions that occur

(iv)Explain why these two chlorides differ in their behaviour with water.
9701/4/O/N/2002

Solutions
(a)(i)

m.p
X
X
X

X
X

C Si Ge Sn Pb

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 (ii)C, Si and Ge have high melting points due to the presence of giant covalent bonding. A large amount
of energy is required to break a large number of strong covalent bonds. Melting points decrease in
the order C, Si and Ge because of increasing bond length. The bonds therefore become weaker and
less energy is required to break them.
Sn and Pb are metals. The metallic bonds are weaker than the covalent bonds in giant covalent
structures.

(b)(i) CCl4 has no reaction with water.

(ii) SiCl4 undergoes hydrolysis in water, liberating white fumes (of HCl) and forming a white solid
(SiO2).

(iii) SiCl4 + 2H2O  SiO2 + 4 HCl

(iv) SiCl4 has accessible d - orbitals which makes initial attack by water molecules possible.

Q2All the Group IV elements form chlorides with the formula MCl4.
(a) Describe the bonding in, and the shape of, these chlorides.

The boiling point of lead(IV) chloride cannot be measured directly because it decomposes
on heating. The following table lists the boiling points of three Group IV chlorides.

chloride b.p. /0C

SiCl4 58

GeCl4 83

SnCl4 114

(b) (i)Plot these data on the following axes and extrapolate your graph to predict what the
boiling point of PbCl4 would be if it did not decompose.

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 (ii)Suggest why the boiling points vary in this way.

(c)SiCl4 reacts vigorously with water whereas CCl4 is inert.

(i) Suggest a reason for this difference in reactivity.

(ii)Write an equation for the reaction between SiCl4 and water.

(iii) Suggest, with a reason, whether you would expect GeCl4 to react with water.

(d) SiCl4 is used to make high-purity silicon for the semiconductor industry. After it hasbeen purified
by several fractional distillations, it is reduced to silicon by heating with pure zinc.

(i) Suggest an equation for the reduction of SiCl4 by zinc.

(ii)Use your equation to calculate what mass of zinc is needed to produce 250 g of
pure silicon by this method.
9701/04/M/J/2004

Solutions

(a) Simple covalent, tetrahedral geometry, bond angle 109.50

(b) (i) From a plotted graph, melting point of PbCl4 is 138 – 151°C

(ii) Van der Waals forces become stronger due to increasing number of electrons in the metal as the
group is descended.

(c)(i) and (ii) See Question 1

(iii) GeCl4 reacts with water since Ge has accessible/ low lying d - orbitals to accept water molecules.

(d) (i) SiCl4+ 2Zn Si + 2ZnCl2

(ii) mass = 250 x 2 x 65.4/28.1

= 1163.7 g

Q3(a) (i) Use the following sets of axes to sketch graphs of the variations in the melting
points and the electrical conductivities of the Group IV elements.

(ii)Explain how the variation in conductivity is related to the structure and bonding in
the elements.

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 melting point electrical conductivity

High High

medium medium

low low

C Si Ge Sn Pb C Si Ge Sn Pb

(b)Going down Group (IV) there is a variation in the relative stabilities of the higher and
lower oxidation states of the elements in their oxides.

Illustrating your answers with balanced chemical equations, in each of the following
cases suggest one piece of chemical evidence to show that

(i)CO is less stable than CO2,

(ii) PbO is more stable than PbO2.

(c) Name one ceramic based on silicon(IV) oxide, and explain what properties of the
oxide make it suitable for this use.

(d)Tin(II) oxide reacts with both acids and alkalis.

(i) What name is given to this property of an oxide?

(ii) Write suitable equations to show these two reactions of tin(II) oxide.9701/04/O/N/2005

Solution

(a) (i) melting point: graph should show

low : silicon
medium : germanium
High : carbon
Sn and Pb: lower than Si/Ge

conductivity: graph should show

Medium : silicon and germanium
Low : carbon (diamond)
High : carbon (graphite)

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 Sn and Pb: higher than Si/Ge

(ii) Sn, Pb are metals and so have delocalized electrons to conduct electricity. Graphite has a giant
layered structure, with electrons delocalized along layers.
Si, Ge and diamond have electrons localized in covalent bonds.

(b) (i) e.g CO burns to give CO2, 2CO + O2→2CO2

OR CO is converted to CO2 by Fe2O3, 3CO + Fe2O3→3CO2 + 2Fe

(ii)e.g. PbO2 is decomposed by heat 2PbO2→2PbO + O2

(c) pottery - high melting point, hard

(d) (i)amphoteric

(ii) SnO + 2HCl →SnCl2+ H2O

SnO + 2NaOH →Na2SnO2+ H2O

Q4Carbon forms two stable oxides, CO and CO2. Lead forms three oxides: yellow PbO, black
PbO2 and red Pb3O4.

(a) Carbon monoxide burns readily in air. Heating black lead oxide produces oxygen gas,
leaving a yellow residue.

(i)Suggest a balanced equation for each reaction.

(ii)Explain how these two reactions illustrate the relative stabilities of the +2 and +4
oxidation states down Group IV.

(b)Red lead oxide contains lead atoms in two different oxidation states.

(i) Suggest what these oxidation states are, and calculate the ratio in which they occur
in red lead oxide.

(ii)Predict the equation for the action of heat on red lead oxide.

When red lead oxide is heated with dilute nitric acid, HNO3, a solution of lead (II) nitrate
is formed and a black solid is left.

(iii) Suggest an equation for this reaction.

(iv) Explain how this reaction illustrates the relative basicities of the two oxidation states
of lead.

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 (c)Both tin(II) oxide and tin(IV) oxide are amphoteric.
Write a balanced equation for the reaction between tin(II) oxide and aqueous sodium
hydroxide.9701/04/M/J/07

Solutions

(a) (i) 2CO + O2→2CO2

2PbO2→2PbO + O2

(ii) +4 state becomes less stable /+2 state becomes more stable down the group

(b) (i) Pb (II): Pb (IV)= 2:1

(ii) Pb3O4→3PbO + ½O2

(iii) Pb3O4+ 4HNO3→2Pb(NO3)2+ PbO2+ 2H2O

(iv) PbO is more basic than PbO2 since PbO2does not react with HNO3

(c)SnO + 2NaOH →Na2SnO2+ H2O (or Na2Sn(OH)4

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 9.2in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

1 (a) Describe how the behaviour of the oxides of tin and lead in their +4 oxidation states
differ on heating.

(b) Explain the following by using data from the Data Booklet where appropriate, and writing
equations for all reactions.

(i) A sample of liquid PbCl4 is placed in a flask and the flask is gently warmed. A gasis evolved
and a white solid is produced. When the gas is bubbled through KI(aq),purple fumes are
produced.

(ii) Repeating the same experiment using liquid SnCl4 instead of PbCl4 results in noevolution of
gas, and no reaction with KI(aq).

(c) The molecule dichlorocarbene, CCl2, can be produced under certain conditions. It is highly
unstable, reacting with water to produce carbon monoxide and a strongly acidicsolution.

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(i) Suggest the electron arrangement in CCl2 and draw a dot-and-cross diagramshowing this.
Predict the shape of the molecule.

(ii) Construct an equation for the reaction of CCl2 with water.9701/41/M/J/10

2The most typical oxides of tin and lead are SnO, SnO2, PbO and PbO2.
The following two generalizations can be made about the oxides of the elements in Group (IV).

• As the metallic character of the elements increases down the Group, the oxides become
more basic.
• The oxides of the elements in their higher oxidation states are more acidic than the oxides of the
elements in their lower oxidation states.

(a) Use these generalizations to suggest which of the above oxides of tin or lead is most
likely to react with each of the following reagents. In each case write a balanced
equation for the reaction.

(i)with NaOH(aq)
(ii) with HCl(aq)

(b) ‘Red lead’ is used as a pigment, and as a metal primer paint to prevent the corrosion ofsteel. It
is an oxide of lead that contains 9.30% oxygen by mass.
Calculate to 3 significant figures the number of moles of oxygen and lead contained ina
100.0 g sample of red lead. Hence calculate its empirical formula.9701/41/O/N/10

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 9.4 GROUP (VII) ELEMENTS

Introduction
The Group (VII) elements are known as the halogens, which literally means salt formers. Table 9.4.1
below shows key facts about the Group (VII) elements, from chlorine to iodine. The halogens are
diatomic and have a simple molecular structure. This explains why they have low melting points and
boiling points. Weak Van der Waals forces exist between the molecules and a small amount of energy
is required to break these forces and bring about melting or boiling.
The Group (VII) elements illustrate some important points, including
 the effect of number of electrons (Mr) on physical properties
 the effect of atomic size on chemical reactivity
Once more, as you go through this section, try to link up with concepts which you studied in physical
chemistry, for example, the use of reduction potentials in predicting the outcome of a reaction.

Group (VII) elements: Facts at a glance

Element Cl2 Br2 I2

Atomic number 17 35 53

Outer shell 3s23p5 4s24p5 5s25p5

configuration

State at 200C gas liquid solid

Colour Greenish - Red-brown black

yellow

m.p0C -101 -7 113 Table 9.4.2 Properties

of the Group (VII)
Solubility in water moderate slight insoluble
elements, from chlorine
to iodine

9.4.1.Physical properties
The elements show a clear trend in physical properties. Chlorine is a greenish-yellow gas, bromine is a
red-brown liquid and iodine is a shiny black solid at room temperature
 There is a clear gradation from gaseous state, through liquid state, to solidstate.
This change is a result of increasing strength of VDW forces down the group. All of the elements
are simple molecular, so the forces of attraction present between molecules are VDW. These
forces are a result of instantaneous distortions of the symmetric electron cloud of the molecules.
Down the group, the number of electrons (Mr) in the molecules increases, so the extent of

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 distortion also increases. Thus strength of VDW forces increases down the group. Molecules are
held more tightly and more closely, and this results in a change of a state.
 Intensity of colour increases down the group. This shows that particles hold to each other more
tightly down the group. If particles of a substance are held close, its colour becomes intense. Solid
iodine appears black, but when its particles are separated by heating to form a gas, the colour of
the vapour becomes less intense (it is purple)
 The melting and boiling points of the elements increase down the group. VDW forces become
stronger down the group, so more energy is required to separate molecules from each other.
 Solubility of the elements in water decrease down the group. The dissolution of the halogens
involves slight reaction with water, to form the acid HXO -. Reactivity of the halogen with water
decreases down the group and so does the solubility.

9.4.2Oxidation numbers in compounds

The halogens are able to expand the octet by using d-orbitals in bonding. Thus they exhibit variable
oxidation numbers in their compounds, ranging from -1 to +7. The lowest oxidation number, -1, refers to
the gain of one electron in the outer shell of the halogen atom, for example, during the formation of ionic
compounds such as NaCl. The halogen atom has 7 electrons in the outer most shell. Any number of these
electrons can be used in covalent bond formation, for example, the use of one valence electron leads to the
formation of compounds such as HCl. Examples of compounds in which the halogen has exceeded an
octet in its outer shell are ICl6 and IF7 molecules . Table 9.4.3 gives representative compounds for the
various oxidation states of the halogens. The electronic structures of CF 3, ClO3- and CF7 are also shown.
Note that in all three compounds, Cl has more than an octet of electrons in the outer shell. The halogens,
except for fluorine which has no d orbitals, are able to expand the octet .

Oxidation Examples
number

-1 Ionic: NaCl, MgBr2

Covalent: ICl

+1 ClO- e.g. in KClO

+3 ClF3

+5 ClO3- e.g. in NaClO3 Table 9.4.3 Some halogen

compounds
+7 ClO4-

CF3 ClO3-
xx
F x charge
x O x
x
. .
..Cl. x F
x

.. . .. Cl ..xx O
x ..
x x
F O
Cl uses 3 electrons out of 7 for Cl uses 5 electrons for bonding
covalent bonding

CF
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7 2011. Please do not photocopy or reproduce Page 403
F
Fx . x. .x F Cl uses all 7 electrons for bonding
. .x
F x .Cl . F
x x
F
 . Cl. x F .. Cl ..xx O
.. . ..
x
x x
F O
Cl uses 3 electrons out of 7 for Cl uses 5 electrons for bonding
covalent bonding

CF7

F
Fx . x. .x F Cl uses all 7 electrons for bonding
. .x
F x .Cl . F
x x
F F

9.4.3 Reactions as oxidizing agents

The Group (VII) elements usually participate as oxidizing agents in reactions.
Table 9.4.2shows the Eθ values for the reaction X2 + 2e Ý 2X- where X2 is a Group (VII) element. Redox
data in this table shows that the Group (VII) elements become weaker oxidizing agents down the group.
Chlorine has the highest oxidizing power of the three elements being discussed, and iodine has the least.

Make sure you can interpret redox data such as

Element Reduction equation Eθ/V that given in this table. Chlorine has the most
positive Eθ/V, showing that the forward reaction
Cl2 Cl2 + 2e-Ý 2Cl- 1.36 which forms the halide ion (by reduction of the
halogen) is the most energetically feasible. In this
Br2 1.07 conversion, the halogen gains electrons (it is
Br2 + 2e-Ý 2Br- reduced) from another substance. This other
substance therefore loses electrons, that is, it is oxi-
I2 I2 + 2e-Ý 2I- 0.54 dized by the halogen. Chlorine, with the most
Table 9.4.2 Redox data for the
positive Eθ value, accepts electrons most easily. It is
the most powerful oxidizing agent of the three
Group (VII)
halogens.

Explanation of the trend in oxidizing power

To start with, all three halogens are oxidizing agents, that is, they tend to react by gaining electrons. Note
that all the electrode potentials are positive, meaning that the halogens can oxidize a large number of sub-
stances.
 Each halogen has a large number of protons in the nucleus, compared with the elements in the
same period at the left hand side of the Periodic Table. The halogens therefore gain electrons
during chemical reactions, since the incoming electrons feel a relatively strong attraction from the
nucleus. In addition, the halogen atom is much smaller than atoms on the left hand side of the Pe-
riodic Table. Small non-metallic atoms are good at attracting an electron because the incoming
electron would be close to the nucleus from which it experiences a relatively strong attraction.
 The valence shell of the halogen has 7 electrons. Each halogen atom only has to accept a single
electron to complete the octet in the outer most shell, which is energetically feasible.

The oxidizing power of the halogens is affected by atomic size and shielding (Fig 9.4.1).
An oxidizing agent accepts an electron or electrons from a reducing agent. The outer shell of the atom
must have the ability to accept and stabilize the electron. Chlorine has the smallest atoms. The outer shell
is therefore close to the nucleus, and so it is able to strongly attract the incoming electron. Once incorpo-
rated into the outer shell, the electron is strongly held to the atom (stabilized) for two reasons.
 It is close to the nucleus from which it feels a strong attraction.
 There are a few inner shells to shield the electronfrom the attractive influence of the nucleus.

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Down the group, the size of atoms increases as new shells are opened. The distance of the outer shell from
the nucleus increases, so it does not easily attract an electron. If the electron is accepted into the outer
shell, it is also shielded by inner shells from the nucleus. The electron would therefore be weakly held to
the atom.

Fig 9.4.1 Oxidizing power of the halogens decrease down the group
in response to increasing atomic size.

Electron affinities of the Group (VII) elements give evidence that going down the group, the elements
become more reluctant to accept an electron in the outer most shell (the electron affinities become less
negative down the group).

Element First electron affinity

/Kjmol-1

Cl -364

Br -342 Table 9.4.3 Electron affinities of the

Group (VII) elements
I -314

4.3.1 Reactions with metals

The halogens, being oxidizing agents, react with metals, which are reducing agents, for example
2Na(s) + X₂(g) → 2NaX(s)
This is a redox reaction which forms a salt. In fact, the term halogen means ‘salt former’. The metal acts
as the reducing agent and the halogen as the oxidizing agent. The speed and vigour of reaction decreases
down the group. For instance, fluorine reacts rapidly and explosively with Na.
2Na(s) + F₂ (g) → 2NaF(s)
The reaction of Na with chlorine is rapid and vigorous but less violent. The reaction of iodine with Na is
relatively slow.

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Explanation
There are two ways of explaining this trend in reactivity.
 In terms of the reactivity of the halogen. It has already been noted that the reactivity of the
halogens decreases down the group, that is, the affinity of the halogen for electrons decreases. In
this reaction, Na metal readily donates its valence electron to the halogen. The vigour and speed
of reaction depends on how readily the halogen atoms can accept an electron in the outer shell.
 In terms of stability of the resulting salt
If the product of a reaction has high stability, then its formation is favourable and the reaction
may occur readily. The stability of ionic compounds can be measured in terms of their lattice
energies.NaI, with the smallest lattice energy (least stable) has the least tendency to be formed,
that is, the reaction between sodium and iodine is the slowest.
The lattice energies of the Group (VII) metal salts, NaX decreases
down the group due to the increasing size of the halide ion (Table
Salt Lattice energy/
Kjmol-1 9.4.4). As the ion gets bigger:
(i) Interionic distance in the salt increases, and this results in
NaCl 771 weaker electrostatic attraction between the metal ion and the
halide ion.
NaBr 733 (ii) Distance between the positive charge on the metal ion and the
nucleus of the halide ion increases. Attractions between the
NaI 684
nucleus of the halide and the positive charge on the metal ion
Table 9.4.4 Lattice energies
therefore become weaker. The tendency of the salt to be
of the sodium salts of the formed therefore decreases down the group.
Group (VII) elements

4.3.2 The halogen - halide redox displacement reactions

Consider the reaction:
Cl₂(g) + 2KI (aq) → I₂ (aq) + 2KCl (aq)
In this reaction, chlorine displaces iodine from its salt.A halogen will displace the halogen which is below
it from a solution of its salt.Once more, this shows that the oxidizing power of the halogens decreases
down the group.
The reaction essentially involves oxidation of the iodide ion by chlorine, to form iodine. Note that the
iodide ion loses an electron from the outer shell to form neutral iodide atoms, which immediately bond to
form I2 molecules. By losing an electron to chlorine, iodide is oxidized, that is, it acts as a reducing agent.
We can use electrode potentials to deduce the feasibility of such reactions.

Eθ/V
Cl₂ + e⁻→ Cl⁻ +1.36 ... (i)
Br₂ + e⁻→ Br⁻+1.07 ... (ii)
I₂ + e⁻→ I⁻+0.54 ... (iii)

Q
Is the reaction between chlorine and KI (aq) energetically feasible?

Using half equations (i) and (iii) above, and reversing (iii), which is the less
A
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positive, gives Cl2(g) + 2KI(aq)  I2(s) + 2KCl(aq).
Eθcell = 1.36 + (-0.54) = +0. 82V
The reaction will take place since the Eθcellis large and positive.

The reaction will take place, since the Eθcell is large and positive.

4.3.3 Reactions of the halogens with transition metal ions in low

oxidation states
Chlorine gas and liquid bromine can oxidize Fe (II) in solution, to iron (III).
Fe³⁺ (aq) + e⁻→ Fe²⁺ (aq) Eθ= +0.77 (IV)
Reversing equation (iv) and combining with equation (i)
Cl₂ (g) +2Fe²⁺ (aq) →2Fe³⁺ (aq) + 2Cl⁻ (aq) Eθcell = 1, 36 + (- 0.77) = +0.59V
The reaction is feasible. The light green colour of Fe (II) changes to the yellowish brown of Fe (III).

4.3.4 Reaction of the halogens with hydrogen

X₂ + H₂ (g) → 2HX
The halogens oxidize hydrogen to form hydrogen halides, HX, where X is Cl -, Br – and I- . In this reaction,
the oxidation number of hydrogen increases from 0 to +1, showing that it has been oxidized. The
oxidation number of the halogen decreases from 0 to -1, showing that it has been reduced.
The vigour, speed and extent of reaction decreases down the group. The enthalpy of reaction also becomes
less negative, that is, it becomes more endothermic.
Fluorine reacts explosively with hydrogen under all conditions, even at freezing temperatures.
F₂(g) + H₂(g) → 2HF(g)
Hydrogen burns in chlorine. No heating is required. The reaction becomes explosive if the mixture is ex-
posed to light.
A mixture of bromine and hydrogen gases will not react unless the mixture is heated to 200⁰C in the pres-
ence of Ni catalyst.
A mixture of iodine and hydrogen gases will not react unless the mixture is strongly heated at about
400⁰C, in the presence of Pt catalyst. The reaction is reversible, that is, once formed, some molecules of
HI will decompose back to its constituent elements.
I₂ (g) + H₂ (g) ⇋ 2HI (g)
The trend observed in the vigour, speed, extent and enthalpy of reaction can be explained in two ways.
 Oxidizing power of the halogens, which decreases down the group?

 Stability of the hydride, which decreases down the group. The hydride becomes less stable due to
the increase in size of the halogen atom. Overlap between the valence s orbital of H and the p or-
bital of the halogen atom becomes less efficient. The distance between the nuclei of the atoms of
the H-X bond and the electrons of the bond also increases. Consequently, the H-Hal bond be-
comes longer and weaker. This explains why once formed, HI has a tendency to decompose back
to its elements.

The enthalpy change of reaction becomes less exothermic because the bonds being formed
become weaker and the product is relatively high in energy (that is, unstable).

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 Hydride Bond Bond energy ∆Hθf
length/nm Kj/mol Kj/mol

HCl 0.128 431 -92.3

Table 9.4.5 Some properties
HBr 0.141 366 -36.2 of the Group (VII) hydrides

HI 0.160 299 +25.9

The hydrides of Group (VII) have the general formula HX. Important information about the Group (VII)
hydrides has been given in Table 9.4.5.
 The hydrides are strong acids. In water, they dissolve and dissociate completely, giving a strongly
acidic solution, for example,
HCl (aq)  H+ (aq) + Cl-(aq)
The dissolution of HX in water can also be regarded as Brønsted-Lowry neutralization in
which HX acts an acid and water as a base.

H H +
O H-Cl H O + Cl -
H H

Thermal stability of the hydrides

Stability of the hydrides with respect to decomposition by heat decreases down the group. This is because
the H-Hal bond becomes weaker down the group as the size of the halogen atom increases.
HCl resists decomposition by heat, even at very high temperatures. HBr will decompose slightly when
strongly heated. Plunging a red hot platinum rod in a jar containing HI will cause it to decompose. A
purple vapour containing I2 and H2 is formed.
2HI (g) Ý H2 (g) + I2 (g)

4.3.5 Reaction of the halogens with thiosulphate, S₂O₃²⁻

The halogens are powerful enough to oxidize sodium thiosulphate. The sulphur containing product
depends on the strength of the halogen as an oxidizing agent. Chlorine and bromine are powerful enough
to oxidize thiosulphate to SO42-. The oxidation state of sulphur increases from +2 in S 2O32- to +6 in SO42-.
In SO42- , sulphur attains the highest possible oxidation state. Let the halogen be X 2, and then the reaction
with thiosulphate can be written as
S₂O₃²⁻ + 4X₂ + 5H₂O → 2SO4²⁻ + 10H⁺ + 8X⁻ … (i)
Since the oxidation state of sulphur changes from +2 to +4, each sulphur atom loses two electrons
(oxidation is loss of electrons; it is accompanied by an increase in oxidation number.) Since there are two
S atoms in thiosulphate, each S₂O₃²⁻ molecule loses four electrons. Thus four moles of the halogen are
required per mole of thiosulphate, since each halogen atom requires one electron.
When X2 = Cl2, the Eθcell for reaction (i)is.

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 Reduction equation Eθ/V

Cl2 + 2e Ý 2Cl- +1.36

Br2 + 2e-Ý 2Br- +1.07

I2 + 2e-Ý 2I- +0.54

Table 9.4.6 Some redox potentials
+0.09 involving the halogens
S 4 O6 2- + 2e-Ý 2S2O3 2-

Iodine is not strong enough as an oxidizing agent to oxidize thiosulphate to sulphate. Instead, the
tetrathionate ion is produced, in which the sulphur has an average oxidation number of +2. The fact that
iodine is not able to bring sulphur to the +6 state shows that it is a weak oxidizing agent.
2S₂O₃²⁻ + I₂→ S₄O₆²⁻ + 2I⁻ ... (ii)

Q
Calculate the cell potential for reaction (ii) above

4.3.6 Reactions of the halogens with water

Halogens react with water in a redox displacement reaction. For chlorine, bromine and iodine, the
reaction can be generalized as
X2(g) + H2O (l) Ý HOX (aq) + X- ,
E.g. for chlorine, the reaction forms chloric (I) acid, HOCl and Cl -
Cl2 + H2O Ý HOCl + HCl
 This is a redox disproportionation reaction because the chlorine undergoes both oxidation and
reduction. Its oxidation number increases from 0 in chlorine to +1 in HOCl, and decreases to -1 in
HCl.
 The HOCl formed is itself a weak acid, so it dissociates to yield the chlorate (I) ion and a H+ ion.
HOCl (aq) Ý H+ (aq) + OCl-(aq) ... (i)

 The reaction of chlorine with water is important in water purification. The OCl - ion is an oxidizing
agent. It oxidizes organic matter, including bacteria and food materials that sustain them. The
presence of H+ ions also makes the water acidic, and this also kills the bacteria. HClO is more
effective as a bactericide than the chlorate ion, so it is important to ensure that its concentration
in the water being treated remains fairly high. This can be achieved by closely monitoring pH. If
pH is too high (that is, large [OH-]), H+ ions in equilibrium (i) are neutralized and removed as
water. By Le Chatelier’s principle, this causes the equilibrium to shift to the right, resulting in
reduction of [HOCl]. However, pH should not be made too low, because this causes chlorine to be
lost from water by shifting equilibrium (ii)below to the left. This also results in lowering of the
concentration of HOCl.
Cl2 + H2O Ý HOCl Ý H+ (aq) + OCl-(aq) + Cl- (aq) ... (ii)

 Concentration of chlorine in water must be kept relatively low to prevent formation of poisonous
substances by the free radical reactions between chlorine and organic matter

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  Bromine and iodine are less reactive towards water. This is because they are weaker oxidizing
agents. Concentration of HBrO and HIO in water would be smaller. This explains why Br 2 and I2
are poorly soluble in water.

4.3.7 Reactions of the halogens with NaOH (aq)

Consider the reaction of chlorine with water
Cl2 (g) + H2O (l) Ý H+(aq) + ClO- + H+(aq) + Cl-(aq) ... (i)
[HClO (aq] [HCl (aq)]

Now, suppose that cold NaOH (aq) is added to the resulting solution. It will neutralize the two H + ions on
the right hand side of the equilibrium. This forces the equilibrium to the right, increasing the amount of
chlorine that reacts with the water.
2H+ (aq) + 2OH- (aq)  2H2O (l) ... (ii)
Combining equations (i) and (ii)

Cl2 (g) + H2O (l) Ý H+ (aq) + ClO- + H+ (aq) + Cl-(aq) ... (i)
2H+ (aq) + 2OH- (aq)  2H2O (l) ... (ii)
Cl2 (g) + 2OH- (aq)  ClO- + Cl-(aq) + H2O (l) ... (iii)

Equation (iii) is a summary of what happens whenchlorine reacts with cold dilute NaOH (aq) (tempera-
ture < 150C). A disproportionation reaction takes place, in which some chlorine molecules are converted
to Cl- and some to ClO- . The formation of wateris expected since the reaction essentially involves neutra-
lization of an acidic solution of Cl2 (aq).
This reaction is used to make household bleach, which is a solution containing sodium chlorate (I) and
NaCl.
With hot concentrated NaOH (aq), further oxidation of chlorate (I) to chlorate (V), ClO 3-, occurs.
Again, this is a disproportionation reaction.
3Cl2(g) + 6NaOH (aq) →5NaCl (aq) + NaClO3 (aq) + 3H2O (l)
Check that the oxidation state of chlorine in the chlorate (V) ion (ClO3- in NaClO3)is +5.
NaClO3 is used as a weed killer.

Cl2 undergoes disproportionation in NaOH (aq). The products formed depend on the conditions
employed. With dilute and cold NaOH, a mixture of NaCl and NaClO is formed. With hot and
concentrated NaOH (aq), a mixture of NaCl and NaClO 3 is formed.

The reactions discussed above are also undergone by bromine and iodine. Bromine forms bromate (I) and
bromate (V) ions (BrO- and BrO3-respectively), depending on the conditions. Similarly iodine forms IO-
and IO3-. However, IO- is very unstable, even at O0C and any attempt to prepare it results in the formation
of IO3- as well, even under ice cold conditions.

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9.4.4Reactions of the halide ions

Important note
Students often treat the terms ‘halogen’ and ‘halide’ as if they were interchangeable. For example, when asked to
describe a particular reaction of a halide ion, they tend to discuss in terms of the halogen. A halogen refers to a
neutral Group (VII) element or atom. A halide is the negative ion formed from a halogen. Reactions and chemical
properties of halogens are different from that of the halides, for instance, the halogens are oxidizing agents, but the
halides are reducing agents.

The halide ions are involved in three major types of reactions in which they behave as
 reducing agents
 precipitating agents
 ligands

The halide ion, being negatively charged, is electron rich, and so has the ability to act as an electron donor
in chemical reactions, that is, as a reducing agent. The trend in reducing power of the halide ions down
the group can be shown and explained using reduction potentials (Table 9.4.7).

When the halide ion acts as a reducing agent, it loses

Element Reduction poten- Eθ/V its charge (electron) and becomes a neutral atom.
tial Two halogen atoms then combine to form a
molecule. To understand the behaviour of the halide
Chlorine Cl2 + 2e- Ý 2Cl- +1.36 ions as reducing agent, the electrode potentials in
Table 9.4.7 above should therefore be read in reverse
Bromine Br2 + 2e-Ý 2Br- +1.07 to show the halide ions losing electrons (a reducing
agent is an electron donor).
Iodine I2 + 2e-Ý 2I- +0.54 After reversing the reduction potentials, the I- to I2
Table 9.4.7 Reduction potentials for the conversion has the most positive Eθ value, showing
Group (VII) elements that this is the most feasible. The Eθ value becomes
more negative up the group, showing that it becomes
more difficult for the halide to lose an electron, that
Halide Reduction poten- Eθ/V
tial is, to act as a reducing agent. Cl- is therefore the
weakest reducing agent, and iodide is the most
Chloride 2Cl- Ý Cl2 + 2e- -1.36 powerful.

Bromide 2Br-Ý Br2 + 2e- -1.07 Reducing power of the halide ions increases
down the group.
Iodide 2I- Ý I2 + 2e- -0.54
Table 9.4.7 Electrode potentials of the
halogens

Explanation
It has already been explained that the halide ion acts as a reducing agent by losing the extra electron
(negative charge) in the outer most shell. Reducing power of the halide ion therefore depends on how
firmly or loosely held this electron is to the atom. Going down the group, size of the halide ion increases as

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new shells are opened. As a result, distance of the outer shell from the nucleus increases (Fig 9.4.2).
Moreover, the outer shell is shielded by inner shells from feeling a strong attractive influence from the
nucleus. Going down the group, it becomes easier to remove an electron from the outer shell of the halide
ion, since this electron becomes loosely held to the atom.

Important note
Students often confuse the trend in the reactivity of the halide
ions with that of the halogens.
The halide ions become more reactive (as reducing agents)
down the group, whereas the halogens become less reactive (as
oxidizing agents) down the group. This is because the halide
ions react by losing an electron, a process which becomes easier
down the group as ionic size increases. On the other hand, the
halogens react by attracting an electron into the outer shell, a
process which becomes harder down the group as the atoms
become larger. Distance of the outer shell from the nucleus
increases, and moreover, the outer shell becomes more
shielded by inner shells. It therefore becomes harder for the
halogen atom to accept an electron, that is, to act as an
oxidizing agent.
Fig 9.4.2 Reactivity of the halide ions as
reducing agents increase down the group

4.4.1 Reaction of the halide ions with concentrated sulphuric

acid (see Table 9.4.8)
Concentrated sulphuric acid is an oxidizing agent. As it oxidizes a substance, it is itself reduced to lower
oxidation states such as sulphrous acid, (H2SO3 = SO2 + H2O), H2S and S.
The final sulphur containing product depends on the strength of the reducing agent.
When concentrated H2SO4 is added to NaCl (aq), white fumes of HCl are produced.
H2SO4 (aq) + Cl-(aq)  HSO4-(aq) + HCl (g)
Note that this is not a redox reaction. Cl- ions are too weak as reducing agent to reduce H2SO4. This is an
example of a displacement reaction in which a volatile acid (HCl) is displaced from a solution containing a
less volatile acid (H2SO4). What happens is that H2SO4 dissociates to produce a hydrogen ion.
H2SO4  H+ + HSO4- ... (I)
The hydrogen ions then combine with chloride ions to produce the less volatile acid, HCl.
(i) If a dilute solution of H2SO4 is used, no white fumes are formed, because the large concentration
of water causes the HCl to dissolve, instead of escaping as a gas.
(ii) In reaction (I) above, H2SO4 does not dissociate fully to form 2H+ and SO42-, because
once formed, the negatively charged HSO4- ion has very little tendency to lose a positive
particle (H+).

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 Add concentrated sulphuric acid
Salt
HX produced(X= Cl-, Br- Other Type of Observation
, I-) products reaction
formed
White and dense
NaCl Yes NaHSO4 displacement fumes (of HCl)

Displacement and Orange vapour, acrid

NaBr Yes , but a little Br2 , SO2 , H2O, redox, displacement smell of SO2, white
NaHSO4 is predominant fumes of HBr.

NaI Yes, but it is immediately A mixture of Displacement and Dark brown

reduced to iodine products , including redox, the product of precipitate of iodine ,
I2, SO2, H2O, H2S displacement (HI) is acrid smell of SO2 ,
immediately foul smell of H2Sand
oxidized to I2 yellow deposit of
sulphur. Some of
these products,
especially H2Sand S,
may not form,
depending on initial
concentration of NaI
and H2SO4
Table 9.4.8 Reactions of the halide ions with concentrated sulphuric acid

When concentrated sulphuric acid is added to a solution of NaBr (aq), white fumes of HBr are produced,
but the white colour is soon masked by an orange vapour of Br 2.
Two types of reactions occur here.
 HBr is displaced
H2SO4 (aq) + NaBr (aq)  HBr (g) + NaHSO4 (aq) ... (i)
Some bromide ions (in the form of HBr produced in reaction (i)) reduce H2SO4 to SO2 and H2O
(a mixture of SO2 and H2O can also be thought of sulphrous acid, H2SO3). Meanwhile, the
bromide ions are oxidized to bromine.
We can construct the equation of this reaction with the aid of a Data Booklet.

Eθ/V
H2SO4 + 2H+ + 2e- Ý SO2 + 2H2O +0.17
(or SO42- + 4H+) (or 2H2SO3)

Br2 + 2e- Ý 2Br - +1.07

We reverse the second reaction so that Br- ions go to the same reactant side as H2SO4 (the
electrode potential for the reaction then becomes -1.07V).
Adding the two equations gives the net reaction for the reduction of H2SO4 by bromide
ions.
H2SO4 + 2H+ + 2Br - SO2 + 2H2O + Br2Eθcell = 0.17 + (-1.07) =-0.90V ... (ii)
(or 2 HBr )

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 The reaction has a negative cell potential and so will not occur when standard conditions
are employed. In this case, hot concentrated sulphuric acid is used (non-standard
conditions), so the reaction does happen, but only a small amount of Br - is converted to
Br2. The major reaction that takes place is displacement of HBr.

(i) If a dilute solution of H2SO4 is used, no bromine is produced, and no white fumes are
observed. With dilute solutions, bromide ions cannot reduce sulphuric acid, since the cell
potential of the reaction is negative. When the sulphuric acid is dilute, the concentration of
water is high, so the HBr which is formed simply dissolves in water, instead of escaping as
white fumes.
(ii) The fact that Br - reduces sulphuric acid to SO2 shows that Br - is a stronger reducing
agent than Cl-.
When hot concentrated sulphuric acid is added to NaI (aq), HI is produced by displacement, but it imme-
diately reduces sulphuric acid to SO2, S and H2S. No white fumes of HI are observed because the HI reacts
with H2SO4 as soon as it is produced.
H2SO4 (aq) + NaI(s)  HSO4-(aq) + HI (aq) ... (i)
Some of the reactions in which HI acts as a reducing agent are shown below
H2SO4 (aq)+ 2HI (aq)  I2(s) + SO2 (g) + 2H2O (l) ... (ii)
The net cell potential for this reaction is obtained using the following half equations
Eθ/V
H2SO4 + 2H+ + 2e- Ý SO2 + 2H2O +0.17
(or SO42- + 4H+) (or 2H2SO3)

I2 + 2e- Ý 2I- +0.54

Reversing the second equation and its reduction potential, and adding the two equations together gives
reaction (ii) . The cell potential is then 0.17 + (-0.54) = -0.37V.
The cell potential is still negative (because sulphuric acid is a weak oxidizing agent). Using dilute solutions
of sulphuric acid and NaI would therefore result in no reaction. However, the cell potential is more
positive than the one obtained for the reaction of NaBr with sulphuric acid. This shows that iodide ions
are more powerful than bromide ions as reducing agent.
The net equation for the reaction of concentrated sulphuric acid and NaI is sometimes obtained by adding
reactions (i) and (ii), giving.
2NaI(s) + 3H2SO4 (aq)  2NaHSO4 (aq) + I2(s) + SO2 (g) + 2H2O (l) ... (iii)
The observations would therefore be a brown precipitate of iodine, and the pungent smell of SO 2.
However, this reaction is misleading because it does not reveal that first HI is formed, which then reduces
sulphuric acid to SO2. Also, further reduction of SO2(aq) to H2S and S is possible.

4.4.2 Redox displacement reactions involving the halide ions

A halide ion can reduce a halogen which is above it in the group. Consider what happens when chlorine
gas is bubbled into a solution containing KI (aq).
Cl2 (g) + 2I-(aq) → I2 (aq) + 2Cl-(aq)
It has already been shown that the reaction is energetically feasible since it has a positive E θ value. In this
reaction, I- acts as a reducing agent (electron donor), and Cl 2 as an oxidizing agent (electron acceptor).

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Iodide, being relatively large, easily lets go of its charge (extra electron in the outer shell), and gives it to
chlorine (Fig 9.4.3). Iodide is thus oxidized, because it loses an electron. Meanwhile, chlorine, having
relatively small atoms, easily accepts an electron from iodine. Cl 2 is thus reduced, since it gains electrons
(each atom in chlorine gains one electron, therefore a total of two electrons is gained per molecule of
chlorine).

Fig 9.4.3 Diagram illustrating why the reaction between iodide ions and chlorine
is feasible. Verify that this reaction is indeed feasible by means of electrode
potentials.

Now consider what happens when iodine is added to a solution containing chloride ions.
I2 + 2Cl -→ no reaction
This time no reaction takes place. The chloride ion is small and so it has a firm hold on the extra electron
its outer shell. It will not easily give it away to iodine. Iodine atoms are large and so they will not easily
accept an electron in their outer shell.

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 The Group (VII) elements and their compounds: uses and other useful information

Chlorine

Origin of name: Greek ‘chloros’ meaning ‘greenish yellow’ or ‘yellowish green’

Colour and state at room temperature: Greenish yellow gas, bleaches litmus paper to white.

Uses of chlorine and its compounds

 Water purification (in water it forms HOCl and HCl, which kill bacteria)
 Manufacture of PVC ( a polymer)
 Manufacture of pesticides, solvents (such as CCl4) and aerosol propellants.
 Used to oxidize Br- ions to Br2 during the extraction of bromine from sea water.
 NaCl is used in food seasoning and as a food preservative.
 Manufacture of mild antiseptics such as trichlorophenol, which is the active ingredient in dettolTM.

Lab preparation of chlorine

Chlorine can be produced on a small scale by the oxidation of chloride ions (from concentrated HCl) by MnO2 (Fig
9.4.4).

4
3

1
2

Fig 9.4.4 Lab preparation of chlorine gas

1. A mixture of concentrated HCl and solid MnO2 (oxidizing agent) are heated. Cl- is oxidized to Cl2 while MnO2 is
reduced to Mn2+.

Eθ/V
Cl2 + 2e-Ý 2Cl- +1.36
MnO2 (aq) + 4H+ (aq) + 2e–ÝMn2+ + 2H2O(l) +1.23
net 2Cl- + MnO2 (aq) + 4H+ (aq) →Mn2+ + 2H2O (l) + Cl2

Eθcell for this reaction is (-1.36 + 1.23) = -0.13V

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 Note that the first reaction and its electrode potential have been reversed so that Cl - is on the same reactant side as
MnO2. Since the cell potential for the reaction between Cl- and MnO2 is negative, the reaction will not take place if the
concentration of Cl- ions is low. Since a high concentration of hot HCl is used, the reaction does take place.

2. Chlorine produced in flask 1 is mixed with HCl(g). When the mixture is passed through water, HCl is absorbed.
Chlorine is slightly soluble in water, but the presence of a strong acid, in this case HCl, makes chlorine almost
completely insoluble.

3. Chlorine leaving flask 2 is contaminated with water vapour. The gas is dried by passing it through concentrated
sulphuric acid, which has a high affinity for water (it is a good drying agent).

4. Dry chlorine is collected in a closed jar.

Industrial preparation of chlorine

The industrial preparation of chlorine by electrolysis of brine (concentrated NaCl) using a diaphragm cell was
discussed in Section 6.

Check to see if you still remember the details of the process

1. State the material used at the anode and the cathode.

2. Write down the equations for the reactions that occur at each electrode.
3. Why is a porous material (asbestos) used to divide the anode compartment from the cathode
compartment ?
4. Why is the level of brine kept higher in the anode compartment than in the cathode compartment?
4. What other two products are produced during this process, besides chlorine gas, and in what
ratio are they formed?
5. If the contents of the two compartments are mixed, another substance is formed. Name this
substance, and by means of a balanced equation, explain how it is formed.

Bromine

Origin of name: Greek ‘bromos’ meaning ‘stench’ due to its characteristic smell.
Colour and state at room temperature: red brown volatile liquid with a characteristic stench.
Solubility: sparingly soluble in water. Dissolves well in organic solvents such as chloroform, in which it forms a red
solution.

NB: Bromine is extremely poisonous.

Uses of bromine and its compounds

 Some compounds of bromine are used as flame retardants, that is, they prevent the spreading of fires.
 Manufacture of pesticides.

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 Lab preparation
The method involves oxidation of Br- ions by MnO2 in the presence of hot concentrated H2SO4 (aq), which is also an
oxidizing agent. The reaction is carried out in a distillation apparatus, so that bromine is collected as a liquid.

Industrial preparation
Bromine is obtained from sea water, which is rich in halide ions. Sea water is treated with chlorine, which oxidizes
the bromide ions to bromine in a redox displacement reaction. Bromine, which is volatile, is then driven out by
blowing air into the water.

Iodine

Origin of name: From Greek ‘iodes’ meaning ‘violet’ because of the colour of the gas.
Colour and state at room temperature: black solid, when heated, it sublimes to a purple vapour.
Solubility: poorly soluble in water, but dissolves well in organic solvents such as chloroform (CCl4) to form
beautiful purple solutions.

Uses of iodine and its compounds

 A mixture of iodine and ethanol, commonly referred to as ‘tincture of iodine’, is used as a mild antiseptic
suitable for small wounds.
 Its salts are useful in photography
 The iodide ion is an important mineral nutrient. Deficiency of iodine in the diet leads to goiter.

Lab preparation of iodine

Same method as the preparation of bromine, that is, it involves oxidation of I- ions, for example, from NaI, by MnO2
in the presence of concentrated sulphuric acid. Solid iodine is produced, which sublimes to a gas due to the heat
applied during the process. The gas can be sublimed back to solid when it strikes a cold surface, for example, the
bottom of a flask containing cold water.

Commercial extraction of iodine

Iodine is found in the earth’s crust as sodium iodate (V), NaIO3, which is usually found mixed with Chile salpetre,
NaNO3, so named because large amounts of this compound are found in Chile.
In the production of iodine from NaIO3, IO3- ions are first reduced to iodide ions by sodium hydrogen sulphite
IO3- (aq) + 3HSO3-(aq)  I-(aq) + 3HSO4-(aq)
A reaction then occurs between IO3- and iodide ions, producing iodine
IO3- (aq) + 5I-(aq) + 6H+ (aq)  3I2(s) + 3H2O (l)

Notes for use in qualitative analysis

Tests for and properties of the halogens
 Chlorine is a greenish yellow gas which bleaches litmus paper. This is in fact an oxidation process.

CAUTION: Chlorine is poisonous. Any experiments that result in the production of chlorine should be
carried out in a fume hood.

Bubbling chlorine gas into a solution containing Fe2+ results in a change of colour from light green to yellowish
brown. This is a result of the oxidation of Fe2+ (aq) to Fe3+ (aq) by chlorine
2Fe2+ (aq) + Cl2 (g)  2Fe3+ (aq) + 2Cl-(aq)

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  Passing chlorine gas into a solution containing KI (aq) results in formation of a brown solution, and a dark
brown deposit may also be formed. This is due to the oxidation of iodide ions to iodine by chlorine. When
formed in the presence of excess iodide ions, iodine dissolves significantly due to the formation of I 3- ions.
The solution formed is brown. Any iodine which does not dissolve forms a dark brown deposit.
 Liquid bromine is too poisonous for use in a school lab.
 Iodine is a shiny black solid. It dissolves poorly in water but dissolves significantly in a solution that contains
iodide ions. When the solid is heated strongly, it sublimes to a purple vapour. Iodine solution can be tested
for using

(i) Starch solution. A blue-black coloration is formed due to the formation of a complex between iodine and
starch molecules.
(ii) Sodium thiosulphate solution. Iodine solution is decolourized because iodine is reduced to iodide ions.
I2 (aq) + 2S2O32-(aq)  2I-(aq) + S4O62-(aq)
Iodine is a weak oxidizing agent, for instance, it has no effect on litmus paper, and it can not
convert Fe2+ (aq) to Fe3+ (aq).

Test for the halide ions

Halide ions usually behave in two ways in their reactions
 as agents of precipitation
 as complexing agents
In addition, iodide is a good reducing agent, and this often allows its detection in qualitative analysis.
Halide ions give precipitates with Pb2+ (due to the formation of the insoluble salt, PbX2, where X is the halide ion) and
with Ag+ due to the formation of insoluble AgX.

Precipitation reactions with Pb2+

A common source of Pb2+ ions in the lab is the white crystalline salt, Pb (NO3)2, which, like all nitrates, is soluble in
water.
Cl- ions form a white precipitate of PbCl2with Pb2+. Br- forms a cream precipitate and I- a yellow precipitate. All three
precipitates dissolve when heated.

Testing for the halide ions using Ag+ ions followed by aqueous ammonia
Cl- forms a white precipitate of AgCl, which is soluble in dilute ammonia. Br- forms cream coloured AgBr, which is
sparingly soluble in dilute ammonia but dissolves in concentrated ammonia.
I- forms a yellow precipitate of AgI, which is insoluble in both dilute and concentrated ammonia.

The underlying principle

The halide ion, X- is precipitated out of solution by Ag+ ions.
Ag+ (aq) + X-(aq)  AgX(s)
The solubility of these precipitates in water is very small, that is, the equilibrium
AgX(s) Ý Ag+ (aq) + Cl-(aq) ... (i)
has a very small solubility product, Ksp , as shown below

Salt Ksp at 298K

AgCl 1.8 x 10-10
AgBr 7.7 x 10-13
AgI 8.3 x 10-17

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  Note that solubility of the silver halides decrease down the group. Compared to the three salts, AgCl is
the most soluble. In water, some AgCl dissolve, releasing free Ag+ ions. Upon addition of aqueous
ammonia, a complexation reaction takes place which removes the Ag+ ion solution.
Ag+ (aq) + 2NH3 (aq)  [Ag (NH3)2] + (aq)
This forces equilibrium (i) to the right, producing more Ag+ ions and causing more AgCl to dissolve. If
an excess of NH3 (aq) is added, all of the AgCl will dissolve, forming a colourless solution containing the
diamine (I) silver ion, [Ag (NH3)2] +.
 In water, the solubility of AgBr is very small and consequently the concentration of Ag + (aq) is minute.
Dilute ammonia will not result in any reaction with the Ag+ ions, because the chances of there being a
collision between NH3 molecules and Ag+ ions is close to zero. However, when concentrated ammonia is
used, the probability of collision between ammonia and silver ions increases. Removal of Ag+ ions from
solution will promote dissolution of AgBr.
 The solubility of AgI in water is so small that no reaction occurs with dilute or concentrated ammonia.

Table 9.4.9summarizes the common reactions and tests for the halide ions.

Ion Test Observation Notes

Cl- Forms white ppt Insoluble precipitates PbX2 formed.

Add Pb2+(aq) The precipitates dissolve when
Br- Forms cream ppt heated.

I- Forms yellow ppt

Cl- Forms white ppt, which dissolves Insoluble precipitates AgX formed.
upon addition of dilute NH3, to AgCl, which is more soluble in water,
form a colourless solution. dissolves in dilute ammonia due to
Add Ag+(aq), followed formation of the complex
Br- by dilute NH3 Forms cream ppt, insoluble in [Ag (NH3)2] +.
dilute ammonia. AgBr, which is less soluble in water,
does not dissolve in dilute ammonia.
I- Forms yellow ppt, insoluble in However, it dissolves in concentrated
ammonia. ammonia, to form a colourless
solution containing the complex
[Ag (NH3)2] +.
AgI, whose solubility in water is
extremely low, does not dissolve in
dilute or concentrated ammonia.

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 Ion Test Observation Notes

Cl- Forms white ppt Insoluble precipitates PbX2 formed.

Add Pb2+(aq) The precipitates dissolve when heated.
Br- Forms cream ppt

I- Forms yellow ppt

Cl- Forms white ppt, which dissolves Insoluble precipitates AgX formed.
upon addition of dilute NH3, to AgCl, which is more soluble in water,
form a colourless solution. dissolves in dilute ammonia due to
Add Ag+(aq), followed formation of the complex
Br- by dilute NH3 Forms cream ppt, insoluble in [Ag (NH3)2] +.
dilute ammonia. AgBr, which is less soluble in water,
does not dissolve in dilute ammonia.
I- Forms yellow ppt, insoluble in However, it dissolves in concentrated
ammonia. ammonia, to form a colourless
solution containing the complex
[Ag (NH3)2] +.
AgI, whose solubility in water is
extremely low, does not dissolve in
dilute or concentrated ammonia.

Cl- White fumes produced. HCl (g) displaced.

Br- To concentrated White fumes, which are soon HBr(g) gas displaced(white fumes)
solutions of the anions, coloured by orange fumes. Acrid Sulphuric acid reduced to SO2(acrid
add hot concentrated smell detected. smell)
sulphuric acid Br- oxidized to Br2 (orange fumes)

I- Purple vapour produced, acrid Iodide oxidized to iodine (purple

smell produced. Smell of rotten vapour). Sulphuric acid reduced to
eggs may also be detected, and a SO2 , H2S and S.
yellow ppt may form.

Cl- Pass chlorine gas into a No change.

solution containing the
Br- anion. Solution turns orange or red Redox displacement occurs; Br- is
brown, a greenish yellow gas is oxidized to Br2, whilst chlorine is
evolved reduced to chloride.
2Br- + Cl2 2Cl- + Br2

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 Ion Test Observation Notes

I- Pass chlorine gas into a Dark brown deposit or brown Redox displacement occurs; I- is
solution containing the solution formed oxidized to I2, whilst chlorine is
anion. reduced to chloride.

Cl- No change

Br- Add bromine solution No change

I- Dark brown precipitate or brown Redox displacement occurs; I- is

solution formed, bromine oxidized to I2, whilst bromine is
decolourized reduced to bromide.

Cl- No change
Redox displacement not possible.
Br- Add iodine solution No change

I- No change

Cl- No change, yellow brown colour of

Fe3+ (aq) observed. Cl- and Br- are too weak as reducing
Br- Add dilute Fe3+(aq), agents to convert Fe3+ to Fe2+.
followed by starch No change, yellow brown colour of
solution Fe3+ (aq) observed.

I- Brown solution formed I- is powerful enough to reduce Fe3+ to

Fe2+. Meanwhile, the iodide ions are
oxidized to iodine (brown).
2I- + 2Fe3+ I2 + 2Fe2+

Cl- White ppt formed, turns purple White AgCl precipitated. AgCl
grey in sunlight. undergoes superficial(surface)
photochemical decomposition in light
Add Ag+ (aq), filter any AgCl(s)  Ag(s) + ½ Cl2(g)
solid formed. Leave the
Br- solid in sunlight for a Cream ppt, turns green yellow in Photochemical decomposition of AgBr
few minutes sunlight. * takes place, as for AgCl.

I- No effect

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 Ion Test Observation Notes

Cl- Cl- and Br- are not powerful enough to

No change reduce hydrogen peroxide.
Br- Add dilute hydrogen
peroxide

I- Solution changes from colourless Iodide ions reduce hydrogen peroxide.

to brown Iodine is formed.

H2O2 (aq) + 2I- (aq) + 2H+ (aq) → I2

(aq) + 2H2O

Cl- No change
Redox displacement not possible.
*The photochemical decomposition of AgBr is used in black and white photography. AgBr on photographic film is
Br - Add iodine solution No change
decomposed by light to Ag(s). Sodium thiosulphate, Na2S2O3 (referred to as ‘hypo’ in photography) is used during
development of the film. The S2O32- ions remove excess AgBr from the film by formation of a soluble complex, [Ag
I(S- 2O3)2]3-. This leaves an opaque shadow
No change
of silver metal on the film.

The halic ions, XO- and XO3-

Cl
You are now aware of the existence of No
- change,
halic yellow
ions, for brown
example colour
ClO of (I) ion and ClO3 (Chloric (V) ion. These
-(chloric
Add Fe 3+(aq), followed Fe3+ (aq) observed.
ions are good oxidizing agents. It whitens fabric by oxidizing dirt to colourlessCl-substances.
and Br- are too weak as reducing
Br - by starch solution agents
Recall that the halic (I) ions such as ClO are prepared by the disproportionation reaction
- to convert Fehalogen
of the
3+ to Fe2+.
with cold
No change, yellow brown colour of
dilute NaOH (aq). When hot concentrated NaOH (aq) is used, the halic (I) ion undergoes further oxidation, forming
the halic (V) ion, XO3-. Fe3+ (aq) observed.
IO is unstable with respect to IO3 . It is therefore difficult to prepare the iodate ion, IO-(also known as the iodic (I)
- -
Iion)
- Brown
because it is immediately converted solution
to IO 3-, evenformed I- is powerful
under ice cold conditions. enough towith
Of the oxyanions reduce
theFe
3+ to
formula
- - - - Fe 2+. Meanwhile, the iodide ions are
XO , ClO is the most stable. Of the oxyanions with the formula XO3 , IO3 is the most stable.
oxidized to iodine
In the presence of a suitable reducing agent and acid, the halic (V) ions are decomposed (brown).
and reduced to the halogen,
for example 2I - + 2Fe3+ I2 + 2Fe2+

2ClO3-(aq) + 12H+ (aq) + 10e- Cl2 (g) + 6H2O (l)

All three halic (V) ions are therefore powerful oxidizing agents, that is, they are easily reduced. This is the basis of
the
Cl- reaction between
Add XOfilter
Ag+ (aq), 3- andany
X- ions,White
for example, IO3-(aq)
ppt formed, oxidizes
turns purple I (aq) according
-
White AgCltoprecipitated.
the equationAgCl
IO3–(aq) +solid formed.
5I–(aq) + 6HLeave
+ (aq) the
 3H2grey
O (l)in sunlight.
+ 3I2 (aq) undergoes superficial(surface)
solid in sunlight for a photochemical
There is a change of colour from colourless to brown. This reaction (whose equation youdecomposition in light by
can easily construct
few minutes AgCl(s)  Ag(s) + ½ Cl2(g)
combining relevant half equations from the Data Booklet) can be used to determine the concentration of IO3– in a
given solution. The procedure involves back titration of the iodine
Br
produced with sodium thiosulphate ofCream
- ppt,
a known turns green yellow in
concentration. Photochemical decomposition AgBr *
sunlight. takes place, as for AgCl.
I2(s) + S2O32-(aq)  2I-(aq) + S4O62-(aq)

I- No effect

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 Questions, solutions and discussions

Q1This question is about the elements of Group VII, the halogens.

(a) Complete the following table.

Halogen colour Physical state at room

temperature

chlorine

bromine

iodine

(b) Concentrated sulphuric acid is added to separate solid samples of magnesium chloride,
magnesium bromide, and magnesium iodide.

(i) Describe, in each case, one observation you would be able to make.
(ii)Give an equation for the reaction of concentrated sulphuric acid with magnesium
chloride.

(c) When dilute nitric acid and aqueous silver nitrate are added to a solution of a magnesium
halide, MgX2, a pale cream precipitate is formed. This precipitate is soluble in concentrated aqueous
ammonia but not soluble in dilute aqueous ammonia.

(i) What is the identity of the precipitate?

(ii) Give an equation, with state symbols, for the reaction of the precipitate with
concentrated aqueous ammonia.

(d)A hot glass rod is plunged into separate gas jars, one containing hydrogen chloride and
one containing hydrogen iodide.

(i)For each gas, state what you would observe, if anything, and write an equation for any reaction
that takes place.
(ii)Explain your answer to (i) in terms of enthalpy changes.
(iii) What is the role of the hot glass rod in any reaction that occurs?
9701/02/M/J/06

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 Solutions

(a) Left for the reader

(b) (i) MgCl2 : white fumes (of HCl)

MgBr2 : red colour (of Br2) and white fumes (of HBr)
MgI2 : purple fumes (of I2 gas) / black solid (I2) / yellow solid (S) /stinking gas (H2S)

(ii)MgCl2+ H2SO4→MgSO4+ 2HCl / MgCl2+ 2H2SO4 →Mg(HSO4)2+ 2HCl

(c) (i)AgBr

(ii) AgBr(s) + 2NH3(aq) →Ag(NH3)2Br(aq)

(d) (i) HCl: no reaction

HI : purple vapour, 2HI →H2+ I2

(ii) The H- Cl bond energy is high but the H-I bond is weaker and is more easily broken .

(iii) Provides activation energy

Q2The elements in Group (VII) show trends in a number of their physical and chemical properties.
(a) Explain the trend in boiling points of the elements as shown.

element Boiling point/0C

chlorine -35

bromine +59

iodine +184

(b) There are also clear trends in both the H-X bond energy and the Eθvalues for the cell
X2(aq)/X -(aq), where X = Cl, Br, I.
Use relevant data from the Data Booklet to describe and explain each of the following.
Give an equation for each reaction that occurs.

(i) The reactions of the halide ions with concentrated sulphuric acid.

(ii) The action of heat on the hydrogen halides 9701/04/SP2007

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 Solutions

(a) Strength of Van der Waals forces increases down the group with increasing number of electrons.
Stronger temporary dipoles are established and so the force of attraction between molecules
becomes stronger.

(b)(i) Reaction of sulphuric acid with the halide ions involves oxidation and displacement of a volatile
acid, HX, where X = Cl, Br, I. The following E0/V are relevant in explaining the ability of the
halide ion to reduce sulphuric acid, that is, to be oxidized by sulphuric acid to form the halogen
X2 .

½ Cl2 + e- Cl- Eθ/V = +1.36

½ Br2 + e- Br- Eθ/V = +1.07
½ I2 + e- I- Eθ/V = +0.54

The Eθ values become less positive down the group, indicating that the halogens become stronger
reducing agents. Thus Cl- is too weak as a reducing agent to reduce sulphuric acid. The only
reaction that takes place is the displacement of HCl (white fumes).
H2SO4 (aq) + Cl-(aq)  HCl(g) + HSO4-(aq).
Br- and I- are powerful enough to reduce sulphuric acid to SO 2, according to the equation.
2X- (aq) + 3H2SO4 (aq)  2HSO4- (aq) + X2(s) + SO2 (g) + 2H2O (l)
For Br- , which is a weaker reducing agent than I-, white fumes of HBr are also formed as a
result of displacement. I- is powerful enough to continue reducing sulphuric acid until low
oxidation states (H2S and S) are obtained. When this happens, a foul smell like that of rotting
eggs is detected due to H2S and a yellow deposit of sulphur is formed.

(ii) The H-X bond energy decreases down the group.

Bond Bond energy/

Kjmol-1

H-Cl 431

H-Br 366

H-I 299

Thus HI has the weakest bond and it is easily broken by heat, resulting in decomposition
2HI (g)  H2 (g) + I2 (g)
Copious violet fumes of iodine are produced when a red hot needle is plunged into a jar
containing HI.
The H-Br bond is stronger and brown fumes of Br2 are only produced upon very strong heating.
The H-Cl bond is the strongest. HCl therefore resists decomposition by heat.

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 426
 Q3Chlorine is a yellow-green gas whilst iodine is a black solid.
With the aid of chemical equations compare and contrast the chemistry of chlorine and iodine by
describing and explaining the following:

(a) Reaction of the two elements with sodium thiosulphate

(b) Reactions of solid halides of the two elements with concentrated sulphuric acid

(c) Reactions of the two elements with hydrogen 9189/01/O/N/ 2010

Solution
(a) The halogens act as oxidizing agents. Oxidizing power decreases down the group. Chlorine is therefore
more powerful than iodine, as exemplified by the reaction of the two elements with sodium
thiosulphate, Na2S2O3. Chlorine is powerful enough to oxidize thiosulphate all the way to the +6 state
of sulphur in SO42-.
4Cl2 (aq) + S2O32-(aq) + 5H2O (l)  8Cl- (aq) + 2SO42- (aq) + 10H+ (aq)
Iodine is a much weaker oxidizing agent, and it can only oxidize S 2O3 to the tetrathionyl ion, S4O62- ,
in which the the oxidation state of sulphur is 2.5.
I2(aq) + S2O32- (aq)  2I- (aq) + S4O62- (aq)

(b) See question 2

(c) Both chlorine and hydrogen react with hydrogen in a redox reaction
X2 (g) + H2(g)  2HX.
However, chlorine, being a powerful oxidizing agent, reacts explosively and completely with hydrogen.
The reaction of hydrogen with iodine is slow and reversible.

Q4 (a) Chlorine is produced by the electrolysis of brine. It has found use in water purification.

(i) Write an equation for the reaction between chlorine and

1. Cold NaOH(aq)
2. Hot NaOH(aq)

(ii) Explain the use of chlorine in water purification

(b)Chlorine can also be used as bleaching agent.

Use chemical equations to explain the role of water in the bleaching action of chlorine.
9189/02/M/J/ 2011

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 427
 Solution
(a)(i) Please refer to main text

(ii)Chlorine reacts with water according to the equation

Cl2 + H2O Ý2H++ OCl- + Cl-
OCl- is a good oxidizing agent. It oxidizes organic matter in water, including bacteria. Organic food
molecules are also oxidized and this depletes the food reserves on which bacteria feed. The
reaction also produces H+ ions which make the water acidic, leading to death of bacteria.

(b) Chlorine reacts with water to form the oxidizing agent ClO-. Bleaching involves the oxidation of
dirt and dyes by ClO-, leading to whitening of materials, for example clothes.

Q5 Bromine has been obtained from sea salt for a number of years. For simplification, sea salt can be
considered to be sodium chloride containing some sodium bromide.
One early method of obtaining bromine is outlined in the following scheme.

sea salt chlorine intense separate with ether yellow

A yellow B solution in
colour ether

cold aqueous
potassium C
hydroxide

ether
recycled two
colourless
layers

warm with acid

red fumes which and distil white aqueous layer is
condense to a red D paste concentrated
liquid ( bromine)

(a) (i) What causes the yellow colour produced in A?

(ii) Write an equation for the reaction in A.

(b) Ether is an organic solvent immiscible with water. Explain why the yellow substance dissolves in the
ether in B but the salt does not dissolve in the ether.

(c) Suggest an equation for reaction C.

(d) Suggest an equation for reaction D, the reaction of acid on the products of reaction.
9701/02/O/N/1998

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 428
 Solution
(a)(i) Bromine (the solution is yellow because it is very dilute).

(ii) 2Br-(aq) + Cl2(aq)  Br2(aq) + 2Cl-(aq) [Recall that this is a redox displacement reaction]

(b) Bromine, being non-polar, easily dissolves in ether which is also non-polar. This is because the
dissolving process only requires the breaking of weak Van der Waals forces in the solvent (ether) and
solute (bromine). On the other hand, the salt is ionic and the solvent is not able to break the strong
forces of attraction between the ions of the salt .

(c) Br2 + 2OH- Br- + BrO- + H2O [This is the disproportionation of a halogen in an alkali]

(d) Br- (aq) + BrO- (aq) + 2H+(aq)  Br2(aq) + H2O(l)

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise
box anywhere9.3
in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

1(a) (i) State three different substances in everyday or industrial use which contain chlorine.

(ii) For each substance, state one use and explain how the use depends on a relevant property of
the substance.

(b) Comment on any problems which arise from the disposal of materials which contain chlorine
9701/02/O/N/2000

2(a) Potassium chlorate (V), KClO3, is widely used in fireworks and match heads. It decomposes when
heated with a catalyst to form potassium chloride and oxygen.
Construct an equation for the decomposition of potassium chlorate (V).

(b)(i) Suggest why potassium chlorate (V) is used in fireworks and match heads.

(ii) Suggest one substance which could be used as the combustible material in fireworks or match
heads.

(c) How can potassium chlorate (V) be obtained from chlorine? Illustrate your answer with an
equation.

(d) The standard redox potential of chlorate (V) ions is given below.

ClO3- + 6H+ + 6e-Ý Cl- + 3H2O Eθ = + 1.45 V

Prepublication manuscript © L. MWANAWENYU 2011. Please do not photocopy or reproduce Page 429
 Use the Data Booklet to predict what you would expect to observe when acidified potassium
chlorate (V) is added separately to each of the following reagents. Write a balanced equation for any
reaction that occurs.

(i) aqueous iron (II) sulphate.

(ii) acidified potassium manganate 9701/02/O/N/1997

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

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 431

9.5 NITROGEN AND SULPHUR

9.5.1Nitrogen

Nitrogen, a Group (V) element, has the electronic configuration 1s²2s²2p³. The valence shell is made up
of two sub shells, the 2s and the 2p (used in bonding). The total number of valence electrons is therefore
five. The electronic configuration of nitrogen has important consequences.
 Nitrogen uses three 2p electrons to bond with another nitrogen atom. This is because these three
electrons are unpaired. An atom usually makes use of its unpaired electronsin bonding. The N to
N bond is therefore a triple bond, since it is formed by the overlap of three singly occupied atomic
orbitals from each atom. Remember that in a multiple bond (double or triple), only one can be
sigma. The rest are pi. The 2s electrons, being paired, are not used in the formation of covalent
bonds in the nitrogen molecule. They remain as a lone pair on each atom.

 overlap
 of
 orbitals

N  N
2s2 px py pz p x py pz
2
1s
2p 2p
N N

 The three unpaired electrons in a N atom can also be used to make three bonds with other atoms,
for example hydrogen (as in NH3) and chlorine (as in NCl3).
 The paired 2s electrons can also be used in dative bond formation, for example in the ammonium
ion and in BF3.NH3. Fig 9.5.1 shows formation of a dative bond between ammonia and a proton,
resulting in the formation of the ammonium ion.
 The maximum oxidation number nitrogen
H+ can achieve in its compounds is +5,
H
corresponding to the participation of all
N
N five valence electrons. Note that N can only
H H
form a maximum of four bonds, for
H
H H H example as in NH4+. It cannot form more
NH3 NH4+ than four bonds because it has no d-
trigonal pyramidal ammonium ion orbitals to accept extra electron density,
bond angle 1070 bond angle 1090 that is, it cannot expand its octet.
Fig 9.5.1

Other Group (V) elements are able to expand the octet, for example phosphorous forms PCl 5.
Phosphorous and the rest of the Group (V) elements have accessible d – orbitals which allow
formation of more than four bonds.
 432

 With five electrons in the outer most shell, nitrogen can form a negative ion by accepting three
electrons. This ion, known as the nitride ion, N3-, exists in ionic compounds such as magnesium
nitride, Mg3N2.

1.1 Occurrence of nitrogen

Nitrogen is a diatomic element. It is a colourless and odourless gas which occupies about 79% of the
atmosphere by volume. It is the most abundant gas in the atmosphere. Nitrogen is also present in a large
number of compounds. It is one of the major elements present in biological molecules, for example
proteins.Nitrogen is obtained industrially from the distillation of liquid air. Its direct uses include
 to provide an inert atmosphere in reactions or processes that are sensitive to oxygen, for example
during the production of transistors
 Refrigerant
 Annealing stainless steel
 in oil extraction to force up oil under pressure

1.2 Ideality
Ideality is the extent to which a particular gas satisfies the properties expected of a gas in general.
At ordinary temperatures and pressures, N₂ closely resembles an ideal gas. This is because the forces of
attraction between the molecules are very weak Van der Waals forces. Because of this, forces of attraction
between the molecules are very weak and collisions are almost perfectly elastic, because when molecules
collide, they do not stick to each other. Also, since the molecules have very little tendency to stick to each
other, they are spread out so that the volume of a single molecule is negligible compared to the volume of
the container.
Nitrogen, like all gases, deviates from ideality at low temperatures and high pressures. When a sample of
Nitrogen is cooled, its particles come closer together so that the forces of attraction between the molecules
are stronger. Also, kinetic energy of the molecules decreases so that most of the times the molecules do
not move away from each other but remain associated by intermolecular attractions. At a sufficiently low
temperature, the molecules come so close that the sample becomes liquid. This happens at -2830C. Thus
nitrogen can be obtained from air by fractional distillation of the liquid.

1.3 Preparation of nitrogen in the lab

Nitrogen can be prepared at a small scale by the thermal decomposition of sodium azide, NaN3.
2 NaN3(s) → 2 Na(s) + 3 N2(s)
(Care is needed here since sodium azide is extremely poisonous. The sodium formed can also pose a fire
risk).
This reaction is the basis of the safety air bags found in some cars. When an impact occurs, a sensor
causes a certain chemical to burn. The heat released results in the rapid decomposition of sodium azide.
The bag is rapidly filled with nitrogen gas and provides a cushion so that the driver or passenger does not
hit against hard surfaces such as the steering wheel. The processes that occur are so fast that the bag is
completely filled with nitrogen approximately 5o milliseconds after a crash.

Q
What is the oxidation state of nitrogen in sodium azide?
 433

1.4 The Haber process for the manufacture of ammonia

Ammonia is commercially manufactured through the Haber process, which involves the equilibrium
N₂ (g) +3H₂ (g) ⇌ 2 NH₃ (g) ... ∆Hr = -94Kj
The operating conditions are

Pressure: 200 atmospheres

Temperature: between 450⁰C and 500⁰C
Catalyst: finely divided iron or powdered iron (III) oxide, Fe2O3

Justification for pressure used in the Haber process

Formation of ammonia is accompanied by a decrease in number of moles of gas. By Le Chatelier’s
principle, a high pressure should be used because this favours the side with the smaller number of moles,
that is, more ammonia would be formed. This explains why the Haber process employs a high pressure of
200atm.

Justification for temperature used in the Haber process

The forward reaction, that is, formation of ammonia, is exothermic. To obtain a high yield of ammonia,
low temperatures would have to be used. By Le Chatelier’s principle, lowering temperature favours the
exothermicside of the equilibrium, that is, formation of ammonia. In this way, the constraint of cooling is
removed by the release of heat energy.
However, in practice, the temperature used is not low, but is moderate. This is because low temperatures
would increase the time required to attain the equilibrium yield of ammonia, that is, it reduces the rate of
reaction. To make the reaction fast, high temperatures would be required, but by Le Chatelier’s principle,
this would decrease the equilibrium yield of ammonia. The actual temperature used (about 450⁰C), is
therefore a compromise between high and low temperature.

Justification for the use of a catalyst

One way to make a reaction fast without using a catalyst is to carry it out at very high temperatures. In the
Haber process, it has already been mentioned that a very high temperature would favour the reverse
reaction which is endothermic, thus reducing the yield of ammonia. Another problem associated with the
use of very high temperatures is the high cost of fuel that would be incurred. The process also becomes
expensive in terms of constant maintenance caused by the weakening of pipes by heat.
The temperature used in the Haber process is therefore relatively low, and the reaction would be very slow
without a catalyst. A catalyst makes the reaction faster under the relatively low operating temperature.
The catalyst used in the Haber process is finely divided iron, containing very fine particles to increase
surface area.
The conditions which are employed give a yield of only 15%. However, any unreacted gases are recycled to
give an overall yield of about 98%.

Fig 9.5.2 is a flow chart which summarizes the key stages in the Haber process.
 434

Fig 9.5.2 Flow chart of the Haber process

 N2 and H2 are cleaned and mixed in the ratio 1: 3. The mixture of gases is heated in a
heatexchanger.
 The converter converts N2 and H2 into ammonia. The converter has several beds containing
finely divided iron or powdered Fe2O3 as catalyst. Several catalytic beds are used to increase the
yield of ammonia. Any gases which are not converted in the first beds are passed onto the next
beds.
 Gases emerging from the converter are ammonia and unreacted N 2 and H2. These gases contain a
lot of heat energy, so they are passed back to the heat exchanger to recover the heat and thus
minimize wastage of energy.
 The gaseous mixture is passed into a condenser where it is cooled. NH3, which is the least ideal
gas in the mixture, easily liquefies since the molecules attract each other through hydrogen
bonding. The liquid ammonia is removed whilst unreacted N 2 and H2 gases are recycled.

About Haber and the Haber process

In 1908, Fritz Haber, a young German research chemist discovered that heating nitrogen and hydrogen gases
at 600atm using a suitable catalyst formed an equilibrium mixture containing ammonia. Prior to this
discovery, nitrogen from the atmosphere had no important uses in industrial chemical reactions because of
its inertness. Haber then made a prototype plant which could produce small amounts of ammonia. Haber
sold his rights to the ammonia process to BASF, a giant German manufacturing company. Carl Botsch,
working for BASF, found a method to scale up Haber’s table top ‘plant’ into a giant plant that could produce
thousands of tonnes of ammonia per year. The Haber process was also fine tuned so that it could produce
satisfactory yields at relatively low pressures and temperatures. Both Haber and Botsch won the Nobel Prizes
for chemistry in 1918 and 1931 respectively (The Haber process is sometimes referred to as the Haber -
Botsch process).
The production of ammonia made an interesting contribution to First World War. Now German did not have
to depend on other countries for food, since it could now greatly enhance the agricultural sector through the
manufacturing of nitrogen fertilizers. It also meant that Germany could now more than double its war effects
by producing explosives which it could not buy from other countries.

Source of hydrogen used in the Haber process

One source is the catalyzed reaction between methane and steam,
CH₄ (g) + H₂O (g)  CO (g) + H₂ (g)
The carbon monoxide produced can poison the catalyst, so it has to be removed from the hydrogen.
Production of hydrogen by this method uses less energy than the electrolysis of water which was used by the
BASF Company.
 435

Uses of ammonia
 Manufacture of nitrogen fertilizers such as ammonium nitrate.
 As a household disinfectant. Ammonia has an antibacterial effect.
 As a refrigerant
 Manufacture of explosives. The ammonia is first catalytically oxidized to nitric acid. Nitric acid is
then used in the synthesis of explosives such as TNT.

The key stages in the industrial synthesis of nitric acid

1. Gaseous ammonia is oxidized in oxygen at 900⁰C and in the presence of platinum or rhodium
(or a mixture of the two metals) .
4NH₃ (g) + 5O₂ (g) ⇌ 4NO (g) + 6H₂O (g) ... ∆H = -950Kj
2. NO is then oxidized to NO₂ by adding more oxygen
2NO (g) + O₂ (g) → 2NO₂ (g) ... ∆H = -114Kj
3. NO₂ then reacts with water to form nitric acid.
3NO₂ (g) + H₂O (l) → 2HNO₃ (aq) + NO (g) ... ∆H = -117Kj.
The process yields about 60% nitric acid. The concentration of the acid is raised by fractional
distillation.

1.5 Chemical reactions of nitrogen

Nitrogen is relatively inert because of the large energy of the N to N triple bond. A large amount of energy
is needed to break this bond during chemical reactions. Nitrogen only reacts at high temperatures since
the activation energy required to start the reactions is overcome by supplying heat energy.
The formation of ammonia by the Haber process has already been discussed. The use of a catalyst in this
process allows moderate temperatures to be employed (450 to 500 θC). Other processes which involve
nitrogen as a reactant include
 The formation of nitrogen dioxide and nitrogen monoxide (NOx) in the internal combustion
engine.
 The formation of NOx in the atmosphere during lightning flashes.
 Formation of magnesium nitride (Mg3N2) together with magnesium oxide during the combustion
of magnesium metal.
 Nitrogen fixing bacteria in soil have an enzyme which converts nitrogen into soluble inorganic
compounds. This process is known as nitrogen fixation.

1.6 Some important compounds of nitrogen

1.6.1 Ammonia
Ammonia is an important chemical manufactured by the Haber process. Its uses include
 Manufacture of nitric acid, whose uses include manufacture of nitrogen fertilizers (for
example ammonium nitrate), manufacture of explosives such as trinitrotoluene (TNT) and
the manufacture of organic dyes.
 As a refrigerant
 As a household disinfectant
 436

Properties of ammonia
Ammonia is a gas with a characteristic pungent odour. It dissolves easily in water, forming a weakly
alkaline solution. When ammonia is added to water, two things happen :
 Some of the ammonia molecules associate with water molecules through hydrogen bonding. This
is a physical process.

hydrogen bonds
H
N O
H H
H
H H O
H

 A smaller proportion of the ammonia molecules react with water in a Brønsted Lowry
neutralization reaction, to form a solution containing NH4+ and OH- ions.
NH3 (aq) + H2O (l) Ý NH4+ (aq) + OH-(aq) ... (i)

These two processes help to explain why ammonia is soluble in water. The solution formed can be
thought of as ammonium hydroxide, NH4OH . However, this compound cannot be separated from the
mixture. An attempt to separateNH4OH by evaporation results in equilibrium (i)shifting to the left,
resulting in ammonia gas being driven out. Equilibrium (i) lies well to the left, that is, ammonia dissolves
poorly in water. The reaction involves Brønsted Lowry neutralization in which ammonia acts as base
(proton acceptor), and water as an acid (proton donor). Like all Brønsted bases, ammonia contains a lone
pair which it uses to form a dative bond with an H⁺ ion from the acid.

Precipitation of metal hydroxides by dilute aqueous ammonia

Dilute ammonia can precipitate some metal ions out of solution, for example

Fe2+ (aq) Fe(OH) 2 (s)

NH3(aq)
light green dirty green
solution precipitate

The hydroxide ions which precipitate the metal come from the reaction of ammonia with water.
In some cases, the concentration of the hydroxide ions in aqueous ammonia is not large enough to cause
precipitation of the metal hydroxide, for example, calcium ions may not be precipitated in this way.

Ammonia as a complexing agent

Ammonia is able to react with transition metal ions to form complexes. In these reactions, ammonia acts
as a ligand. A ligand is an electron rich species which is attracted and forms a dative bond to a metal ca-
tion. Transition metals are able to form complex ions because of the presence of partially filled d orbitals
to accept the electron density from the ligands. When aqueous ammonia is added gradually to a blue so-
lution containing copper (II) ions, a light blue precipitate is formed which dissolves in excess ammonia to
form a deep blue solution. The initial reaction is the precipitation of copper (II) hydroxide by the hydrox-
ide ions present in dilute ammonia. When the ammonia solution is added in excess, ammonia ligands re-
place the OH groups forming a soluble complex with copper (II) ions.
 437

Cu2+ (aq) + 2OH- (aq)  Cu(OH)2(s) [Cu(NH3)4(H2O)2]2+ (aq)

light blue from NH4OH light blue ppt xs NH3 (aq) deep blue solution
solution

Reactions of ammonia with acids

Ammonia reacts with acids to form ammonium salts. In these reactions, NH 3 uses its lone pair to form a
dative bond to an electron deficient H+ ion, which contains a vacant 1s orbital.

H+ vacant 1s orbital

+
H

N N
H H
H
H H H

ammonia ammonium

 Ammonia is trigonal pyramidal, with a bond angle of 107 0. This corresponds to three bond pairs
and one lone pair. The ammonium ion has four bond pairs and no lone pairs. Its shape is
therefore tetrahedral, with a bond angle of 1090.
 The fourth bond in the ammonium ion is a dative (co-ordinate bond). That is, only one atom
provides both electrons of the bond.
 In the reaction above, ammonia acts as a base because it accepts a proton. The ammonium ion is
acidic because it can release a hydrogen ion, forming ammonia (reverse reaction). NH3 and NH4+
therefore constitute a conjugate acid - base pair.

1.6.2 Oxides of nitrogen

Nitrogen dioxide and nitrogen monoxide (commonly referred to as NOx) have been associated with
environmental processes that lead to atmospheric pollution and depletion of the ozone layer. Sources of
NOx are both natural and attributable to human activities.
 Lightning flashes provide the activation energy required to break the very strong triple bond in
nitrogen and initiate the reaction with oxygen.
 Exhaust fumes from the internal combustion engine contain nitrogen monoxide and nitrogen
dioxide. The very high temperatures that develop in the engine provide the activation energy for
the oxidation of atmospheric nitrogen by oxygen.
N2 (g) + O2 (g)  2NO (g)
NO is produced in greater amounts than NO2. This is because there is a limited amount of
oxygen in the internal combustion engine. However, once it enters the atmosphere, NO is further
oxidized to NO2.
NO2 (g) + ½ O2 (g)  NO2 (g)
NOx has been blamed for environmental problems such as formation of acid rain and photochemical
smog, and for the depletion of the ozone layer.
NOx act as catalyst for the processes that form acid rain, for example, NO 2 may participate in the following
reaction scheme.

NO2 (g) + SO2 (g)  NO (g) + SO3 (g) ... (i)

NO (g) + ½ O2 (g)  NO2 (g) ... (ii)
 438

In reaction (i), NO2 is reduced by sulphur dioxide, which is in turn oxidized to SO 3. In step (ii), NO2 is
recovered when NO reacts with atmospheric oxygen. The NO 2 produced in (ii) is recycled back to step (i),
where it converts more SO2 to SO3.
 The formation of SO3 is a significant step in the formation of acid rain. NO 2 and SO2 are only
weakly soluble in water, so their direct contribution to acid rain is slight. SO 3 has a very high
solubility in water, in which it forms a solution of sulphuric acid
SO3 (g) + H2O (l)  H2SO3 (aq)
Note that this is not a redox reaction. Itis simply conversion of an acid anhydride (SO3) to an acid
hydride (H2SO4). Acid rain has adverse environmental effects, including destruction of
vegetation, buildings, metal structures and the killing of aquatic animals. Acid rain also mobilizes
toxic ions in soil, for example, Al3+ ions can be released when acid rain dissolves aluminium oxide
present in the soil. These ions can be carried into water bodies resulting in the death of aquatic
organisms such as fish.
 The ability of NO and NO2 to participate in atmospheric processes is a result of their electronic
structures. Both molecules are free radicals, that is, species which contain an odd total number of
valence electrons. NO contains 11 valence electrons (5 from nitrogen + 6 from oxygen), whilst NO 2
contains 17. The result is that one electron in the outer shell is inevitably unpaired. This odd
electron causes the molecules to be very reactive (that is, to be unstable) as they seek to attain
electronic states in which all valence electrons are paired. NO is one of the chief culprits in the
destruction of the ozone layer, according to the equation
NO (g) + O3 (g)  NO2 (g) + O2 (g).
Halogen atoms, for example, Cl, which are also free radicals, also contribute to the depletion of
the ozone layer.

Preventing NOx pollution

Emission of NOx and other pollutants from the internal combustion engine can be minimized by fitting a
catalytic convertor into the exhaust pipe of the vehicle (Fig 9.6.4). The catalytic convertor converts NO,
NO2, CO, unburnt carbon (soot) and unburnt hydrocarbons to products which are harmless.

Fig 9.6.4 The catalytic convertor

CO, soot (carbon) and hydrocarbons (HC) are oxidized to carbon dioxide and water.
C(s) + O2 (g) → CO2 (g)
 439

2CO(s) + O2 (g) → 2CO2 (g)

CxHy (g) + (x + y/4) O2→ xCO2 (g) + y/2 H2O
Meanwhile, NO and NO2 are reduced to nitrogen gas by combining with CO.
2NO (g) + 2CO (g)→ N2 (g) + 2CO2
This reaction therefore removes two pollutants at once.
The convertor makes use of a mixture of expensive metals (platinum, palladium and rhodium) coated on
the surface of a honeycomb structure to maximize surface area. The catalysis involved is therefore
heterogeneous.
 The catalytic convertor has not yet gained popularity in developing countries because it is
expensive (it uses three of the most expensive metals)
 The convertor is poisoned by lead. Cars fitted with catalytic convertor must run on unleaded
petrol. (In fact, the use of leaded petrol has greatly declined because of the pollution problems
associated with lead compounds released from the internal combustion engine)

1.6.3 Nitric acid

This is a very important industrial chemical prepared by the catalytic oxidation of ammonia. The overall
reaction is
NH3 (g) + 2O2 (g)  HNO3 (aq) + H2O (l)
The process is carried out at 9000C, using a platinum or rhodium (or a mixture of both) catalyst. Some
uses of HNO3 have already been outlined. In addition, HNO 3 acid is used to acidify solutions where other
acids would result in precipitation of some ions, for example, sulphuric acid may cause precipitation of
Ba2+ and Pb2+ as BaSO4 and PbSO4 respectively.
Pure nitric acid is colourless but it soon attains a yellowish taint due to formation of NO 2 by de-
composition. Dilute HNO3 shows the usual chemical properties expected of a strong acid. However,
concentrated HNO3 is also an oxidizing agent. In fact, it is strong enough to oxidize copper metal to
copper (II). HNO3 is itself reduced to NO2 (red brown fumes).

Cu(s) + 4HNO3 (aq)  Cu (NO3)2(aq) + 2NO2 (g) + 2H2O (l)

At the beginning of the experiment, red brown fumes with a disagreeable and choking odour are produced
(Fig 9.65).This gas is NO2, which is poisonous; the experiment should be carried outin a fume hood.

Fig 9.6.5 The action of concentrated HNO3 on copper

metal.
 440

A greenishsolution is formed, which contains a soluble complex of Cu 2+ and nitrate ions.

The concentration of HNO3 soon decreases, and so does the production of NO 2. In fact, at low concentra-
tions of HNO3, NO is produced instead of NO2. The greenish solution is converted to a light blue solution
of copper (II) nitrate by the addition of more water (dilution).

1.7 Organic nitrogen fertilizers

Nitrogen in the form of soluble nitrate ions is an important nutrient required for normal growth of plants.
Common nitrogen based fertilizers include ammonium sulphate, ammonium nitrate and urea
(CO(NH2)2). All three fertilizers are made from the neutralization of concentrated ammonia by an acid.
NH3 + H2SO4(NH4)2SO4
NH3 + HNO3NH4NO3
2 NH3 + CO2 (g) CO(NH2)2 + H2O
NH4NO3 has the following advantages over the other two fertilizers
 It dissolves well in soil water, thus immediately releasing nutrients to plants.
 It has a greater content of nitrogen.
Its major disadvantages are
 It is explosive
 It easily absorbs moisture to form clumps
 The two factors above make it difficult to store
 Because of its high solubility, it may dry up crops by withdrawing water from tissues (through
osmosis).
 It does not stay for a long time in the soil.
The use of nitrogen fertilizers has been associated with the pollution of water bodies. Eutrophication is a
form of water pollution in which there is a sudden bloom of water plants and algae due to increased levels
of nitrate in water. This proliferation of plants and algae cause depletion of oxygen in water in two ways.

 A thick layer of vegetation on the surface of water prevents sunlight from reaching the bottom.
As a result, plants that grow at the bottom of the water bodies cannot photosynthesize to
produce oxygen.
 Some algae and water plants soon die, and their decay uses up oxygen in water.

The human body has a tolerance to moderate concentrations of nitrate ions in water. However, babies are
poisoned by concentrations of NO3- that are greater than 100ppm. The ability of their blood to carry
oxygen is greatly reduced, causing the ‘blue baby syndrome’.

9.5.2 Sulphur
Sulphur, in Group (VI), has the electronic configuration 1s2 2s2 2p6 3s2 3p4. This configuration has
important consequences on the chemistry of sulphur.
 Having six electrons in the outer most shell, it can easily form a negative ion by accepting two
electrons from a metal. A large number of metals form sulphides, some of which are important
ores found in the earth’s crust.
 Sulphur shows a range of oxidation states, up to +6, corresponding to participation of all six
valence electrons.
 441

Sulphur is also able to expand its octet because of the availability of energetically accessible d orbitals to
accommodate some of the electron density. Examples of compounds in which sulphur has more than an
octet of electrons in its outer shell include SF 6 and SO3, whose structures are shown below.

F F
O
S S O
F O
F
SO3 : trigonal planar
F bond angle = 1200
SF6 : octahedral
bond angle = 900

2.1 Occurrence of sulphur

Elemental sulphur, which is a yellow solid, exists as S8 molecules. Sulphur is found in many compounds;
including biological molecules such as proteins (not all proteins contain sulphur). It is also found in
volcanic eruptions, meteorites and medicines such as Epsom salts (MgSO 4). H2SO4 is one of the most
important and well known compounds of sulphur.

2.2 Reaction with O2

Sulphur burns readily with a blue flame, forming sulphur dioxide, which is a colourless gas with a choking
smell.
1/8 S8 (s) + O2 (g) → SO2 (g)
This reaction occurs in volcanoes, and partly accounts for the presence of SO 2 in the atmosphere.
SO2 is an important raw material in the manufacture of sulphuric acid. It is also used in the food industry
as a preservative. It is added in very small amounts to some sauces and drinks to kill bacteria. Its
antibacterial action can be explained in two ways
 It reacts with water to form an acidic solution of sulphrous acid, H 2SO3. This lowers pH and
causes bacteria to die.
 Some of the sulphrous acid is oxidized by oxygen to form sulphuric acid. The removal of oxygen
slows down decay processes that are caused by bacteria.
The concentration of sulphrous and sulphuric acids in the food is too little to have any harmful effects on
humans.

2.3 Sulphuric acid

Sulphur is an important raw material in the manufacture of sulphuric acid by the contact process.
The raw materials for this process are
 Sulphur dioxide from the burning of sulphur or roasting of metal sulphides (such as iron pyrite)
in air.
 Oxygen from the fractional distillation of liquid air.
The two gases are cleaned, mixed in the ratio of 2 volumes of SO₂ to 1 volume of oxygen and passed over a
catalyst. One catalyst commonly used is vanadium pentoxide (vanadium (V) oxide - V₂O₅) because it is
cheaper than metals such as platinum. Vanadium pentoxide is also not easily poisoned.
The following reaction takes place
 442

2SO₂ (g) + O₂ (g) ⇌ 2SO₃ (g) ... -197Kj

The operating conditions used are

Temperature: 450⁰C
Pressure : 1.0 atm (atmospheric pressure)
Catalyst: vanadium pentoxide.

By Le Chatelier’s principle, high yields of SO₃ would be achieved by using low temperature since the for-
ward reaction is exothermic. However, this would slow the reaction, so in practice a compromise temper-
ature of about 450⁰C is used.
The formation of SO₃ is accompanied by a decrease in the number of moles of gas . By Le Chatelier’s prin-
ciple, high yields of SO₃ would be obtained by carrying out the process at high pressures. In practice, the
reaction is carried out at atmospheric pressure. This is because the temperature used, 450⁰C, gives a very
high yield (about 97%) at atmospheric pressure, so there is no need to use high pressures.
The formation of SO₃ is an exothermic process. The use of heat exchangers between catalyst beds keeps
the temperature constant at 450⁰C. If this was not done, there would be a buildup of heat, with two con-
sequences
 the yield of SO3 decreases since high temperatures favour the reverse reaction, which is endother-
mic.
 pipes and equipment are gradually weakened by heat, so this would increase maintenance costs.

The SO₃ gas produced is then absorbed in absorption towers containing concentrated sulphuric acid. This
results in the formation of oleum.
SO₃(g) + H₂SO₄(l) → H₂S₂O₇(l)
oleum

Sulphuric acid, when needed, is then obtained by hydrolysis of oleum in water.

H₂S₂O₇(l) + H₂O(l) → 2H₂SO₄(aq)
One alternative is to absorb the sulphur trioxide in water, which directly produces sulphuric acid.
SO3(g) + H2O(l)  H2SO4(aq)
This process is not satisfactory since the reaction is so exothermic that the heat produced causes the
sulphuric acid to form as a vapour. Condensing the vapour back to liquid is difficult. The flow diagram is a
flow chart summarizing the contact process.
 443

Q
What is the justification for the operating temperature used in the contact
process.

A2SO₂ (g) + O₂ (g) ⇌ 2SO₃ (g) ... -197Kj

Since the forward reaction is exothermic, the yield of SO 3 would be increased by cooling.
However, a very low temperature would slow the reaction. The actual temperature used
is therefore a compromise between the low temperature required to increase yield of
SO3 and the high temperature required to increase the rate of reaction.

Properties of sulphuric acid

 Concentrated sulphuric acid is a viscous and oily liquid. Its viscosity is a result of hydrogen bonds
which are present between its molecules. Very concentrated sulphuric acid also contains some
molecules of oleum. The following diagrams show hydrogen bonding in sulphuric acid, and the
structure of oleum.

oleum
O O O O
O O O O
S S
S x S
H O O H O O H O
HO OH
H
hydrogen bond Suggest the size of bond angle x.

 Sulphuric acid is denser than water, so when it is added to water, it tends to sink, meanwhile
dissociating to release hydrogen ions. The reaction of sulphuric acid with water is very exothermic
and can be explosive. Risk is kept to a minimum by adding the acid to water, because as it sinks,
the reaction occurs gradually. Adding water to concentrated sulphuric acid is dangerous. Water,
being less dense, will briefly settle on the surface of the acid. A violent reaction occurs at the
junction of the two solutions, causing the liquid at the surface to boil, throwing out a hot and
acidic spray.
Always add concentrated sulphuric acid to water, not water to concentrated sulphuric acid.

Uses of sulphuric acid

 As electrolyte in lead acid accumulators
 Washing metal electrodes before they are used in electrolytic processes.
 Manufacture of ammonium sulphate fertilizer.
 Manufacture of explosives
 Manufacture of paints and dyestuffs.
 444

2.4 Pollution by SO2

SO2 is a well known air pollutant. It irritates the respiratory system and may trigger attacks in asthmatic
people. However, the major environmental hazard associated with SO 2 is its contribution to the formation
of acid rain. This can happen in two ways:
 SO2 dissolves directly in rain water, to form a dilute solution of sulphrous acid, H 2SO3.
SO2 (g) + H2O (l) → H2SO3 (aq)
Note that this is not a redox reaction. The oxidation state of sulphur is the same in SO2 and
H2SO3. As the rain passes down through the atmosphere, some H2SO3 is oxidized to sulphuric
acid
H2SO3 (aq) + ½ O2 H2SO4 (aq)
 Some sulphur dioxide molecules are oxidized in the atmosphere, to form sulphur trioxide. The
reaction is catalyzed by oxides of nitrogen, as already discussed.
SO2 (g) + ½ O2→ SO3 (g)
This is reaction is more important in the formation of acid rain because sulphuric acid is more
soluble in water than sulphrous acid (sulphrous acid tends to dissociate to form SO 2 and water).
SO3 then dissolves in rain water to form sulphuric acid.

Some effects of acid rain have already been discussed.

Sources of atmospheric sulphur dioxide

Air naturally contains sulphur dioxide due to natural phenomena such as volcanic eruptions. However, in
recent years, human activities have greatly increased the concentration of this gas in the atmosphere.
These activities include
 the combustion of sulphur containing fuels, for example coal and oil products. Coal and oil were
made millions of years ago from the remains of plants and animals. The presence of sulphur in
these fuels can be traced back to the proteins that were present in the plant and animal matter.
 Industrial activities, such as the extraction of metals by roasting of sulphur containing ores such
as copper iron sulphide, CuFeS.

Methods of minimizing SO2 pollution

 Cleaner sources of fuels or energy should be used, for example, ethanol.
 Exhaust gases from industries and power stations can be treated with chemicals that can absorb
SO2 before it is emitted into the atmosphere. AFlue Gas Desulphurization (FGD) plant, which
contains heated powdered limestone (powdered to increase surface area), can be fitted to the
chimney stacks. Flue gases containing sulphur dioxide, for example from the combustion of coal,
are absorbed into the hot limestone powder and react with CaCO 3, to form calcium sulphite.
SO2 (g) + CaCO3(s) → CaSO3(s) + CO2 (g)
Further oxidation of calcium sulphite occurs, to produce CaSO 4, which can be used in the manu-
factureof plaster board or cement.
CaSO3(s) + ½ O2 (g) → CaSO4(s)

 Sulphur in crude oil can be removed by pumping in hydrogen and using a suitable metallic salt
catalyst. Under these conditions, the organic sulphur containing impurities are reduced by hydro-
 445

gen to hydrogen sulphide.

2RSH (g) + H2 (g) → R2 (g) + 2H2S ... (i)
The hydrogen sulphide is then burnt in a limited amount of oxygen, which converts it to a
mixture of sulphur and sulphur dioxide
4H2S (g) + 4O2→ 4H2O + 2S(s) + 2SO2... (ii)
The sulphur dioxide produced in this reaction is reacted with H 2S that has not reacted in step (i),
to produce more sulphur. This reaction is catalyzed by Al 2O3.
SO2 (g) + 2H2S (g) → 2H2O (l) + 3S(s)
Sulphur which is obtained in this process has important uses, for example, the manufacture of
sulphuric acid.

Questions, solutions and discussions

Q1Sulphuric acid is used in many industrial processes of major importance.

The first stage in the manufacture of sulphuric acid is to pass air over burning sulphur.
The emerging gas has the following composition by volume.
sulphur dioxide 10%
sulphur trioxide 0.2%
oxygen 10%
nitrogen etc. 79–80%

(a) (i) Write an equation for sulphur burning in air.

(ii) Suggest why the air is passed so fast that only half the oxygen is used.

The emerging gas is passed over a catalyst maintained at 450–550 °C in the reaction
chamber.

(b) Name the catalyst used in the Contact process.

(c) The high yield is only achieved under certain conditions.

After each condition explain why this leads to an increased yield of sulphur trioxide.

(i) There needs to be an excess of air in the reacting gas mixture.

(ii) The catalyst needs to be cooled.

 446

(iii) The air used to burn the sulphur must be as clean as possible.

Sulphur trioxide is formed in 98% yield; 2% of sulphur dioxide remains unconverted.

2SO2(g) + O2(g) ∏2SO3(g) ΔH = –197 kJ mol–1
(d)In modern plants, nearly all the SO2/SO3 mixture is absorbed but up to 0.05% by
volume of SO2 may be allowed to pass into the atmosphere through a chimney stack.

Give two reasons why SO2 should not be discharged into the atmosphere.

(e) (i) When concentrated sulphuric acid is warmed with solid sodium chloride, mistyfumes are
produced.

Identify the fumes

Write an equation for the reaction

(ii) When concentrated sulphuric acid is warmed with solid sodium iodide, purple
fumes are produced.

Identify the fumes. 9701/02/M/J/02

Solutions
(a)(i)S + O2 SO2

(ii)The unused oxygen is required for the next stage, which is the conversion of SO 2 to SO3.

(b) Vanadium (V) oxide, V2O5

(c) 2SO2(g) + O2(g) ∏2SO3(g) ΔH = –197 kJ mol–1 … (I)

(i) A large concentration of oxygen drives equilibrium (I) to the right, increasing the yield of
SO3.

(ii) Since the reaction is exothermic, by Le Chatelier’s principle, high temperature would
decrease the equilibrium yield of SO3 by favouring the reverse reaction, which is
endothermic. The catalyst therefore needs to be cooled so that the forward reaction is
favoured.

(iii) The catalyst is easily poisoned by impurities in air.

(d) Sulphur dioxide is a respiratory irritant and may trigger attacks in asthmatic people.
 447

Sulphur dioxide leads to the formation of acid rain which destroys buildings, metal structures,
vegetation and aquatic life.

(e)(i) HCl
NaCl + H2SO4 HCl + NaHSO4
OR 2NaCl + H2SO4 2HCl + Na2SO4

(ii) Iodine

Q2Ammonia is manufactured from nitrogen and hydrogen by the Haber process.

Hydrogen is usually obtained by reacting methane and steam; the by-product is carbon
monoxide.

(a) Construct a balanced equation for this production of hydrogen.

The reaction between nitrogen and hydrogen is exothermic and incomplete.

(b) (i) Write an equation for the Haber process.

(ii) State the three conditions necessary for the efficient working of a Haber process
plant.

(iii) Draw a flow diagram to show how the gases pass through the plant. The part
where the ammonia is formed should be called the converter. Label the flow diagram to
explain the process.

(c) Explain why the pressure you have quoted in (b)(ii) is used.

(d)Most of the ammonia produced which is not used as fertilizer, is oxidized to nitric acid,
HNO3.

Construct an equation for the oxidation of ammonia by atmospheric oxygen to form

nitric acid.

(e) Urea, CO(NH2)2, is a naturally occurring substance which can be hydrolyzed with water
to form ammonia according to the following equation.
H2O(l) + CO(NH2)2(aq) →CO2(aq) + 2NH3(aq)
The standard enthalpy changes of formation of water, urea, carbon dioxide and ammonia
(in aqueous solution) are given in the following table.

Use these data to calculate the standard enthalpy change for the hydrolysis of urea .
 448

Compound ΔHθf / Kj mol-1

H2O (l) -287.o

Co (NH2)2(aq) -320.5

CO2 (aq) -414.5

NH3(aq) -81.0

Solutions
(a) CH4 + H2O  3H2 + CO

(b)(i) N2 + 3H2∏ 2NH3

(ii) - pressure : >200 atm, temperature : 4500C to 5000C, Catalyst : Fe or Fe2O3

(iii)

(c)N2 + 3H2∏ 2NH3

The equation shows that the product side has less moles of gas than the reactant side. The reaction is
therefore accompanied by a decrease in pressure. In the Haber process, high pressure is employed as
this favours the side with the smaller number of moles, that is, the formation of ammonia. According
to Le Chatelier’s principle, increasing pressure favours the side which results in a decrease in
pressure, that is, the side with less moles of gas.

(d) NH3 + 2O2 HNO3 + H2O

(e) 31 Kj mol-1. The working is left as an exercise to the reader.

 449

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 9.5in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

1.When hydrocarbons such as petrol or paraffin wax are burned in an excess of air in alaboratory,
carbon dioxide and water are the only products.
When petrol is burned in a car engine, nitrogen monoxide, NO, is also formed.

(a) Explain how NO is formed in an internal combustion engine but not formed when a small sample
of petrol is burnt in an evaporating basin.

The engines of modern motor cars have exhaust systems which are fitted with catalyticconverters
in order to reduce atmospheric pollution from substances such as NO.

(b)(i)State three more pollutants, other than CO2 and NO, that are present in the
exhaust gases of a car engine.

(ii) What is the active material present in the catalytic converter?

(iii) Write one balanced equation to show how NO is removed from the exhaust gasesof a car
engine by a catalytic converter.

NO is also formed when nitrosyl chloride, NOCl, dissociates according to the following equation.
2NOCl (g)∏ 2NO(g) + Cl2(g)
Different amounts of the three gases were placed in a closed container and allowed to cometo
equilibrium at 230 °C. The experiment was repeated at 465 °C.
The equilibrium concentrations of the three gases at each temperature are given in the following
table.

Concentration / mol dm-3

Temperature / 0C NOCl NO Cl2

230 2.33 x 10-3 1.46 x 1o-3 1.15 x 10-2

465 3.68 x 10-4 7.63 x 10-3 2.14 x 10-4

(c) (i) Write the expression for the equilibrium constant, Kc, for this reaction. Give the units.

(ii) Calculate the value of Kc at each of the temperatures given.

(iii) Is the forward reaction endothermic or exothermic? Explain your answer.

(d)The temperature of the equilibrium was then altered so that the equilibriumconcentrations of
NOCl and NO were the same as each other.
 450

What will be the effect on the equilibrium concentration of NOCl when the followingchanges
are carried out on this new equilibrium? In each case, explain your answer.

(i) The pressure of the system is halved at constant temperature.

(ii)A mixture of NOCl (g) and NO (g) containing equal numbers of moles of each gas introduced
into the container at constant temperature. 9701/02/M/J/08

2Nitrogen makes up about 79% of the Earth’s atmosphere. As a constituent element ofproteins, it is
present in living organisms.
Atmospheric nitrogen is used in the Haber process for the manufacture of ammonia.

(a) Write an equation for the formation of ammonia in the Haber process.

(b)The Haber process is usually carried out at a high pressure of between 60 and 200 atmospheres .

State two further important operating conditions that are used in the Haber process.
For each of your conditions, explain why it is used.

(c) State one large-scale use for ammonia, other than in the production of nitrogenousfertilizers.

(d) The uncontrolled use of nitrogenous fertilizers can cause environmental damage tolakes and
streams. This is known as ‘eutrophication’.

What are the processes that occur when excessive amounts of nitrogenous fertilizers get into
lakes and streams?

In many countries, new cars have to comply with regulations which are intended to reducethe
pollutants coming from their internal combustion engines.
Two pollutants that may be formed in an internal combustion engine are carbon monoxide,CO, and
nitrogen monoxide, NO.

(e)(i)Outline how each of these pollutants may be formed in an internal combustionengine.

(ii) State the main hazard associated with each of these pollutants.

Pollutants such as CO and NO are removed from the exhaust gases of internal combustionengines by
catalytic converters which are placed in the exhaust system of a car.

(f) (i) What metal is most commonly used as the catalyst in a catalytic converter?

(ii) Construct one balanced equation for the reaction in which both CO and NO areremoved
from the exhaust gases by a catalytic converter.

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
 451

9.6 AN INTRODUCTION TO THE

CHEMISTRY OF THE TRANSITION
ELEMENTS

The Transition elements are found in the d-block of the Periodic Table. They have a number of chemical
and physical properties which distinguish them from main group metals such as calcium.

9.6.1What is a transition element?

A transition element has been defined by some as any element which occupies the d -block of the Periodic
Table. However, this is hardly a definition but a general description of location.
A more informative definition of a transition element is:
... a d-block metal that forms at least one ion or compound in which the d orbitals are
partially filled.

This definition excludes some metals which are found in the d- block of the periodic table, such as Sc and
Zn. Scandium forms +3 compounds in which all the d- orbitals are empty (d0). Zinc forms +2 compounds
in which all the d- orbitals are fully occupied (d10). Compounds of these elements tend to be white when
solid or colourless in solution. In this regard they differ from the compounds of transition elements which
are coloured.

9.6.2Electronic structure of the transition elements

The transition elements are characterized by occupancy of the d orbitals. From Sc to Zn (first row of the
transition elements), the number of d electrons increases by one from one element to the next.
There are five degenerate orbitals in a d sub shell, designated dxy, dxz, dzy, dz2 and dx2-y2. Each orbital
carries a maximum of two electrons, so the d sub shell has a maximum capacity of 10 electrons. This
maximum occupancy is found at copper and zinc.
The first three orbitals (dxy, dxz, dzy) each have four lobes that are aligned between the axis, for example,
the dxy has lobes oriented between the x and y axis.
The remaining two d orbitals form their own set (in
terms of geometry) in that they have lobes that are
directed along the axis, as shown below.

Fig 9.6.1 The dxy, dxz and dzy orbitals

have lobes that are directed between the
axis.
Fig 9.6.2 The dz² and dx2-y2 orbitals have lobes that are
directed along the axes.
 452

A transition element has the general configuration [Ar] 4sx3dn, where x is 2, (except in Cr and Cu where
it is 1) and n = 1, 2, 3 ... 10 (but cannot be 4 or 9).

Element Configuration Illustration

Sc [Ar] 3d14s2
[Ar] 4s2

Ti [Ar] 3d24s2 [Ar] 4s2

V [Ar] 3d34s2 [Ar] 4s2

Cr [Ar] 3d54s1 [Ar] 4s1

Mn [Ar] 3d54s2 [Ar] 4s2

Fe [Ar] 3d64s2 [Ar] 4s2

Co [Ar] 3d74s2 [Ar] 4s2

Ni [Ar] 3d84s2 [Ar] 4s2

Table 9.6.1 Electronic

Cu [Ar] 3d104s1 [Ar] 4s1
configurations of the
transition elements from
Zn [Ar] 3d104s2 [Ar] 4s2 Sc to Zn

The d4 and d9 configurations do not exist in a neutral transition metal atom. These two configurations
would have been expected in Cr and Cu respectively. Instead of having d⁴, Cr has d⁵. Instead of having d⁹,
Cu has d10.
Table 9.6.1 shows the electronic configurations of the first row transition elements, from scandium to
zinc.

Which one is the valence shell?

The valence shell is the 4s, not the 3d. There are two principal quantum numbers involved here, 4 and
3. The shell with the higher principal quantum number is the valence shell, which is the 4s in this case.
Some readers may recall that when arranging the orbitals in terms of energy, the 4s comes before the 3d
... 4s 3d...
As explained in section 2, readers should note that this order is what we would expect if we arranged the
empty orbitals in terms of energy. However, when electrons start to enter the d orbitals, they repel the 4s
electrons. This causes the 4s shell to move away from the nucleus, that is, it becomes higher in energy
than the 3d sub shell. The fact that the 4s is the valence shell explains why the +2 oxidation state is so
common among the transition elements. It corresponds to the loss of the two 4s electrons, which are fur-
thest from the nucleus and experience the least attraction from the nucleus.
 453

An important note
Even though the 4s shell is higher in energy, it is so energetically close to the 3d that in chemical reactions, the two
shells behave as one shell. This has important consequences to the chemistry of the transition elements, as explained
later.

The configurations of Cr and Cu

We would have expected the following configurations for Cr and Cu, respectively
Cr: [Ar] 4s23d4 Cu: [Ar] 4s23d9
The actual configurations are formed by transferring an electron from the 4s orbital to a 3d orbital. By so
doing, Cr attains a configuration in which the d orbitals are exactly halffilled (with 5 electrons). Copper
attains a configuration in which the d orbitals are exactly filled with 10 electrons.

There is an extra stability associated with an exactly half filled or exactly filled sub shell. This
stability should be explained in terms of the resulting symmetric occupancy of the sub shells by
electrons, that is, there are no regions which carry more electrons than others.

9.6.3Physical properties of the transition elements

Table 9.6.2 summarizes some of the physical properties of the transition elements.

Ionization energies
Element Density/ m.p./0C b.p.0C Metallic
gcm-3 radius/nm 1st 2nd 3rd

Sc 2.99 1541 2831 0.164 631 1235 2389

Ti 4.50 1660 3287 0.147 658 1310 2653

V 5.96 1890 3380 0.135 650 1414 2828

Cr 7.20 1857 2670 0.129 653 1592 2987

Mn 7.20 1244 1962 0.137 717 1509 3249

Fe 7.86 1535 2750 0.126 759 1561 2958

Co 8.90 1495 2870 0.125 758 1646 3232

Ni 8.90 1455 2730 0.125 737 1753 3394

Cu 8.92 1083 2567 0.128 746 1958 3554

Zn 7.14 420 907 0.137 906 1733 3833

Table 9.6.2 Physical properties of the transition elements

In general, transition elements have the following physical properties

 454

1. Generally small atomic radii.

2. High densities and melting points.
3. Hard and rigid
4. High ionization energies.
5. Excellent electrical conductivities
6. Paramagnetic

3.1 Transition metals generally have small atomic radii and

high densities

Explanation
 Large nuclear charge. The large number of protons in the nucleus results in shells being
attracted strongly towards the nucleus. This causes the atoms to shrink.
 Poor shielding effect of the d orbitals. Because of their shape, the d orbitals poorly shield
the outer 4s shell from the nucleus. As a result, the outer shell feels a strong attraction by the
nucleus, to which it is attracted, resulting in shrinking of size.

The high densities of the transition metals are a direct consequence of the small atomic radii and heavy
nucleus (large number of protons and neutrons).
 the atoms have large masses
 and yet their size is small.
Now, density is given by m/V.This formula shows that
1.density varies directly as mass. The larger the mass, the higher the density.
2.density varies inversely as volume. The smaller the volume, the higher the density.
The atoms of transition elements are quite small compared to their mass. The effect of small atomic
radii (volume) and large mass is to increase density, that is, each atom has a large mass packed in a
small volume.

Trend in atomic radii across the first row transition elements

If you study Table 9.6.2 you will notice that the radii of the transition elements do not change much across
the period, from Sc to Zn. We expect atomic radii to decrease across the row in response to increasing
nuclear charge. As the number of protons in the nucleus increases, so does the attractive influence of the
nucleus for the outer most shell, so the atoms shrink in size. The decrease in atomic radii does occur but
not as rapidly as happens in the non transition periods such as Period 3.
This slow and gradual decrease in atomic size is due to the fact that across the row, electrons enter a
penultimate (underlying) 3d shell, thus shielding the outer 4s sub shell from feeling the full attractive
influence of the nucleus. In other words, the increase in nuclear charge has a small effect on the outer 4s
shell, because this shell is prevented by the 3d electrons from experiencing the full effect of the nuclear
charge.
 455

The outer 4s shell is fully occupied

so electrons enter the penultimate

3d shell

Fig 9.6.3 In the transition elements, electrons enter the penultimate 3d shell. The 4s
shell is therefore shielded by the 3d electrons.

3.2 Transition elements have relatively high ionization

energies which change only gradually across the period
Ionization energy measures how strongly valence electrons are held to the atom. In transition elements,
the outermost electrons are firmly held for two reasons
 The atoms are small, so the valence electrons are close to the nucleus and they feel a powerful
attraction by protons.
 The charge density in transition metal atoms is high. The large number of protons in the
nucleus attracts the valence electrons strongly.

Because of these reasons, the valence electrons are difficult to remove; a very large amount of energy
would be required to do so. Notice that the variation in first and second ionization energy across the first
row of transition elements is only gradual, that is, the increase in ionization energy from one element to
the next is very small, compared to non transition elements.
Generally, ionization energies increase across the first row transition elements, in response to increasing
nuclear charge. Each additional proton increases strength of attraction between the nucleus and the
valence electrons. This increase in ionization energy is not so sharp for a reason already explained:

Across the period, electrons are being added into a penultimate 3d sub shell which shields the outermost
4s electrons from feeling the full attractive influence of the nucleus. This screening (shielding)of theouter
shell by the 3d electrons implies that adding a single proton to the nucleus does not have a large effect
on the size of the attractive force felt by the valence shell.

However, the change in third and fourth ionization energies is rapid across the period is rapid. This is
because this time electrons are being removed from the d-sub shell, which experiences very little shielding
from the remaining electrons (Fig 9.6.4).
 456

ionization energy /
Kjmol-1 IE (3)
3500

2000
IE (2)

IE (1)
500

21 25 30 Fig 9.6.4 Trend in first, second

and third ionization energies
Sc Mn Zn
across the first row of transition
proton number elements

Note that the third ionization energy of Fe is lower than expected because the electron being removed is
from a paired orbital where it experiences repulsion from the other electron.

3.3 Transition elements are excellent conductors of electricity

Conductivity in a metal is a result of delocalized electrons. These mobile electrons move in response to a
potential difference between two points of a conductor. The greater the number of electrons in the deloca-
lized sea, the greater the conductivity. In transition elements, the 4s and the 3d shells, being very close in
energy, act as if they where one shell.
Electrons are thus lost from both the 4s and the 3d sub shells and contributed to a common pool. There
are therefore a large number of electrons in the delocalized seato conduct electric current.
However, somenontransition metals like Mg may have electrical conductivities that are comparable to or
even greater than that of some transition metals. This is because of the small nuclear charge in these non
transition metals. The delocalized electrons in the metals easily move because they experience a relatively
small attraction from the positive charge on the metal atoms and the protons in the nuclei of these atoms.
On the other hand, even though a transition metal has a large number of delocalized electrons, mobility of
these electrons is restricted by attraction to the large positive charge on the metal atoms and the large
number of protons in the nucleus of the atom.

3.4 Transition metals have high melting and boiling points

Melting or boiling a metal requires the breaking of metallic bonds. The melting point or boiling point of a
metal is therefore a measure of the strength of these bonds. Transition metals have high melting points
and boiling points due to the presence of strong metallic bonds. The strength of these bonds can be ex-
plained in terms of
 the large number of delocalized electrons in the metal lattice. Remember that these electrons
come from both the 4s and the 3d sub shells of the atoms.
 the large charge that remains on the metal atoms after they have contributed their 4s and 3d
electrons into the pool of delocalization.
These two factors result in very strong electrostatic attractions between the positive metal atoms
and the sea of delocalized electrons.
 457

 the large nuclear charge of the atoms. Protons in the nucleus also have an attraction for the
delocalized electrons. This attraction is strong in the transition metals due to the large number of
protons in their nuclei.
We expect melting and boiling points of the transition elements to increase across the period in response
to increasing nuclear charge and decreasing atomic radii. A clear trend in melting points is not observed
because the metals tend to have different crystal structures.

3.5 Transition elements and their compounds are paramagnetic

Paramagnetism is the observation that some metals are attracted to a magnet.
The opposite of paramagnetism is diamagnetism, in which a substance is slightly repelled by the magnetic
field of a magnet. Non transition metals such as magnesium and aluminium tend to be diamagnetic.
Paramagnetism in transition metals is a result of unpaired electrons in the d orbitals. This explains why
copper and zinc are diamagnetic. Their d-electrons are all paired.

9.6.4 Chemical properties of the transition elements

Transition elements show the following chemical properties which are not usually shown by non-transi-
tion elements.

1. They exhibit variable oxidation states in their compounds

2. They tend to form complex compounds
3. They tend to form coloured compounds
4. They and their compounds show catalytic activity

4.1 Variable oxidation states

Transition elements tend to exhibit different oxidation states in their compounds, for example,
manganese forms stable compounds whose oxidation states range from +2 to +7. Compare with a non-
transition element such as calcium which has only one oxidation state, in this case, +2, in its compounds.
This tendency of transition metals to exhibit variable oxidation states is caused by the close proximity in
energy of the 3d and the 4s sub-shells.These shells are so close in energy that they behave as one shell.
Consequently, electrons may be lost from both shells. Different oxidation states would be formed
corresponding to the total number of electrons lost from the 4s and 3d sub-shells.
Compare vanadium with calcium. In Ca, only the two valence electrons in the 4s shell may be lost, form-
ing the +2 oxidation state. In Vanadium, the total number of electrons in the 4s and the 3d sub shells is
five. A range of oxidation states, from +2 to +5, is therefore possible.

The following points should be noted:

 In all transition compounds, except copper, the +1 state is very unstable.
To form the +1 state, one electron would have to be lost from the 4s sub shell. This would leave a
single electron in the valence shell. Such a configuration is very unstable. It explains why metals
which have a single valence electron, such as Na, are very reactive.
 458

 Electrons are always lost first from the 4s sub shell, because it is the valence shell.As a result, the
+2 state, corresponding to loss of both valence electrons, is common to all transition elements.
However, note that Cr and Cu have a 4s1, not 4s2 configuration.
 Only unpaired d- electrons may be lost during reactions
A key reason why substances react is to try and pair up electrons. By being paired, electrons attain
stability. In the transition elements, if the d-electrons are already paired, they do not show any
further tendency to react. The range of possible oxidation states therefore decreases when one or
more d orbitals contain paired electrons.
Table 9.6.5 shows that the number of possible oxidation states increases from scandium and reaches a
maximum at manganese. This is a result of increasing number of unpaired electrons in the d sub shell.
After Mn, the number of possible oxidation states start to decrease due to pairing of electrons in the d
orbitals.

Elem- Sc Ti V Cr Mn Fe Co Ni Cu Zn
ent

Configu- [Ar]3d1 [Ar]3d2 [Ar]3d3 [Ar]3d5 [Ar]3d5 [Ar]3d6 [Ar]3d7 [Ar]3d8 [Ar]3d10 Ar]3d10
ration 4s2 4s2 4s2 4s1 4s2 4s2 4s2 4s2 4s1 4s2

+1 +1 +1 +1 +1 +1 +1 +1 +1
states
Possible oxidation

+2 +2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6

+7
Table 9.6.5 Range of possible oxidation states for the transition elements. The stable oxidation states
for each element are highlighted.

The electronic configurations of transition metal ions

To work out the electronic configuration of the cation of a transition metal, we need to know the configu-
ration of the neutral atom. The size of positive charge on the ion is then equal to the number of electrons
lost from the neutral atom. You should remember that the first two electrons are lost from the 4s sub
shell, for example, the electronic configuration of Sc³⁺is 1s²2s²2p63s2 3p64s03d0, corresponding to the loss
of two electrons from the 4s and one electron from the 3d shell. Usually empty orbitals are not shown, so
the electronic configuration can be written as 1s²2s²2p63s2 3p6. This ion is stable since it has the electronic
configuration of a noble element, Ar.
 459

 The lower oxidation states form aqua complexes with water, for example, the species usually
abbreviated as Cu²⁺(aq) is in fact the hexaaqua complex, [Cu (H2O)6] 2+.
 The higher oxidation states, from the +4 and upwards, cannot exist as hexaaqua complexes. These
ions would have a charge density so high that they would immediately polarize water molecules,
releasing hydrogen ions and bonding with oxygen to form anions. In fact, in aqueous solution,
the higher oxidation states may exist as oxo-anions (Table 9.6.4), for example, vanadium forms
the oxo-anions VO₂⁺ and VO²⁺, in which vanadium has oxidation numbers +5 and +4 respectively.
In solution, these oxo-anions exist with counter ions such as the chloride ions, to form, for
instance, VO₂Cl (aq), which is a soluble salt.
Compounds of transition metals in which the metal has a high oxidation state also exist as inso-
luble compounds such as MnO2.

Oxo - anion Oxidation state of Colour of oxo-anion

the transition in aqueous solution
element

VO2+ +4 Blue

VO2+ +5 Yellow

MnO4- +7 Violet/purple

Cr2O72- Table 9.6.4 Oxo-anions of the

+6 Orange
transition elements
CrO42- +6 Yellow

 The lower oxidation states have a tendency to be oxidized to higher oxidation states, that is, they
often react as reducing agents. A well known example is Fe (II). This can reduce a number of
substances, for example, Cl₂. In these reactions, the Fe (II) is oxidized to Fe (III).

Q Use the Data Booklet to show that the reaction between chlorine and aqueous Fe 2+ (aq)is
feasible understandard conditions. Also check if a similar reaction can take place with
iodine. Explain any differences that would be observed in these two situations.

 The higher oxidation states have a tendency to be reduced to lower oxidation states. In this
process, they act as oxidizing agents. Commonly used oxidizing agents include KMnO₄ and
K₂Cr₂O₇. In these compounds, the transition element has its highest possible oxidation state.

4.2 Transition elements tend to form complex compounds

A complex compound is one which is made up of electron rich species known as ligands that are
bonded to a central metal cation through dative bonds.
 460

An example of a complex ion is [Co(NH3)6]3+, in which ammonia ligands form dative covalent bonds to a
central Co3+ ion.

3+ The square bracket shows the co-ordination sphere, that is,

..
NH 3
the central metal ion and its ligands. A charged complex
requires counter ions to balance its charge, for example,
.
.NH 3 ..NH 3
the complex shown may be associated with three chloride
ions. The counter ions are written outside the square
Co bracket, as shown in Fig 9.6.7. The counter ions are not
part of the co-ordination sphere.
H3 N
.. ..NH
3 3+
.
.NH ..
NH 3

Fig 9.6.6 Structure of a typical complex, .

.NH 3 ..NH 3

showing the use of lone pairs by ligands in

[Co(NH3)6]3+. 3Cl- =
forming dative bonds to the central metal Co 3Cl-
ion.
H3N
.. ..NH
3
Fig 9.6.7The salt [Co(NH3)6]3+.3Cl-
showing the co-ordination sphere
.
.NH
3
and its counter ions

In the Fig 9.6.7 NH₃ is involved in the co-ordination sphere because it is a stronger ligand than chloride
ions. A salt in which one of the ions is actually a co-ordination complex, for example, [Ni (NH3)₆]3⁺, can be
analyzed by adding to the aqueous solution a reagent which will react with the counter ions. The reagent
will not be able to react with the ligands of the co-ordination sphere because they are firmly held to the
central metal ion by strong covalent bonds. For example, adding aqueous silver nitrate to the salt shown
in Fig 9.6.7will result in the chloride ions being precipitated out of solution as AgCl. The number of moles
of chloride present in solution can then be determined from the mass of AgCl precipitated. Once the

number of counter ions present per each co-ordination sphere is known, it becomes possible to determine
the overall charge on the co-ordination sphere. For example, if it is shown that there are three chloride
counter ions, then the charge on the co-ordination sphere must be +3.

A ligand can be neutral or negatively charged. All ligands, neutral or negatively charged, contain at least
one atom which bears a lone pair of electrons. It is this lone pair that is used to make a dative bond to the
central metal cation. The central cation itself must have the ability to accept and stabilize extra electron
density.

Why transition metals can form complex ions

Transition elements have partially filled d orbitals which can be used to accept electron density from the
ligands.
It must be mentioned here that a few non-transition metals can also form complex ions. The prerequisite
for complex ion formation is availability of vacancies to accommodate extra electron density, or simply the
ability to attract and form stable compounds with ligands. Non transition elements which can form
complex ions include Al and Pb.
 461

Classification of ligands
A ligand is an electron rich species, either neutral or negatively charged, and carrying one or more lone
pairs of electrons which can be used to form one or more dative bonds to a central metal cation.
Ligands can be classified in terms of the number of dative bonds they can form, per molecule of the
ligand, to the central metal cation (Table 9.6.5). For instance, a bidentate ligand has two sites that it can
use to form two dative bonds during complex formation. Bidentate literally means ‘two toothed’. Note all
lone pairs on a ligand may be used in complex formation. Consider water which carries two lone pairs on
an oxygen atom. Each water molecule can only form one dative bond, not two, to the central metal ion.
The lone pairs in water are on the same atom and are therefore too close to allow formation of two dative
bonds to the metal ion.
In general, if an atom in the ligand contains two or more lone pairs of electrons, only one may be used in
dative bond formation. For lone pairs to form dative bonds to the central metal ion, they must be
sufficiently separated from each other, that is, they must be on different atoms, and they must be correctly
positioned.
A polydentate ligand can form more than two dative bonds with the central metal ion. Sometimes the
shape of the ligand changes to bring the bonding atoms into correct orientation relative to the metal ion.

Type of ligand Examples Examples of complexes that contain such

ligands

Monodentate H2O, Cl-, NH3, OH-, F-, [CuCl4]2- yellow

CO, CN- [Co(NH3)6]3+ golden brown

[ Fe(H2O)6]2+light green

Bidentate C2O42- (oxalate = ethanedioate)

O O O O
O O
C C
binding sites 2+ C
Cu
C
C C
O O
O O O O

H2NCH2CH2NH2 (ethanediamine ) [Cu(C2O4)2]

H NH2
H C
binding sites
H C
H NH2
 462

Hexadentate EDTA (ethanediamine -tetraacetate)

(polydentate)
CH2COO-
H N
CH2COO- [Cu(EDTA)]2-
H C
CH2COO-
H C Deep blue
H N
CH2COO-

Table 9.6.5 Classification of ligands in terms of maximum number of dative bonds that can be
made to the central metal ion per molecule of the ligand.

1. Complexes can be positively charged, negatively charged, or they can be

neutral
The net charge on the complex depends on the charge on the ligands and the metal cation. Consider the
hexa-aqua complex [Cu (H₂O)6] ²⁺, which contains a +2 metal cation and 6 neutral water ligands. The net
charge on the complex is equal to charge on the metal ion, since the ligands do not neutralize the positive
charge carried by the cation. Now suppose that the water ligands are replaced by four chloride ligands to
form the complex CuCl4x . The net charge x on the complex is determined by adding the total negative
charge from the ligands to the positive charge on the metal cation.
x = charge on cation + total charge from ligands = 2 + (-4) = -2
The complex therefore has the formula CuCl42-. All it means is that negative charge in the complex is in
excess by 2. Neutral complexes are usually insoluble in water, and from the way their formulae are
written, it may not be apparent that they are complexes. Consider what happens when NaOH (aq) is
added to an aqueous solution containing Cu 2+ ions. The reaction taking place is usually conveniently
written as
Cu2+ (aq) + 2OH-(aq) → Cu(OH) 2(s) (light blue precipitate)
Written like this, the equation is misleading in two ways:
 It does not show that this is in fact a ligand exchange reaction.
 It does not easily reveal that Cu(OH)2(s) is a neutral complex (insoluble, so it appears as a
precipitate).
The reader now knows that a formula such as Cu2+ (aq) is a convenient way of representing an aqua
complex, in this case, [Cu(H2O)6]2+. The reaction of Cu(II) with OH- ions therefore involves ligand
replacement; two water molecules in the aqua complex are replaced by OH - ligands.
[Cu(H2O)6]2+(aq) + 2OH-(aq) → Cu [(OH) 2(H2O)4](s) (light blue precipitate)
The product formed, Cu [(OH) 2(H2O) 4] (s), is a neutral complex. The net charge on the complex is given
by
charge on metal ion + total charge from two OH- ligands + total charge from four water ligands
= 2 + (-2) + 4(0) = 0
In a neutral complex such as Cu [(OH) 2(H2O)4], it is normal practice to ignore the water ligands and just
show the formula as Cu(OH) 2.
 463

Determine the charge on the metal ion in the following complex

Q (C2O4)3]3-
[Mn

Recall that the ligand (oxalate) in this complex is has a charge of -2 (see Table 9.6.5).
A there are three ligands, they contribute a total charge of -2 x 3 = -6. Let the charge on the
Since
metal be x, then
Net charge on complex = total charge from ligands + charge on metal
But net charge on the complex is -3, so
-3 = -6 + x, x = +3
The charge on the metal is therefore +3. In fact, this is the oxidation state of manganese in this
complex.

2. The co-ordination number of a complex determines its shape

The co-ordination number of a complex refers to the total number of dative bonds around the central
metal ion.
The co-ordination number need not be equal to number of ligands, for example, only one molecule of
EDTA, which is a hexadentate ligand, can make six bonds to the cation, giving a co-ordination number of
six. The smallest possible co-ordination number in a complex is 2, and this gives rise to linear complexes,
for example the diamine silver (I) ion, [Ag (NH3)2]2+. The number of dative bonds (bond pairs) around the
central metal ion determines the shape of the complex. This is a direct application of the VSEPR method
for the determination of molecular geometries. The reader needs to remember that dative bonds differ
only from other covalent bonds in how they are formed. Once formed, a dative bond cannot be
distinguished from any other covalent bond, in other words, it becomes just another bondpair of
electrons. In the diamine silver (I) complex shown below, there are two bond pairs around the central Ag+
ion. These bond pairs must be spaced out at 180 0 relative to each other. This is the optimum geometry
that minimizes inter-electronic repulsion between the two bond pairs. The complex is therefore linear.

1800
H3N Ag NH3

Co-ordination number 4
A co-ordination number of four gives rise to tetrahedral or square planar complexes. Examples are given
below. Note that [Pt(NH3)2Cl2] is a mixedligand complex. There are two NH3 ligands and two Cl- ligands.

[Pt(NH3)2Cl2] [CuCl4]2-

Cl 2-
Cl
NH3

Pt Cu
Cl Cl Cl
NH3
Cl
square planar complex - bond angle 900 tetrahedral complex - bond angle 109 0

Co-ordination number
Fig 9.6.8 Complexes with6a co-ordination number of may show a square planar
or tetrahedral geometry.
 464

This gives rise to an octahedral geometry (bond angle, 900). Examples of such complexes include
[Cu (EDTA)] 2- , [Mn (C2O4)3]3- and [Cu(en)3]2+ where en = ethanediamine. Fig 9.6.9 shows the geometry
of [Mn(C2O4)3]3-. Note that each ligand in the complex is bidentate so there is a total of 3 ligands x 2 = 6
bonds around the central metal ion. [Cu (EDTA)] 2- contains one ligand, EDTA, which makes six bonds to
the central metal ion.

C
O
O C O
C O O

O C Pt
O Fig 9.6.9 An octahedral complex of Mn
O
C O containing three C2O42- ligands
O
C
O

Paramagnetism in complexes of transition elements

Many complexes of transition elements are paramagnetic. This occurs if there are unpaired d electrons in
the transition metal ion. The strength of paramagnetism depends on the number of unpaired electrons.
The greater the number,the greater the paramagnetism.

Work out the number of unpaired electrons in each of the following complexes. Hence
Q the complexes in order of increasing paramagnetism.
arrange

(a) [Mn(C2O4)3]3- (b) CuCl₄²⁻ (c) [V(H₂O)₆]²⁺

(d) VO(H2O)5(OH)]+ (e) [ Ni(NH₃)₆]²⁺

A (a) First determine the oxidation number (charge) on the central metal ion, as this tells us
how many electrons were lost by the metal in forming the complex.
Let the charge on the metal be x.
x + 3(-2) = -3
x = +3
Therefore Mn lost 3 electrons in forming the complex. We deduct these three electrons
from the ground state configuration.

[Ar] 3d5 4s2 -3e- 4

[Ar] 3d
ground state

When a transition metal forms a compound, the 3d orbitals split in energy. In octahedral
complexes, the splitting results in the dxy , dxz and dyz occupying the lower energy level,
whilst the dz2 and the dx2- y2 occupies the higher energy level. Mn in [Mn(C2O4)3]3-has
four d electrons, which are distributed in the orbitals as shown below (the lower orbitals
are preferably occupied since they are more stable).
 465

d x 2 - y2 d z2

dxy dxz dyz

In this case, electrons enter only the lower set of d orbitals because C2O42-, like most bidentate
and polydentate ligands, is a strong ligand which results in a large separation between the
lower and the higher d orbital sets. A large amount of energy would be required to place an
electron in the higher orbital set. In the rest of the complexes in the question, the ligands are
weak and so the energy difference between the two energy levels is small. Electrons therefore
first enter singly in all the orbitals (both lower and higher) , thereafter pairing may take place,
starting with the lower set of orbitals.
The complex [Mn(C2O4)3]3-therefore contains two unpaired electrons. It is paramagnetic.

The reader should determine the number of unpaired electrons in the remaining
complexes and determine which one is the most paramagnetic.

Stability of complexes
Stability of a complex depends on the strength of the dative bonds which the ligands make to the central
ion. In turn, the strength of these bonds depend on
 the nature of the ligand
 charge on the ligand and
 the charge on the central transition metal ion

In comparing the stabilities of complexes of the same transition element in the same oxidationstate, the
important factor determining stability is the nature of and charge on the ligand.

Stability constants, Kstab

Different ligands have different affinities for the central metal cation. When a salt of a transition metal
dissolves in a large amount of water , water molecules act as ligands and form a complex with the transi-
tion metal ion, for example [Cu(H2O)6]2+. Now suppose that a different ligand, for example, NH 3, is added
to the solution containing the complex [Cu (H 2O)6]2+. The introduced ligand may or may not be able to
replace the water ligands in the complex. If the new ligand can form a complex which is more stable than
the aqua complex, then ligand exchange takes place. Water ligands are replaced and a more stable com-
plex is formed. However, if the introduced ligand forms a complex which is less stable than the aqua com-
plex, no ligand exchange takes place.

Stability constants are equilibrium constants that give a measure of the ease with which a particular
ligand can replace water from aspecified aqua complex.

 A very large Kstab value indicates that the ligand easily replaces water ligands in the specified
complex, to form a more stable complex.
 466

 Stability constants are true equilibrium constants, so they are affected by temperature.
The values are therefore quoted at 298 K.
The Kstab for the complex [Co(NH3)6]3+ is 5 x 1033. This value corresponds with the following ligand
exchange equilibrium
[Co(H2O)6]3+(aq) + 6NH3(aq) Ý [Co(NH3)6]3+ + 6H2O(l)
The equilibrium constant, Kstab for this reaction is given by

[{Co(NH3)6}]3+[H2O]6
Kstab = ... (i)
[{Co(H2O)6}]3+[NH3]6

Since the Kstab value is much greater than zero, we infer that the numerator in equation (i) is much larger
than the denominator. In other words, the concentration of the amino complex at equilibrium is much
greater than that of the aqua complex. This shows that the reaction is favoured in the forward direction,
that is, NH3 ligands can easily replace water ligands in [Co(H2O)6]3+(aq) , to form a more stable complex,
[Co(NH3)6]3+. Stability constants are therefore useful in predicting and explaining ligand exchange
reactions. For example, we can use the stability constants given in Table 9.6.6to predict some reactions of
copper (II) ions in aqueous solution.
Consider what happens when aqueous NH3 is added gradually to a blue solution of copper (II) sulphate,
until in excess, followed by a solution of EDTA.
Upon addition of a littleaqueous ammonia, the test solution forms a sky blue precipitate. This precipitate
dissolves in excess ammonia to form a deep blue solution. Upon addition of EDTA, the solution turns even
deeper blue.

Explanation
Aqueous ammonia is actually an equilibrium mixture of NH₃ molecules, water molecules, hydroxide ions
and ammonium ions.
NH₃(aq) + H₂O (l) ⇋ NH₄⁺ (aq) + OH⁻ (aq) ... (i)
Threeof the species in this equilibrium are all ligands and they will have competition for the central metal
ion. The sky blue colour of CuSO₄ solution is due to the aqua complex, [Cu(H₂O)₆]²⁺. When a little
aqueous ammonia is added, the hydroxide ions in equilibrium (i) displaces water ligands from the com-
plex in a ligand exchange reaction, resulting in formation of a sky blue precipitate of copper (II)
hydroxide.
[Cu(H₂O)₆]² ⁺ + 2OH⁻(aq) ⇋[Cu(H₂O)₄(OH)₂] + 2H₂O(l) ... (ii)
This reaction occurs because OH- ions are ligands than H2O. However, note that not all of the water li-
gands are replaced. The precipitate formed, [Cu(H₂O)₄(OH)₂], is usually wrongly written as Cu(OH)₂.
When NH3 is added in excess, the blue precipitate redissolves, giving a deep blue solution. This time the
increase in the concentration of free NH3 molecules results in a displacement of the OH - ligands , forming
the deep blue complex [Cu(NH3)₄(H2O)₂]2+.
Addition of EDTA results in a further ligand exchange reaction. If you check in Table 9.6.6, you will find
that [Cu(EDTA)]2-, has a very large Kstab . EDTA is a stronger field ligand than H2O , OH-and NH3. EDTA
is therefore able to replace NH3 in the complex [Cu(NH3)₄(H2O)₂]2+ to form the very stable octahedral
complex [Cu(EDTA)]2-. The scheme below shows ligand exchange reactions involving complexes of
copper.
 467

NH3(aq) xsNH3(aq)
[Cu(H2O)6]2+ [Cu(OH)2(H2O)4](s) [Cu(NH 3)4(H2O)2]2+
sky blue solution light blue precipitate deep blue solution

EDTA(aq)

[Cu(EDTA)]2-(aq)
deeper blue solution

It might be a useful exercise to try and rank ligands ac-

Complex Kstab Log
cording to the ease with which they can replace water in a
Kstab
ligand. However, this is not easy because the ease with
[Fe(H2O)F5]2- 2.2 x 1015 15.3 which a ligand can replace water depends on the
complex. Compare the stability constants for the
[FeCl4]- 8 x10-2 -1.1 complexes [FeCl4]- and CuCl42-. Note that the stability
constants are different. In the first complex, Cl- ligands
[Fe(CN)6]4- 1 x 1024 24 are not likely to replace water because of the very small
value of the stability constant. However, the Kstab for
[Fe(CN)6]3- 1 x 1031 31
CuCl42- is well above zero, indicating that Cl- ligands can
[Co(NH3)6]3+ 5 x 1033 33.7 easily replace water in this specific complex.
Despite this complication, it is still possible to make some
[Co(CN)6]3- 1 x 1064 64 useful generalizations:
 Complexes containing CN- ligands usually have
CuCl42- 4.2 x 105 5.6
very large stability constants. In most cases, CN-
ligands act as strong field ligands, that is, they
form very strong dative bonds to the central
[Ni(en)3]2+ 6 x 1018 18.8 metal ion. The resulting complexes are very sta-
ble. We infer that CN- can easily replace water in
[Cu(H2O)2(en)2]2+ 4 x 1019 19.6 many complexes
 Bidentate and hexadentate ligands form com-
plexes that have large stability constants. Such li-
gands, for example en and EDTA can easily re-
[Cu(EDTA)]2- 6 x 1018 18.8 place water ligands in a large number of com-
Table 9.6.6 Stability constants of plexes.
some complexes. These refer to the formation of
the given complex from the corresponding
complex that contains water as the only ligand .
The use of log Kstabgives numbers that are easy to
compare.

Chelating agents
EDTA is an example of a chelating agent.A chelating agent is a ligand which forms a complex which is
so stable that further substitution of the ligand by monodentate ligands is unlikely. Chelating agents are
usually bidentate or polydentate ligands such as EDTA. A complex formed in this way is known as a
chelate, for example [Cu(EDTA)]². Chelating agents such as EDTA2- have found use in water purification
where they remove certain poisonous metal ions by forming stable complexes with the ions.
 468

4.3 Transition metals tend to form coloured ions and compounds

Formation of coloured compounds is common among, but not unique to transition metals. The colour of a
transition compound largely depends on

 the strength of the ligand

 which metal ion is present in the complex
 the charge on the central metal ion.

The origin of colour in transition metal compounds

The neutral transition atom has degenerate (same energy) d orbitals. Upon compound formation, the d
orbitals split in energy, forming a higher set and a lower set of orbitals. This separation in energy is a
result of the electrostatic repulsion which the d orbitals experience from the approaching ligands. In
octahedral complexes, which are by far the most common, the dxy, dxz and dzy makes the lower set (more
stable). This is because their lobes are oriented between the axes, so they feel a smaller repulsion from
the ligands, which approach along the axes. This set is referred to as the t₂g set. The dz² and the dx²-y² (eg
set)are higher in energy. This is because their lobes are along the axes. They experience a strong repulsion
from the ligands, which also approach along the axes.

All five d orbitals are raised in energy due to

repulsion by ligands. The eg set experiences
the greater repulsion since ligands (L)
eg set
approach along the axes, in line with the
lobes of the orbitals. These orbitals are
In the neutral transition
therefore higher in energy (less stable).
atom, all five d orbitals are
The t2g set is lower and more stable. This is
degenerate.
because its lobes are oriented between axes,
and so experiences less repulsion from
t2g set ligands, which approach along axes.

Fig 9.6.10Splitting of d orbitals in an octahedral complex. ∆0 is the energy

difference between the higher and the lower set of orbitals.
 469

The separation in energy between the two sets of d orbitals is ∆0. The size of ∆0 for a particular transition
metal ion depends on the strength of the ligand. Strong field ligands result in large values of ∆0.

The splitting in a tetrahedral complex is an inversion of the case for octahedral complexes. The t 2g set is
higher in energy than the e g, and again this has to do with the direction in which ligands approach the d
orbitals.

dxy dxz dzy



d z 2 d x 2 - y2 Fig 9.6.11 Splitting in a

tetrahedral complex
dxy d dzy d z2 d x2 - y2
xz

When light strikes the transition compound, some wavelengths from the visible spectrum are absorbed.
The absorbed energy is used to promote electrons from the lower set of orbitals to the higher set.Light
which is reflected back to the eye therefore has fewer wavelengths, which mix to give a colour which is ob-
served. The colour observed is complimentary to the wavelengths absorbed, for example, red is
complimentary to blue. Cu2+ (aq) (= [Cu(H2O)6]2+ appears blue because it absorbs from the red region of
visible light (actually , orange and yellow are also absorbed since the absorption is not sharp; a range of
wavelengths is absorbed). A necessary condition for a complex to be coloured isthe presence of vacancies
(unpaired electrons or vacant orbitals) in the higher set of orbitals. These vacancies can accommodate
electrons that are promoted from the lower set of orbitals by absorption of light energy. In [Cu(H 2O)6]2+ ,
Cu2+ has a d9 configuration. This hexaaqua complex has the following arrangement of electrons in the d
orbitals of Cu2+.

2 2
d z2 d x - y
vacancy

one electron can be promoted form

any lower orbital Fig 9.6.12 Splitting of orbitals
in Cu2+, which has a d9
configuration.
dxy dxz dzy
 470

V 1. White (visible) light has seven components (wavelengths). If the

I components were viewed separately they would have the following
B
colours: Violet, Indigo, Blue, Green, Yellow, Orange and Red.
G Mixing these seven colours gives white light.
Y 2
O 2. If a compound has vacancies in the higher set of d orbitals, one
R or more components of white light (energy) are absorbed and used
1 to promote one or more electrons from the lower energy level to the
higher. [Cu(H2O)6]2+(aq) , which is an octahedral complex, absorbs
3 the red component from white light.
V
I
B 3. The eye sees an object as a result of light reflected to it from the
G
Y object. In the case of [Cu(H2O)6]2+, the light reflected to the eye has
O
a missing component, the red wavelength.
4
B
4. The colour seen by the eye is a compliment of the absorbed
colour(s). In the case of [Cu(H2O)6]2+, the eye sees blue, which is
eye complimentary to red.

Fig 9.6.13 The origin of the blue colour in Cu2+ (aq)

From this account, it should be easy to see why some compounds of the d block of the Periodic Table are
white when solid and colourless in solution. Complexes of Zn(II) such as [Zn(H₂O)₆]²⁺(aq) are colourless.
The reason is that all the d orbitals (the lower and upper sets) are fully occupied (Zn²⁺ = d₁0). There are no
vacancies in the upper energy level to accommodate electrons from the lower energy orbital (Fig
9.6.14(a)). Compounds of Sc (III) lack colour for a different reason. The d orbitals are completely empty
(d0). Since there are no possible electron transitions, light is not absorbed(Fig 9.6.14(b)). The light which
is reflected back to the eye has a full complement of wavelengths, so the eye will see it as white light, that
is, the compound would appear colourless or white.

2 2 2 2
d z2 d x - y d z2 d x - y

Fig 9.6.14(a) Zn (II) compounds are colourless or

white because they have a d10 configuration .
(b) Compounds of Sc (III) are colourless for a
different reason; the d orbitals are completely
empty. In both cases d-d transitions are not
dxy possible
dxz dzy dxy dxz dzy

(a) (b)
 471

Colours of common transition metal compounds

Remember to treat the ions Mn+ (aq) as compounds of the formula [M(H2O)6]n+. All ions in the following
table are in aqueous solution.

Element Compound/ion colour Oxidation Comments

state
of element

Vanadium VO2+ Yellow +5 Vanadium is named after Vanadis, the

VO2+ Blue +4 Scandinavian goddess of beauty. This
V3+ Green +3 is because all of its stable oxidation
V2+ Violet +2 states exhibit attractive colours in
aqueous solution.

Chromium Cr3+ Green +3 Acidic in solution due to salt hydrolysis

CrO42- Yellow +6 Dominant in alkaline solution

Cr2O72- Orange +6 Dominant in acidic solution

Manganese Mn2+ Pale +2 Easy to miss the colour if solution is

pink too dilute

MnO4- Purple +7 Intense colour is due to charge

transfer, not d-d transitions

MnO2(s) Black +4 A catalyst for the decomposition of hy-

drogen peroxide.

Cu Cu2+ Light +2
blue

CuO(s) Black +2

CuCl42- Yellow +2 CuCl42- is formed when concentrated

HCl or concentrated NH4Cl is added to
a solution containing Cu2+.
[Cu(NH3)4(H2O)2+] Deep +2
blue

Cu2O(s) red +1 A precipitate of red copper (I) oxide,

Cu2O, is formed during the test for
aldehydes, for example glucose.
 472

Fe Fe2+ Light +2
green

Fe3+ Yellow +3 Acidic in aqueous solution due to salt

brown hydrolysis

[Fe(CN6)]4- Yellow +2 Gives dark blue colour with Fe3+(aq)

[Fe(CN6)]3- yellow +3 Gives dark blue precipitate with Fe2+

4.4 Catalysis by transition elements and their compounds

Transition metals and their compounds are associated with catalytic activity. The explanation lies in the
presence of partially filled d orbitals and the ability of the transition element to change oxidation state
during the catalysis.

Heterogeneous catalysis is when the catalyst and the reactant are in different phases. Well known
cases are when the catalyst is solid and the reactants are gaseous. An example is the use of solid iron in the
Haber process for the manufacture of ammonia from nitrogen and hydrogen gases. The partially filled d
orbitals in the transition metal are used to temporarily accommodate electron density from the reactants
during the reaction. The adsorption of reactant molecules onto the surface of the catalyst weakens their
bonds, thus lowering the activation energy of the reaction. By adsorbing the reactants, the catalyst also
brings reactant molecules together so that bonds can form.
The contact process for the manufacture of sulphuric acid also involves heterogeneous catalysis. The
catalyst, solid vanadium (V) oxide, V2O5, participates in the conversion of SO2 to SO3.

SO2 (g) + ½ O2 (g) Ý SO3 (g)

450-5000C
1atm

The mode of action of the catalyst here is thought to involve dissociation to produce O 2, which then
facilitates the oxidation of SO2 to SO3.
V2O5(s) Ý 2V2O4(s) + O2 (g)
Note that the oxidation of V decreases from +5 to +4, that is, vanadium undergoes reduction. The catalyst
is recovered when V2O4 combines with oxygen from the atmosphere, resulting in the oxidation of
vanadium back to the +5 state.
V2O4(s) + ½ O2 (g) Ý V2O5(s)

The ability of vanadium to change its oxidation state is important in this catalysis.

A homogenous catalyst is one which is in the same phase as the reactants. A commonly quoted exam-
ple is the catalysis of the reaction between peroxodisulphate and iodide ions by Fe (III) or Fe (II) ions in
aqueous solution (see section 8 for details of this reaction).
S₂O₈²⁻(aq) + 2I⁻(aq) → SO₄²⁻(aq) + I₂(aq)
 473

This redox reaction is judged to be energetically feasible by consideration of its Ecell value, which is large
and positive. However, the reaction is very slow because the ions involved are likely charged and so in-
stead of colliding to form products, they tend to repel. The reaction therefore has very high activation
energy. That is, a very large amount of energy must be supplied to force the reactants to collide. The
catalyst provides a new reaction pathway involving oppositely charged ions which therefore collide easily
by mutual attraction. The catalyst is able to carry out the catalysis because it has the ability to vary its
oxidation state. During the course of the reaction, the catalyst reacts just as if it were one of the reactants,
and by so doing it changes its oxidation state. At the end of the reaction, the catalyst reverts back to its
original oxidation number.

The ability of a transition element or its compounds to participate in catalysis can be explained in
two ways.
 The transition metal has the ability to switch between oxidation states. This allows the
catalyst to participate as a reactant in the catalysis, and to be converted back to the
original form at the end of the reaction.
 The presence of partially filled d orbitals may allow the reactant molecules to temporarily
adsorb to the surface of the catalyst.

9.6.5UV - Vis spectroscopy of transition complexes

UV –Vis spectroscopy (ultraviolet-visible spectroscopy) is a useful procedure for the

determination of chemical species that can absorb the ultraviolet or visible portion of the electromagnetic
spectrum. Absorption of UV or visible radiation by complexes is a result of the presence of unpaired
electrons in the d orbitals.
As already explained, energy is absorbed in promoting one or more electrons from the lower set of d
orbitals to the higher set in a complex. Every complex absorbs only within a certain range of energies, so
its absorption spectrum acts like a fingerprint that can help to identify it. The absorption of energy is not
sharp, that is, a complex will not absorb a single frequency of energy, but will absorb within a well defined
range. However, each complex will has a particular wavelength of energy at which it will absorb the most.
This point of maximum absorption can be used to identify the complex present in the solution. Fig 9.6.15
shows the key features of a UV - Vis spectrometer. This instrument measures the amount of light
absorbed by a compound as a function of wavelength. Remember that wavelength is related to energy.
The longer the wavelength, the smaller the energy of the radiation, and vice versa.
 Suppose that a reaction occurs in which a complex A undergoes ligand exchange to form complex
B, which has a greater absorption. First the absorption spectrum of pure A is obtained. The reac-
tion is then allowed to proceed. In this case, the recorder will trace out increasing absorbances
due to the formation of product B. At the end of the reaction, a maximum value of absorbance is
obtained due to the presence of a maximum yield of the product B. The graph then levels out as
there is no further reaction taking place. The rate of reaction is the same as the rate of change of
absorbance due to the formation of the product. To find this rate, values of absorbances at
different times are recorded. The rate of reaction at a given time is determined by taking the
slope of the tangent at that time.
 474

Fig 9.6.15 Principles of operation of a UV-Vis spectrometer (also known as a

spectrophotometer)

1.The source produces light with a range of wavelengths.

2. The monochromatic selects light of the same wavelength.
3. This light is split into two beams, a reference beam Ir and a sample beam Is. The sample beam passes
through a sample of the compound (complex) being analyzed. The reference beam passes through a
reference cell which contains a solvent only, for example water. The solvent used must be the same as the
one used in the sample cell.
4. The sample absorbs some energy, and the detector measures the intensity ratio of the transmitted
reference (Ir) beam to the sample beam, Is. The logarithm of this ratio is known as the absorbance, A.

𝐈𝐫
A =log( )
𝐈𝐬
If the sample does not absorb at a certain wavelength, then Ir= Is, so A = log (1/1) = 0
If the sample absorbs, then Ir>Is, and absorbance is greater than zero.
5.The spectrometer continuously scans the wavelengths in the UV-Vis spectrum, and a chart recorder
draws a graph known as a UV-Vis spectrum. This graph measures absorbance as a function of
wavelength .
UV-Vis spectroscopy can be used in the following ways
 identifying a complex present in solution, since different complexes have different maximum
absorbances.
 determining rates for reactions which are accompanied by ligand exchange or complex formation.
The product of the reaction will have a different absorption spectrum from the reactant.

Example
Zinc forms a complex with the ligand PAR
Zn2+ (aq) + 2PAR  [Zn(PAR)2] ... (i)
The rate of reaction (i) has been studied.
Both PAR and its zinc complex absorb radiation in the UV-visible region. The following diagram shows
their absorption spectra.
 475

Fig 9.6.16 Absorption spectra of [Zn(H2O)6]2+and the complex

[Zn(PAR)2].

During the course of the reaction, the absorbance of the solution increases due to the formation of the
complex Zn-PAR. When the reaction is complete, the UV-Vis spectrum reaches a maximum of about 1.2,
which is the maximum absorbance of the complex. An absorbance - time graph therefore shows the rate of
formation of the complex. The rate of reaction at time t is the slope of the tangent at that point (Fig
9.6.17). The experiment can be repeated using different concentrations of Zn 2+ or the ligand PAR, and
noting the change of the slope (rate) at time t.

y
absorbance
x

Fig 9.6.17 Absorbance - time graph

for the reaction between Zn2+(aq) and
PAR.
0 t1
time
rate of reaction at time t = rate of change of absorbance
= y/x

Transition metal ions of biological importance

Some transition metal ions are important for the efficient running of biological processes. Examples
include Cu2+ in the respiratory system, Co2+ in vitamins and Fe2+, which is responsible for the oxygen
binding properties of haemoglobin (See section 4.1 ).
 476

Questions, solutions and discussions

Q1 (a) (i) State one alloy that contains nickel, and give its use.
(ii) State an example of an industrially important reaction that uses nickel as a catalyst.

(b) The ‘crown ether’ A and the ‘crown thioether’ B are polydentate ligands that are used to
remove harmful metals from the environment.

Compound A complexes with ions of Compound B complexes well with ions

metals on the left of the Periodic Table, of metals that are towards the right of
and can be used to extract radioactive the Periodic Table, and can be used to
strontium ions from groundwater. extract nickel, copper and lead ions from
(Complexes formed by the ions of Group solutions of industrial waste.
II metals are similar to the complexes
formed by transition metal ions.)

(i) Explain what is meant by a polydentate ligand.

(ii)What features of both compound A and compound B make them suitable to act as ligands?

(iii)Suggest the co-ordination number in, and the shape of, the complex formed between A
and Sr2+ ions.

(iv) Suggest the co-ordination number in, and the shape of, the complex formed between B
and Ni2+ ions.

(c) The complex [Ni(R3P)2Br2] can exist in two isomeric forms. Draw structural formulae to
show the shapes of these isomers, and describe the type of isomerism shown. [The R group is
an organic group such as methyl, –CH3.] 9701/06/O/N/2006
 477

Solutions

(a) (i) AlNiCo – used in magnets [ alloy of Al, Ni and cobalt- used to make super magnets]. This alloy is
corrosion resistant.

Nichrome –used for high resistance wire

Cupro-nickel – used to make coins

(ii) Hydrogenation of vegetable oils/ hydrogenation of alkenes to alkanes.

(b) (i) Polydentate – forms more than one dative bonds per molecule of ligand.

(ii) They contain oxygen and sulphur atoms which bear lone pairs of electrons.

(iii) Coordination number 6, giving rise to an octahedral geometry. [ since there are six binding sites = 6
oxygen atoms].

(iv)Coordination number 4 , giving rise to a tetrahedral / square planar geometry.

(c) A form of stereoisomerism known as geometric or cis-trans isomerism is exhibited.

Br Br
R3P R3P
Ni Ni
R3P R3P Br
Br
trans cis

Q2 (a) Explain what is meant by the term transition element.

(b)Complete the electronic configuration of

(i) the vanadium atom, 1s22s22p6

(ii) the Cu2+ion. 1s22s22p6

(c)List the four most likely oxidation states of vanadium.

(d)Describe what you would see, and explain what happens, when dilute aqueous ammonia is added
to a solution containing Cu2+ions, until the ammonia is in an excess.

(e) Copper powder dissolves in an acidified solution of sodium vanadate(V), NaVO3, to produce a
blue solution containing VO2+and Cu2+ions.

By using suitable half-equations from the Data Booklet, construct a balanced equation for this
reaction.
 478

Solutions
2 (a) A d-block element which forms at least one ion in which the d orbitals are partially filled.

(b) (i) (1s22s22p6) 3s23p63d34s2

(ii) (1s2 2s2 2p6) 3s23p63d9

(c)+2, +3, +4, +5

(d)Pale blue solution forms a light blue (cyan)precipitate which dissolves in excess NH3 (aq) to give a
deep blue solution.
Blue precipitate is Cu(OH)2
The deep blue solution contains the complex[Cu(NH3)4(H2O)2]2+ formed by ligand replacement .

(e) Exercise to the reader

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 9.6in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

1(a) Explain the following observations using relevant Eθ values from the Data Booklet, and ideas
of the relative stabilities of complexes in the presence of different ligands.

(i) Solutions containing Fe2+(aq) slowly oxidize to Fe3+(aq) in air.

(ii) The precipitate formed when aqueous sodium hydroxide is added to a solution containing
Fe2+(aq) rapidly turns brown in air.

(b) A 6.95 g sample of FeSO4.7H2O was dissolved in water and the volume of solution made up to
250 cm3. The solution was stored in an open container for some time and suffered partial
oxidation. On titration of a 25.0 cm3 portion of the partially oxidized solution with 0.020
mol dm–3KMnO4, it was found that 20.5 cm3 of oxidant were required to reach the endpoint.

Calculate the percentage of Fe2+ ions that had been oxidized.

2Iron metal and its compounds are useful catalysts in certain reactions.
(a) Apart from its catalytic activity, state two properties of iron or its compounds thatshow
that it is a transition element.

(b)You are provided with a solution of KMnO4 of known concentration in a burette.Outline how
you could use this solution to find out the concentration of Fe2+(aq) in asolution. You should
include relevant equations for any reactions you describe.
 479

(c) For each of the following equations, write the oxidation number of the element printed in bold
underneath its symbol, and balance the equation by adding appropriate numbersbefore each
species.

(i) ........ MnO4–+ ........ SO2+ ........ H2O →........ Mn2++ ........ SO42- + …… H+
oxidation numbers: ........ ........ ........ ........

(ii) ........ Cr2O72– + ........ NO2+ ........ H+→........ Cr3++ ........ NO3– + ........ H2O
oxidation numbers: ........ ........ ........ ........

(d) Outline the role that Fe3+ ions play in catalyzing the reaction between iodide ions and
peroxodisulphate(VI) ions.

2I– + S2O82- I2 + 2SO42-

9701/42/O/N/2009
 480

Section 3

Organic Chemistry

Introduction

Organic chemistry is the study of organic compounds. An organic compound is one that contains
C and H or
 481

C, H and any other atom, for example O, N, S, Cl, Br.

An organic compound which contains C and H only is known as a hydrocarbon. The key element in
organic chemistry is carbon. Organic chemistry is essentially the study of carbon compounds. There are
several millions of known organic compounds, and every day new ones are either being discovered or
synthesized. Carbon compounds occur widely in living things and in the environment. Many synthetic
compounds of carbon exist, and these include drugs, dyes, plastics and fabrics.
Carbon has certain unique properties which allow it to form so many stable compounds.
 it can catenate. This means that it can form relatively long chains and rings by forming strong and
stable C-C bonds. These chains may also contain C to C double or triple bonds, which are also very
strong and stable. A wide variety of organic compounds is possible because the chains and rings
can have different sizes.
 It can form four bonds. This is important in the formation of side chains. There are many possible
ways in which this branching can take place, and once more, this increases the number of
compounds that carbon can form.

10.1 The structure of organic compounds

Before you study in depth the chemical and physical properties of organic compounds, you need to
understand their structure first. An organic compound is mainly made up of carbon and hydrogen. These
two elements are always present in any organic compound. However, many organic compounds also
contain other atoms such as O, N, S, Cl and so on. These atoms, which we may refer to as hetero atoms,
occur at regions of the organic molecule known as functional groups. Note, though, that a C to C double
or triple bond is also a functional group, though it contains no hetero atom. The concept of functional
group is very important in organic chemistry because it helps us to predict the chemical behaviour of an
organic compound.
A functional group is the reactive centre of an organic molecule. It is an atom or a group of atoms that
confers reactivity to the organic molecule.

A functional group is an atom or group of atoms that is responsible for the chemical reactions of an
organic compound.

An organic compound that lacks a functional group is known as an alkane. Such a compound is saturated
(it has no C to C double or triple bonds) and it contains carbon and hydrogen only. Table 10.1 below shows
the functional groups that you should study.

10.1.1 Classification of organic compounds

Organic compounds are classified into groups on the basis of the functional group present. Compounds
with the same functional group fall into the same group, which is known as a homologous series. Of
course, if the compound has more than one functional groups, then it cannot be classified into any one
 482

group, for example, a compound could be an alcohol and a carboxylic acid at the same time. In Table 10.1
below we assume that the compounds have only one functional group (or none at all).

Table 10.1 Functional groups and representative compounds

Homologous Functional Examples

series group

Alkanes methane, CH4

None
butane , CH3CH2CH2CH3
HYDROCARBONS

Alkenes C=C ethene, CH2 = CH2

Carbon to carbon double bond
propene, CH3CH=CHCH2

arenes

Benzene (aromatic) ring benzene

CH3

methylbenzene

C-OH Primary alcohol: OH

(OH not attached to benzene ring) H group is bonded to a
H C atom that carries
C OH
two hydrogen atoms.
There are three classes, primary, H
secondary and tertiary alcohols. methanol
Alcohols
CH3 Secondary alcohol:
OH group is bonded
CH3 C OH to a C atom that
H carries one hydrogen
propan-2-ol atoms.

CH3 Tertiary alcohol: OH

group is bonded to a
CH3 C OH
C atom that does not
CH3 carry any hydrogen.
atoms.
2-methylpropan-2-ol

Phenols
 483

OH OH
phenol,

CH3 OH

4- methylphenol

Halogenoalkanes C-X
(C is non aromatic. H H
X = F, Cl, Br, I) chloroethane,
H C C Cl
H H

Halogenoarene C-X
(C is aromatic. X = F, Cl, Br) Br
bromobenzene,
CARBONYL COMPOUNDS

O
Ketones O
C
Both CH3 C CH3
C aldehydes and
ketones propanone
O contain the
Aldehydes C carbonyl
group, O
H
CH3 C H
ethanal

Carboxylic acids
O O

C CH3 C
OH OH
ethanoic acid

Esters O O

C CH3 C
O O CH3
ethyl ethanoate

Acylchlorides O

C
Cl
 484

CH3 C
Cl
ethanoylchloride

Amines
H
primary amine
C N CH3 N
H
methylamine
There are three classes, primary,
secondary and tertiary amines
In a secondary amine, the N is bonded to
only one hydrogen atom. In a tertiary
amine, the N is not bonded to any H
atoms (see amides below).

O H primary amide : N is bonded

CH3 C N to two H atoms
H
O
ethanamide
Amides
C
N O H secondary amide : N is
CH3 C N bonded to one H
There are three classes, primary, atom
secondary and tertiary amides
CH3
N-methylacetamide

O CH3
Tertiary amide : N is not
CH3 C N bonded to any H
atom
CH3
N, N-dimethylacetamide

Homologous series
A homologous series is a group of organic compounds that share the same functional group. The term is
used particularly for:
 straight chain organic molecules.
 organic molecules with only one type of functional group.

Properties of a homologous series

 485

1. Members of the same homologous group share the same functional group.
2.Members of the same homologous group have similar chemical reactions. This is expected, since the
functional group is the weak center in an organic molecule. This fact makes the study of organic
chemistry a light task, for example, instead of studying all alcohols individually, the student need only
study the chemical behavior of the alcohol functional group.
3. One member of a homologous group differs from the next by a single –CH₂- group.
4. Going down the series from one member to the next, the relative molecular mass increases by 14, which
corresponds to the mass of an – CH₂- group which is added on going down the series.
5. The increase in mass down the series is accompanied by an increase in boiling and melting
points. As the number of electrons increases, so does the strength of the Van der Waals forces. More
energy would be needed to break these forces down the series.
6. The increase in strength of Van der Waals forces results in a change in state from gas through liquid to
solid. As the forces of attraction become stronger, the molecules are held more tightly in fixed
positions,and their kinetic energy decreases, that is, the compounds begin to assume a liquid state, and
then finally a solid state. Compare methane, which is a gas, with octane (liquid) and candle wax
(C₃0H₆₂), which is a solid at room temperature. These three compounds belong to the same homologous
series, the alkanes.

10.1.2 Structure and bonding

Here are important guidelines about the structure and bonding in organic compounds.
 Carbon always makes four covalent bonds with other atoms. Take particular care here, especially
if you draw a structure in which a carbon atom is associated directly with a double or triple bond,
or is bonded to a functional group.
 Nitrogen in most organic compounds makes three bonds to other atoms. The fourth position on
the nitrogen atom is occupied by a lone pair, just as in ammonia.
 Oxygen in most of its compounds makes two bonds to other atoms. The other two positions are
occupied by lone pairs, just as in water.

Study the following illustrations .

x
H H H H H

H C C O H H C C N y

H H H H H
ethanol ethylamine

Q
What are the bond angles marked x and y?

X is 104.50(as in water).
A
 486

Y is 107.50 (as in ammonia).

Hint:
Do not be misled by the way the compounds have been drawn. Remember the existence of two lone pairs
of electrons on the oxygen atom in ethanol and one lone pair on the nitrogen atom in ethylamine. These
lone pairs affect the bond angle, according to the VSEPR theory.

Q
Circle and name all functional groups present in the anticancer drug Taxol®. The ‘broken
wedges’ in the diagram show bonds that are pointing to the back of the paper, away from
you. The ‘solidwedges’ show bonds that are pointing out of the paper, towards you.

A are 7 different functional groups, numbered 1 to 7 in the following diagram.

There

1. benzene ring (phenyl group) 2. amide 3.(secondary) alcohol 4. ester

5. Ketone 6. C to C double bond/alkene 7.ether (not in your syllabus)

 487

A
5 3
2 4 6

3 4
3
1

10.1.3 Formulae of organic compounds

You will encounter the following types of formulae:

 Molecular
 Structural
 Displayed
 Skeletal
The molecular formula is rarely used in organic chemistry because it frequently gives rise to a case of
ambiguity known as isomerism.
Consider the molecular formula C2H6O. This compound cannot be named with certainty, because it could
be ethanol or ether (dimethyl ether).
The difference between the two compounds in the
C2H6O diagram above is clearly seen using displayed
formulae. A displayed formula shows (displays) all
the bonds and how atoms are arranged relative to
each other. The displayed formula therefore helps
H H H H us to see exactly which atom is bonded to which.
H C C O H H C O C H One other way in which the displayed formula
becomes handyis in checking the valencies of the
H H H H
atoms used in bonding.
Ethanol ether

Check from the diagrams above that carbon has four bonds around it, oxygen and hydrogen have 2 and 1
respectively.

The structural formula

 488

The illustration in Fig 10.1shows the relationship between structural and displayed formulae.Note that the
groups of atoms shown in the displayed formula also appear in the structural formula, but this time bonds
are not shown. The structural formula is the most used type of formula in organic chemistry because it
overcomes the ambiguity associated with the molecular formula and at the same time it has greater
convenience than the displayed formula.

H H H H

displayed H C C O H H C O C H
H H H H

structural CH3CH2OH CH 3O CH3

Fig 10.1 Relationship between structural and displayed formula

The skeletal formula

This is a shorthand notation for showing the structure of organic molecules. A shorthand formula is very
useful in drawing structures of complex molecules. The diagram below shows the skeletal formula for
propane.

The rules for drawing a skeletal formula are straightforward.

 Carbon atoms are not shown.
 An ‘elbow’ in the structure represents the position of a carbon atom. This position represents a
–CH2 group, unless if there is an associated branch or multiple bond. In these two cases, the
number of hydrogen atoms is reduced from 2 to satisfy the valency of C.
 Hydrogen atoms are not shown unless if they are directly bonded to a non-carbon atom, for
example, O, N and S.
 A carbon chain is shown by a ‘zig- zag’ line, with each ‘elbow’ representing the position of a
carbon atom. However, if the carbon chain is interrupted by a non carbon atom, for example O as
in esters and ethers, the non carbon atom must be shown.
 The end of a line segment represents a –CH3 group unless if there is a functional group (such as
the carbon to carbon double bond) associated with this carbon atom.

Fig 10.2 illustrates the relationship between structural formula and skeletal formula of propane.

CH3 CH2 CH3

end of line segment
end of line segment elbow Fig 10.2
 489

Now consider the following skeletal formula.

end of line : CH3

end of line : CH3
1 4
2
3 O
elbow: elbow: C with no H
O
CH2 5 6
7
elbow with one
branch : CH end of line : CH3

elbow:
CH2

 Carbon 3 has only one H atom because there is a branch here. This gives the carbon atom a
correct valency of four.
 Do not forget that the position marked 4 is a -CH3 group.
 Carbon 5 has no H atom. Notice that at this position the carbon atom already has four bonds
around it because of the presence of the C to O double bond.
 The molecule has 7 carbon atoms, which have been marked 1 to 7. Each of these carbon atoms
can have 3, 2, 1 or 0 H atoms.
 Reading from carbon 1, the structural formula of the molecule is

CH3CH2CH(CH3)OCOCH2CH3 ... (i)

1 2 3 4 5 6 7

Note that branches are shown in brackets, in this case the CH 3 branch bonded to carbon3.
 The molecular formula of the compound is therefore C7H14O2. This compound is an ester.
 The structural formula of the compound could have been written from the other direction, that is,
from carbon 7. This would give

CH3CH2COOCH(CH3)CH2CH3 ... (ii)

7 6 5 3 4 2 1

Structures (i) and (ii) are exactly the same.

Limonene is an oily liquid that occurs naturally in the peels of citrus fruits. Its structure
Q
is shown in Fig 10.3. Calculate the mass of 2 moles of this compound.

limonene

Fig 10.3

AThe molecular formula of limonene is C10H16. Its Mr is 136.

mass = n x Mr = 136 x 2 = 272 g
 490

CH3

C
CH2 CH
= H
CH2 CH2
C
limonene
C

CH3 CH2

Skeletal formulae that involve the benzene ring

The benzene ring is one of the functional groups whose chemistry you will study in detail later on. The
simplest compound that contains the benzene ring is benzene itself. The formula of benzene is C6H6 . It is
a cyclic compound whose structure is shown below.

C
H C C H
=
H C C H
C skeletal form ula
This ring represents
delocalized electrons H

display ed form ula

From the displayed formula it appears that each carbon has only three covalent bonds, instead of four.
This is because the other electrons that would have constituted the ‘missing’ bonds are delocalized within
the molecule.
In a substituted benzene, the number of hydrogen atoms is less than 6, depending on the number of
substituents. In such compounds, one or more hydrogen atoms have been replaced by other groups, for
example, the methyl group in methylbenzene. The structure of methylbenzene and other substituted
benzenes are shown in the following panel. The formula of methylbenzene can be written as C6H5CH3.
Written like this, we can see that one of the six H atoms of the benzene ring has been replaced by a CH 3
group. However, if you were asked to write the molecular formula, it would be C 7H8.

Panel 10.1
 491

m ethy lbenzene
CH 3
0
1 20
C CH 3

H C C H
= = C6H5CH3
H C C H
C skeletal formula
display ed formula
H

NB The position on which the -CH3 group is drawn is not important.

4- chlorom ethy lbenzene 2,4,6 - trichlorophenol (T CP)

= C H Cl(CH ) = C6H2 OH(Cl)3

6 4 3

[TCP is the active ingredient

in Dettol]

two hydrogen atoms replaced four hydrogen atoms replaced

Q displayed formulae from the following skeletal formulae. Hence deduce the
Draw
molecular formula of each compound. The benzene ring is acceptable in a displayed
formula.

O
O
(c)
(a) O (b)
OH

H
O
H C
H C O
H H H H H
A C
(a) C C C C C C H (b) C
C H
H H O H C
H H H
C H
C12H14O H C
C C H
H H H
H
H H H H H
H
C H H
(c) C12H22O2
H C C
C
H O H
H

C4H8O
 H H H H H

(a) C C C C C C H (b)
492 H H O H
H C
C12H14O C
H H H
O H H
H C H
H C O C H H
H H H
C (c)
C C C H C H C C
(b) C
C H
C H O H
H H H H
H
C H
H14O H C
C C H C4H8O
H H H
H
H H H H

C12H22O2

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Exercise 10.1in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]

All of the following compounds are naturally occurring. Work out their molecular formulae

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box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
 493

10.1.4Isomerism

This is a phenomenon in which different compounds share the same molecular formula.
An illustration has already been given using ether and ethanol.

ISOMERISM

Structural Stereoisomerism

chain(skeletal) positional functional cis-trans(geometric) optical

isomerism isomerism group isomerism isomerism
isomerism

 There are two main forms of isomerism, structural and stereoisomerism.

 There are two forms of stereoisomerism, namely optical and geometric isomerism.
 Three forms of structural isomerism are chain (skeletal) isomerism, functional group isomerism
and positional isomerism

Definitions

Stereoisomersare compounds that share the same molecular formula but differ in the spatial arrangement of
groups (spatial means ‘… in space’)

Structural isomers: compounds that share the same molecular formula but differ in which atom is connected to
which.

Optical isomers: these are non-superimposable mirror images of each other. Optical isomerism is a form of
stereoisomerism. Optical isomers differ in the direction in which they rotate the plane of polarized light. One of the
isomers rotates to the right, and the other to the left.

Cis-trans isomers: also known as geometric isomers. These are stereoisomers that share the same molecular
formula but differ in the spatial arrangement of groups about a rigid bond, for example, a carbon to carbon double
bond. Cis-trans isomerism is a result of restricted rotation about a rigid bond.

Functional group isomers: these are compounds that share the same molecular formula but differ in which
functional group is present. Well known cases exist between esters and carboxylicacids,ethers and alcohols and
ketones and aldehydes.

Positional isomers: Positional isomers have the same molecular formula and functional group but differ in the
position of the functional group. Examples of positional isomers are but-1-ene and but-2-ene.

Chain (skeletal) isomers: These differ in the length of the main carbon chain. For example, pentane has three
chain isomers.
 494

1.4.1 Structural isomerism

Structural isomers differ in the exact way in which atoms are connected to each other. This type of
isomerism is very common among organic compounds due to the ability of carbon atoms to form chains
of variable length. The position of functional groups or chemical groups on these chains can also vary,
giving rise to a wide variety of structures that share the same molecular formula.
There are three forms of structural isomerism;chain isomerism,functional groupisomerism and
positional isomerism.

Chain isomerism
Chain isomers, also known as skeletal isomers, differ in the length of carbon chains. They are a direct
consequence of the ability of carbon to catenate. One isomer, termed the normal chainisomer, has one
long continuous carbon chain. The other isomers will be branched, consisting of a main chain and groups
branching at some points along the main chain.Chain isomerism is significant in alkanes or compounds
that contain hydrocarbon chains. The smallest alkane that can have isomeric forms is C₄H₁0
The normal chain isomer is n- butane (which is usually just written as butane). The prefix n is used to
denote the unbranched isomer. This is often referred to as the straight chain isomer, but this term can be
misleading. Carbon chains are not straight (linear), but they tend to be jagged (as shown in skeletal
formulae) so that the geometry around each carbon atom minimizes repulsion between electron groups
(VSEPR theory).

Isomers of C₄H₁₀

H C H

H H H H H H
1 2 3
H C C C C H H C C C H
H H H H H H H
n - butane 2- methylpropane

Nomenclature
This refers to a systematic way of naming compounds. Isomers are named using IUPAC rules (IUPAC
stands for the ‘International Union of Pure and Applied Chemistry’).
Notice how the second isomer of C4H10has been named. The longest continuous carbon chain is identified
and all of its carbon atoms are numbered. The longest continuous carbon chain gives the root of the name.
In this case the compound is a propane because the longest continuous carbon chain has three carbon
atoms. There is a methyl(CH3) branch at position 2 of the longest carbon chain. The compound is
therefore named 2- methylpropane.

Carbon compounds are named on the basis of the number of C atoms in the parent chain (longest conti-
nuous chain), side groups and functional groups present.
 495

The prefixes given in Table 10.2 apply to all types of

Number of organic compounds. Consider, for example, the
carbon Prefix names of the compounds below.
atoms in the
parent chain CH3CH3 CH2 = CH2 CH3CH2OH CH3COOH

1 Meth- ethane etheneethanol ethanoic

2 Eth- Note that all of the compounds contain two carbonacid

atoms, so they have the prefix eth. A suffix is then
3 Prop- added to identify the class to which the compound
belongs, for example:
4 But-

5 Pent-
Suffix Class of compound
6 Hex-
-ane alkanes
7 Hept-
-ene alkenes
8 Oct-
-anol alcohols
9 Non-
-anoic acid Carboxylic acids
10 Dec-

11 Undec-

12 Duodec-
Table 10.2 Prefixes used to name organic carbon
chains

Naming alkyl side groups

Chain isomers show different branching. An alkyl branch contains C and H only. Consider two
compounds below, which contain a methyl and ethyl branch respectively.

methyl side group ethyl side group

CH3
CH2CH3

H H H H H H H H H
1 2 3 4 1 2 3 4
H C C C C H H C C C C C C C H
H H H H H H H H H H H
2 - methybutane 2- ethylhexane

The first compound has a methyl group at carbon 2 of a butane chain. The second compound has an ethyl
group at the second carbon of a heptanes chain. Note that the name of an alkyl contains a prefix (as in
Table 10.2) and the suffix -yl. Examples are shown in Table 10. 3 .
 496

Alkyl group Formula

methyl CH3 -

ethyl CH3CH2-
Table 10.3
pentyl CH3CH2CH2CH2CH2-

Show the structures of the isomers of C5H12 and name them.

Q
. From the given formula, we can infer that the compound is an alkane (general formula
CA
n 2n + 2). The first obvious isomer is n - pentane, which has 5 carbon atoms in one continuous
H
chain. We now draw the other isomers by successively reducing the number of carbon atoms in
the longest chain by one. That is, the second isomer is a butane because it has four C atoms in
the longest chain. The other isomer is a propane. The three chain isomers of C5H12 are shown
below.

I II

CH3
H H H H H H H H H H H
1 2 3 4 12 3
H C C C C C H H C C C C H H C C C H
H H H H H H H H H H
n-pentane CH3 CH3
2 - methylbutane 2,2 - dimethylpropane

Structure I is 2 - methylbutane. The name tells us that there is a methyl group on a butane (4 carbon)
chain. Structure II is 2, 2 - dimethylpropane. The name shows that there are two methyl groups at carbon
2 of a propane chain.
Look again at structure I. It could have been possible to number the main carbon chain from the other
direction. This would place the methyl group at position 3, and the compound would have a different
name, 3- methlypropane. This name would be wrong.
The carbon chain is numbered from that direction which would locate the branch at the smaller number.
The numbering in structure I is correct because it places the branch at the smaller number, 2. The
numbering in structure III below is wrong because it places the branch at the larger number, 3.

III Another point which should be stressed is that the choice of the parent chain
is not important in naming a compound. What is important is that the carbon
H H H H chain selected be the longest and it should becontinuous.Structure Iabove
4 3 2 1 could have been numbered by choosing a ‘different chain’, as shown in
H C C C C H
structure IV.
H H H
CH3
 497

IV
methyl branch at carbon 2
H H H H
4 3 2
H C C C C H

H H 1 H
CH3

longest continuous chain has

4 carbon atoms

Note that structure IV still has a methyl group at carbon 2of a butane chain. Its name is therefore
2-methylbutane, that is, it is exactly the same compound as structure 1. If the name of the structures is the
same, they do not represent isomers. They are the same compound. This is useful in checking for
repetitions. You may draw two structures which, to your eyes, may look totally different. If you properly
assign names to them and the names are the same, then you know that you have not drawn two isomers,
you have simply drawn the same compound twice!
Consider the case of a student who draws the structures V and VI and claims that he has drawn two chain
isomers of C5H₁₂.

H structure VI
structure V H
H C

H H H H H
H C C C C H H C C CH3
H H H H
CH3
H C H
H

Notice that in both structures, the longest continuous carbon chain has four carbon atoms and that in
both cases there is a methyl group at position 2 of that chain. Both structures are identified by the name
2- methylbutane. They represent the same compound.

Positional isomerism
Positional isomers differ in the position of the functional group.
As before, numbers are used to locate the position of the functional group. Consider the molecular
formula C₄H₈. This compound is an alkene (general formula CnH2n).But the formula does not tell us where
the double bond is located. There are two different alkenes which share this formula:
 498

I II

H H H H H H H H
1 2 3 4 1 2 3 4
displayed formula H C C C C H H C C C C H

H H H H
butene but-2-ene

skeletal formula

structural formula CH2CHCH2CH3 CH3CHCHCH3

Compound IIis but-2-ene. The prefix but- tells us that there are four carbon atoms in a continuous chain.
The suffix- ene tells us that the compound is an alkene. The locant (locator number) 2 shows that the
double bond beginsat carbon 2. The locant is always where the double bond begins.
The rules for naming organic compounds given in the previous discussion apply here. The carbon chain
should be numbered from the direction that locates the double bond by the smaller number. The carbon
chain should therefore always be numbered from the end which is closer to the double bond, as has been
done for structure I above. If the double bond begins at carbon 1, it is not necessary to include a locator
number in the name of the alkene.

Structures III and IV represent the same compound, pent-2-ene, that is, the two structures do not
represent positional isomers. The carbon chains have been numbered from the end closest to the double
bond.

III IV

H H H H H H H H H H
1 2 3 4 5 5 4 3 2 1
H C C C C C H H C C C C C H

H H H H H

pent-2-ene pent-2-ene

Other classes of organic compounds may also exhibit positional isomerism.Consider the alcohols whose
molecular formula is C₃H₈O.There are two positional isomers, as shown below. They differ only on the
carbon to which the –OH group is attached. The names of the isomers tell us where to find the functional
group.
Propanol may also be written as propan-1-ol, but if
H H H H OH H the name is written without a locator number then it
refers to the isomer in which the functional group is
H C C C OH H C C C H at the first carbon. Note that the two structures refer
H H H H H H to different compounds, despite the fact that they are
both alcohols.For instance, the two compounds form
propanol propan-2-ol totally different esters.
 499

The two isomers also have different boiling points. Propan-1-ol has the higher boiling point because there
is less hindrance around the OH group by surrounding groups. Consequently, hydrogen bonding is strong
(hydrogen bonding requires the participation of an orbital carrying a lone pair of electrons. In propanol
this lone pair is freely available to participate in hydrogen bonding).

Functional group isomerism

A third type of structural isomerism is functional group isomerism.
Functional group isomers are compounds that share the same molecular formula but have different
functional groups.
This type of isomerism is common among
 ethers and alcohols.
 esters and carboxylic acids
 ketones and aldehydes.

Functional group isomerism among esters and carboxylic acids

Both esters and carboxylic acids contain two oxygen atoms. Consider the formula C₃H₆O2. It could imply
propanoic acid, CH₃CH₂COOH, which is a carboxylic acid, or it could represent methyl ethanoate,
CH₃COOCH₃, which is an ester.

O O

CH3 CH2 C CH3 C O CH3

OH
propanoic acid methyl ethanoate

Functional group isomerism among ketones and aldehydes

Both ketones and aldehydes contain the carbonyl group.

The difference between aldehydes and ketones is that in aldehydes there is a

O hydrogen atom bonded to the carbonyl group. The presence of this hydrogen
atom in aldehydes and its absence in ketones affects the chemistry of these
C carbonyl group
compounds so significantly that they are classified into different classes.
Consider the molecular formula C₃H₆O. It could imply propanone, which is a ketone, or it could represent
propanal, which is an aldehyde.

O O

CH3 CH2 C CH3 C CH3

H
ethanal - aldehyde propanone - ketone

O
skeletal formula O
H
 500

1.4.2 Stereoisomerism

Stereoisomerism is the phenomenon in which compounds of the same molecular formula and sharing the
same functional group differ in the spatial arrangement of atoms( spatial arrangement= 3D arrangement
in space).
There are two types of stereoisomerism, cis - trans (geometric) and optical isomerism.

Cis- trans isomerism

This is also known as geometric isomerism. Cis - trans isomerism frequently arises in alkenes because of
restriction to rotation about the rigid double bond. It can also arise in cycloalkanes because their ring
structures also cause single C to C bonds to become rigid and resist rotation.
Consider the alkene whose molecular formula is C₄H₈. Recall that there are two positional isomers that
share this formula:

I II

H H H H H H H H
1 2 3 4 1 2 3 4
H C C C C H H C C C C H

H H H H
butene but-2-ene

Now, structure II also has two isomeric forms, which are cis-trans isomers. First, notice that structure II
can also be drawn as below.

3 4 Each carbon atom of the double bond is bonded to two groups, which have been
1 2
CH3 C C CH3A labeled A and B. Now, recall that geometry at each carbon atom of the double
A bond is trigonal planar (bond angle 1200). The following structures are drawn to
H H
B B clearly show the geometry at carbon 2 and 3.

1200
1 4 A 4 A
A CH B
3 CH3 H CH3
III 2 IV
C= C 3 2 C = C3
1
H H A CH3 H
B B B
cis but-2-ene trans but-2-ene

Structures III and IV do not represent the same compound. These are different compounds, known as
cis-trans isomers. The groups labeled A and B are locked in their respective positions in space because it
is not possible to rotate the double bond and convert one structure into the other.
Structure IIIis the cis isomer (cis = adjacent). Note that similar groups are adjacent (on the same side of
the double bond) to each other.Structure(IV) represents the trans isomer (trans = opposite). Note that
similar groups are diagonally opposite each other with respect to the double bond.
 501

Important note
For cis - trans isomerism to be possible, each carbon atom of the double bond must be bonded to two
different groups. In the example above, there is an H and aCH₃ group on each carbon.

Consider two alkenes P and Q whose structures are shown below.

PC2H5COHCOHC2H5QCH3CHCH2

First draw out the structures to show correct geometry at the double bond. You can then see that cis -trans
isomerism is possible in compound P because each atom of the double bond is bonded to two different
groups.

CH2CH2 CH2CH3
OH CH2CH3
C C
C C
OH OH
CH3CH2 OH

cis isomer trans isomer

Cis - trans isomerism is not possible in compound Qbecause one of the carbon atoms bears the same
group, H.

H H
C=C cis - trans isomerism is not possible if one
or both C atoms of the double bond carries
CH3 H identical groups.

Optical isomerism
This is the second type of stereoisomerism.
Optical isomerism is the phenomenon in which compounds with the same molecular formula, same
structural formula and possessing the same functional group(s) exist in two forms which are non-
superimposable mirror images of each other.
A compound can exhibit optical isomerism only if it possesses a carbon atom to which four
differentgroups are bonded. Such a carbon atom is said to be chiral (From German cheir, meaning ‘hand’:
The left hand and the right hand palms are non superimposable mirror images, just like optical isomers).
The structure of lactic acid(2-hydroxypropanoic acid) is shown.
OH The carbon atom marked with an asterisk (*) is chiral. It is an asymmetric

CH3 C* COOH
centre that gives rise to a pair of non-superimposable images known as optical
isomers, or enantiomers, as shown in Fig 10.4.
H
 502

mirror
line

CH3 CH3
1090

C C
HO COOH HOOC OH
H H

The two optical isomers (entantiomers) of lactic acid.

Fig 10.4

Whenever you draw a pair of optical isomers, you must emphasize the three dimensional aspect by using
the solid wedge ( ) to show a bond pointing out of the paper towards you and a broken wedge ( )
or dashed line to show a bond pointing to the back of the page, away from you. Ordinary lines are used for
bonds which are in the plane of the paper. You should also make sure that one structure is the exact mir-
ror image of the other. Note that it is not important which group you actually put at the end of each bond.
Optical isomerism is possible in compounds such as lactic acid due to the tetrahedral geometry at the
chiral carbon atom. If the bond angle was 900 (square planar), optical isomerism would not be possible,
because the mirror images obtained would be superimposable.
Optical isomers undergo the same chemical reactions. This is expected; sincethey have the same
functional group; they must have similar chemical properties. Optical isomers differ in the direction in
which they rotate the plane of polarized light. One isomer rotates the plane of polarized light clockwise (to
the right), and the other isomer rotates anticlockwise (to the left). Enantiomers are distinguished from
each other on the basis of the direction of rotation of the plane of polarized light using the notation (D)
and (L). The (D) enantiomer rotates the plane of polarized light to the right (D is short for
‘dextrorotatory’which means ‘rotating to the right’). The (L) enantiomer rotates the plane of polarized
light in an anticlockwise direction (L comes from ‘laevorotatory’, which means ‘rotating to the left).
Light from a light source is made up of mutually perpendicular electric and magnetic waves vibrating in
all directions. It is possible to filter light so that the emergent light vibrates in a single direction along a
single plane. Such filtered light is known as polarized light. This is done by passing the light through an
optical filter such as polaroid.
A molecule with a chiral carbon atom is able to rotate the plane of polarized light, to the right or to the
left, depending on whether it is the (D) enantiomer or the (L) enantiomer. Compounds which are able to
rotate the plane of polarized light are said to be optically active. (D) and (L) -Lactic acid are examples of
optically active compounds. 19 of the 20 naturally occurring amino acids are optically active. Glycine is
the only amino acid which has no optical isomers, because it has no chiral carbon atom. The structures of
glycine and alanine, which is optically active, are shown below.

glycine alanine
H O CH3 O

H2N C C H2N C
* C

H OH H OH

Not optically active optically active since a chiral carbon atom

is present
 503

Racemates
If lactic acid is synthesized using usual lab methods, it is found that the product does not rotate the plane
of polarized light. This is not surprising. The synthetic method used is not selective; the yield will contain
50% of the (D) enantiomer and 50% of the (L) enantiomer. Since the two forms rotate the plane of pola-
rized light in opposite directions, the net effect is a cancelling out of therotation. An equimolar mixture of
(D) and (L) isomers of a compound is known as a racemate or racemic mixture and it is optically inactive.

N.BThe notations D and L can be substituted by the notations (+) and (-) respectively.

Biological significance of optical isomers

Biological reactions are carried out by efficient biological catalysts known as enzymes. Enzymes are
specific, that is, in most cases they will recognize only one type of substrate (the reactant on which it acts).
Enzymes are able to recognize and distinguish between optical isomers. Often they can only work on one
of the isomers and not the other. An example is provided by the mould Penicillium glaucum. It can feed
on the (D) enantiomer of lactic acid, but it cannot use the (L) isomer. Geometry of molecules is important
in the action of enzymes. An enzyme has a catalytic region known as the active site. The active site has a
shape complimentary to the shape of the substrate, so the substrate can fit into the active site like a key
fitting into a lock. Only the correct molecule, or a molecule with the correct shape, will fit into the
activesite. In the case of P. glaucum, (L)-lactic acid does not have the correct geometry, so it will not fit
into the active site (This is rather like trying to fit a left glove into the right hand palm).
Sometimes the isomer which is not metabolized acts as a poison. A good example is provided by the drug
thalidomide, which was the preferred sedative for pregnant women in the early ‘60s. The drug at that time
was produced as a racemate. One isomer had the required medical effect, but the other one proved to have
teratogenic effects(causes babies to be born with deformities such as shortened limbs). The structure of
thalidomide is shown below. The chiral carbon atom has been marked with an asterisk.

Chiral carbon. Do not forget that there is

a hydrogen atom at this carbon.
O O

N * O

O
Thalidomide

Q
What is the molecular formula of thalidomide?

A C14H11O4N

Number of possible optical isomers

A compound such as lactic acid with only one chiral centre will give rise to two optical isomers. If a
molecule has two chiral centres, each center will give rise to a pair of optical isomers so there will be a
total of four. In general, the number of optical isomers possible for a molecule is given by 2nwhere n is the
number of chiral centres.
 504

Glucose is commonly represented by the structure below:

CHO

H C* OH There are four chiral C atoms, marked with asterisks. The

total number of possible optical isomers is therefore 2⁴ =
* 16.
HO C H

H C
* H

H C
*
OH

CH2OH
(D)- glucose

(a)The structure of the drug cortisone is shown below. Mark out all the chiral
Q present.
centres

(b) State which functional groups are present in cortisone?

OH
O
cortisone
HO
O

It is important to be able to interpret such skeletal formulae. Always check the number of bonds
Aaround each carbon atom (remember to treat a double bond as two bonds, and a triple bond as
three bonds).If you see only three bonds around a carbon atom, then the fourth position is
occupied by a hydrogen atom. Similarly, if you see only two bonds around a carbon atom, the
other two positions are occupied by two hydrogen atoms, giving a -CH2 group (‘elbow’).
 505

OH
cortisone Carbons with two H atoms (CH2)
O
21
HO 20 4, 5, 9, 10, 13, 14, 17, 21
19
O * Total H = 16
17 15
18 * 16 14
11 Carbons with one H atom
* 6
*
9 7 12
13 2, 6, 7 , 12
10 8 * * Total H = 4
1
5
O 3 Carbons with no H atom
2 4
1, 3, 8, 15, 16, 18, 20
Total H = 0
Analysis of the structure of cortisone
Carbons with 3 H atoms (CH3)
There are 21 C atoms , marked 1 to 21
The molecular formula is C21 H28O5 11, 19
There are 6 chiral carbon atoms, marked* Total H = 6
Other H atoms
Note that a carbon atom which is part of a
OH
double bond can not be chiral (1, 2, 3, 18,
2o). The geometry at these carbon atoms is Total H = 2
1200, not 1090. grand total 28
Never forget that the end of a line segment (11,
19) represents a -CH3 group.

The functional groups present in cortisone are ketone, alkene/C to C double bond and alcohol.

Effect of symmetry
Now study the compound below.
Each of the highlighted carbon atoms has four bonds around it. However, both atoms
are not chiral (they are achiral). Note the perfect symmetry at each of the
highlighted carbon atom with respect to its right and left hand sides.

The groups to the left and to the right of these carbon atoms are therefore identical. The compound is
optically inactive. The molecule below is given to help clarify further the effect of symmetry.

1 This time both highlighted C atoms are chiral, because there is no symmetry around
each, with respect to the LHS and the RHS. For instance, if you look at C2, you will
notice that there are more –CH₂ groups (‘elbows’) going to its left than going to its right.
2 The LHS group is therefore different from the RHS group. However, the molecule is still
optically inactive, despite the presence of two chiral carbon atoms!The explanation is in the internal
symmetry exhibited by the molecule, as shown below.
 506

line of symmetry In this compound, there is internal compensation, whereby the two
1 carbon atoms rotate the plane of polarized light in opposite
directions. The effects of the two carbon atoms therefore cancel
each other out.
2 The concept of internal compensation has been used to explain why
tartaric acid exists as three isomers, of which only two are optically active. The isomers are shown below.

COOH COOH COOH

H OH HO H H OH
HO H H OH H OH
COOH COOH COOH
(+)- tartaric acid (-)- tartaric acid meso - tartaric acid
(optically active) (optically active) (optically inactive)

enantiomers line of symmetry

Explain whether or not optical isomerism is possible in the compound shown

Q
below.

Optical isomerism is possible due to the carbon atoms marked *. Both atoms are asymmetric.
A the whole molecule has no internal symmetry, so the effects of the two chiral carbon atoms
Also,
do not cancel each other out.

*
*

Summary: optical isomerism

 A molecule is optically active if it has a chiral carbon atom, that is, a carbon atom to which are
bonded four different chemical groups. The geometry around a chiral carbon atom is always
tetrahedral, bond angle 109.5⁰. The term ‘optically active’ is used for a compound which is able
to rotate the plane of polarized light.
 507

 Presence of a chiral centre gives rise to a pair of optical isomers, also known as enantiomers or
enantiomeric pair, designated (+) or (-) depending on the direction in which they rotate the plane
of polarized light. Alternatively, the notation D and L is used. Enantiomers differ in the direction
in which they rotate the plane of polarized light; otherwise they have similar chemical reactions.
A racemate (racemic mixture) is a 50%-50% mixture of the (+) and the (-) isomers. A racemate is
optically inactive.
 The theoretical number of optical isomers possible for a molecule is given by 2 n, where n is the
number of chiral carbon atoms present.

Questions, solutions and discussions

Q1Draw the displayed formula of two different compounds that share the molecular formula C4H8O2.
Circle and name the functional group in each structure you have drawn.

Solution

ester group carboxylic acid group

H O H H H H H O
H C C O C C H H C C C C
H H H H H H OH

ethyl ethanoate butanoic acid

This is an example of functional group isomerism.

Tip: If an organic compound contains two oxygen atoms, it could be an ester or a carboxylic acid; otherwise
it is a compound containing two –OH groups, or two different functional groups that contain oxygen.

Q2Lactic acid is one of the chief products of anaerobic respiration in animal tissues. It is responsible for
muscle cramps.
HO (a) Circle and name the group which is responsible for the acidity of lactic
acid.
O
( b) Write down the molecular formula for lactic acid.
OH
( c) Name the functional groups present in lactic acid.
lactic acid
(d) Calculate the mass of lactic acid required to react with exactly 25.00
cm3 of 0.1 moldm-3 NaOH.
 508

Solutions
(a)

carboxylic acid group

HO

OH

(b)C3H6O

(b) Carboxylic acid and secondary alcohol.

(c) Left as an exercise to the reader.

Q3(a) Explain the term optical isomerism.

(b) State a structural feature which must be possessed by an organic compound for it to
show optical isomerism.

(c) Draw the two optical isomers of lactic acid (see question 2).

Solutions
(a) Optical isomerism occurs when two different compounds share the same molecular and structural
formula but differ in the arrangement of groups in space.

(b) A chiral carbon atom should be present. Such a carbon is surrounded by four different groups.

(c)
CH3 CH3

C C
HO OH
H H
COOH COOH

mirror line

Notes

Optical isomers, also known as enantiomers, are stereoisomers. Stereoisomers have the same molecular and structural
formula. The only difference is the three dimensional arrangement of groups in space. The notation used to draw optical
isomers (a mixture of normal lines, solid wedge and broken line) emphasizes the 3D orientation of groups in space
 509

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 10.2
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
The structure of a derivative of one of the primary (b) State which carbon atoms
sex hormones is shown below.
(i) have trigonal planar geometry
18 OH
(ii) bear only one hydrogen atom
16
17 14 (iii) are tetrahedral but not chiral.
15
5 10 13 OH
6 (iv) contain two hydrogen atoms
4 11 12
9
(v) contain no hydrogen atoms
1 3 8
HO 2 7 (c) Name all the functional groups present in this
compound.
(a) Mark out all chiral centres.

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
10.2 Mechanistic organic chemistry
We now discuss in detail the chemical reactions of functional groups. It would be worthwhile to invest
time and effort in this section to make the study of the individual classes of organic compounds easy and
interesting.

Too often students try to learn organic chemistry by memorizing individual reactions of compounds.
This usually turns out to be a difficult task. There are several millions of known organic compounds, and
every day new ones are being discovered or synthesized. The brain finds it very difficult to organize and
store information which is not systematically presented to it. It must see an order and a pattern if it is to
process and store information efficiently. In organic chemistry, the ordering of information can be done
by understanding a few reaction mechanisms thoroughly. The reactions of organic compounds fall
into one or more of these mechanisms. By understanding reaction mechanisms, you do not have to be
intimidated by molecules that look complex on paper, for example, the anti-cancer drug Taxol® (Fig 10.5).
In fact, chances are that in your final exam, you will encounter organic compounds you have never heard
of or learnt about. All you need to do is retrieve information from your brain about how certain reactive
centres in an organic molecule react. These reactive centres are known as functional groups.

A functional group is a group of atoms that is responsible for the chemical behavior
of an organic molecule.
 510

Fig 10.5
The structure of Taxol®, an anti-
cancer drug.
Name the functional groups
present and identify any chiral
centres.

A functional group is the reactive center of an organic molecule. No matter how complex an organic
molecule is, it will always react in a predictable way. This is because its functional group(s) will always
react in a specific way with the specified reagent and under the specified conditions.
A reaction mechanism can be defined as the specific method by which a reaction occurs. In a more strict
sense, a reaction mechanism is the detailed sequence of steps leading from reactants to products. In this
section we will focus on six reaction mechanisms that should be understood thoroughly in ‘A’ Level
chemistry.

10.2.1Addition versus substitution reactions

During a substitution reaction, an atom or group of atoms replaces another atom or group ofatoms
from the organic reactant. Reaction I is an example of a substitution reaction. In this reaction, the OH
group replaces the Cl group in chloroethane.
CH3CH2Cl + NaOH(aq)  CH3CH2OH + NaCl ... I
Note that a substitution reaction results in the formation of two products.

During an addition reaction, two reactants combine to formone product. An example is the addition of
bromine to the double bond of an alkene.

H H Br H
C C + Br2 H C C H
H H H Br
ethene 1,2- dibromoethane
In some cases it may appear as if an addition reaction has formed two or more products. This happens
when the product of the addition reaction further reacts by a different mechanism to form other
substances.

10.2.2 Homolytic versus heterolytic bond fission

Bond fission (breaking) may take place by one of two possible methods, homolysis or heterolysis.

During homolysis (homolytic bond fission), the bond breaks in such a way that each atom of
the bond leaves with a single electron of that bond. This results in the formation of two free
radicals.
 511

odd electron
Homolysis of bond A-Bresults in the formation of two free
radicalsA and B. Notice that we show homolysis by a half-
A B A + B headed arrow. This notation shows the movement of a single
electron.
free radicals

Free radicals are neutral particles which are very reactive by reason of them containing an odd
number of electrons in the outer-most shell.

One electron in the outer-shell is thus unpaired (it is an odd electron). The formula of a free radical is
usually written to emphasize the odd electron, ignoring the paired electrons, as illustrated for a chlorine
atom, which is a well known example of a free radical.

odd electron

lone pair Cl Cl

During heterolysis, the bond breaks so that one atom leaves with both electrons of the bond.

The leaving group takes both electrons of the bond and so becomes a negatively charged ion. In the
following illustration , B is the leaving group. The remaining group may or may not become a cation.

+
Ax B A + Bx

For example, the C-Cl bond in 2 -chloro-2-methylpropane undergoes heterolysis as shown below.

CH3 CH3
CH3 C x Cl +
CH3 C + Cl x
CH3 CH3
2-choro-2-methylpropane

Heterolysis of a bond in intermediates of some reactions generates an anion, but does not generate a
cation, for example.

H H
-
H C x Cl H C OH + Cl x

HO H H

intermediate
(transition state)
 512

Take note of the use of the arrow notation. An arrow is used to show the movement of an electron or a
pair of electrons. A half headed arrow shows the movement of a single electron, for example, during ho-
molysis. A full headed arrow shows the movement of a pair of electrons, for example during heterolysis.

10.2.3 The importance of reaction conditions

Organic reactions frequently involve the breaking of strong covalent bonds. The reactions therefore have
high activation energies, and relatively harsh conditions must be used to overcome this energy barrier to
reaction. Harsh conditions may be provided by using high temperatures and pressures. A special tech-
nique known as refluxing ensures that reactants remain in contact and at high temperatures for a long
time. This increases the yield of the reaction. Refluxing is carried out in a refluxing apparatus (Fig 2.1),
which is in fact a reaction vessel attached to a condenser
During refluxing, the reaction mixture is heated to its
boiling point for a long time. Reactants rise as vapour
and are cooled in the condenser, allowing them to fall
back into the reaction vessel. In this way, the
reactants remain in contact for a long time.
One other reason why organic reactions are
sometimes slower than inorganic reactions is the
orientation factor. According to the collision theory
of reaction kinetics, reactant particles must first
collide with sufficient energy and with the correct
orientation for them to react.The orientation factor is
not much of a problem when the reacting particles
are small. However, in organic reactions, relatively
large molecules are often involved, and this decreases
the chances of the molecules colliding with the
correct orientation. Consider the reaction between
ethanoic acid and methanol to form methyl
ethanoate.

Fig 10.6 A reflux apparatus

If a collision is to be successful, the two molecules should approach each other in such a way that the –OH
group on ethanol collides with the –COOH group on ethanoic acid. Collisions which do not occur in this
way will not result in a reaction, as shown in the following illustration.
 513

The need to specify reaction conditions

The product of an organic reaction is affected by the reaction conditions employed. Changing the
conditions of the reaction usually results in the formation of different products. For this reason, the
student of organic chemistry needs to be aware of the reaction conditions that must be used for specific
reactions. The term condition here refers to
 temperature
 whether or not refluxing is necessary
 pressure
 catalyst
 whether reagent should be used in excess or in limited amounts.

10.3 Organic reaction mechanisms

We are now ready to explore reaction mechanisms that are encountered in ‘A’ level chemistry. The student
is reminded once more: it is better to spend a large amount of time trying to understand these mechan-
isms than rushing to memorize reactions of individual compounds. A reaction mechanism in organic
chemistry is the method by which a particular functional group reacts. Once you understand this method,
you can apply the knowledge gained to predict the reactions of any other compound that bears the same
functional group.

Six reaction mechanisms

1. Nucleophilic reactions
2. Electrophilic reactions 4. Free radical substitution reactions

3. Elimination reactions 5. Organic redox reactions

. 6. Organic neutralization reactions

10.3.1 Nucleophilic reactions

A nucleophilic reaction involves the participation of a particle known as a nucleophile.
Nucleophilic reactions can occur by substitution or by addition.

A nucleophile is an electron rich species which is therefore attracted to a relatively

positively charged carbon atom in an organic molecule, to which it makes a dative bond.

 Nucleophiles are either neutral or negatively charged.

 A nucleophile, whether it is neutral or negatively charged, contains a lone pair which it uses
to attack an electron deficient (relatively positively charged) carbon atom. This carbon atom

is denoted, C
 514

The carbon atom attacked by a nucleophile is relatively positively charged by reason of it being bonded to
a more electronegative atom, for example, the halogen or oxygen atom.

this bond could be single or

multiple


C Y
more electronegative atom
nu

Some of the functional groups which contain an electron deficient carbon and are therefore likely to be
attacked by nucleophiles include

 
  
OH O O
 
 C
C

 C
 
Cl
carbonyl(aldehydes
alcohol and ketones) acyl chloride

   
O O
     
C   C C Hal
N O

amide ester halogenoalkane

Whether nucleophilic addition or substitution occurs depends on the nature of the C-Y bond. If the bond
is relatively weak, the likely reaction is substitution, because the bond can easily break to make room for
the incoming nucleophile. If the bond is double (particularly the C to O double bond), substitution does
not take place because the bond does not easily break. In this case nucleophilicaddition occurs.

The following panel shows the nucleophiles commonly encountered in organic chemistry.

Panel 10. 2

Examples of neutral nucleophiles Examples of negatively charged nucleophiles

 Cyanide, CNʒ
 H2O
 Hydroxide, OHʒ
 NH3
 Halide, e.g. Clʒ
 Amines, e.g. CH3CH2NH2 (ethylamine)
 Hydride, H-
 Alcohols, e.g. ethanol
 515

3.1.1 Nucleophilic substitution

This is a reaction in which an electron rich species, known as a nucleophile, replaces an atom or a group of
atoms in an organic molecule that has an electron deficient (relatively positively charged) carbon atom.
The atom or group of atoms replaced is known as a leaving group and it is itself nucleophilic in nature. A
nucleophilic reaction therefore involves replacement of one nucleophile by another, e.g.
CH₃Cl(aq) + OH⁻(aq) →CH₃OH(aq) + Cl⁻ (aq) …(i)
The nucleophile is the OH⁻ ion from a reagent such as NaOH. The leaving group is the chloride ion. Notice
that the leaving group is also nucleophilic in nature since it is electron rich. This raises an important
question. Why should the nucleophile replace the leaving group if both are nucleophilic in nature? Is it
not likely that once freely available in the reaction mixture, the leaving group, Cl⁻ in this case , will attack
the product, forming the reactants once more (both the reactant and the product carries an electron
deficient centre and so both are susceptible to attack by a nucleophile). This is a very valid argument. We
should turn our attention to bond strengths to understand why one nucleophile can replace another. In
the example above, a weaker C-Cl bond is replaced by a stronger C-O bond. The product is therefore more
energetically stable, so the forward reaction is favoured. However, it is important to know that the reverse
reaction can still happen under certain conditions. If the concentration of Cl⁻ ions in the reaction mixture
is increased , for example, by adding concentrated HCl, followed by heating, then the reverse reaction will
take place, with the Cl⁻ now being the nucleophile and the OH⁻ the leaving group.

Nucleophilic substitution bimolecular (SN2)

Reaction (i) is an example of an SN2 reaction. The mechanism is as follows.

H The C-Cl bond is polarized since chlorine has a greater electronegativity than
 carbon. The carbon atom of this bond is therefore partially positively charged
 since chlorine takes a greater share of electrons of the bond.
HO C Cl
H The nucleophile, being electron rich, is attracted to the Cδ+ of the C-Cl bond,
H resulting in the formation of a new C-O bond. Note that the new bond formed
is dative since it makes use of a pair of electrons from only one atom, the
oxygen of the -OH group. As the C-O bond forms, the C-Cl bond becomes
longer and weaker as it prepares to break.

A transition state (very unstable intermediate) is formed. Instability of this

H transition state is caused by the presence of too many bonds around the
 central carbon atom. Carbon, in Period 2, is not able to expand its octet, that

HO C Cl is, it can only have four bonds (eight electrons) around it in its compounds.
H The transition state is said to be pentavalent, since the carbon atom has five
H bonds (10 electrons) around it. Interelectronic repulsions between these
bonds is responsible for the instability of the transition state. To relieve the
excess electron density around the carbon atom, the C-Cl bond undergoes
heterolysis. The chlorine atom leaves with both electrons of the bond, and so
becomes an anion. Heterolysis of the C-Cl bond results in the formation of a
product in which the carbon atom has the correct number of bonds (four)
around it.
 516

The final product of the reaction, methanol, is more stable than the
reactant, chloromethane. This is because the new C-O bond in the
H product is more stable than the C-Cl bond broken in the reactant.

C + Cl-
H OH
H

The kinetics of the reaction

The reaction mechanism is said to be concerted. In other words, the intermediate (transition state) is so
unstable and short lived that the reaction may be considered as taking place in one step
CH₃Cl(aq) + OH⁻(aq) →CH₃OH(aq) + Cl⁻ (aq)

The rate law is written as

R = K [CH₃Cl]m[OH⁻]n

Now, the values of both m and n have been experimentally determined to be 1. That is, the reaction is first
order with respect to both reactants. Overally, the reaction is second order. It can also be said that the
reaction is bimolecular, that is, the rate determining step involves the collision of two particles. The
mechanism of the reaction between a primary halogenoalkane such CH 3Cl and NaOH has been
appropriately termed SN2.

substitution SN2 second order (bimolecular)

nucleophilic

You can split the rate law above so that it reads

R = K [CH₃Cl] first order kinetics with respect to chloromethane
R=K [OH-] first order kinetics with respect to NaOH
The rate/concentration graph is therefore linear for both reactants. That is, changing concentration of
either reactant results in a proportional change in the rate of reaction.
Rate The energy profile of the reaction is shown in Fig 10.6
 The value of ∆H is negative, that is, the product, CH 3OHis
lower in energy than the reactant, CH3Cl, as already explained.
 The reaction is not spontaneous since Ea is quite high. This is
usually the case with organic reactions. Activation energy is the
minimum energy reactant molecules must possess when they
collide so that a reaction can take place. In this reaction, the
reactant collisions between CH3Cland must be energetic enough to
concentration initiate breaking of the C-Cl bond.
 517

transition state
Energy

Ea

Fig 10.6 Energy profile of an SN2

H reaction. The reaction has only
one ‘hump’ since it is concerted.

progress of reaction

Other SN2 reactions involving halogenoalkanes

In the reaction we have just studied, the OH - nucleophile replaces the Cl atom from the organic reactant.
Other nucleophiles can also replace the chloride atom, and these include CN - and NH3. The same
reactions are also possible in other halogenoalkanes, for example, bromoethane.
Some reactions of bromoethane which occur by nucleophilic substitution second order (S N2)are shown
below.

(i) (ii)
CH3CH2OH CH3CH2Br CH3CH2CN

(iii)

CH3CH2NH2

Reaction (ii) : formation of a nitrile

It is clear that in this reaction the nucleophile is the cyanide ion, which replaces the Br atom from the
reactant. The result is that a halogenoalkane is converted to a nitrile. Now, here we need to make a clear
distinction between a nucleophile and a nucleophilic reagent. The nucleophile is the CN - ion; but it does
not exist on its own, rather, it is found in some reagents such as potassium cyanide, KCN. If you wish to
carry out this reaction, you do not look for cyanide ions; you look for a suitable reagent which can easily
dissolve to release the CN- nucleophile.

ethanol
CH3CH2Br + KCN CH3CH2CN + KBr
reflux

 KCN is not the nucleophile. It is simply a reagent that supplies the nucleophile, CN -.
 Ethanol serves as a solvent. Recall that organic reactants do not dissolve well in water.
 The reagent used should be a salt that can easily release the CN - ions. HCN should not be used.
It is a weak acid and liberates only a very small amount of CN- ions.
 Nucleophilic substitution by CN- is very important in synthesis as it increases the length of the
carbon chain by one atom. If a synthesis involves conversion of an organic reactant to a
product that has one more carbon atom in the carbon chain, you may suspect that CN - was
used as a nucleophile.
 Note that the organic product in the reaction above contains a new C-C bond.
 518

H H
H C C C N
H H new bond
This information is important because it allows us to see that during the reaction, the cyanide
ion attacks the Cδ+ centre of the organic reactant using the carbon atom, not the nitrogen atom.
In other words, the negative charge on the CN-ion is on the carbon atom, not on the nitrogen
atom! The cyanide ion is usually written with the negative charge on the nitrogen atom, but
this is only for convenience. From this point on, we will show the negative charge on the
carbon atom, as shown on the dot - and - cross diagram below.

C . . . N..
x xxx
If you study the dot-and-cross diagram, you will notice that carbon
appears to have used 5 electrons in bonding, and yet it has only
extra electron on C four valence electrons in its outer shell. The extra electron
= charge of -1 therefore originally came from another atom, for example H in
HCN. When HCN dissociates, the H-C bond breaks and the H
atom leaves without any electrons, so the remaining cyanide ion
will have an extra electron on its carbon atom, as illustrated below.

H x C . . . N..
xxx x electron from C
HCN
. electron from N
dissociation electron from H

C . . . N.. + H
x xxx +
extra electron on C,
left behind by H cyanide ion

Reaction (iii): formation of an amine

heat in bomb
CH3CH2Br + NH3 CH3CH2NH2 + HBr

 The reaction is carried out in a sealed vessel known (bomb). This allows pressure to build up. In
turn, this speeds up the reaction.
 The reaction results in the formation of an amine. The mechanism is outlined below.
 519

H H H
H +  
H N .. CH3 C Br H N C Br
H H H
H CH3

H H
.. N C CH3 + HBr
H H

Remember that N in its neutral organic compounds usually forms three bonds, remaining with a lone pair
of electrons. A nitrogen atom bonded to four groups is positively charged, as in the intermediate above.
Notice how one N-H bond breaks by heterolysis, supplying electrons to the N atom and neutralizing the
positive charge.

Nucleophilic substitution first order (SN1) reactions

Consider the reaction below which also occur by nucleophilic substitution,but the mechanism is different.
The difference in the details of the reaction can be traced to the nature of the organic reactant.

reflux
(CH3)3CCl + OH - (CH3)3COH + Cl-
H2O

In this reaction, the OH⁻ nucleophile replaces the Cl⁻ as in the previous example. The mechanism of the
reaction consists of two steps. In the first step, the organic reactant dissociates into positive and negative
ions, just as if it were an ionic compound. The organic ion formed is positively charged and is known as a
carbocation. In the second step, the nucleophile, being electron rich, is attracted electrostatically to the
carbocation, to which it forms a dative bond, forming the product.
( CH₃)₃C-Cl → ( CH₃)₃C⁺ + Cl⁻… step 1: slow
( CH₃)₃C⁺ + OH⁻→ ( CH₃)₃COH … step 2: fast
Step 1 is the slower step because it involves heterolysis of a strong covalent bond. Moreover, a very
unstable intermediate (the carbocation) is formed.
Step2 is faster because it involves the attraction of two ions of opposite charge. Step 1 is therefore the rate
determining step, and we use it to write the rate law.

R = k[( CH₃)₃CCl]
The order of reaction has been experimentally shown to be 1. This reaction is termed SN1 (nucleophilic
substitution first order). Such a reaction involves only one reactant in the slow rate determining step.
The mechanism of reaction was proposed after it was noticed that the rate of reaction varies directly as the
concentration of (CH₃)₃CCl but is not affected by changing the concentration of sodium hydroxide. The
only explanation is that OH- does not appear in the rate law because it is involved in a fast step
(non-rate determining).
The rate/concentration graphs with respect to both reactants are shown in Fig 10.7.
 520

Rate Rate

first order zeroth order

[(CH3)3CCl] [NaOH]
Fig 10.7

The energy profile of the reaction is shown below.

CH3
H3C C
+
intermediate
Energy CH3

Ea1 Ea2
Ea1



progress of reaction

 The reaction is non-concerted. There are two distinct steps leading from reactants to products.
This is a result of the relative stability associated with the intermediate. An intermediate is more
stable than a transition state. It can exist for a relatively longer period, so that there is a clear
separation in time between the first and the second step of the reaction.
 Since the reaction has two steps, the energy profile also has two activation energies (two
‘humps’). In this case, the first step has the higher activation energy, since it requires the
breaking of a relatively strong covalent bond. The second step has the lower activation energy
because it involves conversion of a very unstable intermediate (carbocation) into a stable
product.
 Overally, the reaction has a negative enthalpy (exothermic) because it involves replacement of a
relatively weaker bond (C-Cl) by one which is stronger(C-O).

SN1 or SN2?
Reaction (i) below proceeds by SN2. Reaction (ii) proceeds by SN1.
CH₃Cl (aq) + OH⁻(aq) →CH₃OH(aq) + Cl⁻(aq) … (i)

(CH₃)₃CCl (aq) + OH- (aq) → ( CH₃)₃COH(aq) + Cl⁻(aq) ... (ii)

 521

But why should the reactions occur by different mechanisms? Both reactants are halogenoalkanes and
they are reacting with the same reagent. The answer is in relative stabilities of the carbocation interme-
diates that could be formed from each of the halogenoalkanes.
The halogenoalkane in reaction (ii) is tertiary, that is, the carbon atom that bears the halogen atom is
bonded to 3 alkyl groups, as shown below.

H3C The carbocation formed from this molecule by heterolysis of the C-Cl bond has a
C Cl positively charged C atom which is bonded directly to three alky (methyl groups),
H3C which have an electron pushing (positiveinductive) effect, as shown by the arrows in
CH3 the structure shown below.
The effect of this positive inductive effect is to partially neutralize the positive charge
H3C and make the carbocation relatively stable. Formation of this carbocation is
C
+ therefore favourable, explaining why (CH₃)₃CCl reacts via the carbocation (SN1).
H3C Chloromethane (CH₃Cl) can not react via a carbocation. If this were to happen, the
CH3 carbocation intermediate formed would be as shown below. The carbocation has a
positively charged C atom to which is bonded three H atoms. Hydrogen atoms do
not have the electron pushing ability associated with alkyl groups. The positive
H
C
+ charge on this carbon is well pronounced, making the intermediate very unstable, so
unstable that it is not formed at all.
H
H The reaction route chosen avoids a carbocation and proceeds via a pentavalent intermediate
(SN2 ), which is more stable than the carbocation that could havebeen formedhad the reaction proceeded
by SN1.
In general, SN1 would be the favoured mechanism if there are three alkyl groups bonded to the carboca-
tion. The stability of the carbocation depends on this. The length of the alky groups is also important. The
longer an alkyl group is, the stronger its electron pushing effect and the more stable the carbocation would
be.
Compare the three carbocationsshown in fig below:

H H3C
+ + +
C C C CH2CH2CH3
H H3C H3C
H
CH3 CH2CH3

(I) (II) (III)

Carbocation(I)would be the least stable and its formation is unlikely. Both carbocation(II) and (III)are
stable enough to be formed as intermediates during nucleophilic substitution. However, carbocation (III)
is more stable since it has longer alkyl groups which have a stronger electron pushing effect.

Water as a nucleophile: hydrolysis reactions

Water can act as a nucleophilic reagent since it possesses lone pairs of electrons. Nucleophilic substitution
of a halogen atom from a halogenoalkane can take place, for example
CH3CH2Br + H2O → CH3CH2OH + HBr ... (i)
In this reaction, the nucleophile is actually the hydroxide ion which is derived from water. This is
therefore an example of a hydrolysis reaction, since it involves splitting of a water molecule.
 522

In a hydrolysis reaction, water acts as a reactant and it is split into OH- and H+

Reaction (i) is very slow and an insignificantly small amount of product is formed. This is because the
O-H bond in water is so strong that it does not easily dissociate to release the OH - nucleophiles. Another
way to explain this is to say that the autodissociation of water is so slight (K w is a very small number =
10 -14 mol2dm-6) that the concentration of OH- ions is very small. The probability of collisions between the
halogenoalkane and OH- ions is therefore very small. The rate of formation of the product is increased by
boiling or refluxing the halogenocompound with an alkali such as NaOH, as already explained. The
reaction taking place is then referred to as alkaline hydrolysis. The mechanism of the hydrolysis reaction
between a halogenoalkane and water occurs by S N2 in primary halogenoalkanes and by S N1 in tertiary
halogenoalkanes. This is illustrated for a primary halogenoalkane below. In a primary halogenoalkane, the
carbon atom that carries the halogen is bonded to two hydrogen atoms.

H H H H H H
 
C C Br H C C Br H C C OH
H .. H H
O.. H H H
H H .
O.
H H + H
+ HBr
H2O attacks electron deficient
carbon atom. New C-O bond unstable pentavalent transition
begins to form. At the same state.
time, C-Br bonds begin to
Note positive charge on the bonded
break.
'H2O' group. Heterolysis of C-Br
bond continues.

 If the halogenoalkane contains more than one carbon atoms, it is the carbon atom which is di-
rectly bonded to the halogen atom which is attacked by a nucleophile. This carbon is partially
positive.
 The mechanism of the reaction is concerted, as already explained. Bond formation and
bondbreaking occur simultaneously.
 In the transition state, the O atom from water has three bonds, not two as is the usual case. The
oxygen atom is therefore positively charged. An O-H bond then undergoes heterolysis, and the
electrons from this bond are shifted onto oxygen, neutralizing the positive charge. The hydrogen
ion produced from this heterolysis then combines with the Br - ion from the heterolysis of the
C-Br bond to form HBr.
 The mechanism of the reaction is SN2because the slower rate determining step involves collision
of two reactant particles, H2Oand the primary halogenocompound. If the halogenocompound
was tertiary, the reaction would be SN1.
 523

Table 10.3Differences between SN2andSN1 reactions in halogenoalkanes

SN2 SN1

Concerted mechanism. Bond formation and Non- concerted mechanism. Breaking of the C-Hal
breaking of the C-Hal bond is simultaneous. bond and formation of a new bond with the
nucleophile occurs in two distinct steps.

Nucleophile attacks in ‘first step’. However, in a Nucleophile participates in the second step.
strict sense, it is difficult to really distinguish
between one step and the next.

Nucleophile directly attacks the reactant Nucleophile does not attack the organic reactant.
(halogenoalkane). Rather, it attacks the intermediate formed in the
first step.

A very unstable and extremely short-lived A relatively stable carbocation intermediate is

pentavalent transition state is formed. formed.

The energy profile of the reaction has only one The energy profile of the reaction has two ‘humps’,
‘hump’, that is, one activation energy, since the that is, two activation energies, since the reaction
reaction essentially takes place in one step. essentially takes place in two steps.

Takes place in primary halogenoalkanes. Takes place in tertiary halogenoalkanes and some
secondary halogenoalkanes.

Example : CH3CH2Br + OH- CH3CH2OH + Br- (CH3)3CBr + OH- (CH3)3COH + Br-

Conditions required for nucleophilic substitution

From the foregoing discussion, it has probably become clear that the following conditions are required for
a nucleophilic substitution reaction to take place:
 Presence of a nucleophile.
 An organic reactant with an electron deficient (relatively positively charged) C atom, as in haloge-
noalkanes.
 A relatively weak bond in the organic reactant (such as the C-Hal bond) which can break to make
room for the incoming nucleophile.
This condition is important in deciding whether nucleophilic substitution or addition takes place.
If the first two conditions are satisfied, and yet there is no bond that can easily break to allow
substitution, then the reaction likely to take place would be nucleophilic addition.

Effect of C-Hal bond strength on the rate of nucleophilic substitution

Which of the following halogenoalkanes will react the fastest with OH - ions?

CH3CH2Cl CH3CH2Br CH3CH2I

There are two things to consider

 524

 the ability of the Cδ+ in the organic reactant to attract the nucleophile. This depends on the
polarity of the C-Hal bond.
 the strength of the C-Hal bond. Nucleophilic substitution depends on the ability of the C-Hal to
undergo heterolysis. The weaker the bond, the faster the rate of substitution of the halogen atom
by a nucleophile.
If we consider the first point, then we expect CH 3CH2Cl to react the fastest with nucleophiles. This is
because the C-Cl bond is the most polar. CH3CH2I will react the slowest because the C-I bond has the least
polarity. It is not so easy for the carbon atom of the C-I bond to attract a nucleophile.
However, from a consideration of bond strength, we would expect CH 3CH2Cl to have the smallest rate of
reaction, since the C-Hal bond is the strongest. It does not easily break to make room for the incoming
nucleophile. CH3CH2I would react the fastest since the C-I bond is the weakest. Bond polarity and bond
strength therefore have opposite effects on the rate of substitution with nucleophiles. However, bond
strength has the greater effect, so reactivity of the halogenoalkanes is in this order :

CH3CH2I > CH3CH2Br > CH3CH2Cl

most reactive least reactive
weakest strongest
C - Hal bond C - Hal bond

Summary: nucleophilic substitution

 In these reactions, a nucleophile replaces an atom or group of atoms from the organic reactant. A
nucleophile is an electron rich species (neutral or negatively charged) which is therefore attracted
to an electron deficient carbon in the organic reactant.
 Nucleophilic substitution can occur by SN1 or by SN2, as summarized in Table 10.4.
 Nucleophilic substitution is well known in, but not limited to halogenoalkanes. The product of the
reaction between a halogenoalkane and a nucleophile depends on which nucleophile has been
used. Let the nucleophile be Nu:, then the substitution reaction can be written as

R-Hal + Nu: → R-Nu + Hal-

nucleophile Product formed Conditions

OH- (e.g. from KOH) alcohol Boil or reflux in water.

H2O alcohol Yield is very poor even when

the reaction mixture is boiled.

CN- (e.g. from KCN) Nitrile (need to reflux Reflux in ethanol (solvent)
in alcohol solvent)

NH3 Amine Heat in a sealed bomb.

 All of the reactions above require refluxing or strong heating because they involve breaking of a
relatively strong covalent C-Hal bond.
 Nucleophilic substitution with water as the nucleophile is known as hydrolysis. The reaction is
very slow because water does not easily release OH- nucleophiles.
 525

3.1.2 Nucleophilic addition

First recall the difference between a substitution and an addition reaction.In a substitution reaction, an
atom or group of atoms replaces another in the reactant, resulting in the formation of two products, e.g.
CH₃Cl (aq) + OH⁻ (aq) →CH₃OH (aq) + Cl⁻ (aq) … 1
In an addition reaction, atoms from one reactant are incorporated into another reactant, resulting in the
formation of one product, e.g.
BCl₃ + NH₃→BCl₃.NH₃

Nucleophilic addition is a reaction in which atoms of a nucleophilic reagent are incorporated into
an organic reactant which has a relatively positively charged C atom.

Nucleophilic addition reactions involve compounds that possess the carbonyl group.
 . . 
carbonyl group C O.
.
Addition of a nucleophile to a molecule would result in the increase of electron density around the
electron deficient carbon of the organic reactant. This leads to instability. There are two possible ways of
removing this instability: either a bond breaks by heterolysis, resulting in an atom or group of atoms
moving away with the extra electron density. This happens in nucleophilic substitution reactions in which
there is available a bond weak enough to be broken and make room for the incoming nucleophile.
The second way of redistributing electron density to accommodate the incoming nucleophile involves
shifting the extra electron density from carbon and accommodating it on an atom that has the ability to do
so. The carbonyl group is unique in this sense. The oxygen atom of the carbonyl group is able to accept
and stabilize an electron pair to create room for the incoming nucleophile. Also the carbonyl bond, being
double, is strong and cannot be easily broken as in nucleophilic substitution.
Here is a well known example of a nucleophilic addition reaction.

atoms from HCN

trace NaCN/
CH3COCH3 + HCN CH3C(OH)CH3CN
NaOH
propanone 2-hydroxybutanenitrile
(ketone) ( cyanohydrin)

Notice why this is an addition reaction; atoms from the nucleophilic reagent (HCN) have been incorpo-
rated into the organic reactant, to form one product. The reaction is very slow without a catalyst. NaCN or
NaOH are effective catalysts.The Mechanism of the reaction is as follows.
 526

H3C   Carbonyl compounds are trigonal planar (flat) at the carbonyl group

C O  (bond angle,1200).The C=O bond is polarized, since O is more electro-
negative than C. The C atom of the carbonyl group is relatively positively
CH3 charged and is therefore prone to attack by a nucleophile. The nucleo-
propanone phile (-CN in this case) approaches and attacks perpendicularly from
-. below or above the plane of the molecule to minimize repulsion from the
.CN lone pair of electrons on the O atom. The nucleophile is generated from
the dissociation of HCN, which is a weak acid.
HCN Ý H+ + -CN
As the nucleophile bonds to the electron deficient C, there is an increase
in electron density around the central carbon atom, leading to instability.
The excess electron density brought in by the nucleophile is shifted on to
the O atom. This involves breaking of the pi bond of the carbonyl group
(a π bond is weaker than a σ bond). The electron pair from the pi bond is
accommodated by O. It is the ability of O to accept and stabilize a pair of
electrons which makes nucleophilic addition possible.
H+ The intermediate is a negatively charged ion. Note that this ion has a
tetrahedral geometry, bond angle 1090. The extra electron density that
came in with the nucleophile is now accommodated on the O atom of the
H3C
..- intermediate. The negative charge on the O atom is now neutralized by
C O ..
H3C
-
.. the H+ ion from the dissociation of HCN. A stable product is thus formed.

CN

negatively charged
intermediate

The product of this reaction is a compound known as a cyanohydrin or a

H3C
2-hydroxynitrile.
H3C C OH
-
CN
cyanohydrin
(2-hydroxynitrile)

The reaction described above gives rise to a cyanohydrin. On their own, these compounds have limited
uses, but they are extremely important as intermediates in the synthesis of more useful compounds. These
synthesis reactions rely on the conversion of the nitrile group, particularly to an amine (reduction) and
carboxylic acid (hydrolysis).
 527

OH

C
H3C CH3 LiAlH4 (lithium tetrahydrido aluminate) is a
C N very powerful reducing agent used to carry out
reductions where many other reducing agents
cyanohydrin cannot. Its major disadvantage is that it is very
sensitive towards water, in which it explodes to
give a mixture of products. This reagent adds H
atoms to the nitrile group.

LiAlH4 /ether H2SO4(aq) / reflux The nitrile group can be converted to a

(reduction) (hydrolysis) carboxylic acid by hydrolysis. The reactant in
all hydrolysis reactions is water, but an acid
catalyst is often required. In this case, H2SO4
supplies H+ ions which catalyze the reaction.
OH OH

C C
H3C CH3 H3C CH3
CH2NH2 COOH

Catalytic role of NaOH or NaCN

The reaction between propanone and HCN is very slow. This is because HCN is a weak acid; its dissocia-
tion in water is only slight, so the concentration of CN - nucleophiles is very small. The reaction can be
made faster by adding trace amounts of NaCN or NaOH.

Catalysis by NaOH
The following equilibrium exists in the reaction vessel
HCN Ý H+ + CN-(aq) ... (i)

Upon addition of NaOH (aq), H+ ions are removed from the equilibrium
H+ (aq) + OH-(aq) → H2O
This forces equilibrium (i) to the right, releasing more CN - nucleophiles (Le Chatelier’s principle). The
increase in the concentration of cyanide ions increases the probability of collisions with propanone
molecules, and this in turn increases the rate of reaction.

Catalysis by NaCN
Being a salt of high solubility, NaCN dissociates in water to release CN - nucleophiles. These are the ligands
which participate in the first step of the reaction, resulting in the formation of a negatively charged inter-
mediate. The intermediate has a high affinity for hydrogen ions, so it rapidly removes H + from HCN,
generating - CN ions (the catalyst is thus regenerated). Once the first anion intermediates are formed, the
reaction becomes rapid as these anions rapidly remove H+ ions from HCN, thus generating more CN- ions.
 528

H CN

H3C  
O   H3C
C ...-
CH3
H3C
-
C
.O. .
propanone CN
-.
. CN from NaCN, not HCN anion intermediate

H3C
..
C O .. H + CN
H3C
-
..
catalyst regenerated
CN

Conditions for nucleophilic addition

 A nucleophilic reagent must be present.
 A carbonyl group should be present in the organic reactant. This group has an electron deficient
carbon atom which can be attacked by the nucleophile.

Questions, solutions and discussions

Q1The kinetics of the reaction between (CH3)3CCl and NaOH has been studied.
(a)Construct a balanced equation for this reaction.

(b) State the conditions required for the two substances to react.

(c) The rate of the reaction changes proportionally when the concentration of (CH 3)3CCl
is changed. Changing the concentration of NaOH does not affect the rate of reaction.
Comment on these observations as fully as possible.

Solutions

(a)(CH3)3CCl + NaOH  (CH3)3COH + NaCl

(b) Reflux in aqueous solution.

 529

(c)From the given facts, we conclude that the reaction is first order with respect to
(CH3)3CCl and zeroth order with respect to NaOH. NaOH is therefore involved in a fast
non-rate determining step.

(CH3)3CCl (CH3)3C+ + Cl- … I slow

(CH3)3C+ + OH-  (CH3)3COH … II fast

Step I is the slower rate determining step because it involves the breaking of a relatively
strong C-Cl bond and the formation of a very unstable intermediate (a carbocation).
The rate law is written using the slower rate determining step,
R = K [(CH3)3CCl]
That is, the reaction is first order with respect to the halogenoalkane. A change in the
concentration of the halogenoalkane results in a proportional change in the speed
of reaction. Step II, involving NaOH, is the faster non-rate determining step. Changing
concentration of NaOH therefore has no effect on the rate of reaction.
The reaction is said to proceed via an S N1 mechanism since the slow rate determining step
involves only one reactant molecule.

Q21-(4-hydroxyphenyl)butan-2-one, A is responsible for the aroma of raspberries.

O
A H
O
1 -(4-hy drox y pheny l)butan-2-one

(a) Circle and name the functional groups in A.

(b) How would you expect A to react with

(i) dilute HNO3

(ii) HCN in the presence of a little NaCN?

Draw the structure of the product formed in each case.

Solutions
(a)
 530

(b)(i) Electrophilic substitution (nitration) in the benzene ring.

[ no catalyst is needed since the benzene ring is activated by the -OH group]
The product formed is

(ii) Nucleophilic addition to the carbonyl group, to form

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Exercise 10.5
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1.The cyanide ion reacts with both chloropropane and propanone.

(a) Name the type of reaction which takes place in each case

(b) What are the reagents and conditions required for each reaction?

(c) Outline the reaction mechanism for each reaction.

(d) Suggest why chlorobenzene has no reaction with cyanide under ordinary lab conditions.

2. Draw the structure of the product formed when benzaldehyde reacts with HCN in the presence of a
trace amount of NaOH(aq).

(a) What type of reaction takes place?

(b) Why is the reaction very slow in the absence of OH- ions?

(c) What other substance can be used to catalyze the reaction?

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 531

10.3.2 Electrophilic reactions

Electrophilic reactions involve electrophilic reagents.

An electrophile is an electron deficient species, usually positively charged, that therefore seeks
an electron rich centre.
(Electrophile literally means ‘electron lover’. To ‘love’ electrons, a species must be relatively posi-
tively charged).

Most electrophiles are positive ions generated insitu, that is, they do not have an independent existence
but must be generated during the reaction in which they participate.
Electrophiles are attracted to electron rich centres, notably the C to C double bond and the benzene ring.
Examples of electrophiles include Br⁺(generated insitu from bromine), H⁺ from a mineral acid such as
HCl, and the nitronium ion, NO2⁺, generated insitu from the reaction between concentrated sulphuric and
nitric acids.
There are two types of electrophilic reactions, addition and substitution. Electrophilic addition occurs to
the carbon to carbon double bonds in alkenes, whilst electrophilic substitution occurs in the benzene ring.

Elecctrophilic reactions

Addition substitution
Occurs in C to C double bond occurs in benzene ring

3.2.1 Electrophilic addition

This is a reaction in which atoms of an electrophilic reagent are incorporated to the electron rich centre
of the organic reactant.
These reactions occur at the C to C double bond of alkenes.

Halogenation of ethene
You will probably remember that alkenes decolourize cold bromine in the dark. This is a reaction of the C
to C double bond, for example

CH₂ = CH₂ (g) + Br₂ (l)→CH2BrCH2Br (l)

In this reaction, ethene is converted to 1, 2- dibromoethane. The numbers 1 and 2 emphasize that the Br
atoms are added across the double bond, rather than on the same carbon atom. The reaction above does
not reveal the electrophile. This is because the electrophile, Br⁺, is generated insitu from bromine.
 532

The mechanism

π electrons of the double bond repel the lone pairs of electrons in bromine.
H H
This polarizes bromine, that is, one end of the molecule becomes richer in
C  C electrons and the other becomes deficient in electrons. The electron deficient
 pole of the molecule is relatively positively charged, so it is attracted to the
H H electron rich double bond, and a C-Br bond begins to form. At the same
time, the Br-Br begins to break. Heterolysis of the Br-Br bond produces the
.
Br x Br
bromonium ion, Br+, which is the electrophile in this reaction. However, the
Br+ ion is not released in solution but it immediately forms a bond to one
carbon atom of the double bond. This requires breaking of the π bond of the
C to C double bond; it is the electron pair from this bond which is used to
form the new C-Br bond. The first step in the reaction is very slow because it
involves breaking of a strong Br-Br bond.

H H
Breaking of the π bond in ethene leaves one carbon atom with three bonds
C C+
H (electron deficient) instead of four. The intermediate of this reaction is there-
Br H fore a carbocation.

carocation intermediate
The intermediate is very unstable and it immediately reacts with the bro-
mide ion from the heterolysis of bromine. In this reaction, the bromide ion
actually behaves as a nucleophile. However, this step is very fast (it
involves attraction of oppositely charged ions) and so it is non rate
H H
Br .. - determining. The reaction is termed electrophilic addition because the
C C+ slower rate determining step involves the participation of an electrophile.
H
Br H

The product of this reaction is an oily colourless liquid known as 1,2-dibro-

H H moethane. The reaction of an alkene with bromine is a test for
C C Br unsaturation (presence of a C to C double bond). Alkenes decolourize
H bromine liquid in the cold.
Br H
1,2-dibromoethane

 What evidence is there that the reaction proceeds via a carbocation?

If the reaction is carried out using pure bromine liquid, only one product, 1, 2-dibromoethane is formed.
However, when bromine water (bromine in water) is used, a mixture of products is formed, 1,2-
dibromoethane and 1-bromoethanol, whose structure is shown below. This shows that the reaction
proceeds via a relatively stable cation which then reacts indiscriminately with whatever nucleophile is
present. When pure bromine is used, the only nucleophile available to react with the carbocation is Br -.
 533

However, when bromine water is used, there are also OH - ions from the autodissociation of water. These
also react with some of the carbocations, to form a different product, 1-bromoethanol.

H H
1
C C+
H
Br H
carbocation intermediate

Br- from the heterolysis of

OH- from the dossociation of
Br2 attacks C1 water attacks C1

H H H H
1 1
C C Br C C
H H OH
Br H Br H

1,2-dibromoethane 1-bromoethanol

If other negatively charged ions are added, for example, NO3- and Cl-, corresponding products are
formed, in addition to 1, 2 - dibromoethane, as shown below.

CH2Br CH2NO3

NaNO3(aq)

CH2Br CH2
NaCl(aq)

CH2Br CH2Cl

 Why does electrophilic addition to the double bond in alkenes involve breaking of
a pi bond, not a sigma bond?
A pi bond is weaker. This is because on average, pi electrons are a larger distance from the nuclei of both
atoms of the C to C bond.

Addition of HX to the double bond (X = Cl, Br, I)

Hydrogen halides can also be added to the double bond via electrophilic addition. The electrophile in this
case is the H⁺ ion generated insitu from the hydrogen halide.Consider the addition of HCl to ethene.
CH₂CH₂ + HCl →CH₃CH₂Cl
 534

In this reaction, an alkene is converted to a halogenoalkane. The mechanism is similar to that of the
addition of bromine to the double bond. If a pure product is required, then the reaction should not be
carried out in water. As already explained, the reaction proceeds via a carbocation and if water is present,
the carbocation may react with OH- ions from water. The product, chloroethane, will be contaminated
with ethanol. A suitable organic solvent such as hexane can be used.

H H H H
H H 1 Cl-
C C+ C C Cl
C  C H 2 H
H H H H

H H
carocation intermediate
H Cl

Once more, note that atoms of the electrophilic reagent, HCl, are added across the double bond. The first
atom of the double bond (1) accepts the electrophile and the C to C pi bond breaks. The other atom of the
double bond (2) acquires a positive charge, which attracts a negative ion (nucleophile) generated from the
electrophilic reagent.
If water is used as the solvent, contamination of the product by ethanol cannot be avoided. The OH⁻ ions
from the auto- dissociation of water can also react with the carbocation intermediate, resulting in the for-
mation of ethanol. The amount of ethanol formed can be kept at a minimum by using concentrated HCl.

Markownikoff’s rule
Addition of HX to the double bond can give rise to a mixture two isomeric products.
Consider the reaction of propene with HCl. The electrophile can bond either to carbon 1 or to carbon 2.
This affects the carbon at which the positive charge develops, and in turn this affects the position where
the negative ion from HX bonds. Markownikoff’s rule helps us to predict the isomer which is formed in
greater amounts.

Markownikoff’s rule says:

During the reaction of an alkene with a hydrogen halide HX, the H+ electrophile from HX attacks that
carbon of the double bond which already contains the larger number of hydrogen atoms.

The following illustration pertains to the reaction of propene with HCl. Two possibilities are shown
 Markownikoff addition in which the H+ ion attacks the carbon of the C=C bond that bears the
larger number of hydrogen atoms.
 AntiMarkownikoff addition in which the H+ ion attacks the carbon of the C=C bond which
bears the smaller number of hydrogen atoms.

AntiMarkownikoff addition is not favoured because t results in the formation of an unstable intermediate.
 535

H
1 2 When propene reacts with HCl, two products
H C C C H are formed,chloropropane and 2-
H H H chloropropane. The major product is 2-
chloropropane, as predicted by
Markownikoff’s rule. H+ ions mostly attack
If electrophile (H+) attacks carbon 1 since it is the one that already has the
larger number of hydrogen atoms.
A large number of the carbocation
intermediates will therefore have a positive
Carbon 2 Carbon 1 charge on carbon 2.

positive charge develops at C 1 positive charge develops at C 2

H H H H Cl-
+1 2 +2
C C C A larger proportion of the carbocation
H C C C H H H
1 intermediates formed have a positive
Cl- H H H H H H charge on carbon 2. This is because the
positive charge would then be stabilized
by the electron pushing effect of two
alkyl (methyl) groups. This is the
Cl H H H Cl H reasoning behind Markownikoff’s rule.

H C C C H H C C C H
H H
H H H H H H +
H C C C H
chloropropane 2-chloropropane
H H H

What would be the product or products formed when but-2-ene reacts with HBr in
aQ
suitable organic solvent?

H H

H C C C C H

H H H H
but-2-ene

Only one product, 2-chlorobutane is formed. This is because the double bond in but-2-
Aene is symmetrically positioned. It does not matter which carbon is attacked by the
electrophile, the same product will be produced.
 536

Summary: electrophilic addition

 Occurs to the C to C double bond in alkenes
 During the reaction, atoms from the electrophilic reagent are added across the double bond, to
form only one product.
 The reaction is initiated by polarization of the electrophilic reagent by π electrons of the C to C
double bond. The πelectrons have theability to cause this polarization because they occupy a
diffuse (spread out) π orbital which is therefore only weakly attracted and stabilized by the
nucleus.
 Examples of electrophilic reagents which can add to the double bond in alkenes are the halogens,
X2 and hydrogen halides, HX. For the halogens, the electrophile is the ion X + which is generated
insitu from heterolysis of the X-X bond. For HX, the electrophile is H+.
 The reaction proceeds via a carbocation intermediate. This explains why it is possible to form a
mixture of products when two or more nucleophilic particles (e.g. OH - from water) are present in
the reaction mixture.
 The addition of HX to the double bond is governed by Markownikoff’s rule, which says that the
H+ electrophile attacks the carbon atom which has the greater number of hydrogen atoms. If the
double bond is asymmetrically located in the molecule, two positional isomers are formed. The
more abundant isomer is the one that is formed according to Markownikoff’s rule.

Q
Predict the products formed when cyclohexene reacts with

(a) Liquid bromine

(b) HBr in the presence of a suitable organic solvent
(c) HBr in the presence of dilute NaCl (aq)

A Br
(a) + Br2 Br
cyclohexene C6H10Br2

(b) + HBr Br
C6H11Br

NaCl
(c) + HBr Br + +
Cl OH
C6H11Br C6H11Cl C6H12O

Q
 537

When an alkene X was reacted with HBr in a suitable solvent, a mixture of two
isomeric products A and B with the formula C4H9Br were formed. Hydrolysis
of isomers A and B with aqueous NaOH gives rise to alcohols C (primary)
and D (tertiary) respectively.

Determine the skeletal formula of A, X, B, C and D.

Ina tertiary alcohol, the O-H group is bonded to a carbon atom that is bonded to three alkyl
A groups. A tertiary alcohol that contains four carbon atoms has the structure D shown below.
OH
D. H3C C CH3
CH3

C is a positional isomer of D (C is a primary alcohol, that is, the -OH group is bonded to a
carbon atom that bears two hydrogen atoms).

H H H
C. H3C C C C OH
H H H
D is produced from halogenoalkane B by nucleophilic substitution

H Br H H OH H
OH-(aq)
B. H C C C H D. H C C C H
reflux
H H3C H H H3C H

C is produced from halogenoalkane A.

H H H H H H
OH-(aq)
A. H3C C C C Br C. H3C C C C OH
reflux
H H H H H H
X has the structure shown below. HBr is added to the double bond, giving rise to two
products. One of the products is present in larger amounts, according to Markownikoff’s rule.

H H H Br H H H H
HBr
H3C C C C H H3C C C C H + H3C C C C Br
H H H H H H H H
X A B
greater percentage
 538

3.2.2 Electrophilic substitution

The C to C double bond and the benzene ring are prone to attack by electrophiles because of their electron
rich nature. Electrophilic addition occurs preferably to the double bond in alkenes. Electrophilic substitu-
tion occurs preferably to the benzene ring.

The benzene ring

Benzene has the molecular formula C₆H₆. For a long time no scientist could figure out the structure of
benzene based on its molecular formula. Then one day, Augustus Friedrich Kekulé ‘saw’ the structure of
benzene in a dream. His structure(Kekule’s benzene) is shown below.
H
Kekulé received great acclaim for coming out with this structure, but the
H H fame was short-lived, for the structure failed to account for some
important observations about benzene, for instance:
 Bromine does not decolourize benzene. If it had three double
H H bonds as depicted in the Kekuléstructure, then it would
H certainly decolourize bromine in an electrophilic addition
reaction. In this reaction, one mole of benzene would react with
Kekule's benzene with
three double bonds and three moles of bromine, since the Kekulé structure has three
three single bonds double bonds.
 The enthalpy change of hydrogenation of cyclohexene, which
has only one double bond is -120Kj/mol. If benzene had three double bonds, then its enthalpy of
hydrogenation would be-120 x 3 = -360Kj/mol. The actual enthalpy of hydrogenation of
benzene has been found to be -208Kj/mol.
 All C to C bond lengths in benzene are equal. If Kekulé’s structure was correct, benzene would
have shorter double bonds and longer single bonds.
Because of these discrepancies, the structure of benzene has been revised. It is now known that the pi
electrons in benzene, which would have formed the double bonds, are not localized as depicted in
Kekulé’s benzene. Instead they are delocalized throughout the molecule. The structure of benzene is now

drawn like this, . This structure is usually referred to as the benzene ring. The hexagon represents
the sigma skeleton C₆H₆. The circle inside this skeleton represents six electrons delocalized in a single pi
molecular orbital.The consequence is that there are no pure single or pure double bonds in benzene. The
C to C bonds are intermediate between being single and being double.
The fact that less heat is evolved upon hydrogenation than would have been expected from Kekulé’s
structure also shows that the bonds in benzene are not double.
The effect of delocalization of six electrons in benzene is to stabilize the benzene ring. Resonance energy
of benzene is the extra stability of benzene relative to Kekulé’s structure. This can be worked out from the
enthalpies of hydrogenation of benzene and cyclohexene.
Resonance energy = extra stability of the ring = 360-208= 152Kj/mol
[360Kj/mol = enthalpy of hydrogenation of Kekulé’s structure = 3 x enthalpy of
hydrogenation of cyclohexene.
-208Kj/mol = The observed enthalpy change of hydrogenation of benzene]
Benzene seeks to maintain this stability in its reactions. Any reaction that destroys the delocalized system
of electrons destroys the stability of the ring. Such reactions are not favoured. This explains why benzene
 539

does not prefer to react via electrophilic addition. This type of reaction would require the use of the
delocalized pi electrons in making new bonds with the electrophile.
The favoured reaction is electrophilic substitution as it conserves the delocalized electron system, and
hence the stability of the ring.
The benzene ring, because of its stability, is less reactivetowards electrophiles than alkenes. Electrophilic
substitution reactions occur, but the use of a catalyst or harsh conditions is required for the reactions to
take place.

Electrophilic substitution reactions of the benzene ring

Three important electrophilic substitution reactions of the benzene ring are
 Halogenation
 Nitration
 Friedel - Crafts alkylation and acylation.

Halogenation
The benzene ring reacts with the halogens X2 according to the reaction

X
AlX3
+ X2(g) + HX(g) X is usually Cl and Br

(C6H6) (C6H5X)

 In this reaction, a halogen such as chlorine acts an electrophilic reagent and produces the
electrophile insitu, for example, Cl+.
 The benzene ring is rich in electrons, so it has an affinity for electrophiles. However, the affinity of
the benzene ring for electrophiles is less than that observed in alkenes. Being delocalized, the
electrons in the benzene ring are not so effective at attracting electrophiles. In other words, the
benzene ring is relatively inert (relatively stable).
 Because of its relative inertness, the reaction of the benzene ring with electrophilic reagents does
not occur unless a suitable catalyst is added. The catalyst used, for example, AlCl 3 or FeCl3 in the
chlorination of benzene, has an affinity for electrons in the reacting halogen molecules. The
catalyst therefore helps to polarize the halogen molecule and release the X + electrophile.
 During the reaction, the electrophile, X+, replaces a hydrogen atom on the benzene ring. The
released H+ ion then combines with the halide ion from heterolysis of X 2, forming white fumes of
a hydrogen halide, for example, HCl.

Mechanism of the chlorination of benzene

 540

Cl

AlCl3 dark
+ Cl2 + HCl
or FeCl3
white fumes
C6H6 C6H5Cl
chlorobenzene

The reaction is carried in the dark using a suitable organic solvent such as CCl4 (benzene is insoluble in
water). The reaction has high activation energy because of the stability of the benzene ring. A catalyst is
used to lower the activation energy and make the reaction faster. The catalyst used should have an affinity
for electrons, for example, AlCl₃, having only six electrons around Al, is electron deficient and has an
affinity for electrons. FeCl₃ can also be used because iron has vacancies in its d orbitals to accept
electrons fromchlorine as part of the catalysis. The major steps in the mechanism are shown in the
following panel.

The first step is polarization of chlorine by the catalyst. Since the cat-
Cl alyst is electron deficient, it attracts electrons from one side of the
Cl Cl Al Cl chlorine molecule. This creates two poles on the chlorine molecule, a
Cl δ+and a δ- pole. The relatively positively charged δ+end is then at-
tracted to the delocalizedπ electron cloud of the benzene ring.This
causes a concerted fission of the Cl-Cl bond, generating the electro-
phile (Cl+)insitu and a chloride ion.

Cl Cl A pair of electrons from the delocalized system is used to
make a covalent bond to the Cl+electrophile.This temporarily
disrupts the ring of delocalized electrons, forming an unstable

carbocation intermediate. Meanwhile, the chloride ion from
  the heterolysis of the Cl-Cl temporarily bonds to the catalyst
Cl Cl through a dative bond, to form the AlCl4- ion.

1090
Cl Cl
Al
1200 Cl -
Cl
Cl
- Al
Al Cl + Cl
Cl Cl Cl
trigonal planar Cl
Cl
tetrahedral
-
H + AlCl4
A C-H bond in the carbocation intermediate undergoes
heterolysis and electrons from this bond enter the ring,
neutralizing the positive charge and completing the delocalized
π system. The product, chlorobenzene, now has an intact
benzene ring and is therefore stable. The net result is
replacement of a H atom from the benzene ring by a Cl atom.
 541

The last step involves regeneration of the catalyst.

H+ + AlCl4-→ AlCl3 + HCl
The reaction produces white fumes due to the formation of HCl (g).

N.B: The catalyst is referred to as a halogen carrier because it takes up a

+ H
chloride ion to form AlCl4-. FeCl3 can also be used as a halogen carrier.
During the reaction, it is temporarily converted to FeCl 4-.

The bromination of benzene occurs by the same mechanism. AlBr 3 or FeBr3 is used as a catalyst.
Bromobenzene, C6H5Br and white fumes of HBr are produced.
Electrophilic substitution is typical of the benzene ring. Even if the benzene ring has substituents,
electrophilic substitution will occur in the ring provided the right conditions are employed. Consider the
reaction of methylbenzene with chlorine in the presence of a halogen carrier:

AlCl3
+ Cl2 + + HCl
dark
A B

This reaction illustrates clearly the importance of reaction conditions in determining the products of an
organic reaction. The conditions used promote electrophilic substitution in the ring. It is important that
the reaction be carried out in the presence of a halogen carrier and in the absence of light. If the reaction
with chlorine (or bromine) is carried out in the absence of a catalyst and in the presence of light, it is the
methyl side group (substituent) that would react, and a different product would be formed.
The reaction above forms two isomeric products A and B. This is because alkyl groups such -CH3 direct
incoming groups to carbon 2 and 4 of the benzene ring. Note how carbon atoms on the benzene ring are
numbered. The substituent takes position 1. The rest of the carbon atoms are then numbered 2, 3 and 4,
with respect to the substituent group. Note that the positions marked 2 are equivalent, and so are those
marked 3.

CH3 carbon 2 = ortho

1
2 2 carbon 3 = meta
3 3
carbon 4 = para
4

Nitration of benzene
This is another example of electrophilic substitution to the benzene ring. In this reaction, an NO₂ group
substitutes a hydrogen atom from the benzene ring. The reagent used is a mixture of concentrated nitric
and concentrated sulphuric acid (known as a nitrating mixture). The electrophile in the reaction is the
nitronium ion, NO₂⁺, generated insitu from the reaction between concentrated sulphuric and nitric acids.
 542

NO2
concH2SO4(aq)/concHNO3
+ H2O
60oC - 65oC
nitrobenzene

The reactant is HNO₃. Sulphuric acid serves as a catalyst.

The first step in the reaction is generation of the electrophile by the reaction between sulphuric acid and
nitric acid.

H₂SO₄ + HNO₃→ NO₂⁺ + HSO₄⁻ + H₂O

In this reaction, sulphuric acid acts as an acid and donates a proton to nitric acid. Meanwhile, nitric acid
acts as a base and uses a lone pair of electrons to accept the proton. Protonation of nitric acid results in
formation of a ‘water group’, which then dissociates from the molecule since it can have a stable
independent existence.

H H
O-H O +O
H-O H +
S + N O N O O N=O + H2O
O
O O O NO2+
H2SO4 HNO3 +
HSO4-

The nitronium ion, NO2+, then attacks the benzene ring and replaces a hydrogen atom as H +.

NO2 NO2
NO2+ + H + H+

The released H+ ion then combines with HSO4- to form H2SO4, thus regenerating the catalyst. The
mononitration of benzene requires close monitoring of temperature. If the temperature is too low, the
reaction is very slow. On the other hand, if the temperature is too high, it promotes disubstitution, as
shown in Fig 10.8. Note that disubstitution results in the formation 1,3-dinitrobenzene because the first
nitro group to enter the ring directs any other incoming group to the meta (3) position. This is because as
a ring deactivator the nitro group directs incoming groups to the third carbon with respect to itself.
 543

NO2
2NO2+ + 2H+

C6H6
NO2
1,3-dinitrobenzene ( C6H4(NO)2)
Fig 10.8

Friedel-crafts reactions
There are two types of very important electrophilic substitution reactions known as Friedel-crafts alkyla-
tion and Friedel-Crafts acylation.
Alkylationinvolves introduction of an alkyl group into the benzene ring. In this reaction, a halogenoal-
kane such as CH3Cl acts as an electrophilic reagent. As explained earlier, the benzene ring is rather inert
and requires a catalyst for electrophilic substitution to take place, except in activated ring systems which
will be discussed later.
Consider the methylation of benzene to form methylbenzene

CH3

AlCl3
+ CH3Cl + HCl

C6H6 C 6H5CH3

The electrophile in this reaction is CH3+, generated insitu from the polarization of chloromethane by the
catalyst (halogen carrier). The electrophile replaces a H atom from the ring.
The mechanism is outlined below. Note that the catalyst plays the same role as in halogenation of the
benzene ring. It helps to release an electrophile by polarizing the electrophilic reagent, in this case CH3Cl.
The reactant molecule is already polarized since it contains a polar C-Cl bond. The Cδ+ end ofthemolecule
is attracted to the delocalized π electrons in the benzene ring, this leads to further polarization of the C-Cl
bond. However, this polarization is not strong enough to break the C-Cl bond and release the electrophile,
CH3+. The catalyst used has a strong affinity for electrons, so it contributes significantly to the polarization
of the C-Cl bond, resulting in formation of the electrophile by heterolysis of the C-Cl bond.

AlCl3

 
CH3
CH3 Cl + CH3 + HCl
H
methylbenezene

As in the halogenations of benzene, the catalyst is temporarily converted to AlCl 4-but is regenerated when
this ion donates a Cl- ion to the H+ ion that has been replaced by Cl on the benzene ring.
 544

Q
Which halogenoalkanes should be used in the synthesis of the following alkyl
benzenes?

(a) (b)

A‘Split’ the molecule to see how it was formed.

H3C CH3

CH3 H
formed from CH3
+
C
+
The fragment shown in the box is positively charged because after splitting the molecule as shown,
one carbon atom has only three bonds around. In fact, this fragment is the electrophile during the
formation of the compound in (a). To obtain the halogenoalkane that participates in this reaction,
simply create a fourth bond (C-Hal) to the positive carbon of the electrophile, for example

CH3 H
CH3
C
=
Br Br
2-bromopropane

Friedel - Crafts acylation involves introduction of an acyl group, RCO, to the benzene ring, where R is
an alkyl or aryl (benzene ring) group.
 Important compounds which contain the acyl group are the acyl chlorides,
O
RCOCl. In the presence of a halogen carrier, an acyl chloride reacts with
acyl group C 

benzene in an electrophilic substitution reaction. The catalyst helps to release
R the electrophile (RCO+) from the acyl chloride.
Consider the reaction of benzene with ethanoyl chloride in the presence of a
suitable halogen carrier such as AlCl3. The reaction introduces a ketone side group into the benzene ring.
Note that the carbonyl group of the introduced side group is directly bonded to the benzene ring.
 545

  O
O

C
C  AlCl3 CH3
+ H + H+ + AlCl4-
H3C Cl

C CH3

phenylethanone - a ketone

The C-Cl bond in ethanoyl chloride, CH3COCl, has a large dipole moment because the carbon atom is
bonded to two electron withdrawing groups (O and Cl). The halogen carrier further polarizes this bond,
leading to its heterolysis and generation of the electrophile

 
O
O

C  AlCl3 + AlCl4-
Cl C+
H3C
H3C
electrophile
The reader should note that in Friedel - Crafts alkylation and acylation reactions, a carbon atom on the
benzene ring makes a bond to the Cδ+ of theelectrophilic reagent (halogenoalkane or acychloride). No
matter how complex the electrophilic reagent is, its reactive centre is its δ+ carbon atom, as illustrated in
the question below.

Q
Draw the structure of the product formed when benzene is acylated by compound
X shown below, in the presence of a suitable halogen carrier.

CH3
X
Cl O

AThe benzene ring attacks the δ+ carbon atom of compound X.

 546

This arrow shows formation

of a new bond.
CH3 CH3


Cl O O

Activated and deactivated ring systems

Halogenation of the benzene ring by electrophilic substitution depends on the polarization of the halogen
molecule by electrons delocalized in the benzene ring. In a non- activated benzene ring, the pi electrons
are not effective in polarizing the halogen. Groups that push electrons into the benzene ring (ring activa-
tors) for example the –OH, –NH2and -OCH3groups, activate the ring by increasing the size of delocalized
electron density required to polarize the halogen molecule. For this reason, a catalyst is not required. Ring
activators are derivatives of bases, for example the OH group is derived from a base such as NaOH, and
the -NH2 group from ammonia. The effect of a ring activator is summarized in the followingpanel.

Naming positions on the benzene ring

X
1 The substituent X occupies position 1.
2 2
3 Carbon 2 ortho(o-)
3
4
Carbon 3 meta(m-)
Carbon 4 para (p-)

If X is a ring activator
1. The incoming group is directed to the ortho or para positions.
2. No catalyst is required.
3. Polysubstitution occurs, that is, more than one hydrogen atoms are replaced by the electrophile.

Comparing the reaction of benzene and phenol with

bromine

AlBr3 Br
+ Br2 + HBr
benzene (non-activated)

OH OH
no catalyst
Br Br
+ 3Br2 + 3HBr
needed
Phenol(activated) Br
2,4,6-tribromophenol (white precipitate)
 AlBr3 Br
+ Br2 + HBr
547
benzene (non-activated)

OH OH
no catalyst
Br Br
+ 3Br2 + 3HBr
needed
Phenol(activated) Br
2,4,6-tribromophenol (white precipitate)

In benzene, only one hydrogen atom is substituted. The reaction is difficult and so needs a catalyst.
In phenol, the benzene ring also reacts via electrophilic substitution. However, the ring is activated by the
-OH group.

 The reaction is fast

 No catalyst is needed
 Three hydrogen atoms on the benzene ring are replaced.

Note that the Br atoms are bonded at the ortho and meta positions.
Phenylamine, C6H5NH2, behaves in the same way as phenol with respect to electrophilic substitution. A
white precipitate of 2,4,6-tribromophenylamine is readily formed in the cold and in the absence of a
catalyst.
Some groups are only weakly activating, for example, alky groups. In this case, electrophilic substitution
requires a catalyst and polysubstitution does not take place. Weak activators direct incoming groups to
the ortho or para positions, but both positions are not substituted in the same ring. Consider the reaction
of methylbenzene with bromine.

CH3 CH3 CH3

Br
AlBr3
+ Br2 + xHBr

ortho- isomer
Br
para- isomer
greater yield

 Since the benzene ring in methylbenzene is weakly activated, the two possible positions (meta and
para) are not substituted in the same ring. Rather, a pair of positional isomers is formed.
 The para - isomer is more stable and is formed in larger amounts. This is because the two
substituents of the benzene ring, -CH3 and -Br, are well separated in space. Compare with the
ortho - isomer in which the two substituents are very close to each other and so experience
mutual repulsion. This repulsion destabilizes the whole molecule.
 In weakly activated systems, electrophilic substitution requires the use of a catalyst.

Ring deactivators, such as the –NO2 , –SO3Hand -COOH groups tend to withdraw electrons from the
benzene ring. This makes the ring less reactive towards electrophiles. A catalyst is required and
polysubstitution is not likely unless temperature is relatively high. In addition, substitution occurs at
carbon 3 (meta-).Note that ring deactivators are derived from acids, for example, -NO2 from HNO3 and -
SO3 H from H2SO4.
 548

Consider the reaction of nitrobenzene with bromine

NO2 NO2

AlBr3
+ Br2 + HBr
Br
Nitrobenzene A
(deactivated)

Note that the organic product of the reaction can also be drawn as
NO 2
A and B are exactly the same compound, that is, they are not isomers.
The halogen atom is a weak deactivator, but unlike other deactivators, it is an ortho, para
director.

Br
B

Summary: electrophilic substitution reactions

 These reactions result in one or more hydrogen atoms in the benzene ring being replaced by an
electrophile. A catalyst is required due to the relative inertness (stability) of the benzene ring.
However, in activated benzene rings, a catalyst is not required. Three important electrophilic
substitution reactions are

 halogenation
 nitration
 Friedel - Crafts alkylation and acylation

Reaction Electrophilic Electrophile Catalyst Product

reagent

Halogenation Halogen , Hal+ e.g. Br+ Halogen carrier e.g. A halobenzene e.g.
particularly Cl2 and AlBr3 or FeBr3 bromobenzene,
Br2 C6H5Br.

Nitration HNO3 NO2+ H2SO4 Nitrobenzene

(concentrated) (concentrated) C6H5NO2

Friedel- Halogenoalkane, R+ , e.g. CH3+ Halogen carrier Alkyl benzene ,

Crafts e.g. CH3Cl e.g.
alkylation methylbenzene,
C6H5CH3
 549

Friedel- Acylchloride, e.g RCO+ Halogen carrier Benzene ring with

Crafts ethanoyl chloride a side group
acylation CH3COCl containing a
carbonyl (ketone)
group.

 A halogen carrier such as AlCl3 and FeCl3 has an affinity for electrons and so helps to polarize
electrophilic reagents such as Cl2, CH3Cl and CH3COCl during electrophilic substitution reactions.
This is necessary because the delocalized electrons in benzene are not so effective at polarizing the
electrophilic reagent to generate the electrophile.
 The benzene ring usually reacts via electrophilic substitution as this preserves the delocalized π
electrons which give stability to the benzene ring.
 The benzene ring can be activated or deactivated by electron pushing and electron withdrawing
groups, respectively. Ring activators generally direct incoming groups to the ortho and para
positions. Examples are -OH, -NH2, -OCH3 and -CH3. Deactivating groups direct incoming
groups to the meta position. Examples are NO2, -COOH and -SO3H. The halogen atom is weakly
deactivating but it is ortho, para directing.

Questions, solutions and discussions

Q1(a)Outline the mechanism for the reaction between ethene and bromine. Why should water not
be used as a solvent in this reaction?

(b)Write down two observations that are made during this reaction.

(c)What is the electrophile in this reaction, and how is it generated?

Solutions
(a)

H H H H
+ +
C C C C Br
H H H H
Br

Br Br

H H

H C C H

Br Br
1,2- dibromoethane
 550

The presence of water results in the formation of a mixture of 1, 2-dibromoethane and

1- bromoethanol, CH2BrCH2OH.

(b) Bromine is decolourized and an oily liquid (1, 2-dibromoethane) is formed.

(c) The electrophile is the bromonium ion, Br+, generated insitu. Repulsion between π electrons of the
C=C bond and the lone pairs on Br2results in the polarization of the Br-Br bond. This leads to
heterolysis of the Br-Br bond, generating the electrophile, Br+ and the bromide ion, Br -.

Q2 Predict the products formed when compound X below reacts with the given reagents under the
stated conditions. In each case, state the type of reaction

(a)KCN (aq), reflux

(b) HCl in hexane

Solutions
(a)Nucleophilic substitution, to form
CN

(b)Electrophilic addition to the double bond, to form a mixture of two isomers

and
 551

Q3Benzene can be converted to compound X as shown below.

O
step 1 step 2

What are the reagents and conditions required for steps 1 and 2?

Solutions

Step 1 CH3Br/CH3Cl in the presence of a halogen carrier, e.g. AlBr3 (AlCl3)

Step 2 CH3COCl in the presence of a halogen carrier e.g. AlCl3

[Step 1 is a type of electrophilic substitution known as Friedel -Crafts alkylation. It is an important

reaction because it introduces an alkyl group, in this case, methyl, onto the benzene ring.
Step 2 is also electrophilic substitution (Friedel-Crafts acylation).]

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1.Bythe use of a suitable example of each mechanism, describe the similarities and differences between
those reactions classified as electrophilic substitutions and those classified as electrophilic additions.
You should include in your answer

(a) The reagents used and their function

(b) The reaction conditions used

(c) The products formed

(d) The mechanism of each reaction

(e) How the structure of a molecule determines the mechanism.

9701/04/M/J/07

2(a)Outline the mechanism of the reaction that takes place between concentrate nitric acid in the
presence of concentrated sulphuric acid. Use diagrams involving curly arrows showing movement
of electrons and also show any reaction intermediates formed.

(b) By means of a balanced equation, explain the role of sulphuric acid in this reaction.
 552

3.Phenylamine can be converted to 4-nitrophenol by the following steps.

(a) Suggest the identity of intermediate B by drawing its structure in the box above.

(b) Suggest reagents and conditions for the three steps in the above scheme
9701/04/O/N/2011

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10.3.3Free radical substitution reactions

Free radical substitution is a reaction in which a free radical replaces an atom or a group of atoms
in a reactant.

A free radical is a neutral species that bears an odd electron and is therefore relatively reactive as it seeks
to get the odd electron paired. The halogen atom is an example of a free radical. With only seven electrons
in the outer-most shell, one electron is inevitably unpaired (odd). A free radical is often drawn with only
the odd electron shown.

Free radical substitution reactions are important in alkanes, for example,

odd electron methane reacts with chlorine in the presence of UV, according to the
equation
Cl Cl CH4 + Cl2  CH3Cl + HCl
UV
A mixture of methane and chlorine reacts explosively when exposed to light or when heated.
It is easy to see at a glance that the reaction is of the substitution type: A chorine atom substitutes a
hydrogen atom in methane. What is not so obvious is that the reaction involves free radicals. These are
formed as very reactive intermediates and so they do not appear in the overall equation.

The mechanism
The reaction can be broken down into three main stages, initiation, propagation and termination.

Initiation
 553

This step generates chlorine free radicals bythe homolysis of a chlorine molecule. Homolysis (homolytic
bond fission) is a type of bond breaking in which each atom leaves with an electron of the bond.The
differences between homolysis and heterolysis were explained in section
A half- headed arrow is used to show the movement of a single electron during homolysis.

Cl .. Cl UV
2Cl.
This is the slowest (rate determining step) as it involves breaking of a
relatively strong Cl-Cl bond. This process requires light energy or heat to
overcome the activation energy.
Once Cl atoms (free radicals)have been formed, the reaction occurs rapidly and sustains itself even when
the reaction vessel is put in the dark. Light which has less energy than UV is not able to initiate the
reaction because it cannot cause homolysis of chlorine.
Propagation
This stage is made up of two steps. In the first step, a chlorine atom(free radical) abstracts a hydrogen
atom from methane, forming an organic free radical (methyl) and white fumes of HCl. A free radical is
very reactive, so once formed, the methyl free radical immediately reacts with chlorine in the second step,
thus regenerating the Cl radical and forming the organic product, chloroethane.
.
Cl + CH4 .
CH3 + HCl ... (i)

CH. 3 + Cl2 CH3Cl + Cl . ... (ii)

The chlorine free radical produced then goes back to react with more methane molecules in step (i),
producing more methyl free radicals. Thus a chain reaction is produced, revolving around steps(i) and
(ii)of the propagation stage.
This explains why the reaction is self- sustaining. Even if the reaction vessel is put in darkness, the free
radicals that are already present participate in a never ending chain reaction. All that is required is
presence of free radicals to initiate the reaction. A way to form the free radicals is to irradiate the reaction
mixture with UV radiation. It is also possible to start the reaction by adding a chemical which can easily
release free radicals (Cl·or CH3·) when heated or warmed. In this case, UV is not necessary.
If the reaction is not closely monitored there is also a risk of explosion due to the rapid increase of
pressure as gaseous products are formed.

Termination
Termination involves collision and reaction between any two free radicals:

.
Cl + CH3 . CH3Cl

CH. 3 + CH3 . CH3CH3 + Cl .

Cl. .
+ Cl Cl2

The usefulness of free radical substitution in synthesis is limited by the fact that a mixture of products is
produced, which is difficult to separate. From the foregoing account, the following products are produced:
chloromethane, CH₃Cl (intended product), HCl, and ethane. Further substitution is possible, producing
an even larger number of different products. This involves step by step substitution of hydrogen atoms in
the product by chlorine, until no hydrogen atoms are left. The products of this step by step substitution
are CH2Cl₂, CHCl₃ and CCl4.
 554

The reaction scheme below shows how dichloromethane is formed by further free radical substitution in
chloromethane.
from the initiation stage

CH3Cl + Cl CH2Cl + HCl

propagation
CH2Cl + Cl2 CH2Cl2 + Cl

Termination may invove the reaction

CH2Cl + CH2Cl ClCH2CH2Cl

To minimize further substitution, a limited amount of chlorine (that is, excess alkane) should be used.
When only a few products are formed it is relatively easy to separate them by fractional distillation.

Free radical substitution in methylbenzene

Methylbenzene can react in different ways to form different products, depending on the reaction
conditions used. With chlorine in the presence of light, free radical substitution takes place on the methyl
side group.

CH3 CH2Cl

limited Cl2
+ HCl
UV
methylbenzene

Initiation

Cl .. Cl UV
2Cl.

Propagation

CH3 CH2
Cl +

CH2 CH2Cl
+ Cl2 + Cl
 555

Termination

CH2 H2C CH2 CH2

CH2 CH2Cl

Cl +

Cl + Cl Cl2
The reaction of methylbenzene with chlorine illustrates the importance of reaction conditions in
determining the outcome of an organic reaction.
 With chlorine in the presence of UV, free radical substitutionin the methyl side group takes place
 However, when chlorine is used in the dark and in the presence of a halogen carrier, electrophilic
substitution takes place in the benzene ring.

(i) CH 2Cl

CH 3 UV
Cl2

Cl 2
(ii) CH 3
AlCl
Cl
dark 3

10.3.4 Elimination reactions

An elimination reaction is one in which a small molecule (such as water and HCl) are lost from a
larger reactant molecule.

Well known elimination reactions are dehydration in which the eliminated molecule is water, and
dehydrohalogenation in which the eliminated molecule is a hydrogen halide (HX), for example HBr.
The following reaction involves elimination of a hydrogen halide, in this case, HCl, from a
halogenoalkane.
KOH ethanol
CH3CH2Cl CH2=CH2 + H2O + KCl
reflux
chloroethane ethene
Elimination of HX from a halogenoalkane using alcoholic potassium hydroxide results in the formation
of an alkene.
 556

The reaction involves removal of a halogen and hydrogen atom from adjacent carbon atoms, as illustrated
for chloroethane below.

-HCl Reaction conditions are important here. Absolute

ethanol, and not water, should be used as the solvent. If
H Cl H H
water is used as the solvent, elimination will not take
H C C H C C place. Instead nucleophilic substitution of Cl by -OH
takes place, resulting in the formation of an alcohol
H H H H (ethanol)

chloroethane ethene

A halogenoalkane can react in the presence of KOH to give different products, depending on the solvent
used. With a concentrated alcoholic solution of KOH, elimination of HX takes place, to form an alkene.
In the presence of water (and heat), nucleophilic substitution takes place, to form an alcohol.

The mechanism of elimination of HX is described in the following panel. So far you have encountered
reactions that proceed via a carbocation (a species bearing a positive charge on a carbon atom). Elimina-
tion of HX from a halogenoalkane proceeds via a carboanion. This is a very reactive and transient
(short-lived) species that bears a negative charge on a carbon atom. A strong base such as KOH is
required in the formation of the carboanion. The mechanism is as follows.

The tendency of chlorine to withdraw electrons towards itself

H H causes electrons to move away from a C-H bond on carbon 2.
2 1 The H of this bond is now deficient of electrons and it becomes
H C C Cl
slightly acidic (that is, it now has the ability to be dissociated
acidic H H from the molecule as an H+ ion)
H atom
A strong base such as OH-is able to remove this acidic hydrogen,
forming water. The electrons of the C-H bond are left behind on
OH-
carbon 2. This carbon atom now bears a negative charge. The
intermediate formed is therefore a very unstable carboanion.
H H The lone pair of electrons on C2 immediately shifts to form a
2 1 πbond between C1 and C2. This creates too much electron
H C C Cl + H2O
.. density around C1. One bond must break to decrease electron
H density at this carbon. The weakest bond here is the C-Cl bond,
very unstable carboanion so it is the one that breaks by heterolysis, releasing a chloride
ion.
Comparing the initial reactant and the product, it can be seen
H H that an HCl molecule has been removed. However, HCl is not
C C + KCl one of the products because the hydrogen atom removed in the
first step forms water with OH- ions from KOH.
H H

Elimination of HX from a halogenoalkane often results in the formation of a mixture of two alkenes which
are positional isomers of each other, for example
 557

Cl
KOH/ethanol
reflux +
hexene hex-2-ene

This is because the reaction involves removal of a hydrogen atom and a carbon atom on the adjacent
carbon atom. Now, the hydrogen atom can be removed from either side of the halogen atom, resulting in
the formation of two alkenes which differ in the position of the double bond.

-HCl
Cl
H
C1 2
3
H H hexene
H removed from C1.

-HCl Cl
H
H
C1 2
3
H H hex-2-ene
H
H removed from C3

Sometimes only one alkene is formed. Here are examples of such situations.
 For primary halogenoalkanes there is only one position from which the hydrogen atom can be
removed.

-HBr
Br H H H H H H H
KOH/ethanol
H C C C C C H H C C C C C H
reflux
H H H H H H H H H H

bromopentane pentene

 Sometimes there are two carbon atoms from which a hydrogen atom can be removed, but the
position of these hydrogen atoms are such that the same product is formed. This happens when
the halogen atom is symmetrically situated on a carbon chain with an odd number of carbon
atoms.
 558

H H Br H H H H H
1 2 3 4 5
H C C C C C H H C C C C C H
1 2 3 4 5
H H H H H H H H H H
hydrogen removed from C2 pent-2-ene

Pent-2-ene is formed by removal of a hydrogen atom from C3 in 3-bromopentane. Notice that

the same product is produced when the hydrogen atom is removed from C4.Recall that the
carbon chain is numbered from the end that will place the functional group (double bond) at the
smaller locator number.

H H Br H H H H H H
5 4 3 2 1
H C C C C C H H C C C C C H
1 2 3 4 5
H H H H H H H H H
hydrogen removed from C4 pent-2-ene
In some cases, elimination does not take place because both carbon atoms which are adjacent to the C-Hal
bond do not carry any hydrogen atoms, as illustrated below.
2 Cl In the structure, elimination is not possible because the carbon atoms marked 1 and 2 do
1 not bear any hydrogen atoms.

Summary: Elimination of hydrogen halide from a halogenoalkane

 In this reaction, a halogen and a hydrogen atom are removed from adjacent carbon atoms. This
type of elimination is known as dehydrohalogenation.
 Reaction conditions are extremely important in this reaction. The halogenoalkane should be
heated or refluxed with concentrated ethanolic KOH. Under these conditions, nucleophilic
substitution is suppressed and the major product formed is an alkene. It is still possible for a
small amount of an alcohol to be formed together with the alkene product due to nucleophilic
substitution. The use of NaOH (aq) only gives a satisfactory yield of alkene for the smaller Mr
halogenoalkanes such as bromoethane.
 Sometimes a mixture of isomeric alkenes is formed during elimination.

The concept of functional group interconversion

Before we study two more mechanisms, organic redox and neutralization reactions, let us discuss a very
important aspect of organic chemistry, functional group interconversion. You are now aware of the fact
that an organic molecule, no matter how complex, will usually react at its functional group(s). When a
functional group reacts, it is actually converted to another. This is important in organic synthesis, as it is
possible to convert a less useful compound to one which is more useful by simply changing the functional
group. Examiners are always testing candidates’ knowledge of the conditions and reagents required to
convert one functional group into another. In this book, you will find a large number of functional
 559

groupinterconversions charts (we will refer to them as FGI charts) to give you practice in converting
one functional group to another. FGI 1 is such a chart. It involves the three mechanisms which have been
studied so far, that is
 nucleophilic addition and substitution
 electrophilic addition and substitution
 free radical substitution
 Elimination

FGI 1
Required:
 State the type of reaction occurring at each numbered step
 State the conditions and reagents required where this has not been shown
 Draw the structures of the lettered compounds
 State the bond angles marked x and y

Br2 / AlBr3
(7)
Cl CN

(1) (2) x
(3)
(8) HO
OH
T
(4) (5)
O y
Br
HCN/trace NaCN (6)
reflux
(9) + U

H2SO4 (aq) Q
LiAlH4 / ether
reflux
(11)
(10)
R S
 560

Solutions

x = 109.50 (Do not forget the presence of two hydrogen atoms present at the
‘elbow’ )
y = 1200 (there is a hydrogen atom at the ‘elbow’)

1. Add Limited Cl2 in the presence of light. Free radical substitution.

2. Add KCN (ethanolic), reflux. Nucleophilic substitution.
3. Add KOH, concentrated and ethanolic, heat. Elimination.
4. Add Liquid bromine. Electrophilic addition occurs. T is
Br
Br
Br
( NOT Br Check that you have the
correct number of carbon atoms
( 'elbows' / end of lines).

5. Add NaOH (aq), reflux. Nucleophilic substitution occurs. Both Br atoms in T are replaced by -OH
groups, to form a diol (a dialcohol in which the two -OH groups are on adjacent carbon atoms).
6. Add HBr in a suitable organic solvent e.g. hexane (avoid water). Electrophilic addition occurs. Two
isomers are formed. The one whose structure is shown is the major product as it is formed according
to Markownikoff’s rule. The other isomer, U, is formed by antiMarkownikoff addition.

Br
U

7.Electrophilic substitution in the benzene ring. P is

Br

8. Add ethanoyl chloride, CH3COCl, in the presence of a non-polar organic solvent. Avoid
water, otherwise CH3COCl hydrolyzes rapidly. Electrophilic substitution (Friedel-Crafts
acylation) occurs in the benzene ring.

9.Nucleophilic addition occurs to the carbonyl group. NaCN catalyzes the reaction. Compound Q is a
cyanohydrin (a compound in which a carbon atom is bonded to both an -OH and a CN group).

HO

CN
 561

10. Hydrolysis of the nitrile group to a carboxylic acid. In all hydrolysis reactions, the inorganic reactant
is water. Most organic hydrolysis reactions require a catalyst. In this case the catalyst is H 2SO4.
Compound R is

HO

COOH

11. Reduction. LiAlH4 is one of the most powerful reducing agents used in organic chemistry. However,
it is very sensitive to water and is usually used in dry ether. Compound S is

HO

H2N

Note that hydrogen atoms have been added to the nitrile group (reduction)

-CN → -CH2NH2

LiAlH4 provides hydride ions, H-, which can reduce many functional groups.

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(i) (ii)
CH3 CHCHCH2CH3 CH3 CHClCH2CH2CH3 CH3CHCNCH2CH2CH3
(v)
(iii)
(viii) X
(vi) Q. C6H12O2

S (iv)
(vii)
R. C6H11O2Na
P. C6H11ON
 562

(a) Supply the reagents and conditions required for all numbered steps.

(b) Draw the structures of the lettered products.

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10.3.5
text box.] Organic redox reactions

In organic chemistry, reduction and oxidation reactions frequently involve the transfer of oxygen or
hydrogen atoms. It is therefore easy to notice when a redox reaction has taken place. For example, the
following reactions involve reduction of the organic reactant by gain of one or more hydrogen atoms.

O [H] OH
O [H] OH
H C H C
H3 C 3 H3 C 3
CH3 CH3
CH3 CH3
propanone(ketone) propan-2-ol( secondary alcohol)
propanone(ketone) propan-2-ol( secondary alcohol)

4 [H]
CH3CN4 [H] CH3CH2NH2
CH3CN CH3CH2NH2
ethanenitrile ethylamine
ethanenitrile ethylamine

The following reaction is clearly reduction because it results in the removal of O and the addition of H.

NO2 NH2
2[H]

The following reactions are oxidation because they are accompanied by gain of O atoms.

HO
2[O] (CH2OHCH2OH)
1. H2C = CH2
OH
ethene ethane-1,2-diol

[O]
2. CH3CH2OH CH3COOH
ethanol ethanoic acid

We may use the notation [H] and [O] to show reduction and oxidation without exactly specifying the
reagent being used.

The following table is a list of reducing and oxidizing agents commonly used in organic chemistry. The
pages that follow give a discussion of the applications and limitations of these reagents.
 563

Oxidizing agents Reducing agents

KMnO4 NaBH4

K2Cr2O7 LiAlH4

AgNO3 (aq)/NH3 (Tollen’s H2

reagent)
Sn/concHCl
Cu2+ (aq), NaOH(aq)/sodium
Na(s)
tartarate (Fehling’s solution)

NaNO2/HCl (aq) (=HNO2,

nitrous acid)
Table 4 A list of commonly used oxidizing and reducing agents

3.5.1The use of oxidizing agents in organic chemistry

Potassium permanganate

KMnO4 is a powerful oxidizing agent which can be used to carry out the following conversions
 primary alcohols to carboxylic acids
 secondary alcohols to ketones
 aldehydes to carboxylic acids
 alkenes to diols
 alkenes to carboxylic acids and/or ketones and / or CO 2
 Alkyl benzenes to benzoic acid

Oxidation of alcohols
Recall that alcohols are classified as primary, secondary and tertiary.

Class of alcohol General formula Examples

Primary RCH2OH

(The carbon bearing the

-OH group is bonded to
two hydrogen atoms)
ethanol
2-phenylethanol
 564

Secondary R1CH(OH)R2

(The carbon bearing the -

OH group is bonded to
one hydrogen atom)
propan-2-ol
Propan-2-ol

Tertiary R3 COH

(The carbon atom

bearing the -OH group is
not bonded to any
hydrogen atom)

 KMnO4 oxidizes primary alcohols to carboxylic acids. The reaction proceeds via an
aldehyde but it is not possible to stop at this stage. This is because KMnO4 is a powerful oxidizing
agent. The conversion is achieved using cold alkaline or acidic KMnO4. Examples are given below.

1. CH3CH2OH  CH3COOH

Notice that the reactions are accompanied by an increase in the number of oxygen atoms and a decrease
in the number of hydrogen atoms.

 KMnO4 oxidizes secondary alcohols to ketones, for example

KMnO 4 / H+(aq)
1 warm

1-phenylethanol 1-phenylethanone

2 CH3CH (OH) CH2CH3CH (OH) CH3CH3COCH2CH3COCH3

 Tertiary alcohols resist oxidation by KMnO4. The oxidation of alcohols depends on the
loss of hydrogen atom (s) from the carbon atom of the C-OH group. In tertiary alcohols, the
carbon of the C-OH group bears no hydrogen atoms. Tertiary alcohols are therefore inert with
respect to oxidation.
 565

Oxidation of aldehydes
Aldehydes are easily oxidized by cold or warm KMnO4 to form a carboxylic acid. Examples are shown
below.

KMnO 4 / H+(aq)
1 warm
benzoic acid
benzaldehyde

2. CH3CH2OH  CH3COOH

Oxidation of alkenes
The product(s) of oxidation of an alkene byKMnO4depends on the reaction conditions employed. The use
of cold alkaline KMnO4 results in the formation of a diol, for example

KMnO 4 cold, dilute

+ MnO 2
OH-

ethene ethane-1,2-diol

 A diol is a dialcohol in which the two hydroxyl groups are on adjacent carbon atoms.
 This reaction occurs with ice cold KMnO4. This is also used as a test for the double bond. In this
reaction, KMnO4 is decolourized, and a muddy brown precipitate of MnO2 is produced. There are
other classes of compounds which decolourize KMnO 4, for example, the aldehydes, but the
reactions may not take place with ice cold KMnO4.
 The product of the reaction above is known as ethane -1,2-diol (glycol). It is used in large amounts
in the cold regions of the world as antifreeze.
 Here are more examples

OH
OH
KMnO 4 cold, dilute
OH-
OH

KMnO 4 cold, dilute

OH- OH

The use of hot, concentrated and acidified KMnO4 results in the formation of different products. Initially,
 566

a diol is formed , but it immediately undergoes further oxidation, resulting in the breaking of the double
bond. The products of this further oxidation depend on the nature of the groups bonded at the double
bond, as described below.

R1 R4  If a carbon atom of the double bond contains two hydrogen atoms, (e.g.
R1 and R2 = H), this carbon atom is oxidized to CO2.
C C
 If the carbon atom of the double bond contains one hydrogen atom and
R2 R3 one R group, it is oxidized to a carboxylic acid.
 If the carbon atom contains two R groups and no hydrogen atoms a, it is
oxidized to a ketone.
Here are examples

H CH3 C1 contains two hydrogen atoms, so it is oxidized to carbon dioxide. C2

1 2 contains no hydrogen atoms and two methyl groups, so it is oxidized to a
C C
ketone. The bond between C1 and C2 then breaks.
H CH3
H CH3 CH3
1 2 1 2
C C CO2 + O C
H CH3 CH3

In the following example, one carbon atom of the double bond contains one hydrogen atom and so
becomes a carboxylic acid. The other carbon atom contains no hydrogen atom and so it is oxidized to a
ketone.

H CH3 O CH3
1 2
C C C1 + O=C 2
OH
CH3 CH3

The oxidation of alkenes by hot concentrated and acidified KMnO4 is of little use in chemical synthesis
because it is difficult to control and it also gives rise to a mixture of different substances, which are
difficult to separate. However, this type of reaction is useful in determining position of the C to C double
bond in an alkene.

The oxidation of an alkene Q by hot concentrated and acidified potassium

Q
permanganate resulted in the formation of two products A and B.
Deduce the structure of compound Q.

CH3 O CH3
CH3 C C O C
CH3 OH
CH2CH3
A B

Bring the two molecules A and B so that their functional groups face each other. Join
A
 567

the carbon atoms bearing the functional groups, as shown below.

CH3 O CH3
CH3 C C O C2
1
CH3 OH CH2CH3

A B

Join C1 and C2 w ith a double bond. Remove the non-carbon atoms

bonded to each of the tw o C atoms you have joined. The atoms to be
removed are circled.

CH3 CH3
CH3 C C C
CH3 H CH2CH3

Compound Q

Oxidation of alkylbenzenes
An alkylbenzene contains an alkyl group such as -CH3directly bonded to the benzene ring. Concentrated
acidified or alkaline KMnO4 oxidizes an alkylbenzene to benzoic acid. It does not matter how long or
short, simple or complex the alkyl chain is, the same product is always obtained.

conc KMnO 4 / H+
reflux
methylbenzene benzoic acid

conc KMnO 4 / H+
reflux

Potassium dichromate

Potassium dichromate is also a good oxidizing agent, but it is weaker than KMnO4. Potassium dichromate,
just like KMnO4, can oxidize the following compounds
 568

 primary alcohols to aldehydes

 primary alcohols to carboxylic acids
 secondary alcohols to ketones
 aldehydes to carboxylic acids
K2Cr2O7 cannot oxidize alkenes.
The conversion of primary alcohols to aldehydes by K2Cr2O7must be done with care. This is because the
aldehyde can easily be oxidized further to form a carboxylic acid, for example

K2 Cr2 O7 / H+(aq) K2 Cr2 O7 / H+(aq)

further oxidation
primary alcohol aldehyde carboxylic acid

If the aim is to produce an aldehyde, reaction conditions can be controlled to minimize further oxidation
of the product.
 A limited amount of K2Cr2O7 is used
 The reaction is carried out in a distillation apparatus so that the aldehyde distills out before it
undergoes further oxidation.
There are, however, better reagents for oxidizing a primary alcohol to an aldehyde
 Chromic acid is a solution of K2Cr2O7, acidified with dilute sulphuric acid and dissolved in
acetone (propanone). This reagent gives a good yield of the aldehyde
 An even higher yield is obtained by using pyridinium chlorochromate (PCC), for example

O
OH
PCC
H

2-ethylhexanol 2-ethyhexanal (87%)

PCC =
N CrO3 HCl

Oxygen as an oxidizing agent

Oxygen is used as an oxidizing agent in some types of organic reactions, for example, the conversion of
ethanol to ethanoic acid. This can be achieved by bubbling pure oxygen through the ethanol solution.
CH3CH2OH (aq) + O2 (g)  CH3COOH (aq) + H2O (l)
The advantage of this method is that the reaction leaves no residues or unwanted species such as ions.
This is useful in the preparation of substances that are meant for human consumption, for example, vine-
gar (dilute ethanoic acid). Another common oxidation reaction involving oxygen is combustion of fuels
such as methane.

CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g)

 569

Selective oxidation
It is sometimes necessary to oxidize one functional group, and not another, in a compound. In such cases,
the oxidizing agent should be selected carefully. KMnO4 is a powerful oxidizing agent and will usually
oxidize several oxidizable groups in the organic compound. Moreover, with KMnO4, it is almost
impossible in many cases to prevent further oxidation of a product (where the product can be oxidized
further), for example, when used to oxidize a primary alcohol to an aldehyde, it is not possible to prevent
further oxidation of the aldehyde to a carboxylic acid. K2Cr2O7 is a weaker oxidizing agent, but still it is
stronger than many oxidizing agents. It can oxidize many functional groups that are capable of being
oxidized, except alkenes. However, with K2Cr2O7, it is possible to control reaction conditions so that the
desired product is obtained.
Consider the compound P shown below.

Circle and name the functional groups present in compound P.

What are the reagents and conditions required to convert Pinto the following compounds?

The functional groups present in compound P are shown below

 570

In compound R, the alcohol groups (primary and secondary) as well as the aldehyde group have been
oxidized. The alcohol groups have been converted to a carboxylic acid and a ketone respectively. The
aldehyde group has also been converted to a carboxylic acid. KMnO 4 is not suitable for this conversion
because it will also oxidize the carbon to carbon double bond. A suitable reagent is acidified K 2Cr2O7. The
reagent is warmed and used in excess.
In compound Q all oxidizable groups have been oxidized, including the carbon to carbon double bond.
Note that the C=C bond is also ruptured in the process. A suitable reagent for this conversion is hot
acidified KMnO4. The reader should particularly recall the action of this reagent on the C=C bond.

Now suppose that we wish to oxidize the aldehyde group only in compound P. K2Cr2O7 and KMnO4 are
not suitable for this conversion because they will also oxidize the alcohol groups. Tollen’s reagent or
Fehling’s solution can be used here because they are mild and specific. They will oxidize the aldehyde
group to a carboxylate (both Fehling’s solution and Tollen’s reagent are alkaline and so if a carboxyl group
is formed, it is neutralized to a carboxylate).
Tollen’s reagent and Fehling’s solution is a good test for the presence of an aldehyde group. With Fehling’s
solution, a positive test is obtained if a brick-red precipitate (of Cu2O) is formed. In the Fehling’s test,
formation of a silver mirror on the walls of the test tube indicates presence of an aldehyde.

The use of nitrous acid

Nitrous acid, HNO2, is used to oxidize the -NH2 group as in phenylamine. The nitrous acid is produced
insitu from the reaction between concentrated HCl and sodium nitrite.
NaNO2 (s) + HCl (aq) → HNO2 (aq) + NaCl (aq)
The oxidation of phenylamine by nitrous acid forms a salt known as benzene diazonium chloride. This
oxidation reaction is known as diazotization.

+ -
Cl
NaNO 2
conc HCl(aq)
< 50

This reaction is carried out under ice cold conditions. This is because the diazonium salt is very unstable
with respect to hydrolysis. If the temperature is raised, say, to 100C, hydrolysis occurs, resulting in the
formation of phenol. In fact, preparation of phenol from benzene is best done via benzene diazonium salt.
 571

+ -
Cl H2O
+ N 2(g)
100C

The diazonium ion, C6H5N2+ can be converted to many other useful substances, as shall be discussed later.
Aliphatic (non - aromatic) amines are also oxidized to diazonium salts, but these salts are very unstable.
At 100C, the diazonium salt formed cannot beseparated because it hydrolyzes in water to produce nitrogen
gas. This reaction converts a primary amine to a primary alcohol, for example

NaNO 2
CH3CH2NH2 CH3CH2OH + N2
conc HCl
100C
The following tables summarize information about oxidizing agents used in organic chemistry and the
functional groups they act on.

Oxidizing agents commonly used in organic chemistry

Reagent What it oxidizes Remark

KMnO4 (aq)/H+ Primary alcohols to A powerful oxidizing agent.

carboxylic acids Yield is good.
( / H+ means
acidified)
R-CH2OH RCOOH

Primary alcohols to This is not a good method for

Aldehydes preparing an aldehyde. This is
because KMnO4 is so powerful
R-CH2OH  RCHO as an oxidizing agent that it
oxidizes the aldehyde further to
a carboxylic acid.

Aldehydes to carboxylic acids Good yield

Secondary alcohols to ketones Good yield. Warming is

required.
 572

C C

Alkenes to a mixture of products (with  The products depend on

hot concentrated KMnO4) the nature of the alkene.

 The C=C bond raptures

 Products that may be

formed are carboxylic
acid, carbon dioxide and
ketone. In all cases, the
product has no further
tendency to be oxidized.

KMnO4 (aq)/OH- Alkenes to diols Under these conditions, KMnO4

(cold) acts as a mild oxidizing agent. It
R′-CH=CH-R′′  R′-CH2(OH)CH2OH
does not lead to further
(/OH- means alkaline) oxidation of the diol or rapture
of the C=C bond.
A brown deposit of MnO2 is
produced.

KMnO4 (aq)/H+ OR Alkylarenes to carboxylic acids The product is a carboxylic acid

/OH- or its salt, depending on whether
the conditions are acidic or
alkaline.
Refluxing is necessary.
(R = any alkyl group)

K2Cr2O7 / H+ Primary alcohols to carboxylic acids. A good oxidizing agent, but

(warm/hot) weaker than KMnO4.

Primary alcohols to aldehydes Better synthetic method for

aldehydes than KMnO4, since
K2Cr2O7 is a weaker oxidizing
agent.

Aldehydes to carboxylic acids Good yield.

Secondary alcohols to ketones Good yield

Notes
1. K2Cr2O7, being a weaker oxidizing agent, is a better reagent than KMnO4 where it is necessary to
 573

prevent further oxidation of the product. Thus K2Cr2O7 is used to oxidize primary alcohols to aldehydes
because KMnO4 would further oxidize the aldehyde to a carboxylic acid. However, even with K 2Cr2O7,
the reaction should be carried out in a distillation apparatus so that the aldehyde is removed before it
is oxidized to an acid.
Better yields of aldehyde are obtained by using PCC or Jones reagent, which are milder oxidizing
agents than K2Cr2O7 and KMnO4.

2. In these reactions, K2Cr2O7 is reduced to green Cr3+(aq) .

3. K2Cr2O7 is always used under acidic conditions.

4. K2Cr2O7 (unlike KMnO4) cannot oxidize the C to C double bond in alkenes. Neither can it oxidize
alkylbenzenes.

5. Tertiary alcohols are resistant to oxidation by both KMnO4 and K2Cr2O7.

Selective oxidizing agents

The following oxidizing agents are more selective towards what functional groups they
oxidize. They are therefore often used to test for the presence of certain functional groups.

Amines to diazonium salts, for example This reaction is more useful for
aromatic amines than for
NaNO2 / conc + - aliphatic (non aromatic)
HCl(aq) amines such as
NaNO2/conc HCl
CH3CH2NH2.The reaction
O0 C
should be carried out under ice
cold conditions to prevent
hydrolysis of the product.
The actual oxidizing agent here
is nitrous acid, HNO2,
generated insitu from the
reaction
H+ + NO2-  HNO2.
The reaction

Fehling’s solution Aldehydes to carboxylic acids Strictly speaking, the reaction

[Cu2+ complexed to produces a salt of a carboxylic
tartarate ions in acid, since Fehling’s solution is
NaOH(aq)] alkaline.
his is a good test for an
aldehyde, in which a positive
test gives a brick-red
precipitate.

Tollen’s reagent Aldehydes to carboxylic acids The active oxidizing agent in

(AgNO3(aq)/NH3) Tollen’s reagent is the diamine
 574

silver (I) amine ion,

[Ag(NH3)2]+, a complex
produced when Ag+ reacts with
NH3 ligands.
Tollen’s reagent is alkaline, so it
converts an aldehyde to a
carboxylate.
Tollen’s reagent is a good test
for the presence of an aldehyde,
in which a positive test gives a
silver deposit on the walls of the
vessel. This is the basis for the
silver mirror test for aldehydes.

Notes
The Fehling’s and Tollen’s tests are good methods for distinguishing between aldehydes and ketones,
which often exist as functional group isomers. Consider propanone and propanal, which are such
isomers.
CH3CH2CHO CH3COCH3
Propanal - an aldehyde propanone (ketone)
Propanal, like all aldehydes, gives a positive test with Fehling’s solution and Tollen’s reagent. Propanone,
like all ketones, gives a negative result with these reagents.

3.5.2The use of reducing agents in organic chemistry

In organic reactions, most reducing agents work by adding hydrogen to or removing oxygen from the
reactant. Most of the oxidation reactions we have already discussed can be reversed by using a suitable
reducing agent. This is illustrated below. The forward reactions involve oxidation and the reverse
reactions involve reduction.

K2Cr2O7 K2Cr2O7
CH3CH2OH CH 3CHO CH 3COOH
H+ H+

LiAlH4 LiAlH4
-

(In practice, LiAlH4 reduces carboxylic acids all the way to primary alcohols. It is not possible to stop the
reaction at the aldehyde stage)

LiAlH4 and NaBH4

These are among the most powerful reducing agents used in organic chemistry. Lithium tetrahydrido
aluminate (LiAlH4) is more powerful than sodium tetrahydrido borate (NaBH 4). The major disadvantage
of LiAlH4 is that it is very sensitive to water, in which it hydrolyzes violently, posing a fire risk. For this
reason, LiAlH4 must strictly be used in the absence of water, even trace amounts. It is usually used in dry
ether as the solvent. This reagent is capable of carrying out the following conversions.
 575

 Nitriles to primary amines, for example

LiAlH4 / ether

Note that the reaction involves addition of hydrogen (reduction) to the nitrile group.

 Carbonyl compounds to alcohols. Ketones are reduced to secondary alcohols, whilst aldehydes
are reduced to primary alcohols, for example

LiAlH4
ether
benzaldehyde phenylmethanol

propanone propan-2-ol
(secondary alcohol)
 Carboxylic acids to primary alcohols, for example

 Esters to alcohol and carboxylic acid, for example

propylethanoate propanol ethanoic acid

This reaction results in lysis of the ester linkage, forming two products.
 576

 Primary amides to carboxylic acid and ammonia, for example

benzamide benzoic acid

 This reaction results in the lysis of the C-N bond.

NaBH4 is a more selective and weaker reducing agent. It can reduce aldehydes and ketones to primary
and secondary alcohols respectively, but it cannot reduce esters, amides, nitriles and carboxylic acids. The
major advantage of NaBH4 over LiAlH4 is that it can be used in water. In fact, it decomposes in water to
produce compounds which are even better reducing agents. Note that all compounds reduced by NaBH4
and LiAlH4 contain the C=O group. These two reagents are sources of the hydride ion, H -, which acts as a
nucleophile and attacks the C=O group. This converts the C=O group to the C-OH group.

.. ....-
H+

H-

Other reducing agents commonly used in organic chemistry include a mixture of tin and concentrated
HCl, hydrogen gas and sodium metal.

The use of Sn in concentrated HCl

This reagent reduces the nitro group, NO2 to the -NH2 group, for example

Sn/conc HCl

nitrobenzene pheny lam ine

Sn/conc HCl

2-nitropropane propan-2-am ine

 577

In such reactions, the metal is first oxidized by the acid to Sn 2+. The Sn2+ ion is the active reducing agent.
It is oxidized by the nitro compound to Sn (IV). Meanwhile, the NO 2 group in the organic reactant is
reduced to NH2.

Hydrogen as a reducing agent

Hydrogen acts as a reducing agent in the following reactions. In all cases, a d-block metal catalyst is
needed as a catalyst. In the school lab, hydrogen may not be used as a reducing agent because
 obtaining and storing hydrogen is a challenge (hydrogen is explosive)
 hydrogen often has to be used under high pressure which is difficult to achieve

I. Nitro compounds to amines, for example

H2, heat
M = Pt, Pd or Rh

II. Nitriles to amines

C RCH2NH2
heat

III . Aldehydes to primary alcohols

RCHO  RCH2OH

IV. Ketones to secondary alcohols

RCOR′  RCH(OH)R′

Conversions III and IV above give good yields but the reactions are rather slow. The conversions require
a catalyst, particularly Raney nickel.

V.Benzene to cyclohexene

cy clohex ane

The hydrogenation of benzene requires high temperature and pressure. Ruthenium or rhodium is usually
used to catalyze the reaction. The reaction requires stringent conditions because of the stability associated
with the benzene ring. The benzene ring resists any reaction which destroys the delocalized π system of
electrons.

VI.Alkenes to alkanes, for example

 578

H2

4-m ethy lpent-1-ene 2-m ethy lpentane

 Pt, Pd or Ni are used to catalyze the reaction

 Catalytic hydrogenation of alkenes is faster and easier than that of the benzene ring. Most alkenes
are hydrogenated at room temperature
 Hydrogenation of alkenes is used in the manufacture of margarine from long chain unsaturated
oils.

Questions, solutions and discussions

Q1The flow diagram below summarizes the synthetic route for the formation of phenol from
benzene.

NO2 NH2 N2+Cl- OH

Sn/HCl H2O
(i) reflux warm
(iii)
(ii) (iv)

(a)Name the type of reaction occurring at each numbered stage.

(b) What are the reagents and conditions required for steps (i) and (iii)?

(c)Give a mechanistic outline of reaction (i)

Solutions
(a)(i) Electrophilic substitution (nitration)
(ii) Reduction

(iii) Oxidation(diazotization)

(iv) Hydrolysis

(b)step (i): Concentrated nitric and sulphuric acids at around 600C.

step (iii): NaNO2(aq) in concentrated HCl, < 50C

 579

( c)

H2SO4(aq) + HNO3(aq) NO2+(aq) + H2O + HSO4-

H NO2

NO2+ + NO2
+ H+

Hint. You should always show organic mechanisms using curly arrows to indicate the movement of electrons.
The arrows should always point from a region of high electron density to one of low electron density.

Q2The structure of the sex hormone testosterone is shown below.

What type of reaction occurs when testosterone reacts with the following reagents? Also draw
the structure of the product formed in each case.

(i) hot concentrated potassium permanganate

(ii) sodium tetrahydridoborate in ether

(iii) heated ceramic surface

Solutions
(i) Oxidation, to form

(ii) Reduction of the carbonyl (ketone) group to a secondary alcohol, to form

580
 581

[Hot concentrated KMnO4 oxidizes

 the secondary alcohol group to a ketone

 the double bond, leading to its rapture.

Note that one carbon atom of the double bond (carrying one
hydrogen atom) is oxidized to a carboxylic acid, whilst the
other carbon atom (containing no hydrogen atoms) is
oxidized to a ketone)]

(iii) Dehydration, to form

Ceramic contains Al2O3 and SiO2 which catalyze the

dehydration of an alcohol.

Q3(a) Name the following organic compounds

(b) Give the structural formula of the organic products formed when compound B reacts with
the following reagents.

(i) K2Cr2O7 in dilute H2SO4

(ii) HCN
9189/01/O/N/2010
 582

Solutions
(a)A phenylethanone B 1-hydroxypropan-2-one C 2-phenylacetaldehyde

(b) (i) CH3COCOOH (ii) CH3C(OH)CNCH2OH

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 10.4
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
1.In the first ‘breathalyzer’ test for alcohol, drivers were asked to expel air from their lungs into
acidified potassium dichromate crystals.
State and explain what would be observed when the test was positive.
9189/01/O/N/2010

2. But-1-ene, CH3CH2CH=CH2, is an important compound in the petrochemical industry.

Some reactions of but-1-ene are given below.

In each empty box, draw the structural formula of the organic compound formed.cie N 2011

CH 3CH2CH=CH 2 -
MnO4 /H hot ,
H2O(g) concentrated
-
H3PO4 MnO4 /H
cataly st cold dilute

V
T

2-
Cr 2O7 /H heat
under reflux

9701/02/O/N/2011
 583

3. Hydroxyethanal has the formula HOCH2CHO

Give the skeletal formula of the organic compounds formed when hydroxyethanal reacts with

(i) NaBH4 (ii) Cr2O72-/H+ under reflux. 9701/02/O/N/2011

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

FGI 3
Required
 State the type of reaction taking place at each numbered stage.
 Supply reagents and conditions for steps marked (?)

? NH3 CH3Cl
CH4 CH3Cl CH3NH2 P
UV 1 2 3

4 ?

? 5
CH3OH HCOOH
6
? 7
8 ?
? HCHO

Solutions
Reaction 1
Free radical substitution, reagent: chlorine.

Reaction 2
Nucleophilic substitution. Conditions: heat in a sealed bomb.

Reaction 3
Nucleophilic substitution
The nucleophile is methylamine, CH₃NH₂. The nucleophilic centre of this molecule is the N of the amine
group. It is this nitrogen that attacks the electron deficient C of the C-Cl bond in chloromethane.
 584

H H H H
CH3 N  
H C Cl CH3 N C H + HCl
H
nucleophile
H H
P
secondary amine

The product P is a secondary amine. White fumes of HCl are produced.

Reaction 4
Nucleophilic substitution. Reagent and conditions: NaOH (aq), reflux.
This is conversion of a halogenoalkane to a primary alcohol.

Reaction5
Oxidation of a primary alcohol to a carboxylic acid (note the increase in the number of oxygen atoms).
Reagent and conditions: KMnO₄ (aq) /H+, warm or K₂CrO₇(aq)/H+ used in excess, warm.

Reaction 6
Oxidation of methanol to methanal, an aldehyde. Mild conditions are required.
Reagent: Limited K2Cr2O7, acidified, boil in a distillation apparatus. Alternative reagent: PCC.
Limited quantities of K2Cr2O7are used to minimize further oxidation of the product to a carboxylic acid.
The reaction is carried out in a distillation apparatus so that the volatile aldehyde is removed before it is
further oxidized to an acid.

Reaction7
Further oxidation of the aldehyde to a carboxylic acid using excess acidified K2Cr2O7. Alternatively use
acidified (hot or cold) KMnO4.

Reaction 8
Reduction of an aldehyde to a primary alcohol using a strong reducing agent such as lithium tetrahydrido
aluminate, LiAlH4 or sodium tetrahydridoborate, NaBH4.

Q
State the reagents and condition required for each of the following one or two step
conversions.

(a)

(b)
 585
(a)

(b)

(c)

(a) KMnO4/H+, under reflux, followed by LiAlH4/dry ether.

A
In the first step, the -CH3 group on methylbenzene is oxidized to -COOH.

KMnO 4 / H+
reflux

In the second step, benzoic acid is reduced to phenylmethanol.

LiAlH4 / ether

(b) CH3Cl/ AlCl3 followed by KMnO4/H+, under reflux.

In the first step, Friedel-Crafts alkylation occurs, forming methylbenzene

CH3Cl
AlCl3

In the second step, methylbenzene is oxidized to benzoic acid by hot acidified KMnO 4.

(c) Excess K2Cr2O7/H+ (aq), warm.

This reagent oxidizes the secondary alcohol group to a ketone, but has no effect on the C to C
double bond. KMnO4 would not be suitable here because it can also oxidize the C to C double
bond.
 586

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
Exercise
text box.] 10.5: Functional group interconversions

The following scheme shows a possible method for the synthesis of lactic acid.

i) State the reagents and conditions required for steps (1) and (3). State the type of reaction
taking place at each of these stages.
ii) Suggest why step (4) requires a catalyst. Name a suitable catalyst for this step.
iii) Draw the displayed formula of the intermediate X.
iv) State the reagent and condition required for step (5). What type of reaction is this?

NaOH(aq)
CH3CH3 CH3CH2Cl CH3CH2OH CH3CHO
reflux
(1) (2) (3) HCN(aq) (4)

H OH OH

H C C C
(5)
H H O X
lactic acid

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
10.3.6Organic neutralization reactions

3.6.1Organic acids
The carboxylic acids are the only stable organic acids. They are weak acids, that is, in aqueous solution
they undergo partial dissociation:

O O
R R + H+
OH O

Carboxylic acids, though weak, do show the properties expected of an acid, including
 Reaction with reactive metals such as Na, liberating hydrogen gas and forming a salt.
 587

 Reaction with alkalis to form a salt. Water may or may not be formed, depending on the
nature of the base. In neutralization reactions, carboxylic acids behave as typical Brønsted acids
by donating a proton to the base, for example

1. CH3COOH + .. OH - CH3COO- (aq) + H2O(l)

ethanoic acid ethanoate
ACID BASE BASE ACID

conjugate acid - base pair

conjugate acid - base pair

The ethanoate solution is weakly alkaline because it can accept a proton from water, thus
releasing OH- ions. This results in reversal of reaction 1. Note that by giving a proton to
ethanoate ions, water acts as an acid.
A similar neutralization reaction takes place with ammonia:

2. CH3COOH + .. NH3 CH3COO- (aq) + NH4+(aq)

ethanoic acid ethanoate ammonium
ACID BASE BASE ACID

conjugate acid - base pair

conjugate acid - base pair

 Effervescence with carbonates and hydrogen carbonates. The effervescence is a result

of the production of carbon dioxide. The other products of this reaction are a salt and water, for
example
2CH3COOH(aq) + Na2CO3(s) 2CH3COO- Na+(aq) + CO2(g) + H2O(l)

 Turn blue litmus paper red

In addition to these reactions, the –COOH group undergoes other types of reactions, for example,
nucleophilic substitution with PCl5.

Explaining the acidity of carboxylic acids

There are three ways of explaining the acidity shown by carboxylic acids.
 There are two oxygen atoms on the carboxyl group. These, being highly electronegative, have a
tendency to withdraw electrons from the O-H bond. Recall that a covalent bond is simply a region
of electron density shared between two atoms. The greater the density (as in a double or π bond),
the stronger the bond. The two oxygen atoms of the carboxyl group therefore weaken the O-H
bond by withdrawing electron density. The bond can easily break and release a hydrogen ion in
solution.
 Oxygen has the ability to accommodate and stabilize a pair of electrons. When the O-H bond of
the COOH group breaks, a hydrogen ion enters solution, leaving behind the pair of electrons that
constituted the bond. This process of bond breaking is made possible by the fact that oxygen has
the ability to stabilize this pair of electrons.
 588

 The carboxylate ion is stabilized by resonance. Dissociation of the COOH group results in the
formation of a negatively charged carboxylate ion. Now, the negative charge on this ion does not
reside on a single atom. The resonance structures below show that the negative charge can reside
on either oxygen atom of the -COOH group.

1 1
O O
C 2 C 2
O O

The negative charge is therefore continuously shifting between the two oxygen atoms, in other words, it is
delocalized between the two atoms, as shown below.

O
C
O

The negative charge is delocalized over

three atoms.

This delocalization of charge imparts stability to the carboxylate ion. Now, do not forget that chemical
stability actually means inertness or resistance to reacting. Since the negative charge is not localized, it is
not easily available to attract a hydrogen ion from solution. In other words, the carboxylate ion, once
formed, does not easily revert back to the -COOH group by attracting a hydrogen ion. The stability of the
carboxylate ion also implies that its formation is favourable.
The strength of an acid therefore depends on the instability of the O-H bond in the undissociated acid and
the stability of the carboxylate ion. Any factor that weakens the O-H bond, for example by withdrawing
electron density, makes the acid stronger since it becomes easier for a hydrogen ion to be released.
Similarly, any factor that increases the stability of the carboxylate ion increases acid strength because,
being stable, the formation of the carboxylate ion is energetically favourable. Of course, formation of the
carboxylate ion occurs by release of a hydrogen ion, which in turn is responsible for acidity.

Comparing the acidities of carboxylic acids

Acid strength is the extent to which an acid dissociates in water. The stronger an acid, the greater is its
extent of dissociation in water. The acidities of different carboxylic acids can be compared using acid
dissociation constants (Ka). Alternatively, pKa values can be used. The larger the Ka value of an acid, the
stronger it is. However, the larger the pKa value, the weaker the acid. Consider the following pairs of
carboxylic acids. We wish to determine which of the acid in each pair the stronger acid is.

Pair 1 : CH3COOH and CH2ClCOOH

 CH2ClCOOH is the stronger acid, that it is, it has the greater K a value (or smaller pKa) value.
 Cl, because of its high electronegativity, pulls electrons from the O-H bond towards itself. This
weakens the bond and makes release of a hydrogen ion easy.
 589

Cl O

O H
 The carboxylate ion formed is also stabilized by the electron withdrawing effect of the Cl atom. By
partly withdrawing the delocalized negative charge, the ability of the carboxylate ion to recombine
with hydrogen ions decreases, that is, hydrogen ions are not so easily removed from solution.
 The presence of chlorine in CH2ClCOOH therefore increases acidity by destabilizing the acid so
that it dissociates easily, and by stabilizing the carboxylate ion so that it does not easily combine
with hydrogen ions.

Pair 2 : CH2ClCOOH and CHCl2COOH

 CHCl2COOH has the greater acidity since there are two chlorine atoms withdrawing electrons
from the O-H bond. This bond is greatly weakened. Also, the two Cl atoms have a greater
stabilizing effect on the carboxylate ion since they effectively disperse the negative charge on the
ion.

Pair 3 : CH2BrCOOH and CH2ClCOOH

 CH2ClCOOH has the greater acidity since Cl is more electronegative that Br. Chorine withdraws
electrons from the O-H bond of the acid and from the carboxylate ion more effectively.

Pair 4 : CH3COOH and CH3CH2CH2COOH

 CH3COOH has the greater strength. Alkyl groups have an electron pushing effect. This reinforces
the O-H bond, making it stronger so that an H + ion is not easily released into solution. Similarly,
the negative charge on the carboxylate ion becomes more intense. Such a charge is more effective
at picking up H+ ions from solution, thus shifting the dissociation equilibrium in favour of the
undissociated acid. In other words, an electron pushing group stabilizes the acid but destabilizes
the carboxylate ion. In CH3CH2CH2COOH, the alky group (CH3CH2CH2-) is longer and so has the
greater ability to stabilize the O-H bond in the acid, and to destabilize the carboxylate ion.

OH

Pair 5 : CH3COOH and O

benzoic acid

 Benzoic acid is the stronger acid because of the electron withdrawing effect of the benzene ring.
 590

OH OH

Pair 6 : O and O

A
B NO2

 Compound B is more acidic. The nitro group, NO2, like any other group derived from an acid, has
an electron withdrawing effect. In compound B, there are therefore two electron withdrawing
groups, the benzene ring and the -NO2 group. This greatly weakens the O-H bond of the carboxyl
group.

Pair 7 : CH2ClCH2CH2COOH and CH3CH2CHClCOOH

 The second compound has the greater strength. This is because the electron withdrawing chlorine
atom is closer to the O-H bond. It withdraws electrons from this bond more effectively, thus
weakening it. The ability of the chlorine atom to withdraw electrons from the O-H bond decreases
with distance. In the first compound, the chlorine atom is a larger distance from the O-H bond.
This bond is therefore weakened to a smaller extent, that is, the O-H bond in the first compound
is stronger than in the second compound.

The following table gives the Ka and Pka for different acids. Try to explain the differences in these values in
your own words.

Acid Ka/moldm-3 pKa

CH2ClCOOH 1.3 x 10-3 2.89

CHCl2COOH 5.12 x 10-4 3.29

HCOOH(methanoic 1.78 x 10-4 3.75

acid)

C6H5COOH(benzoic 6.31 x 10-5 4.20

acid)

CH3COOH 1.74 x 10-5 4.76

Acidity in other hydroxy compounds

We have said that one reason for the acidity of carboxylic acids is the ability of the oxygen atom of the O-H
group to accommodate and stabilize a pair of electrons. We would therefore expect other hydroxy com-
pounds, namely, the phenols, the alcohols and water to show acidity since they also contain the O-H
group. Indeed, these compounds have a degree of acidity, but the acidity is so slight that the compounds
are not classified as acids.
 591

Phenol
Phenol is many times weaker as an acid than carboxylic acids, for instance, phenol has no reaction with
carbonates or hydrogen carbonates, whereas carboxylic acids gives a brisk effervescence. However, phenol
shows some properties expected of an acid.
 It reacts with sodium metal, forming a salt and releasing hydrogen gas. This reaction is slower
than the corresponding reaction of carboxylic acids. When sodium metal is added to phenol, it
dissolves gradually with a steady liberation of bubbles of hydrogen gas. The corresponding reac-
tion in carboxylic acids is rapid.

OH O- Na+
+ Na + H2

sodium phenoxide

In this reaction, a colorless solution containing the salt sodium phenoxide is formed. When the
solution is evaporated, white crystals of the salt are formed.
 Phenol neutralizes NaOH(aq), forming sodium phenoxide and water

OH O- Na+
+ NaOH + H 2O

sodium phenoxide

This reaction involves Brønsted- Lowry neutralization:

hy drox ide
(proton acceptor-
base)
..
.. OH
..

H2 O

phenol
(proton donor - acid)
 Phenol is poorly soluble in water, but it dissolves easily in aqueous NaOH since a neutralization
reaction takes place to form a soluble salt.

Why does phenol show some degree of acidity, and why is it weaker than carboxylic ac-
ids?
The benzene ring has an electron withdrawing effect. This has the effect of weakening the O-H bond in
phenol, so that it can break relatively easily. When this happens, a hydrogen ion is released, and a phe-
noxide ion is formed.

OH O-

+ H+ ... (i)
 592

Once formed, the phenoxide ion experiences some stabilization from the electron withdrawing effect of
the benzene ring as this disperses the negative charge to some extent. Phenol is many times weaker as an
acid than carboxylic acids. This is because the stabilizing effect of the benzene ring on the phenoxide ion is
much smaller compared to the stabilizing effect of resonance and delocalization in the carboxylate ion. In
other words, a phenoxide ion is many times less stable than a carboxylate ion. The phenoxide ion there-
fore easily picks up hydrogen ions from solution. This reduces acidity of the solution and reduces dissoci-
ation of phenol by pushing equilibrium (i) to the left.
To show that phenoxide ions are very unstable relative to phenol, solid sodium phenoxide is dissolved in
water to form a colourless solution, and then carbon dioxide is bubbled into the resulting solution. The
solution begins to turn cloudy as the relatively insoluble phenol is formed. When carbon dioxide is added
to water it slightly dissolves to form a weakly acidic solution containing hydrogen and hydrogen carbonate
ions. The hydrogen ions are instantly picked up by phenoxide ions, resulting in the formation of
phenol.

Ethanol
Ethanol is only feebly acidic. It is many times weaker than phenol. The fact that ethanol has no reaction
with NaOH but phenol reacts shows that ethanol is a weaker acid. However, ethanol has a degree of acidic
character, though extremely small. This is supported by the fact that ethanol reacts with sodium metal.
The reaction is slow; the metal sinks in the liquid and dissolves slowly, gradually releasing hydrogen gas.
Compare with the reaction of sodium in water. The reaction is rapid and a large amount of heat is pro-
duced, which may cause the water to boil. The metal does not sink but rapidly skitters on the surface
because of its low density.
The extremely small degree of acidity in ethanol can be explained in this way:

 The alkyl group (CH3CH2) in ethanol has an electron pushing effect. The effect is to strengthen the
O-H bond. This bond is therefore stable and does not easily dissociate to release H +.
 If the O-H bond in ethanol dissociated, an alkoxide ion would be formed

CH3CH2O-H CH3CH2O - + H+
alkoxide ion
The electron pushing effect of the alkyl group increases density of negative charge on the oxygen
atom of the alkoxide ion. This increases the affinity of the alkoxide ion for hydrogen ions, thus
promoting the reverse reaction and decreasing the tendency of ethanol to dissociate.
 Compare with phenol in which the negative charge on the phenoxide ion is partially dispersed by
the electron withdrawing effect of the benzene ring, and with ethanoic acid in which the negative
charge on the ethanoate ion is dispersed by delocalization. The absence of resonance or electron
withdrawing groups greatly destabilizes the alkoxide ion, making its formation energetically
unfavourable.

3.6.2Organic bases
The important organic bases are the amines. They act as Brønsted bases by using a lone pair of electrons
on the NH2 group to attract a proton from an acid.
 593

H+
R NH2 R NH3+
an ammonium salt
Amines are weak bases, but they have properties expected of a base, including
 Reaction with acids to form salts
 Turn red litmus paper to blue.

In addition to these reactions, the –NH2 group in amines behaves as a nucleophile. The lone pair of
electrons on the N atom of the –NH2 group can be used to attack an electron deficient carbon (Cδ+), for
example in halogenoalkanes.

Comparing basicities ofdifferent amines

Recall that carboxylic acids react by releasing a hydrogen ion. For amines, the reverse happens; they react
by attracting protons from solution. An amine uses a lone pair of electrons on the -NH2 group to attract
and form a dative bond to a hydrogen ion. The basicity of an amine depends on its affinity for hydrogen
ions. Any factor which increases electron density on the nitrogen atom of the -NH2 group increases
basicity by increasing affinity for hydrogen ions. Conversely, any factor which reduces electron density on
the -NH2 group decreases basicity by reducing affinity for hydrogen ions. Consider the following pairs of
bases. We wish to determine which of the base in each pair is stronger.

Pair 1 : CH3CH2NH2 and CH2ClCH2NH2

ethylamine 1- chloroethylamine

 Ethylamine is the stronger base. The ethyl group (CH 3CH2-) pushes electrons towards the -NH2
group. The increase in electron density at the nitrogen atom increases the ability to react with
acids. On the other hand, the chlorine atom in 1-chloroethylamine has an electron withdrawing
effect. This reduces electron density on the nitrogen atom and thus the ability to attract protons is
reduced.

Pair 2 : CH2ClCH2NH2 and CH3CHClNH2

 Both compounds contain a chlorine atom which reduces basicity. The effect is greater in the
second compound, since the chlorine atom is closer to the -NH2 group. The second compound is
therefore the weaker base.

Pair 3 : CH3NH2 and CH3CH2CH2NH2

methylamine propylamine
 594

 Propylamine is the more basic. Alkyl groups are electron pushing and so they tend to increase
electron density on the nitrogen atom. In propylamine, the alkyl group is longer, so it has the
greater electron pushing effect.

NH2
Pair 4 : CH3CH2NH2 and
ethylamine
aniline

 Aniline is less basic because the-NH2 group is bonded to a benzene ring which has an electron
withdrawing effect. Ethylamine is more basic because the -NH2 group is bonded to an alkyl group
which has an electron pushing effect.

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 10.6
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]

1(a) Write the equation for a reaction in which ethylamine, C2H5NH2 acts as a Brønsted-Lowry base.
(b) Ammonia, ethylamine and phenylamine are three nitrogen containing bases
Place these three compounds in order of basicity, with the most basic first.
Explain why you have placed these three compounds in this order.

(c) Write an equation for a reaction in which phenol acts as a Brønsted-Lowry acid.

(d) Suggest an explanation for the difference in the pKa values of phenol and nitrophenol
9701/42/O/N/2011

2. Explain the relative acidities of water, phenol and ethanol

9189/01/O/N/2010

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
10.3.7 Organic reactions that involve water
Hydration, dehydration, condensation and hydrolysis are important reactions in organic chemistry. They
have one thing in common; they all involve water, either as a product or as reactant. However, these
reactions should not be thought of as separate mechanisms. Instead, they fall under some of the mechan-
isms which have already been discussed.

 hydration – electrophilic addition(of water)

 595

 Dehydration- elimination (of water)

 Condensation-nucleophilic substitution, resulting in loss of water
 Hydrolysis - Nucleophilic addition of water, accompanied by bond breaking.

In hydration and hydrolysis, water is a reactant.

In dehydration and condensation, water is a product.

It is often difficult for students to see any difference between these pairs of reactions. The best way to see
that these pairs of reactions are indeed different is to look at examples of such reactions.

Hydration and hydrolysis (H2O= reactant)

1. CH3COCl + H2 O CH3COOH + HCl ... hydrolysis

2. CH2=CH2 + H2O CH3CH2OH ... hydration

Although both reactions involve water as a reactant, they proceed by different mechanisms.

Reaction 2, which forms a single product, is an addition reaction. This is in fact electrophilic addition of
water to the double bond. Recall that acids of the type HX (e.g. HCl) are added to the double bond by
electrophilic addition. We may think of water as being of the acid type HX, where X = OH.
Hydration at the double bond occurs when the H+ ion from water attacks and bonds to one of the carbon
atoms of the double bond, generating a carbocation. The OH- ion from water then neutralizes the
carbocation, forming an alcohol. However, water is only weakly acidic and its tendency to produce the
electrophile (H+) is very small. Stringent conditions are therefore required (strong heating, the use of
steam and a catalyst).

H3PO4
CH2 CH2 CH3CH2OH H3PO4 on silica = catalyst
silica
H2O(g)

Reaction 1 occurs by a different mechanism. The fact that two products are formed hints at a
substitution reaction. Water is also a reactant, but this time it acts as a nucleophile.


O
 O
H O H3 C O
 H3 C
H Cl  H3 C + H+ + Cl-
OH
H O+
ethanoic acid
H
HCl
white fumes

This reaction therefore involves nucleophilic substitution of the Cl atom by the OH group from water. The
term hydrolysis implies that a bond in water must undergo lysis (breaking) to generate the OH
nucleophile.
 596

In organic chemistry, hydrolysis involves water splitting to generate the OH- nucleophile which
then attacks an electron deficient carbon (which is bonded to one or more electron withdrawing
groups).

Hydrolysis occurs in
 acylchlorides
 hydrogenoalkanes
 amides, including polyamides such as proteins and nylon
 esters, including polyesters such as terylene.

The following table below gives the products of hydrolysis of the classes of compounds given above

Class of compound Conditions required for Organic product(s) of

hydrolysis hydrolysis

Acylchlorides Cold water Carboxylic acid

Hydrogenoalkanes NaOH(aq), reflux alcohol

Amides NaOH (aq) OR a strong aqueous Carboxylic acid and amine

acid, e.g. H2SO4. Boil the mixture

Esters Same as above Carboxylic acid and alcohol/phenol

 Ethanoyl chloride (an acylchloride) fumes in moist air due to hydrolysis with water vapour in the
atmosphere. The white fumes are a result of the formation of HCl. When added to cold water,
ethanoyl chloride undergoes rapid hydrolysis. The reaction produces large amounts of heat
energy.
In this nucleophilic substitution reaction, the -OH group from water replaces the chlorine atom in
ethanoyl chloride. Acylchlorides are very reactive towards nucleophiles because the carbon atom
of the -COCl group is bonded to two electronegative atoms. These atoms withdraw electrons
towards themselves, leaving the carbon atom of the -COCl with a large partial positive charge.
This carbon atom is therefore very good at attracting nucleophiles.


O O

H3C + H2O H3C + HCl

Cl OH white fumes
ethanoyl chloride ethanoic acid
 597

Mechanism

O O O
H3C H3C H3C + HCl
.. . Cl + Cl OH
H O. H O
H H

a water molecule attacks C O from water now has
three bonds instead of 2, so it
develops a positive charge.
An O-H bond breaks, and its
electrons neutralize the positive
charge. At the same time, there is
too much electron density around
C, so the C-Cl bond breaks.

 Amides and polyamides (for example proteins and nylon) undergo acid or base catalyzed hydroly-
sis in water. The reaction mixture must be boiled. Hydrolysis of a primary amide results in the
formation of a carboxylic acid and ammonia. However, if we wish to be strict, we should say that
the products formed depend on the pH of the reaction mixture. If an acid catalyst is used, the
ammonium ion, not ammonia is formed. This is because NH3 bonds with hydrogen ions
(neutralization) to form NH4+. Similarly, if an alkali is used to catalyze the reaction, a carboxylate
ion, not carboxylic acid, is formed. This is because any carboxylic acid formed is neutralized by
the alkali.


 O O
 H2O boil
H3C H3C + NH3
NH2 H+ or OH- OH pungent gas
ethanamide ethanoic acid

Note that the reaction results in the breaking of the C-N bond. You can visualize the reaction by
doing this: Split H2Ointo H and OH. The -OH group (nucleophile) bonds to Cδ+ to form a -COOH
group. The H atom bonds to the -NH2 group, to form NH3. The C-N bond then breaks. You can do
the same analysis for the hydrolysis of acylchlorides and esters.

 Esters and polyesters (for example, Terylene) undergo acid or base catalyzed hydrolysis in water,
just as the amides. The reaction mixture must be warmed. The reaction results in the formation of
a carboxylic acid and an alcohol.

O
O
H3C H2O warm
H3C + CH3OH
O H+ or OH- OH methanol
H3C
ethanoic acid
methyl ethanoate
Note that this reaction is reversible. Under the same conditions, the products of the reaction undergo
condensation (esterification) to reform the reactant.
 598

Hydrolysis of halogenoalkanes
It has already been explained that halogenoalkanes undergo very slow hydrolysis in water, to form an
alcohol. The reaction occurs via nucleophilic substitution. The reaction is faster when NaOH (aq) is used,
under reflux.

R''' R'''
NaOH(aq)/heat '
R '
C Hal R C OH + Hal-
R'' R''
(One or all of the R groups could be H
or alky/phenyl groups.)

Comparing the ease of hydrolysis of different halogenoalkanes

Presence of the C-Hal bond can be tested for using hot NaOH (aq) followed by AgNO 3 (after neutralizing
unreacted alkali with HNO3). A positive result in this test depends on the C-Hal bond breaking, releasing
free halide ions in solution, during the nucleophilic substitution reaction with NaOH (aq).
e.g. CH3CH2Cl + NaOH (aq)  CH3CH2OH + Clʒ
A precipitate is then formed when Ag+ ions combine with the liberated halide ion. The colour of the silver
halide precipitate depends on the halide ion present; Cl ʒ gives a white precipitate of AgCl, Brʒ gives a
cream precipitate of AgBr and Iʒ gives a yellow precipitate.
Given three halogenoalkanes, chloroethane,bromoethane and iodoethane, which one hydrolyses the
fastest?
An experiment can be carried out to determine how fast a precipitate of silver halide appears according.
Iodoethane gives the fastest result, followed by bromoethane. Chloroethane hydrolyses the least readily
and it takes the longest time for the first trace of precipitate to occur. This observation can be explained in
terms of bond energies (see Table 10.6 below). The C-I bond is the weakest due to the large atomic size of
the iodine atom. This bond therefore breaks easily, that is, hydrolysis of iodoalkanes is relatively rapid. As
the halogen atom becomes smaller, the C-Hal bond becomes stronger and rate of hydrolysis decreases.
The C-Cl bond is the strongest and so it takes the longest time to break.

Bond Bond energy Rate of formation of

in Kj/mol a precipitate of AgHal

C-Cl 338 Slow. A thin white ppt appears

after several minutes

C-Br 276 Faster. An off-white ppt

appears after several seconds.

C-I 238 Rapid. A yellow ppt appears within

a few seconds

Table 10.6Rate of hydrolysis of the C-Hal bond depends on the relative strength of
the bond. This affects the rate at which a precipitate is formed when the
halogenocompound is boiled with a mixture of NaOH (aq) and AgNO3 (aq)
 599

Comparing the ease of hydrolysis of CH3CH2Cl, CH3COCl and C6H5Cl

Ethanoylchloride hydrolyses the most rapidly, giving an instant result with cold AgNO 3 (aq)
(white precipitate of AgCl). Addition of NaOH is not necessary, because the -COCl group is so very
reactive. This is because of the large partial positive charge on the carbon atom of the –COCl group. This
large partial charge is a result of the fact that the carbon atom is bonded to two very electronegative atoms
(Cl and O). The carbon atom is therefore easily attacked by the OHʒ nucleophile from H2O.

Chloroethane, CH3CH2Cl, hydrolyzes less readily (it takes longer for a white precipitate of AgCl to appear)
because it has a less polar C-Cl bond. Chlorobenzene, C6H5Cl resists hydrolysis under ordinary lab
conditions. This is because the benzene ring withdraws some electron density from the Cl atom, giving the
C-Cl bond some double bond character. The bond is therefore very strong and is not easily broken to make
room for the –OH group.

Dehydration and condensation (water = product)

1. OH
1. OH
+ H2O ... dehydration
+ H2O ... dehydration
cyclohexanol cyclohexene
cyclohexanol cyclohexene

2. CH3OH + CH3COOH CH3COOCH3 + H2O ... condensation

2. CH3OH + CH3COOH CH3COOCH3 + H2O ... condensation
methanol ethanoic acid methyl ethanoate
methanol ethanoic acid methyl ethanoate
 600

Reaction 1involves only one reactant, from which a molecule of water is removed. Dehydration is
therefore clearly an elimination reaction.

Dehydration is the elimination of water from a single reactant molecule

In acid-catalyzed dehydration, the OH group of the alcohol is first protonated to form an H2O+ group,
which is a good leaving group. The C-O bond then undergoes heterolysis, and the electrons of the bond
shift to form a new carbon to carbon pi bond. This forces the H 2O+ group to leave the molecule.

H+ H
..OH +
O
cyclohexanol H + H2O
The -OH group is protonated C-O bond breaks, water leaves. cyclohexene
Electrons of C-O bond are used
to make a C to C pi bond.

Once more, conditions are important in this reaction.

OR
OH
conc H2SO4
+ H2O
1700C
(vapour)

The acid acts as a catalyst. Other possible catalysts include Al 2O3 and phosphoric acid.

OH
Al2O3(s)
+ H2O
3000C
(vapour)

This reaction is reversible. In fact, the same catalyst can be used for the forward dehydration (elimination
of water) reaction and the reverse hydration (electrophilic addition of water) reactions.

Reaction 2(condensation) also results in the formation of water, but this time two reactants are
involved. This type of reaction is known as esterification between an alcohol and an acid. This is actually a
nucleophilic substitution reaction. The alcohol acts as the nucleophile, and uses a lone pair of electrons on
the oxygen atom to attack the Cδ+ of the –COOH group of the acid. An acid or alkali is required as a
catalyst. Formation of polymers such as polyesters, proteinsand starch also occur by condensation.
 601

Mechanism of acid-catalyzed esterification: a condensation reaction

O
H3C H+
acid protonates the -OH group, creating a good
..OH from acid
leaving group, H2O+.

 Alcohol acts as a nucleophile, a water molecule is

O
removed from the intermediate.
H3 C
 +
O

CH3
.
O. H
H

ester group
O
O
H3 C
H3C
O CH3 + H2O + H+
O CH3 catalyst
H regenerated
O-H bond from 'alcohol' breaks, releasing a
H+ ion

FGI 4
Required
 State the type of reaction taking place at each numbered stage.
 Supply reagents and conditions for steps marked (?)
 Draw the structures of the lettered products.
 602

F
Br2(l)

G
Br2
Conc KMnO4 , conc H+ H2SO 4(aq), boil
E NH3 +B
Na (s)
A ??

H2SO4(aq), cold
D
C
??

Questions, solutions and discussions

Q1When compound X was vapourised and passed over hot porcelain, a mixture of two products,
A and B were formed. Both A and B decolourize cold dilute and alkaline KMnO4 as shown
below.

HO
MnO4
- OH
A

-
MnO4 OH
B
HO
Y

(a)What is the size of the bond angle marked Y?

(b)What type of reaction occurs when the vapour of compound X is passed over hot porcelain?

What is the function of the porcelain?

(c)Draw the structures of compounds A and B. Hence deduce the structure of compound X.
 603

Solutions

(a) 109.50

(b) Dehydration. To catalyze the reaction

(c)

OH
compound X A B

Q2 Which of the following substances undergo hydrolysis? For those substances which
hydrolyze, state the conditions required for the reaction to take place, and write down the
structural or displayed formulae of the products formed.

(a) Ethanoyl chloride

(b)Chloroethane

(c)Chlorobenzene

(d)Ethylmethanoate

(e)Propanamide.

Solutions

 Ethanoylchloride

H O
H2O
CH3COCl H C C
cold
H O-H

 Chloroethane

H H
H2O
CH3CH2Cl H C C OH
NaOH
H H
reflux
 604

 Ethyl methanoate

H H
H2O
CH3CH2OCOH H C C OH + HCOOH
H2SO4
H H
warm

 Propanamide

H2O
CH3CH2CH2CONH2 CH3CH2CH2COOH + NH4+
H2SO4
heat

[chlorobenzene resists hydrolysis under ordinary conditions. This is because the C-Cl bond has a
partial double character due to the electron pulling effect of the benzene ring]

10.3.8Polymerization reactions

Polymerization is a reaction in which a large number of molecules, known as monomers, join

chemically to form a single organic macromolecule knownas a polymer.

Polymerization in which the monomers are identical is known as homopolymerization. Polymers formed
in this way are known as homopolymers. When the monomers are different, the type of polymerization is
known as copolymerizationor heteropolymerizationand the polymers formed in this way are known as
copolymers or heteropolymers.
A large number of polymers exist naturally, and these include starch (a food store in plants), glycogen (a
food store in animals), Nucleic acids (DNA and RNA), proteins and rubber.
Many polymers are formed synthetically, and these include plastics such as polyethene, polypropene,
PVC, Terylene and nylon.
Polymers can be classified, on the basis of how they are formed, as addition or as condensationpolymers.
Examples of addition polymers are PVC and natural rubber. Examples of condensation polymers are ny-
lon, Terylene and proteins.

Addition polymerization
This is a reaction in which a large number of alkene molecules link to form a macromolecule. One type of
functional group (the C to C double bond) is therefore involved in the formation of the polymer.
 605

Condensation polymerization
This is a reaction in which a large number of monomers link to form one long chain molecule, with the
loss of small molecules such as water.
Each monomer used has two functional groups, or one functional group repeated twice, for example, one
monomer can be a diamine and the other a dicarboxylic acid. During the polymerization process, the
monomers approach each other in an orientation that brings together functional groups that have an
affinity for each other. For example, the –NH2 group on a diamine approaches the –COOH group on a
dicarboxylic acid.

The differences between addition and condensation polymerization

Addition polymerization Condensation polymerization

One product is formed. Two products are formed, the polymer and a
small molecule such as water.

The Mr of the polymer is the sum of the Mr The Mr of the polymer is less than the sum of
values of all the monomers present. the Mr values of all monomers present, due to loss
of small molecules such as water.

Is a free radical addition reaction. Is of a nucleophilic type.

Irreversible Can be reversed by hydrolysis.

A ‘carbon only’ main chain is formed. The main carbon chain formed is interrupted at
regular intervals by non-carbon atoms, for example
N in proteins and nylon.

Examples: polyethene, PVC, polystyrene, Examples: proteins, nylon, silk fibroin, terylene,
Polypropene carbohydrates

The structure and formation of addition and condensation polymers will be discussed later under the
relevant topics.
 606

Part 2

STUDY OF INDIVIDUAL HOMOLOGOUS

SERIES
 607

10.4 Hydrocarbons
Hydrocarbons are compounds that contain carbon and hydrogen only. We will discuss the following
hydrocarbons.
 Alkanes
 alkenes
 aromatic hydrocarbons

10.4.1Alkanes

Non - cyclic alkanes are hydrocarbons that have the general formula CnH2n+ 2, for example, an alkane with
11 carbon atoms has the formula C11H2(11)+ 2 = C11H24. Cyclic alkanes have the general formula CnH2n, that
is, the number of hydrogen atoms is twice that of carbon atoms. Examples of cycloalkanes are shown
below.

cyclopropane

= cyclohexane

cyclobutane

All alkanes are saturated, that is, they do not contain any C to C double or triple bonds.

4.1.1 Source of alkanes

The main source of alkanes is petroleum (crude oil), which is a complex mixture of hydrocarbons. The
hydrocarbons in petroleum are separated by fractional distillation. Crude oil also contains aromatic
hydrocarbons.

Fractions from the distillation of crude oil

The different hydrocarbons in petroleum can be separated as fractions, since they have different boiling
points.
1. Refinery gas contains hydrocarbons that are gases at normal temperature (C1 to C4) hydrocarbons.
Methane (natural gas) is a major component of the refinery fraction. The major use of the refinery gas is
as a gaseous fuel.
 608

2. Gasoline fraction is a mixture of C5 to C10 hydrocarbons, with boiling points between 40⁰C and 180⁰C.
This fraction is liquid at normal temperatures. It is mainly used as a fuel in internal combustion engines.
A part of the gasoline fraction known as naphtha is used to manufacture petrochemicals (petroleum based
chemicals)

3. The kerosene fraction, used as a fuel for jet engines, consists mainly of C11 and C12 liquid
hydrocarbons, whose boiling points range between 160⁰C and 250⁰C.

4. Diesel oil fraction, used in diesel engines, contains C13 to C25 liquid hydrocarbons. One of its uses is as
a fuel in the diesel internal combustion engine.

5.Residue, so called because it is a mixture of involatile hydrocarbons, is made up of C26 to C28

hydrocarbons whose boiling points are above 350⁰C. It is mainly used as a fuel oil in large furnaces. A
fraction of it is used to make waxes and lubricating oils. Theses hydrocarbons are solid at normal
temperature when pure.

Cracking
This is the decomposition of a long chain alkane into smaller molecules, usually an alkane and an alkene.
Sometimes hydrogen is produced as well. Here is an example of a cracking process
C11H24 C9H20 + CH2 = CH2
There are two methods of cracking, thermal and catalytic.
 Thermal cracking is carried out at very high temperatures. The heat energy causes vigorous
molecular vibrations which lead to bond breaking. This process wastes energy as large amounts
of fuel must be burnt to drive the cracking process.

 Catalytic cracking is carried out at a relatively lower temperature (of about 500 0C) in the
presence of a catalyst.

Cracking is a very important industrial process as it produces small chain alkenes which are very
useful in the synthesis of a wide range of products, including plastics and drugs. Cracking also
produces branched chain alkanes which are used as petrol additives. Branched chain alkanes burn
smoothly and thus prevent knocking of the engine due to sudden and irregular combustion of fuel.
The addition of branched chain alkanes to a fuel makes the use of leaded fuel unnecessary. Leaded
fuel contains an additive that smoothens out the combustion of fuel. Unfortunately, the use of leaded
petrol results in the release of harmful lead compounds into the atmosphere.

4.1.2 Nomenclature of alkanes

The IUPAC method of naming organic compounds has already been discussed. Check your memory by
naming the following alkanes. CH3
A. CH3 CH2 CH CH3 B.
CH3 CH2 CH CH CH3
CH3 CH3
A. CH3 CH2 CH CH3 B. CH2 CH3
CH3 CH2 CH CH CH3
CH3
CH2 CH3
CH3 CH3
C. CH3 C CH2 CH3 D. CH3 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2
CH3
CH3 CH2 CH2 CH3 CH3
C.
Bonding and structure
C D. CH3 CH2 CH2 CH3
CH2 CH2 CH2 CH2
CH2 CH3
CH3
CH2 CH3
CH3 CH2
CH3
 609

The geometry around each carbon atom in an alkane is tetrahedral, with a bond angle of 109.5 0. Consider
pentane, whose structural formula is CH3CH2CH2CH2CH3. The structure below emphasizes that the car-
bon chain is not straight, but takes a conformation which allows a tetrahedral geometry at each carbon
atom.
Chain (skeletal) isomerism is possible in alkanes. This is a form of
109.50
structural isomerism in which compounds of the same molecular
formula differ in the number and length of branches along the main
chain (see part 1 of this section 1).

4.1.3 Physical properties of alkanes

1. They are insoluble in water but dissolve well in organic or non polar solvents.
2. They are relatively volatile.

Solubility of alkanes
Alkanes are immiscible with water. They are non-polar and so they dissolve better in other non-polar sub-
stances.When a substance dissolves in another, forces of attraction must be established between mole-
cules of the solute and the solvent. This requires breaking of the intermolecular forces between solvent
molecules so that new forces of attraction are established between the solute and solvent particles. An
alkane does not dissolve in water because the hydrogen bonds that must be broken in water are much
stronger than the Van der Waals forces that would be established between the alkane and the water
molecules.

Trend in melting points and viscosity

The alkanes are volatile (can easily be turned to a gas ) relative to polar substances of comparable Mr. This
is because the forces of attraction holding molecules of the alkane together are weak Van der Waals
forces . A relatively small amount of heat energy is required to overcome these forces and separate the
molecules into the gaseous state.
The boiling points of the alkanes increase down the homologous series(Fig 10.9).

This is caused by an increase in the number of

electrons. Van der Waals forces are a result of the
boiling point / K momentary asymmetric distribution of electron
density in a molecule. The larger the number of
electrons, the greater is this distortion and the
stronger the Van der Waals forces. More energy is
therefore requiredto break the Van der Waals
forces going down the homologous series. This
increase in melting and boiling points is
accompanied by change in physical state at room
Fig10.9
temperature. The lowest Mr alkanes (C1 to C4) are
gases. C5 to C15 are liquids, and C20 upwards are
number of carbon atoms
solids.
Viscosity of the liquid alkanes depend on their Mr. As Mr increases, the liquids become more and more
viscous, that is, their ability to flow decreases. Once more, this is a result of the increase in the strength of
Van der Waals forces. Attractions between molecules increase and this restricts the ability of the mole-
cules to move independently.
 610

Density of the alkanes

The alkanes have low densities compared to other substances of comparable Mr. This can be explained in
terms of the intermolecular forces present. The weak Van der Waals forces present between the molecules
cannot hold the molecules close together. Since the molecules are spaced out, the alkane has a large
volume compared to its mass. The formulae for density, D= m/V, tells us that D varies inversely as V. The
greater the volume, the smaller the density.The density of alkanes is lower than that of water, so the
alkanes tend to float on water.
The density of the alkanes increases gradually down the homologous series. Going down the group, both
mass and volume increases. Density is directly proportional to mass, that is, as mass increases, so does
density. On the other hand, as volume of the molecules increases, density is expected to decrease. Mass
and volume therefore have an opposite effect on density. However, the increase in mass down the
homologous series of alkanes is faster than the increase in volume. This explains why density increases
gradually

Table 10.7 below summarizes some key information about the first ten normal chain alkanes.

Number of C Name state at 298K Bpt/K Mpt/K density/gcm -3

atoms and formula

1 methane CH4 g 112 90 0.424

2 ethane C2H6 g 184 101 0.546

3 propane C3H8 g 231 85 0.501

4 butane C4C10 g 273 138 0.579

5 pentane l 309 143 0.626

6 hexane l 342 178 0.657

7 heptane l 371 182 0.684

8 octane l 399 216 0.703

9 nonane l 424 219 0.718

10 decane l 447 243 0.730

11 undecane l 469 247 0.740

12 dodecane l 489 263 0.749

15 pentadecane l 544 283 0.769

20 eicosane s 617 310 0.785

Table 10.7 The first ten alkanes

 611

Note that the change in physical properties down the group is not sharp. This steady gradation is due to
the steady increase in Mr down the group. Each alkane differs from the next by a single CH₂ group, that is,
Mr increases uniformly by 14 units from one homologue(member) to the next.

Branched chain alkanes

Branched chain alkanes do not form a homologous series. There is no clear trend in physical properties of
these alkanes. The effect of branching is to increase volume and reduce the total contact area between
molecules. An increase in volume results in a decreasein density. A decrease in contact area reduces the
extent of Van der Waals forces between molecules and hence lowers boiling points, that is ,volatility
increases, for example, pentane boils at 309 K, whilst its isomer,2,2- dimethylpropane boils at 283 K. The
diagrams below illustrate how spherical geometry of branched chain alkanes reduces contact area
between two molecules, compared with the normal chain (unbranched) isomer.

contact area contact area

2,2-dimethylpropane n-pentane

4.1.4 Reactions of the alkanes

The alkanes are generally inert and this can be explained in the following ways.
 They do not have a reactive centre (functional group)
 They are non-polar, and so cannot attract polar or charged reactants such as nucleophiles.
 Absence of a relatively weak bond that can break during a chemical reaction. An alkane contains
relatively strong C-C and C-H bonds. Being strong, these bonds do not form weak centres in the
molecule. This is different from other compounds which bear functional groups. In such com-
pounds, there is a relatively weak bond at the functional group which becomes a weak centre of
the molecule.
The alkanes do undergo a few types of reactions, of which oxidation (combustion) and free radical subs-
titution are the most common.

Combustion of alkanes
The alkanes can react with oxygen. The products, assuming complete combustion, are carbon dioxide and
water vapour. This reaction is not spontaneous. A mixture of an alkane and oxygen will not react until
sufficient energy is supplied to overcome the activation energy of the reaction, which is quite high. The
alkanes are thus kinetically stable in the presence of oxygen because there is a high energy barrier
(activation energy) to oxidation. However, from an energetic point of view, the alkanes are unstable with
respect to their combustion products, that is, the products of complete combustion are more stable than
the alkane. Combustion of alkanes is therefore exothermic and energetically feasible.
Combustion of an alkane is a gas phase reaction and it involves a complex free radical mechanism. Solid
and liquid alkanes burn more slowly than gaseous alkanes. This is because they must evaporate first
 612

before they can burn. This can be an advantage, for example, where gradual burning is required as in a
candle. The candle wax melts and evaporates gradually.
The exothermic nature of the combustion reaction of the alkanes makes them useful as fuels in the home,
in the industry and in the internal combustion engine.
Recall that the complete combustion of an alkane can be represented by the general equation

𝐲 𝐲
CxHy + ( x + ) O2  xCO2 + H2O
𝟒 𝟐

Q
10 cm3 of an alkane were completely burnt in 100 cm3 of oxygen. The residual gas
obtained at the end of the reaction occupied a volume of 70 cm3. When the residual
gas was passed through KOH(aq), the volume dropped to 20 cm3. Calculate the
percentage of carbon in the alkane.

y y Residual vol = Vco2 + Vexcess O2

ACxHy + (x + ) O2  xCO2 +
4 2
H2O
Vco2 = 70 - 20 = 50 cm3, since
y y
1 : (x + ) : x : CO2 was absorbed in KOH.
4 2
Excess O2 = 20 cm3 (not absorbed
y 10y
10 : 10 (x + ) : 10 x : in KOH).
4 2
O2 that reacted = 100 - 20 = 80
10x = 50, x = 5
y
10(x + ) = 80 , but x = 5
4

y
10(5 + ) = 80, so y = 12
4

12 x 5
The alkane is C5H12. % of C is x 100 = 83.3% (72 is Mr)
72

Combustion of alkanes in the internal combustion engine

The internal combustionengine converts chemical energy to heat and kinetic energy. The chemical energy
is stored in the bonds of the fuel, which is usually an alkane. In the petrol engine, the fuel is introduced
into the engine cylinders in the form of a vapour. A spark provided by the spark plug, which obtains
electrical energy from the battery, provides the activation energy required to start the reaction. The
combustion reaction is explosive and it results in a sudden increase in the pressure inside the cylinder. It
is this pressure which causes the pistons of the cylinders to move. The movement is then conveyed to
other parts of the car. The fuel used (petrol) is gasoline vapour, which contains mainly C5 to C10 alkanes,
of which the C8 alkane is a major constituent.
The internal combustion engine makes use of normal chain alkanes because they are cheaper than
branched chain alkanes. The major disadvantage of straight chain alkanes is that they burn too rapidly
and cause engine knocking. On the other hand, branched chain alkanes burn more smoothly but their
production (through cracking) is an expensive process. As a compromise, normal chain fuels are mixed
with small quantities of highly branched alkanes to smoothen out the combustion process.
 613

Pollution problems associated with the internal combustion engine

The following pollutants are associated with the combustion of fuel in the internal combustion engine.

NOx CO SO2 CO2 Soot (unburnt carbon) unburnt hydrocarbons

Carbon monoxide, soot and unburnt hydrocarbons are associated with incomplete combustion in the
engine. The origin and harmful effects of NOx and SO2 have already been discussed in Inorganic
Chemistry(section 9.5).

 Carbon dioxide is a well known green house gas. It traps heat reflected from the earth’s surface,
preventing it from escaping into space. This leads to global warming. Some effects of global
warming include
 increased incidence of disease since micro-organisms that cause disease multiply rapidly
in hot conditions
 increased incidence of drought as water bodies that supply the atmosphere with water
vapour dry out
 melting of polar ice, which may lead to flooding

Carbon dioxide is a natural component of the atmosphere and would not be considered a
pollutant if it remained at its natural level of about 0.03%. This gas is very important as it is the
original raw material from which food is synthesized by plants through photosynthesis.

 Unburnt hydrocarbons such as methane also lead to global warming.

 Carbon monoxide is a well known respiratory poison. It has a greater affinity for haemoglobin,
compared with oxygen. It therefore binds preferably to haemoglobin, thus inhibiting the uptake of
oxygen. Carbon monoxide poisoning may therefore lead to death by lack of oxygen. Formation of
carbon monoxide occurs in the internal combustion engine as a result of incomplete combustion.
This occurs because the engine cylinders are confined and only limited amounts of oxygen are
available.

 Soot contains very tiny particles of carbon and appears as black fumes through the exhaust pipe.
It is a potential respiratory irritant and defaces buildings and vegetation.

Q
Explain the role of NO in the formation of acid rain

ANO is unstable and combines with atmospheric oxygen to form nitrogen dioxide
NO2(g) + ½ O2 (g)  NO2 (g)

NO2 then catalyses the conversion of SO2 to SO3. This is an example of homogeneous catalysis
involving gases.

NO2 (g) + SO2 (g)  NO (g) + SO3 (g)

The catalyst (NO2) is recovered when NO combines with O2.

 614

SO3dissolves readily in water to form a solution of sulphuric acid (acid rain).

SO3 (g) + H2O (g)  H2SO4 (aq)

The amounts of pollutants emitted as car exhaust fumes can be reduced by fitting a catalytic convertor to
the exhaust pipe. The convertor contains a mesh of platinum and rhodium wires which catalyzes the
conversion of the pollutants to less harmful products, as outlined in the following table.

Pollutant How it is removed from car exhaust fumes

by a catalytic convertor

Carbon monoxide Combines with oxygen to form CO2

CO(g) + 1/2O2(g) CO2(g)

Unburnt hydrocarbons Are oxidized to carbon dioxide and water

such as methane
CH4(g) + O2(g) CO2(g) + 2H2O(l)

Nitrogen dioxide and React with carbon monoxide to form nitrogen and
nitrogen monoxide carbon dioxide. This reaction removes two pollutant
gases at once.

NO2(g) + 2CO(g) 2N2(g) + 2CO2(g)

Q
What is the major component in car exhaust fumes?

A. NO2 B. NO C. CO2 D. N2

D. The air that enters the engine is mainly N2. Because of its inertness, only a small amount
Areacts to form NOx. The rest of the gas passes out as the major component of car exhaust fumes.

 The combustion of leaded petrol has also been associated with the production of lead compounds,
which are serious pollutants. Leaded petrol contains tetraethyl lead (II), which acts as an anti-
knocking agent.

CH2CH3 Knocking happens when combustion of fuel is rapid and occurs in bursts.
This results in unpredictable performance of the engine and wearing of
CH3CH2 Pb CH2CH3 the piston rings. When heated, tetraethyl lead decomposes, producing
ethyl free radicals, (CH3CH2.). These free radicals regulate combustion of
CH2CH3 the fuel by combining with some free radicals that are produced when
the fuel burns. This reduces knocking by ensuring smooth combustion of
tetraethyl lead (IV) - Pb(C2H5)4
the fuel.
 615

 When leaded fuel burns, lead and lead oxide can accumulate in the engine, reducing its
performance. Moreover, a catalytic convertor cannot be used if the engine runs on leaded
petrol. This is because the decomposition of tetraethyl lead (II) results in the deposition of
lead oxide on the catalyst, leading to poisoning of the catalyst. Another compound, 1,2-
dibromoethane (CH2BrCH2Br ) can be added to leaded fuel to prevent the accumulation of lead
in the engine. This results in the formation of the volatile lead (II) bromide, which easily
escapes into theatmosphere. Unfortunately, this introduces a toxic pollutant into the
atmosphere. PbBr2 canbe inhaled and be absorbed into the blood. Pb2+ ions act as a nerve
poison (neurotoxin) which can lead to brain damage. For this reason, most countries no longer
use leaded petrol.

Free radical substitution reactions in alkanes

Alkanes undergo halogenation in a reaction known as free radical substitution. This reaction introduces a
polar bond (functional group) in the alkane molecule, thus making it more reactive.
An example of a free radical substitution reaction is the conversion of methane to chloromethane.

UV
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)

The reaction is initiated by the generation of chlorine free radicals when the Cl-Cl bond undergoes homo-
lysis. UV supplies energy for this process.
When free radical substitution involves longer chain alkanes, hydrogen atoms are mainly replaced from
the middle of the carbon chain. This is because the organic free radical produced in this way is more stable
than the free radical that would be produced by substitution of a terminal hydrogen atom. This is
illustrated for propane. In this case, the major product of free radical substitution with chlorine is
2-chloropropane.

H H H H H H
H C C C H H C C C

H H H H H
more stable radical less stable radical

Cl2 Cl2

H H H H H H
H C C C H H C C C Cl
H Cl H H H H
2-chloropropane (major product) 1- chloropropane (minor product)
 616

10.4.2 Alkenes

Normal chain alkenes are unsaturated hydrocarbons that have the general formula C nH2n. The normal
chain alkenes form a homologous series with the same trends in melting points, boiling points, melting
points and densities as shown by the alkanes. However, alkenes are less dense and have smaller melting
points than alkanes of comparable Mr. This is because the C to C double bond forms a point of
irregularity in the molecule (a ‘kink’) which prevents the molecules from packing efficiently. As a result,
the molecules occupy a relatively large volume, giving a small density. Also, the contact area between two
molecules is reduced, and so Van der Waals forces act over a smaller area. The forces of attraction be-
tween the molecules are therefore weaker. This explains why alkenes have lower melting and boiling
points than alkanes of similar Mr.

4.2.1 Nomenclature of alkenes

The name of an alkene ends in -ene. The same rules used for naming alkanes apply here.
Positionalisomerism is possible in which alkenes with the same molecular formula differ in the position of
the double bond. The position of the double bond is identified by a locator number. This number locates
where the double bond begins. The carbon chain is numbered from the end which is closest to the double
bond. If the name of an alkene is written without a locator number, it is assumed that the double bond is
at the beginning of the chain (carbon 1). The compound labeled I in the diagrams below can thus be
named as pent-1-ene or just pentene.

I II III

4 32 1 1 3 4
2 5
5

pentene pent-2-ene pent-2-ene

IV

2-methylbut-2-ene

 All of the structures shown above share the molecular formula C5H10.
 Structures I and II are positional isomers.
 Structures II and III are not isomers, they represent the same compound. Note how the chains
have been numbered.
 617

 Structure IV is a structural isomer (skeletal or chain) to structure I or II. Structural isomers differ
in the number and length of chains. In structures I and II there is only one carbon chain. In
structure IV there is a main chain with four carbon atoms, and a methyl branch at carbon 2.
 Cis-trans (geometric) isomerism is also possible in alkenes as a result of restriction to rotation
about the rigid C to C double bond. Structure II (= III) exhibits cis-trans isomerism because each
carbon atom of the double bond is bonded to two different groups. This is illustrated below.

Carbon 3 is bonded to two Carbon 2 is bonded to two

different groups, a H atom different groups, a H atom
and an ethyl group. and a methyl group.

H H H methyl group
5 4 3 2 1
H C C C C C H
ethyl group H H H H H

H group H group

5 4 1
CH3CH2 1
CH3 H CH3
2 2
3C C 3
C C
5 4
H H CH3CH2 H
cis pent-2-ene trans pent-2-ene

Here are more examples illustrating the naming of alkenes. Which of the alkenes exhibit cis-trans
isomerism?

4-methylpent-1-ene cyclobutene
2,3-dimethylbut-2-ene

cyclohexene 4-propylcyclohexene 2-methylprop-1-ene

 618

4.2.2 Bonding in alkenes

The bonding at the C to C double bond gives rise to a trigonal planar geometry with a bond angle of 1200.
Consider the structure of propene

H H 0
H x x = 120
C C
H x 0
H y = 109
yC
H

Each carbon atom of the double bond is sp2 hybridized. This implies that of the three 2p orbitals to be
used for bonding, only two are used to make sigma bonds. Each carbon atom has three hybrid orbitals
made by mixing one 2s orbital and two 2p orbitals. There are therefore three sigma bonds around each
carbon atom of the double bond. The fourth electron from each carbon atom of the double bond is unhy-
bridized and occupies a pz orbital. The pz orbital of one carbon atom overlaps sideways with the p z orbital
of the other carbon atom, forming a π bond.

H H represents one  bond

0 C C
120
CH3 H represents a  bond

The carbon to carbon double bond therefore has two types of electron density
 the two electrons in the sigma bond are closer to the nuclei of both carbon atoms. The electrons
therefore experience a strong attraction from the nuclei. The sigma bond is therefore relatively
strong and does not break easily during chemical reactions.
 the two electrons in the π bond are further from the nuclei of both carbon atoms. This is because
the position of the π bond places it a relatively large distance from the nuclei of both atoms of the
bond. As a result, electrons that occupy the π bond are relatively weakly attracted to the nuclei of
both atoms of the bond. The π bond is therefore more diffuse (spread out) and weaker than the
sigma bond. Being diffuse, the π bond is an electron rich centre which easily attracts electrophiles
in chemical reactions. Being weak, the π bond easily breaks during chemical reactions, for
example, during electrophilic addition.

4.2.3 Sources of alkenes

Alkenes, like other hydrocarbons, are a component of petroleum. They are separated by fractional
distillation.
Smaller alkenes, which are very important as precursors in the petrochemical industry, are also obtained
from the cracking of alkanes. These alkenes have a wide range of uses, for example, the synthesis of drugs,
plastics, solvents and fire retardants.
On a small scale, for example in the lab, alkenes can be obtained from

 elimination of HX from halogenoalkanes (X = Cl, Br, I), using hot ethanolic KOH, for example
 619

CH3CH2Cl KOH
CH2 = CH2 + H2O + KCl
ethanol/heat

+ H2O + Br-

 elimination of water from alcohols (dehydration). This happens when the alcohol in its vapour
state is passed over heated aluminium oxide. Alternatively, hot H 3PO4 over silica can be used, for
example

Al2O 3
3000C

menthol

Explain why the reaction above produces two products.

Q

4.2.4 Reactions of alkenes

Alkenes contain an electron rich C to C double bond, which makes them more reactive than alkanes. The
double bond attracts electron deficient particles known as electrophiles. Reactions at the double bond are
also possible since the π bond of the double bond is relatively weak and can easily break during chemical
reactions. Alkenes undergo some important types of reactions, including electrophilic addition, hydra-
tion, oxidation and hydrogenation.

Electrophilic addition
This mechanism has already been discussed in detail. Test your memory by answering the following
question. Check your solutions with the ones given.

(a) What are the reagents and conditions required for the conversions (i), (ii) and (iii)
Q In the following scheme?

(b) What reagents and conditions are requiredto reverse reaction (iii)? What type of
reaction takes place?
 620

(i)

(ii)

(iii)

(a)(i) HBr in a suitable organic solvent (electrophilic addition)

A
(ii) Liquid bromine (electrophilic addition)

(iii) H3PO4 over SiO2, 3000C (hydration-addition of water)

(b) Al2O3 / 3000C, dehydration - elimination of water

Hydrogenation of alkenes
In this reaction, a molecule of hydrogen is added across the double bond, for examples

H2(g)
CH2 = CH2 CH3CH3
Ni , 1500
From an energetic point of view, the reaction is feasible (exothermic) because it replaces a weaker π bond
with two stronger C-H bonds. However, the reaction has very high activation energy and therefore re-
quires a catalyst. Ni is used and it participates in a typical case of heterogeneous catalysis. It adsorbs hy-
drogen and alkene molecules, bringing them closer together and weakening the H-H bond.
Hydrogenation of long chain liquid alkenes is important in the manufacture of fatty solids such as marga-
rine. These alkenes have low boiling points and so are liquid at room temperature. This is because pres-
ence of double bonds prevents the alkene molecules from packing efficiently. The contact area between
any two molecules is small and this reduces the strength of Van der Waals forces between molecules.
When the alkene is hydrogenated, all bonds are saturated and the alkane chains so formed can pack effi-
ciently. Van der Waals forces are therefore extensive, and this causes the alkane to become less volatile,
that is, it solidifies at room temperature.
The alkenes that are hydrogenated during the manufacture of margarine are in fact unsaturated fatty ac-
ids. These are carboxylic acids which contain long unsaturated hydrocarbon tails, for example oleic acid.
The following structure shows that presence of a double bond introduces a ‘kink’ in the alkene molecule,
which causes the chain to change direction. In turn, this affects the packing of molecules, as already ex-
plained.
 621

kink
H

oleic acid - an example of a monounsaturated

fatty acid (a liquid). The change
0
in bond
0
angle at the
C to C double bond (from 109 to 120 ) causes the
chain to change direction. Oleic acid is naturally
occuring, for example, it is abundant in olive oil.

H2(g) /Ni(s)
0
150

CH3(CH2)16COOH -solid fat

Upon hydrogenation, the molecules 0

are
saturated. All bond angles are 109 and
the 'kink' in the structure is removed.

Polymerization of alkenes
Alkenes undergo addition polymerization to form polymers which are generally known as plastics
(polyalkenes). This reaction is a complex free radical reaction which results in the formation of long
saturated hydrocarbon chains. The addition polymers formed in this reaction are alkanes, even though
they are referred to as polyalkenes. Well known examples of polyalkenes include poly(ethene),polyvinyl-
chloride (PVC = poly(chloroethene)),polystyrene, also known as poly(phenylethene) and polypropene.
You should recall that there are two major types of polymers, condensation and addition polymers.
Polyalkenes are addition polymers, which means that
 they are formed from unsaturated monomers
 the polymer is the only product of the polymerization reaction
 The Mr of the polymer is equal to the sum of the Mr values of all the monomers present in the
polymer.

Most polyalkenes are homopolymers. This means that they are made up from identical monomers. Com-
pare with heteropolymers(copolymers) in which the monomers are different.
The polymers given in Table 10.8are all synthetic. A few polyalkenes are naturally occurring. A well
known example is rubber.
 622

Polymer monomer Structure of polymer Major uses

Poly(ethene) ethene  Plastic packing

H H H H H H bags
C C C C C C  Collapsible
squizzy bottles
H H H H H H  Water buckets
 Crates for
repeat unit packing
bottled drinks

polystyrene Styrene  Expanded

(phenylethene) H H H H H H polystyrene is
C C C C C C used to make
packing
CH CH2 H H H material for
fragile objects
 Toys
repeat unit  Ball points

polypropene Propene H H H H H H  Making rope

C C C C C C
CH3 H CH3 H
H CH H CH H CH
C C1 2C C 3 3 3

H H H H repeat unit

polyacrylonitrile Acrylonitrile  Wool

(propenenitrile) H CN H CN H substitutes in
C C C C C the textile
C C CN industry
H
H H H H H
H H

PVC Chloroethene  Water gutters

H Cl
C C Cl  Insulation
H
C C tubing for
H H electrical
H H cables

4.2.5 Polyalkenes
 623

Alkenes undergo polymerization to produce polymers known as polyalkenes. This involves opening up of
the double bond and bond formation between carbon atoms of the double bond. Consider the formation
of polypropene from its monomer, propene

CH3 CH CH2

Written in this way, it might not be clear how two molecules of propene link to form the polymer. Two
molecules of polypropene can be drawn, with their bonds opened up as shown below. In that way, it
becomes apparent how the monomers link up at the C to C double bond.

CH3 H CH3 H CH3 H CH3 H

C C C C C C C C

H H H H H H H H n
repeat unit
new bond forms here

Factors that affect the properties of a polymer

The following are properties of polymers which may determine their uses.
 Rigidity(hardness)
 Strength
 Melting point and heat resistance
 Elasticity
 Brittleness
 Biodegradability
These properties are determined by the following factors
 Chain length
 Branching
 Intermolecular forces
 Cross linkages

Effect of chain length

Polymers are solid at room temperature. This is true even in those cases in which the polymer contains
non- polar groups, that is, the intermolecular forces present between strands are Van der Waals forces, as
in many addition polymers. Even though Van der Waals forces are regarded as very weak forces of attrac-
tion, their strength increases with increasing number of electrons in a molecule(increasing Mr). The Van
der Waals forces operating in polymers, even those which are non-polar, are strong enough to cause the
polymers to have relatively high melting points, causing them to be solid at room temperature. The
strength of the Van der Waals forces becomes even greater when the length of the chains becomes very
large. Such polymers tend to be harder and more heat resistant. Polymers containing short chains have
weaker forces of attraction between molecules (chains) and thus tend to have low viscosity when molten,
allowing them to be moulded easily into different shapes.

Intermolecular forces
 624

Stiffness (rigidity) and strength of the polymer is mainly determined by the type and strength of intermo-
lecular forces acting between separate chains. The stronger the forces, the harder the polymer and the
higher its tensile strength.The effect of intermolecular forces on strength and rigidity is remarkably
illustrated by poly (ethene) and PVC.
In polyethene, the forces between separate strands are weak Van der Waals forces. In PVC, chains are
held together by attractive forces between chlorine atoms on one chain and hydrogen atoms on an adja-
cent chain. These forces are relatively strong dipole forces which hold separate chains tightly together.

   
Cl H Cl H Cl H Cl H
C C C C C C C C
H H H H H H H
 H   
Relatively strong permanent
dipole Relatively
- dipolestrong permanent dipole-dipole
attractions
betweenattractions between
chains chains
give confer
the strength,
Cl Cl  
H Cl
 rigidity and heat resistance
polymer strength, rigidity and to the polymer.
H H Cl H resistance to heat .
C C C C C C C C
H H H H H H H H

The major disadvantage of PVC is that it is brittle, that is, it shatters when relatively strong compressive
forces act upon it. The same factor which gives PVC its strength and rigidity is responsible for its
brittleness. This factor is the presence of permanent dipole- dipole forces between chains. When subjected
to pressure, the chains may slide slightly against each other, resulting in dipoles of like charge being
aligned. This cause a sudden repulsion between the chains, causing the material to shatter.

Effect of branching
Branching affects the properties of a polymer in a number of ways. The effect exerted by the branches on
the physical properties of the polymer depends on
 whether the branches contain polar groups or not.
 frequency of branches along the main chain.
 how the branches are arranged along the main carbon chain.
 how bulky the branches are

Does the branch contain a polar group or not?

If the branches contain polar groups, then permanent dipole-dipole attractions are possible between
different chains. This will have the effect of increasing strength, rigidity and melting points. However,
presence of dipole-dipole forces may also confer brittleness to the polymer as discussed for PVC above.

How frequently do the branches occur along the main carbon chain?
The effect of extend of branching is illustrated remarkably by high density and low density poly (ethene).
LDPE is made by using an initiator molecule at high temperature and pressure. This method exerts very
little control on the reaction, and it results in branches being formed frequently along the main chains.
The resulting chains are therefore not able to pack well because of the steric hindrance imposed by the
branches. This has two main effects:
 625

 Strength is reduced. This is because the total contact area between adjacent chains is reduced.
This reduces the area over which Van der Waals forces act, that is, the extent of Van der Waals
forces is reduced.
 Density is reduced. This is because the chains pack loosely, so that the volume of the polymer is
much higher compared with its mass. This is why the resulting polymer is referred to as Low Den-
sity Poly (ethene) (LDPE).

High Density Poly (ethene) (HDPE) is made by the Ziegler- Natta process, named after Ziegler and Natta,
the scientists who developed the method. The process is carried out at low temperature and pressure, us-
ing a Ziegler-Natta catalyst. The Ziegler-Natta process exerts greater control on the outcome of the
reaction, so branching is very little, or does not occur at all. The chains formed can therefore pack more
closely. As a result, Van der Waals forces act on a large area between any two strands. This confers
strength to the polymer. The polymer also has a relatively high density since packing of chains is tight.

The following table summarizes the effect of method of production on the properties and applications of
poly(ethene).

Polymer Method of preparation Properties of Use of polymer

polymer

LDPE High temperature (1700), high Polymer chains are Plastic packing bags and
pressure of about 1 200 atm. highly branched. This film
An initiator molecule such as benzoyl prevents them from
peroxide is used. packing well. As a result
the polymer is relatively
soft and has a low
density.

HDPE Low temperature (700) and low Polymer chains show Used to make rigid
pressure (2atm). A Ziegler - Natta little or no branching. objects such water
catalyst is used. The chains therefore buckets and packing
pack more closely, crates.
conferring rigidity and
high density to the
polymer.

How are the branches arranged along the main carbon chain?
If arrangement of branches along the main chain is regular, then the chains can pack closely. This results
in a relatively rigid, strong and high density polymer. There are three possible ways in which branches can
arrange along the carbon chain.

 Isotactic, in which groups are arranged regularly on one side of the chain.
 Syndiotactic, in which groups alternate regularly from one side of the chain to the other.
 Atactic, in which groups are randomly arranged on either side of the chain.
 626

These types of arrangement are illustrated below for the polymer polystyrene(poly (phenylethene)). The
monomer of this polymer is styrene(phenylethene), shown below.

CH CH2

styrene

Two monomers are shown below to illustrate how they would link during polymerization.
H H H H
C C C C
H H

The resulting polymer can have any of the following structures, depending on the method of production.

Isotactic

H H H H H H H H H

C C C C C C C C C

H H H H H

Syndiotactic

H H H H H H H

C C C C C C C C C

H H H H H H H

Atactic

H H H H H H H H H

C C C C C C C C C C C C

H H H H H H H H H

The isotactic and syndiotactic conformations are stereoregular and they are made by closely controlling
conditions during the production stage. Finer control can be achieved by the use of catalysts. If the
production process is not controlled, the irregular atactic conformation is formed. The manner in which
 627

branches are arranged along the main chain affects tensile strength and rigidity by affecting the way in
which the chains can pack.
In the stereoregular forms of polystyrene, especially the isotactic form, chains can pack closely, resulting
in a relatively strong and rigid structure.
Rigidity is also caused by the regularly repeated phenyl branches. These groups, being relatively bulky,
prevent chains from sliding against each other. If chains could easily move, then the polymer would be
soft and flexible.
Ball points made of polystyrene, for example, the bic brand, can be recognized by their tendency to crack
or shatter. This is because the rigidity of polystyrene inevitably causes it to be brittle.
Polystyrene is used to make expanded polystyrene, toys and ball point pens. Expanded polystyrene is
made by mixing beads of the polymer with hexane, heating the mixture and then allowing it to solidify.
Expanded polystyrene is used to protect breakable goods in transit.

Effect of cross- linkages

Cross linkages help to confer rigidity to a polymer by restricting movement of chains when forces are
exerted.
The cross- linkages may also help chains to align more regularly, increasing the extent of Van der Waals
forces acting between the chains. This can increase melting point and heat resistance of the polymer. The
effect of cross- linkages is well illustrated by vulcanizedrubber.
Natural rubber, an addition polymer, comes from the rubber tree, Heva brasiliensis, native to Brazil.
When the bark of the tree is cut, a milky liquid, known as latex, oozes out. Latex contains small globules of
rubber which can be separated and put to use. However, such rubber is soft and becomes runny in hot
weather. In 1839, Charles Goodyear discovered vulcanization, a process in which molten rubber is heated
with sulphur. When the rubber solidifies, sulphur bridges form between polymeric strands. Such rubber,
known as vulcanized rubber, is tougher and more heat resistant. The invention of vulcanized rubber
meant that rubber could now be used in a larger number of applications, including in the manufacture of
shoes and car tyres. The diagram below shows a section of vulcanized rubber.

CH3
CH C CH CH2
S
S CH3
CH C CH CH2
Vulcanised rubber.

Plastics
The term plastic can be used in a loose sense to imply addition polymers which are relatively flexible and
have relatively low melting points. This would include polymers such as LDPE, HDPE, PVC,
poly (propene), e.t.c.
Plastics find a wide range of uses because of certain advantages associated with them.

 They are light, making them suitable for making packing materials.
 They are non- toxic.
 They are non-biodegradable. This makes them durable.
 They are good insulators.
 628

 They are versatile- their properties can be modified, making it possible to use them in a wide
range of applications.

However, plastics have certain draw backs, including

 They cannot conduct electricity

 They are weak and so are not suitable for most construction work
 Being non-biodegradable, they tend to accumulate in the environment, leading to plastic
pollution.

Thermoplastic (thermosoftening) and thermosetting plastics

Plastics with a small number of covalent cross-linkages tend to be soft and they are easily deformed by
heat. This is because heat energy creates vibrations within the polymer which pushes chains apart. Such a
plastic is described as a thermoplastic. It can easily be moulded into shapes during the manufacture of
objects. However, the products have little resistance to heat energy. They are easily softened and
deformed by heat.
Cross- linkages can be introduced in the polymer, thus firmly holding chains in place. Such a polymer is
rigid, inelastic and more resistant to heat energy. These polymers are described as thermosetting. The
major disadvantage of such polymers is that they tend to be brittle.

The problem of plastic disposal

The major disadvantage associated with plastics is the difficulty of disposing them.
Their non - biodegradability, though an advantage in the sense that it increases their durability, is also a
disadvantage because the plastics are not easily decomposed by micro-organisms. As a result, they tend to
accumulate in the environment. In fact, plastic pollution has become one of the worst forms of modern
pollution.

Possible methods of plastic disposal

Combustion
Plastics can be used as a source of fuel. However, this is not a desirable method of plastic disposal because
it does not solve the problem of pollution. It simply changes one form of pollution into another.
Combustion of plastics cannot be complete because of the very large number of covalent bonds present.
The more bonds a fuel has, the greater the demand for oxygen during combustion, and the less complete
the combustion process.
Pollutants from the combustion of plastics include CO, soot, HCl, SO₂, HCN and dioxins. Sulphur dioxide
production is associated with the combustion of rubber products such as tyres. These products contain
sulphur bridges between polymer strands.
Combustion of chlorine containing products such as PVC results in the production of HCl, a poisonous
gas. In controlled incinerators, the HCl and other acidic gases produced can be absorbed in alkalis.
(An incinerator is a specially designed furnace for the combustion of litter). Combustion of poly
(acrylonitrile) produces HCN, which is a serious nerve poison.
Dioxins are toxic substances produced during the incineration of domestic litter. The presence of PVC in
such litter enhances the production of dioxins. An example of a dioxin is 2, 3, 7, 8-TCDD shown.
 629

Cl O Cl
Cl O Cl
2,3,7,8- TCDD

Levels of dioxin produced during the incineration process can be reduced by controlling the combustion
process. Optimum dioxin production is at its maximum at around 550⁰C and in the presence of a limited
amount of oxygen, but at around 850⁰C and in the presence of a large supply of oxygen, they are de-
stroyed.

Pyrolysis
This is the thermal decomposition of litter in the absence of air.
This is a better method of plastic disposal because the products of the process, for example, ethene, are
useful petrochemicals. The other advantage is that pollution by oxides such as SO₂ is reduced.

Recycling
This is potentially one of the best methods of reducing plastic pollution. It is also economically sensible as
it reduces the exploitation of resources such as petroleum which are used to produce plastics. The current
challenge associated with recycling of plastic is that it is difficult to collect different types of waste plastics
separately. Different types of plastics have widely differing properties and so must be collected separately.
When a mixture of different types of plastics is melted and used to produce a new product, the product
would be much weaker than the plastics which were originally in the mixture.

Use of biodegradable and photodegradable plastics

A biodegradable plastic is one which can be broken down by micro-organisms, particularly bacteria
and fungi.
Biopol®, produced by ICI, is a naturally occurring polymer (biopolymer). It is made by certain types of
bacteria using glucose as a substrate. The bacteria can be cultured under controlled conditions to produce
large amounts of the polymer. This polymer, whose systematic name is poly (3-hydroxybutanoic acid), is
currently being used for surgical stitches which are slowly dissolved by enzymatic action in the body.
When the polymer is discarded in the environment it is degraded by bacteria and fungi, which can use it
as a food source.
A photodegradable plastic is one which is broken down by prolonged exposure to UV radiation.
A photodegradable plastichas been developed, which can be used to make products such as disposable
coffee cups. When plastic litter made up of the polymer is left exposed to the sun for some time, it
crumbles into tiny particles. Use of such plastics is currently limited because the products are more
expensive than conventional plastics.

Q the displayed formula of a monomer of Biopol®. What type of polymer is

Draw
Biopol®?
 630

A H OH H O
H C C C C
H H H OH

Biopol® is a condensation polymer.

Polytetrafuoroethene (PTFE) is one of the most slippery substances known.

Q
Draw

(a) the structure of a monomer of this polymer

(b) a short section of the polymer, showing one repeat unit.

(a) A (b)

F F F F F F F
C C C C C C C
F F F F F F F
tetrafluoroethene n
poly(tetrafluoroethene)

10.4.3 Arenes

These compounds contain the benzene ring. The simplest arene is benzene itself. It is a colourless
flammable liquid with a sweet (aromatic) smell. Like other hydrocarbons, its major source is petroleum.
On its own, benzene is not a good fuel because, having a high C to H ratio (compared with alkanes), it
undergoes incomplete combustion, releasing large quantities of soot (unburnt carbon).

A sweet smelling liquid that burns with a very sooty flame is likely to be benzene or a compound that
contains the benzene ring.

Being non-polar, benzene is insoluble in water but dissolves well in organic solvents.

Benzene is a very important hydrocarbon. Its uses include

 As a precursor for the synthesis of many substances, including drugs, explosives, dyes and
plastics.
 631

 As a fuel additive. Its presence in fuel helps to smoothen out combustion of fuel, and thus reduce
knocking. However, the use of benzene as a fuel additive is limited by the fact that it is thought to
be carcinogenic (cancer inducing).
 As an industrial solvent

Recall the following facts about benzene, C6H6

 Each carbon is sp2 hybridized, with a bond angle of 1200. The benzene ring is therefore planar
(flat).
 Each carbon atom forms three sigma bonds, two to neighbouring carbon atoms, and one to a
hydrogen atom. A hexagon shows the C to C and C to H sigma skeleton.
 Each carbon atom uses a pz orbital for π bond formation. Six π orbitals therefore overlap, forming
one delocalized π bond. The six delocalized electrons are represented by a circle drawn inside the
hexagon (Fig 10.10).
 Benzene is sometimes represented by a Kekulé structure, in which double bonds and single bonds
alternate. This structure is now known to be wrong for reasons that were discussed in Part 1 of
this section.

0
120

sigma six p z orbitals, one from each carbon

skeleton
atom, overlap sideways ( pi bonding).
Each orbital contributes one electron
to the pi bond, giving a total of six
delocalized pi electrons.

The six delocalized pi electrons are

represented by a circle inside the
sigma skeleton.
Fig 10.10The structure of benzene

 Since benzene is electron rich it reacts with electrophiles. However, since it has no pure double
bonds, benzene does not react easily. In other words, it is relatively inert, for example, unlike
alkenes, it does not decolourize KMnO4 and it has no direct reaction with bromine, except in the
presence of a suitable catalyst.
 632

 The inertness (relative stability) of benzene is a direct consequence of delocalization of π elec-

trons. The benzene ring usually reacts via electrophilic substitution as this does not disrupt the
delocalized π system of electrons. Addition reactions do not usually happen as these would
destroy the π system.
 Important reactions of the benzene ring have already been discussed.

i.Nitration by concentrated nitric acid using concentrated sulphuric acid as the catalyst
ii.Halogenation in the presence of a halogen carrier (catalyst)
iii.Friedel - Crafts alkylation and acylation using a halogen carrier

4.3.1 Alkylbenzenes
These are derivatives of benzene in which one or more hydrogen atoms on the benzene ring have been
replaced by an alkyl group, for example, methylbenzene (toluene).

methylbenzene (C6H5 CH3)

Methylbenzene is a colourless liquid with a sweet smell characteristic of paint thinners. It is found in
small amounts in crude oil. Since methylbenzene is a very important industrial compound, it is produced
in large quantities from the catalytic reforming of heptane. In this process, heptane vapour is passed
over a special catalyst which causes the heptane chain to close and form a ring. This is accompanied by
dehydrogenation.

catalyst catalyst
reforming reforming
continues
heptane
heptane
methylcyclohexane

hydrogen removed

Methylbenzene (toluene)

Toluene has several uses, including

 petrol additive
 manufacture of drugs and food additives
 633

4.3.2 Reactions of methylbenzene

Reactions of methylbenzene have already been discussed. Take particular note of the following
 The reactions can be divided into those of the benzene ring and those of the methyl side group.
 The benzene ring modifies properties of the methyl group. Usually, we would not expect alkanes
and alkyl groups to undergo oxidation. However, the benzene ring has an electron withdrawing
effect and this makes it easy for the methyl group to lose electrons, that is, to undergo oxidation.

The reactions of methylbenzene are summarized below

FGI 5
Required
 State the type of reaction taking place at each numbered stage.
 Supply reagents and conditions for steps marked (?)
 Draw the structures of the lettered compounds
 634

COO -Na + 2
13 H+
CH3 OH
A
14
conc HNO 3
conc HNO 3 cystallize, then dissolve
700C 15 in ether

B C 3 5
??

16 ??
OH 4
7
Na(s)
6
D ??
H2N 8 9

E
C7 H6O 2
F
10
?? 11

HCl(aq) G
H
12 C8H11 ON

Solutions
1. Oxidation of -CH3 side group to carboxylic acid.
Alkaline KMnO4 is used under reflux. Since an alkaline environment is used, the acid is neutralized to
its salt, sodium benzoate.

2. Acid catalyzed esterification. A is the ester

3.Reduction of carboxylic acid to primary alcohol.

LiAlH4(powerful reducing agent) is used in the presence of ether (solvent).

4.Oxidation of primary alcohol to aldehyde.

Suitable reagents: K2Cr2O7 in the presence of strong mineral acid, reaction is carried out in a
distillation apparatus.
OR PCC
 635

OR Chromic acid

5.Reduction of aldehyde to primary alcohol

Suitable reagents: H2/Ni catalyst-heat
OR NaBH4 in water or ethanol
OR LiAlH4 / ether

6. Oxidation of primary alcohol to carboxylic acid.

Suitable reagents: K2Cr2O7 in the presence of strong mineral acid, heat
KMnO4 (aq)/ H+, warm
Compound E is

7. Metal-acid reaction /redox. Primary alcohol group (acting as an acid), is converted to a salt (an
alkoxide). Compound D is
Na +

8. Oxidation of aldehyde to carboxylic acid.

Q. State four reagents that can be used to carry out this conversion, and the conditions under
which they are used.

9.Nucleophilic addition to the aldehyde group. HCN is used (not KCN or NaCN) in the presence of
trace NaCN or NaOH (catalyst)/ reflux.Compound F is a cyanohydrin (2-hydroxynitrile).

10. Reduction of nitrile group to amine, CN -> CH2NH2 using LiAlH4 (not NaBH4) in dry ether. G is

11.Hydrolysis of the nitrile group, CN -> COOH, using H2O in the presence of sulphuric acid (catalyst)/
reflux.
 636

12. Neutralization of the -NH2 group, -CH2NH2 + HCl -> CH2NH3+Cl-

The remaining problems are left as an exercise to the reader.

Free radical substitution in methylbenzene

This reaction has already been discussed on page 557. Check to see that you can write the equations for
the termination, propagation an termination steps in the mechanism.

10.5Halogen derivatives
These compounds contain a C-X bond, where X = F, Cl, Br or I. In halogenoarenes, the halogen atom is
directly bonded to the benzene ring. In halogenoalkanes the halogen atom is bonded to an alkyl (aliphatic
group). Acyl chlorides are halogenocompounds which contain the group -COCl.

Organic halogen compounds

halogenoarenes halogenoalkanes acychlorides

Cl O
example CH3CH2Br
Cl
chlorobenzene bromoethane ethanoylchloride

The reactions of halogenoalkanes have already been discussed. Check that you still remember about
 Alkaline hydrolysis, in which an alcohol is formed, for example, the reaction of bromoethane with
aqueous KOH under reflux. This is in fact nucleophilic substitution involving the nucleophile OH -
CH3CH2Br + KOH (aq)  CH3CH2OH + KBr
 Reaction with other nucleophilic reagents such as KCN and ammonia
 SN2 reactions in primary halogenoalkanes versus SN1 reactions in tertiary halogenoalkanes
 The relative ease with which halogenoalkanes undergo nucleophilic substitution. This depends on
the strength of the C-Hal bond. Iodoalkanes react the fastest since the C-I bond is the weakest.
This bond can easily break, allowing the incoming group (nucleophile) to form a new bond.
Chloroalkanes have a relatively strong C-Cl bond, so nucleophilic substitution reactions tend to be
very slow.
 Elimination of HX (X= Cl, Br, I) by refluxing with ethanolic KOH. This dehydrohalogenation
reaction results in the formation of an alkene.
 637

All of these reactions depend on the polarity of the C-Hal bond. The carbon atom of this bond has a
partial positive charge, and so can attract nucleophiles. In addition, the C-Hal bond is relatively weak,
so it can break during the reaction, allowing a new bond to be formed between a carbon atom and the
nucleophile.

10.5.1 Nomenclature
 If a halogen atom is present in a halogenoalkane or halogenoarene, it is referred to as fluoro,
bromo, chloro and iodo.
 Locator numbers are used as usual to specify position of the halogen atom.
 If there are different halogen atoms in the molecule, they are written in alphabetical order, for
example, bromo is mentioned before chloro.

Panel 10.2shows some halogenocompounds and their IUPAC names.

2-chloropropane dichloro(fluoro)methane
3-bromo-4-chloro-2-methylhexane

iodomethylbenzene 2-(iodomethyl)phenol chlorocyclopentane

4-chlorohex-2-ene

2-bromo-1,1,1,2-tetrafluoroethane bromobenzene

chlorocyclohexane
1-bromo-3-chloro-cyclohexane
 638

10.5.2 Preparation of halogenoalkanes

Here are some methods for the synthesis of halogenoalkanes
 Halogenation of an alkane by free radical substitution, for example

UV
CH4 + Cl2 CH3Cl + HCl

The major disadvantage of this method is that it results in the formation of a mixture of products,
including polysubstituted alkanes such as CHCl3.
 Electrophilic Additionof HX to the double bond in alkenes. The reaction occurs by
electrophilicaddition, for example

HBr(aq)

Note that in this case two isomers are formed because there are two possible positions where the
Br atom could bond.
 Replacement of -OH in alcohols by a halogen atom (nucleophilic substitution) using PX5/PX3 or
concentrated HX (X = Cl, Br). PX5 and PX3 act as a source of halide nucleophile. Here are exam-
ples

PCl5
CH3CH2OH CH3CH2Cl + POCl3 + HCl
organic solvent

PCl3
CH3 OH CH3Cl + H3 PO 3

Bromoalkanes and iodoalkanes can be prepared in a similar way, but in this case, PBr 3 and PI3 are
prepared insitu from the reaction of Br2 or I2 with red phosphorous, for example

I2
CH3 CH2OH CH3 CH2I + H3PO 3
red phosphorous
Note that PI5 and PBr5 are too unstable to exist due to crowding of large halogen atoms around
the central phosphorous atom.

10.5.3 Uses of halogenocompounds

 They are good organic solvents
Haloalkanes such as dichloromethane, CH2Cl2 find widespread use as solvents. CH2Cl2 is used as
paint stripper because it can dissolve dried paint. It is also less toxic than CHCl 3 (trichlorome-
thane) and CCl4 (tetrachloromethane).
 They are useful precursors in the synthesis of many other substances, including pesticides, drugs
and polymers.
 They are used in fire extinguishers, for example, bromochlorodifluoromethane, CClBrF 2.
 639

i. This compound does not burn since it has no C-H bonds (Combustion of organic compounds
is an oxidation process which proceeds by loss of hydrogen atoms from the reactant).
ii. It has a high density (its Mr is much larger compared with volume of a single molecule) so it
tends to settle on the burning objects. This helps to smother the flame.

 As refrigerants and propellant gases in aerosol cans (for example, perfume cans). Fluoroalkanes
and chlorofluoroalkanes have been used in this way since they have the following properties

i. They are chemically inert and do not burn, that is, they do not pose a fire risk. The chemical
inertness can be explained in terms of the large bond energy of the C-F bonds.
ii. They have low melting points (that is, they are volatile). They can be kept in a liquid form
when pressure is high, for example in an aerosol can, but as soon as pressure is lowered (by
opening the can), the halogenocompound rapidly expands and boils out.
iii. They are relatively non-toxic

Q why halogenoalkanes that are used as refrigerants and propellants do not

Explain
contain Br.

APresence of Br would increase the total number of electrons in the halogenoalkane molecules. In
turn, this would increase strength of Van der Waals forces. The boiling point of the compound
increases and so it does not easily turn to a vapour. A goodrefrigerant and propellant mustbe
volatile.
However, there are cases where the boiling point of the halogenocompound must be high
enough to make its storage easy. An example is illustrated by the anaesthetic halothane ® which
contains one bromine atom.

C C

10.5.4 The environmental problems associated with

chlorofluorocarbons (CFCs)
A CFC is a compound of carbon, fluorine and chlorine. CFCs such as CF₂Cl₂
were introduced in the 1920s. They soon found widespread use as refrigerant
Anaesthetic:
substance that compressor liquid, propellants in aerosol cans, anaesthetics and in air
induces a sleepy conditioning systems. CFCs were introduced to replace the substances which
condition in a were in current use for the above stated functions. These substances, which
patient during include sulphur dioxide and ammonia, had to be replaced since they were
amedical operation. found to be poisonous. The main advantages associated with CFCs have been
already outlined.
 640

CFCs have become a well known culprit in the depletion of the ozone layer. The key to their role in ozone
destruction is their inertness. Since they are not easily destroyed by chemical reactions in the lower
atmosphere, they easily escape intact and diffuse through the atmosphere, until they reach the
stratosphere. In the stratosphere, the intensity of ultraviolet radiation is high enough to initiate the
photodissociation of C-Cl bonds by homolysis, resulting in the formation of Cl free radicals. These radicals
catalyze the destruction of ozone in a chain reaction :

homolysis

R-Cl .
R + .
Cl initiation
UV
.
Cl + O3 ClO . + O2 (i)
propagation
.
ClO + O Cl. + O2 (ii)

net O3 + O 2O2 (iii)

 The C-Cl bond energy is smaller than that of the C-F and C-H bond. It is therefore the C-Cl bond
of the CFC which undergoes homolysis.
 The homolysis of the C-Cl bond occurs in the stratosphere, where the intensity of UV radiation is
high enough.
 The destruction of ozone by chlorine atoms is a free radical reaction. Steps (i) and (ii)above
constitute the propagation step. The chlorine free radical produced in step (ii) goes back to
participate in reaction (i), destroying more ozone molecules. A single chlorine atom can therefore
destroy thousands of ozone molecules.
 The conversion of ozone to oxygen, as shown in step (iii) is a natural process, occurring even in
an unpolluted atmosphere. The oxygen atom shown in step (iii) is generated when oxygen
molecules are photo dissociated by UV radiation. The role of chlorine radicals is simply to catalyze
reaction (iii), so that it occurs faster that would be the case in the absence of the chlorine atoms.
 Destruction of ozone by the natural process(iii) is countered by a regeneration process.

O2 + 2O  O3

In an unpolluted atmosphere, the destruction of ozone would be balanced by its formation, so

atmospheric levels of ozone would remain fairly constant. However, catalysis of the destruction
of ozoneimplies that its rate of removal from the atmosphere is higher thanthe rate of its replace-
ment. This has led to formation of the ozone hole, particularly over the Antarctic.
 The destruction of ozone is also catalyzed by NO.

Ozone is particularly effective at absorbing harmful ultraviolet radiation. The ozone layer is therefore a
natural screen against UV light. Depletion of the ozone layer increases the intensity of UV light reaching
the earth. This results in increased incidences of skin cancers and eye problems, especially among
societies that frequently engage in sunbathing, for example at beaches.
Sunscreen lotions containing nanoparticles are being developed that can reflect UV radiation away from
the skin, thus protecting sunbathers.
 641

Alternatives to CFCs
Substances which are more environmentally friendly are replacing CFCs. These replacements all have one
thing in common. They are more reactive than CFCs, so they can be destroyed in the lower atmosphere,
before they can reach the ozone layer which is in the stratosphere. Alternatives to CFCs include
 Volatile hydrocarbons, such as butane.
 HCFCs (hydrochlorofluorocarbons)

HCFCs are CFCs which contain at least one hydrogen atom. The C-H bond in the HCFC is fairly reactive,
for example, the hydrogen atom of the bond can be replaced by free radicals, especially the hydroxide free
radical, in the lower atmosphere (troposphere). In this way, the HCFC is converted to an alcohol, which
can be broken down fairly easily by processes in the troposphere.

Global campaigns against CFCs have resulted in a decrease in their use and production, and already there
is evidence that the ozone hole has begun to reduce in size.

10.5.5 Testing for haloalkanes and haloarenes

 The use of NaOH (aq) followed by AgNO3 (aq) has already been discussed.

Q.Briefly outline the chemical principles underlying this test. Explain how the test can be used to
distinguish between the following compounds:

Chloroethane, bromoethane, iodoethane, chlorobenzene

Questions, solutions and discussions

Q1 Methylbenzene can react with chlorine in two ways, depending on the conditions of the
reaction.

Cl2 Cl2

(a) State the condition needed for

(i) reaction I

(ii) reaction II.

 642

(b) One of the two compounds A and B reacts with NaOH (aq), but the other is inert.

(i) Which one (A or B) does not react? Give a reason for your answer.

(ii)Write an equation for the reaction with NaOH (aq) that does occur.

[UCLES 9701/J2002/4]

Solutions
(a) (i) Cl2 / AlCl3 or FeCl3 (catalyst).
(ii) Cl2 / UV/ light or heat

(Reaction (i) is electrophilic substitution; (ii) is free radical substitution).

(b) (i) A does not react. The C-Cl bond is partially double and therefore too strong to break.

(This is a result of the fact that the benzene ring withdraws some electron density from the
chlorine atom).

(ii)

+ NaOH + NaCl

Q2 Propylamine can be synthesized from bromoethane by the following route.

step 1 step 2
CH3CH2Br CH3CH2CH2NH2

(a) Draw the structure of the intermediate compound X in the box above.

(b) Suggest reagents and conditions for

step 1
step 2

[9701/04/M/J/2010]
 643

Solutions

(a)Xis CH3CH2CN

(b)Step 1 is KCN in ethanol, heat [NOT HCN ]

Step 2 is H2 over Ni or Pt (or LiAlH4 or Na in ethanol) [NOT NaBH4 or Sn/HCl]

3 Exercise to the reader

Chloroacetophenone (compound D, below) was formerly the most widely used tear gas,
under the codename CN. It was used in warfare and in riot control. It can be synthesized
from ethylbenzene, A, by the following route.

(a) Suggest reagents and conditions for step I.

(b) Suggest reagents and conditions for converting ethylbenzene into compound E, an
isomer of B.

(c) Residues of CNcan be destroyed by hydrolysis with an aqueous alkali.

+ OH- + Cl-

D
Compounds G and H are isomers of compound D.
 644

(i) Arrange the three isomers D, G and H in order of increasing ease of hydrolysis.

(ii) Explain the reasoning behind your choice.

9701/M/J/04/2010

10.6 Hydroxy compounds : alcohols and

phenols

10.6.1 Alcohols

Alcohols are organic compounds which contain the functional group shown below.

The OH is attached to an aliphatic (non-aromatic) carbon atom. If the –OH group is directly
C attached to a benzene ring (aryl/ phenyl group), the compound is not an alcohol. It is a
phenol.

Naming alcohols
The name of an alcohol ends in –ol, e.g. methanol, ethanol, propanol, etc. IUPAC rules are used to
designate the longest chain present, or to name and locate branches or other functional groups which
Solutions
might also be present in the molecule.
Panel 3shows some alcohols and their names. You should be able to classify the alcohols in this panel as
(a)Cl2secondary
primary, + light/heat (not aqueous)
or tertiary.
(b)Cl2+ AlCl3/FeCl3/Fe etc. (not aqueous)

Notes
 I is free radical substitution. The halogen atom normally replaces a hydrogen atom on a central
carbon atom because the corresponding free radical from which the product is formed has an
unpaired electron on a central carbon atom. Such a free radical is more stable than one in which
the unpaired electron is on a carbon which is at the end of the molecule.
 II is nucleophilic substitution using an alkali such as NaOH (aq) under reflux. This results in the
formation of a secondary alcohol.
 III is oxidation of a secondary alcohol to a ketone. Possible reagents for this conversion include
warm acidified and excess KMnO4 or K2Cr2O7.
 IV isfree radical substitution.
 Two compounds in the scheme exhibits optical isomerism. Identify these compounds.
 645

Panel 3

propan-2-ol 2-methylbutan-1-ol cyclohexanol prop-1-en-1-ol

phenylmethanol
2-methylpropan-2-ol
hexane-1,5-diol

1-bromo-3-chloro-pentan-2-ol

6.1.1 Alcohols as a homologous series: Physical properties

Solubility
The first members of the homologous series are completely soluble in water because of hydrogen bonding
that occurs between the alcohol and water molecules, as illustrated in Fig 10.11.

H O
H
.. .
C O. hydrogen bond
...O.
R H
H
H

Going down the homologous group, that is, as Mr increases, solubility of the alcohols decreases. Very long
chain alcohols are insoluble. In this case, there are two forces to consider; Van der Waals forces between
the long hydrocarbon tail of the alcohol and water molecules and hydrogen bonds between
the –OH group of the alcohol and water molecules. Formation of the weak Van der Waals forces is signifi-
cant because of the large number of electrons in the non- polar hydrocarbon tail. However, formation of
these weak forces would require the breaking of the relatively strong hydrogen bonds between water mo-
lecules. This process is endothermic and energetically speaking, it is not a favourable process. Interaction
of the –OH group of the alcohol and water molecules is energetically favourable, but this process is over-
come by the hydrophobic interactions between water and the hydrocarbon tail. Overally, the dissolution
process is not energetically favoured.
 646

Long non polar hydrocarbon tail forms weak

Van der Waals forces with water. This decreases
the tendency of the alcohol to dissolve in water.

Effect of branching on solubility

In general, an unbranched alcohol is more soluble than a branched one (such as tertiary alcohols) of
comparable Mr. Branching partially hides the –OH group and therefore hinders the efficient formation of
hydrogen bonds with water.

Boiling points
Alcohols have higher boiling points than hydrocarbons of comparable Mr. This are because of the pres-
ence of hydrogen bonds between the alcohol molecules. Hydrogen bonds are the strongest intermolecular
forces. A relatively large amount of heat energy is required to break them.

 Once more, it is noticed that branched chain alcohols have slightly lower boiling points than un-
branched chain alcohols of comparable Mr (compare the boiling points of butanol and 2-methyl-
propanol, which are isomers)
 Boiling and melting points increase down the group due to increasing strength of Van der Waals
forces as number of electrons (Mr) increases.
 Presence of a benzene ring results in poor solubility and high boiling point. The hydrophobic
(non-polar) nature of the benzene ring results in poor solubility in polar solvents such as water.
Since the benzene ring has a large number of electrons (large Mr), Van der Waals forces are
strong and this explains the high boiling points of alcohols which contain the benzene ring.

Table 10.9Boiling points and solubilities of the normal chain alcohols.

Alcohol Structure Boiling Solubility

point

methanol CH3OH 64.5 vs

ethanol CH3CH2OH 78.5 vs

propanol CH3CH2CH2OH 97.2 vs

butanol CH3CH2CH2CH2OH 117 s

pentanol CH3CH2CH2CH2CH2OH 138 ss

phenylmethanol
205 ss
 647

82.4 vs
Propan-2-ol

2-methylpropanol 108 s

s = soluble vs = very soluble ss = slightly soluble.

6.1.2 Chemical reactions of alcohols

By now the reader is aware of the following chemical properties of alcohols
 They are very weakly acidic. Thus they react with sodium metal, but they have no reaction with
bases, carbonates and hydrogen carbonates. In addition, they have no effect on litmus paper.
 Alcohols which have two carbon atoms or more may undergo dehydration (elimination of water),
resulting in the formation of alkenes.
 Alcohols undergo condensation reactions with carboxylic acids, resulting in the formation of
esters (esterification).
 Primary alcohols can be oxidized to aldehydes or all the way to carboxylic acids. Secondary
alcohols can be oxidized to ketones. Tertiary alcohols are resistant to oxidation.

Nucleophilic substitution in alcohols

You probably recall that nucleophilic substitution is likely to occur in an organic molecule
 which contains a polarized C-X bond, such that the carbon atom of the bond is partially positive
(Cδ+)
 in which the polar C-X bond is relatively weak so that it can easily break to allow formation of a
new bond between the carbon atom of the bond and a nucleophile.

The C-O bond in alcohols is polarized, and so the carbon atom is prone to attack by nucleophiles.
   Two important reactions of this nature are
C O
(i)Reaction with HX, where X = Cl, Br, I
H
(ii)Reaction with PX5, PX3

Reaction with hydrogen halide, HX

In this reaction, hydrogen chloride is prepared insitu from the reaction of hot concentrated sulphuric acid
with a halide salt:

NaCl(s) + H2SO4 (aq)  HCl (aq) + Na2SO4 (aq)

The HCl formed immediately participate pates in a nucleophilic reaction with the alcohol. The nucleophile
here is the chloride ion from the dissociation of HCl, for example.
 648

CH3CH2OH (aq) + HCl (aq)  CH3CH2Cl + H2O ... (i)

You should be able to see why using NaCl alone without concentrated sulphuric acid would not result in a
reaction. NaCl provides Cl- nucleophiles. Suppose that the Cl- ion from the salt replaces the -OH group in
the alcohol

CH3CH2OH (aq) + Cl-(aq)  CH3CH2Cl + OH- ... (ii)

This reaction produces a halogenoalkane, and a powerful nucleophile, OH -. So the reaction would simply
go in the reverse direction. In fact, the reverse reaction would be more favourable since it replaces a
weaker C-Cl bond with a stronger C-O bond.
When a mixture of concentrated sulphuric acid and NaCl is used, the OH - ions produced in reaction (ii)
are immediately neutralized by hydrogen ions to form water. This prevents the reverse reaction from
taking place.
If you study reaction (i) above you will notice that it is not energetically favourable. This is because the
reaction results in the replacement of a strong C-O bond by a weaker C-Cl bond. In other words, the
reaction is endothermic since more energy is absorbed in breaking bonds than is released in making new
bonds .Why then does the reaction take place if it is not energetically favourable?

 If a reaction is endothermic it means it requires a net absorption of heat energy in order to take
place. For the reaction under discussion, the enthalpy change of reaction can be obtained from
bond energies

∆Hθ= energy released 0n formation of C-Cl+ energy released on breaking of C-O

= -338 + (+360)

= + 22 Kj.
The reaction must therefore absorb 22 Kj of energy per mole of reactant in order to take place.
The energy required to drive the reaction is supplied by heating the reaction mixture.

 As already explained, the reaction can be considered to be reversible

CH3CH2OH (aq) + Cl-(aq) Ý CH3CH2Cl + OH-

Using concentrated sulphuric acid and NaCl, an acidic environment is provided which removes
the -OH ions as water. By Le Chatelier’s principle, this drives the reaction to the right, increasing
the yield of the product. Also, since the forward reaction is endothermic, it is favoured by an
increase in temperature.
 649

chloroethane : less stable

since C-Cl bond is weaker

ethanol : more stable since

CH3 CH2 Cl
O-H bond is strong
CH3 CH2 O H 

C - O bond energy C - Cl bond energy = 338Kjmol -1

= 360 Kjmol- 1

Fig 10.12 The endothermic nature of the reaction between ethanol and HCl

The formation of a bromoalkane from an alcohol takes place in a similar way:

CH3CH2OH (aq) + HBr (aq)  CH3CH2Br + H2O ... (iii)

The HBr can also be prepared insitu from the reaction between concentrated sulphuric acid and NaBr.
However, the yield of HBr is small since some of the Br - ions are oxidized by sulphuric acid to Br2. This
side reaction lowers the yield of reaction (iii)above.

The reaction between an alcohol and HI can not take place in the presence of concentrated sulphuric acid:

NaBr
CH3CH2OH
conc H2SO4

This is because I- ions are a good reducing agent. They reduce sulphuric acid to sulphur dioxide,
hydrogen sulphide and sulphur. Meanwhile, the iodide ions are oxidized to iodine. As a result of this
reaction, there won’t be any iodide nucleophiles to react with the alcohol.
The conversion of an alcohol to an iodo compound can be achieved by using concentrated phosphoric acid
instead of sulphuric acid. This is because phosphoric acid can not oxidize iodide ions.

H3PO4 (aq) + I-(aq)  HPO4-(aq) + HI (aq)

R - OH + HI  R-I + H2O

Reaction of alcohols with PX3 or PX5

This method of producing a halogenocompound from an alcohol has already been discussed. Recall that
 PX5 or PX3 supplies halide nucleophiles which replaces the -OH group in the alcohol. This is
therefore another example of a nucleophilic substitution reaction. Chloride nucleophiles can be
obtained from both PCl5 and PCl3. Bromide and iodide nucleophiles can be obtained from PBr 3
and PI3 respectively. PBr5 and PI5 are too unstable to have an independent existence.
 PCl5 and PCl3 can be used directly to convert an alcohol to a halogenocompound, for example
 650

CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl

3 + PCl3 3 + H3 PO 3

 The reaction with PCl5 produces white fumes of HCl.

 To make iodo and bromo compounds, the nucleophilic reagent, PI3 or PBr3 is prepared insitu by
mixing the corresponding halogen with red phosphorous in the presence of an alcohol, for
example

Br2
CH3 CH2OH CH3 CH2Br + H3PO 3
red P

I2
+ H3PO 3
red P
pentan-2-ol 2-iodopentane

In these reactions, a dry organic solvent should be used because the phosphorous pentahalides and
trihalides hydrolyze rapidly in water, for example

PCl5 + 4H2O  H3PO4 + 5H+ + 5Cl-

Esterification
This is the reaction that takes place between an alcohol and a carboxylic acid. The reaction is condensa-
tion because it results in the loss of a water molecule, for example

H+(aq)
CH3 CH2OH + CH3COOH CH3CH2COOCH3 + H2O
heat

H+(aq)
+ HCOOH + H 2O
heat

Esterification is reversible and requires the use of a mineral acid catalyst, or an alkali. The reaction is
accompanied by a sweet and fruity smell of the ester.
 651

Reaction of alcohols with acylchlorides

An alcohol reacts with an acylchloride, in the presence of a dry organic solvent, to produce an ester. This is
a better method of producing an ester; the reaction is fast and the yield is high since the reaction is irre-
versible. The reaction is fast because an acylchloride is very reactive towards nucleophiles.
δ- The carbon atom of the acyl group is under the influence of two highly electronegative
atoms (Cl and O) which have an electron withdrawing effect. This makes the carbon
δ+ δ- atom very electron deficient and very prone to attack by nucleophiles.

In addition, the C-Cl bond is weakened by the electron withdrawing effect of the oxygen atom. This bond
can easily break during nucleophilic substitution. The mechanism of ester formation is illustrated below.

δ-
δ-
C
C
.. .
...
+
... acychloride
.
ester group

alcohol

The net effect is loss of an HCl molecule and formation of a new C-O bond

- HCl

This type of reaction should be carried out in a dry organic solvent since an acylchloride hydrolyzes
rapidly in water.

6.1.3 Ethanol
Ethanol is a colourless liquid with a characteristic beery smell. It is produced on a large scale by the anae-
robic fermentation of glucose (anaerobic = without air).
Yeast cells use glucose as a food substrate and respire anaerobically on it to produce ethanol and carbon
dioxide.
 The ethanol solution obtained is dilute since large concentrations of ethanol kills the yeast cells.
 Since yeast cells are living, they require optimum conditions to ensure that they do not die and
their enzymes are not destroyed. Temperature should be kept warm , pH should be kept near 7
and air should be excluded.

Ethanol has several uses, including

 Active ingredient in alcoholic beverages

 antiseptic - kills bacteria on surfaces, for example lab benches and the skin
 652

 precursor for the synthesis of many other chemicals, including drugs

 manufacture of vinegar (dilute ethanoic acid)
 as a fuel.

Ethanol is often sold in small quantities as methylated spirit. This is ethanol which has been laced with a
small quantity of the poisonous alcohol methanol to make it unfit for human consumption. A purple dye is
also added as a warning.
Ethanol is a good fuel in the following ways
 It is liquid and so it can be stored more easily than a gaseous fuel
 It is volatile so it can easily turn to gas to allow combustion to take place (combustion of a fuel is a
gas phase reaction)
 It produces large amounts of heat energy
 Because of the small percentage of carbon per molecule, ethanol burns with a relatively clean
flame, that is, there is little production of soot (unburnt carbon).
 It is more environmentally friendly than petroleum based fuels, for instance, its combustion does
not result in the formation of sulphur dioxide
Many countries are now using petrol which has been blended with ethanol (blend petrol). This reduces
the cost of importing petrol.

The reactions of ethanol shown in Fig are typical of all alcohols

CH3 COOCH2CH3

CH3 COOH/H+
heat
conc HCl
heat Al2O 3
CH3 CH2OH CH 2 = CH2
3000C
PCl5

PCC
CH3 CH2Cl CH3 CHO
Na(s) KMnO 4 /H+(aq)
KMnO 4/H+(aq)

CH3 CH2O -Na+ CH3 COOH

6.1.4 Test for alcohols

a) Testing for alcohols in general

The following tests can not distinguish between primary, secondary and tertiary alcohols.
 653

 Add PCl5 to the test compound in the absence of water (to prevent hydrolysis of the PCl 5). White
fumes (of HCl) are evolved as nucleophilic substitution takes place, converting the C-OH group to
the C-Cl group. Carboxylic acids give the same result, but the white fumes are denser and are
produced more rapidly.
 Add ethanoic acid and a little concentrated sulphuric acid. Boil the mixture for a few minutes.
Alcohols produce a sweet smell, due to the formation of an ester. This reaction, known as esterifi-
cation,is very slow in the absence of a catalyst. An alkali or mineral acid can catalyze the reaction.
 Reaction with sodium metal: All alcohols react slowly with sodium metal, with a gradual
liberation of bubbles of hydrogen gas. The metal sinks and is used up slowly.

b) Distinguishing between primary, secondary and tertiary alcohols.

 Add the test compound to a little potassium dichromate that has been acidified with dilute
sulphuric acid. Primary and secondary alcohols are oxidized to carboxylic acids and ketones
respectively. Meanwhile, the potassium dichromate is reduced to green (or deep blue) Cr 3+.
Tertiary alcohols are not oxidized and there is no observable change.
The major draw-back of the test is that it does not distinguish between primary alcohols,
secondary alcohols and aldehydes.
A similar test can be carried out using KMnO4. Primary and secondary alcohols decolourise
KMnO4 but tertiary alcohols do not.

 Lucas test: Add concentrated HCl (aq) and Zinc (which is then converted by the acid to ZnCl 2) to
the test solution and heat over a boiling water bath. Tertiary alcohols are easily detected because
they give an almost instant cloudiness due to formation of the insoluble tertiary halogenoalkanes,
(R)3CCl. For secondary alcohols, cloudiness appears in about five minutes due to the formation of
the corresponding halogenoalkanes. For primary alcohols, cloudiness is very slow to appear or
may not appear at all.

c) Distinguishing between primary and secondary alcohols

Oxidize with K2Cr2O7 (aq)/H+ as described above (Remember that K2Cr2O7 is always used under acidic
conditions). Then test the product for the presence of a carboxylic acid or a ketone as described later. A
positive test for a carboxylic acid (e.g. white fumes upon addition of PCl5) indicates that the test solution
contained a primary alcohol. A positive test for a ketone, for example, formation of orange crystals with 2,
4-DNPH, shows that the test solution contained a secondary alcohol.

d) The triiodomethane (also known as the iodoform test)

The reagent in this test is a mixture of iodine and aqueous NaOH (aq), a weak oxidizing reagent. A
positive result (cream precipitate of CHI3) is obtained for alcohols which contain the group

OH
CH3 C
H

For example,
 654

OH H
CH3 C H and CH3 C CH3
H OH

Ethanol propan-2-ol
(primary alcohol) (secondary alcohol)

During the reaction, oxidation of the alcohol takes place, resulting in cleavage of a C-C bond. One carbon
atom appears in the precipitate CHI3 and the rest of the organic reactant becomes the salt of a carboxylic
acid, for example

becomes HCOO- (methanoate)

OH

CH3 C H
H
becomes CHI3

The iodoform test is not conclusive because different alcohols may give the same result. Carbonyl
compounds which contain the group CH3CO- also give the same result, for example ethanal and
propanone.

10.6.2 Phenols
A phenol is a compound in which the hydroxy group is bonded to the benzene ring. The simplest phenol is
phenol itself, whose structure is shown below

= C6H5 OH

skeletal formula
partial displayed
formula
 655

Panel 4shows some substituted phenols and their names

p-cresol
2,4,6-tribromophenol
4-methylphenol 1,4-dihydroxybenzene

2-nitrophenol
2,4,6-trichlorophenol
4-nitrophenol
(antiseptic found in Dettol)

6.2.1 Properties of phenol

 It is a white crystalline solid, partially soluble in water. It dissolves poorly because of the presence
of the hydrophobic benzene ring. It dissolves to some extend because it can form hydrogen bonds
with water.
 In solution , it forms a slightly acidic solution
 It has a relatively high boiling point of 1810C. This is due to the presence of hydrogen bonds
between its molecules. It also has a large number of electrons (large Mr) and this makes the Van
der Waals forces acting between its molecules strong.

Chemical properties related to the -OH group

I. The acidity of phenol
 The reasons for the acidity of phenol have already been discussed. Make sure you can explain this
acidity carefully in terms of stability of the phenoxide ion and relatively small bond energy of the
O-H bond in phenol.
 Phenol is acidic enough to react with sodium metal to form sodium phenoxide and release
hydrogen gas. When phenol is added to cold water, the resulting mixture appears cloudy because
phenol does not dissolve completely. When sodium metal is added, bubbles of a gas are produced
and the cloudiness of the mixture is removed. This shows that the product formed, sodium
phenoxide, is more soluble in water than phenol. Sodium phenoxide is also formed from the
neutralization of phenol by sodium hydroxide
 656

+ Na + 1/2 H 2

+ NaOH + 1/2 H 2O

 Phenols do not react with carbonates or hydrogen carbonates. This shows that they are weaker
acids than carboxylic acids. However, the fact that they neutralize NaOH shows that they are
stronger acids than alcohols.
 Sodium phenoxide is a white crystalline solid that dissolves easily and completely in cold water,
forming a colourless solution. When carbon dioxide is passed into the colourless solution, thin
white ‘clouds’ begin to appear. This is due to the formation of phenol, which is partially soluble in
water. Carbon dioxide dissolves in water to release hydrogen ions, which then bond with
phenoxide ions to form phenol. Once more, this shows that phenol is poorly soluble and so can
easily precipitate out of water.

IIPhenol as a nucleophile
The OH group in phenol is not only responsible for the acidity ; it also explains the ability of
phenol to react with acylchlorides to form esters, for example,

+ CH3 COCl + HCl

 The reaction must be carried out in the presence of a dry organic solvent. This is because the
acylchloride hydrolyzes rapidly in water.
 This is an example of a nucleophilic substitution reaction in which the Cl atom in the acylchloride
is replaced by the phenoxide nucleophile.

-Cl -H
.. ..

phenoxide group has

replaced Cl in CH3 COCl
 657

 Phenol is not strong enough as a nucleophile to react with carboxylic acids to form esters. Instead,
the carboxylic acid must be converted first to an acyl chloride, which, as explained earlier, is very
reactive towards nucleophiles. Phenol is relatively weak as a nucleophile because the benzene ring
withdraws some electron density from the lone pairs on the oxygen atom. This oxygen atom is
therefore not electron rich enough to be attracted to the carbon atom of the COOH group of a
carboxylic acid.

Reactions of the benzene ring

The benzene ring in phenol is activated by presence of the OH group. A p orbital containing a lone
pair of electrons on the oxygen atom overlaps with a p orbital on carbon of the C-O bond. This causes
some electron density from the oxygen atom to be delocalized into the ring. The benzene ring is thus
richer in electrons, and so can easily attract electrophiles.
The benzene ring in phenol reacts via electrophilic substitution. Here are some examples of such
reactions.

Bromination
 Bromine is decolourized and a white precipitate of 2,4,6-tribromophenol is formed. Phenol reacts
in a similar way with chlorine, to form 2,4,6-trichlorophenol.

+ 3/2Br2 + 3HBr

2,4,6-tribromophenol
white precipitate

 No catalyst (halogen carrier) is required since the benzene ring is activated towards electrophiles.
 The incoming Br atoms replace hydrogen atoms at positions 2 and 4 of the benzene ring. This is
because -OH is an ortho-para director.
 Polysubstitution occurs because the benzene ring is activated. All possible positions on the ben-
zene ring are substituted by Br atoms.
 The product is formed as a solid because it has a very large number of electrons (large Mr). Van
der Waals forces are therefore strong between molecules of the product.

Nitration
Phenols react with cold dilute nitric acid to produce a mixture of 2-nitrophenol and 4-nitrophenol
 658

+ HNO 3 + + H2O

2-nitrophenol

4-nitrophenol
major product

 No catalyst is required since the benzene ring is activated.

 Two products are formed because the OH group directs at two possible positions, the ortho and
the para, and yet polysubstitution cannot take place since once the nitro group enters the ring it
deactivates it. A second nitro group cannot enter into the same ring unless if the mixture is
heated.
 The reaction produces two positional isomers. The para isomer is the major product because the
OH and NO2 groups are well spaced and therefore their electron clouds do not interact.
Inter-electronic repulsions between NO2 and OH groups is great in the ortho isomer. This causes
instability, so formation of the ortho isomer is less favourable.
 The ortho isomer has a lower boiling point (it is more volatile). This is because
intramolecularhydrogen bonds exist between the OH and the NO2 groups. Since each molecule
uses its capacity for hydrogen bonding within itself, it cannot form hydrogen bonds with nearby
molecules. The forces of attraction between molecules aretherefore weak Van der Waals forces. A
relatively small amount of heat energy is required to break these forces and separate the
molecules during boiling (or melting). In the second isomer, the NO 2 and OH groups are too far
from each other to participate in intramolecular hydrogen bonding. The molecule is therefore able
to form intermolecular hydrogen bonds with neighbouring molecules.

6.2.2 Substituted phenols

These compounds have one or more other groups (apart from the OH group) attached to the benzene
ring. These groups may modify the properties of the benzene ring, for example, making it more or less
reactive than phenol. Here are examples.

1,2 - benzenediol

4-nitrophenol 2,4,6 - trichlorophenol (TCP)

4-nitrophenol is more acidic than phenol. This is because of the electron withdrawing effect of the NO 2
group. The NO2 group therefore increases the tendency of the benzene ring to withdraw electrons from
the O-H bond. This bond is thus weakened and it breaks easily, releasing H+, which is responsible for
acidity. Once formed, the phenoxide ion is also stabilized by the electron withdrawing effect of the
 659

NO2group. In other words, the negative charge on the oxygen atom cannot easily combine with protons to
reform phenol. This is because the negative charge is partly pulled away from the oxygen atom.
4-nitrophenol is also less reactivetowards electrophiles than phenol. This is because the NO2 withdraws
some electron density from the benzene ring, which becomes relatively deficient in electrons. The ability
of the benzene ring to attract electrophiles or polarize electrophilic reagents is therefore reduced.

2,4,6-Trichlorophenol (TCP) is several times more acidic than phenol. This is because of the presence
of three electron withdrawing chlorine atoms. In fact, TCP is acidic enough to be used as an antiseptic. It
is found in DettolTM , and when applied to surfaces, its low pH kills bacteria.

1,2-benzenediol is more reactive with respect to electrophilic substitution in the ring due to the pres-
ence of two ring activating groups.

Preparation of phenol
Small scale preparation of phenol in the lab is not easy because the -OH group cannot be introduced di-
rectly into the benzene ring, for example

NaOH

A reaction does not take place because both the benzene ring and the hydroxide ion are electron rich and
so tend to repel. Phenol can be prepared in several steps via benzene diazonium chloride (diazo salt). The
sequence of steps in the following synthetic route has already been discussed.

I Nitration (electrophilic substitution)

II Reduction of nitro group to amine
III Diazotization, forming a diazonium salt
IV Hydrolysis, in which the N2+ group is replaced by the OH group from water

+
(I) (II) (III)
conc H2SO 4 Sn/ concHCl conc HCl
conc HNO 3 reflux NaNO 2
600C <50C diazonium salt

H2O
100C
(IV)

phenol
 660

6.2.3 Test for the presence of a phenol

 Add bromine liquid (no need of warming). The bromine is decolourized and a white precipitate is
formed.

OH OH
Br Br
Br2
+ HBr

Br
2,4,6-tribromophenol
(white ppt)
Alkenes also decolourize bromine, but small Mr alkenes such as ethene do not form a precipitate.
 Reaction with sodium metal: This converts a phenol to a salt (sodium phenoxide).
Phenol forms a cloudy mixture with water because of its poor solubility. During the reaction with
sodium, bubbles of hydrogen gas are liberated, and a clear colourless solution is formed since the
product of the reaction (sodium phenoxide) is completely soluble in water.

 The most sensitive and conclusive test for a phenol is the FeCl3 (aq) test. Phenols give an instant
violet coloured complex.

6.2.4 Uses of phenols

 2,4,6-trichlorophenol is used an antiseptic
 Phenol is used in the manufacture of a polymer known as Bakelite
 Phenol and its derivatives are also used in the manufacture of drugs and dyes

Questions, solutions and discussions

Q1 The acid ClCH2CO2H features in the industrial synthesis of the important weedkiller
2,4-D.

+ NaOH
phenol + ClCH2CO2H

(a)Suggest a possible reagent for reaction I.

 661

(b) What type of reaction is reaction Iand II.

(c)Describe a test (reagents and observations) that would distinguish phenol from
compound A.

Solutions
(a) Cl2

(b) Reaction I: electrophilic substitution

Reaction II: nucleophilic substitution

(c) Phenol decolourises Br2 (aq) and gives a white ppt

OR phenol give a purple colour with FeCl3 (aq)
OR Compound A decolourizes KMnO4 / changes K2Cr2O7 from orange to green

Q2 The phenol 1-naphthol is a starting point for the manufacture of carbaryl, an insecticide and
a plant growth inhibitor.
C

+ NaOH + CH3NHCOCl

(a) (i) Suggest a structure for the intermediate C and draw it in the box above

(ii) Name the functional groups in carbaryl

(iii)Suggest structures for the three products formed when carbaryl is hydrolyzed

(iv) What reagents and conditions would you use for this hydrolysis?

(b) Suggest reagents and conditions for converting 1-naphthol into each of the following
compounds.
 662

(i) (ii)

(c) Compound D is an isomer of 4-nitro-1-naphthol. D is formed as a by-product during the

reaction in b(ii). It can be converted into 2-amino-1-naphthol, E.

(ii)

(i)Suggest the structural formula of the isomer D.

(ii) Suggest reagents needed for reaction I.

(iii) Suggest the structural formula of the compound formed when compound E reacts
with an excess of CH3COCl.

(d)When an alkaline solution of compound E is added to a solution containing Cu2+ (aq) ions, a pale
green-blue precipitate F forms. Analysis of F shows that its formula is Cu(C10H8NO)2(H2O)2.

(i)Complete the following structural formula of F.

When an excess of concentrated NH3(aq) is added to F, the precipitate dissolves toform a deep blue
solution.

(ii) State the formula of the ion responsible for the deep blue colour.

(iii) What type of reaction is occurring here?

 663

Solutions
(a)(i) (ii)tin/Fe in concentrated HCl

Na + (iii)

(ii) Amide, ester

(iii) CO2, CH3NH2 and (d)(i)

(iv) H+(aq) and heat/ boilor OH–(aq)

and heat / boil

(b) (i) Br2(aq) (or other suitable solvent)

(ii) [Cu(NH3)4]2+ / [Cu(NH3)4(H2O)2]2+
(ii) dilute/aqueous HNO3
(iii) ligand exchange
(c) (i)D is

10.7 Carbonyl compounds : aldehydes and

ketones
Carbonyl compounds contain the carbonyl (C=O) group. In ketones, the carbonyl carbon is not bonded to
any hydrogen atom. Rather, it is bonded to two R (alkyl or aryl) groups. In aldehydes, the carbonyl group
is bonded to one hydrogen atom and one alkyl group, except in methanal in which the carbonyl C atom is
bonded to two hydrogen atoms.
 664

O O
C H C R2
R R1
Aldehydes. The R group is an alkyl or aryl
Ketones. R = H
group, except in methanal in which it is
another hydrogen atom.
Examples of aldehydes and ketones are given in Table 10.9below.

Aldehydes Ketones

(Name ends in-al) (Name ends in-one)

propanone
methanal

ethanal pentan-2-one

ethanedial
phenylethanone

benzaldehyde
camphor

Table 10.9 Aldehydes and ketones

10.7.1 Nomenclature
The name of an aldehyde ends in -al whilst that of a ketone ends in -one. In aldehydes, the functional
group is always at the end of a chain, so it is not necessary to use locator numbers to specify position of
the aldehyde group. However, if the carbon chain contains one or more branches, for example, a methyl
 665

branch, it is necessary to specify the position of that branch using locator numbers. Similarly, if there
other functional groups present, apart from the aldehyde group, it is necessary to specify their positions.
Here is an example

1 main chain has 6 carbon atons

3 6
2 4
5

methyl branch at C2

Name : 2-methylhexanal
Note that the main chain is numbered so that the aldehyde group is at the first carbon atom.
For a ketone, it is not necessary to specify position of the carbonyl group if the name does not lead to
ambiguity. The following compounds are thus correctly named.

propanone

butan-2-one or just butanone

However, the name pentanone is ambiguous because there are two ketones (positional isomers) which
could share this name. In this case it is necessary to specify the position of the carbonyl group.

pentan-2-one
pentan-3-one

Panel 10.6 gives more examples of aldehydes and ketones and their names.

hex-4-en-2-one hex-3-enal cyclohexanone

3-hydroxybutanal

cyclohexanecarbaldehyde
 666

10.7.2 Physical properties of aldehydes and ketones

 They are generally volatile. This is because the molecules are held together by relatively
weak permanent dipole- dipole attractions. Aldehydes and ketones therefore have lower boiling
points than compounds of comparable Mr which can form hydrogen bonds, for example, water
and alcohols. However, the permanent dipole -dipole attractions between molecules of aldehydes
and ketones are much stronger than the Van der Waals forces in alkanes. Compare ethanal, an
aldehyde, with propane, which is an alkane. These two compounds have the same Mr.Propane
boils at -42⁰C and so it is a gas at room temperature. Ethanal, with a boiling point of 20⁰C,is a
liquid, though it is very volatile.

 The first members of the aldehyde and ketone families are very soluble in both water
and organic solvents. The following compounds dissolve very well in water:

methanalHCHO

ethanal CH₃CHO

propanalCH₃CH₂CHO

butanone CH₃CH₂COCH₃

pentan-3-oneCH₃CH₂COCH2CH3

Solubility of these compounds in water can be explained in terms of the polar interactions
(hydrogen bonds) that occur between water molecules and molecules of the carbonyl compound,
as illustrated for ethanal below.

hydrogen bonds
.
.. .
.. ..

10.7.3 Bonding at the carbonyl group

The C=O bond consists of a sigma and a pi bond. The carbonyl carbon atom is sp 2 hybridized, giving a
trigonal planar geometry, that is, the three electron groups around the carbon atom are in the same plane.

1200

10.7.4Chemical properties of carbonyl compounds

Aldehydes and ketones are structurally similar, but their chemical properties are different enough to
justify their separation into different homologous series. However, they do have some common reactions,
including nucleophilic addition to the carbonyl group and reduction. Chemical reactivity of the aldehydes
 667

and ketones is influenced by the polar nature of the carbonyl group. Oxygen, being more electronegative
than carbon, tends to draw electrons of the C to O bond more strongly to itself.
The carbon atom of the carbonyl group is relatively positively charged and is therefore
δ- prone to attack by nucleophiles. In fact, nucleophilic addition is the predominant
reaction undergone by aldehydes and ketones. There is another important factor about
δ+ the carbonyl group that makes it susceptible to attack by nucleophiles. The oxygen
C atom of the carbonyl group has the ability to accept and stabilize an extra pair of
electrons. This prevents too much electron density around the carbonyl carbon, and
allows the incoming nucleophile to bond to this carbon atom.
It is hoped that the reader recalls the following reactions that are undergone by both aldehydes and
ketones.
 Nucleophilic addition
 Reduction

Nucleophilic addition
This type of reaction was discussed in detail in Part 1 of this section. The reader should do a self check by
working out the problems given below .It is advisable to revise the section on nucleophilic addition
reactions first.

Self check - Nucleophilic addition in aldehydes and ketones

QCamphor is a chemical obtained from the camphor tree. It is commonly used in cosmetic products
such as skin lotions.

camphor

(a) Calculate the mass of 2 moles of camphor.

(b) How and what conditions does camphor react with HCN? Using the curly arrow notation to show
movement of electrons or bond breaking/formation, describe the mechanism of the reaction.

(c) Explain how the product of this reaction can be converted to

(i) a compound P, which gives a brisk effervescence with sodium carbonate

(ii) a compound Q, which dissolves in HCl(aq), forming a colourless solution which yields white
crystals of a soluble salt upon evaporation.

Draw the structures for compound P and Q.

 668

Reduction of aldehydes and ketones

The following reagents can be used to reduce aldehydes and ketones.
 NaBH4
 LiAlH4
 H2 / Ni

Recall that
 aldehydes are reduced to primary alcohols whilst ketones are reduced to secondary alcohols.
 LiAlH4 is the most powerful reducing agent of the three reagents given above. However, it has the
disadvantage that it has no tolerance for water (it decomposes violently in water) and so must be
used with a dry solvent such as ether.
 NaBH4 is a powerful reducing agent though weaker than LiAlH 4. However, it can be used in
water.

10.7.5 Reactions peculiar to aldehydes

Aldehydes can be oxidized to carboxylic acids. Ketones resist oxidation. This shows that aldehydes are
more reactive. Oxidation here depends on the loss of a hydrogen atom from the carbonyl group. In
ketones, this hydrogen atom is absent, so oxidation cannot take place.

Oxidizing agents can therefore be used to distinguish between

an aldehyde and a ketone. Consider ethanal and propanone,
isomers which share the molecular formula C3H6O.
aldehydes ketones Ethanal gives the following results but propanone does not
 decolourizes KMnO4
 Gives a silver deposit (mirror) with Tollen’s reagent ( an ammoniacal solution of silver nitrate)
 Gives a brick red precipitate of copper (I) oxide with Fehling’s solution (an alkaline solution of
Cu2+ in the presence of tartrate ions).
 Turns potassium dichromate from orange to green.

10.7.6 The 2,4-DNPH test for ketones and aldehydes

2,4-dinitrophenylhydrazine (2,4-DNPH) is sensitive to the presence of an

aldehyde or a ketone group. Its major drawback is that it cannot easily
distinguish between an aldehyde and a ketone.
The carbonyl group in aldehydes or ketones reacts with 2,4-DNPH to form
yellow or orange crystals of a compound known as 2,4-
dinitrophenylhydrazone, whose structure is shown below
 669

 2,4 -dinitrophenylhydrazone is formed in a condensation reaction in which the carbonyl oxygen is

lost as water. This results in the formation of a C=N bond, as illustrated.
 670

.. ..

First, the O atom of the carbonyl group is protonated

by a hydrogen ion from solution. The positive charge on O
w ithdraw s electrons from the carbonyl carbon, making it very
electron deficient.

The -NH2 group in 2,4 -DNPH acts as a nucleophilic

centre and attacks the electron deficient carbon
of the carbonyl group. This causes π electrons to
shift from the C=O bond and reside on the O atom.
δ+
.. Meanw hile, a N-C bond is formed betw een 2,4-DNPH
and the carbonyl carbon.

The nitrogen atom w hich has been used to form

new C-N bond now has four bonds around it,
instead of the usual three. This nitrogen atom

.. therefore becomes positively charged. One N-H

bond breaks and the released H+ ion is taken up
by the -OH group. The OH group is thus
C converted into an H2O group, w hich is a good
leaving group

A lone pair on N shifts as show n. This results

in the formation of C to N double bond.
.. Meanw hile, H2O is driven out and another N-H
C bond breaks.

a 2,4-dinitrophenylhydrazone
 671

2,4-dinitrophenylhydrazones have sharp melting points which are characteristic of the carbonyl com-
pound that was used in the formation of the hydrazone. It is therefore possible to deduce the identity of
the carbonyl compound by comparing its melting point with experimental values found in Tables.

10.7.7 Lab preparation of carbonyl compounds

 Aldehydes can be prepared by the oxidation of primary alcohols and ketones by the oxidation of
secondary alcohols. Here are examples

PCC
1

phenylmethanol benzaldehyde
primary alcohol

excess K2Cr2O 7 /H+

2 CH3 CH2CH(OH)CH2CH3 CH3 CH2COCH2CH2
pentan-3-ol pentan-3-one
secondary alcohol

excess K2Cr2O 7 /H+

3

cyclohexanol cyclohexanone
secondary alcohol

 Friedel -Crafts acylation can be used to prepare ketones that contain a benzene ring, for example

C
AlCl3
+ CH3COCl dark + HCl

phenylethanone

Recall that this is an electrophilic substitution reaction, involving the acyl ion (electrophile),
CH3CO+, generated insitu from heterolysis of the C-Cl bond in the acylchloride. Make sure you
can describe the mechanism of the reaction, including
-the use of curly arrows to show movement of electrons or bond breaking/formation.
-The structure of the intermediate
-the role played by the catalyst
-regeneration of the catalyst
 672

10.8.8 Uses of carbonyl compounds

 Solvents. An example is propanone, CH3COCH3 which is used as a solvent for plastics, greases
and varnishes (e.g. it can remove dried nail vanish)
 A solution of methanal in water is known as formalin. It is used as a disinfectant and as a
preservative for biological specimens.
 As food flavourants. Here are examples

Cinnamon is a spice used in sweets and savoury foods. The substance responsible for the flavour
of cinnamon is the aldehyde cinnamaldehyde, which occurs naturally in the bark of the cinnamon
tree. The structure of cinnamaldehyde is shown below.

Structure of cinnamaldehyde
Cinnamon sticks and powder

The Old Testament of the Holy Bible has many references to this
spice.

Vanillin is a commonly used flavourant, for example, in ice cream and chocolates. It is obtained
from the vanilla bean plant, native to Mexico and Central America. Global cultivation of this plant
only became possible after a 12 year old slave working on the French island of Réunion discovered
a method for hand pollinating the plant. Vanillin is a phenolic aldehyde, whose structure is shown
below.

vanillin

 In cosmetic products. An example is camphor, which is added to some skin lotions because of
it skin conditioning properties.
 673

Questions, solutions and discussions

Q The following substances are naturally occurring compounds that contain the aldehyde or ketone
group, in addition to other functional groups.

A B C
(c) Suggest the reagents and conditions required to convert compound E above into a compound F
which has the following properties

piperitone-used in It
the camphor-used
gives a brisk in cosmetic
effervescence with both sodium metal and sodium carbonate
vanillin-flavourant
 It
manufacture of menthol reacts products.
with NaOH(aq)
and thymol  It gives a fruity smell when heated with an acidified solution of ethanol

(d) How and under what conditions will vanillin, C, react with the following reagents under the given
conditions? In each case state the type of reaction that takes place and draw the structure of the
Dproduct formed. If no reaction takes place, say so.
(i) Liquid bromine (limited)

(ii) NaBH4 followed by a hot acidified solution of ethanoic acid

carvone-an oil found in caraway
seeds.Used
(iii) PCl5 as a food flavourant and
as an agent that prevents premature
sprouting in potato
(e)Carvone, tubers.
D, has two stereoisomers. One of the isomers is useful in preventing sprouting of stored
potatoes, but the other is not. What do you understand by the term in italics? Explain clearly why
(a)Piperitoneorishow
obtained from a Gumistree
stereoisomerism (Eucalyptus)
possible found in South Africa. It can be converted to
in carvone.
menthol, which has many medical applications. Menthol has the same number of carbon atoms
and Outline
(f) hydrogen atoms as
a simple labpiperitone. However,
test that can be used menthol
to distinguish between the following pairs of compounds.
 In has
eachfour more
case, statehydrogen atoms
the reagent used and how any observations made help in distinguishing
 between thedecolourize
does not compounds. bromine liquid bromine but does decolourize KMnO 4 solution
 Gives a steady liberation of hydrogen gas with sodium metal
(i)A and B
(i) Suggest a possible structure for menthol. Briefly explain your reasoning.
(ii)C and D
(ii) Suggest the reagents and conditions required to convert piperitone to menthol

(b)State the reagents and conditions required to convert camphor, B, into compound E below.

E
 674

Solutions

(a) (i)

Menthol does not decolourize liquid bromine because it does not have a C to C double bond.
However, it is oxidized by KMnO4 because of the presence of a secondary alcohol group.
The molecular formula of piperitone and menthol are C10H16Oand C10H20O respectively.
Menthol has four more carbon atoms.

(ii)H2(g)/Ni(s), heat. Under these conditions, both the C to C double bond and the carbonyl group
are reduced.

H2(g)/Ni

heat

piperitone menthol

(b)

NaBH4/ethanol
(solvent)

camphor compound E

(c) From the clues given, compound F is a carboxylic acid.

KCN/H2O H2SO 4(aq)

reflux reflux

compound E compound F
 675

The first step is nucleophilic substitution and the second is hydrolysis. Compound F forms an
ester with ethanoic acid. Formation of the ester is responsible for the sweet fruity smell detected.

(d) (i) Electrophilic substitution into the ring. Reaction is carried out in the dark and in the cold. No
catalyst is needed since the benzene ring is activated by the -OH group. A mixture of products
might be formed, but the most abundant is likely to be

(ii) With NaBH4, reduction takes place in which the

aldehyde group is converted to a primary alcohol.
When the secondary alcohol is treated with a hot
mixture of ethanoic acid and strong mineral acid,
esterification occurs. The two step conversion is
shown below.

NaBH4
ethanol/H2O

(iii) Vanillin has no reaction with PCl5. Recall that phenols do not react with PCl5 because the -OH
group is bonded to the benzene ring by a bond which has a partial double character and is
therefore very strong.

(e) Stereoisomers are compounds which share the same molecular and structural formula but
differ how groups are arranged in space. There are two forms of stereoisomerism, cis-trans
(geometric) and optical isomerism.

In carvone, optical isomerism is possible because of the presence of a chiral carbon atom,
marked with an asterisk in the structure below.

*
(f)(i)A decolourizes liquid bromine, B does not.

(ii) C gives an instant violet colour with FeCl3 (aq). This is a sensitive test for the presence of a
phenol. D gives no change.
Note that both compounds decolourize liquid bromine and aqueous KMnO 4.
 676

10.8 Carboxylic acids and their derivatives

10.8.1 Carboxylic acids

By now you know that carboxylic acids contain the carboxyl group, which is in fact a hydroxy group
bonded to a carbonyl group
The O-H bond is under the influence of two oxygen atoms which, being strongly
electronegative, tends to pull electrons from the bond. This weakens the bond so that
C it can dissociate relatively easily in solution, liberating a hydrogen ion. It is of course
the presence of hydrogen ions in solution that are responsible for the acidity of
carboxylic acids.
Another explanation of the acidity of carboxylic acids has already been explained in terms of the
stabilization of the carboxylate ion by delocalization of the negative charge on the ion.

8.1.1 Physical properties

Boiling and melting points
Carboxylic acids have relatively high boiling and melting points. Compare the boiling point of ethanoic
acid with that of ethanol and propan-2-ol

Compound Boiling point/0C

Of the three compounds, ethanoic acid has the
highest boiling point, even though all compounds
Ethanoic acid 1180C
have hydrogen bonds between their molecules,
Ethanol 780C and propan-1-ol has a similar relative molecular
mass. This observation can be explained in the
Propan-1-ol 970C following ways

 The hydrogen bonds in ethanoic acid are the strongest. That is, the O-H bond in ethanoic acid is
the most polar. This is because the bond is under the electron withdrawing effect of two oxygen
atoms

 Because of the presence of two oxygen atoms, molecules can pair up in a process known as
dimerization. This leads to extensive hydrogen bonding in the pure liquid. Evidence for this
dimerization is provided by measurements of relative molecular masses, for example, the
apparent Mr of ethanoic acid in benzene is 120, not the expected 60. This doubling of Mr
indicates existence of dimers as shown in Fig 10.13.
 677

Fig 10.13 Dimerization in

ethanoic acid. Two molecules
are associated through two
strong hydrogen bonds

The melting points of the carboxylic acids increase with increasing Mr. This is because Van der Waals
forces become stronger as the number of electrons increases.
Volatility of the carboxylic acids is lower compared to other compounds of comparable Mr. Volatility is the
tendency of a liquid to turn into its vapour, and of course, this is related to the boiling point of the sub-
stance. Molecules of a carboxylic acid are closely associated through strong hydrogen bonds, so they do
not easily escape into the gaseous state. One way of estimating the volatility of a substance is by the
strength of the smell (if any) it gives out at room temperature. Smell is detected by olfactory structures in
the nose. This implies that the liquid substance must turn into a vapour first and diffuse into the nose.
Many carboxylic acids give a strong odour at room temperature, not because they are very volatile, but
because the sensory receptors in the nose are very sensitive to these substances. Here are examples of
such carboxylic acids and a description of their smells.

 Butanoic acid is responsible for the smell of rancid butter. In fact, the name butter is derived
from the name of this acid. Butanoic acid does not only feature in butter that has gone bad. It is
responsible for the sweaty smell of humans. Even when not visibly sweating, we continue exuding
butanoic acid, and it is its smell that a police dog traces when it hunts for a person. Dogs can
detect concentrations of butanoic acid as low as 0.00000000000000oo10 (that is, 1.o x 1017)
moldm-3.
 Caproic acid (hexanoic acid) isresponsible for the smell of goats. Its name is derived from
the Latin word ‘ caper’ which means goat.
 Ethanoic acid (acetic acid) is responsible for the smell and taste of vinegar.

Solubility
Carboxylic acids have higher solubilities in water than alcohols of similar Mr. This can be explained in this
way:
 The O-H bond in carboxylic acids has a large dipole moment and this results in the formation of
strong hydrogen bonds with water.
 Some acid molecules dissociate in water, and this increases solubility.

Solubility in water decreases with increasing Mr, as expected. As the carbon chain becomes longer, on
average there are more interactions between water molecules and the hydrocarbon chains, than between
water and the polar COOH group. The interactions between water and the hydrophobic (non- polar)
carbon chains are energetically unfavourable as it would require the breaking of strong hydrogen bonds
between water molecules.

8.1.2 Nomenclature
The name of a carboxylic acid ends in -oic acid, after a prefix which denotes the number of carbon atoms
and the nature of the group bonded to the -COOH group. If branches or other functional groups are
present their positions must be specified, as usual, by locator numbers. In such situations, the carbon
atom of the -COOH group assumes the first position from which the rest of the carbon atoms are
numbered. Panel 6 shows some carboxylic acids and their names.
 678

Panel 6

methanoic acid (formic acid) propanoic acid butanoic acid

deca-5,8-dienoic acid
3-methylbutanoic acid

but-2-enoic acid cyclohexanecarboxylic acid 2-chlorobutanoic acid

3-bromo-2,2-dichlorobutanoic acid 4-hydroxyhexanoic acid 4-oxohexanoic acid

5-oxopentanoic acid
benzoic acid 2-phenylethanoic acid

Note that if an -OH group is present, it is referred to as ‘hydroxy’. Similarly, an aldehyde group or ketone
is referred to as ‘oxo’.

8.1.3 Chemical properties

The following reactions of carboxylic acids have been discussed
 Acid - base reactions

Reactions with nucleophiles

 esterification
 reduction with LiAlH4
 679

 Reaction with PCl5

Acid-base reactions
These depend on the acidity of the -COOH group. Carboxylic acids are weak acids in the sense that their
dissociation in water is reversible

C C + H+

However, they show the characteristics expected of an acid

 They neutralize bases to form (carboxylate) salts
 They give a brisk effervescence with carbonates and hydrogen carbonates to form salts. The
effervescence is a result of the production of carbon dioxide.
 They react with sodium metal, with a brisk evolution of hydrogen gas
 They turn moist blue litmus paper red

Reactions with nucleophiles

The carbon atom of the COOH group has a partially positive charge because of the electron withdrawing
effect of two oxygen atoms. This carbon atom is therefore susceptible to attack by nucleophiles.
Esterification, reduction, and acylation all involve initial attack of the C δ+ by a nucleophile . The reactions
that take place are essentially nucleophilic substitution because they result in the replacement of the -OH
group in the acid by another group, for example, Cl from PCl5.

Nucleophilic reagent Nucleophilic Product formed and notes

particle

PCl5 or PCl3 or SOCl2 Cl- Acylchloride

Acylchlorides are readily hydrolyzed by water, so

the reaction should be carried out using a dry or-
ganic solvent. The inorganic reactants used are also
subject to hydrolysis in water.

Alcohol, e.g. CH3CH2OH The alcohol Ester

molecule
 680

The reaction is reversible and very slow without a

catalyst. An acid or alkali is required to catalyze the
reaction. It is also necessary to heat or warm the
reaction mixture. The reaction is accompanied by a
sweet smell due to the formation of an ester. Also,
an oily layer may appear on the surface of water
due to formation of insoluble ester.

LiAlH4 Hydride ion, Primary alcohol

H-

LiAlH4 is powerful enough to reduce carboxylic

acids all the way to primary alcohols. The nucleo-
phile here is the hydride ion, which is produced
insitu from LiAlH4. LiAlH4 must be used in dry
ethersince decomposes in water.

8.1.4 Ethanoic acid

This is a colourless liquid, which is soluble in water in all proportions. It is responsible for the
characteristic smell of vinegar. FGI 7 chart shows some simple methods of preparing ethanoic acid
under lab conditions.
 681

FGI 7
Possible synthetic routes for the preparation of ethanoic acid

9
Cl2(g)
CH4 CH3 Cl
UV 8
KCN(aq)
CH3 CONH2 reflux
CH3 CN
10 7
6
H2O CH3 COOH H2SO 4(aq)
CH3 COCl CH3 COOCH2CH3
ethanoic acid heat
5 1
KMnO 4(aq) 2 KMnO 4(aq)
CH3 CHO
CH3 CH2OH

3 reflux NaOH(aq) 4
HCl
CH3 CH2Cl CH2 = CH2
ethanol

Small scale preparation of carboxylic acids can be carried out in the following ways. For examples, refer to
FGI 7 . The numbers given in brackets refer to a reaction in this diagram.

 oxidation of primary alcohols (2)

 oxidation of aldehydes (5)
 hydrolysis of acyl chlorides (6)
 hydrolysis of nitrile (7)
 Hydrolysis of amides (10)
 682

8.1.5 Benzoic acid

Benzoic acid is a white crystalline solid which dissolves only sparingly in water.
 It is solid because of the presence of strong hydrogen bonds and strong Van der Waals forces. The
strength of the Van der Waals forces is a result of the presence of a large number of electrons in
the molecule.
 It is poorly soluble in water because of the presence of the large non-polar benzene ring.

Some reactions of benzoic acid are shown in FGI 8 chart. For each conversion, make sure you can state
the type of reaction taking place.

FGI 8
Reactions of benzoic acid

Na2CO 3
Br2/AlBr3 PCl5

conc HNO 3 Na(s) Na+

conc H2SO 4
NaOH(aq)
CH3 OH
 683

8.1.6 Methanoic acid and ethanedioic acid

We give special mention to these acids because they undergo a reaction which is not undergone by other
carboxylic acids. We do not expect carboxylic acids to be oxidized because they are the end product of an
oxidation sequence, for example

[O] [O] [O]

CH3CH2OH CH3CHO CH3COOH No further oxidation

When ethanol is added to an acidified solution of KMnO4, the purple colour of permanganate quickly
disappears. A colourless solution with a vinegary smell is produced. Presence of an acid at the end of the
reaction can be verified by adding sodium carbonate. Brisk effervescence occurs due to the liberation of
carbon dioxide. Now consider what happens when the procedure is repeated with methanol instead of
ethanol. First, the permanganate is decolourized, and this is accompanied by effervescence even without
the addition of sodium carbonate. This shows that the final product of oxidation of methanol (methanoic
acid) is oxidized further by the KMnO4, producing carbon dioxide. The half equation for the oxidation of
methanoic acid is shown below.
HCOOH  CO2 + 2H+ + 2e-
Ethanedioic acid undergoes the same reaction with KMnO4
(COOH)2 2CO2 + 2H+ + 2e-

More information: ethanedioic acid

This acid, which is usually known by its non-systematic name, oxalic acid, is a white crystalline
solid, whose formula is shown below.

C
= (COOH) 2 = C2H2O 4
C

This acid is diprotic (dibasic), for example, one mole of the acid requires two moles of NaOH (aq)
for complete neutralization.

(COOH)2 + 2NaOH(aq)  Na2(COO)2 + 2H2O(l)

The salt solution formed (sodium ethanedioate or sodium oxalate) in this reaction can be
separated as a white crystalline solid.Some plants and unripe fruits contain oxalic acid. This is
probably a defense mechanism which makes unripe fruits bitter. This discourages animals from
eating the unripe fruit. As the fruit matures, the concentration of oxalic acid decreases and the
concentration of sugars may increase. This makes the fruit palatable to animals.
 684

The consequence is that the fruit is only consumed when its seeds are mature. When the seeds
are later egested through faeces by the animal they can germinate in new locations.

10.8.2 Esters
These acid derivatives contain the ester group,

1 04 0 .. .. 1 20 0

.. ..
You now know that there are two ways of forming esters
 By reacting a carboxylic acid with an alcohol.
 By reacting an acylchloride with an alcohol
In both cases, the alcohol acts as a nucleophile. Formation of an ester from an acyl chloride is faster and
gives a better yield since an acyl chloride is very reactive towards nucleophiles.

8.2.1 Nomenclature
An ester is named as if it were a salt of a carboxylic acid. The name therefore ends in - oate. The first part
of the name indicates the alcohol from which the ester may have been derived. This part of the name ends
in -yl and has a prefix that indicates the number of carbon atoms present, for example ‘butyl’ indicates
four carbon atoms. Suppose that we wish to name the ester Q below.

Mentally dissect the molecule just after the bridging

O atom. In this way you can easily visualize which
Q
part of the molecule came from an acid and which
came from an alcohol.
bridging O atom

2 4 1
1 3 The name of the ester is therefore
2 Butyl ethanoate
This 3 carbon
This 4 carbon part came from
part came from propanoic acid
butanol
 685

Panel 7 below shows some esters and their names

Panel 7Some esters and their names

methyl methanoate ethyl ethanoate propyl methanoate

positional isomers

methyl benzoate
[dec-5-enyl] ethanoate

8.2.2 Isomerism
 Esters may share the same molecular formula but differ in the position of the ester group. This is
an example of positional isomerism. Ethyl ethanoate and propyl methanoate are examples of
positional isomers.
The structures below represent aspirin, a well known pain killer (analgesic) and its positional
isomer. Study the structures carefully to notice the difference between them. Note that the two
compounds are isomeric esters.

Aspirin - a well known analgesic This positional isomer is toxic

Q
Suggest why the positional isomer of aspirin is toxic.

AThe acidic environment promotes hydrolysis of the ester. One product of this reaction is
methanol, which is poisonous and acts swiftly since its high solubility allows it to be
absorbed easily into the blood.
 686

 An ester has a carboxylic acid with which it shares the same molecular formula. This is an exam-
ple of functional group isomerism. Here are examples

C4H8O2

ethylethanoate (ester) butanoic acid

 It is also possible for esters to exhibit chain isomerism, for example, two chain isomers that share
the molecular formula C4H8O2 are shown below. Chain isomers differ in the number of carbon
chains present.

P Q
ethyl ethanoate

isopropyl ethanoate

Q
Suggest a simple lab test that could help you to distinguish between esters P and
Q.

AAcidify the test substance with sulphuric acid, and then boil the mixture for a few minutes. The
hydrolysis product of P includes a primary alcohol, whilst that of Q includes a secondary alcohol.
When KMnO4 (aq) is added to the reaction vessel, it may or may not be decolourized, depending
on the nature of the alcohol present.

QIn which case is the KMnO4 decolourized? Explain your answer.

8.2.3 Physical properties of esters

 Esters have low melting and boiling points than alcohols and carboxylic acids of
comparable Mr. This is due to the absence of hydrogen bonding between the ester molecules. The
forces of attraction that hold the molecules together are relatively weak permanent dipole - dipole
attractions. Esters are therefore volatile because their molecules easily separate from each other
when a small amount of heat is applied.
 Esters are poorly soluble in water. This is because of the absence of a hydrogen atom which
is bonded to a very electronegative atom (N, O or F). Such a hydrogen atom would be very
electron deficient and so would form a strong hydrogen bond with water, which would facilitate
the dissolving process. Hydrogen bonding with water molecules is possible, but the hydrogen
 687

bonds are rather weak due to the weakly polar nature of the C=O group. In addition, position of
the ester group may restrict hydrogen bonding with water.

8.2.4 Chemical reactions of esters

Two important reactions which occur at the ester group have already been discussed
 hydrolysis
 reduction

Hydrolysis of an ester is a reversible and slow process, for example

H2O
CH3OH
H+(aq)
heat

The reaction is considerably faster in the presence of an alkali or strong acid, which catalyzes the reaction.
When an ester is added to neutral water and heated, at first the ester molecules hydrolyze very slowly, but
after some time, the rate becomes faster, as illustrated in Fig 10.14.

Rate of reaction

Fig 10.14

Time

The phenomenon demonstrated here is known as autocatalysis. This occurs when a product of the
reaction catalyzes the reaction. In this case, the hydrolysis of an ester produces a carboxylic acid, which
dissociates in solution to release hydrogen ions, which actually act as the catalyst. When the concentration
of the H+ ions is large enough, the rate of reaction suddenly increases.

Reduction of an ester requires a powerful reducing agent. This can be achieved by using LiAlH 4. The
reaction results in the formation of two molecules of alcohol per molecule of ester, for example

LiAlH4
CH3CH2CH2COOCH2CH2CH3 CH3CH2CH2CH2OH + CH3CH2CH2OH
ether

Polyesters
These are condensation polymers that contain the ester linkage repeated at regular intervals throughout
the polymer strand.
 688

The monomers of polyester are a dialcohol and a dicarboxylic acid, or diacyl chloride. Terylene®
(Dacron®) is the most common polyester. Its monomers are shown below.

H H
O O
HO C C OH C C
H H HO OH
Ethane-1,2- diol(glycol) Benzene-1,4- dicarboxylic acid,
(terephthalic acid)

The geometry of the monomers allows linear chains to be formed, which are suitable for the synthesis of
fibres. The linear nature of the polymer chains allows them to pack closely, producing strong intermole-
cular forces of attraction between the chains.
The monomers are mixed in a 1:1 ratio and heated at around 180⁰C in the presence of antimony (III) oxide
which acts as a catalyst.The polymerization process involves reaction between the –OH group of the dial-
cohol and the –COOH group of the diacid (esterification). The mechanism of the reaction is nucleophilic
substitution.

H H H O O
HO C C O C C
H H HO OH

dimer
polymer grows ester linkage.

H H O O H H O O
O C C O C C O C C O C C O
H H n H H
A short section of terylene,
Fig 10.15Formation a polyester,
of Terylene showing
®. One repeat repeated ester linkages. A
unit is shown
repeat unit of the polymer is shown in square brackets.
Terylene has regular linear strands which therefore pack closely, giving rise to a crystalline material of
high tensile strength. Terylene fibres are used in the manufacture of fabrics which are crease resistant,
easy to wash, dry and iron.
(Terylene is the ICI trade name. The same polymer is also known as Dacron, which is the DuPont trade
name.)

 Terylene is an example of a condensation polymer.

(i) Its formation is accompanied by the loss of a small molecule, in this case, H 2O
(ii) Each monomer is difunctional. The functional groups of the monomers are polar
(iii) The Mr of the polymer is less than the same of all the monomers involved in forming the
polymer
(iv) The polymer can be degraded back to its monomers by hydrolysis
(v) The polymer chain has three different functional groups; an ester linkage repeated
throughout at regular intervals, a -COOH group at one end, and an -OH group at the other.
 689

 Terylene is an example of a copolymer (heteropolymers) in which the monomers are non-iden-

tical. Most condensation polymers are copolymers. However, condensation homopolymers are
also known.
A homopolymer is made from identical monomers. Each monomer has a carboxyl group at one
end and an alcohol group at the other end. During the polymerization process, monomers must
link with the correct orientation. The -COOH end of one molecule must collide with the -OH end
of the other molecule.

Qpolyester polycaprolactone is a homopolymer made from the cyclic six

The
carbon ester caprolactone . One repeat unit of the polymer is shown .
Deduce the structure of the open chain monomer from which the polymer is
made. Hence deduce the structure of the cyclic ester caprolactone.

polycaprolactone

A
HOCH2CH2CH2CH2CH2COOH
repeat unit
caprolactone

Notes
The repeat unit is obtained from the hydrolysis of the cyclic ester. This reaction opens up the chain as
shown below.

bond breaks

H2SO 4(aq)/boil
 690

10.8.3 Acyl chlorides

These are compounds which contain the group

Here are examples of acylchlorides and their names

ethanoyl chloride benzoyl chloride 4-chloropentanoyl chloride

3-bromo-4-chloro-pentanoyl chloride pentanedioyl dichloride

hex-4-enoyl chloride

8.3.1 Reactions of acyl chlorides

Acyl chlorides are very reactive towards nucleophiles. This is because the acyl chloride group contains two
electronegative atoms, chlorine and oxygen. These two atoms withdraw electrons from the carbon of the
acyl chloride, causing it to have a large partial positive charge. This carbon atom therefore attracts
nucleophiles easily.

Acyl chlorides react with the following nucleophiles

 water (hydrolysis), to form HCl and a carboxylic acid
 ammonia, to form a primary amide.
 a primary amine to form a secondary amide
 phenol to form an ester
 691

 an alcohol to form an ester.

Reaction with water

Acyl chlorides hydrolyze rapidly in water, for example
CH3COCl (l) + H2O (l)  CH3COOH (aq) + HCl (aq)

 Ethanoyl chloride, CH3COCl, is a colourless oily liquid that fumes in moist air due to reaction with
water vapour. It hydrolyzes rapidly in cold water to produce a mixture of two acids. White fumes
of HCl are observed, but if the volume of water is very large, this observation might not be made,
since all of the HCl produced would dissolve in the water.
 The reaction of an acyl chloride produces large amounts of heat. The reaction is very exothermic
because a weaker C-Cl bond in the reactant is replaced by a stronger C-O bond in the organic
product.
 The solution formed after the hydrolysis reaction has a very low pH due to the presence of HCl,
which is a strong acid.

Reaction with ammonia

An acyl chloride reacts with ammonia to form an amide

R C + NH3 R C + HCl

acyl chloride amide

An acyl chloride reacts with a nucleophile (for example water and ammonia) by nucleophilic substitution.
The mechanism for the reaction of an acyl chloride with ammonia is described below.

R C R C
R C
..
..

Acylchlorides react with primary amines to form secondary amides. The mechanism of the reaction is
similar to that of the reaction with ammonia, for example

CH3COCl + CH3NH2 CH3CONHCH3 + HCl

 692

amide group

R C R C
CH3 C
..
..
secondary amide

Note that in a secondary amide the nitrogen atom is bonded to only one hydrogen atom. The second
position is occupied by an R group (aromatic or aliphatic).

Q
What is the structural formula of the organic product formed when ethanoyl
chloride reacts with phenyl amine?

ACH3COCl + C6H5NH2CH3CONHC6H5 + HCl

The structural formula of the organic product is highlighted in the equation. Its structure is
shown below

amide group

Reactions of acyl chlorides with alcohols and phenols

Acyl chlorides react readily with alcohols and phenols to form esters. In this reaction, the Cl atom in the
acyl chloride is replaced by an R-O group from the alcohol or phenol. Here are examples

1. CH3COCl + CH3CH2OH  CH3COOCH2CH3 + HCl

ethyl ethanoate (ester)

2. + CH3 COCl + HCl

3. HCl
2. + CH3 COCl + HCl
693

3. HCl

When you draw the structure of the ester product, recall that the two reactant molecules link through
their functional groups, with subsequent loss of HCl, as illustrated below.

-HCl

acyl chloride alcohol

10.9 Nitrogen compounds

Here we discuss the following compounds, which contain nitrogen
 amines
 amides
 polyamides

10.9.1 Amines
Aliphatic amines contain the group shown below.
107 0
In primary amines, the nitrogen atom is bonded to two hydrogen atoms. In
secondary amines, it is bonded to one hydrogen atom and in tertiary amines; it is
not bonded to any hydrogen atom. Here are examples
C
.N.

pentan-1-amine N-methylpentan-1-amine N,N-dimethylpentan-1-amine

primary amine secondary amine tertiary amine
 694

9.1.1 Nomenclature
The name of a primary amine ends in -amine. The prefix can be written in two ways, for example, ethyl or
ethan. Long chain alkanes are often written with a locator number 1, emphasizing that the amine is at the
end of a chain. However, even if written without a locator number, the name does not cause any confusion
because in unbranched primary amines the -NH2 group is always at the end of the chain. If other
functional groups or branches are present, their positions should be indicated with locator numbers, as
usual. Here are examples of primary amines and their names.

methanamine ethanamine propan-1-amine 4-methylpentan-1-amine

or methylamine or ethylamine

pent-2-en-1-amine phenylamine
decan-1-amine aniline

phenylmethanamine
2,3-dichlorobutan-1-amine

9.1.2 Physical properties

 Amines have melting points that are higher than that of alkanes of similar Mr. This is because of
the hydrogen bonds that exist between the molecules of the amine.
 Low Mr amines are very soluble in water. Once again, this is because hydrogen bonds exist
between the molecules of the amine and water.
 Amines have a characteristic fishy smell. The smell of rotting fish is due to the release of amines.

Preparation of amines
Primary amines can be prepared at a small scale by
 reduction of a nitrile by LiAlH4. Catalytic hydrogenation of the nitrile is also possible
 heating a halogenoalkane with ammonia in a sealed bomb. Nucleophilic substitution occurs
 hydrolysis of a secondary amide
 reduction of a secondary amide
 695

The scheme below shows various methods of preparing ethanamine

1
* CH3CONHCH2CH3

H2SO 4(aq)/ boil

NH3 / heat
LiAlH4 CH3 CH2NH2 in bomb
CH3 CN CH3 CH2Br
dry ether ethanamine

LiAlH4
dry ether
1 a carboxylic acid is also produced
1
*CH *
3 CONHCH2 CH3

 Phenylamine can be prepared from the reduction of nitrobenzene

Sn/conc HCl
reflux

9.1.3 Chemical properties

Chemical behaviour of the amines can be explained in three ways
 Reactions related to the basic nature of the -NH2 group
 Reactions related to the nucleophilic nature of the -NH2 group.
 Oxidation of the -NH2 group by nitrous acid

Basicity of the amines

You may recall the following from Part 1 of this section.
 Amines act as Brønsted - Lowry bases (electron acceptors) due to the presence of a lone pair of
electrons on the nitrogen atom of the -NH2 group.
 Amines, like ammonia, are weak bases. In aqueous solution, some amine molecules react reversi-
bly with water, to form an alkyl or aryl ammonium hydroxide. This hydroxide dissociates
reversibly in water, releasing OH- ions, which are responsible for the basicity associated with
amines. Recall that the basicity of ammonia in water is explained in the same way.
 696

NH3 + H2O NH4OH NH4 + OH-

CH3CH2NH2 + H2O CH3CH2NH3OH CH3CH2NH3 + OH-

 Aliphatic (non-aromatic) amines are stronger bases than ammonia. This is because the alkyl
group pushes electrons towards the -NH2 group. This increases electron density on the N atom of
the -NH2 group. This N atom therefore attracts hydrogen ions with greater ease. The strength of
abase is measured by its ability to attract and neutralize protons.
 The basicity of a primary amine increases with increasing length of the alkyl chain. This is
because longer alkyl chains have a greater electron pushing effect than shorter ones.
 Phenylamine is a weaker base than ethylamine. This is because the benzene ring has an electron
withdrawing effect. This reduces electron density on the -NH2 group. In turn, this decreases the
ability of the nitrogen atom of the -NH2 group to attract hydrogen ions.

..
CH3 CH2 N ..

ethylamine - electrons are phenylamine - electrons are

pushed towards the -NH2 pulled away from the -NH2 group
group.

 An amine is neutralized by a strong acid to form an alkyl or phenyl ammonium salt, for example

CH3CH2NH2 + HCl CH3CH2NH3+Cl-

ethy lammonium chloride

+ HCl

pheny lamine pheny lammonium chloride

Diazotization
This is a reaction in which the -NH2 group of an amine is converted to the -N2+ group. This conversion is
achieved by using nitrous acid, HNO2 (aq), generated insitu from the reaction of NaNO 2(s) and
concentrated HCl. The reaction is particularly important in aromatic amines. Recall that in this reaction
nitrous acid acts as an oxidizing agent.
 697

Conc HCl
NaNO 2 + Cl-
< 50C benzene diazonium
salt

 This is an oxidation reaction since the -NH2 group losses hydrogen atoms.
 The organic product is a salt which contains the benzene diazonium ion, C 6H5N2+. This salt is
unstable, so the reaction is carried out under freezing conditions to prevent further reaction of the
salt.
 The benzene diazonium ion is a very important intermediate in the synthesis of many other
substances, including phenol, benzene nitrile and chlorobenzene. These conversions of the
benzene diazonium ion into other substances are known as the Sandmeyer reactions(Fig 10.14 ).
In these reactions, temperature is raised to 100C to promote the replacement of the -N2 group on
the benzene ring with another group. With cuprous salts (copper (I) salts), some of the reactions
can even be occur at 00C. These salts catalyze the reactions.

CuCl H2O
HCl 100C
1 0 0C phenol

CuCN 1 0 0C

Fig 10.14 Sandmeyer reactions

The Sandmeyer reactions provide a method for introducing groups into the benzene ring where direct
methods are not possible, for example, phenol cannot be prepared by simply mixing benzene and an alkali
such as NaOH. Both the benzene ring and the hydroxide ion are electron rich, so instead of reacting, they
tend to repel.

Diazo dyes
The diazotization of phenylamine is a very important step in the manufacture of synthetic dyes known as
diazo dyes. The reaction involves coupling of the diazonium ion with a phenol or a phenylamine. Consider
the synthesis of the dye Sunset Yellow, which is used as a food colourant, for example, it is partly
responsible for the orange colour of Fanta.
 698

Na+ - -
Na+
Sunset Y elow

The coupling reaction which produces a diazo dye is actually an example of electrophilic substitution. The
benzene diazonium ion replaces a hydrogen atom on the phenol or phenyl amine. The mechanism for the
formation of Sunset Yellow is shown below.

1 2
2 3
-
3 4
- A phenol: The OH group directs
attack to carbon 2 and 4, but
benzene diazonium ion: carbon 4 is unavailable, so the
Electrophile electrophile attacks position 2 (ortho)

-
-

intermediate

+ H+

Na + - -
Na +
Sunset Y elow

 The benzene diazonium ion has a positive N2+ group, which makes it electrophilic in nature.
 The benzene diazonium electrophile attacks and couples with an electron rich benzene ring. The
benzene ring attacked by the electrophile is activated by presence of a ring activating group such
as -NH2 (or its derivatives) or -OH (or its derivatives). These ring activating groups direct the
incoming electrophile to position 2 or 4. However, if position 4 (para) is free, it is the one attacked
because the product formed has less crowding of groups.
 699

 A diazo dye has the group -N=N- bridging two benzene rings.

Diazo dyes can also be synthesized by coupling benzene diazonium ion with a phenyl amine. An example
of a dye that can be made in this way is methyl orange, which is commonly used as an acid-base indicator.

methyl orange

You can easily recognize a diazo dye because it has an N=N group bridging two aromatic groups, for
example, you can ‘split’ methyl orange as shown below to identify the reactants from which it is made.

2 3
1 4 -

2 3
benzene diazonium ion:
arom atic tertiary Electrophile, attacks carbon
am ine: 4 of the aromatic amine
The amine group directs
attack to carbon 4

In this analysis, you split the diazo dye so that one part is an aromatic group that bears a ring activating
group, for example the -N(CH)3 group in methyl orange, and the other part is the electrophile (benzene
diazonium ion).

Diazo dyes have a number of uses, including

 as food colourants
 for dyeing cloth
 as acid base-indicators

The use of diazo dyes for dyeing cloth

A diazo dye sticks well to the cloth if its molecules have a high affinity for the fibres in the cloth. The exact
nature of the chemical interactions that bind the dye molecules to the fibres in the cloth depends on the
chemical nature of the cloth and the dye.
 700

 Some dyes have charged groups, for example, the -SO3- group. Such dyes have a strong affinity for
cloth fibres which also carry charged groups
 Some fabrics, for example, those made from cotton, contain fibres that contain many chemical
groups that can participate in hydrogen bonding. A cotton fabric contains cellulose fibres that
contain a very large number of -OH groups. For a dye to stick well to such a fabric, it must also
contain groups that can form hydrogen bond with the cellulose fibres.
 If a dye is made up of non polar molecules, it binds well to cloth that contains relatively non-polar
fibres. The dye molecules interact with the cloth fibres through Van Der Waals forces.
 Some dyes stick to the cloth by forming strong covalent bonds with the fibres in the cloth.

Amines as nucleophiles
The nitrogen atom of the -NH2 group of an amine bears a lone pair of electrons which makes it a
nucleophilic centre. Amines therefore react with organic compounds that bear an electron deficient
carbon (Cδ+), for example, halogenoalkanesand acylchlorides. In both cases, nucleophilic substitution
takes place.

Reaction with halogenoalkanes

Consider the reaction of ethanamine with bromoethane.

heat in
CH3CH2Br + CH3CH2NH2 CH3CH2NHCH2CH3 + HBr
sealed bomb

 The reaction results in the formation of a secondary amine. This reaction is similar to the
reaction of a halogenoalkane with ammonia, in which a primary amine is formed.
 The N atom of ethylamine acts as the nucleophilic centre. It attacks the carbon atom of the C-Br
bond. This bond is polar and so its carbon atom carries a partial positive charge. It is susceptible
to attack by nucleophiles.
 The mechanism of the reaction is outlined in Fig. Notice that the Br atom in bromoethane is
substituted by a CH3CH2NH- group of ethanamine. One hydrogen atom from the amine group
combines with Br to form HBr.
 701

δ+ δ- C
CH3 CH2 N.
. C
Br
CH3 CH2 N
A new N to C bond begins to form
At the same time, the C-Br bond
begins to break.
Very unstable transition state . Note the positive charge
on the N atom, and that the carbon atom of the C-Br
bond is now bonded to five groups. This is what causes
the transition state to be very unstable. An N-H bond and
the C-Br bond immediately undergo heterolysis.

Secondary amine (CH3 CH2NHCH2CH3 )

C
The N atom is bonded to two R
groups CH3 CH2
..N

Reaction of amines with acylchlorides

 Acyl chlorides are very reactive towards nucleophiles. You should be able to explain this fact.
When an acyl chloride reacts with an amine, the product formed is a secondary amide. Ammonia
reacts in a similar way, but the product of the reaction is a primary amine (see reactions of
acylchlorides).

10.9.2Amides and polyamides

9.2.1 Amides
These compounds contain the amide group, CONH 2. Examples of amides and their names are shown in
the following panel.
 702

ethanamide propanamide urea benzamide

2-ox opropanamide pent-3-enamide piperidin-2-one

 Low Mr amides such as urea are soluble in water through hydrogen bond formation.
 Hydrogen bonds exist between molecules in a pure sample of an amide. Both the -NH2 group and
the oxygen atom of the amide group can participate in hydrogen bonding. This increases the
extend of hydrogen bonding, leading to relatively high melting and boiling points.
 In water, amides are weakly alkaline. In fact, the solution is almost neutral. For this reason,
amides are not usually classified as bases. Contrast with amines which show basic behaviour.
Amides are very weak bases because the lone pair of electrons on the nitrogen atom of the amide
group is partially pulled by the electronegative oxygen atom. The reduced electron density at the
nitrogen atom implies that the nitrogen atom can not easily pick up a proton from solution.
 Amides undergo acid or alkaline hydrolysis, resulting in the breaking of the C-N bond, for
example

HCl(aq)
1.
boil

NaOH(aq)
2 2 NH3 + CO2 (or Na 2CO3)
boil

urea

NaOH(aq)
3 boil + NH3
pent-3-enamide
pent-3-enoate

 Amides are reduced to a carboxylic acid and ammonia by LiAlH 4, for example

LiAlH4
+ NH3
Dry ether
 703

 An amide can be prepared from the reaction of an acyl chloride with ammonia. This is an example
of a nucleophilic substitution reaction, for example
CH3COCl + NH3 CH3CONH2 + HCl.

NH3(l)
cold
cy clohex anecarbony l chloride
No heating is required and the yield is good since acyl chlorides are very reactive towards
nucleophiles.

9.2.2 Polyamides
These are condensation polymers that contain the amide linkage that repeats at regular intervals.
Naturally occurring polyamides include proteins and silk fibroin, which makes up the strands in a spider
web.

Nylon
Nylon is in the same class (polyamides) as proteins. However, the two polymers are formed from totally
different monomers, and so their properties are also remarkably different.

The monomers
Recall that a large number of condensation polymers are co-polymers (heteropolymers), which
meansthey are formed from different monomers. An amide is an organic compound formed from a
carboxylic acid (or acyl chloride) and an amine.
The monomers below are used in the synthesis of nylon 6.6, which is an example of a copolymer.

Hexane-1, 6-dioic acid Hexane-1, 6-diamine

(adipic acid)

Condensation polymerization occurs between two functional groups that have an affinity for each other.
In this case, the carboxylic acid group on one monomer reacts with the amine group on the other
monomer. This is essentially a nucleophilic substitution reaction. The –NH₂ group of the diamine acts as
a nucleophilic centre and attacks the carbon atom of the diacid. This carbon attracts nucleophiles because
it is relatively positively charged by virtue of it being bonded to two oxygen atoms which are electron
withdrawing.
 704

The step shown above results in the formation of a dimer, which contains three functional groups; an
amine group on one end, a carboxylic acid group on the other end, as well as an amide group. The
polymer can therefore attract another monomer, resulting in the formation of a trimer. The addition of
monomers therefore continues in steps. It is for this reason that condensation polymerization is also
referred to as step growth polymerization. The diagram below shows a short section of nylon 6.6, so
called because both of the monomers used in its synthesis contain six carbon atoms. A repeat unit of the
polymer is shown in square brackets.

A strand of the polymer has three functional groups: the amide linkage repeated at regular intervals
throughout the length of the polymer, a carboxylic acid group at one terminal of the chain, and an amine
at the other terminal. Recall that one chain is simply one molecule of the polymer. In practice a compound
cannot be made up of one molecule. Thus in one fibre of nylon, there are many chains packed together
and held by intermolecular forces. In nylon, the important intermolecular forces holding the chains to-
gether arehydrogen bonds. These bonds are established between the C=O groups on one chain and the
–NH groups on the adjacent chain.

O O O
C N C N CC N
H H H
Hydrogen
bonds
O O O
C N C N C N
H H H
Hydrogen bonds holding separate chains
in nylon.

Nylon is a very strong polymer because of the large number of hydrogen bonds between the chains.
 705

The discovery of nylon by Carothers in 1935opened a new era in the textile industry. Before the discovery
of nylon, fabrics were made of plant and animal fibres, which were not so strong and were prone to decay.
Nylon quickly gained popularity because of its high strength and wash-and -wear nature (the fabric dries
quickly). Because of its high strength, very fine strands of nylon could be made. These were used in the
manufacture of sheer fabrics (‘see - throughs’) and the almost invisible socks which became an instant hit
among western women. Because of its low weight and high tensile strength, nylon is also used to make
rope, fishing lines and bristles for cleaning brushes and tooth-brushes. Nylon has the additional advan-
tage of being resistant to decaying.

Nylon 6
Nylon-6,6, is a copolymer. It is made from two different monomers.Nylon 6 is an example of a conden-
sation homopolymer. The monomers which link up during the polymerization process are identical. The
monomer for nylon 6 is 1-aminohexanoic acid, which in turn isobtained by heating caprolactam, a
cyclic amide, in the presence of water. This causes hydrolysis of the amide bond, so that the chain opens
up, as shown below.

The C-N bond breaks, water is added

2600C
H2NCH2CH2CH2CH2CH2COOH

caprolactam 1-aminohexanoic acid

The monomer has an amine group on one end and a carboxyl group on the other. The monomers are
therefore able to react by linking ‘head to tail’, so that the amino group on one molecule reacts with the
carboxylic acid group on another molecule, as shown below.

Notice the similarity in structure with nylon-6, 6. Nylon -6 is softer and has a lower melting point than
nylon -6, 6.

Proteins
Proteins are polyamides that are made up from monomers known as amino acids. The amide group in
proteins is often referred to as the peptide linkage. Proteins are discussed in greater detail in section 4.1
(Chemistry of Life).
 706

Questions, solutions and discussions

Q1(a) Polyvinyl acetate, PVA, is a useful adhesive for gluing together articles made from wood,
paper or cardboard. The monomer of PVA is ethenyl ethanoate, B.

PVA is formed from B by the process of addition polymerization.

(i) Draw a section of the PVA molecule containing at least 2 monomer molecules, and
identify clearly the repeat unit.

The ester B can be hydrolyzed in the usual way, according to the following equation.

+ H2O +

(C2H4O)

(ii) Use this information to suggest a possible structure for C and draw it in the box
above.

When substance C is extracted from the product mixture, it is found that it does not
decolourize Br2(aq), but it does form a pale yellow precipitate with alkaline aqueous
iodine.

(iii) Suggest a structure for C that fits this new information.

(iv) Suggest a confirmatory test for the functional group in the structure you have drawn
in (iii). Your answer should include the reagent you would use and the observation
you would make.

(b)The following diagram represents a section of another polymer.

 707

(i) On the above formula draw brackets, [ ], around the atoms that make up the repeat unit of
this polymer.

(ii)Name the functional group in polymer D.

(iii) Suggest and draw the structure of the monomer, E, that could form this polymer.

(iv) What type of polymerization is involved in making polymer D from its monomer?

(v)What is the relationship between the repeat unit of polymer D and the repeat unit of
PVA?

(c) Monomer E exists as two stereoisomers. Heating either isomer with Al2O3 gives a mixture of two
unsaturated carboxylic acids F and G, which are stereoisomers of each other.

(i) Name the type of stereoisomerism shown by compound E.

(ii) Suggest structures for F and G, and name the type of stereoisomerism they show.
9701/43/M/J/2011

Solutions
708
 709

(a) (i)

(ii) C : CH2=CHOH

(iii) C is CH3CHO

(iv) Reagent: 2,4- DNPH , orange crystals [of a hydrazone] are formed
OR use Fehling’s solution: Brick red precipitate [of Cu2O] is formed
OR use Tollen’s reagent : A silver mirror is formed e.t.c

(b) (i)

(ii)ester

(iii)E is CH3CH2CH (OH)CO2H (2-hydroxybutanoic acid)

(iv) condensation polymerization

(v) they share the same “molecular” formula, C4H6O2

(c) (i) optical isomerism

(ii)

cis-trans / geometrical isomerism

 710

Q2 (a) Compound G can be synthesized from benzene by the route shown below.

HNO3 +
H2SO4 step 2
55 0 C

step 3

step 5 step 4

(C6H5N2Cl)

(i) Name the functional group formed in step 5.

(ii) Draw the structures of the intermediates H and J in the boxes above.

(iii) Suggest reagents and conditions for steps 2 to 5

(b) In a reaction discovered just over 100 years ago by the German chemist Karl Fries, compound G is
converted into compound K when it is heated with AlCl3.Compound K is a structural isomer of G.

C8H8O2

Compound K is a 1, 4-disubstituted benzene derivative. It is insoluble in water, butdissolves in

NaOH(aq). It gives a white precipitate with Br2 (aq), and a yellow precipitate with alkaline aqueous
iodine.

(i) What is meant by the term structural isomerism?

(ii) Use the information given above to name two functional groups in compound K.

(iii) Suggest the structural formula of K, and draw it in the box above.

(iv) Suggest structures for the aromatic products of the following reactions.
 711

I 2 + NaOH(aq) NaOH(aq)
Br 2(aq)

9701/41/O/N/2010

Solutions
(a) (i) ester

(ii) H is nitrobenzene

J is phenyldiazonium chloride
N2+Cl-

(iii) Step 2: Sn/Zn + HCl or H2+ named catalyst or NaBH4/ LiAlH4 or Na + ethanol

Step 3: NaNO2+ concentrated HCl at < 50C

Step 4: heat/warm to T > 10°C

Step 5: CH3COCl

(b) (i) Compounds that have the same molecular formula, but different structures

(ii) Phenol , ketone

(iii) K is 4-ethanoylphenol
 712

I 2 + NaOH(aq) NaOH(aq)
Br 2(aq)

CO2-

2. Menthone, C10H18O, is a cyclic ketone that occurs in oil of peppermint.

(a) Use asterisks (*) on the formula above to identify any chiral centres in the molecule of
menthone.

(b) Menthone can be reduced to menthol, which can be dehydrated to a mixture of two alkenes, L
and M.
 713

(i) Suggest reagents for steps 1 and 2.

(ii) Suggest structures for L and M and draw them in the boxes above.

(c) When heated with concentrated, acidified KMnO4 (aq), one of the two alkenes L or Mproduces the
dicarboxylic acid N.

(i) Give the letter of the alkene that produced N by this reaction.

(ii) Suggest the structure of the product, P, of the reaction between the other alkene
you have drawn and hot concentrated acidified KMnO4.

(iii) Suggest one chemical test that would enable you to distinguish between N and P. State any
observations that would be made.

(d) Chlorocyclohexane can be prepared by bubbling HCl (g) through a solution of cyclohexene.

+ HCl

Suggest the mechanism of this 2-stage reaction by means of a diagram. Include all whole or partial
charges, and represent the movements of electron pairs by curly arrows.
9701/41/O/N/2010

solutions

(a)

* *

(b) (i) Step 1 LiAlH4or NaBH4or Na + ethanol or H2+ Ni

Step 2 heat with Al2O3/ porous pot or conc. H2SO4/ H3PO4
(ii)
 714

(c) (i) M

(ii) 3,7 -dimethy l-6-ox o-octanoic acid

(iii) 2, 4-DNPH, orange precipitate is formed withP(none with N)

(d)

δ+ δ-

+ Cl-
..

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1.Menthol and menthone, the main constituents of oil of peppermint, can be made synthetically from
thymol by the following route.

(a) State the type of reaction ofReaction I and reactionII

(b) Suggest one test for each of the three compounds that would give a positive result with the stated
compound but a negative result with both the other two compounds. State the observation made in
each case.

thymol
menthol
 715

menthone

2(a) Complete the following equations showing all the products of each of these reactions ofphenol.
Include reaction conditions where appropriate in the boxes over the arrows. If no reaction occurs
write no reaction in the products box.

+ Na

+ NaOH

+ CH3CO2H

+ Br 2

(c) The analgesic drug paracetamol can be synthesized from phenol by the following route.
Suggest reagents and conditions for the each of the three steps, and suggest the structure
of the intermediate H.
 716

step 1 step 2 step 3

NHCOCH3

9701/43/M/J/2011

10.10 Testing for functional groups

By now , it is hoped that you can state the reagents needed to test for the presence of certain functional
groups, as well as describe and explain the observations made. Here we summarize the key tests for the
different functional groups.

Functional Test Observations Notes

group

(i) Add ice cold KMnO4 KMnO4 immediately Aldehydes , secondary

decolourized alcohols and primary
C=C
alcohols give the same
result, but the KMnO4
must be warm to get
immediate results.

(ii) Add liquid bromine Bromine decolourized Br2 adds to the double
bond through
electrophilic addition.

(a) Primary, (i) Add PCl5 White fumes produced HCl is produced.
secondary  Carboxylic
and tertiary acids give the
alcohols. same result, but
the fumes are
copious.
 717

(ii) Add Na(s) Sodium metal sinks, H2 produced. Carboxylic

bubbles of gas are acids and phenols give
produced, hissing sound the same result but with
is heard. these compounds, the
reaction is more
vigorous.

(i) Add warm acidified KMnO4 decolourized Primary alcohol is

KMnO4 oxidized to carboxylic
acid

(ii) Add warm acidified Orange K2Cr2O7 turns Primary alcohol is

(b) Primary and K2Cr2O7 green oxidized to carboxylic
secondary acid, K2Cr2O7 is reduced
alcohols to green Cr3+.

(iii)The Cream precipitate I2/NaOH is an oxidizing

triiodomethane formed if the alcohol reagent. Oxidation of
(iodoform) contains the group alcohol occurs, leading
test(warm mixture CH3CH(OH)- to breaking of a C-C
of I2 and NaOH(aq)) bond. The yellow
precipitate is CHI3
(triiodomethane).
 Ethanol, a
primary alcohol,
gives a positive
test.
 Propa-2-ol, a
secondary
alcohol, gives a
positive test.
 Tertiary
alcohols cannot
give a positive
result.

Lucas Test: Tertiary alcohols are

(c) Tertiary alcohols Add concentrated HCl easily detected because
(aq) and Zinc (which is they give an almost
then converted by the acid instant cloudiness due
to ZnCl2) to the test to formation of the
solution and heat over a insoluble tertiary
boiling water bath. halogenoalkanes,
(R)3CCl.
(For primary and
 718

secondary alcohols,
cloudiness does not
easily appear).

Carbonyl compounds (i) Add 2,4-DNPH Orange crystals formed Sensitive test for
Carbonyl compounds.
(ii) Triiodomethane test This gives a positive Orange crystals of a 2,4-
(aldehydes and
(cream ppt ) result with dinitrophenylhydrazone
ketones)
carbonyl compounds are formed.
which contain the group  Ethanal , an
CH3CO- aldehyde, gives
a positive test.
 Propanone, a
ketone, gives a
positive test.

(i) Fehling’s solution Brick red precipitate Aldehyde oxidized to

(Cu2+ in NaOH(aq) formed carboxylic acid. Brick
and tartarate ions) red precipitate is Cu2O

(ii) Tollen’s reagent Silver mirror deposited Aldehyde oxidized to

(Ammoniacal on the walls of the carboxylic acid. Ag+ is
Aldehydes solution of AgNO3) reaction vessel reduced to Ag metal.

(iii) KMnO4/H+/warm KMnO4 decolourized Aldehyde oxidized to

carboxylic acid.

(iv) Cr2O72- / H+), warm Orange Cr2O72- turns Aldehyde oxidized to

green carboxylic acid. Cr2O72-
reduced to Cr3+.

(i) Add PCl5 Copious white fumes HCl produced. Alcohols

produced give the same result, but
production of fumes is
less copious.

(ii)Add ethanol, acidify A pleasant fruity smell is An ester is produced

Carboxylic acids with a mineral acid, detected
for example, H2SO4
and warm.
 719

(iii) Add sodium metal Brisk effervescence Hydrogen produced.

Alcohols and phenols
produce the same result,
but the reaction is less
vigorous.

(iv) Add sodium Brisk effervescence CO2 produced. Good

carbonate method to distinguish
carboxylic acids from
phenols and alcohols.

(v) Use of indicators, Blue litmus paper turns Carboxylic acids are
for example blue litmus red. acidic enough to give
paper clearly visible colour
changes with acid-base
indicators

Add a small amount of Copious white fumes HCl produced due to

Acyl chlorides cold water produced hydrolysis.

Esters Boil in HCl(aq) for a few White fumes are Esters are sweet
minutes, then add PCl5 or produced upon addition smelling oils that are
KMnO4. of PCl5 hydrolyzed to produce
an alcohol and a
KMnO4 decolourized carboxylic acid.

(a) Add (i) Primary amines HNO2 acid (generated

NaNO2/concentrated produce a product insitu) oxidizes primary
HCl at 100C which decolourizes amines to diazonium
Aliphatic amines
KMnO4. Bubbles of a salt which immediately
colourless gas are also hydrolyses in water,
produced producing a primary
alcohol and liberating
(ii) Secondary amines hydrogen gas.
produce a yellow oil
Secondary amines are
(iii) For tertiary oxidized to oximes
amines, changes are not yellow oil)
immediately visible.
 720

(b) Use red litmus Paper turns blue Amines, just like
paper ammonia, are basic
enough to change blue
litmus paper. In fact,
aliphatic amines are
stronger bases than
ammonia.

Add A bright dye formed HNO2 (generated insitu)

NaNO2/concentrated oxidizes phenyl amine
Phenylamine group to diazonium ion
HCl at 00C. Add
phenol and warm to (diazotization), which
10 0C. couples with phenol to
form a brightly coloured
diazo dye.

Primary amides Boil in NaOH(aq) for a Ammonia (pungent Hydrolysis produces

few minutes, acidify then smell) produced upon ammonia and a
add PCl5 carboxylic acid
boiling with NaOH.
Copious white fumes
produced upon addition
of PCl5 to the acidified
solution.

Phenols Add FeCl3 (aq) Violet solution formed Phenol acts as a ligand
and forms a violet
complex with Fe3+.

Benzene Not easy to test under lab Small proportion of

conditions. carbon in benzene leads
Benzene is a sweet to incomplete
smelling liquid, combustion, resulting in
immiscible in water, and the formation of soot.
which burns with a smoky
flame
 721

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1. Suggest reagents that can be used to distinguish between the following pairs compounds. Explain
clearly the observations made in each case.
(a) Ethanol and phenol
(b) Ethanoyl chloride and chloroethane
(c) Phenol and phenylamine
(d) Butanone and butanol
(e) Butene and butane
(f) Ethanamide and ethanoyl chloride

2. (a) Thymoland menthol are two indicators which can be used in acid-base titrations.
Their structures are as shown below,

thy mol menthol

Compare and contrast the reactions ofthese indicators with
(i)sodium metal.
(ii) aqueous sodium hydroxide.
(iii) acidified potassium dichromate.
(iv)hot aluminium oxide.
Your answer should include the type of reaction undergone and the structures of the organic
products formed in each case.

(b) Would you expect thymol to be more or less acidic than phenol. Explain your answer.
9189/o1/O/ N/2003

3. A compound X hasan empirical formula CH3O. In an experiment, 0.20g of Xwas vapourized at 400K
and the vapour produced had a volume of 107.2cm3 at 100kPa pressure.

(a)What is themolecular formula of X?

(b)When X was mildly oxidized it produced a dicarboxylic acid. Deduce thestructure of X.

(c)X reacts with excess sodium giving off a gas. Write a balanced equation for this reaction.
 722

When Xwas reacted with benzene-1,4- dicarboxylic acid it formed a type of fibre used in clothing.
Deduce the structure of this fibre.9189/o1/O/ N/2003

4. The pop sensation Michael Jackson died as a result of a Propofol overdose. The structure of this drug
is shown below.

propofol

(a) What is the molecular formula of propofol?

(b) What type of reaction occurs when propofol reacts with bromine liquid. State two observations
made and draw the structure of the product .

(c) Refluxing propofol with acidified potassium permanganate for a long time results in the
formation of a compound P. 0.2 moles of P reacts with 0.4 moles of sodium hydroxide.
Suggest the structure of compound P.

5. Mandelic acid is a derivative of a compound found in almonds. It has many medicinal uses, including
treatment of infections of the urinary tract.

m andelic acid

Mandelic acid exists as a pair of stereoisomers.

(a) Explain clearly how or why stereoisomerism is possible in Mandelic acid.

(b) Explain how Mandelic acid reacts with each of the following reagents. In each case state the
type of reaction undergone and the observations made , if any.

(i) Sodium metal

(ii) NaOH

(iii) Hot acidified KMnO4

(iv)Phenol in an alkaline solution of NaOH

6. The bombardier beetle (Carabidae), when disturbed by a predator, ejects a boiling noxious chemical
spray from glands in its abdomen. The beetle stores two reactant compounds, hydroquinone and
hydrogen peroxide, in separate chambers at the rear of its abdomen.When the beetle is threatened ,
 723

muscle contraction forces the two reactants into a reaction chamber which contains enzymes that
drive the highly exothermic reaction labeled (i)below.

... (i)

The sudden increase in pressure in the reaction chamber forces out a boiling spray of hot irritating
chemicals into the face of the enemy.

(a) Draw a clearly labeled energy profile for reaction (i).

(b) Suggest the formula of the other product of this reaction.

(c) What type of reaction is this?

(d) Suggest one chemical test to distinguish between quinone and hydroquinone. Explain clearly how
your test works.

7. The major psychoactive chemical in marijuana is tetrahydrocannabinol (THC).

(a) Mark with an asterisk (*) any chiral centre(s) in THC.

(b) Explain how the presence of chiral centres in THC implies that it can exist in more than one
different forms.

(c) State the type of reaction undergone when THC reacts with each of the following reagents. In each
case, state the observations made and draw the structures of the organic products.

(i) NaOH
(ii) Cold alkaline KMnO4
(iii) Hot concentrated KMnO4
(iv) Liquid bromine.
 724

8. Many health reform activists refuse to eat eggs because they claim it contains the ‘harmful’ compound
cholesterol. What is not usually taught to these people is that cholesterol is a very important chemical
in cell structure, where it helps to regulate fluidity of the cell surface membrane. In addition,
cholesterol is required for the synthesis of many important compounds, including the principal male
sex hormone, testosterone.

(a) How many chiral centres are present in

(i) Cholesterol

(ii)Testosterone

(b) Suggest a simple test that could help you to distinguish between cholesterol and testosterone.
State the reagent(s) needed as well as the observations made with one or both of the compounds.

9. Many foods we eat would poison us, were it not for the the efficicient working of the liver and kidneys
in regualting the concentrations of certain substances in the blood that would lead to poisoning if
present above the normal level. People with kidney failure are not allowed to eat apples because it
contains malic acid, which could lead to poisoning if its levels are not kept low.

(a) Draw diagrams to show the type of stereoisomerism which is possible in malic acid.

(b) Suggest reagents and conditions, as well as steps needed to convert malic acid into a diamide.

(c) Suggest reagents and conditions required to convert malic acid to compound Q .

Explain why PCl5 is not suitable for this conversion

 725

10. Derivatives of squaric acid are useful in medicine, for example, in the treatment of autoimmune hair
loss. The acidity of squaric acid derives from the fact that its anion is stabilized by resonance.

(a) What is the molecular formula of squaric acid?

(b) Squaric acid has two pKa values. Suggest an equation that represents the second pKa.

(c) Suggest a simple test to show the presence of the carbonyl group in squaric acid. What
observation is made?

(d) Show the structure of the product formed when squaric acid reacts with HCN in the presence of
a trace amount of NaCN.

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 726

11.2APPLICATIONS OF
ANALYTICAL CHEMISTRY

11.2.1 MASS SPECTROMETRY

This powerful analytic technique, which uses a machine known as a massspectrometer, is used to
determine

 The numbers of isotopes in an element, and their relative isotopic masses.

 Relative molecular masses.
 The structure of a compound by piercing together the fragments identified from the mass
spectrum.
 The presence of halogen- containing compounds.
 The number of carbon atoms in a molecule.

A simplified diagram of a mass spectrometer is shown below.

Particles accelerate
in an electric field

Ionisation
chamber

Vaporised Electromagnet
sample
Electron gun

To vacuum pump

Detector

Amplifier

Chart recorder
 727

The sample is introduced into the machine in its gaseous state. The electron gun produces high speed
electrons which bombard the sample, knocking out electrons from atoms or molecules of the sample. An
atom or molecule M loses a single electron to form a positive ion, M⁺.

M (g) → M⁺ (g) + e-
The positive ions formed are then accelerated through an electric field and eventually pass through a
magnetic field, which will deflect them from their path of straight line travel. The deflected ions pass
through a narrow slit and are collected into a collector plate which is connected to an amplifier. For a
given strength of the magnetic field, only ions of a specific mass pass through the slit and strike the metal
plate. Thus ions of different masses can be collected onto the collector plate by varying the strength of the
magnetic field. As the positive ions hit the plate, they cause a current to flow in the amplifier. The greater
the number of positive ions striking the plate, the greater the current that flows, that is, the current
flowing in the amplifier is directly proportional to the abundance of the positive ions that are collected on
the plate. A computer then generates a mass spectrum which shows the relative masses of positive ions
(collected at different strengths of magnetic field) on the x- axis and abundance of each ion on the
y- axis. Abundance can be expressed in terms of peak height or in terms of percentages.
Fig 11.51 shows the mass spectrum that could be obtained for ethanol.

peak intensity
(height)

Fig 11.51 Mass spectrum

ofethanol

15 17 29 31 45 46
m/e

Q
Work out the species that are responsible for the peaks that are shown in the mass
spectrum in Fig11.51 .

Mass spectra can be used to determine the structure of an organic compound by piercing together the
fragments worked out from the spectra. Another very useful feature of the spectrum is the molecular
ionpeak, M. This peak is generated by the full undissociated molecule of the compound. It therefore has
the highest mass on the spectrum. This mass is the relative molecular mass of the compound being
analyzed. From the mass spectrum in Fig 11.51, we can see that the compound has the relative molecular
mass of 46. If we did not know which compound it was, then we have a starting point in the determination
of the structure of the compound.
 728

2.1.1The M and the M+1 peak

Carbon contains 98.9% C-12 (12C) and 1.1% C-13 by mass. On the mass spectrum of an organic compound,
the molecular ion peak will be located at mass M on the x- axis. There will be another peak one unit away,
which is the M+1peak. The M peak is generated by the molecular ion bearing carbon 12. The M+1 peak
is generated by the molecular ion bearing carbon 13. (C-13 is one unit heavier than C-12). Consider a
compound such as methane. The highest mass peak is due to the molecular ion 12CH₄⁺, which is located at
mass 16 (12 + 4). This is the position of the M peak. However, another peak will be found at mass 17. This
is the M+1 peak, and it is caused by the species 13CH₄⁺. The M+1 peak will have a very small intensity
(very short, very small abundance) because of the very small proportion of C-13 in carbon compounds.

peak height
(intensity) M

M+1

0 16 17
m/e
Fig 11.52 The M and the M +1 peak in the mass
spectrum of methane.
The proportion of C-13 in a carbon containing compound is very small but it increases with increasing
number of carbon atoms in the compound. The number of carbon atoms, n, in a molecule is related to the
intensities (abundances) of the M and the M+ 1 peak by the formula

100 AM+1
n =
1.1 AM

Where AM+1= abundance of M+1 peak and

AM = abundance of the M peak.

Example
A saturated molecule of formula CxHyNO was subjected to analysis by mass spectrometry and
NMR spectroscopy. In the mass spectrum of the compound, the M peak was at m/e = 73 and the
ratio of the heights of the M: M+1 peak was 48: 1.7.
Using the data from the mass spectrum, determine the values of x and y in the formula of the
compound.

Solution
In this question, abundances have been given as a ratio of peak heights. First we find the number of
carbon atoms, n, using the formula
 729

100 AM+1
n =
1.1 AM

Substituting the given abundances,

100
n = (1.7/ 48) = 3.2
1.1

The number of carbon atoms is therefore equal to 3.

The relative molecular formula of the compound is C ₃HyNO, giving it a relative molecular mass of 36 + y
+ 14 + 16, which is equal to 73. The value of y is therefore 73- (36+14+ 16) = 7

2.1.2 The M and the M+1 peak

We have seen that if the mass spectrum of a compound contains an M peak, and another smaller peak one
mass unit away, the M+1 peak, then the spectrum is revealing the presence of two isotopes of carbon, that
is, C-12 and C-13. Sometimes the mass spectrum will show presence of peaks two or four units away from
the M peak. These peaks are designated the M+2 and the M+4 peaks respectively.

The M+2 peak often shows the presence of chlorine in the molecule. The M+4 peak often shows the
presence of bromine.

Consider the compound CH₃Cl. The molecular ion peak, M will occur at a mass of 50.5, showing the
presence of one atom of chlorine in the compound. Check that the mass 50.5 corresponds to the molecular
ion CH₃35Cl+. However, chlorine consists of two isotopes:

Cl-35 75%

Cl-37 25%

These two isotopes differ in mass by two units. The mass spectrum of CH₃Cl will therefore have a smaller
peak two mass units away, corresponding to the molecular ion, CH₃37Cl (Fig 11.53).

peak height
M

M+2

50.5 52.5
m/e
Fig 11.53The M and the M + 2peak on the mass spectrum of
chlorine
 730

If Q
the M peak is 12 cm high, what would be the height of the M +2 peak?

The M + 2 peak would be shorter since Cl-37 is less abundant than Cl-35. In fact the ratio of the
A
M to the M + 2 peaks would be 3:1, reflecting the relative abundances of the two isotopes of
chlorine. The height of the M + 2 peak is therefore 4 units.

If the chlorine compound contains two chlorine atoms per molecule, a third peak, the M+4 peak is
expected in the spectrum, as illustrated in the example below.

Example
How many peaks, having a mass equal to or greater than M, are expected in the mass
spectrum of the compound CH₃Cl₂? What would be the ratio of heights of these peaks?

Solution
Three peaks are expected. These peaks, and their relative masses, have been designated A, B and C below.
Note that the peaks are in the arithmetic order of M, M+2 and M+4.

species relative mass

+
A. CH235Cl35Cl 84 (M)
+ 37 35
B. +
CH235Cl37Cl , CH2 Cl Cl 86 (M+2)
C. +
CH237Cl37Cl 88 (M+4)

The relative intensities of these peaks are 9:6:1, as worked out below.

Peak species Relative peak height

+
A CH235Cl35Cl 3/4 x 3/4 = 9/16
+ 37 35
B +
CH235Cl37Cl , CH2 Cl Cl ( 1/4 x 3/4) x 2 = 6/16
+
C CH237Cl37Cl 1/4 x 1/4 = 1/16

The ratio of the peak heights A: B: C is therefore 9:6:1.

Presence of the M, M+2 and M+4 peaks may also imply the presence of bromine in the compound. This is
because the two isotopes of bromine also differ by two mass units.Bromine consists of two isotopes, Br-79
and Br-81. The relative abundances of these isotopes is approximately 1:1.
 731

How many molecular ion peaks are expected in the mass spectrum of the compound
CHQ
3Br+ ? What would be the ratio of heights of these peaks?

Two peaks are expected, corresponding to the molecular ions CH₃79Br+ and CH₃81Br+. The peaks
A be in the ratio of 1:1. This is the ratio of isotopic abundances of the isotopes of bromine.
would

How many molecular ion peaks are expected in the mass spectrum of the
Q compound CH₃CH₂BrCl?

Three molecular ion peaks may be found in the mass spectrum, due to the species shown below.
A
Molecular ion relative mass relative height of peak

[CH3CH235Cl79Br ]+ 143 3/4 x 1/2 = 3/8

[CH3CH235Cl81Br ]+ 145 (3/4 x 1/2) + (1/4 x 1/2)

appear as
single peak = 4/8
[CH3CH237Cl79Br]+ 145

[CH3CH237Cl81Br]+ 147 (1/4 x 1/2) = 1/8

2.1.3Molecular formula from accurate masses

Very high-resolution mass spectrometry can be used to distinguish between compounds whose Mr values
are very close to each other. This is because the machine can measure m/e ratios to an accuracy of 5
significant figures.
For example, try working out the molecular formula of the two compounds below.

Pentene CH3CH2CH2CH=CH2

Aminopropanonitrile CH3CH (NH2) CN

You might have noticed that the Mr of both compounds is around 70. This is caused by using rounded
figures for the Ar values of the elements present in the molecules. High resolution mass spectrometry
supplies very accurate Ar values. By using these values, it is found that the two compounds have different
Mr values.
 732
Accurate relative atomic masses obtained
from high resolution mass spectrometry

Element Relative atomic masses

H 1.0078

C 12.000

N 14.003

O 15.995

Table 11.4Accurate relative atomic masses obtained by

high resolution mass spectrometry

Use the values in the table above to confirm that the two compounds have Mr values of 70.078 and
70.0543 respectively.

2.1.4 Distinguishing isomers from fragmentation patterns

Two mass spectra are given below for two compounds A and B. The fact that the highest mass peak for
both compounds appears at the same m/e values tells us that the two compounds are isomers. It is
possible to work out the structures of the two compounds by piercing together the different fragments
worked out from their respective spectra.

compound A compound B
C3H6O C3H6O
intensity intensity

43 43
29 58
15 58 15

m/e m/e
The mass spectra of two isomers of molecular
Fig 11.54 mass spectra of two isomers of molecular formula C3H6O formula
C3H6O.

The presence of a peak at m/e 29 in the spectrum for compound B shows presence of the –CH₃CH₂ group.
This group is absent in compound A. We conclude that compounds A and B are structural isomers,
differing in which atom is connected to which. Both spectra contain a peak at m/e 43. We can deduce the
formula of the fragment giving rise to this peak. Using the spectrum for compound B, the relative mass of
the fragment at m/e 43 is 58-29 = 29. The fragment must bear an oxygen atom, since the other fragments
we have considered do not contain the oxygen atom. If we subtract the relative mass of oxygen from 29,
we get 13, suggesting presence of a –CH group. The peak at m/e 43 is therefore due to the –CHO group.
Compound B is therefore an aldehyde. Since the compounds are structural isomers, compound A must be
an ketone.

Compound A CH₃COCH₃ ( propanone)

Compound B CH₃CH2CHO (propanal)

Verify that the formulae do contain chemical groups that give rise to the peaks shown in the spectra.
 733

11.2.2 Nuclear magnetic resonance

spectroscopy
This is a qualitative procedure is used to determine the structure and hence the identity of a compound. It
is particularly useful in the analysis of organic compounds. NMR spectroscopy is a relatively modern
analytical procedure. It is now routinely used in the identification of chemicals such as drugs and in
medicine to locate tumours in tissues.

Nuclear: the technique is based on the spin properties of the proton inside the nucleus.
Magnetic : the proton behaves like a tiny magnet, and this feature is employed in NMR
spectroscopy.

We will study hydrogen atom NMR spectroscopy (1HNMR), which is the simplest case, since there is only
one proton in the nucleus of the H atom. This is the technique routinely used in the identification of
organic compounds.

2.2.1 Magnetic behaviour of the atom

The proton is charged, and it has kineticenergy. Whenever a charged particle moves, it becomes a tiny
magnet, with a magnetic field of a definite magnitude. The proton has two possible spin states, a clockwise
spin, designated +1/2 and an anti- clockwise spin, designated -1/2.

CASE 1: The H atom nucleus in the absence of an external magnetic field

Since the proton behaves like a tiny magnet, with its own magnetic field, it is likely to interact with the
magnetic field of an external magnet. In the absence of an external magnetic field, the two spin states of
the nucleus are degenerate, that is, they are at the same energy level. Since the two states have equal
stabilities, they exist in the ratio of 1:1 in any compound that contains hydrogen atoms. In other words, at
any given moment, the number of atoms that contain protons with a clockwise spin is equal to the number
of atoms that contain protons with an anticlockwise spin,

Energy

+1/2 - 1/2

The +1/2 and -1/2 thespin

Fig 11.55In states
absence are magnetic field, the +1/2
of an external
degenerate in and
the-1/2
absence of are
spin states an of
external
equal energy
mangnetic field.
 734

CASE 2 : The hydrogen atom nuclei in the presence of an external magneticfield

An external magnetic field interacts with the magnetic field of the proton. This external magnetic field
causes the two spin states to split in energy.
 The - ½ state becomes higher in energy (less stable) than the +1/2 (Fig 11.56). The difference in
energy between these two states is ∆E. It should be mentioned at this point that the difference in
energy, ∆E, between the two spin states, is very small. In a sample, there would be more protons
in the +1/2 state than in the -1/2 state. This is because the +1/2 state is slightly lower in energy,
that is, it is more stable.
 The -1/2 state represents protons whose magnetic moment has a direction opposite that of the
external magnetic field. Protons with the +1/2 spin has a magnetic moment which is in the same
direction as that of the external magnetic field.

energy -1/2 against the external

magnetic field

ΔE2
ΔE1

aligned with the external

+1/2
magnetic field

external magnetic field

Fig 11.56 Separation in energy between the -1/2 and +1/2 spin states of a proton due
to the presence of an external magnetic field.

The separation in energy (∆E) between the two spin states increases proportionally with increasing
strength of the external field. Compare ∆E1(weaker strength) and ∆E₂ (stronger external magnetic field)
in Fig 11.56. This fact shall be important in explaining the NMR spectrum of compounds.

CASE 3: The H atom in the presence of an external magnetic field and infra red
radiation
Whenever there is separation in energy between two states, there is capacity for absorption of energy,
causing atoms in the lower state to be promoted to the higher state. Infrared radiation (IR) is absorbed by
hydrogen atoms of a sample which has been subjected to an external magnetic field. Since the separation
in energy between the +1/2 and the -1/2 states is very small, energy of very small frequency (low energy),
is required to excite protons in the lower state to the higher state. This is the reason why IR, which is very
weakly energetic, is used in NMR spectroscopy.
Since the sample absorbs some energy, the IR radiation which emerges from the sample will have a
smaller frequency (less energy) than the light entering the sample. A detector detects this absorption in
energy, and a computer calculates the amount of energy absorbed. The computer then displays the
absorbed frequencies in the form of an NMR spectrum (Fig 11.57).
 735

IR in
recorder
sample cell
source of IR NMR spectrum
sample
IR in IR out IR detector

N S detects absorption
of IR

strong electromagnet

Each peak (signal) on the NMR spectrum represents an absorbed frequency of energy. In most cases,
several peaks are observed, indicating a range of absorptions. This is caused by the presence of different
hydrogen atom environments in the sample. This is illustrated by ethanol:

CH2 environment

H H
OH environment
H C C O
H
H H
CH3 environment

There are three distinct hydrogen environments. Hydrogen atoms sharing the same electronic environ-
ment, for example in the –CH₃ group, absorb at the same frequency, so they will give rise to a single peak.
The number of different hydrogen atom environments is therefore equal to the number of peaks observed.
For ethanol, we therefore expect three peaks in the mass spectrum (Fig 11.58).
Hydrogen atoms on the same C atom share the same environment and will therefore give rise to a single
peak.
Hz
downfield upfield

CH3

CH2
absorption(peak
intensity) (3) TMS
OH
(2) Fig 11.59
(1) Low resolution NMR
spectrum of ethanol

10 0
δ, ppm
 The horizontal axis on the NMR spectrum shows chemical shifts,δ in parts per million (ppm).
 736

The chemical shift is the difference in the strength of the magnetic field at which the protons
absorb and the strength of the magnetic field at which the protons in the reference chemical
(TMS) absorb.δ is measured in units of parts per million (relative to the TMS peak.) Note that the
scale on this axis runs from right to left. The size of the chemical shift is directly proportional to
the energy absorbed. The larger the value of δ, the greater the energy absorbed. From the NMR
spectrum of ethanol above, you can easily see that the -OH proton has the greatest absorption and
the -CH3 proton the least.
 Note the use of the terms up field anddownfield. These terms refer to the strength of the applied
external magnetic field. The recorder records strength of applied magnetic field on the x- axis.
Higher values of the external magnetic field are towards the right, so this direction is upfield.
 TMS (tetramethylsilane) is a reference chemical added to the sample tube in the NMR
spectrometer. The purpose of TMS is to generate a reference signal (the zero mark). The structure
of TMS is shown below:

TMS has been selected as the reference material for the following reasons.

(i)It is chemically inert. It will not react with the sample.

(ii) It dissolves well in the organic sample.
iii)It is volatile and so it can easily be removed from the sample at the end of the analysis.
iv)All of its hydrogen atoms are in the same chemical environment, so they generate one
intense peak, which is easily distinguished from tiny peaks caused by instrumental noise.
v) Its absorption frequency is well below and away from the normal absorptions of other H
atoms, so it does not interfere with signals from the sample.

 The NMR spectrum of ethanol has three peaks, since there are three hydrogen atomenviron-
ments. Number of peaks is equal to number of different hydrogen atom environments.
 The vertical axis represents the absorption (intensity or strength of signal). The intensity of
absorption increases with increasing number of hydrogen atoms in an environment. If the num-
ber of hydrogen atoms is large, then the amount of IR absorbed at a specific frequency on the
x-axis is large. If there are no hydrogen atoms in an environment, then it does not absorb any
energy. Such an environment does not give rise to any peak. This is because in H-NMR spectros-
copy, it is hydrogen atoms that absorb energy.

Ratio of peak heights is equal to ratio of number of hydrogen atoms that give rise to the peaks.

Thus for ethanol the three peaks have heights in the ratio of 1:2:3. The ratio is shown against the
peaks on the spectrum. The OH peak absorbs the greatest frequency (IR actually has waves of
different energies/frequencies. The OH proton absorbs energetic waves, that is, waves of high fre-
quency, as shown by its position on the x-axis).
However, the OH proton only absorbs a small amount of this high energy IR, as shown by its
very short peak. This is because there is only one hydrogen atom absorbing at this frequency.
The CH₃ peak absorbs IR waves of low frequency (low energy), that is, the environment has the
smallest chemical shift on the x-axis. However, this environment absorbs a large amount of this
low energy IR. In other words, the peak is the tallest. This is because the CH 3 environment has the
largest amount of hydrogen atoms.
 737

2.2.2 Explaining position of peaks: shielding and deshielding

Why is it that some peaks (such as the –CH₃ peak) absorb at low frequencies (near the RHS = up field),
and some absorb at higher frequencies (towards the LHS= downfield), for example, the -OH group. The
concept of shieldingand deshieldingis used to explain this observation.

Shielding
The diagram below shows that an electron density exists between the H atom under study and the
external magnetic field. In other words, the hydrogen atom should not be considered as if it were a naked
nucleus. Rather, the nucleus of the hydrogen atom is surrounded by an electron cloud which shields the
hydrogen atom nucleus from the external field(Fig 11.60). The effect is that the nucleus of the hydrogen
atom will feel a smaller strength of the external magnetic field.
The energy gap between the +1/2 and the -1/2 spin
states of the proton depends on the strength of the
ex ternal
magnetic external magnetic field that it feels. The higher the
field effective magnetic field strength felt by the nucleus, the
H
greater the energy gap between the two spin states (Fig
11.61).Shielding by an intervening electron cloud
C reduces the strength of the magnetic field felt by the
nucleus of the H atom. Consequently, the energy gap
between its two spin states would be relatively small.
This electron cloud
shields the proton of the
H atom from feeling
the full strength of the external Fig 11.60 Shielding of a hydrogen
magnetic field atom by an electron cloud around it

The separation in energy, ΔE, between

Energy the +1 /2 and -1 /2 spin states of a proton
is small when the proton feels a weak
external magnetic field due to shielding.

ΔE

Fig 11.61
Effect of strength of
external magnetic
Strength of ex ternal
field on the size of
magnetic field felt by a
ΔE
proton

When the value of ∆E is small, small energies are required to promote the lower +1/2 spin states to the
higher -1/2 states. The resulting peak would be located at a low frequency towards the right hand side on
the NMR spectrum.
 738

If an H atom or group of H atoms is well shielded, it will absorb at low energies. Its value of δ would be
small and the peak would be situated close to the TMS peak.

Shielding of protons is always present in any organic compound, but the extent of shielding differs
depending on the specific environment in which the hydrogen atom is. Electron groups which increase
the density of electrons around the H atom increases shielding and reduce the absorption frequency of the
H atom. These groups include those with a positive inductive effect (electron pushing) effect such as the
alkyl groups.

Electron pushing groups increases shielding and so cause low absorption frequencies, close to the TMS
peak (up field).

Deshielding
This is the reverse of shielding. It is caused by electron withdrawing groups or π systems such as the
benzene ring. Electron withdrawing groups are usually atoms of high electronegativity, for example, the
oxygen atom and the halogen atoms. These atoms have a negative inductive effect, that is, they tend to
withdraw electrons towards themselves. The effect is to reduce electron density between the H atom and
the external magnetic field.The benzene ring also has a deshielding effect. In fact, its deshielding effect is
stronger than that of the electronegative atoms such as oxygen.

The separation in energy, ΔE, between

Energy
-1/2 the +1 /2 and -1 /2 spin states of a proton
is large when the proton feels a strong
external magnetic field due to deshielding.

ΔE

+1/2

Strength of ex ternal
magnetic field felt by a
proton
Fig 11.62 Deshielding increases the difference in energy between the -1/2 and the +1/2 spin
states of a proton. This increases the absorption frequency (chemical shift) of the
protonproton.

Deshielding by the benzene ring

The benzene ring has a strong deshielding effect, which is explained in terms of the relatively strong
induced field created around the benzene ring. The external magnetic field induces the π electrons of the
benzene ring to move in a circular direction. The π electrons thus produce their own secondary magnetic
field, which reinforces the natural magnetic fields of the hydrogen atoms on the benzene ring.
The benzene ring therefore has a strong magnetic field, which deshields the protons bonded to the
benzene ring. The separation in energy, ∆E, between the spin states of the benzene protons is thus
increased, resulting in the absorption of large amounts of energy (downfield).
 739

Fig 11.63 The benzene ring has a strong magnetic field which is a sum of the induced
magnetic field and the magnetic field of the protons in the hydrogen atoms.

Explaining the NMR spectrum of ethanol

Hz

absorption(peak deshielding shielding

intensity)
CH3

CH2
(3) TMS
OH
(2)
Fig 11.64
(1)
NMR spectrum
of ethanol

5 3 1 0

δ, ppm

The hydrogen atom of the -OH group is deshielded by being directly bonded to the electronegative oxygen
atom. This proton therefore absorbs at high frequencies (around 5.0ppm), that is, it is well separated from
the TMS peak.
The -CH₂- protons have a higher absorption frequency than the CH₃ protons. This is because the -CH₂-
group is closer to the electronegative oxygen atom of the –OH group.

Deshielding decreases with increasing distance from the electron withdrawing group.
Thus the absorption frequency of The -CH₂- protons is smaller than that of the OH proton, since the
-CH₂- protons are further from the oxygen atom. The CH₃ group, being the furthest from the oxygen
atom, is the most poorly deshielded (that is, it is the most well shielded) and so it has the smallest
absorption frequency.
 740

How many peaks would be expected on the NMR spectrum of ethane?

Q

Only one peak is expected. This is because the H atoms on both -CH₃ groups are in identical
A
electronic environments, so they absorb at the same frequency. The peak is intense (tall)
because of the large number of H atoms (6) responsible for it.

C C

The two -CH3 groups are

electronicall equivalent, so they
constitute one environment.

How many peaks are expected in the NMR spectrum of the compound shown
Q below? Sketch a diagram to show the likely appearance of the spectrum.

C C

There
A are four different hydrogen environments.
2

C C
4
1
3

As a guideline, treat H atoms bonded to the same atom (e.g. bonded to the same carbon atom)
as sharing the same electronic environment. A hydrogen atom of the -OH group is in its own
separate environment.
There are five H atoms on the benzene ring. These constitute one environment.Environment1 produces
the highest energy(largest chemical shift) peak due to the strong deshielding effect of the
benzene ring. This is followed by environment2, in which the H atom is shielded by being
bonded to the electronegative oxygen atom. Environment3 produces a peak which is less
energetic than that of environment 2. The hydrogen atom in 3is not bonded directly to an
electron withdrawing group. However, its absorption is relatively higher than expected for CH
hydrogen atoms which are bonded to alkyl groups, due to the nearness to groups which cause
deshielding (oxygen and the benzene ring). Hydrogen atoms in environment4 produce the least
energetic peak (closest to TMS). This group is the farthest from deshielding groups, so it is the
most shielded.The expected low resolution NMR spectrum is sketched below.
 741

absorption

(5)

(3)
(1) (1)

10 5 o
δ ppm

Integrated peak areas

We have said that the ratio of peak heights is equal to the ratio of hydrogen atoms represented by the
peaks. Frequently the NMR spectrometer is associated with an integrator which calculates the area under
the peaks instead of height. The area under each peak can then be shown next to that peak. The ratio of
peak area is equal to the ratio of number of hydrogen atoms in the different environments. The integrator
draws a second trace on the NMR spectrum. This line trace becomes vertical when it encounters a peak.
The length of the vertical portion of the trace then gives the relative area under that peak. Fig 11.65shows
the NMR spectrum of a compound P, with an integration trace.

absorption

δ ppm 9 8 7 6 5 4 3 2 1 0
Fig 11.65An NMR spectrum showing an integration trace

The vertical sections of the trace are in the ratio 1:3:4. This is the ratio of hydrogen atoms in the three
separate environments represented by the three peaks (excluding the peak at zero, which is the reference
TMS peak).

2.2.3High resolution NMR spectra

 742

When the NMR spectrometer is adjusted to show finer details, ahigh resolution NMR spectrum is
obtained, which may show further splitting of the peaks shown in the low resolution NMR spectrum.
The splitting pattern for ethanol is shown in Fig 11.66. Both low and high resolution spectra are shown for
comparison.

CH3
absorption(peak
intensity) low resolution
CH2
(3) TMS
OH
(2)
(1)

5 3 1 0
δ, ppm

absorption(peak
intensity) high resolution

CH3 TMS Fig 11.66

The low and high
OH CH2
resolution
spectrum of
ethanol

5 3 1 0
δ, ppm

The -CH₂- peak splits into a quartet (four peaks), the CH₃ splits into a triplet. The OH peak is not split.

Explaining the splitting of peaks

Splitting of peaks is caused by a phenomenon known as spin- spin coupling. The magnetic field of a
particular proton interacts (couples) with that of protons on the adjacent carbon atom. This coupling
leads to splitting of a peak. The number of peaks formed by the splitting of a peak is given by (n+1),
where n is the number of neighbouring hydrogen atoms. Neighbouring hydrogen atoms are those which
are located on the carbon atom(s) immediately adjacent to the resonating proton(s).

The structure of ethanol is shown below

 743

2 1

C C 3

There are three different hydrogen atom environments, giving rise to three peaks. Consider the environ-
ment labeled 1(the –CH₂- group). The magnetic field of a hydrogen atom in this environment interacts
(couples) with the magnetic field of the threehydrogen atoms on the neighbouring carbon atom
(the –CH₃ group,labeled environment 2).This coupling causes the peak due to environment 1 to split into
(n+1) = 3 + 1 = 4(a quartet), where n is the number of hydrogen atoms on the neighbouring carbon atom.
Similarly, a hydrogen atom on environment2 has two neighbouring hydrogen atoms on carbon 1. Thus
the peak due to environment 2 splits into 2 + 1 = 3 peaks (a triplet). The splitting pattern due to
neighbouring hydrogen atoms can be remembered using Pascal’s triangle (Fig 11.67)(make sure you see
the pattern in the numbers shown in this triangle). The numbers inside each row in the triangle shows the
ratio of peak intensities (heights or area = absorbance).

number of 0 1 singlet( no splitting)

neighbouring
1 1 1 doublet
hydrogen
2 1 2 1 triplet
atoms
3 1 3 3 1 quartet
4 1 4 6 4 1 quintet
Fig 11.67 Pascal’s triangle for predicting the splitting pattern due to neighbouring
hydrogen atoms.

These ratios can be explained as follows:

The strength of the local magnetic field felt by a resonating proton is not only influenced by electrons in
the bonds around it, but also by the orientation of the local magnetic fields of nearby protons with respect
to the external magnetic field.
There are two possible orientations of the magnetic moment of a nearbyproton:
 The magnetic moment of the nearby proton can be aligned withthe external field. In this case, the
local magnetic field felt by the resonating proton is stronger.
 The magnetic moment of the nearby proton can be aligned againstthe external field. In this case,
the local magnetic field felt by the resonating proton is weaker.
A resonating proton will therefore absorb at twoslightly different frequencies because the neighbouring
proton has two possible effects on the strength of the magnetic field felt by the resonating proton. A
doublet is thus observed in the high resolution spectrum, and the ratio of the areas (or heights) under the
two peaks will be 1:1.
Now consider the case in which the resonating proton has two neighbouring protons. The magnetic field
of each neighbouring proton can be aligned either with or against the external field, giving rise to different
possible combinations, as shown in Fig 11.68.

Direction H H H H
of
external field C CH3 C CH3 C CH3 C CH3
H H H H
I II III IV
 744

Fig 11.68combinations of magnetic moment of two nearby protons

Cases II and III are equivalent. In both cases, the magnetic moments of the two neighbouring protons on
the -CH2- group cancel each other out, so the strength of the magnetic field experienced by the
resonating -CH3 protons is not affected. The resulting peak will be the central peak. Its value of δis the
same as that of the same peak on the low resolution spectrum. In cases I and IV, the magnetic fields of
the -CH2- protons reinforce each other. Thus the field experienced by the resonating -CH3 protons will
change; it will increase in case I and decrease for case IV. The -CH3 protons will therefore absorb at three
different frequencies, a frequency due to case I, a frequency due to cases II and III, and a frequency due
to case IV. Note that the chance of the –CH3 protons experiencing nochange in field (states II and III) is
twice that of the protons feeling either a strengthened or a weakened field (states I and IV respectively).
This explains the 1:2:1 splitting pattern (triplet) observed for the –CH₃ protons. Remember that the ratio
is that of the absorbance of the peaks, which can be expressed in terms of peak heights or in terms of peak
area.

Labile protons
The high resolution NMR spectrum for ethanol shows that the peak due to the -OH proton does not split.
This is because the proton is labile. This means that the -OH proton rapidly and reversibly exchanges with
the proton on the –OH groups of solvent molecules, for example water. Even if the solvent does not
contain –OH groups, exchange of protons still occurs between different ethanol molecules. However, the
effect is most pronounced if water is present, even in trace amounts (the peak due to the –OH group does
appear if ultra-dry ethanol is used).
This rapid exchange of protons is in fact a result of hydrogen bonding between the –OH group and other
groups which are able to hydrogen bond with it.
The rapid exchange of a proton explains why the peak due to the –OH group does not split. Another effect
of this proton exchange is that the –OH proton does not split the signals of neighbouring hydrogen atoms.
For example, in ethanol, CH₃CH₂OH, the signal due to the two protons on the –CH₂ group is only affected
by the CH₃- protons, and not by the –OH proton. The –OH proton does not therefore count as a
neighbour. As a general rule, a neighbouring hydrogen atom refers to the hydrogen atom on the adjacent
carbon atom.

The effect of heavy water, D₂O on the spectrum

If the sample is shaken with a little heavy water, D₂O, it is found that the peak due to the –OH group
disappears. This is because the labile -OH proton rapidly and reversibly exchanges with the heavy
hydrogen atom (D= 2H = deuterium) in heavy water,
R-OH + D₂O ⇌ R-OD + HDO
The –OH group is thus converted to -OD . The deuterium nucleus does not absorb in the same
frequency range as 1H, and so the signal due to the –OH group disappears from the spectrum. Its absorp-
tion frequency is outside the range of absorption frequencies within which the spectrometer operates. The
disappearance of the –OH signal is important in structure determination. If we know that a certain peak
on a spectrum disappears upon shaking the sample with a little heavy water, we may infer the presence of
an –OH group in the compound being analyzed.

Peak broadening due to hydrogen bonding and proton exchange

 745

It is often observed that the peak due to the -N-H and -O-H groups broaden out on the NMR spectrum.
Broadening occurs as protons exchange from one molecule to another during resonance. During the
exchange, the protons pass through a variety of chemical environments, and so there will be a range of
frequencies at which the protons can absorb. The diagram below shows the broadened peak due to
the - N-H group in propanamide, CH₃CH₂CONH₂.

Fig 11.69 Peak broadening of the N-H group in propanamide,

CH3CH2CONH2

2.2.4 Typical chemical shifts

1. Hydrogen bonded protons

The chemical shifts of the -N-H group in amines and the -O-H group in alcohols is affected by concentra-
tion of the solution. Hydrogen bonding has the effect of deshielding the protons, so they tend to have
relatively high chemical shifts, typically 3.5 ppm for the amine group and 4.5 ppm for the alcohol group.
These are the values quoted in the data booklet. If the solutions are diluted by a non- hydrogen bonding
solvent, the deshielding effect decreases, and the protons thus absorb at relatively high magnetic fields,
that is, at low absorption frequencies close to the TMS peak.

2. Aromatic and vinyl protons

Aromatic protons are typically deshielded, as already explained. They therefore have typically high
chemical shifts in the range δ = 7 ppm to δ = 8 ppm. (Benzene absorbs at δ = 7.2).
The π electrons in the double bond in alkenes also cause deshielding in a similar way. A vinyl proton
(bonded to an atom of the carbon to carbon double bond) therefore absorbs at relatively high chemical
shifts, typically in the range δ = 5 ppm to δ = 6 ppm. It should be clear that the extent of deshielding is
less than that experienced by the aromatic proton. This is because of the smaller number of π electrons in
the carbon to carbon double bond of the alkenes.
 746

Table 11.5 Typical chemical shifts of

hydrogen atoms in different environments.
All values are in ppm.

3. Aldehyde protons
Aldehyde protons absorb at frequencies higher than those for the aromatic and vinyl protons. This is be-
cause the aldehyde proton is deshielded both by the circulation of electrons in the carbon to oxygen
double bond and the electron withdrawing effect of the carbonyl oxygen.

4. Carboxylic acid protons

The chemical shifts of carboxylic acid protons is high, typically over δ = 10 ppm. This is a result of strong
deshielding caused by the electrons of the carbon to oxygen double bond and the combined electron with-
drawing effect of two oxygen atoms. The peak frequently broadens out due to proton exchange.
 747

Example 1
Sketch the high resolution NMR spectrum expected for propanone.

Solution
There are two -CH3 groups on propanone, but notice that they are equivalent so they constitute only one
hydrogen atom environment. Therefore only one peak is expected on the NMR spectrum. This peak is
expected to be intense (tall), since there is a total of six hydrogen atoms that give rise to the peak.

1
C
2 3

These groups are in

identical environments and so
they are equivalent.
The peak does not show splitting on the high resolution NMR spectrum. This is because there are no
hydrogen atoms on the neighbouring carbon atom, that is, the carbonyl group. If you refer to Table 11.5,
you will find that the absorption of hydrogen atoms of a CH 3 group which is bonded to a carbonyl group is
2.1.

absorption

δ ppm 2.1 o

Example 2
Sketch the low and high resolution NMR spectrum expected for the compound Q below. Explain the
relative energies of the peaks and their splitting pattern.
 748

Q.

Solution
 First determine the number of different hydrogen atom environments. Number of these environ-
ments is equal to number of peaks. Always check that the environments are indeed different (non-
equivalent).
 To place the peaks in correct order on the x-axis, look out for presence of deshielding groups,
such as the benzene ring and the oxygen atom. A hydrogen atom bonded directly to such a group
is deshielded and so it will absorb at relatively high frequencies. Such a peak is located well away
from the TMS peak. Deshielding is still felt by hydrogen atoms not bonded directly to the deshiel-
ding group, but to a smaller extend. As hydrogen atom environments move further and further
from the deshielding groups, the deshielding experienced by the hydrogen atoms diminishes. The
hydrogen atoms actually become more shielded and will be located at small values of δ (up field),
close to the TMS peak.

There are five different hydrogen atom environments in compound Q, as shown below
Five peaks are therefore expected on the NMR spectrum of compound
4 Q, corresponding to the environments numbered 1 to 5 . The ratio of
peak areas (absorption) would be 1:2:1:3:5 respectively, corresponding
5
to the number of hydrogen atoms in the numbered environments. Let
3 us now determine the relative positions of the five peaks, starting from
the left hand side of the x-axis (largest value of δ). Hydrogen atoms on
the benzene ring (environment 5) are the most deshielded. The peak
2 1 due to the benzene ring is therefore to the far left on the NMR
spectrum.
On the high resolution NMR spectrum, the splitting pattern due to the benzene ring is complex and
cannot be explained easily by the (n+1) rule.
Next to the peak caused by the benzene ring is the peak due to the single hydrogen atom in environment
1. This hydrogen atom is deshielded by being directly bonded to the electronegative oxygen atom.
However, the deshielding effect of the oxygen atom is less than that of the benzene ring, so the peak due to
environment 1 would be at a lower δ value. This peak does not show splitting on the high resolution NMR
spectrum because the hydrogen atom of the OH group is labile.
The next peak is due to environment 3(CH).There is only one hydrogen atom in this environment. This
hydrogen atom is not directly bonded to the benzene ring or to the oxygen atom, so it is relatively shielded
and it is closer to the TMS peak than the previous two peaks. However, this hydrogen atom experiences a
degree of deshielding due to its proximity to the benzene ring. This explains why the peak is at a higher
frequency than the peaks due to environments 2 and 4. This peak has five neighbouring hydrogen atoms
(three on carbon 4 and two on carbon 2). Recall that neighbouring hydrogen atoms are those on the
adjacent carbon atom(s). The peak is therefore expected to split into (5+1) = 6 (a sextet, ratio =
1:5:10:10:5:1 using Pascal’s triangle).
 749

absorption
low resolution
TMS

(5)
CH3
(3)
CH
CH
(1) (1) (2)

8 7 6 5 4 3 2 1 0
δ ppm

absorption

high resolution TMS

CH3
CH CH2
OH

δ ppm

The next peak is due to environment 2(-CH2-). The peak is close to the oxygen atom, so it has a higher
absorption frequency than expected of an R-CH2 -R peak (Table 11.5).The hydrogen atom in this
environment has only one neighbouring hydrogen atom on carbon3(The hydrogen atom in environment 1
(OH)does not count as a neighbor since it is bonded to an oxygen atom). This peak therefore splits into a
doublet (ratio = 1:1).
Hydrogen atoms on position 4 (CH3) are farthest from either the benzene ring or the oxygen atom. These
hydrogen atoms are therefore the least deshielded (they are the most shielded) and so the corresponding
peak is at the smallestδvalue, that is closest to the TMS peak.
The hydrogen atoms in this environment have only one neighbouring hydrogen atom on carbon 3. The
peak therefore splits into a doublet.

Example 3
The NMR spectrum for compound P, whose molecular formula is C₉H₁₂O, is given.
Further information about P:
The singlet at around δ = 5.5 disappears when the sample is shaken with a little of heavy water,
D₂O.
 750

Deduce, with reasons, the chemical groups that give rise to each peak. Hence deduce the structure
of compound P

absorption
NMR spectrum of compound P

(6)
(4)
(1) (1)

9 8 7 6 5 4 3 2 1 0

δ ppm

Solution
Since there are four groups of peaks, we conclude that there are four hydrogen atom environments in
compound P. The peak at around δ = 7.5 has an absorption frequency typical of a benzene ring. The fact
that there are four hydrogen atoms in this environment suggests that the benzene ring is disubstituted.
The peak at around δ = 5.5 is likely to be due to an –OH group. This is supported by the data booklet and
the fact that the peak does not show splitting in the high resolution NMR spectrum. Moreover, there is
only one hydrogen atom in this environment. Another piece of evidence supporting that the peak is due to
the –OH group is the fact that the peak disappears upon shaking the sample with heavy water, D₂O. This
is typical of a labile proton bonded to an oxygen atom. The absorption frequency of this peak is higher
than that expected of an –OH group attached to a non-aromatic group. We therefore conclude that the –
OH group is attached directly to the benzene ring, that is, it is one of the two substituents on the benzene
ring.
The multiplet at around δ = 2 is likely to be caused by the group
The data booklet gives the absorption frequency due to this group as being between
C δ = 1.4 and δ = 1.7. The fact that the absorption frequency on the spectrum is actually
around δ = 2 hints at the nearness of the benzene ring, which causes deshielding and
thus increases the absorption frequency.The group giving rise to the peak at around δ = 2 is therefore
likely to be bonded to the benzene ring, as shown below.
This group is therefore the second substituent on the benzene ring. The fact that
C the peak has split into a septet (seven peaks) shows that it has a large number of
H neighbouring hydrogen atoms.
This occurs when the group under discussion is bonded to two –CH₃ groups, giving a total of six
neighbouring hydrogen atoms). The chemical groups we have deduced so far give the fragment below, or
one of its positional isomers.
The doublet at just over δ = 1 is likely to be due to two equivalent methyl
C groups. This is because the total number of hydrogen atoms in this
HO H environment is 6. The absorption frequency of the –CH₃ group is given in the
data booklet as 0.9.
 751

The absorption frequency on the spectrum for compound P is slightly higher, showing that an electron
withdrawing group (the benzene ring) is nearby. The fact that the peak has split into a doublet shows that
the two methyl groups are bonded to a carbon atom bearing only one hydrogen atom.

Joining the various pieces we have obtained so far gives the structure of P as

Example 4
A compound R, whose Mr is 90, gave the NMR spectrum shown below. Shaking the sample with D ₂O
caused no change to the spectrum.

absorption
NMR spectrum of compound R

(6) (3)
(1)

9 8 7 6 5 4 3 2 1 0
δ ppm

Solution
There are three peaks on the spectrum, showing that the compound R has three different hydrogen atom
environments.
The peak at around δ = 1.2 has an absorption frequency typical of a –CH₃ group which is close to a
deshielding group, such as the oxygen atom or the benzene ring. However, the benzene ring is clearly
absent in compound R since there is no peak with an absorption frequency typical of the benzene ring.
The fact that there are three hydrogen atoms that give rise to the peak further shows the presence of a
–CH₃ group. This peak has split into a doublet, showing that it is bonded to a –CH group, that is, it has
only one neighbouring hydrogen atom.
The intense peak at around δ = 3.2 is probably due to two equivalent –CH₃ groups. This corresponds to
six hydrogen atoms sharing the same electronic environment. The absorption frequency of this peak is
within the absorption range of the –OCH₃ group given in the data booklet. The fact that the peak has not
split shows that the –CH₃ group has no neighbouring hydrogen atoms.
 752

The quartet at aroundδ = 4.5 is likely to be caused by a –CH group bonded to a –CH₃ group.
The CH hydrogen atom therefore has three neighbouring hydrogen atoms. This peak
thus splits into a quartet. The fact that there is only one hydrogen atom giving rise to
the peak further supports the fact thatthe peak is due to a –CH group.
The absorption frequency of this peak is within the absorption range of the –OH group, but the –OH
group is absent since the spectrum is not affected by shaking the sample with D₂O. The high absorption
frequency of the peak shows that the –CH group is likely bonded to two electronegative atoms. From the
evidence gathered so far, a possible structure for compound R is

Verify that this structure is consistent with the given NMR spectrum.

2.2.5Applications of NMR spectroscopy

 Structure determination
1HNMR spectroscopy is now one of the techniques routinely used to determine the structure of
organic compounds. This can be used, for example, to identify drugs and food poisons. Some
useful chemicals are frequently extracted from natural sources such as plants. Before the
compound can be synthesized, its structure must be determined. NMR spectroscopy is very useful
here.

 In synthesis
NMR spectroscopy can be used to determine the product of a chemical reaction. This will help to
determine if the reaction forms the desired product or not.

 In medicine
The technique known as magnetic resonance imaging (MRI) is used to scan living tissue,
for example the brain. The term ‘nuclear’ is omitted as some people automatically link it with
radioactivity. The technique of MRI does not make use of radioactive substances.

How MRI works

This technique is used to obtain a scan of living tissues. For example, to obtain a brain scan, the human
subject is allowed to slide into the machine, which scans different sections of the brain as the subject
moves. The scan obtained can then be compared with that of healthy brain tissue. MRI can reveal the
presence of tumors in the brain. A tumor is an extra mass of organic matter, which would give a dense
spectrum due to the large number of hydrogen atoms present in the tumour. Darkened patches on the
scan where they would not be expected in healthy brain tissue may imply presence of a tumour.
 753

Advantages of NMR spectroscopy

 The major advantage of NMR spectroscopy is that it is a non-evasive technique. This means
that it does not destroy the sample, since the form of energy used (IR) is very weak. The technique
is therefore suitable for use on living tissues or on the whole organism since it causes no side
effects. Compare with x-ray crystallography which makes use of a highly energetic form of
radiation and is therefore likely to damage the sample.
 The technique is more straightforward than some techniques such as x-ray crystallography. Level
of expertise required is relatively low, and results are obtained fairly easily. However, like most
analytic techniques, great care, patience and skill is often needed in solving the structures of some
compounds.
 The sample does not need special treatment before it can be analyzed. For instance, the sample
need not be crystallized (as in x-ray crystallography), but is used in solution.
 The technique is very sensitive, so very small amounts of sample (for example, just a few
micrograms) are all that is required to produce an NMR spectrum of the compound.
 The instrument can be tuned to examine specific tissues or organs during tissue MRI.
 The technique can easily be used to distinguish between isomers. For instance, the NMR
spectrum of propanone would be different from that of its isomer, propanal.
 The technique can detect hydrogen atoms. X-ray crystallography cannot detect hydrogen atoms
because of the very small size of the hydrogen atoms.
 754

Questions, solutions and discussions

Q1The NMR spectrum of compound D is shown below. Deduce a possible structure for this
compound.

Discussion
There are three hydrogen atom environments. The integrated areas under the three groups of peaks are in
the ratio 1:3:6. This is equivalent to the ratio of hydrogen atoms giving rise to the peaks (recall that the
area under each peak is proportional to the length of the vertical segment of the line trace). The doublet at
δ = 1.0 is typical of two –CH₃ groups with the same electronic environment. This is due to the fact that
there are six hydrogen atoms which give rise to this signal. The absorption frequency is also close to that
expected by the –CH₃ protons. The frequency is slightly higher than that given in the data booklet and this
may be due to the close proximity of an electron withdrawing group, such as an oxygen atom. The fact that
the peak splits into a doublet shows that the two methyl groups are bonded to a carbon atom that bears a
single hydrogen atom, as shown below left.
The singlet at δ = 2.0 is likely to be caused by –CH₃ protons. The fact that the peak is not
CH3
split shows the absence of neighbouring hydrogen atoms. In fact, the absorption frequency
CH is typical of a methyl ketone group, shown below.
C H3 CH3 C

O
The septet at around 2.5 is caused by a single hydrogen atom, that is, a –CH group (area under the curve is
1). This hydrogenatom must have six neighbours, since it has split into seven peaks (a septet). This is
possible if we assume that that the –CH group is bonded to two methyl groups, as already shown above.
Joining the pieces of evidence together gives the structure of D as 3-methyl-2-butanone.

The reader should verify that the structure of the compound agrees with the given spectrum.
9701/04/M/J/07
 755

Q2The NMR spectrum shown below was obtained from a simple organic molecule, G,
CxHyO2. When a sample of G was placed in a mass spectrometer, the ratio of the
M: M+1 peak for the molecule was 14.5:0.66.

(i) Calculate how many carbon atoms there are in the molecule.
(ii) Use the NMR spectrum and the Data Booklet to work out the structure of G.
9701/04/O/N/07

Discussion
The number, n, of carbon atoms in a molecule of compound G can be found using the formula
𝐴(𝑀+1) 100
n=
𝐴(𝑀) 1.1

Where A(M+1)is the relative abundance of the M+1 peak and A M is the relative abundance of the M
peak.Thus
𝐴(𝑀+1) 100
n=
𝐴(𝑀) 1.1
(0.66) 100
= = 4
(14.5) 1.1

A molecule of compound G contains four carbon atoms.

The signal near δ = 1.2 is typical of a –CH₃ group in close proximity to an electron withdrawing
group such as an oxygen atom. The fact that this peak has split into a triplet implies that the –CH₃
group is bonded to a –CH₂ group. Part of the molecule is therefore
-CH2CH3
The –CH₂ group gives the quartet near δ = 4.0. The absorption frequency of 4.0 is higher than that
expected of RCH₂- protons. This shows that the CH₂ group is bonded to an electron withdrawing
group (oxygen in this case, since the formula of g shows presence of oxygen).
-O-CH2-
Note that this signal is caused by two hydrogen atoms. The peak splits into a quartet because of the
presence of three hydrogen atom neighbours on the adjacent- CH₃ group.
 756

Always look out for the presence of a triplet and a quartet on an NMR spectrum. This shows pres-
ence of the -CH2CH3 group (the quartet and triplet need not be adjacent to each other on the spec-
trum). The singlet atδ = 2.0 is likely to be caused by a –CH₃ group which is close to an electronega-
tive atom, oxygen in this case. The nearness of the electron withdrawing atom has the effect of in-
creasing the absorption frequency of the –CH₃ group beyond the value given in the Data Booklet. In
fact, the absorption frequency of this peak is typical of a methyl group bonded to a carbonyl group.
C

Joining the pieces together gives the structure of G as ethyl ethanoate.

CH3CH2 O C CH3

Q3Nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry are also
used in the detection of certain molecules, particularly those containing hydrogen
atoms. Explain how and why the NMR spectrum of propanal, CH3CH2CHO, would be
different from that of propanone, CH3COCH3, which contains the same atoms.

9701/04/M/J/07

Discussion

The two compounds are isomeric. The NMR spectra of the two compounds would be different, as
explained below.

For propanal, there are three H atom

environments, so three peaks are expected
on the NMR spectrum.

The CH3 and the -CH2 groups split each two equivalent
other, resulting in the appearance of a hydrogen atom environments
quartet and a triplet. The -CHO proton has give one intense peak
two neighbouring hydrogen atoms, so it
splits into a doublet (Fig )

The NMR spectrum of propanone has only C

one peak, which shows no splitting since the
two -CH3 groups have no neighbouring H
atoms. propanone
 757

Q4(a)MRI scanning is a medical technique based on NMR spectroscopy. It is

particularly useful for looking for tumours in healthy tissue.
Suggest how this technique can distinguish tumour tissue from healthy
tissue.

(b) A saturated molecule of formula CxHyNO was subjected to analysis by

mass spectrometry and NMR spectroscopy. In the mass spectrum of the
compound, the M peak was at m/e 73 and the ratio of the heights of the M:
M+1 peak was 48: 1.7

(i) Using the data from the mass spectrum, determine the values of x and y in
the formula of the compound.

(ii) Use the data from (i) together with the NMR spectrum below to deduce a
structure for the compound, explaining how you arrive at your answer.

9701/04/M/J/07

Discussion
(a)The hydrogen atoms in a tumour are in a different chemical environment from that of
hydrogen atoms in normal tissue. Tumours and healthy tissues therefore absorb at different
frequencies. Comparison of the scan obtained by MRI imaging with the scan expected for a
healthy tissue reveals the presence of a tumour, if any.

(b)(i) By formula, number of carbon atoms, x, in a molecule of the compound = 3. The compound
therefore has the formula C3HyNO, from which we can deduce that the value of y = 7, since
the Mr of the compound is known to 73 (M peak on the mass spectrum corresponds with
the Mr of the compound).

(ii)Thepresence of atriplet and a quartet in the NMR spectrum shows presence of the
- CH3CH2- group. The broad peak at around δ = 6 shows presence of an -NH2 group. In
fact, the value of δ is typical of the group -CONH2. The compound is therefore
propanamide, CH3CH2CONH2.
 758

Q4NMR spectroscopy, in contrast to X-ray crystallography, is frequently used

to examine protons in organic molecules.

(i) What feature of protons enables their detection by NMR spectroscopy?

(ii) The NMR spectrum below was obtained from a compound X, CxHyOz. In the mass
spectrum of the compound, the M: M+1 ratio was found to be 25:2. Determine the
values of x, y and z in the formula of X and deduce a possible structure for the
compound, explaining how you arrive at your conclusion.

9701/04/O/N/07
Discussion
(i)The fact that protons are both charged and tend to spin about an axis allows them to be
detected by NMR spectroscopy.

(ii)The value of y, that is, number of hydrogen atoms, is given by adding the numbers of hydrogen
atoms shown against the peaks on the NMR spectrum. y is therefore equal to 4+1+3 = 8.
x, the number of carbon atoms, is found by formula, as shown in the previous examples. Thus
x = 7.From the data booklet, it will be seen that the absorption at δ = 3.7 is due to the
methoxy group, CH3O-. This peak shows no splitting, showing that the hydrogen atoms on the
methyl group have no neighbouring hydrogen atoms.
The absorption peak at 5.6 is within the range expected of the phenol group. The peak at 6.8 is
in the range of the absorption frequency of the benzene ring. Since the peak is caused by four
hydrogen atoms, the benzene ring must be disubstituted.
The compound is therefore 4- methoxyphenol

and the value of z is 2.

 759

Q6Exercise to the reader

A range of modern analytical techniques has made the identification of molecules, and
atoms in compounds, much more rapid than traditional laboratory analysis.

(a) One instrumental technique is NMR spectroscopy, which uses the fact that under certain
conditions protons can exist in two different energy states. Explain how these different
energy states arise.

(b) When methanol, CH3OH, is examined using NMR spectroscopy, it absorbs at two
different frequencies. Explain why, and predict the relative areas of the two peaks.

(c) The NMR spectrum below is that of one of three possible isomers of molecular formula,
C3H6O2.

The compound could be propanoic acid, methyl ethanoate or ethyl methanoate.

(i) In the boxes provided, draw the structures of the three compounds.

propanoic acidmethyl ethanoateethyl methanoate

(ii) Explain which compound produced the spectrum shown, indicating which protons
are responsible for each of the peaks A and B.

(iii) The NMR spectrum of another of the compounds has a peak at δ 11.0.
State which compound this would be, and identify the proton(s) responsible for this
peak.
 760

11.2.2 X-RAY CRYSTALLOGRAPHY

X-rays are a type of high energy (short wavelength) electromagnetic waves. The diagram below shows the
position, in terms of energy, of X-rays, in the electromagnetic spectrum.

decreasing wavelength

increasing frequency(number of vibrations per second

radio infrared ultraviolet X- rays gamma rays

waves

INCREASING ENERGY
Diagram(not to scale) showing position of X-rays in the
Fig 11.70 Diagram showing position of X-rays in the electromagnetic spectrum
electromagnetic spectrum. X-rays are a form of
electromagnetic waves with a very high frequency and energy.

2.2.1 X-ray crystallography

As the name suggests, this technique involves the use of X-raysto determine the structure of a substance
in its solid crystalline form. Metals have been analyzed by this technique because they have a solid
crystalline form. Amino acids, nucleic acids and proteins have also been analyzed by this technique
because they can be crystallized from solution. The technique does not work well for non-crystalline
substances, or substances that cannot be crystallized.
The X-ray spectrometer, the machine used to analyze substances by X- ray crystallography, makes use of
the diffraction of monochromatic X-rays by a crystal. Diffraction is geometrically identical to reflection,
so to keep the account simple, we will use the term reflectioninstead ofdiffraction.

source of X-rays
incident rays detector display/read-out
reflected rays nature of the read-out
depends on the type of
detector used.

Sample - must be in its

solid crystalline form

Fig 11.71 Analysis of a crystalline sample by X-ray crystallography

 761

Why X-ray crystallography works only for crystalline solids

A crystalline solid is made up of regularly spaced layers of ions, atoms or molecules. The
interatomicdistance in the crystal is very small, and is approximately equal to the wavelength of X-rays
(about 0.1nm). The crystal is therefore able to act as a diffraction grating, that is, a surface which is
able to scatter (defract) electromagnetic waves. When X- rays from an X-ray tube strike a crystal, some of
the incident rays are reflected from the top layer of atoms of the crystal, but some rays are reflected by
underlying layers.

How the technique works

Consider two adjacent planes of the crystal in the diagram below. X- rays striking the crystal are known
as incident rays. The angle marked θ is the angle of incidence, which is equal to the angle of reflection. θ
is the angle of inclination of the incident and reflected rays to the surface of the crystal (Fig 11.72).

source of
X-rays
reflected rays
incident X-rays

 X  layer 1 Fig 11.72 reflection

of X-rays from the
W d
Z layer 2 layers of a crystal
Y
Diffraction
Let us considerof two
two waves
reflected of X-rays
waves, from
one from eachtwo adjacent
layer, as shownlayers of a crystal.
in the diagram above. Two things may
The wave from the
happen to these waves: second layer lags by a distance(path difference) given
by WY + YZ. When this difference in the distance travelled by the two
diffracted(reflected rays) is equal to a whole number of wavelengths, the
 Constructive interference
wavesThis
areissaid to be
when the twoin phase, andtothey
waves add each interact constructively
other, with trough adding to produce
to trough, and peak adding to
an intense resultant wave.
peak, so that a more intense wave is formed. For this to happen, the two waves must be in phase,
that is, the waves must travel relative to each other so that peaks coincide with peaks, and troughs
coincide with troughs. If this happens, the detector picks up the intense signal and processes it as
discussed later.

 Destructive interference
This is when the two waves are out of phase, that is, one wave lags relative to the other in such a
way that troughs coincide with peaks. The effect is that the waves cancel each other out, and no
wave is transmitted to the detector.

2.2.2 Detection of x-rays

Structure analysis by X- ray crystallography depends on the detection of the rays reflected from the layers
of the crystal. There are several methods of detecting these rays, including theGeiger-Müller counter,
photographic film and scintillators.
 762

Electron density maps

These are obtained in an X-ray diffractometer using X-ray film as the detector. X-rays strike the crystal
(sample) at an angle and they are reflected to the X-ray film. A black spot is formed where the X-rays
strike the film. As the crystal is rotated on the diffractometer head, different planes of the crystal are
exposed to the incoming X-rays. New spots therefore appear on the film, corresponding to the new layers
of the crystal.

spots form where X- rays

strike the film

X-rays reflected from the surface

X-ray of the crystal
beam
crystal mounted on
a rotatable head

crystal rotates about

X-ray film its axis
Fig 11.73
X-ray
axis of crystal diffractometer

At the end of the process, the film now has a pattern of spots, known as a diffraction pattern. This pattern
is unique to different substances. The density of spots on the film reveals something about the density of
electrons in the crystal. This is because the diffraction of X-rays is caused by electrons in the atoms of the
crystal. Regions of high electron density refract the X-rays more, and consequently the spots on the film
will be intense. By analyzing the intensity and the position of spots, it is possible to deduce the density
distribution of electrons in the crystal. An electron density map is then obtained by joining spots of equal
density. Such maps are useful in determining positions of atoms and bonds. It is also possible to distin-
guish between single, double and triple bonds.

The electron density map in Fig 11.74 was obtained for a certain organic compound.

Fig 11.74 Electron density map

1. Circular concentric contours represent positions of atoms or groups of atoms.

 763

2 and 3.Contours connecting such groups represent bonds. If the bond is single, then the contour
lines might be absent due to the very small number of electrons present in the bond. Triple and
double bonds give more intense ‘electron densities’.

Hydrogen atoms do not appear in the electron density map since a very small electron cloud surrounds
the atom, that is, electron density in the hydrogen atom is not sufficient to diffract X- rays.
X - ray crystallography is able to distinguish between covalent and purely ionic compounds such as NaCl
(Fig 11.74 ).

Fig 11.75Electron density map of NaCl. The numbers represent electron density in number of
electrons per cubic nanometer.

 Groups of circular contour lines show positions of ions.

 Notice that between these groups, there are regions of no electron density. This shows that NaCl
is an ionic compound, made up of discrete lattice particles known as ions. There is no shared
electron density (covalent bond) between the ions.
 The chloride ion is larger than the sodium ion. The contour lines of the chloride ion occupy a
larger space.
 Notice how electron densities increase towards the centre of the ions. This is due to the fact that
electrons in the inner shells occupy a smaller volume due to their nearness to the nucleus.
 Measurements from electron density maps such as the one above enable the determination of
ionic and atomic sizes. However, these sizes are only average values because the distribution of
electron density in the outer shell of ions or atoms is influenced by nearby atoms or ions.

2.2.3Application of X-ray crystallography

X-ray crystallography is useful in the analysis of crystalline samples, for example metals, nucleic acids and
amino acids.

Advantages of X-ray crystallography

 Position of atoms can be determined.
 Allows the determination of other features of a substance, such as size of atoms and bond lengths.
 Can be used to determine shapes of molecules. Such information is important in explaining and
understanding the behaviour of complex molecules such as enzymes.

Disadvantages of X-rays
 764

 High level of expertise is required in the interpretation of the data obtained by X-ray
crystallography. Analysis of results often requires not only skill, but patience and intuition, and
determination of the full structure of a complex substance may take a very long time.
 X-rays are invasive. Being of high energy, they can destroy the sample. For this reason, the
technique is not suitable for analyzing living tissues and cells. (In radiology, relatively safe soft
X-rays are used to obtain an image of internal body parts. Soft X-rays are not suitable for
structure determination by X-ray crystallography). Compare with non-evasive techniques such as
NMR spectroscopy.
 X-rays are potentially harmful. Exposure to ionizing radiation such as X-rays may cause cancer.
Ionizing radiation is radiation of very short wavelength (high energy), which can ionize
substances by knocking out electrons.
 The technique is largely limited to analysis of crystallinesubstances or substances that can be
crystallized. Most amorphous or non-crystallizable substances cannot be analyzed by this
technique.
 The sample should be obtained first in its pure crystalline form, which may be difficult. Often the
need for obtaining relatively large crystals from solution means the substance should be present
in solution in large amounts. Compare with NMR spectroscopy in which the substance to be
analyzed need not be in large amounts.

Questions, solutions and discussions

Q1This question is about the modern techniques of analysis which may be used to
determine molecular structures.

(a) In X-ray crystallography, X-rays are diffracted by the electron clouds surrounding
individual atoms in the structure.

(i) What useful information is provided by X-ray crystallography?

(ii) Why cannot hydrogen atoms in a structure be detected by this technique?

(b) Suggest how structures of complex molecules such as enzymes, derived from X-ray
crystallography, can help explain their biochemical behaviour.

9701/04/M/J/07

9701/04/M/J/07
 765

Discussion

(a) (i)X- ray crystallography provides useful information about the structure and composition of
substances, including

 Positions of atoms or ions.

 Size of atoms
 Bond angles
 Bond lengths
 Type of bonding

(ii)Diffraction of electrons is caused by electrons in the atoms of the substance being analyzed. There
is insufficient electron density around hydrogen atoms to cause scattering of X-rays.

(b)X-ray crystallography can show the geometry of the arrangement of atoms .This can help explain
how complex molecules such as enzymes work.

................................................................................................................................

Q2Explain why the technique of X-ray crystallography works well for crystalline
solids, but not for non- crystalline substances.

Discussion

Lattice particles in a crystalline solid are evenly spaced out. The distance between the particles is
approximately equal to the wavelength of X-rays. A crystalline solid can therefore act as a
diffraction grating for X-rays, that is, it is able to scatter X-rays.

.....................................................................................................................................

Q3The structure of DNA was determined by X-ray crystallography. What properties

of DNA allows it to be analyzed in this way?

 It has a regular molecular structure, which allows it to form crystals. Regularity of the DNA
molecule is a result of the fact that the two chains run antiparallel to each other, thus allowing a
double ring base (purine) to pair with a single ring base (pyrimidine).
 The presence of charged groups within the DNA double helix allows the molecules to attract each
other electrostatically. This allows the molecules to arrange themselves in a regular three
dimensional manner, forming crystals.
 DNA can be obtained in large amounts as pure crystals.
 766

11.2.3 SEPARATING AND IDENTIFYING

SUBSTANCES

2.3.1Methods of separating and identifying substances

Some methods of separation include

 Solvent extraction
 Chromatography
 Electrophoresis

Reasons for separating substances

 Purification- frequently there is a need to separate the product of a process from reactants and
other impurities.
 Isolating useful substances – a mixture may contain a variety of useful substances. These
substances cannot work in the mixture, but must be separated from each other so that each can be
put to its use.
 During qualitative analysis – we may wish to find the identity of a substance, say a drug present
in the blood of a poisoned person. The drug must be separated from other substances before it
can be analyzed further to identify it.

2.3.2Solvent extraction

This technique is also known as partitioning. It is used to obtain a substance based on itsrelative
solubilities in two different immiscible liquids. The substance to be separated must be much more soluble
in one of the liquids and not the other. The two liquids used are usually water and an organic solvent. If
the substance is polar and has a low Mr it may dissolve better in the aqueous phase, and not in the organic
phase. If the substance is non- polar then it will dissolve better in the organic phase. The substance to be
extracted then moves from the liquid in which it is less soluble to the one in which it is more soluble.

In the lab, solvent extraction can be carried out using a separating funnel. Suppose that we wish to
separate bromine from water. An organic solvent such as trichloromethane is added to the bromine/
water mixture in a separating funnel. The contents of the separating funnel (water, bromine and
trichloromethane) are shaken thoroughly in the funnel, which must be fitted with a good tight fitting
stopper. The stopper should be opened at times during the shaking to prevent pressure build up. Bromine,
being non-polar, is more soluble in trichloromethane than in water. Shaking facilitates the transfer of
bromine molecules from the water layer to the trichloromethane layer. After the mixture has been
thoroughly shaken, it is left undisturbed for some time, allowing equilibrium to be achieved. During this
time, two distinct layers can be seen in the separating funnel. The organic layer, being less dense than
water, forms the upper layer, into which bromine molecules are attracted. This layer will therefore appear
red because of the large amount of bromine present. When the tap is opened, the bottom aqueous layer,
containing very small amounts of bromine, is drained out, leaving the bromine rich trichloromethane
 767

layer (Fig 11.76). The bromine can then be separated from the organic solvent e.g. by distillation or
evaporation.

Solvent extraction using

a separating funnel.
organic layer
separating funnel aqueous layer
tap

Fig 11.76

Why bromine dissolves better in trichloromethane than in water

In general, if a substance is non- polar, e.g. bromine, then it dissolves better in organic solvents than in
water. Similarly, if a substance is polar, it dissolves better in water than in an organic solvent. This
observation can be explained in terms of the intermolecular forces that must be broken and be formed for
the dissolving process to take place. For bromine to dissolve in water, bromine molecules must first be
separated from each other, by breaking the Van der Waals forces between them. Similarly, water
molecules must be separated from each other by breaking the hydrogen bonds between them. Hydrogen
bonds are relatively strong and breaking them requires a relatively large amount of energy. This would not
be a problem at all if the energy absorbed in breaking the hydrogen bonds in water could be compensated
for when new bonds form between the water molecules and the bromine molecules. In this case this does
not happen because bromine, being non- polar, cannot make hydrogen bonds with water. Rather, weak
Van der Waals forces are established between the water and the bromine molecules. Since weaker
attractions are formed between water and bromine, the dissolution is not favoured. From an energetic
point of view, more energy is used in breaking (hydrogen) bonds than is released in forming new ones; the
system would therefore be at a higher energy level after the dissolution process, and this is not
energetically favoured.

3.2.1 Choice of solvent

In the example above, trichloromethane is given as a suitable solvent to dissolve bromine during its
extraction from water. The solvent used should have the following properties
 it should be inert towards the solute, that is, it must not react with the substance which it is
supposed to dissolve.
 it should be volatile so that it is easily separated at the end by evaporating it out .
 It must have a very low solubility in water. The separation technique depends on the solvent and
water forming two layers. In most cases, the solute is then transferred from the aqueous layer to
the organic layer.
 It must have a high solubility for organic compounds. Organic solutes can therefore move easily
into it from the aqueous layer.
 768

Ether is frequently used for solvent extraction because it has all of the properties above. The major
disadvantages of ether are

 it is highly flammable. It poses a high fire risk because its vapour can easily spread. It should only
be used in an environment with no naked flames.
 it has a tendency of forming explosive peroxides upon storage. To avoid this, it is often stored
upon a bed of iron (II) sulphate, which inhibits peroxide formation by acting as a reducing agent.

3.2.2 The partition constant (Partition co-efficient)

This is an equilibrium constant which measures the extent to which a solute is partitioned (dissolved) in
one solvent relative to another.
Consider a solute S being partitioned between water and an organic solvent. Partition, in this case,
involves the following equilibrium

S(aq) ⇌ S(organic)

Two processes are involved here. In the forward process, the solute S is being transferred to the organic
layer. In the reverse reaction, some solute molecules leave the organic layer and enter the aqueous layer. A
question which immediately arises is, which side is favoured, the forward or the reverse? To answer this
we need to assess the relative affinity of the solute for water and for the organic substance. Possible
interactions that can exist between the solute and water or the organic solvent are

 hydrogen bonds
 Van der Waals forces
 dipole- dipole attractions
 ion- dipole attractions
 ion – ion attractions.

Whether the solvent dissolves better in the organic or in the aqueous layer can be explained in terms of
energetics. In general, a solute will dissolve well in a solvent if the types of intermolecular forces estab-
lished between the solute and the solvent are comparable in strength or similar to the forces that existed
between the solute molecules and the solvent molecules before the dissolution. For example, the inter-
molecular forces in bromine are Van der Waals forces, which are similar to the forces in trichloromethane.
Bromine will therefore dissolve well in a solvent to which it can establish Van der Waals forces. Thus
bromine will dissolve well in an organic solvent such as trichloromethane, to which it can form Van der
Waals forces. However, it will not dissolve well in water because the forces of attraction between bromine
molecules are Van der Waals, and those between water molecules are the relatively strong hydrogen
bonds. A relatively large amount of energy would be required to break the hydrogen bonds in water to al-
low new interactions with bromine molecules. Now, these new interactions, which are Van der Waals
forces, are much weaker than the hydrogen bonds that had to be broken. Energetically, the dissolution of
bromine in water is relatively unfavourable.For the equilibrium

S(aq) ⇌S(organic) ... I

it is the forward process which is favoured, that is , at equilibrium, the amount of bromine in the organic
phase would be greater than the amount in the aqueous layer. The extent to which the solute dissolves in
one solvent relative to another is expressed by the partition co-efficient. For cases involving water and an
organic solvent, the partition co-efficient, Kpc, is written based on equilibrium I above
 769

[S]organic concentration of solute in 𝐨𝐫𝐠𝐚𝐧𝐢𝐜 𝐥𝐚𝐲𝐞𝐫 at equilibrium

Kpc =
[S]aqueous
=
concentration of solute in 𝐚𝐪𝐮𝐞𝐨𝐮𝐬 𝐥𝐚𝐲𝐞𝐫 at equilibrium

In other words, the partition co-efficient is the ratio of the concentration of solute present in the organic
layer to the concentration of solute in the aqueous layer at equilibrium. K pc is therefore a measure of how
well the solute dissolves in one liquid, compared with another.
The expression for Kpc given above holds true only when the solute exists in the same form in the two
layers of solvents used in the separation. There are two well known cases where the expression above does
not hold true

 When the solute dimers in one of the liquids and not the other. A good example is provided by
ethanoic acid when an attempt is made to separate it using water and benzene as the solvents.
When they enter the benzene layer, ethanoic acid molecules tend to form dimers by hydrogen
bonding.

In the aqueous layer, ethanoic acid exists mainly as CH₃COOH molecules.

 When the solute molecules dissociate in one solvent and not the other. For instance, a carboxylic
acid such as ethanoic acid ionizes in water, but not in organic solvents.

3.2.3 Interpretation of Kpc

A large value of Kpc (>1) implies that the numerator in the expression for K pc is larger than the
denominator. For example, if the Kpc value is 20, then the concentration of the solute in the organic layer
is 20 times the concentration in the aqueous layer. A value of Kpc which is larger than 1 therefore implies
that the solute is more soluble in the organic solvent than in the aqueous layer. Most solvent extractions
involve separation of organic solutes into an organic solvent. If the K pc value is much larger than 1, then it
will be possible to extract a large amount of the organic solute from water.
A small value of Kpc(between 0 and 1) implies that the solute does not dissolve well in the organic layer but
it does dissolve well in the aqueous layer. When Kpc = 1, the solute is equally soluble in both water and the
organic solvent. In this case, the separation does not work out well.

3.2.4 Factors that affect the value of Kpc

Kpc is constant only for a particular system at a particular temperature. For example, the partition co-
efficient of iodine between water and hexane is constant at 25⁰C, provided the same solvents (water and
hexane) are referred to. It does not matter what volumes of solvent or mass of solute is used; the value of
Kpc remains constant. If one of the solvents is changed, e.g. hexane is replaced by ether, this becomes a
different system, and the partition coefficient will change. The solvent actually used should give a high
value of Kpc and it should have the desirable properties that have already been discussed. A large value of
Kpc will lead to an efficient separation.
 770

Example 1
An experiment is to be carried out to determine the partition co-efficient of iodine between water
and trichloromethane.
Explain whether the iodine would be more soluble in the aqueous or in the trichloromethane layer.

A certain quantity of iodine was shaken with a mixture of water and trichloromethane in a
separating funnel. The apparatus was left undisturbed for a few minutes to allow equilibrium to be
achieved. When the two solutions had settled into two distinct layers, they were separated by
opening the tap of the funnel. The quantities of iodine in each of the solvents was then determined
by titrating with 0, 02 moldm-3 sodium thiosulphate.

(a) Construct a balanced equation for the reaction between iodine and thiosulphate ions.

(b) What could have been used as an indicator in this titration?

5.00cm3 of the trichloromethane required 7.70cm3 of the sodium thiosulphate

solution whereas 12.50cm3 of the aqueous layer required 20.00cm3 of the sodium
thiosulphate solution.

(c) Calculate the concentration of iodine that was present at equilibrium in

(i) the organic layer

(ii) the aqueous layer

Hence calculate the value of the partition co-efficient for iodine in water and
trichloromethane.

(d) Assess the suitability of trichloromethane as a solvent in this extraction.

Solution
(a) 2S₂O₃2- + I₂→ S₄O₆2- + 2I⁻
(b) Starch
(c) (i) Calculating number of moles of iodine dissolved in CHCl ₃
moles of S₂O₃2- used = C x V = 0.02 x (7.70/1000) = 1.54 x 10⁻⁴
moles of iodine = ½ moles of thiosulphate = ½ x 1.54 x 10⁻⁴
Concentration of iodine in the CHCl₃ = mol/vol
= ( ½ x 1.54 x 10⁻⁴)/5.00cm3
= (½ x 1.54 x 10⁻⁴)/0.005
= 0.0154 moldm⁻3
(ii) Finding concentration of iodine in the aqueous layer:
Moles of S₂O₃2 used = C x V = 0.02 x( 20/1000)
= 4.0 x 10⁻⁴
Moles of iodine present = ½ x 4.0 x 10⁻⁴=2.0 x 10⁻⁴
 771

Concentration of iodine in the aqueous layer

=(2.0 x 10⁻⁴)/ 0.125
= 0.0016 moldm⁻3
[I₂] in CHCl₃
The partition coefficient is given by
[I₂] in H₂O
= 0.0154/0.0016
= 9.625
Note that the partition co-efficient has no units.
Comment
Iodine is more soluble in trichloromethane than in water. In fact, judging by the partition co-efficient,
iodine is about ten times more soluble in trichloromethane , at the temperature at which the separation
was carried out.
Trichloromethane is a suitable solvent, because the calculation above has shown that it dissolves iodine
much better than water does. Trichloromethane is also volatile (easy to separate from the solute), inert
towards the solute and a good solvent for the non-polar iodine. However trichloromethane is a polar
molecule and therefore it dissolves in water to some extent. This reduces its effectiveness as a solvent. A
non polar solvent such as tetrachloromethane, CCl₄, could give an even higher partition co-efficient and
hence a more efficient separation. However, CCl4 is rather involatile and it is more toxic.

Once we know the partition co-efficient, we can use it in related calculations. For instance, we may wish to
calculate the volume of iodine that is required to extract a certain minimum mass of iodine from water.

Example 2
A large number of organic compounds are soluble in both water and non-aqueous solvents such as
hexane. If such a compound is shaken with a mixture of water and the non-aqueous solvent, it will
dissolve in both solvents depending on the solubility in each.

A large number of organic compounds are soluble in both water and non-aqueous solvents
such as hexane. If such a compound is shaken with a mixture of water and the non-aqueous
solvent, it will dissolve in both solvents depending on the solubility in each.

When 100 cm3 of an aqueous solution containing 0.50 g of an organic compound X was shaken
with 20 cm3 of hexane, it was found that 0.40 g of X was extracted into the hexane. Calculate the
partition coefficient of X between hexane and water.

Solution
(ii)
0.5−𝑦
[X] in water =
100

[X]in hexane
Kpc =
[X]in water
 772

We use the value of Kpc found above:

y
y
20 = 10 = x 100
0.5 - y 10 0.5 - y
100
10y
= which givesy = 0.33
0.5−y

Therefore the first 10.00 cm3 of hexane extracts 0.33g of the solute X.
The amount of X left in water is now 0.5 – 0.33 = 0.17.

Extraction with the second portion of hexane (10cm3):

Let amount of X separated into the hexane layer be p.
p
[X] in hexane =
10

0.17−p
[X] in water =
100

[X]in hexane
Kpc =
[X]in water

p 0.17−p
20 = ( )/ ( )
10 100

10p
20 =
0.17−p

p = 0.11

The amount of solute X separated by the second 10cm 3 of hexane is 0.11g. The total amount separated is
therefore 0.33 + 0.11 = 0.44g.

Comment
When one 20cm3 portion of hexane was used, 0.40g of solute X were separated. When two smaller
portions of hexane were used successively, a larger amount of solute was separated.
The efficiency of the extraction can be expressed as a percentage
Efficiency of extraction using one large 20cm3 portion = 0.40/0.50 = 80%
Efficiency of extraction using two 10cm3 portion = 0.44/0.50 = 88%.
Excessive extractions using smaller volumes of solvent gives a better extraction than using one large
volume of the solvent in a single extraction.
 773

Q
Calculate the total amount of x that could be extracted by using four 5.00cm3 portions of
hexane rather than one portion of 20cm3.

Your answer above shows that the efficiency of the extraction increases with increasing number of small
portions used. (However, very small portions become impractical, and in practice it is not possible to
achieve 100% separation because it is not really possible to shift equilibrium completely to one side).
The other advantages of successive extractions, apart from a higher efficiency of separation, are
 Wastage is reduced and the cost of buying solvents is minimized.
 Risk of fire is reduced when small amounts of solvent are used.
 Pollution to the environment is minimized as relatively small volumes are required to separate
relatively large amounts of solute.

3.2.5 Continuous solvent extraction

This technique greatly increases the amount of solute that can be separated. Fig 11.77 shows an apparatus
for continuous solvent extraction. This technique works well when the solvent is highly volatile and the
solute is involatile and stable towards heat. The process is said to be continuous because transfer of the
solute from the aqueous to the ethereal layer occurs continuously. As the organic solvent (ether) rises
through the aqueous layer, it dissolves and carries solute particles with it to the top. This transfer of solute
from the aqueous to the ethereal layer occurs as a continuous process, as long as there is still ether vapour
being delivered from the reservoir (flask). The solvent is therefore used in small amounts in one
continuous process. This greatly increases the efficiency of the separation process.

Fig 11.77 Continuous solvent extraction

 774

2.3.3 Chromatography

The term “chromatography” comes from two Greek words, chroma (colour) and graphein (to write). This
term is suitable in view of the fact that originally, the technique of chromatography was used to separate
coloured substances. However, nowadays, colourless substances can also be analyzed by this method.
Chromatography is particularly useful in the separation of a mixture of substances which are
 very chemically similar to each other
 are present in very small quantities.

3.3.1 How chromatography works

Chromatography involves the partitionor adsorption of different solutes in a mixture between a
stationery phase and a mobile phase.

 Stationary phase – this is a material of uniform composition which is held firmly in place as part
of the chromatographic column. The substance to be analyzed (known as theanalyte), which can
be in liquid or gaseous form, flows over the stationary phase. The stationary phase can be a solid
or a thin layer of a liquid supported on the surface on an inert solid.
 The mobile phase – This is a carrier substance responsible for carrying particles of the analyte
over the stationary phase. The process in which the analyte passes over the stationary phase is
known as elution. When the analyte comes out through the other end of the chromatographic
column, it is known as the eluant.
 Adsorption – This is the process whereby particles of the solute stick onto the surface of the
stationary phase by the formation of intermolecular forces [Do not confuse with the term
‘absorption’ in which particles pass through a substance].
 Partition – This involves differential dissolution of the solute in the mobile and stationary phase.

As the analyte moves over the stationary phase, its particles adsorb weakly to the surface of the stationary
phase, or the solute partitions itself between the mobile phase and a liquid stationary phase.
Separation by chromatography depends on two things.
 The different solubilities of the solutes (contained in the analyte) in the stationary and in the mo-
bile phase. A substance which dissolves well in the mobile phase is more easily carried through
the chromatographic column. A substance with poor solubility in the mobile phase will not be
carried so easily, but it will tend to remain for a relatively long time in solution with the liquid
stationary phase. A partition equilibrium is set between the stationary phase and the
mobile phase. However, this is not a true equilibrium since the system (the chromatographic
column) is not a closed system (in which there is no net gain or loss of particles). Any given
section of the chromatographic column constantly receives new particles from points behind it,
and loses particles to points ahead of it.

 The different affinities of the solutes for the stationary and for the mobile phase. The greater the
affinity a solute has for the stationary phase, the more firmly it adsorbs. Such a substance there-
fore moves more slowly compared with a substance with a weaker affinity for the stationary
phase.Adsorption of a substance to the stationary phase is only temporary. At the end, substances
in the analyte will eventually be able to travel through the chromatographic column and be eluted
at the other end. However, for a substance to move from one point to another, its particles must
be detached first from the stationary phase. The role of the mobile phase is not only to transport
 775

the analyte, but also to detach molecules from the surface of the stationary phase. Those particles
which adsorb firmly or which have a poor solubility in the mobile phase tend to lag behind.
Particles with a smaller affinity for the stationary phase and a greater solubility in the mobile
phase are detached more easily and therefore move relatively rapidly through the chromato-
graphic column. There are therefore two opposing processes at work: adsorption which tends to
restrict movement of particles, and desorption, which allows the solute to be carried in the mobile
phase.

Four chromatographic techniques

We will discuss the following chromatographic techniques
• paper chromatography (PC),
• thin layer chromatography (TLC),
• gas/liquid chromatography (GLC) and
• high performance liquid chromatography (HPLC).

Table 11.6 below shows key facts about these techniques.

Technique Mobile phase Stationary phase Separation

occurs by

Paper chromatography liquid thin film of water partition

Thin layer chromatography liquid solid adsorption

Gas/liquid chromatography gas thin film of involatile partition

liquid

High performance liquid gas solid adsorption

chromatography

3.3.2 Paper chromatography

This technique has been used frequently to illustrate the principles of chromatography. This is because it
is easy to set up the apparatus and the method has an additional advantage of being cheap.
The mixture to be separated (analyte) is dissolved in a solvent, such as water or ethanol. The solvent
becomes the mobile phase. It is also possible to use a mixture of liquids for the solvent.Fig 11.78 shows a
set up for paper chromatography.
A small spot of the analyte is placed about 1 cm from the edge of a rectangular sheet of chromatography
paper. It is usual to applyspots of “reference” compounds at the same starting line as the sample. The
starting line is marked in pencil because the pencil mark does not dissolve in the solvent used in the sepa-
ration. The part of the paper just below the pencil mark is then dipped into the solvent. The use of refer-
ence compounds allows the different substances in the sample to be identified. Used in this way, paper
chromatography is therefore both a method of separation and of qualitative analysis (identification). The
solvent (mobile phase) is drawn up the paper by capillary action, carrying the sample with it. The
stationary phase is a thin film of water held through hydrogen bonding with the –OH groups in cellulose
fibres found in the paper. This film of water is present even when the paper looks or feels dry. Solutes in
the mobile phase may or may not dissolve well in the stationary phase. Polar substances, especially those
 776

with the ability to form hydrogen bonds with the stationary phase, tend to stay longer in thisphase. On the
other hand, less polar substances, or those with fewer polar groups, dissolve poorly in the stationary
phase, but dissolve well in the mobile phase. Such substances therefore move relatively rapidly up the
paper. In this way, a separation pattern of spots, known as achromatogram, is formed. If the separation is
very efficient, each spot will represent a pure substance from the sample. If the technique is not so
efficient, it is possible that a spot will still contain a mixture of substances.

Fig 11.78 Separation by paper chromatography

Referring to Fig 11.78:

 The sample in this case contained three substances, represented by the three spots E, F and G.
The reference spots A, B, C should be pure substances used for comparison. Thus each of the
reference substances produced a single spot, labelled D, H and I respectively.
 D, H and I are known substances. By comparing the distances moved by the reference substances
with that moved by substances in the sample, it is possible to determine if the sample contains
some or all of the substances used for reference. It can be concluded that one substance present in
the sample (substance E) is the reference compound C. Note that spot E is at the same level with
spot I from compound C.
 It is possible to compare the solubilities of the substances in the sample in the stationary phase.
Substance G has the least solubility in the stationary phase, but it has the greatest solubility in the
mobile phase.
 Substance E has the greatest solubility in the stationary phase but the least solubility in the
mobile phase. It must be the most polar substances, or it must have the largest number of polar
groups, allowing it to dissolve well in the stationary phase. In other words, the partition of solute
E between the stationary and the mobile phase lies in favour of the mobile phase.
 One substance in the sample has been identified by comparing with spots from the reference
substances. Two of the substances in the sample have not been identified because they do not
match with any spot from the reference substances. However, it is still possible to identify these
substances by referring to Rf tables. Rf refers to the retention ratio of a particular substance. It is
expressed a
 777

Distance moved by solute

Rf =
Distance moved by solvent

For substance B, represented by spot H on the chromatogram above

Rf= y/x
The maximum level reached by the solvent at the top of the chromatographic paper is known as the
solvent front. The distance marked ygives the distance of the solvent front from the start line, that is, the
maximum distance moved by the solvent. The value of Rf obtained for a particular substance(spot) on the
chromatogram can be used to identify the substance from R f tables. These tables give the Rfvalues that are
expected for certain substances under certain conditions. It follows that the same substance will always
move through the same distance on chromatographic paper. Of course, the experiment must be carried
out under the conditions at which the tabled Rf values were obtained, otherwise the comparison would not
make sense at all. By conditions here we mean the solvent used, the temperature at which the process is
carried out and the exact nature of the paper used. Draughts must also be prevented by placing the paper
inside a glass tank closed with a lid.

Detection of the substances separated by paper chromatography

Coloured solutes on the chromatogram can be detected by eye. For example, it is possible to separate and
observe the number of different dyes in ink or chlorophyll. The detection becomes easy and straightfor-
ward if the spots are well separated from each other. If this is the case, the chromatogram is said to have a
high resolution, that is, it gives a clear distinction between spots of different solutes. Sometimes different
spots tend to overlap and it becomes difficult to distinguish between different solutes. This happens when
the different substances in the sample have similar R fvalues. This problem of low resolution can some-
times be solved by changing the solvent.
Some years back it was not possible to detect by eye colourless substances separated by chromatography.
Nowadays, colourless substances on the chromatographic paper can be made visible by spraying the paper
with certain dyes. The dye interacts with the substances on the paper, forming coloured products. Amino
acids can be identified by spraying the chromatographic paper with ninhydrin.

Two - way paper chromatography

This method is more suitable for a complex mixture of substances. Two way paper chromatography
achieves a better resolution. One solvent is first used as described above. The paper is then removed when
the solvent front stops changing position. The paper is then rotated through 90⁰ and its left side placed in
a second solvent in the usual way. This technique is often used to analyze a complex mixture of amino ac-
ids from the hydrolysis of a protein. At the end of the second development, the amino acids, which are
colourless, are made visible by treating the paper with special reagents.
A chromatogram after this two way treatment can be explained as below

S  Assume that a spot of the sample to be analyzed was

placed at point X on the paper in solvent 1(Fig 11.79).
P Q The start line is marked MN. The paper was held in the
D D' position shown for the arrow for solvent 1. Solvent 1
C C' moved vertically up the paper, as shown by the arrow,
solvent 1

B B' pulling along the sample with it. The solvent front for
solvent 1 is represented by the line PQ. After
A A' development with solvent 1, the chromatographic paper
M X N had four spots, labeled A, B, C and D. This shows that
solvent 2 R the sample could have been a mixture of four substances.
Fig 11.79
 778

 The paper was then rotated through 90⁰, and placed in solvent 2, so that the side marked MP was
in contact with the solvent.
 Solvent 2 moved vertically up the paper as shown by arrow 2. The second development could
reveal if there were actually more than four substances in the sample. The second solvent will now
wash up the spots A, B, C and D up the paper. If any of these spots contains more than one
substance, then the second solvent will be able to separate them.
 In this case, solvent 2 does not achieve any further separation, showing that the sample indeed
had four substances in it. The second solvent washes up the spots A, B, C and D, displacing them
to new positions up the paper. The solvent front for solvent 2 has been marked SR. The ‘primed’
letters show the final positions of the spots A, B, C and D after the second development for
example, the letter A′ shows the final position of spot A.

Q
Estimate the Rf value of substance D in solvent 1 and in solvent 2.

3.3.3 Thin layer chromatography (TLC)

This chromatographic technique is similarto paper chromatography. The main difference is in the statio-
nary phase used.TLC makes use of a thin layer of a solid such as aluminium oxide (alumina) or silicon
dioxide (silica). The stationary phase is supported on an inert base such as glass or insoluble plastic. The
chromatographic plate, containing the stationary phase, is relatively small (about 15cm by 15cm) and can
be obtained from laboratory suppliers. Plates from these sources usually have standard and uniform solid
layers of the stationary phase.
The procedure of TLC is similar to that for paper chromatography. Different substances in the original
spot of the sample are separated into spots as before.This separation involves adsorption of the solute
particles on to the stationary phase. The solvent, as in paper chromatography, moves up the plate through
capillary action by filling in the spaces between the particles of the stationary phase. Particles of the
solute adsorb to the stationary phase via polar attractions such as hydrogen bonding. Acid-base
interactions are also possible, for example, if the stationary phase is made of alumina which is
amphoteric, then it will be able to interact with both acidic and basic solutes in the mobile phase.
Separation occurs because different substances in the sample have different affinities for the stationary
and for the mobile phases. If a solute has a strong affinity for the stationary phase, it easily leaves the
mobile phase and adsorbs strongly to the stationary phase. Such a solute moves slowly up the
chromatographic column.

Detection after separation

Detection can be achieved visually, as in paper chromatography. Colourless solutes can be identified by
spraying the plate with certain chemicals.
Chemicals have been used which are able to absorb invisible UV light and emit it as visible white light, in
a process known as fluorescence. This method is particularly used to locate substances which can absorb
UV without giving out the gained energy as light. The silica or alumina is impregnated with the chemical
agent after which the plate is exposed to UV from a UV lamp. The plate fluoresces white light, except at
certain spots containing solutes that can absorb UV light, for example aromatic compounds. These spots
do not give out light and so they appear dark.
 779

Applications of TLC
The industrial applications of TLC include
 detection of the progress of a reaction
 detection of reaction intermediates.
Detection of reaction intermediates is an important step in the determination of reaction mechanisms. A
reaction mechanism is the detailed sequence of small steps leading from reactants to products. If reaction
intermediates are known, then it is possible to build up a mechanism for the reaction. In this respect, TLC
is used as follows:
A sample is withdrawn from the reaction vessel. The sample is then applied as a thin line on the start line
of the chromatographic plate. As the solvent moves up the plate, particles of the different substances
present in the reaction mixture also move up, and adsorb onto the plate in lines. Different substances
have different affinities for the stationary phase so they form lines at different levels on the plate. The
lines can be cut out of the plate and the substances present dissolved in appropriate solvents. The identity
or nature or quantities of these substances can then be determined by other analytic techniques.

Advantages of thin layer chromatography over paper chromatography

 The results of TLC are more reproducible. That is, the chances are higher that the same results
will be obtained when the experiment is repeated by the same person, or by another person,
provided the same conditions are used.
 Separation by TLC is more efficient because of the very small particle size of the stationary phase.

The obvious disadvantage of TLC over paper chromatography is that it is more expensive. However, the
cost of a TLC plate for a school lab can hardly be regarded as being prohibitive.

3.3.4 Gas/liquid chromatography (GLC)

This technique differs from PC and TLC in that it uses a gas as the mobile phase. The stationary phase is
an inert and non-volatile liquid coated onto a thin layer of small inert solid particles. The glass column
into which the liquid coated particles are packed is very fine, being only a few millimeters in diameter. The
column is typically between 1 and 3 meters long. Fig11.80shows the basic structure of the machine used in
GLC.
 780

Fig 11.80 Basic structure of the GLC machine

 Unlike PC and TLC in which the sample is carried in solution with the mobile phase, in GLC,the
sample is carried through the apparatus as a vapour. The sample should therefore be introduced
into the sample port in vapour form. However, a volatile liquid can be introduced because the
heat in the injector oven evaporates the sample.
 The mobile phase is an inert gas, typically hydrogen or nitrogen. This gas is referred to as the
carrier gas. It carries the gaseous sample through the chromatographic column. The carrier gas
must be dried first to remove water vapour that would otherwise interfere with the separation.
The gas can be dried by passing it over anhydrous copper (II) sulphate or silica impregnated with
cobalt (II) chloride.
 Substances in the sample partition themselves between the carrier gas and the liquid stationary
phase. Since different substances have different solubilities in the mobile and the stationary
phase, they will move through the column at different speeds.
 Unlike in PC and TLC, temperature control in the chromatographic column is very important.
The chromatographic oven is controlled by a thermostat and it can be adjusted to achieve the best
separation. Temperature affects the ability of the apparatus to separate substances. It also affects
the speed at which substances are eluted at the end of the chromatographic column.
 Substances in the sample are eluted out at the end of the chromatographic column, where they
are detected by a suitable detector such as the flame ionization detector. The substances in the
sample are eluted at different times. The retention time of a substance refers to the time it
takes the substances to reach the detector. Some substances have known retention times, so it is
possible to identify such substances when they are eluted at the end of the chromatographic
column (of course, this works if the GLC is carried out under the same conditions at which the
retention times were obtained). Different substances in the sample differ in their retention times
because of the different solubilities they have in the stationary phase. If a substance dissolves well
in the stationary phase, then it spends a long time in the chromatographic column, that is, it will
have a high retention value.
Fig shows a retention-intensity graph for an analyte that contained five solutes A to E.

B
intensity

A
E
C
D

0 5 10 15 20 25 30
retention time/min
Fig 11.81
A GLC chromatogram of aAmixture
GLC chromatogram
of organic compounds.
 The sample was introduced into the GLC column at time 0. The sample contained five substances,
A, B, C, D and E. Substance E spent the most time in the chromatographic column. It had the
highest retention time. We can also infer that it also had the greatest solubility in the stationary
phase.
 The first substance to be eluted from the chromatographic column was A. It had the smallest
retention time. It was also the leastsoluble in the stationary phase.
 The most abundant substance in the sample was B. It gave rise to the most intense (tallest) signal.
 781

 The retention time of a substance depends on a number of factors, including, its volatility,
temperature of the oven, chemical properties of the substance and the flow rate of the carrier gas.

Applications of GLC
GLC is routinely used to analyze gaseous or liquid mixtures of organic compounds. It is a very sensitive
technique, that is, it can be used to detect minute quantities of a substance, for example, pesticide residue
in food. The technique also has a high resolution, that is, the ability to distinguish between compounds
with similar chemical and physical properties. GLC has been used in the following ways:
 Analysis of the composition of an oil slick found at sea can help to identify the source of the
spillage.
 Analysis of organic compounds in exhaust fumes.
 Analyzing the composition of alcoholic beverages.
 To check the dosage of drugs in urine or blood samples.
 To analyze food substances for the presence of pesticides.

The major limitation of GLC is that the sample must be gaseous, or it must easily turn to a gas. Moreover,
some substances cannot easily be analyzed by this method, for example carboxylic acids. These substances
are too polar and tend to bind rather too firmly to the stationary phase.

3.3.5 High performance liquid chromatography (HPLC)

The principle behind HPLC, and the instrumentation, is similar to that of GLC. There are some
differences though. In HPLC,
 the mobile phase is a liquid of high purity, which also acts as the solvent for the substances in the
sample. In GLC, the mobile phase is a gas.
 the chromatographic column is shorter ( typically 10 – 30cm). Compare with GLC in which the
column is typically between 1 and 3m long.
 the components are usually detected by UV spectroscopy. This involves measuring UV absor-
bance of the separated components.

Fig 11.82belowshows the basic structure of the HPLC machine.

sample injection waste

port

mobile phase detector

(liquid)
high
pressure chromatographic
pump column

chart recorder

Fig 11.82
 782

The stationary phase in the chromatographic column consists ofporous particles of silica of a uniform
diameter. The particles are very small, typically with a diameter of1 x 10 -6 m. The very small size results in
a very large surface area over which adsorption may occur. The stationary phase is therefore solid, just as
in TLC. However, in some machines, a thin layer of involatile and chemically stable liquid is coated on the
solid silica layer. In that case, the stationary phase can be said to be both liquid and solid, because the
solutes in the sample will be attracted to the polar groups on both the liquid and the solid particles.
The high pressure pump in the set up provides a constant flow rate of the mobile phase through the
column. It also forces the mobile phase to move through the tightly packed solid particles in the column.

Detection of eluant
Substances exiting at the end of the column are mainly detected by UV spectroscopy. This involves
collecting the substance in a microcell at the end of the column and then measuring UV absorbance of the
substance. Different substances give different absorption patterns.

Applications of HPLC
HPLC can be considered to be an improvement of GLC. Many substances that can be analyzed by GLC can
also be analyzed by HPLC. Many other substances which cannot be analyzed successfully by GLC can be
analyzed by HPLC. Like GLC, HPLC is typically used for the separation and analysis of organic
substances. HPLC has been useful in the identification of drugs in the blood or urine of athletes and
horses. In such cases, it may be necessary to obtain results rapidly. HPLC is useful in this respect because
it gives results almost immediately. HPLC allows separation and analysis of a wider range of substances
than any other chromatographic technique, including residual pesticides in food and detection of residual
chemicals from explosives.

3.3.6 Applications of chromatography in chemical analyses

The relative use of the different chromatographic techniques depends on a number of factors, including
 the complexity of the mixture to be separated and analyzed. Complex mixtures are best analyzed
by GLC or HPLC.
 the purpose of the analysis. To show or introduce the principles behind chromatography, it is
usual to use paper chromatography in school labs.
 the industry concerned. Some industrial analyses require the use of sophisticated techniques such
as HPLC, but in some industries the use of relatively simple technique such as TLC is sufficient.
 the compounds to be separated. Some substances decompose at the operating temperature of the
GLC ovens. This problem can be avoided by using HPLC.
 Urgency. If results are required urgently, then HPLC is the best technique to use.

An example of the practical applications of chromatography

Dope testing in race horses
It is against the law to dope race-horses with the intention of enhancing or retarding performance. Race-
horses are frequently tested for the presence of performance enhancing or retarding dope (drugs). The
method actually involves testing for the break-down products of the drugs in urine. First, the urine is
separated into components of different acid-base nature by passing it through various silica based
chromatographic columns. After separation, strongly acidic components are analyzed by silica or alumina
based TLC. Neutral components are analyzed by HPLC and basic components by GLC followed by mass
spectrometry.
 783

2.3.4 Electrophoresis

3.4.1 Principles of electrophoresis

We have studied two methods of separation so far, solvent extraction and chromatography. A third
method of separation is known as electrophoresis.
Electrophoresis involves separation of substances in an electric field, based on their charge and size. This
technique is particularly useful in the separation of amino acids, nucleotides, DNA fragments and
proteins.
The mixture to be separated is placed at the centre of the electrophoretic bed, which is moistened by an
appropriate buffer solution. Positive ions in the mixture are attracted to the cathode, whereas negatively
charged ions migrate to the anode. The factors which affect separation of ions by electrophoresis are

 Type of charge. The general direction of movement of the ions depends on whether they are
positively or negatively charged. If an uncharged substance is also present in the mixture, it does
not move in the electric field. It remains at the starting point, and thus it is separated and
distinguished from charged substances.
 Size of charge. Ions of the same type of charge will move in the same direction. However, those
ions with the larger charge will move faster. In this way, it is possible to separate ions of the same
type of charge. For example, M⁺ and M2+ ions will both move towards the cathode. However, M 2+
ions will move faster.
 Size (relative mass) of the ions. Heavier ions move more slowly than lighter ones, even when they
have the same size of charge.
 pH of the buffer. This affects ionization of the species present in the mixture. In turn, this affects
the direction in which the ions move.
 Strength of the electric field. The greater the potential difference between the anode and the
cathode, the faster an ion will move.
 Shape. A highly branched molecule experiences greater resistance to movement by interfering
with other molecules. Such a molecule moves more slowly compared with an unbranched
molecule.
 Temperature. Increasing temperature increases the speed of movement of ions, but high
temperatures may cause denaturation of proteins in a sample.

The technique of electrophoresis can be demonstrated in the lab as illustrated for the amino acids glycine,
glutamic acid and lysine in Fig 11.83(a).
The filter paper is soaked in a suitably buffered solution, in this case at a pH of 7. It is necessary that the
paper strip be buffered, to prevent changes in pH caused by electrolytic processes. Changes in pH would
affect the ionization of amino acids, and in turn this affects the migration of the amino acids. One example
of an electrolytic process is the conversion of OH⁻ to form oxygen. This would result in a decrease in pH.
After the clips have been disconnected, the amino acids would have been separated according to their
charge and mass. Spraying the paper with ninhydrin shows the separation pattern. Fig 11.83 (b)shows the
separation pattern expected for the three amino acids, glutamic acid, glycine and lysine.
At pH 7, glycine undergoes self-neutralization, with a hydrogen ion from the carboxyl group protonating
the amine group (Fig 11.83 c). The result is the formation of zwitterions with one centre of positive charge
and one centre of negative charge. The net charge in the molecule is therefore 0. Consequently, glycine
molecules remain stationary at the starting point.
 784

Glutamic acid has two carboxylic acid groups. One of the groups protonates the amine group. This self
neutralization creates a positive charge on the amine group and a negative charge on the carboxylic acid
group. These two charges, being equal but oppositely charged, cancel each other out. The second carbox-
ylic acid loses its proton into solution, forming a carboxylate ion. Glutamic acid therefore has a net charge
of -1 at a pH of 7. Thus it will move towards the anode.

rectangular
piece of filter paper
on microscope glass microscope slide
slide

crocodile clip

drop of a solution containing

three amino acids; glycine ,
glutamic acid and lysine.

50V DC supply

glycine glutamic acid lysine

O
H O H + _ O
H + H +
C C _ H N CH C O _
H N O H H N CH C O
H H CH2 H
CH2
CH2
C O CH2
CH2
O_
CH2
+N
H H
H
Fig11.83(a)

Start of experiment After 1 hour

+ _ + _

start line glutamic acid glycine lysine

Spot containing
three amino acids
Fig 11.83 (b)Separation of glutamic acid, glycine and lysine by electrophoresis
Separation pattern of a mixture of glycine, glutamic acid
and lysine.
 785

amine group: carboxyl group:

proton acceptor proton donor

H O H O
H H +
H N C C H N C C _
O H O
H H H

Self neutralisation in glycine, resulting in the

formation of a zwitterion.

Fig 11.83 (c)

Lysine has two basic amine groups. One of these neutralizes the carboxyl group, resulting in the formation
of an-NH₃⁺ and an –COO⁻ group. The effects of these two groups cancel each other out, so they do not
contribute to the movement of the amino acid in the electric field. The second –NH₂ group on the amino
acid accepts a proton from the solution, even from other amino acids, and becomes the –NH₃⁺ group.
Lysine has therefore a net charge of +1 at pH 7 and it will migrate towards the cathode.
Notice the pH dependence of this separation. Suppose that the separation is to be carried in a solution
buffered at pH 9. At that alkaline pH, the acidic –NH₃⁺ group on lysine would be converted to the basic
and uncharged –NH₂ group. Meanwhile, the carboxylate group –COOH is unaffected. Overally, glycine
molecules would have a net charge of -1 and would migrate towards the anode (At pH 7 the amino acid
molecules do not move). Glutamic acid would have a net negative charge of -2. It will therefore move
towards the anode as before, but this time it will move faster because the magnitude of negative charge is
now larger.

Q
Predict the direction, if any, in which lysine will move during electrophoresis at pH 8

You might have noticed that lysine will have a net negative charge at pH 8, so it will move towards the
anode. Thus at pH 8, the amino acids lysine and glutamic acid moves in the same direction, which might
not give very satisfactory results. However, the amino acids can still separate due to the fact that one of
the ions, glutamic acid, has the larger magnitude of charge, so it will be attracted more rapidly to the
anode. However, there is also the issue of molecular mass. Glycine, even though it has only a charge of-1,
will also move fast because of its small size. Thus the separation of glycine and glutamic acid might not be
so satisfactory. Thus to demonstrate the principle of electrophoresis using these three amino acids, it is
recommended that a pH of 7 be employed. At that pH, one amino acid will migrate to the anode, one to
the cathode, and one will not move at all. In practice, we may not know which amino acids are present,
and so we may not be able to choose a pH that will give the best separation results.

Q
Predict the direction, if any, in which lysine, glutamic acid and glycine will move during
electrophoresis at pH 6.

3.4.2 Gel electrophoresis

 786

Paper electrophoresis as described above is rather imprecise. In industry, one electrophoretic technique,
know as gel electrophoresis, involves separation of ions on a bed of gel. This is illustrated in Fig 11.84. A
gel is used because its properties can be precisely controlled during the electrophoresis in order to get
optimum results. Moreover, a gel provides a more chemically stable support to the constituents in the
mixture.

Sample is
placed here
wick wick
_
+
glass plate

buffer solution buffer solution

Fig 11.84
apparatus for Apparatus for gel electrophoresis
gel electrophoresis

The sample mixture is placed in a gel which is buffered by a solution from reservoirs. The buffer solution
seeps up gradually through paper wicks from the reservoirs and is uniformly distributed through the gel
bed. When an electric field is applied, the charged particles in the sample are separated as already dis-
cussed. Gel electrophoresis is routinely used in the separation of proteins, amino acids, nucleotides and
fragments of DNA.
Proteins can be separated in this way because they can have a net positive or net negative charge at the pH
used for the separation, causing some to move towards the anode and some towards the cathode. Proteins
which happen to move in the same direction can still be separated if they have different masses, which is
usually the case. Fragments of nucleic acids such as DNA usually bear a negative charge at the phosphate
groups at the pH which is usually used for the separation. Thus the fragments tend to migrate to the
anode. Separation is possible because fragments of different size move at different speeds. In gel electro-
phoresis, components of the mixture are separated into bands which can be analyzed using a number of
techniques, such as bioassays and silver staining. These techniques are very sensitive and can be used to
detect minute quantities of a substance from a separation band.
If substances in the mixture to be separated by electrophoresis have similar electrophoretic mobilities,
then complete separation may not be possible. This problem can be solved by changing the buffer pH or
altering the properties of the gel support medium. Two way gel electrophoresis can be used to achieve a
better separation. In this technique, the separation is repeated twice, using a different buffer each time.

Applications of gel electrophoresis

Gel electrophoresis has a wide range of applications, including
 genetic fingerprinting
 chromosome sequencing
 checking for the presence of contaminants in food.
 screening milk formulae for α- lacto globulin, a protein which can lead to death if ingested by
infants.

The medical applications of gel electrophoresis include

 Investigating the extent of alcohol abuse. This is done by taking blood samples and then
separating the proteins by gel electrophoresis. Excessive abuse of alcohol leads to an alteration of
some blood proteins. Gel electrophoresis can show the presence of such altered proteins.
 787

 Checking for fitness. The human kidney does not usually allow proteins to be lost from the blood
in urine. A serious increase in the amount of proteins in urine is a general indication of a
deterioration of health. It can also signal the onset of diabetes. Gel electrophoresis can be used to
check urine for the presence of proteins.

3.4.3 Case study: the use of electrophoresis in genetic

fingerprinting
DNA contains coding and non coding regions. The coding regions have sequences of bases organized into
genes.Recall that a gene is a sequence of consecutive bases which codes for a specific protein.Between
these genes are found sequences of bases which do not really code for any protein or trait. These
non - coding regions of DNA are known as minisatellite regions. In fact,if all coding regions of DNA were
brought together, they would constitute only about 10% of the chromosomal DNA.
The technique of DNA fingerprinting involves obtaining a pattern of base sequences in the minisatellite
regions of an individual’s DNA. Each person in the whole world has a unique pattern of bases in these
satellite regions. This pattern can be shown as a genetic fingerprint by the technique of electrophoresis.

genes(coding minisatellite (non-coding)

regions). regions.
These are used to obtain a genetic
fingerprint of an individual.
Strand of DNA showing
Fig 11.85 genes
Strand and
of DNA showing genes and minisatellite
minisatellite regions.
regions

Steps in obtaining a genetic fingerprint

 Extraction of DNA from sample (blood, inner cheek cells, skin, semen etc).
 Formation of DNA fragments by restriction enzymes.
 Polymerase chain reaction (PCR) to multiply the amount of DNA. This is only necessary if the
amount of DNA obtained from the source is much smaller than 25mg.
 Separation of fragments by gel electrophoresis.

The use of restriction enzymes

Certain enzymes, obtained from bacteria, are capable of slicing DNA into pieces. These enzymes, known
as restriction enzymes, are highly specific; a particular restriction enzyme can only cut DNA at a specific
point. The use of restriction enzymes enables the DNA to be cut in such a way as to obtain fragments of
DNA from the minisatellite regions. Several restriction enzymes are used together since one enzyme is
only able to cut the DNA at one point.

The polymerase chain reaction (PCR)

This technique is used to amplify tiny quantities of DNA to get amounts that are sufficient for use in gel
electrophoresis. The amplification process is carried out by an enzyme known as DNA polymerase. Since
 788

the process requires heating, an ordinary enzyme would fail to function due to denaturation. The enzyme
used comes from an unusual source; Thermusaquaticus, a bacterium that lives in hot springs. The PCR
occurs in the following stages:

 A double stranded fragment of DNA is unwound into separate strands by heat. There are now two
segments present.
 Primer molecules, free bases (G,A,C,T) and DNA polymerase are added.Primer molecules are
necessary in the initiation of the reaction.
 Each of the two strands from the DNA attracts free bases according to the rules of base pairing: G
attracts C, and A attracts T.
 DNA polymerase then catalyzes the condensation reaction that joins the free nucleotides together.
In this way, a new strand is formed which pairs up with the old strand to form a DNA fragment,
which is an exact copy of the original DNA. Thus one DNA fragment gives rise to two DNA
molecules.
 The process is repeated many times (by automation) until a sufficient amount of DNA has been
formed.

Separation of the fragments by gel electrophoresis

The DNA fragments are now placed in wells near the cathode of a gel plate. The DNA fragments are
repelled by the cathode and migrate to the anode. This is because the fragments carry a negative charge at
the dissociated phosphate group. Separation of fragments occurs because they move at different speeds.
The smaller fragments move faster.

Development of the DNA pattern

In theory, the separation pattern of the fragments could be obtained on the gel plate by spraying with a
suitable dye. However, the separation bands would appear very faint due to the very small quantities of
DNA present in each band. In practice, DNA fragments labeled with heavy phosphorous (32P) are
transferred from the gel onto a nylon membrane.
An X - ray sensitive film is now placed over the film. The heavy DNA on the nylon membrane produces
gamma radiation which then develops the X-ray sensitive film. The film is darkened where the rays from
the nylon membrane strike it. The dark bands on the film correspond to the position and pattern of DNA
fragments on the nylon membrane and on the gel. The pattern of bands obtained on the X-ray film form
the genetic fingerprint of the individual whose DNA has been used.

3.4.4 The applications of genetic fingerprinting

The technique has been used in
 Forensic investigations to determine the criminal among suspects. In this case, the DNA can be
obtained from body tissues or fluids left at a crime scene by the criminal. Of course, the
investigation depends on the availability of at least one suspect. The separation pattern of DNA
from the crime scene is now compared with the DNA fingerprint of the suspect. If the DNA
fingerprint from the suspect matches the DNA fingerprint for the DNA taken at the crime scene,
then the suspect moves from the status of suspect to that of criminal.
 Paternity testing. This involves comparing the suspected father’s genetic fingerprint with that of
the child. Certain regions on the two genetic prints should match if the man is indeed the child’s
father.
 789

Questions, solutions and discussions

Q1(a) Electrophoresis can be used to separate amino acids which are produced by the
hydrolysis of a polypeptide.
Using glycine as an example, explain why the result of electrophoresis depends on pH.

(b) The diagram below shows the results of electrophoresis in neutral solution. At the start of
the experiment a spot of a solution containing a mixture of amino acids P, Q, R and S was
placed in the middle of the plate. Following electrophoresis, the amino acids had moved to
the positions shown in the lower diagram.

before + _

after + _
P Q R S

(i) Which amino acid existed mainly as a zwitterion in the buffer solution?
Explain your answer.

(ii) Assuming amino acids R and S carry the same charge when in this buffer solution,
which is likely to be the larger molecule? Explain your answer.

(c) Amino acids may also be separated by using two-dimensional paper chromatography.
This involves putting a spot of the mixture on the corner of a piece of chromatography
paper and allowing a solvent to soak up the paper. The paper is then dried, turned
through 90° and placed in a second solvent. This method gives better separation than a
one solvent method.

(i) Paper chromatography relies on partitionbetween the solvent applied and another
phase. What is this second phase?

(ii) The table below shows the Rf values for some amino acids in two different
solvents.

amino acid Rf solvent 1 Rf solvent 2

A 0.1 0.2
B 0.0 0.4
C 0.3 0.0
D 0.8 0.9
E 0.6 0.5

Use the grid below to plot the positions of the amino acids after two-dimensional
paper chromatography using solvent 1 followed by solvent 2.
 790

solvent
front

solvent 1

solvent 2
spot applied here solvent
front

(iii) Which amino acid travelled fastest in both solvents?

(iv) Which amino acid did not move at all in solvent 2?

9701/04/M/J/07

Solutions and discussions

a) The zwitterionic form of Glycine is shown below.

H O This structure is formed at pH 7 when the –NH₂ group is protonated by the –
H +
H N C C _ COOH group. Because the net charge on the molecule is zero, it will not move in
O
H H
the electric field during electrophoresis. At a higher pH, say 12, glycine exists in the
form shown below.
At pH 12, the buffer solution is alkaline, and so it neutralizes the acidic –COOH
H O group, converting it into a carboxylate group. During electrophoresis, the amino
H
H N C C _ acid molecules will therefore move to the anode. At an acidic pH, say 5, glycine
O
H
exists in the form shown below.At this pH, the buffer solution has an excess of H⁺
ions, which neutralizes the –NH₂ group, forming the positively charged –NH₃⁺
H O
H + group. The amino acid molecules will therefore move towards the cathode.
H N C C
OH
H H
 791

(b) (i)Q. The amino acid molecules did not move, so they bore a net charge of zero.

(ii)R. The molecules lag behind S, so they must be heavier.

(c) (i)A film of water trapped within the paper.

(c) (ii)
solvent
front
30

D
25

20 C E
solvent 1

15

10

5
A
B
0 5 10 15 20 25 30 35 40
spot applied here solvent
solvent 2
front

(iii)Amino acid D

(iv)Amino acid C.

To plot positions of the amino acids on the grid:

Distance moved by solute
Rf =
Distance moved by solvent

Dsolute
Rf =
Dsolvent

Dsolute = Rf x Dsolvent

Dsolute represents the distance moved by the amino acid, for example, to plot the position of
amino acid A, we note that Dsolvent 1 = 33 units. So distance moved by the amino acidAin
solvent 1 is 0. 1 x 33 = 3.3 units. Similarly, in solvent 2, the amino acid A moves through a
distance of 43 x 0.2 = 8.6 units. The position of A on the grid is therefore given by the co-
ordinates (8.6, 3.3) .
 792

Q2PCBs are highly toxic compounds released into the atmosphere when some plastics are
burned at insufficiently high temperatures. In recent years PCB residues have been found in
the breast milk of Inuit mothers in northern Canada. Foods, such as oily fish, seal and whale
meat, which are high in fat, form an important part of the Inuit diet.

(a) Suggest why berries and drinking water are not contaminated by PCBs in the same way that
oily fish, seal and whale meat are.

(b) Based on the information provided, what can you say about the partition coefficient
between fat and water for PCB residues?

(c) The diagram shows the result of two-way paper chromatography.

solvent 2

X
starting point
solvent 1

(i) How many spots were there after the first solvent had been used?

(ii) Circle the spot that moved very little in solvent 2, but moved a greater distance in
solvent 1.

(iii) Draw a square around the spot that could be separated from the rest by using
only solvent 1.

Solutions and discussions

(a)Berries contain an aqueous medium, in which PCBs are only sparingly soluble. PCBs dissolve better
and so are stored in large amounts in the fatty tissue of fish , whales and seals.

(b)Partition coefficient, that is, [fat]/ [water] is greater than 1.

(c) (i)4 .
(ii)
solvent 2

X
starting point
solvent 1
 793

Q3The technology of DNA fingerprinting has enormously advanced scientific identification

techniques in medicine, crime detection and archaeology in recent years.

(a) In order to prepare a DNA sample for analysis, the DNA is treated with restriction
enzymes.

What do restriction enzymes do?

(b) What is the next stage in DNA analysis, after the treatment with restriction enzymes?

(c) How are the DNA fragments made visible?

9701/04/O/N/08

Solutions and discussions

(a) (i)Cut DNA into sections(minisatellite)

(ii)These undergo electrophoresis on a bed of agarose gel. It might be necessary to amplify the
DNA using the PCR.

(iii)Radioactive phosphorus (32P) is used to darken photographic or X-ray film.

Q4Electrophoresis can be used to separate amino acids produced by hydrolyzing

proteins. The amino acids are placed in a buffered solution in an electric field.

In a solution of given pH, what two factors affect the movement of a given amino acid?

9701/04/M/J/08

Answer and discussion

Please refer to main text.

 794

11.1 CHEMISTRY OF LIFE

11.1.1 PROTEIN CHEMISTRY

Proteins are biological polymers made from monomers known as aminoacids

Proteins have a wide range of uses in living systems, including

 Catalysis of biological reactions. Biological catalysts are known as enzymes. All enzymes are
protein in nature.
 Transportation of oxygen. Haemoglobin is a protein responsible for the transportation of
oxygen by blood.
 Defence.Antibodies are proteins which help to destroy pathogens and toxins. All antibodies are
proteins. The clotting of blood is also brought about by enzymes. Formation of a blood clot
prevents pathogens from entering the body through a wound.
 Structure formation. Many structures in living systems are built from proteins. Examples
include hair, the skin, cartilage and some components of muscles.
 Snakes paralyze prey using venom, which is a protein.

1.1.1Amino acids
These are the building blocks (monomers) for proteins. There are 20 naturally occurring amino acids. All
amino acids have the structure shown below.

The naturally occurring amino acids contain an alpha (α) carbon. This is a
carbon atom bonded directly to a carboxylic acid group, an amino (amine)
group, a hydrogen atom and a variable R group. The groups labelled 1, 2 and
3 are common to all amino acids. The R group, labelled 4, is variable. The R
group therefore gives an amino acid its identity. It is responsible for the
different physical and chemical properties of different amino acids.
The R groups are important in determining how a protein folds into a functional molecule.
The simplest amino acid is glycine in which the R group is a hydrogen atom. The next amino acid,
alanine, has R = CH₃.

Nature of the R group

The R group varies in structure from one amino acid to another. One way of describing the R group is in
terms of its polarity. Some amino acids contain a non-polar R group; some contain a polar R group (Panel
11.1).
 795
Panel 11.1

Amino acids with non- polar (hydrophobic R groups)

H O H O H O
H H H
N C C N C C N C C
H OH H OH H OH
H CH3 C
CH3 CH3
glycine(Gly) R = H alanine(Ala) R = CH 3
valine (Val) R= -C(CH3)2

H O
H H O
N C C H
H OH N C C
CH2 H OH
CH2
C
CH3 CH3
phenylalanine (Phe) leucine (leu)

Amino acids with polar (hydrophilic R groups)

H O H O
H H
N C C N C C
H OH H OH
CH2OH CH2
serine (Ser) CH2
CH2
CH2NH2
lysine(Lys)

Amino acids are not always drawn as shown in the diagrams above. You should be able to identify amino
acids, no matter how they are drawn. The trick is to identify the α carbon, that is, a carbon atom which is
bonded to four groups; a carboxylic acid group, an amino group, a hydrogen atom and an R group.
It might not be obvious at first sight that the two compounds in Fig 11.1 are amino acids.

A B
Fig 11.1
 796

However, if you analyze the two structures carefully, you will notice the presence of an α carbon (Fig 11.2).
The compounds have been redrawn below, emphasizing the existence of four groups around an α carbon.

R group

α carbon R group

A B
Fig 11.2

Important information
Examiners do not expect you to recall the chemical structures of all 20 naturally occurring
amino acids, but you may be expected to recall the structures of glycine, alanine and cysteine.
Glycine and alanine are the simplest amino acids, in which R = H and -CH3 respectively.
Cysteine contains sulphur in its R group and this is important in the formation of -S-S-
(disulphide) bridges in some proteins, for example, insulin. The structure of cysteine is shown
below.

Optical isomerism in amino acids

All amino acids, except glycine, are chiral. Glycine does not show optical isomerism because of the ab-
sence of a chiral carbon atom. Enzymes are able to distinguish between the two optical isomers of an
amino acid. In living systems, only one of the optical isomers of an amino acid is usually used by enzymes,
for example, in the synthesis of larger proteins.

Q
Mark with an asterisk (*) the chiral carbon atom in alanine. Draw the two optical isomers of
this amino acid.

Chemical properties of amino acids

1. They are amphoteric
This means that they exhibit both acidic and basic behaviour. The carboxyl group gives an amino acid the
properties of an acid. The amino group gives an amino acid the properties of a base. An amino acid can
therefore react with both bases and acids, forming salts. This is illustrated for alanine :
 797

Reaction with an acid

CH3 CH3

C + HCl(aq) C + H 2O

Cl-

This is a Brønsted-Lowry neutralization reaction in which the amino group uses the lone pair on the
nitrogen atom to accept a proton from the acid.

CH3 CH3

C C

..
H+
Reaction with a base

CH3
CH3
C
+ NaOH C -
Na+

2. Amino acids are nucleophilic

The –NH₂ group behaves as a nucleophilic centre, capable of attacking and forming a dative bond to a
relatively positively charged carbon atom. Combination of amino acids to form proteins involve nucleo-
philic substitution, in which the –NH₂ group on one amino acid attacks the Cδ+atom of the –COOH group
of another amino acid.

Zwitterions
Amino acids can form zwitterions.

A zwitterion is a species that possesses positive and negative charge of equal magnitude.

The net charge on a zwitterion is therefore zero. Zwitterion formation depends on the pH of the medium
in which the amino acids are found. At a pH of 7, glycine and alanine exist as zwitterions. Zwitterion for-
mation involves self-neutralization, in which the acidic –COOH group protonates the basic –NH₂ group.
This is illustrated for alanine:
 798

.. C
pH = 7
C
-

Presence or absence of zwitterions can be determined by checking electrical conductivity of the solution.
At a pH of 7, a solution of alanine does not conduct electricity, showing that the molecules have a net
charge of zero, that is, they are zwitterionic. An electrolyte conducts electricity when ions in the
electrolyte move towards the positive or negative terminal of the electrical field. At pH 7, molecules of
alanine have a net charge of 0 and so they cannot move towards the positive or negative terminals.
However, suppose that the pH of the solution is lowered to 3. The high concentration of H⁺ ions in the
solution results in the protonation of the amino group.

CH3 CH3
pH < 7
C C
i.e high [H+]
..
H+

At this pH, alanine does not exist in zwitterionic form. It exists as positive ions which therefore migrate in
an electrical field towards the cathode, thus conducting electricity. Different amino acids have different
pH values at which they exist as zwitterions. This pH is known as the isoelectric point for that amino acid.

One consequence of zwitterion formation is that amino acids can be crystallized. The positive and
negative ends of the zwitterions electrostatically attract, thus forming ionic bonds. The solid state
therefore contains regularly arranged lattice particles (amino acids) held together by ionic bonds. The
ability of amino acids to form crystals has been important in their analysis by x- ray crystallography.
This technique works well for crystalline substances. The crystalline forms of amino acids are also soluble
in water due to the interaction of the dipoles in water with the charges on the amino acids.

1.1.2 Dipeptide formation

Two amino acids can react to form a dipeptide. The reaction is a condensation reaction because it results
in the loss of a water molecule. In the reaction, the electron rich -NH₂group of one amino acid behaves as
a nucleophile and attacks the relatively positively charged C atom of the carboxyl group on the second
amino acid.
A new bond, known as the amide (peptide) linkage is formed. This is illustrated for alanine and glycine in
Fig 11.3.
 799

amide (peptide) linkage

C C C C C C

gly cine alanine

-H2O 2-[(2-aminoacety l)amino]propanoic acid
Mr = 61 Mr = 7 5
dipeptide, Mr = 118

Fig 11.3 Condensation reaction between alanine an glycine to form a dipeptide

 The sum of the Mr values of the two amino acids is (61 + 75) = 136. The Mr of the dipeptide is
118. The difference between these two values is 18, which is equal to the Mr of water. This shows
that when the two monomers join, water is lost.
 The reaction above can be reversed using appropriate reagents. The reverse reaction, in which the
dipeptide is broken down into its respective amino acids, is known as hydrolysis. This is the
reverse of condensation (Fig 11.4).

C C C C C C

Fig 11.4 Hydrolysis (nucleophilic addition of water) of the amide bond

Notice the following about this hydrolysis reaction

 Water is both a solvent and a reactant. It splits (lyses), providing an OH group which bonds to the
Cδ+of the C=O group of the amide linkage, and a hydrogen atom which bonds to the nitrogen
atom of the amide bond.
 The C-N bond of the amide group breaks, resulting in the formation of two amino acids.
 The net effect of the reaction is addition of water to the amide group. This is therefore an example
of a nucleophilic addition reaction.
 For best results, the hydrolysis is carried out using a hot (boiling) aqueous solution of a strong
acid, for example, HCl.

1.1.3 Polypeptide formation

A polypeptide is formed by the step-wise addition of an amino acid to a growing chain. A dipeptide
contains an amino group on one end and a carboxyl group on the other. It can there react with another
amino acid. Theoretically, a single dipeptide can react with two amino acids. The –COOH terminal of the
 800

dipeptide condenses with the –NH₂ group of the first amino acid. The –NH₂ terminal of the dipeptide
condenses with the –COOH group of another amino acid to form a tripeptide.
In living systems, a polypeptide grows in one direction only, the –COOH direction. This is because protein
synthesis in living cells is controlled by enzymes.

O R1 O H O R3 O H O O
H direction of growth
N C C C N C C N C C N C C N C
H R5 O
H H R2 H H H R4 H H
n N C C
chain grows from
H OH
the amino terminal. H
Fig 11.5. Growth of a polypeptide chain, like in all condensation polymers, is by the step-wise
addition of a monomer (condensation polymerization is also known as step-growth
polymerization). In living systems, protein synthesis is controlled by enzymes so that the
polypeptide chain grows in one direction, that is, from the -NH2 terminal in the -COOH
direction. A repeat unit has been included in the diagram above. Notice that the repeat unit
is drawn to cover two amino acid residues, from the NH group of the first amino acid
residue to the CO group of the second amino acid residue. Note that when an amino acid has
been incorporated into the protein structure it is now referred to as an amino acid residue.

Structure of a polypeptide
The terms protein chain and polypeptide can be used interchangeably. However, the term protein, in a
strict sense, refers to a polypeptide or collection of polypeptides of known biological function, for example
insulin.

1. A polypeptide always contains the following groups

 the – COOH group at one end. This end is known as the C- terminal.
 the- NH₂ group on the other end. This end is referred to as the N- terminal.
 the amide bond, -CONH. The amide bond repeats at regular intervals along the polypeptide
chain. All polypeptides have the back- bone shown in Fig 11.6(R groups on the α carbon atoms
have been omitted). Notice that the framework of the polypeptide chain is …C-C-N-C-C-N-C-C-
N-C-C-N…

α α α α
C C N C C N C C N C C C

N terminal C terminal
Fig 11.6 All polypeptides have a common back-bone

What distinguish one protein chain from another are the R groups, otherwise the main skeleton is the
same in all protein chains.
 R branches. The nature of the R side groups in a polypeptide depends on which amino acid resi-
dues are present in the polypeptide. The term amino acid residue refers to an amino acid which
has been incorporated into a polypeptide.
 801

2. Different polypeptides differ only in the nature of the R group. The R groups therefore give a polypep-
tide its unique properties.
3. A polypeptide is a condensation polymer, classified as a polyamide because of the presence of the
amide (peptide) linkage repeated at regular intervals throughout the chain. Polypeptides are in the same
class of polymers (polyamides) as nylon and silk fibroin (a protein found in spider silk and silkworm silk).

A polypeptide with a known biological role is referred to as a protein. The number of amino acid
residues in the protein varies from one protein to another. Insulin, with 51 amino acids, is considered to
be a very short chain protein. Other proteins contain thousands of amino acid residues.

Hydrolysis of proteins
Proteins can be hydrolyzed into free amino acids or into shorter protein chains. This is done by boiling the
protein in water to which has been added a strong acid (e.g. HCl) or a strong alkali(e.g. NaOH). During
the hydrolysis reaction, water is added to the amide linkages, resulting in the breaking of the C-N bonds.
In biological systems, hydrolysis is carried out more efficiently by enzymes. The enzymes allow proteins to
be broken down into free amino acids or protein fragments under mild conditions of pH and temperature.
The food we eat contains proteins in different amounts, depending on the nature of the food. In the
digestive system, the polymeric proteins are digested by enzymes known as proteases into amino acids.
The amino acids can then be absorbed into the blood stream. Cells of the body then reassemble the amino
acids into proteins of a specific function, for example, haemoglobin for carrying oxygen.

1.1.4 Levels of protein organization

Protein structure can be discussed in terms of levelsof organisation. There are four such levels, the
primary structure, the secondary structure, the tertiary structure and the quaternarystructure.

The primary structure

This refers to the linear sequence, identityand number of amino acids in a polypeptide chain, as
well as any covalent cross-linkages connecting different sections of the polypeptide.

The primary structure determines the way a protein chain can fold into a three dimensional structure. The
function of many proteins depends on this folding. The primary structure is genetically determined and
any change in this structure leads to changes in the folding of the protein and in turn this may affect how
the protein works.
Changes in the primary structure occur when the sequence, the number or identity of amino acids in the
protein chain changes. The change is usually a result of a genetic mutation (error on or associated with
DNA) and it may give rise to signs and symptoms of genetic diseases such as sickle cell anaemiaandcystic
fibrosis.
 Intermolecular forces are not important in the primary level of protein organization. The only
important chemical forces are strong covalent bonds linking the amino acids together.
 Insulin A,shown in Fig 11.7, is a protein that contains a disulphide bridge. Such covalent
cross-linkagesfall under the primary level of protein organization.
The structure of insulin A illustrates important points about the primary structure of a protein
 The primary structure is directional. The polypeptide chain has a definite N terminal and C-
terminal. The amino acids in the primary structure are numbered from the N-terminal. This is
because in living cells, polypeptide chains are synthesized from the N - terminal towards the C-
terminal.
 802

 The primary structure carries amino acid residues, linked by peptide linkages. The linear
sequence, number and identity of these amino acids is important in defining the primary
structure. Any change in one or all of these properties changes the primary structure. In fact, if
any such change occurs, we get a different protein altogether. Amino acid residues in the primary
structure are often represented by the first three letters from the name of the amino acid, but note
that the first letter is always capitalized.
 Any covalent cross linkages holding different sections of the same chain together are part of the
primary structure. Of particular importance is the presence of cysteine. This sulphur containing
amino acid is important in the formation of covalent disulphide bridges.

Fig 11.7 Primary structure of insulin A, a very short protein containing only 21
amino acids, Note that of the 20 naturally occurring amino acids, only 10 are used
here. Also note the amino acid residues are numbered from the N-terminal
towards the C-terminal.

Secondary level of protein organization

This refers to the folding of the primary structure into a three dimensional conformation,
stabilized by hydrogen bonds.

There are two main forms of the secondary level; the alpha (α) helix and the beta (β )– pleated sheet. The
secondary structure arises because the C-C-N-C-C-N-C-C-N… backbone of the protein chain is flexible
and at certain regions of the polypeptide it can fold to give a specific conformation. The chemical
interactions in the secondary structure are covalent bonds and hydrogen bonds (intermolecular forces).

peptide(amide) linkage
Secondary structure of amino acid A.

O
hydrogen bond
C N

helix pleated sheet. H

O peptide linkage
3D conformation of amino acid B.
stabilised by hydrogen bonds C N
Fig 11.8The secondary structure of a protein is stabilised by hydrogen bonds between the amide
groups of different amino acid residues.
 803

The α helix
The α-helix is a spiral structure stabilised by hydrogen bonds, which hold together the turns of the spiral,
thus conferring stability and regularity to the structure.

Fig 11.9Part of an alpha helix, showing one complete turn. The positions of individual
amino acid residues in the primary structure have been numbered R1, R2 and so on.

Some proteins have a predominantly α- helical form. A well known example is keratin (a structural
protein found in hair, wool, feathers, nails etc) and collagen, found in bone matrix, tendons and other
connective tissue. Proteins which are entirely α-helical are fibrous in nature, and they tend to be
insoluble, which is important to their function. The hardness and stretchability vary with the degree of
covalent cross-linking by disulphide bridges between neighbouring chains. Hair is rather inelastic due to
disulphide bridges (-S-S-) that tend to hold separate chains together. The elasticity of hair can be
improved by chemical treatments which break these covalent cross-linkages (Panel 11.2).

Panel 11.2
Chemistry in the hair salon

The ease with which hair can be stretched can be improved by using a reducing agent which breaks the
-S-S- bridges between strands and adds hydrogen to the sulphur atoms. By using rollers, the hair can
then be set into curls. Afterwards, an oxidizing agent is applied which results in the loss of hydrogen
atoms from the -SH groups on cysteine residues. This allows formation of -S-S- bridges in new
positions. Formation of the disulphide bridges makes the hair inelastic once more, so the curls are
stabilized.

S S
Cov alent disulphide cross linkages
between cy steine residues in hair
S S m akes it inelastic.

S S
reduction
addition of H
SH HS A m ild reducing agent breaks som e of the
-S-S- linkages by adding hy drogen atom s.
SH HS Chains are now relativ ely free to m ov e
indendently . T his m akes the hair m ore
elastic so that it can easily be set into a
SH SH new shape using rollers.
-S-S- bridges between strands and adds hydrogen to the sulphur atoms. By using rollers, the hair can
then be set into curls. Afterwards, an oxidizing agent is applied which results in the loss of hydrogen
atoms from the -SH groups on cysteine residues. This allows formation of -S-S- bridges in new
positions. Formation of the disulphide bridges makes804the hair inelastic once more, so the curls are
stabilized.

S S
Cov alent disulphide cross linkages
between cy steine residues in hair
S S m akes it inelastic.

S S
reduction
addition of H
SH HS A m ild reducing agent breaks som e of the
-S-S- linkages by adding hy drogen atom s.
SH HS Chains are now relativ ely free to m ov e
indendently . T his m akes the hair m ore
elastic so that it can easily be set into a
SH SH new shape using rollers.

mild oxidizing agent

removal of hydrogen

S S T he ox idizing agent, usually dilute

hy drogen perox ide, rem ov es hy drogen
S S
atom s from the -SH groups in cy steine
S S residues. T his allows -S-S bridges to
reform in new positions.

The β pleated sheet

This is the second form of the secondary structure. The β pleated sheet can be formed by one polypeptide
folding on itself to form strands that run in opposite directions, or from several polypeptide chains
running antiparallel to each other. The antiparallel chains are folded into a three dimensional pleated
structure. The folds of the pleat are held together by hydrogen bonds (Fig 11.10 (a) and (b))

These dotted lines have been drawn to emphasize the

regularity in the arrangement of chains. They DO NOT
represent hydrogen bonds.
C- terminal

O protein chain folds on itself

O

H3N+
N- terminal

Outline diagram of the  pleated sheet as in silk fibroin, showing antiparallel
chains. The black spots( ) indicate position of the  carbon. Remember that R
groups are bonded to this carbon. The small rectangles indicate position of the Fig 11.10 (a)
nitrogen atoms(N-H) groups.
 805

R groups

C- terminal O H
O H
H
O O
O H H O
HO O H H O
O H O H
H H O O
H O O H
H O O H
O H H
H H O
O
O H
O H
H3N+
N- terminal
hydrogen bonds

Diagram of the  - pleated sheet consisting of antiparallel chains, as Fig 11.10 (b)
in silk fibroin.

 The R groups are staggered regularly above and below the plane of the sheet. Notice that if one R
group is directed upwards, then the R group closest to it on the adjacent chain is directed
downwards. This arrangement spaces the R groups as far from each other as possible. This
minimizes steric hindrance between the groups, which would otherwise destabilise the sheet.
Steric hindrance occurs when chemical groups are so close to each other that their electronic
clouds tend to repel each other.
 Note that the geometry at the –C=O groups is trigonal planar, with a bond angle of 120⁰, as
shown below left.

 The geometry at the α - carbon is tetrahedral. On the diagram of the β-pleated

sheet shown above, the geometry at the α- carbon is shown as below.

1200 If you find yourself disputing

the given bond angle, you have
probably forgotten that there is
also a hydrogen atom bonded
1090C to the alpha carbon atom.

A large number of proteins showing the secondary level of organisation are neither purely α- helical nor
purely beta - pleated but contain a mixture of both conformations. An example is pepsin, a digestive
enzyme found in the stomach and required for the digestion of proteins. The enzyme contains both α -
helical and β- pleated regions.

The tertiary structure

This refers to the three dimensional folding of the polypeptide chain into a globular (roughly spherical)
conformation.

The tertiary structure is stabilized by four types of interactions, ionic bonds,hydrophobic

interactions,hydrogen bonds and disulphide bridges, as shown in the following illustrations.
 806

Ionic attractions (ionic bonds)

These exist between the –COO⁻ group from one amino acid residue and the NH₃⁺ group from another.
These groups are part of the R groups of the respective amino acids. The two amino acids below (lysine
and glutamic acid) contain an R group bearing a COOH group and an –NH₂ group respectively. When the
two amino acid residues are near each other, strong ionic bonds may form as shown in Fig 11.11 below.

α - carbon

..

....... -

Fig 11.11 Formation of an ionic bridge. A neutralization reaction takes place between the NH2
on the R group of lysine and the -COOH on the R group of glutamic acid. This converts NH2 to
NH3+ and COOH to COO-. The oppositely charged groups then attract electrostatically, resulting
in the formation of an ionic bond, also known as an ionic or salt bridge.

Covalent disulphide bridges between cysteine residues

These residues are at different locations on the polypeptide chain but they are relatively positioned in
such a way that their R groups can bond through their –SH groups, forming strong disulphide (-S-S-)
bridges (Fig 11.2). Disulphide bridges are covalent bonds that are formed as a result of loss of hydrogen
from the sulphydryl (-SH) groups of adjacent R groups of two cysteine residues. This process is therefore
an oxidation reaction.
For disulphide bridges to be established, the protein must fold precisely so that cysteine residues are close
to each other and are not obstructed by other groups. This precise folding is only possible if the primary
 807

structure of the protein is correct. Any change in the primary structure affects the way in which a
polypeptide folds. In turn, this interferes with the formation of disulphide bridges and the other forces
that stabilize the tertiary structure of a protein.
Note that disulphide cross-linkages can also be present in the primary structure, for example in insulin A.
In such cases, the protein is not folded into a globular shape as in the tertiary structure.

Back-bone of protein chain( -N-C-C-N-C-C-N-C-C...)

When two cysteine residues are close

together along the protein chain, their
R groups may interact through
oxidation (loss of hydrogen), resulting
R group of
in the formation of a covalent
one cysteine
disulphide bridge.
residue
R group
of another cysteine
-2H+
residue

Position of R group

Covalent disulphide
bridge
Fig 11.12 Formation of a disulphide bridge

Hydrogen bonds
The tertiary structure of a protein is also stabilized by hydrogen bonds which originate on the R groups.
Compare with the secondary structure which is stabilized by hydrogen bonds which originate on amide
linkages on the - -N-C-C-N-C-C-- back-bone of the polypeptide chain. For hydrogen bonds to form in a
tertiary protein, the two R groups must contain polar groups that have the ability to form hydrogen
bonds, for example, serine and glutamic acid (Fig 11.13). Moreover, they should be close enough to each
other to allow establishment of the hydrogen bonds.

Hydrophobic interactions (Van der Waals forces)

These stabilizing forces are established between non-polar R groups (Fig 11.13). Although they are the
weakest of the intermolecular forces, Van der Waals forces can be quite significant in stabilizing a protein
if they occur extensively in the structure.
 808

Important considerations in the formation of the tertiary structure

Building up of the tertiary structure depends on the following factors
 Positions of R groups relative to each other determines the types of chemical attractions that can
occur between them.
 The protein chain must fold in such a way that hydrophobic (non-polar) R groups are hidden
from the aqueous environment but are exposed to each other. These groups therefore tend to
cluster, forming relatively weak Van der Waals forces between them. On the other hand, folding of
the protein chain exposes polar groups to each other and to the aqueous environment. Polar
interactions (hydrogen bonds) therefore form between the R groups. Globular proteins also tend
to be soluble because the polar R groups are exposed to water molecules, allowing formation of a
large number of hydrogen bonds between the R groups and water.
 Presence of proline is of particular importance in the formation of the tertiary structure. This
amino acid is oddly shaped and its presence causes a sudden twist in the protein chain. These
twists, which are also caused by repulsion between R groups of like charge, are important in the
building up of the tertiary structure.

 Existence of the tertiary structure does not imply non-existence of the

secondary structure in the globular protein. In fact, the tertiary structure
is a further folding of the secondary structure (alpha helix or beta pleated
sheet, or both).
proline

Comparing the tertiary structure and the secondary structure

Note the following key differences between the tertiary and the secondary structure of a protein.

Secondary structure Tertiary structure

Protein chain folds into a three dimensional alpha Protein chain folds into a three dimensional
helix or beta pleated sheet. globular shape

The three dimensional structure is stabilized by The globular shape of the protein is stabilized by
hydrogen bonds . four types of chemical interactions
 hydrogen bonds between polar R groups
 Van der Waals forces (hydrophobic
interactions)
 Disulphide bridges
 Ionic bridges

Peptide linkages in the back-bone of the protein The stabilizing forces stated above occur between R
chain provides the groups (C=O and -N-H) which groups.
participate in forming stabilizing hydrogen bonds.

Proteins in which the secondary level is Proteins in which the tertiary structure is
predominant tend to be fibrous and insoluble. predominant tend to be roughly spherical and
soluble
 809

Examples of proteins in which the secondary Examples of proteins in which the tertiary
structure predominates: structure predominates:

 Keratin (alpha helix)  All enzymes

 Collagen (alpha helix)  antibodies
 Silk fibroin ( β - pleated sheet)

Fig 11.13 below illustrates the nature and origin of the four forces that stabilize the tertiary structure of a
protein.

Fig 11.13 The chemical interactions

responsible for stabilizing the tertiary
structure of a protein.

Importance of R groups
The R groups are important in protein chemistry because they are responsible for the forces that stabilize
the tertiary structures of the proteins. These forces hold the protein in a specific globular shape. The shape
of the protein is a key factor to its function. The exact shape of the protein depends on which R groups are
present and how they are arranged relative to each other. In turn, this depends on the primary structure
of the protein, that is, on which amino acids are present, in what numbers, and in which sequence. A
change in the primary structure changes the nature of the R groups, or their relative positions in the
tertiary structure. This changes the shape of the protein, leading to loss of function.
 810

The quaternary level of protein organization

A protein is said to be quaternary if it has one or both of the following properties
 two or more tertiary (globular) protein chains associated to form a single functional unit.
 a tertiary protein associated with a non-protein group.
Haemoglobin is an example of a quaternary protein. The presence of a globular (tertiary) conformation is
necessary in the definition of the quaternary structure. If a protein contains more than one polypeptide
chains, or has a prosthetic group, or both of these properties, but lacks a globular shape, it can not be said
to be quaternary*.

CASE STUDY: Haemoglobin

Haemoglobin is the pigment responsible for the transportation of oxygen in the blood of all vertebrates
(except the fish family known as Channichthyidae). It exhibits both the tertiary and the quaternary levels of
organization. It is tertiary because of its roughly globular shape. It is said to be quaternary because it has a
non-protein group known as haem, and it has more than one tertiary polypeptide chains. The protein part
of haemoglobin is known as globin. Haemoglobin is classified as a metalloprotein because of the presence
of a metal ion (Fe2+) in its structure. It is this iron (II) which is responsible for the transportation of oxygen

Haem + globin haemoglobin

(non - protein) (protein)

 There are four polypeptide chains in haemoglobin. Two chains are of the α type and they are
identical. The other two chains are of the β type, and they are also identical. The α chains are 141
amino acids long, whilst the β chains are 146 amino acids long. These four chains are connected to
each other by salt bridges, hydrophobic interactions and hydrogen bonds. There are no disulphide
bridges.
 Each of the four polypeptide chains is folded in such a way to create a pocket in which a haem
group is tightly contained. There are therefore four haem groups in each haemoglobin molecule.
All the levels of protein organisation are present in haemoglobin. The protein chains exhibit the
secondary structure in the form of alpha helical regions which are connected by short non- helical
regions. The alpha helix is further folded into a roughly globular conformation (tertiary structure).
The folding of each of the two types of globins (α and β) gives rise to a specific shape, which is
important to the function of the protein.
 Each haem molecule is covalently bonded to its polypeptide chain. Haem in haemoglobin is a
prosthetic group, that is, a non- protein group which is firmly held to the protein by strong
covalent bonds.
 811

Structure of haem
haem groups Haem is the iron containing group of haemoglobin. It
- chains
is this divalent iron which is responsible for the
transportation of oxygen. Haem can be considered to be
a complex ion because it contains a transition metal
cation to which dative bonds are made by certain
electron donating groups on the ligand molecules.
Actually, there are only threeligand molecules. One of
the ligands, a ring molecule known as porphyrin, is
chains haem groups tetradentate, that is, it can form four dative bonds to
the central metal cation. The porphyrin ring makes use
A model of haemoglobin showing two  globin chains and two  - globin
Fig centre
chains. At the 11.14Model of haemoglobin
of each showing
folded protein of its four nitrogen
twois a prosthetic
chain group atoms, each bearing a lone pair of
known as alpha
haem.globin
The chains
four polypeptide
and two betachains electrons,through
are associated
globin chains. to make dative covalent bonds to the
hydrogen bonds,
At theVan derof
centre Waals forces protein
each folded and ionic interactions.
chain is a Fe2⁺centre. The second ligand is the polypeptide chain
prosthetic groupchain
The polypeptide known asahaem.
uses nitrogen atom to form atodative
whichbond
the haem
to thegroup is metal
central associated.
ion. It is this bond This
This polypeptide chain is responsible for connecting the haem group to the protein chain. The sixth site on the
haem complex is reversibly occupied either by oxygen or a water molecule (the third ligand). Haem is
therefore a six co-ordinate complex (the co-ordination number of a complex refers to the total number of
dative bonds between the metal cation and the ligands), and is therefore octahedral at the iron centrein
(Fig11.14).

sixth co-ordination site is reversibly

occupied by a H2O or by an O2 ligand

COOH COOH
H2 O

N N Four nitrogen atoms from

2+ a porphyrin ring make four
Fe dative bonds to the metal ion
N N
CH2= CH
The rest of the protein
chain folds on itself in
such a way as to enclose N CH= CH2
the haem group. N

The fifth co- ordination site

is occupied by the protein chain.

Structure of the haem group. There are four such groups per haemoglobin unit
 812

H2 O

N N
2+
Fe
Fig 11.15 Diagram showing
N N octahedral geometry (bond angle,
900) around the metal iron in haem.
N
ram showing octahedral geometry around the haem group. All bond angles are
al to 900. How haemoglobin transports oxygen
The haem group is the one responsible for the transportation of oxygen. It uses the Fe 2+centre to attract an
oxygen ligand. This happens in the lungs where the partial pressure of oxygen is high. The reaction is
reversible, with oxygen exchanging with water at the sixth co-ordination site. In the lungs, where partial
pressure of oxygen is high, the favoured reaction is the uptake of oxygen. The sixth co-ordination site gives
up a water molecule and takes up oxygen instead, to form oxyhaemoglobin (Fig 11.16). Until recently, it was
thought that the reaction between haemoglobin and oxygen was not redox, that is, the iron centre remained
in its +2 oxidation state. Recent experiments involving X-ray photoelectron spectroscopy suggests an
oxidation state of about +3.2 for iron in oxyhaemoglobin. Infrared stretching frequencies of the O-O bond
in oxyhaemoglobin is consistent with a superoxide, O₂⁻, in which oxygen has an oxidation state of -1(oxygen
is thus reduced). Experiments have also shown that haemoglobin is diamagnetic, that is, it is slightly
repelled by a magnetic field. Diamagnetism in complexes is a result of the absence of unpaired electrons. In
Hb-O₂, the single unpaired electron on superoxide aligns with the single unpaired electron in Fe 2+. All
electrons are thus paired in haemoglobin, so there is no net spin to the entire configuration, making it
diamagnetic.

O
O
N N
Fe2+
N N
N

Oxygen forms a weak dative bond to the Fe2+ centre in haem, resulting in the
oxidation of Fe2+ to Fe3+. Meanwhile, O2 is reduced to superoxide, O2-. Fig 11.17

Other functions of haemoglobin

Haemoglobin has other functions apart from the transportation of oxygen. These include
 Transportation of carbon dioxide from the tissues to the lungs. Carbon dioxide bonds with
haemoglobin to form carbaminohaemoglobin, which dissociates in the lungs to form haemoglobin
and carbon dioxide. The carbon dioxide is then exhaled out of the lungs.
 Buffering of blood. Haemoglobin helps to maintain a near constant blood pH. When the pH de-
creases below the set point, the excess hydrogen ions are neutralised by the –NH₂ groups in
haemoglobin. On the other hand, the –COOH groups can neutralise excess hydroxide ions, and so
prevent the pH from increasing above the set point.
 813

5.2Enzymes

Enzymes are biological catalysts. All enzymes are protein in nature, and exhibit the tertiary or
quaternary level of organization. As catalysts, enzymes exhibit the following properties, which also apply
to inorganic catalysts.
 They speed up reactions by providing an alternative reaction pathwaywith lower
activationenergy.
 If a reaction is reversible, then the enzyme speeds up both the forward and the reverse reactions
to the same extend.
 They do not alter the enthalpy of a reaction. This observation is expected from a consideration of
Hess law. The uncatalyzed and catalysed routes have the same enthalpy of reaction.

We can use an energy profile diagram and the Boltzmann curve to explain the effect of an enzyme (or a
catalyst in general) on a reaction.

Energy

E a 2 activ ation energy for

Ea2 the uncataly zed reaction
Ea1
Ea1 activ ation energy for the
cataly zed reaction
reactants
ΔH

products

progress of reaction
Fig 11.18Energy profile showing the lowering of activation energy by an enzyme

Proportion of
particles

y x
Ea1 Ea2 Energy
Fig11.19Boltzmann curve showing the lowering of activation energy by an enzyme

The energy profile diagram shows that the enzyme reduces the energy barrier (activation energy) that
reactant molecules must overcome in order to form products. The Boltzmann curve shows that when
activation energy is lowered by the catalyst from Ea 2 to Ea1, the proportion of particles with sufficient
energy to react increases from x to (x + y). On average, more particles are able to overcome the energy
barrier and form products.
 814

5.2.1 The unique properties of enzymes

The features of catalysis described above apply to all catalysts in general. The following properties are
unique to enzymes.
 Specificity. Enzymes are much more selective towards what substrates (reactants) they act on.
For example, when a product exists as a pair of optical isomers, enzymes will recognize and act on
only one of the isomers. Similarly, enzymes are usually capable of producing only one of the two
possible enantiomers (optical isomers) of a product. For example, an attempt to produce lactic
acid in the school lab will result in the formation of an optically inactive equimolar mixture
containing D and L lactic acid. Enzymes produce lactic acid in animals during anaerobic respira-
tion. Only one of the optical isomers is produced.
 High catalytic efficiency. The efficiency of a catalyst is measured by its rate of turnover. This
is the number of substrate molecules that the enzyme converts to product molecules per minute.
The rates of turn - over for some enzymes are given below.

Enzyme Rate of turn - over

carbonic unhydrase 36 000 000

catalase 5 600 000

succinate dehydrogenase 1 150

This rate of conversion of reactants to products is spectacular compared to what most inorganic
catalysts can achieve. It should be noted that these high rates of turn-over are obtained at
relatively mild conditions of temperature and pressure. Many inorganic catalysts require very
high temperatures and pressures in order to show significant catalytic activity. Even under these
harsh conditions, the catalytic efficiency is still much smaller compared to an enzyme working
under mild conditions.
 Sensitivity to heat and changes in the chemical environment. Inorganic catalysts are
quite capable of working over a wide range of temperature and pressure. On the other hand,
extremes of temperature can destroy enzymes. Enzymes are also rendered non - functional by
extremes of pH and salt concentration.

are protein in nature

show a high degree
of specificity

are globular (tertiary )

are sensitiv e to heat ENZYMES proteins

are denatured by are soluble proteins

ex tremes of pH
hav e v ery high rates
of turn - ov er
Fig 11.20 Key properties of enzymes
 815

Many industrial processes now involve the use of enzymes. The advantages associated with the use of
enzymes, for example, in biotechnology, have already been mentioned.
 High catalytic efficiency
 Ability to work efficiently under mild conditions of temperature and pressure.
 Greater specificity than inorganic catalysts. The desired product is formed with little or no
contamination by side products.
The key disadvantage of using enzymes in industrial conversions is that they are very sensitive to changes
in temperature and the composition of their chemical environment, for example, an increase or decrease
in the concentration of hydrogen ions.

5.2.2 Mode of action of an enzyme

Action of an enzyme is usually described using the lock and key hypothesis.
 The enzyme has a catalytic centre known as the active site. This is a groove on the surface of the
enzyme, made up of a few amino acid residues (between 5 and 12).
 The active site has a shape designed to accommodate only a substrate of a specific shape. The
lock and key model, proposed by Fischer in 1894, compares the enzyme to a lock, which is
designed to accept a key of specific shape. In this model, the key represents the substrate. The
shape of the substrate is said to be complimentary to that of the active site. The lock and key
model is useful in explaining the high degree of specificity exhibited by enzymes. If a substrate
has ‘a wrong’ shape, it does not fit into the active site.
 The substrate enters the active site and is held in place by chemical forces between it and the
amino acid residues in the active site. These chemical forces include ionic attractions, covalent
bonds and hydrogen bonds.
 The substrate is then converted to the product. The product molecule can no longer fit well into
the active site, so it is ejected, and the catalyst is recycled.

Fig 11.21summarizes the mode of action of an enzyme.

active site

Enzyme(E) + substrate(S) Enzyme - Substrate(ES) complex

enzyme recycled

products

Enzyme

Fig 11.21 The enzyme

The enzymecycle
cycle
 816

CASE STUDY: Carbonic anhydrase

Carbon dioxide reacts with water to form carbonic acid, according to the equation

CO₂ + H₂O ⇌ H₂CO₃ … I

This reaction is important in vertebrates as it allows carbon dioxide to be transported rapidly in solution
to the excretory organs. This is the major mechanism by which carbon dioxide is transported in
mammals. Transportation of carbon dioxide in solution would not be a significant method of carrying
carbon dioxide were it not for the enzyme carbonic anhydrase. This enzyme makes reaction I above
many thousand times faster than the uncatalyzed reaction. In fact, carbonic anhydrase, with a turn- over
rate of 36 000 000, is one of the most efficient enzymes known. Carbonic anhydrase is classified as a
metalloenzyme, that is, an enzyme which is associated with a metallic prosthetic group. A prosthetic
group is a non-protein component which is firmly bound by covalent bonds to the protein. The
prosthetic group in carbonic anhydrase is divalent zinc, which is located in the active site.
This Zn2+ group plays a central role in the conversion of carbon dioxide to form carbonic acid, as
described below. Like all enzyme- catalysed reactions, the conversion of carbon dioxide to carbonic acid
by carbonic anhydrase has properties of both homogeneous and heterogeneous catalysis. Carbonic
anhydrase has two pockets (active sites), one for accommodating water and the other for
accommodating carbon dioxide.

bond broken
2 O 3
H
O O C
H 1 H
Zn2+ O
Zn2+

+ H+

carbonic anhydrase

HO O
O O
C H+ C
HO 4 HO

carbonic acid(H2CO3) hydrogen carbonate

leaves the active site, and
the catalyst is recycled.
 817

1 The zinc(II) group in the active site of the enzyme attracts and forms a covalent
co-ordinate bond to a water molecule.
2 Movement of electron density from water to zinc weakens an O-H bond in water,
which breaks, producing a hydrogen ion and the hydroxide ion. The hydroxide ion
acts as a nucleophile and attacks the partially positive carbon atom (C ) in carbon
dioxide, to which it forms a dative bond.
3 The increase in electron density at the carbon atom causes a pair of pi electrons to
shift from a C-O double bond onto the O atom. The O atom therefore acquires a
negative charge.

4 The negatively charged oxygen atom is then neutralised by a hydrogen ion, to form
the product, carbonic anhydrase
acid .

5.2.3 Factors that affect enzyme activity

These are
 temperature
 pH
 substrate concentration
 presence of inhibitors

Effect of temperature
Fig 11.22 allows you to see the effect of temperature on the rate of an enzyme catalysed reaction at a
glance

enzy me
activ ity C

A B
D
0 40 60
temperature/ 0 C
Fig 11.22 Graph showing the effect of temperature on the rate of an enzyme
catalyzed reaction.
 818

At very low temperatures, the rate of reaction is very small (A). This is because reactant particles have
very little kinetic energy. Consequently, the frequency of particle-particle collisions and particle-enzyme
collisions is very small. Even when particles do collide, they do so weakly, that is, the collisions are not
energetic enough to result in a chemical reaction. Most particles have energies which are less than the
activation energy of the reaction.
Increasing temperature increases the kinetic energy of particles. The particles collide more frequently
with each other and with the enzyme. Moreover, the collisions are energetic enough to result in the
formation of a product. On average, more reactant particles acquire energies equal to or greater than the
activation energy. Thus rate of reaction increases almost linearly with an increase in temperature (region
BC of the graph). For most enzymes, the maximum rate of reaction is achieved at a temperature of about
400C. This is the optimum temperature. Beyond this temperature, the rate of reaction begins to decrease
(Region CD of the graph). Molecular vibrations within the enzyme become more and more energetic and
this results in the disruption of the forces that stabilize the correct three dimensional conformation of the
enzyme (Van der Waals forces, hydrogen bonds, ionic attractions). This loss of shape is known as
denaturation, and it causes the enzyme to become non-functional. The rate of reaction does not drop
straightaway to zero, because the enzymes are not denatured all at once. At about 65 0C, the rate of most
enzyme catalysed reactions drop to zero because at that temperature all the enzyme molecules become
permanently denatured. An interesting exception is shown by enzymes found in thermophiles. These
remarkable bacteria have heat resistant enzymes, and so are able to exist at temperatures well above 65 0C.
An example is the bacterium Thermus aquaticum, which lives in hot springs. DNA polymerase (an
enzyme) from this bacterium is used in the polymerase chain reaction (PCR), a technique which is used
to multiply DNA outside living cells. The reaction requires high temperature, which would destroy the
DNA polymerase from other organisms.

Effect of pH
Enzymes work well within very narrow limits of pH. Different enzymes have different pH values
(optimum pH) at which they work best. Salivary amylase, an enzyme in saliva which digests cooked
starch to maltose, works well at a near neutral pH.Pepsin, which digests proteins in the stomach, work
most efficiently at a very low pH of about 2. Hydrochloric acid, secreted by the walls of the stomach,
provides the acidic environment required for the action of this enzyme. Trypsin, which digests proteins in
the small intestines, works best at pH which is slightly alkaline.

pepsin amy lase try psin

enzy me activ ity

0 2 7 8 pH
Fig 11.23 Graphs showing that (i) different enzymes may have different optimum pH
(indicated by broken lines) (ii) enzymes work within very narrow limits of pH
(narrow graphs). A slight increase or decrease in pH results in a large decrease in the
rate of reaction.
 819

How pH affects enzyme activity

Extremes of pH disrupt the ionic forces that hold the tertiary structure of an enzyme in the correct shape.
Breaking of these forces lead to loss of the specific three dimensional shape of the enzyme and its active
site (denaturation). The substrate then fails to fit into the active site (Fig11.23).

NH3+
Ionic attraction holding COO active site
the enzyme in correct shape

OH- H+
pH becomes too low
pH becomes too high

NH+
3

COOH

NH2 ionic bonds broken

COO

Fig 11.24How extremes of pH affect the tertiary structure of a protein. When pH becomes too low,
the excess H+ ions convert the negatively charged -COO-group to the neutral -COOH group. This
breaks the ionic bond holding the tertiary structure in the correct shape. When pH becomes too high,
the excess OH- ions neutralize the charged NH3+ group to the neutral -NH2 group. Once more, the
ionic attraction is broken.

In the illustration above, the ionic bonds broken are away from the active site, but the subsequent change
in shape affects the whole enzyme, including the active site. However, the disruption of the ionic forces
may also happen directly in the active site.

Effect of substrate concentration

Fig11.25 shows how the activity of an enzyme catalyzed reaction varies with changing substrate concentra-
tion.

rate of reaction

B C
A

O substrate concentration Fig 11.25

 820

The first region of the graph (OA) is linear, showing first order kinetics. In other words, increasing the
concentration of reactant (substrate) increases the rate of reaction proportionally. Increasing concentra-
tion of a reactant increases the frequency of collisions between reactant molecules. Between A andB, the
reaction shows mixed order (first and zeroth order) kinetics, since a large number of enzyme molecules
are, at any given time, occupied by a substrate molecule. Between B and C, the reaction shows zero order
kinetics, that is, an increase in reactant concentration is not accompanied by any further increase in the
rate of reaction. When this happens, the enzyme is said to be saturated. Enzyme saturation means that on
average, every enzyme has a substrate in its active site. Adding more substrate does not affect the rate of
reaction because there won’t be any free enzyme molecules to take up the reactant molecules.

5.2.4 Enzyme inhibition

An inhibitor is a chemical which decreases the catalytic efficiency of an enzyme. Enzyme

inhibition can be reversible or irreversible. There are two main forms of inhibition, competitive and non-
competitive.

Competitive inhibition
In this type of inhibition, the inhibitor has a shape similar to that of the substrate. There is therefore
competition for the active site between the substrate and the inhibitor. The inhibitor does not destroy the
enzyme molecules but simply prevents them from participating in the reaction by blocking the active site
so that it is not able to take up the substrate. The enzyme does not convert the inhibitor into any product.
The diagram below shows the effect of increasing inhibitor concentration on the rate of reaction.

rate of reaction

O
inhibitor concentration

Fig 11.26Effect of an inhibitor on the rate of an enzyme

catalysed reaction
As the concentration of inhibitor increases, the speed of reaction decreases. This is because, on average,
the active site of most of the enzyme molecules is blocked by the inhibitor.
Fig 11.27compares the rate of reaction in the presence and in the absence of an inhibitor.
The effect of the inhibitor is to decrease the rate of reaction (displacement of the graph to the right, that is,
the slope of the rising part of the graph decreases). However, maximum rate of reaction is still achieved,
but it requires a higher concentration of substrate to achieve this maximum. Another important feature of
competitive inhibition is that it is usually reversible. The inhibitor
 does not denature the enzyme.
 does not permanently bond to the active site.
An enzyme molecule is therefore only temporarily disabled by the inhibitor. Sooner or later the inhibitor
disengages from the active site, freeing the enzyme and temporarily binding to another enzyme molecule.
 821

The effect of competitive inhibition, in most cases, is therefore reversible by increasing the concentration
of the substrate so that on average more enzymes have substrate molecules, rather than inhibitor mole-
cules, engaged in their active sites.

Rate of reaction

V max
without inhibitor

with inhibitor

0 C1 C2
substrate concentration
Fig11.27Graph showing the effect of an inhibitor on the rate of an enzyme catalyzed reaction.
The rate of reaction decreases but maximum rate of reaction (V max), is still achieved,
although at a higher concentration (C2) of the substrate. In the absence of an inhibitor, the
maximum rate of reaction is achieved at a lower concentration of the substrate, C.

Fig 11.28below illustrates competitive inhibition

substrate molecule

Inhibitor molecule. Its shape is similar to

that of the substrate , and complimentary
to that of the active site

There is competition for the active site, so

the enzyme may take up the substrate ... or it may take up the inhibitor

product formed no product is formed

Fig 11.28An illustration of competitive inhibition

 822

CASE STUDY: Inhibition of succinic dehydrogenase by malonic acid

A classic example of competitive inhibition is provided by the effect of malonic acid (inhibitor) on succinic
dehydrogenase, a respiratory enzyme. This enzyme catalyzes the conversion of succinic acid to fumaric
acid (reaction I).
succinic
succinic acid fumaric acid ... reaction I
dehydrogenase
COOH COOH
CH2 CH
CH2 CH
COOH COOH

A dehydrogenase is an enzyme which brings about oxidation of a substrate by removing one or more hy-
drogen atoms. Succinic dehydrogenase oxidizes succinic acid in this way during respiration (removes two
hydrogen atoms). Malonic acid inhibits this reaction.

COOH

CH2 malonic acid

COOH
The shape of malonic acid is similar to that of the substrate, succinic acid. It acts as a competitive inhibi-
tor to the reaction above. Large amounts of malonic acid can stop the reaction by fitting into the active
sites of the enzyme molecules. Reaction I above is thus inhibited, and this prevents later reactions in the
respiratory mechanism to take place. By inhibiting one step of respiration, malonic acid therefore affects
the whole respiratory process.

Q (a) Write down the systematic (IUPAC) names for succinic acid and malonic acid.

(b) Fumaric acid exhibits stereoisomerism. Explain the underlined term. Draw
structures to show the two stereoisomers of fumaric acid.

A(a) Succinic acid - butanedioic acid

Malonic acid - propanedioic acid

(b) Stereoisomerism is the phenomenon whereby two compounds share the samemolecular
and structural formula but differ in the three dimensional arrangement of groups in space.
Fumaric acid exhibits cis - trans isomerism (the other form of stereoisomerism is optical
isomerism).
 823

H H H COOH
C C C C
HOOC COOH HOOC H

cis but-2-enoic acid trans but-enoic acid

Non- competitive inhibition

This is inhibition by an inhibitor which binds away from the active site of the enzyme. The
inhibitor’s shape bears no resemblance to that of the substrate. Neither does it show complimentarity to
the shape of the active site. A well known example of non-competitive inhibition involves heavy metal ions
such as Hg2+ and Ag+.
 These ions have been associated with the inhibition of enzymes that contain cysteine. The ions
bind to the sulphydryl group of the R group of cysteine.

active site

 - carbon of the
cysteine residue cysteine residue
CH2
R group of a cysteine residue
SH
sulphydryl group loses
this hydrogen atom(it
is oxidised) Ag+ ( inhibitor)

Enzyme molecule inhibited by Ag+. Shape

of the active site and the enzyme as a
whole is altered.
CH2

SAg
Fig 11.29 An illustration of non-competitive inhibition

There is no direct competition for the active site. However, the bonding of the inhibitor on the enzyme has
two possible effects.

(i) The resulting increase in number of electrons (Mr) of the enzyme - inhibitor complex increases the
strength of Van der Waals forces, causing the enzyme to solidify(recall the Group VII elements
which become solid going down the group due to the increasing strength of Van der Waals forces).
The enzyme therefore precipitates out of solution and is not able to carry out its function.
 824

(ii) Introduction of a heavy metal into the structure of the enzyme also results in change of the shape of
the enzyme, including the active site. Thus even when the enzyme does not precipitate out of
solution, it is rendered non - functional by the change in the shape of its active site.

 Heavy metal ions have a strong affinity for sulphur. Consequently, they tend to break the
disulphide bridges in some enzymes, and bond to the sulphur atoms (Fig 11.30). This disrupts the
shape of the enzyme, leading to loss of functionality.

disulphide bridge

activ e site

2Ag + (inhibitor)

disulphide bridge broken

shape of enzy me, including activ e site, Fig 11.30

changes.

 Heavy metal ions also have a strong affinity for the -COO- groups in proteins. By bonding to these
groups, the metal ions disrupt ionic bridges, leading to losss of shape of the enzyme and its active
site (Fig 11.31).

Fig 11.31
 825

Fig 11.32shows the effect of a non - competitive inhibitor on the rate of an enzyme catalysed reaction.

Rate of reaction
Vm ax

V'm ax
without inhibitor

with inhibitor

0 C1 C2
Fig 11.32
substrate concentration

Fig 11.32 Effect of a non - competitive inhibitor on the rate of reaction. The rate of reac-
tion decreases (as in competitive inhibition). However, in this case the maximum rate of
reaction cannot be achieved because of the irreversible nature of the inhibition.

Fig 11.32 above shows that in non - competitive inhibition, the rate of reaction is not only lowered, but the
reaction is prevented from achieving the maximum possible rate. This shows the irreversible nature of
non - competitive inhibition. Once an enzyme molecule is inhibited, it is denatured and it is permanently
prevented from participating in the chemical reaction. Moreover, the inhibitor is usually strongly and
permanently bonded to the enzyme. Thus the number of enzymes that has the ability to catalyse the reac-
tion decreases, leading to a decrease in the maximum rate of reaction that can be achieved. Compare with
non- competitive inhibition in which the total number of enzymes with the ability to catalyse the reaction
does not decrease. As a result, it is possible to achieve maximum rate of reaction.

A comparison of competitive and non- competitive inhibition

Competitive inhibition Non- competitive inhibition

Inhibitor resembles substrate in shape. Inhibitor bears no resemblance to substrate in

terms of shape.

Shape of inhibitor is complimentary Shape of inhibitor is not complimentary to

to that of substrate. that of substrate.

Inhibitor and substrate compete for Inhibitor binds at a point away from the active
the active site, to which they can both site.
bind.

Reversible by increasing concentration can not be reversed by simply increasing the

of the substrate concentration of the substrate.
 826

5.2.5 Enzyme co-factors

Enzyme co-factors are non - protein molecules or ions required for the functioning of an
enzyme.
Without the co-factor, the enzyme shows no catalytic activity. Co-factors are often classified into two
groups; prosthetic groups and co-enzymes.
 Prosthetic groups are held firmly to the enzyme by strong covalent bonds. They are an integral
part of the enzyme, so that the enzyme and the prosthetic group behave as one functional unit. An
example is provided by carbonic anhydrase, which contains zinc as the prosthetic group. Divalent
zinc is firmly held to the active site of the enzyme by strong dative covalent bonds from an amino
acid residue in the active site of the protein. Cytochrome oxidase, a key enzyme in respiration,
contains haem as the prosthetic group.
 Co-enzymes form temporary associations with the enzyme during the catalysis. A co-enzyme is
not an integral part of the enzyme. It can detach from the enzyme when no catalysis is taking
place. When required, the co-enzyme is taken up from solution by the enzyme. Most co-enzymes
are organic molecules, often derived from vitamins. NAD (nicotinamide adenine dinucleotide)
and FAD (flavin adenine dinucleotide) are examples of such co-enzymes. They are both derived
from the water soluble vitamin B12 group. During the catalysis, a co-enzyme temporarily binds to
the active site of the enzyme. Its function is usually to transfer chemical groups such as CH₃COO
(acetyl group) and Hatoms between reaction intermediates. NAD and FAD act as proton carriers
during respiration. They help to transfer hydrogen ions and electrons from one substance to
another.
 827

Questions, solutions and discussions: Protein chemistry

Q1(a) (i) In a protein, amino acids are joined together by a process called condensation
polymerization. Addition polymerisation is used in some synthetic polymers, such
as poly(propene).

State two important differences between condensation polymerization and addition

polymerization.

(ii) Using the amino acids glycine and alanine shown, draw the displayed formula of
the dipeptide ala-gly, clearly labelling the peptide link. [2]

H O H O
H H
N C C N C C
H OH H OH
H CH3
glycine alanine

9701/04/M/J/07

Solutions

(a) (i)-Addition requires an alkene/C=C bond.

-Condensation produces two products, that is, a small molecule such as water in addition to
the polymer itself.
-Condensation is accompanied by loss in mass, that is, the Mr of the polymer is less than the
sum of the monomers present. In addition polymerization, there is no loss of mass upon
formation of the polymer.

(ii)

H H O H O
N C C N C C
H OH
CH3 H H

peptide link
NOTE the order is Ala-Gly not Gly-Ala
 828

Q2When an egg is boiled, the protein changes from a viscous liquid to a solid.
(a)Suggest what causes this change as the protein is heated.

(b) Why is there no change to the primary structure of the protein under these
conditions?

9701/04/O/N/07

Solutions

(a)There is disruption of the 3D conformation of the protein, that is, denaturation. This occurs
because heat energy causes molecular vibrations which break stabilizing intermolecular
forces such as hydrogen bonds.

(b)The primary structure would change if covalent bonds holding the amino acid
residues together broke. These covalent/peptide bonds in the (protein) chain are verystrong
and so do not easily break.

............................................................................................................................................

Q3(a) Explain briefly what is meant by the term protein.

(b) Describe how peptide bonds are formed between amino acids during the formation of a
tripeptide. Include diagrams and displayed formulae in your answer.

(c) Describe how proteins can be broken down into amino acids in the laboratory without
the aid of enzymes. [2]

(d) When a small polypeptide S was broken down in this way, three different amino acids
were produced according to the following reaction.
 829

Q4 (a) State and show, using suitable diagrams, the types of bonding that occur in the primary,
secondary and tertiary structures of a protein.

(b) Analysis of a polypeptide A showed that the amino-(N-) terminal end is methionine (met)
and that the carboxyl-(C-)terminal end is lysine (lys).
Enzymic hydrolysis of the polypeptide produced the following tripeptides, with the amino
acid residue on the left having the free amino group.

met-ala-gly gly-arg-val ala-gly-arg arg-val-lys ala-gly-ala gly-ala-gly

Work out the sequence of amino acids in A, using the 3-letter abbreviations. Use each
tripeptide once only.

(c) Give two examples of how interchanging the positions of two amino acids could affect
the bonding in, and hence the overall structure of, the protein.

9701/04/M/J/08

Solutions

(a)Primary structure
- covalent bonds
- diagram showing displayed formula of the peptide linkage, CONH

Secondary structure
- hydrogen bonds between peptide linkages found along the protein chain
- diagram showing N-H ··· O = C, and the hydrogen bond labeled.
- use simplified diagram of alpha helix and beta pleated sheet.

Tertiary structure
All chemical attractions stabilizing the structure originate from side R groups, not the N-C-
C-N-C-C ... back -bone (compare with secondary structure in which stabilizing forces are
hydrogen bonds originating from the protein back - bone.

• hydrogen bonds , except the N-H ... O=C found in the secondary structure
• electrostatic/ionic attractions (-NH3+ ... -OOC-)
• Van der Waals’/hydrophobic forces/bonds
• (covalent) disulphide (links/bridges) (S-S)

Can draw one large annotated sketch showing these four chemical interactions.
 830

(b)met-ala-gly-ala-gly-arg-val-lys

Any possible sequence with more than 8 residues, that “uses” all 6 tripeptides
(overlapping or not), and that starts with met and ends with lys is worth
Any sequence that does not start with met or end with lys gets zero.

(c) See section(genetic diseases)

Q5Whilst small amounts of some metal ions are vital in the human body, others can be
highly toxic.

(a) Hg2+ ions are toxic for a number of reasons. Hg2+ ions can react with the R–S–S–R
group, which is found in proteins.

R–S–S–R + 2Hg2+ + H2 2R–S–Hg+ + 2H+ ... reaction 1

(i) What is the name of the R–S–S–R group in proteins?

(ii) Which level of protein structure will be affected by reaction 1?

(iii) Why will this affect the activity of an enzyme?

(b) Ag+ ions can combine with free –COOH groups in the side chains of the amino acid
residues in proteins to form partially covalent silver carboxylates.

RCOOH + Ag+ RCOOAg + H+ ... reaction 2

(i) What type of behaviour is the –COOH group showing in reaction 2?

(ii) What types of R group interactions will be affected by reaction 2? Explain your
answer.

(c) By contrast, iron is an extremely important metal used in haemoglobin to transport

oxygen molecules from the lungs to muscle cells and to carry carbon dioxide in the reverse
direction.
One haemoglobin molecule contains four haem groups, each of which contains one iron
atom. In the haem group, four nitrogen atoms are in the same plane as the iron atom.
The oxygen molecule is attached above this plane, and the iron atom is joined to a
protein chain below this plane.
 831

(i) How many oxygen atoms could one haemoglobin molecule transport?

(ii)By what type of bonding is the oxygen molecule likely to be held to the iron atom in
haem?

(iii) What is the geometry of bonding around the iron atom?

© UCLES 2010 9701/41/O/N/10

Solutions

(a)(i)Disulfide bond / group / bridge

(ii)The tertiary structure
(iii)The substrate will no longer bond to / fit into the active site
or shape of active site is changed

(b) (i)Acid-base / proton donor / neutralisation / salt formation

(ii)The ability of the –CO2H group to form hydrogen bonds and ionic interactions.
 832

The –COOH/–COO2-group is no longer able to interact with –NH2/–NH3+, so hydrogen

bonds / ionic interactions can no longer form.
The Ag+ forms a strong bond with –COO-

(c)(i)8atoms
(ii) Dative / co-ordinate
(iii)Octahedral / 6 co-ordinate

............................................................................................................................................

Q6(a) Enzymes are particular types of protein molecule. Explain briefly how enzymes are able
to help to break down molecules in the body.

(b) The graph below shows the effect of inhibition on an enzyme-catalysed reaction.

State the type of inhibition shown, giving a reason to support your answer.
type of inhibition
reason

9701/42/O/N/09

This question is left as an exercise to the reader

 833

Solutions

(a)Substrate binds to the active site of the enzyme

Chemical interaction /bonding with active site causes a specific bond to be weakened (and
break)
Orchange in shape of substrate weakens bond(s) / lowers activation energy

(b)Non-competitive inhibition [1]

Rate never reaches Vmax/maximum rate.

11.1.2NUCLEIC ACIDS

A nucleic acid is a biological polymer made from monomers known as nucleotides.

There are two types of nucleic acids, deoxyribonucleic acid (DNA) and ribonucleic acid (RNA).

DNA is now known to be the genetic material. It contains genetic information in the form of sequences of
organic nitrogen bases. During fertilization, maternal (from mother) DNA combines with paternal DNA
(from father) in equal proportions, to form a new organism which has a complete set of instructions
required to start a new life.

1.2. 1Structure of a nucleotide

A nucleotide is the monomer from which all nucleotides (DNA and RNA) are made. In turn, a nucleotide
is built from three compounds, an organic nitrogen base, a five C sugar (pentose sugar), and a phosphate
group.
Nucleotide = Nitrogen base + Pentose sugar + Phosphate

Organic nitrogen bases found in nucleic acids

There are five different organic bases found in nucleic acids, but there can only be four in any given
polymer chain. These bases are guanine (G), adenine (A), cytosine(C) , thymine (T) and uracyl (U). The
four bases found in DNA are G, A, C, and T, whilst RNA contains G, A, C and U. You can therefore see the
first structural difference between DNA and RNA. In RNA, uracyl takes the place of thymine.
The four bases found in a nucleic acid owe their basicity to the presence of NH 2 (amine) groups which
behave as typical Bronsted-Lowry bases (Fig 11.33). There is a lone pair on the NH2 group, which accepts
 834

a proton from an acid. Also note the presence of amide groups (CONH) in G, C, T and U. Recall that the
amide group has very little basicity; it almost neutral.

purines - double ringed pyrimidines - single ringed

bases bases

guanine adenine cytosine thymine uracil

Found only in
RNA, taking
the place of
thym ine
Fig 11.33Organic bases found in nucleic acids

Pentose sugars found in nucleic acids

These are shown inFig 11.34 below.

5 5

4 4 1
1
3 3 2
2

Deox y ribose - found in DNA Ribose - found in RNA

Fig11.34 Pentose sugars found in nucleic acids. The numbers represent position of carbon
atoms.

Note that deoxyribose is ‘deoxy’ in the sense that it has no oxygen (OH group) on carbon 3.

Phosphate
Nucleotides and nucleic acids are acidic because they contain a residue derived from phosphoric acid.
This residue still contains hydrogen atoms that can be dissociated and enter solution as H + ions.
 835

phosphate residue

During the formation of

a nucleotide, one of the
-OH groups is lost in
a condensation reaction,
forming a phosphate resi-
phosphoric acid due, shown on the right.
(H3PO4)

Fig 11.35 A nucleotide contains a phosphate residue which is derived from

phosphoric acid.

A nucleotide is built from the condensation reaction that takes place between a pentose sugar, an organic
base and phosphate (phosphoric acid).Fig 11.36below shows formation of a DNA nucleotide. Notice that
the sugar used is deoxyribose. The base could be any from the list guanine, adenine, cytosine and thymine.
A nucleotide of RNA is built up in the same way, but it has the sugar ribose instead of deoxyribose, and
the base uracil, instead of thymine.

phosphoric acid

-H2O

5 -2H2O

4 1
-H2O organic base
3
2
nucleotide
Deoxyribose

Fig 11.36 Formation of a nucleotide of DNA by condensation

The structure of a nucleotide can be shown as a simple block diagram, as illustrated in Fig 11.37.

Fig 11.37 structure

of a nucleotide

1.2.2Building up of DNA
 836

DNA is a double stranded polymer of nucleotides. A single strand of DNA is formed by condensation
reaction between many nucleotides. Fig 11.38shows condensation between two nucleotides to form a
dinucleotide.

 Condensation takes place between the -OH group on carbon 3 of one nucleotide and the
phosphate group on carbon 5 of the other nucleotide.

 Once bonded together, the nucleotides are now referred to as ‘nucleotide residues’ because they
no longer have exactly the same structure as free nucleotides. In the growing polynucleotide
chain, nucleotide residues are linked together by phosphodiester bridges.

Fig 11.38 Formation of a

dipeptide by condensation
between two nucleotides

The dinucleotide still has a ‘ free’ -OH group on carbon 3 of one nucleotide residue, and a free phosphate
group on carbon 5 of the other nucleotide residue. In theory, the dinucleotide can form a trinucleotide by
condensing with another nucleotide either at carbon 3 or at the phosphate group on carbon 5. In practice,
the addition of new nucleotides to the growing polymer chain is under the control of enzymes and so
occurs in one direction, that is, in the 53 direction.
 837

4 1
3 2

5
chain grow s
in this direction 4 1
3
2

-H2O
free nucleotide condenses
w ith the -OH group on carbon 3
of the grow ing chain.

5
4 1
3 2

Fig 11.39 A polynucleotide grows in the 5 3 direction.Basesrepresented by the longer

rectangles are purines (that is, double ringed bases, G or C). Those represented by the shorter
rectangles are pyrimidines (single ringed bases, cytosine or thyamine).
Bases represented by the longer rectangles in Fig 11.40are purines (that is, double ringed bases,
G or C). Those represented by the shorter rectangles are pyrimidines (single ringed bases,
cytosine or thyamine).

This step-wise addition of nucleotides continues until a very long polymer (polynucleotide) is formed. One
end of the chain ends with an –OH group. This end is termed the 3 prime (3′) end because this –OH
group is on C3 of a nucleotide . The other end ends with a phosphoric acid residue (phosphate).It is this
group that causes DNA to be acidic. This is the 5 prime (5′) end because the phosphate group is bonded to
C5. One strand (polynucleotide) has the following features.

 It is a directional molecule, with a distinct phosphate (5′ ) and hydroxyl (3′) terminal.
 One chain of DNA is a very long molecule, containing up to 106 nucleotides. This polynucleotide is
based on the framework sugar-phospate-sugar-phosphate ..., with organic bases attached to the
sugars.
 Each polynucleotide chain has a specific sequence of bases which is genetically determined.

Structure of DNA
 838

DNA is double stranded. It contains two antiparallel polynucleotide chains, that is, the two chains are
parallel but run in opposite directions (Fig 11.40). This antiparallel arrangement has two consequences:
 Bases face each other and so are able to pair up through hydrogen bonds. It is these hydrogen
bonds that hold together the two chains.
 Bases pair up in a specific way, G with C through three hydrogen bonds, and A always pair with
T through two hydrogen bonds.

G with C through
 In other words, a purine always pair with a pyrimidine. This
3 hy drogen bonds is known as the rule of complimentary base pairing.
 The pairing of a single ring base with a double ring base
allows the regularity of structure which is observed in DNA.
If two large double ringed bases were to pair on their own,
and two small bases do the same, the structure would be
G A C T irregular, having bulges along its length. The regularity of
purines pyrimidines
DNA allows for efficient packing in the nucleus. The nucleus
is quite small, and yet in higher organisms it has to
accommodate a large amount of DNA.
A with T through
2 hy drogen bonds

 One consequence of the complimentary rule of base pairing is that the ratio G:C and A:T in DNA
from all organisms is 1:1.
 The two chains of DNA are held together by hydrogen bonds.

3'
5'

2 3
5
1 4
4 G C
1
5
3
2

T A

T A

2 3
5
1 4
G C
4 1
5
3' 3 2
5'

 The hydrogen bonds are extensive throughout the DNA molecule, so they are strong enough to
stabilize the two chains. However, they are weak enough to allow separation of the two chains
 839

during replication, a process whereby one DNA molecule gives rise to an identical daughter DNA
molecule.

In living cells, DNA exists as a double helix (Fig 11.41). This is a conformation in which the double
stranded structure is twisted into a helical shape, giving the appearance of a twisted ladder.The term
‘double’ indicates presence of two polynucleotide chains. The term ‘helix’ indicates the twisting of the
double stranded structure into a spiral shape
The sequence of bases in DNA acts as a storage of genetic information. This sequence is a code (secret
message) which can only be interpreted by living cells. Interpretation of this code by cells is known as
translation, and it results in the synthesis of a protein molecule in the cytoplasm of the cell. The sequence
of amino acids in a polypeptide (protein) is therefore determined by the sequence of bases in DNA.

1.2.3 Ribonucleic acid (RNA)

RNA, like DNA , is a nucleic acid. The key differences
between DNA and RNA are shown in Table 11.2. There
are different types of RNA.
 Messenger RNA (mRNA) copies
information from the nucleus and carries it to
the cytoplasm. This information is necessary
in the assembly of proteins in the cytoplasm.
 Transfer RNA (tRNA) binds amino acids
and brings them to structures known as
ribosomes, where protein synthesis takes
place.
 Ribosomal RNA builds up ribosomes.

Fig 11.41 The DNA double helix

DNA RNA

Double stranded Single stranded

Contains deoxyribose sugar Contains ribose sugar

Has the bases guanine , adenine, cytosine The base uracil replaces thymine
and thymine

Is longer Is shorther

Table 11.2 Comparison of DNA and RNA

1.2.4DNA as the genetic material

 840

DNA is the molecule which carries genetic information. Transmission of characteristics from parents to
offspring essentially involves the passage of DNA molecules from both parents to the offspring during
sexual reproduction. The paternal DNA is contained in sperm cells, and the maternal DNA in ova. Sperms
and ova are collectively known as gametes (sex cells). When gametes fuse during fertilization, the zygote
formed contains 50% of its DNA from the female parent and 50% from the male parent.
DNA is suitable as the genetic material because of the following features.

 It has a vast store of information in the sequence of its bases. The total number of ways in which
the four bases can be arranged in DNA is very large. Each different sequence of bases has its own
genetic meaning.
 It is chemically stable. If DNA was not stable, it would undergo chemical changes that would
result in an alteration of its genetic code. This would affect the offspring in adverse ways.
 It can replicate accurately and participate in transcription with very little expenditure of energy.
Replication of DNA involves breaking of the weak hydrogen bonds between the two strands.
Although these bonds are strong enough to hold the two strands of DNA together, they are weak
enough to allow easy separation of the chains during replication. Each chain then acts as a
template (molecular mould) for synthesis of a new DNA molecule. During replication, one
molecule of DNA gives rise to two daughter DNA molecules.

1.2.5Transcription

Transcription is the process whereby the sequence of bases on a specific section of DNA is copied
onto a strand of mRNA(to transcribe is to copy).

DNA is mainly confined to the nucleus (a very small amount is found in mitochondria and chloroplasts),
and yet protein synthesis occurs in the cytoplasm. There must therefore be a method of transferring
information from the DNA in the nucleus to the protein synthesis site in the cytoplasm.
Transcription is the process whereby the sequence of bases in DNA (genetic information) is copied onto
messenger RNA (mRNA). The mRNA then leaves the nucleus and enters the cytoplasm, carrying infor-
mation from the DNA. mRNA is therefore appropriately named. It acts as an intermediate (messenger)
between DNA in the nucleus and the protein assembly point in the cytoplasm.
The process of copying base sequences in DNA actually involves synthesis of mRNA molecules, using one
strand of DNA as the template strand. The details of mRNA synthesis by transcription are as follows.
 A part of the DNA, known as the cistron, unwinds and its two strands separate. The cistron is the
part of DNA which carries the base sequence (gene) to be copied.
 One strand of the cistron is selected to be the template strand for the synthesis of DNA. It is not
known why or how one of the chains is selected.
 Free nucleotide triphosphates align along the template strand, according to the rules of base
pairing, just as described for DNA replication. The structure of a nucleotide triphosphate is
shown in Fig 11.42.
 841


Note that this time, the base adenine on the
DNA template strand attracts a free
nucleotide triphosphate bearing the base
uracil. The mRNA molecule to be
phosphate
synthesized, like all RNA molecules, has
groups
uracil in place of thymine.
 A nucleotide triphosphate has three
organic base phosphate groups (instead of just one)
sugar bonded to each other. Hydrolysis of the two
Fig 11.42 Structure of a nucleotide
terminal P-P bonds occurs, producing a
triphosphate
nucleotideand releasing energy which
drives the transcription process. The free nucleotides are then used in the synthesis of mRNA. The
polymerization reaction which links nucleotides to form mRNA is catalyzed by the enzyme RNA
polymerase

Nucleotide triphosph-
ates align along
template strand acco-
The section of DNA to
rding to rules of base
be copied unwinds.
pairing

This section
of DNA is not
going to be
copied. G C C
G C
A T A U T
A T A
G U T
C G
C C
G G C
T C C G
G G G
T A
1 C
C T C
A U
G C A
T C
2 U

1 A
Bases on the nucleotide
triphosphates are attracted
2
to bases on template strand 1
by hydrogen bonding
The nucleotide triphosphates are hydrolysed
by condensation, producing nucleotides C
and releasing energy. The nucleotides then
G C C link by condensation, forming a strand U
of mRNA.
A U T U
C
1
A U T
G G
C
C
C G C
G G U mRNA
C
T C C
U mRNA
G A U
C
T mRNA detaches from the
U C template strand and enters the
A cytoplasm, carrying the base sequence
1 copied from DNA. Note that the sequence of
bases in the mRNA is the same as in strand 2
2 (non - template) of the DNA (note also that T is replaced
by U). Meanwhile, strands 1 and 2 of DNA pair up and the
double strand coils into a helix.
Fig 11.43 The process of transcription
 842

Once all the appropriate bases on the DNA template strand have been copied onto mRNA, the mRNA
strand leaves the template and enters the cytoplasm through the nuclear pores. It then carries the base
sequences copied from DNA to ribosomes. Ribosomes read and interpret the base sequence in mRNA,
resulting in the formation of a protein.

1.2.6Translation: interpreting the genetic message

The genetic information in DNA is expressed through protein synthesis.

Translation is the process whereby the sequence of bases in mRNA (hence in DNA) is converted to
a sequence of amino acids in a protein chain.

Translation takes place in the cytoplasm, on structures known as ribosomes.

Requirements for protein synthesis by translation

 Ribosomes. These provide the surface on which protein synthesis occurs. The ribosomes hold
together mRNA, tRNA and enzymes required for protein synthesis. Ribosomes are also the ones
which read the bases on mRNA, resulting in protein synthesis. If bases are not in contact with a
ribosome they are not read, and their base sequence is not converted to a protein.
 mRNA. This carries the genetic code (blue print) for protein synthesis. Protein synthesis involves
converting the base sequence on mRNA to a sequence of amino acids in the protein.
 Transfer RNA (tRNA). These molecules attract free amino acids from the cytoplasm and bring
them to the protein assembly point on the ribosome. There are thousands of tRNA molecules
involved in the synthesis of a single polypeptide chain. Each of them will be responsible for
bringing in a particular amino acid to the ribosome. It is important that a tRNA molecule brings
its amino acid at the right moment, so that the resulting protein has a correct sequence of amino
acids. The order in which tRNA molecules bring in amino acids to the ribosomes is determined by
the sequence of bases in mRNA, and hence in DNA.

Structure of tRNA
tRNA is a relatively short molecule (Fig 11.44). Each tRNA molecule has a specific sequence of bases (G,
A, C or U).

The transfer RNA molecule has two binding sites. One site
binds an amino acid, bringing it onto the ribosome. The other
binding site is known as an anticodon. This is a triplet of three
bases that has an affinity for a specific triplet of bases (codon)
on mRNA. Bases of the anticodon are attracted to bases of the
codon by hydrogen bonds.
The molecule is folded to give a clover leafed structure. This
folding is important to the function of tRNA.
 Folding of the tRNA molecule brings complimentary
bases together, which attract by hydrogen bonding (G
to C and A to U). These hydrogen bonds stabilize the
molecule, helping to maintain its shape.

Fig 11.44
 843

 The tRNA molecule is directional, as expected of a nucleic acid. One end is the -OH end (3′ end)
and the other is the phosphate end (5′ end). The 3′ end is used to bind an amino acid.

The genetic code

You now know that DNA carries genetic information in the form of sequence of bases. This information is
copied onto mRNA and transferred to the ribosomes for protein synthesis. Genetic information is in the
form of a triplet code. This means that a set of three bases on mRNA, known as a codon, codes for one
amino acid. The genetic code has been worked out and the triplets of bases that correspond to specific
amino acids is now known (Fig 11.45). The triplet of bases that codes for a particular amino acid is read
from the middle of the diagram outward. Examples are given in Table 11.3(verify using Fig 11.45). Recall
that the name of an amino acid can be abbreviated by taking only the first three letters from the name.

Table 11.3 Somecodons and the amino

acids they code for.

Codon Amino acid

UGG Trp

UGU Cys

UGC Cys

UAA None (stop

codon)

AUG Met (start

codon)
Fig 11.45 The genetic code

Consider a short chain of amino acids from the protein insulin A.

-Val-Glu-Gln-Cys-Cys-Thr
Using Fig 11.45 , the following facts can be gathered.
 this section of the protein requires 6 x 3 = 18 bases on mRNA.
 the sequence of the triplets which codes for the protein could be
-GUU-GAA-CAG-UGU-UGU-ACC-
 the corresponding sequence of bases on the DNA template strand is
CAA-GTT-GTC-AGA-AGA-TGG
 The actual sequence of bases on mRNA and in DNA may differ from those given above. This is
because one amino acid can be coded for by two different codons, for example, Glu can be code
for by GAA or by GAG. The existence of alternative codons for a particular amino acid minimizes
errors in protein synthesis. As an example, suppose that Glu was coded for by GAA only. An error
on mRNA that changes GAA to GAG would imply that the amino acid Glu cannot be incorporated
into the protein. In other words, the protein would have a wrong primary structure, possibly
causing a genetic disease.
 844

The details of protein synthesis by translation

Protein synthesis involves three stages, known as initiation, chainelongation and termination (Fig 11.46).
 mRNA binds to the surface of a ribosome. The first triplet of bases (codon) on mRNA to be in
contact with the ribosome is known as a start codon. This codon is on the 5′ end of mRNA, that
is, mRNA is always read in the 5′→3′ direction. This codon is AUG, and it codes for the amino
acid methionine (see Fig11.45).
The process whereby the amino acid methionine is brought to the ribosome is known as
initiation.

The codon AUG attracts a correct tRNA molecule by the rule of base pairing. Even though there
are thousands of tRNA molecules, it is only the tRNA which has a triplet of bases (anticodon)
complimentary to the codon AUG that is attracted. The anticodon of tRNA binds to the codon of
mRNA through hydrogen bonds. In this way, tRNA brings in methionine to the ribosome. The
incorporation of methionine as the first amino acid ensures that the rest of the codons on the
mRNA strand are read correctly.

 The ribosome slides along the mRNA. In this way, new codons get in contact with the ribosome.
A new codon attracts an anticodon of a new tRNA molecule. Thus a new amino acid is brought to
the ribosome. Meanwhile, the previous codon is no longer in contact with a ribosome. It disso-
ciates form its tRNA molecule. This tRNA molecule can be recycled for further incorporation of
the same amino acid when the same codon on mRNA is encountered again. As the ribosome
slides along the mRNA molecule, it gets in contact with more codons, and as a result more amino
acids are brought to the ribosome. The amino acids link by condensation in the order in which
they come to the ribosome. This order (sequence) defines the primary structure of the protein.
The process whereby amino acids condense to form a growing polypeptide chain is known as
chain elongation.

 The ribosome continues reading the sequence of bases on mRNA, until it reaches a stop codon. A
stop codon is a triplet of bases on mRNA which does not code for any amino acid. In other words,
there is no tRNA which corresponds to this triplet of bases. When a ribosome comes to the stop
codon, no tRNA is attracted, and thus no amino acid is brought to the ribosome. This therefore
results in the termination of the protein synthesis process. A particular protein is defined by its
primary structure, that is, the number of amino acids and their sequence. It is therefore essential
that translation produces an amino acid with the correct number of amino acids. The stop codon
ensures that the number of amino acids in the protein chain is not exceeded.
Termination is the process whereby a ribosome encounters a stop codon on mRNA and
therefore brings to an end the process of protein synthesis.

 The process of translation produces a polypeptide chain with a specific primary structure. The
protein chain is then sent to other parts of the cell where it is modified and folded into its correct
three dimensional shape (secondary or tertiary structure). In most cases, the amino acid methio-
nine is also removed from the first position of the protein chain.

 The sequence of amino acids in the protein chain is determined by the order in which tRNA
molecules bring amino acids to the ribosome. In turn, this is determined by the sequence of bases
on mRNA. Since the sequence of bases on mRNA was copied from DNA, it can be said that the
sequence of bases in DNA determines the sequence of amino acids in the protein chain.
 845

methionine
tRNA

ribosome ribosome slides along mRNA,

UAC reading new codons

anticodon
3'
5'
AUG C A C UCA CCC mRNA

first codon
codes for
methionine

first
second amino
amino acid Protein chain grows
acid
(methionine) as ribosome reads more
codons

Ribosome moves from 5' end (phosphate end)

towards 3' end (OH end) on mRNA. This results in a
polypetide being assembled from the N to the C
terminal.

5' A U G C A C U C A C C C 3'

Fig 11.46 The process of translation

Definition of Terms
Codon - A triplet of consecutive bases on mRNA and DNA that codes for a particular amino acid.
Start codon - Triplet of bases on mRNA which dictates the first amino acid to be incorporated into the
protein chain. The start codon is AUG and it codes for the amino acid methionine.
Stop codon - This is a triplet of bases on mRNA which codes for no specific amino acid. It therefore
signals the end of the protein synthesis process.
Anticodon - A triplet of bases on tRNA that is complimentary to a specific codon on mRNA.
An anticodon binds to a specific codon on mRNA through hydrogen bonds. This binding process allows a
tRNA molecule to bring in its amino acid to the ribosome.
 846

Genetic information and its interpretation: key concepts at a glance

DNA carries genetic information in the

sequence of its bases. This information
acts as a blue print for the synthesis of
protein molecules.
protein
Transcription is a process whereby the
NUCLEUS base sequence on one strand of DNA is
translation copied onto mRNA.
transcription
mRNA is a molecular vehicle that
DNA
mRNA transfers genetic information (base
sequences) from DNA to cytoplasm.

Translation is a process whereby the

base sequence on mRNA, and hence DNA,
CY TOPLASM is used to synthesize a protein molecule.
The sequence of bases on mRNA and
hence in DNA determines the primary
Fig11.47 Diagram of the key processes and structure of the protein.
molecules involved in storing and decoding
genetic information

1.2.7Mutations and genetic diseases

A mutation is an error on the molecular structure or amount of DNA in the cells of an

organism.

An error on the molecular structure of DNA implies that a faulty mRNA is also synthesized during
transcription. Thus a faulty protein will be synthesized at the ribosomes. A genetic disease is one which
occurs in an organism when it inherits faulty DNA from one or both of the parents. The affected organism
will not be able to synthesize normal proteins, or it will not be able to synthesize the protein at all. In some
cases the protein is synthesized in less than sufficient quantities. The signs and symptoms of genetic
disease are directly linked to a faulty protein, or its absence. The link between proteins and genetic
diseases should be easy to understand. Recall that proteins play key roles that include building up of
structures, enzymes in metabolic processes, transportation of oxygen and other substances, and defence.
For proteins to carry out these crucial roles, they must have the correct shape (secondary or tertiary
structure). In turn, this shape is determined by the primary structure of the protein. Faulty DNA gives rise
to a protein with a wrong primary structure. Such a protein gives rise to wrong secondary or tertiary
structure. Such a protein cannot carry out its function or works inefficiently, leading to the signs and
symptoms of genetic disease.
 847

Sources of mutations
 Errors during the replication process. Replication is the process whereby a DNA molecule
gives rise to an identical daughter DNA molecule. Errors may arise during this process, but such
errors are usually corrected by the cell’s own corrective mechanisms.
 UV and other harmful forms of radiation such as gamma rays from radioactive fallout.
These damage DNA, altering its molecular structure.
 Carcinogens. These are chemicals which destroy DNA. Cigarette smoke is particularly rich in
carcinogenic compounds.

Types of mutations
We will discuss two types of mutation (errors) that can occur in DNA and examples of genetic diseases
that result from them.
(i) Substitution error
(ii) Deletion error

Substitution error: Sickle cell anaemia

Substitution is an error of base replacement in DNA. A well known example of a genetic disease caused by
substitution of a base is sickle cell anaemia.

Sickle cell anaemia: facts at a Sickle cell anaemiais a result of the substitution of
glance a base in the gene (base sequence) that codes for a β
haemoglobinchain (recall that DNA contains two α
Type of error (mutation) : substitution and two β protein chains). The error occurs on the
codon GAG in which A is replaced by T. The correct
Protein affected: β chain of haemoglobin
codon GAG codes for the amino acid glutamic acid.
How protein is affected: The wrong codon GTG causes a hydrophilic amino
A polar amino acid , glutamic acid, is replaced by acid residue (glutamic acid) to be replaced by the
valine, which is non-polar. hydrophobic (non polar) amino acid residue,
valine. This results in a wrong primary structure of
Signs and symptoms:
a β chain of haemoglobin. Even though it is only
(Usually experienced in environments of low
one base in DNA and one amino acid in the protein
oxygen concentration). These include
 blueing of extremities, e.g. fingertips
which are wrong, the error is significant enough to
 fatigue give signs and symptoms of sickle cell anaemia.
 severe pain due to damage in organs Haemoglobin containing the faulty β- chain is
 severe cases may lead to stroke and heart known as HbS, to distinguish it from normal
attack. haemoglobin, HbA. Presence of HbS in the blood
does not lead to any signs or symptoms at normal
Cure: none oxygen partial pressures.

However, when the partial pressure of oxygen in the blood becomes very low, HbS molecules tend to
associate and form long insoluble and rigid polymers. Formation of these polymers requires a
hydrophobic patch to be present in the haemoglobin β chain. This explains why replacement of a polar
amino acid in a β haemoglobin chain by one which is non-polar leads to sickle cell anaemia. Presence of
rods of these polymers causes red blood cells to become rigid and to assume a sickle shape. The signs and
symptoms of anaemia are directly linked to the presence of these sickle shaped cells. At normal partial
pressures of oxygen, HbS does not lead to signs and symptoms of anaemia.
 848

 Obstruction of blood capillaries by sickle cells may occur because these red blood cells, being
rigid and wrongly shaped, cannot easily squeeze their way through the narrow blood vessels. This
obstruction is known as vaso-occlusion. It cuts oxygen and nutrient supply to organs, leading to
pain and possible organ damage. Depletion of blood to the brain and to the cells of the heart may
lead to stroke and heart attack, respectively.
 Sickle cells cannot carry oxygen efficiently. Their shape greatly reduces their total surface area
(Fig 11.48 ). Normal blood cells are biconcave disc shaped. This shape optimizes surface area for
the transportation of oxygen. In addition, sickle cells cannot move rapidly to and through tissues.
Presence of a large number of sickle shaped cells in the blood therefore leads to a general shortage
of oxygen in the body, leading to fatigue, dizziness and fainting.
 A crisis known as splenic sequestration is frequently associated with people who are anaemic.
The spleen has a role in the destruction of faulty red blood cells. This, accompanied by the fact
that it has very narrow vessels, lead to clogging of the spleen. This causes pain, enlargement of the
spleen and bloating of the stomach. Chances of bacterial infections of the spleen also increase,
leading to complications.
Deletion error: Cystic
fibrosis (CF)
Cystic fibrosis is a genetic disease caused by a
deletion of bases on DNA. There are several
forms of such error, but in the most common
case, there is a missing triplet of bases on the
DNA molecule. As a result, transcription gives
rise to an mRNA molecule that has a missing
codon. Consequently, a protein is synthesized
which has a missing amino acidThe protein
affected in this case is known as the Cystic
Fibrosis Transmembrane
Regulatory(CFTR) Protein, in which the
amino acid Phenylalanine is missing. The role
of this protein is pumping out Cl- ions from
mucus producing cells that line body cavities,
for example in the lungs and the pancreas. This
Fig 11.48 Red blood cells taken from the blood of
an anaemic person. Some of the red blood cells have protein is found in all people but in CF patients,
a sickle shape. The amount of such sickle cells the protein is faulty and so cannot pump out the
increases when oxygen supply in the blood is low. chloride ions at all, or it does not work properly.
The pumping out of chloride ions from these
cells is necessary in maintaining a runny layer
of mucus on the surface of the cells.

How a normal CFTR protein works

CFTR protein is a channel protein through which chloride ions are pumped from cells (Fig 11.49). This
pumping process is driven by energy provided from the hydrolysis of an energy carrier molecule known as
adenosine triphosphate (ATP).
In a CF patient, absence of an amino acid in the CFTR protein causes it to fold improperly, and as a result
it cannot pump out chloride ions from the cells, or it works inefficiently. As a result, chloride ions
accumulate in the cell. To maintain electroneutrality of the cytoplasm, Na + ions are attracted from the
aqueous environment outside the cell into the cell, leading to accumulation of sodium chloride in the
 849

cytoplasm. The high concentration of salt in the cytoplasm attracts water from the mucus layer on the
surface of the cell. The mucus therefore becomes thick and sticky. Most of the signs and symptoms of CF
are associated with this viscous layer of mucus which lines the walls of certain cavities including the
respiratory air ways, digestive tract and pancreatic ducts.
 Accumulation of mucus in the air passages causes difficulties in breathing. Mucus in the air
passages trap and provide food and shelter for bacteria. Chronic infections of the respiratory
system, including the lungs, is common in CF patients ( an infection is said to bechronic if it is
long- lasting).

Cystic fibrosis: facts at a glance

Type of mutation: Base deletion
Protein affected: CFTR protein, which is a channel
protein involved in pumping out chloride ions from
cells.
How protein is affected:
protein has a missing amino acid, which affects the way
it folds.
Signs and symptoms:
 breathing difficulties
 chronic infections of the respiratory system,
including the lungs.
 infertility in males
 white scars of dead tissue (cysts, hence the
name cystic fibrosis) in the pancreas.
 excessively salty sweat
Fig 11.49 The CFTR protein pumps out
 Retarded growth
chloride ions from mucus producing cells.
Cure : none

 Accumulation of mucus in the pancreatic ducts result in death of pancreatic cells and the blocking
of channels which transport digestive enzymes. Dead patches of tissue in the pancreas appear as
white cysts, and this is where the name cystic fibrosis is derived from. Obstruction of the flow of
digestive enzymes from the pancreas to the digestive system results in poor conversion of food
into soluble nutrients. This causes malnutrition and related diseases.
 850

11.1.3 SMALL MOLECULES AND IONS IN

LIVING SYSTEMS
We have discussed the role played by proteins and nucleic acids in living systems. These compounds are
complex condensation polymers. Of equal importance in living systems are small molecules such as water
and ATP, and small ions such as Na+ and Fe2+. However, some ions, particularly heavy metal ions such as
Hg2+ and Ag+, are poisonous.

1.3.1ATP and energy transactions in living cells

Living systems need energy to run processes such as protein synthesis, pumping ions into or out of cells,
muscle contraction etc. The energy required for these life processes comes from food molecules. Respira-
tion is the exothermic cellular process whereby food molecules are slowly oxidized by oxygen, releasing
energy and waste products (CO2 and H2O). The energy produced by respiration is not directly used by
living systems. Instead, it is transferred to an energy carrier molecule known as adenosine triphosphate
(ATP). This transfer of energy actually involves synthesis of ATP from adenosine diphosphate (ADP). This
reaction is endothermic. In other words, formation of ATP is accompanied by a net absorption of energy.
The ATP molecule is therefore at a higher energy level than ADP. The energy absorbed during the reaction
is stored in the new P-P bond formed when ADP is converted to ATP (Fig 11.50).
 The structures of ADP and ATP are shown in Fig 11.50. These compounds are derived from a
nucleotide that contains ribose sugar and the organic base adenine. Recall that a nucleotide has
one phosphate group. ADP and ATP have two and three phosphate groups respectively.
 The conversion of ADP to ATP is reversible.
ADP + P Ý ATP + H2O ∆H = +30.5 Kjmol-1 ...(i)

energy is stored
in this bond

phosphate
groups ribose sugar
adenine
(organic base)

ATP

Δ H = energy absorbed in conv erting ATP

to ADP. This energy comes from
respiration.
Fig 11.50
The endothermic
conversion of ADP to
ATP.
ADP
 851

The forward reaction is endothermic and it results in energy from respiration being stored in the new
bond formed in ATP. The formation of ATP is a condensation reaction. An inorganic phosphate molecule
(indicated P in equation (i)) bonds to a phosphate group in ADP, forming a new bond and releasing water.

 When cells need energy, reaction (i) is reversed, that is, ATP undergoes hydrolysis. Recall that for
an equilibrium process, if the forward reaction is endothermic, then the reverse reaction is
exothermic. The hydrolysis of ATP therefore releases energy from the terminal P-P bond in ATP.
The energy is then used to drive endothermic processes such as pumping ions out of
cells.
ATP + H2O Ý ADP + Pi ... ∆H = -30.5Kjmol-1
The reaction involves breaking of an O-H bond in water (hydrolysis) and the terminal P-P bond in
ATP. This process of bond breaking is endothermic. The inorganic phosphate formed (Pi) has a
new P-OH group, and the terminal phosphate in ADP now has a new O-H bond (Fig). Formation
of two new bonds in the products releases energy, which more than compensates for the energy
used in bond breaking. Overally, the reaction is therefore exothermic. However, the energy
released by the hydrolysis of ATP is more than would be expected from a comparison of energy of
bond breaking and energy of bond formation. A more complex account explains the exothermic
nature of the reaction in terms of charge distribution in ATP and ADP.

Bond breaks

- - - - - -
- 1 2
HO
H

new P-O
new O-H bond
bond
H2O splits, H
is added to O1 and OH
to P2.

From the foregoing discussion, it is clear that cells do not use energy from respiration directly in
carrying out vital processes of life. Instead, the energy is transferred and stored in ATP. When
cells require energy, ATP undergoes hydrolysis, releasing energy. ATP acts as an energy currency
in all living organisms. All processes which require energy in living organisms obtain the energy
from ATP. The advantages are
 ATP is soluble in water. It is therefore very mobile, that is, it is easily carried in solution to the
cells which need energy.
 Energy is conserved since
(i) ATP is only hydrolyzed in response to a specific need
(ii) hydrolysis of ATP produces energy in manageable amounts. The use of ATP therefore
prevents the release of sudden bursts of energy as this would damage cells and lead to loss of
excess energy as heat.
 ATP releases its energy rapidly and without difficulty. The hydrolysis of ATP is a single step
reaction which ensures that urgent energy needs are instantly addressed.
 ATP can easily be replenished from ADP.
 852

 Although the hydrolysis of ATP is energetically favourable (exothermic) it does not occur
spontaneously because the reaction hashigh activation energy. ATP is therefore kinetically stable
and is easily stored in cells. When energy is required, an enzyme known as ATPase is activated to
act upon the ATP molecules. The enzyme lowers the activation of the reaction and so increases the
rate of reaction.
NBThe enzyme ATPase also catalyzes the conversion of ADP to ATP. Recall that if a reaction is
reversible, an enzyme is able to catalyse both the forward and the reverse reaction.

1.3.2Biologically important ions

Some ions are extremely important in living systems. Here are examples of such ions and their uses in
organisms.

1. Iron
Iron is required in the formation of blood. It is an integral part of haem, which is the oxygen carrying unit
in haemoglobin. The structure of haem as a complex compound has already been discussed.
Iron, in the form of Fe (II), is also found in the following locations:
Myoglobin in muscle cells
Myoglobin, like haemoglobin, contains a haem group with a central Fe 2+ ion. However, myoglobin is made
up of only one protein chain. Myoglobin has a very high affinity for oxygen. Since it does not easily give up
its oxygen, it acts as a storage of oxygen in the muscles, and will only give up oxygen to the tissues under
extreme cases of oxygen deficiency. Since myoglobin has only one haem group, it can carry only one
oxygen molecule.

Cytochrome oxidase
This is an enzyme found in the mitochondria. It is one of the key respiratory enzymes. It participates
towards the end of the respiratory chain. Any substance which inhibits this enzyme will result in
accumulation of respiratory intermediates, and the whole process soon stops.

2. Zinc
The role of zinc as an enzyme co-factor has already been discussed. A co-factor can be thought of as a non
protein species that helps an enzyme to carry out its function. Some co-factors like Zn2+ in the enzyme
carbonic anhydrase, are classified as prosthetic groups. Such co-factors are bonded to the enzyme by very
strong covalent bonds. The enzyme and the co-factor therefore behave as one functional unit. Carbonic
anhydrase catalyses the reaction between water and carbon dioxide to form carbonic acid.
CO2 + H2O Ý H2CO3Ý H+ + HCO3- ... (i)
Zinc is also found in the following locations
Carboxypeptidase in the digestive tract
Zinc is a prosthetic group in the enzyme carboxypeptidase. This is an enzymewhich catalyzes the
hydrolysis of polypeptides into smaller molecules.

Alcohol dehydrogenase in the liver

The human body regards alcohol as a poison. The liver plays an important role in detoxification processes.
The enzyme alcohol dehydrogenase catalyzes the removal of hydrogen from ethanol (dehydrogenation =
oxidation). This results in the formation of the aldehyde ethanal. Because of its volatility and poor
 853

solubility in water, ethanal is easily expelled though the lungs. The presence of ethanal and unconverted
ethanol is responsible for the unpleasant breath of a drunken person. The concentration of ethanol and
ethanal in the breath can be large enough to give visible changes with some oxidizing agents, for example
orange potassium dichromate is reduced to green Cr 3+. Meanwhile, the ethanal and ethanol are oxidized
to ethanoic acid. This reaction can be used in some very simple breathalysers to estimate the amount of
alcohol in drunken drivers. More advanced digital breathalysers make use of the flow of electrons during
this type of redox reaction to generate a flow of current. The size of current that flows is directly
proportional to the amount of ethanol or ethanal in the breath.

3. Potassium and sodium

K+ and Na+ ions are required for the transmission of nerve impulses along neurones (nerve cells). These
types of cells have a permanent ability to allow movement of K+ and Na+ ions across the cell membrane.
When no nerve impulse is being transmitted, Na+ ions continuously enter the neurons whilst K+ ions are
continuously moved out. Now, for a neurone at rest (no impulse being transmitted) the outflow of
potassium ions is faster than the inflow of sodium ions. In other words, at any given moment, the neurone
loses positive charges faster than it gains them. The net effect is that the inside of the neurone is nega-
tively charged relative to the outside. This negative internal charge in the neurone is known as a
resting potential. The resting potential is maintained by a Na-K pump which runs on energy from the
hydrolysis of ATP. The role of this pump is to maintain the differential rate at which Na + and K+ ions
move across the cell membrane of the neurone. When an impulse reaches a nerve from a sensory cell (e.g
receptors cells in the skin), the conductance of the neurone is reversed. The inflow of Na + ions becomes
greater than the outflow of K+ ions. The sudden influx of positive Na+ ions reverses the negative potential
inside the cell, that is, the inside becomes positive whilst the outside becomes negative. This reversal of
potentials is necessary for the transmission of the impulse along the neurone.
K+ ions are also found in saliva and they have been shown to act as co-factors for the enzyme salivary
amylase. This enzyme digests (hydrolyzes) cooked starch to a sugar known as maltose.

The role of specific ion channels

The movement of ions across the membranes of cells is not only under the control of energy driven pumps
as described above.
In some cells, the cell membrane contains channel proteins which allow the movement of certain ions
without necessarily using energy from ATP.
A well known example is the potassium specific channel which selectively allows K+ ions into cells.
Usually, both Na+ and K+ ions are present in large amounts in the fluid surrounding cells. However, K
specific pumps are highly selective; they will allow only K+ ions into the cell, not Na+.
The selectivity of the K-specific pump is not what we would have expected from a consideration of ionic
sizes. Na+ ions are smaller than K+ ions, so we would have expected Na+ ions, and not K+ ions, to pass
through the channel. To explain this apparent paradox, we need to consider the energies of hydration and
dehydration of these ions. In water, ions electrostatically attract water molecules around them, forming
hydration shells. This is an exothermic process known as hydration, and the energy released by the
process is known as the enthalpy change of hydration. Now, the enthalpy change of hydration of Na+ is
greater than that of K+. This is because
 854

 the charge density on the Na+ ion is larger, so the ion

attracts water molecules more strongly
 the nucleus of the Na+ionis closer to the hydration shell,
that is, water molecules experience a stronger attraction
to the nucleus.

The sodium ion therefore holds onto its hydration shells more
strongly than the potassium ions. The presence of hydration
shells makes the hydrated Na+ ions large, so that they cannot fit
through the channel of the K-specific pump.
On the other hand, hydration shells in K+ are weakly held and so
the ions can easily lose some water molecules from the
hydration shells. The hydrated K+ ions are therefore smaller
(than hydrated Na+ ions) and can easily pass through the pore of
the channel protein.

1.3.3Toxic metals
Not all metal ions are helpful in living systems. Some metal ions are well known poisons. The harmful ef-
fects of heavy metal ions such as Hg2+ and Ag+ have already been discussed. Recall that these ions usually
exert their effects by acting as non-competitive inhibitors. Hg2+ is a poison of the nervous system.
Pregnant women who experience mercury poisoning are also at risk of giving birth to deformed babies.
Industrial processes and their products are often the sources of heavy metal pollution in the environment.
Electrolysis of brine by the mercury cathode process used to be a major source of mercury ions found in
water bodies. Nowadays, many countries now produce chlorine from brine using a different method
which does not involve the use of mercury. Mercury is also found in some fungicides. These mercury
compounds easily enter food chains, for example, through water bodies. Some organisms such as fish then
concentrate these compounds into their tissues. Humans who feed on the fish are therefore at risk of
mercury poisoning.
Heavy metals are also important in the manufacture of computers and rechargeable batteries.
Unfortunately, these products are often improperly disposed of and in this way, heavy metal ions such as
cadmium end up in the environment. Cadmium can lead to kidney and lung cancer.
Another poisonous heavy metal ion is Pb2+, which is a well known poison of the nervous system, including
the brain (Hg2+ has similar effects). Presence of lead (II) compounds in the environment has been associ-
ated with the burning of leaded petrol and the use of lead in water pipes. Most countries have stopped
using leaded petrol and lead water pipes, and this has greatly reduced human exposure to lead
compounds.
855
 856

Questions, solutions and discussions: Protein chemistry

Q1The molecule that contains the genetic information for an individual organism is called
deoxyribonucleic acid, DNA.

(a) The diagram shows part of a DNA molecule. Study the diagram and identify the blocks
labelled J, K, L and M as accurately as you can.

Block letter identity

(b) The DNA molecule is formed from two polymer strands.

What stops these strands from separating from each other?

(c) List three differences between the structures of DNA and RNA.

(d) Outline the different roles of mRNA and tRNA in the processes of transcription and
translation.
 857

9701/41/O/N/10

Solutions

(a)J Deoxyribose
K Guanine
LPhosphate
M Thymine

(b)Hydrogen bonds between the bases

(c)
 RNA is a single strand; DNA is double strand
 RNA contains ribose; DNA contains deoxyribose
 RNA contains uracil; DNA contains thymine
 RNA is shorter than DNA

(d)mRNA – copies the DNA gene sequence

or forms a template for a particular polypeptide / in protein synthesis
tRNA – carries amino acids to the ribosome

...................................................................................................................................................

Q2Metals play a vital part in biochemical systems. In this question you need to consider why
some metals are essential to life, whilst others are toxic.

(a) For each of the metals, state where it might be found in a living organism, and what its
chemical role is.

iron

sodium

zinc
 858

(b) Heavy metals such as mercury are toxic, and it is important that these do not enter the
food chain.

(i) Give a possible source of mercury in the environment.

(ii) Describe and explain two reasons why mercury is toxic, using diagrams and/or equations
to help your explanation.

9701/04/M/J/09

Solutions

(a) Please refer to section

(b)(i) Manufacture of NaOH by the mercury cathode process (now banned in most countries) /
manufacture of batteries / extraction of gold/mercury fungicides /mercury compounds used
in timber preservation

(ii) breaks disulphide bonds or Hg bonds to S-H groups

–CH2-S-S-CH2- + 4Hg+2 –CH2-S–Hg + 2Hg2+

orR-S-S-R + 4Hg+2 R-S-Hg + 2Hg2+

bonds to carboxyl side chains (R groups) of a protein.

–CO2H + Hg+–CO2Hg + H+or2RCO2H + Hg2+(RCO2)2Hg + 2H+

.....................................................................................................................................

Q3(a)Explain how protein synthesis occurs in cells, including in your answer the role of
ribosomes .

(b)Explain why the enzyme lysozyme, which consists of 129 amino acid residues, requires
a triplet code of 393 bases.

(c)(i)Name a disease brought about by a mutation in the DNA of the individual.

(ii)Give a symptom of the disease.

9701/04/SP07
 859

Solutions

(a)Key points:

• 2 strands of DNA separate

• mRNA reads (copies) the ‘code’/base sequence on template srand of the DNA
• mRNA moves out of the nucleus
• mRNA binds to the ribosome
• tRNA binds to amino acids
• amino acids are transferred to ribosome and joined to growing chain
• until Stop codon is reached

(b)Each amino acid needs 3 bases to code for it

3 x 129 = 387, this leaves 3 bases to code for Start and 3 for Stop

(c) (i)A variety of answers possible e.g.

• sickle cell disease

• cystic fibrosis
• haemophilia etc.

(ii) Please refer to section

.............................................................................................................................................................

Q4(a) DNA carries the genetic code in living organisms and consists of a double helix.
(i) Describe what is meant by a double helix.

(ii) How are the strands of the double helix held together?

(b) In replicating the genetic code two RNA molecules, mRNA and tRNA, are used to perform
functions called transcription and translation.

Describe the role of the RNA molecules in these two functions.

(c) When an egg is boiled, the protein changes from a viscous liquid to a solid.

(i) Suggest what causes this change as the protein is heated.

(ii) Why is there no change to the primary structure of the protein under these conditions?
 860

(d) Describe in outline how energy is provided in animal cells.

Solutions

(a) (i)Two interlinked spirals /two parallel strands twisted into a double spiral

(ii) By hydrogen bonds between bases

(b)Transcription
 DNA unravels and one strand is used as a template
 mRNA reads / copies the sequence on the template strand and transfers the sequence to
the ribosome

Translation
 mRNA binds to the ribosome , exposing its codons to the ribosome surface
 tRNA translates the codon from mRNA by carrying amino acids in the correct sequence
to the ribosome.

(c) (i)Disruption of the secondary/tertiary/quaternary/three dimensional structure of the protein

OR internal vibrations in the enzyme break stabilizing forces such as hydrogen bonds and
hydrophobic interactions. The three dimensional shape of the enzyme is disrupted.

(ii)The covalent/peptide bonds in the (protein) chain are too strong

(d)Energy is provided by the hydrolysis of adenosine triphosphate (ATP)

ATP + H2O  ADP + Pi+ energy
Energy from respiration/oxidation of glucose is used to reconvert ADP back to ATP.

.............................................................................................................................................

Q5 (a) The diagram in Fig shows a section of DNA.

Identify the blocks labelled X, Y and Z.

(c) Tableshows the 3-base codes used by RNA.

(i) What amino acid sequence would the following base code produce?
(You may use abbreviations in your answer.)

-AUGUCUAGAGACGGGUAA-
 861

(ii) What would be the effect on the amino acid sequence if a mutation caused the
base G at position 13 in the sequence to be replaced by U?

(d) (i)Name a disease which results from a genetic defect.

(ii) Explain how the genetic defect can bring about your named disease.

Fig A section of DNA

Table The three base codes used by RNA

9701/04/M/J/07
 862

Solutions

(b)X = deoxyribose
Y = phosphate
Z = thymine

(c)(i)(met)- ser-arg-asp- gly (the words stop or start should not be included in the sequence)

(ii)The amino acid gly (or the last amino acid) would be replaced by trp

(d)(i)e.g. Huntington’s, cystic fibrosis, haemophilia, sickle cell anaemia, thalassemia, muscular
dystrophy, Down’s syndrome, phenylketonuria

(ii)Suitable explanation e.g. wrong amino acid coded or different aminoacidsequence or incorrect
protein produced or extra chromosome (for Down’s)
... causes change in 3D structure/change in active site/loss of enzymeactivity (or a specific
description pertinent to the mentioned disease)
 863

11.3DESIGN AND MATERIALS

11.3.1 MEDICINAL CHEMISTRY AND

DRUG DELIVERY

Chemistry has greatly improved our quality of life in many ways. New drugs are being synthesized
everyday to combat or prevent illnesses. There are different types of drugs and there are equally different
ways of defining the term drug. Our discussion will mainly focus on medicinal drugs, which are designed
to
 cure diseases by destroying disease causing agents such as bacteria. An antibiotic is an example of
such a drug. It cures disease by destroying bacteria that cause disease.
 prevent disease. Preventive drugs are known as prophylactics.
 alleviate the signs and symptoms of disease , for example, skin rashes, pain and inflammation.
Analgesics (pain killers) such as aspirin are well known drugs in this category.
 enhance the way the body performs

3.1.1 Methods of drug administration

Some drugs are designed for superficial problems such as light burns and skin bruises. Such drugs can be
applied directly to the affected area, for example in the form of a lotion. Some drugs are designed to work
in tissues and organs which are deep in the body. These drugs must be administered in a way that allows
them to enter the blood and be carried to the target organs or tissues. The methods of drug delivery that
can be used in such cases include
 oral (through the mouth)
 anal (through the anus)
 parenteral(using injections)
 inhalation (through respiratory pathways and the lungs)

Factors that determine the method of drug delivery include

 Urgency - if the drug is required to produce immediate results, a fast method of drug delivery
should then be used. The parenteral method is suitable here since it introduces the drug straight
into the blood, allowing it to be carried rapidly to the affected areas.
 location of affected tissues - the method used to administer the drug clearly depends on the
location of the target tissue, for example asthma, which affects the respiratory passages, requires
the use of inhalants. Similarly, some problems of the rectum can be alleviated using the anal
method of delivery.
 Reactivity of the drug. Some drugs are prone to hydrolysis and degradation by the acids and
enzymes present in the stomach. For such drugs, it may be necessary to use a method of drug
delivery that by-passes the digestive tract, for example, the use of injections. However, some
 864

drugs depend on initial hydrolysis in the digestive system before they can be absorbed into the
blood. For such drugs, the oral method of delivery cannot be avoided.
 State of the patient. Some medical conditions may make the use of certain methods of delivery
impossible, for example, a comatose patient is not able to take drugs orally.

3.1.2 Major challenges of drug delivery

Drug delivery aims at ensuring that the drug is not only administered to the patient, but that it re aches
the tissue or organ where it is required to take action (target tissue/organ). Here are the major challenges
encountered in this quest.
 Drug degradation
 side effects
 drug unpalatability
 the problem of targeting

1. Drug degradation
Sometimes the drug is broken down by enzymes, for example in the digestive system and in blood, before
it reaches the target tissue. The stomach is a particularly hostile environment for drugs because it contains
enzymes and the strong acid HCl. These conditions promote hydrolysis of some types of drugs, for
example, drugs that contain the ester and the amide linkage. Drugs of a protein nature, for example,
insulin, cannot be administered orally because digestive enzymes will mistake them for food and digest
(hydrolyze) them to produce amino acids.
Some methods of reducing the problem of drug degradation include protecting the drug in a liposome or
in a nanosphere(Figs 11.86 (a) and (b)).

(a)

(b)
Fig 11.86 Methods of drug protection (a) nanosphere (b) liposome
 865

Nanospheres are very tiny spherical particles, with a diameter in the range of 10 to 500 nm. Nanos-
pheres have a wide range of possible uses, including in drug delivery. The wall of the nanosphere shields
the drug from the acids and enzymes of the digestive tract. The nanospheres are absorbed into the blood
stream where they undergo slow hydrolysis, thus gradually releasing the drug.

Liposomes are spherical structures made from a phospholipid bilayer. A phospholipid has a polar
phosphate end and non polar hydrocarbon chains. The polar ends are said to be hydrophilic (‘water
loving’) because they form ion-dipole attractions with water molecules. The hydrocarbon chains are said
to be hydrophobic (‘water hating’) because they are repelled by water. In water, phospholipids therefore
tend to aggregate in such a way that the hydrophobic tails move away from water and cluster together
through Van der Waals forces. Meanwhile, the hydrophilic tails are attracted to aqueous environments,
labeled A and C in Fig 11.86 (b).
 A liposome has a relatively large volume and so can carry large amounts of a drug.
 Another advantage of a liposome is that it can carry two types of drug. Polar (hydrophilic) drugs
can be carried in the part labeled A. Non polar drugs can be carried in the part labeled B.

Another method of protecting a drug is bonding it to carrier molecules. These molecules are then carried
to the target organ or tissue where the bonds between the drug and the molecule are broken, for example
by hydrolysis, thus releasing the drug. The carrier molecule can be designed so that it diffuses rapidly
from the digestive tract into the blood. This ensures that the bonds between the drug and the carrier
molecules are not broken down in the digestive tract. The polymer polyethylene glycol(PEG) has
been successfully used as a carrier molecule. Solubility of the carrier molecule can be controlled by
altering size of the polymer chains. Short chains are soluble in water and this allows the carrier
molecule , together with the bonded drug molecules, to diffuse rapidly, for example, from the digestive
tract into the blood.

(a) -
n

(b)
n
The structure of PEG (a) expanded structure showing a
repeat unit. (b) abbreviated form of PEG

For a drug to bond to PEG, it must have a functional group that can react with the -OH groups at the end
of the PEG molecule. For instance, a drug that contains a carboxyl group can bond to PEG by forming an
ester linkage, which can be broken by hydrolysis at the target organ or tissue. Possible disadvantages of
using PEG are
 Only two molecules of the drug can be carried per molecule of PEG
 The method works only for drugs that can form covalent bonds to PEG

2. Side effects
In addition to bringing about the desired medicinal effect, a drug may also have undesirable effects,
known as side effects. These include nausea, allergies and drowsiness. In most cases, side effects cannot
be avoided, but some people are more vulnerable than others. In such cases, it might be advisable to find a
drug replacement. A fairly recent method of lowering side effects of a drug involves drug targeting. This
technique allows the drug to be carried only to the target tissue or organ, by-passing unaffected organs or
tissues.
 866

3. Drug unpalatability
Most drugs are not so appealing to the sense of taste. This can be a real challenge if the drug is to be
administered to young children. This problem is usually overcome by enclosing the drug in a capsule that
has a pleasant taste.

4. The challenge of drug targeting

Drug targeting is a way of ensuring that the drug reaches only the affected tissue or organ. This has
several advantages.
 Only a small amount of the drug is required since there is no wastage associated with the drug
reaching unaffected tissues. This cuts on the cost of the drug.
 The drug acts quickly because it does not circulate around the body, but goes straight to the target
organ or tissue.
 Side effects are minimized. Healthy tissues may show a reaction towards the drug. Drug targeting
reduces this risk by ensuring that the drug is conveyed straight to the affected tissue or organ.
 It is possible to monitor the effects of the drug on only one part of the body.

One method of targeted drug delivery involves attaching the drug to an antibody, which is a protein that
has a strong affinity for a disease causing agent known as an antigen. An antibody is very specific, so it can
be used to direct a drug to the affected tissue or organ.

3.1.3 How drugs work

Different types of drugs act in different ways. In fact, one way of classifying drugs is in terms of their
effects. Some classes of drugs are shown below.

Drugs

Antibiotics Analgesics Purgatives Sedatives

Analgesics are drugs that relieve pain. Well known examples are paracetamol and aspirin. Drugs which
relieve digestive disorders such as constipation and acid indigestion are known as purgatives. Sedatives
are drugs which induce calmness.

analgesics

aspirin (acetylsalicylic acid) salicylic acid paracetamol

Salicylic acid is a natural pain killer found in the leaves of thewillow. Aspirin is a common
Q the-counter pain killer.
over-

(a) Write down the molecular formula of aspirin.

(b) State the reagents and conditions required to convert salicylic acid to aspirin.
 867

(c) Both paracetamol and aspirin have groups which can be hydrolyzed by enzymes and acids
in the stomach. For each drug, circle and name the functional group which experiences
hydrolysis. Also show the structures of the products of hydrolysis.

Antibotics
These drugs have an internal antibacterial effect. Antibiotics should not be confused with antiseptics.
Antiseptics are chemicals which are designed to kill bacteria on surfaces such as the top of kitchen sinks.

A nurse may also swab the surface of the skin of a patient with an
antiseptic (such as ethanol) before administering an injection.
Penicillin is a broad spectrum antibiotic, that is, it is effective
against a wide range of bacteria. The structure of penicillin is
shown below.

Drug design
Before a medicinal drug is synthesized, it has to be designed on ‘paper’.This design seeks to address
certain issues about how the drug is expected to work.

1.Mode of action of the drug: how will it act? The exact chemical structure and nature of the drug
is related to how it carries out its function. For example, if it alleviates the signs and symptoms of a
bacterial disease, then it must have the ability to interact with chemical groups on the bacteria, or to
render harmless the toxins which are produced by the bacteria.

2. Side effects. Any possible side effects associated with the drug should be predicted before the drug
is synthesized and made available on the market. It is almost impossible to synthesize a drug which has no
side effects. In the body, a drug may be identified as a foreign substance. Reaction of the body to this
foreign substance produces side effects. The important thing is therefore to make sure that the side effects
are known in advance and that they are not life threatening. When the drug is finally made available on
the market, it must be packed, not only with instructions for its use, but with a warning on the possible
side effects and what counter remedies (antidote) there are for these side effects. Examples of side effects
associated with drugs include

nausea - a feeling that one wants to vomit.

drowsiness- feeling sleepy
lethargy - general body weakness
tachichardia– uneven heart beats
Stupor- drugs containing ethanol(alcohol) may cause drunkenness
Euphoria- these drugs produce a sense of general happiness and well being. Such drugs
maytherefore be abused and used as recreational drugs. These drugs are either
banned in many countries or they are only given under prescription.
Melancholia- depression and a feeling of sadness
 868

Teratogenic effects- such drugs affect the foetus, causing it to be born with body
deformities such as shortened limbs.

A well documented case of a drug whose side effects where only known after it had caused irreversible
harm is thalidomide, which was prescribed to pregnant women as a sedative in the 1960’s.
Thalidomide contains a chiral carbon atom, marked * on
the diagram below, so it may exist as a pair of optical
isomers. Conventional methods of synthesis, which were
used in the manufacture of thalidomide, produced optical
* isomers, the R and the S isomers. (The R isomer rotates
the plane of polarized light to the right, whereas the S
isomer rotates to the left). The R isomer had desirable
effects but the S isomer proved to be teratogenic.
The thalidomide tragedy gives an example of the importance of stereochemistry in drug design. Another
example is provided by the anticancer drug whose molecular formula is PtCl₂(NH₃)₂. This compound,
which is a complex of platinum, has two possible stereoisomers (cis - trans or geometric isomers).One of
the isomers has an anticancer effect because being polar, it is able to bind to polar groups of the DNA in
cancerous cells. This prevents the cells from dividing.

Cis-platin is effective as an anticancer drug because it has a net dipole moment. In trans-platin, equal
dipole moments operate in opposite directions and so cancel out(Fig 11.87). Overally, the molecule is non-
polar and so it has no affinity for the DNA of cancerous cells.

Fig 11.87

3. Cost: a drug should be affordable. A lot of research goes into finding ways of producing a drug
which is not only effective, but is also affordable. The final cost of the drug will depend, among other
things, on the source and cost of the raw materials, the synthetic methods used and on whether mass
production is possible or not. One way to make drugs cheap and affordable is to use natural sources for
the raw materials. Many drugs are now being synthesized from precursors found in plants.

4. Potential for addiction. Drugs sometimes contain chemicals which may lead to addiction. If a
drug has an addiction risk associated with it, it must be made a prescription drug to minimize its
consumption.
 869

3.1.4 Designing drugs from natural templates

Many naturally occurring substances have medicinal value, and some of these substances have been
known to man since pre-historic times. Such substances may be extracted from their natural sources (for
example, plants), purified, packed and sold in convenient forms such as syrups or tablets.
There are limitations associated with drugs from natural resources such as plants.
 The sources may get depleted or extinct.
 The drug may be present in very low concentrations, so that its extraction becomes uneconomic.
 The source of the drug may be found in only one part of the world.

To overcome these limitations, chemists analyze the chemical structures of the drugs and once they have
the full structure, they try to find ways of synthesizing the drug. Methods of structure analysis that can be
used include x-ray crystallography and NMR spectroscopy. Aspirin, an analgesic (painkiller), and Taxol ®,
an anticancer drug, are examples of drugs that have been developed from naturally occurring precursors
or templates. A drug precursor is a chemical which is modified to produce the desired drug. A drug
template is a compound, with a known structure, which is copied by synthetic methods so that the drug
can be produced at a large scale.
Taxol (Fig 11.88) is naturally found in the leaves of the yew plant. This compound has anticancer
properties. However, it is produced in very small quantities by the plant, and so chemists have developed
methods of synthesizing the drug. This became possible after the structure of Taxol was elucidated using
x- ray crystallography.

Fig 11.88 The structure of taxol

11.3.2 POLYMERS
It is hoped that the reader recalls about addition and condensation polymers. This section is designed to
extend your knowledge of these topics.
 870

3.2. 1Silks : natural condensation polymers

The term silk refers to a class of naturally occurring fibrous proteins produced by certain animals such
as the spider, the silk worm and the silk moth.

Silk is a condensation polymer. As a protein, it mainly exhibits the secondary level of protein
organization. Usually, both forms of the secondary levels are present; the α- helix and the β- pleatedsheet.

 α - helical regions confer elasticity to the polymer. The more extensive the α- helical regions, the
more elastic the protein fibres.
 The β- pleated regions form crystalline regions, that is, sections in which protein fibres are
arranged in a regular manner. These regions have numerous hydrogen bonds, and this restricts
the tendency of the protein fibres to be stretched. These regions also confer high tensile strength
to the polymer. Some β- pleated sheets of the same silk are more regular than others. The more
regular the sheets, the more crystalline they are. Such a silk will be relatively inelastic and it
would have a high tensile strength.
 In general, silk has a very high tensile strength, and some forms of silk are estimated to be many
times stronger than steel of the same thickness. The strength of silk can be attributed to the
presence of a very large number of hydrogen bonds holding strands together, and the fact that a
single silk fibre contains many strands of the silk protein.

Spider silk
Spiders secrete silk from special glands. They use the silk to construct traps (webs) for insects, upon which
they feed. They also use the silk for transporting themselves from one point to another, wrapping and
storing prey and for making egg sacs. A spider has different glands for producing different forms of silk.
Each form of silk has unique properties adapted to its function.

Capture silk. It is used to make a web in

which small insects are trapped. Capture
silk is very elastic, that is, it is not brittle.
This property prevents the silk from being
broken by a struggling victim. Capture silk
is made from the protein silk fibroin.
Spider silk is acidic. The
acidic conditions destroy Dragline silk. It is used by the spider as a safety
bacteria and fungi which line when jumping or when escaping from
would otherwise digest danger. Dragline silk is made of the protein silk
the silk protein for food. fibroin. The dragline of the Golden Orb Weaving
spider is the strongest spider silk known. The
high density of crystalline regions in the polymer
increases strength and reduces elasticity.

Dragline silk, capture silk and other forms of spider silk are all condensation polymers (a protein known
as silk fibroin) made up of amino acid monomers. The exact proportion of the different amino acids in silk
fibroin and how they are grouped within the polymer varies from one form of spider silk to another. This
affects strength and elasticity of the silk. The dragline silk of many spider species is usually the strongest
spider silk in the web of that particular spider. In fact, the dragline of the Golden Orb Weaving spider is
the strongest known form of spider silk.
 871

Dragline silk
The silk fibroin (protein), in dragline silk is made up of 42% glycine and 25% alanine, and 33% of seven
other amino acids.

H O H O
H H
N C C N C C
H OH H OH
H CH3
glycine alanine

There are two structurally distinct regions of the polymer, polyalanine regions and polyglycinere-
gions(Fig 11.89).Polyalanine regions are rich in alanine residues which occur in consecutive order, where
about 4 to 9 of them form crystalline blocks of beta pleated sheets(Fig 11.89 (a). The presence of these
crystalline regions confers great strength to the polymer and reduces its elasticity. In fact, drag line silk is
several times less extensible than other forms of spider silk, and this is attributable to the crystalline
polyalanine regions.
Polyglycine regions are rich in glycine residues which are linked in consecutive order in α- helical
conformation(Fig11.89 b). These regions, stabilized by relatively weak hydrogen bonds, give some degree
of elasticity to the silk. Some parts of the protein chain have no secondary form at all. Such a structureless
part is known as a random coil.

Polyalanine regions
These sections exhibit the secondary level of
protein organisation, in form of the -
pleated sheet. A single strand of the protein
folds on itself to form a regular crystalline
block, stabilised by hydrogen bonds.

Polyglycine regions
These sections of the silk exhibit a secondary level of
protein organisation. Repeating units of glycine occur
in an - helical conformation, stabilised by hydrogen
bonds. These regions confer a degree of elasticity to
(a) the polymer.
 872

(b)

Fig 11.89 (a) illustration showing presence of polyalanine and polyglycine regions in dragline
silk (b) presence of beta pleated regions in silk fibroin.

How does silk fibroin of spider silk compare with silk from other sources?
Silk from different organisms has the same basic structure, that is, it is a protein with regions of secondary
organization; the α - helix and the β- pleated sheet. The structural differences between silk from different
sources lie in the frequency of crystalline beta pleated regions.
Compare the structure of dragline silk with silk of the silk worm, shown below in Fig 11.90.

Fig 11.90

The following differences exist between the two silks and this affect their physical properties.
 Crystalline regions occur more frequently in the silkworm silk. This makes the silk less elastic and
tougher (more rigid).
 The number of folded regions is greater in silkworm silk. This increases the capacity of this silk to
absorb water.
 873

 α- helical regions made up of glycine occur more frequently in dragline silk of the spider. This
makes the silk more elastic and more flexible.

Despite these differences, both types of silk are very strong and this is attributed to the large number of
hydrogen bonds and hydrophobic interactions acting between strands of the polymer.

Silk from the silk moth

The silk moth also produces silk, but this has a different structure from spider silk and silkworm silk. Silk
from the moth is entirely β- pleated. The pleats are held together by hydrogen bonds. The absence of α-
helical regions implies that the silk is inelastic and tough. The silk is therefore similar in structure and
properties to collagen, the protein in mammals which is found in bone matrix, tendons and ligaments.

3.2.2 Learning from nature

Naturally occurring substances such as silk have certain desirable properties. Such substances can be
obtained directly from the organisms which make them, for example, silkworms are farmed for their silk,
which is used to make fibres for the textile industry. Alternatively, scientists may wish to copy from nature
and design synthetic materials which have the desired properties found in the natural material. The
synthetics can be modified to suit certain needs. Silk has been emulated by scientists for its high strength.
A polymer has been developed which bears certain resemblances to spider silk. This polymer, known as
Kevlar®,was developed by DuPont TM.It is a tough polymer with strength similar to that of spider silk. It
is five times stronger than steel. Some uses of Kevlar® include
 the manufacture of bullet proof vests. Such vests could be made stronger by reinforcing them
with spider silk.
 it is replacing steel in tyres. The use of Kevlar in place of steel in tyres greatly reduces their
weight, and this in turn cuts on fuel consumption.
 reinforcement in aircraft wings.
 in suits for racing car drivers.

The monomers
Kevlar® is a condensation polymer made from benzene-1,4- dicarboxylic acid and benzene-1,4- diamine.

benzene-1,4-dicarboxylic acid benzene-1,4- diamine

Notice the similarity of the monomers to those which are used in the synthesis of nylon. The resulting
polymer is a polyamide, just as nylon and the proteins. The two monomers condense to form a dimer as
shown below.

C N

amide linkage

-H2O
 874

The following diagram shows a section of the polymer. The repeat unit is shown in square brackets.

C C N C C N N

The strength of Kevlar® is attributed to the way separate chains can pack to form a single fibre. The
rigidity associated with the flat benzene molecules allow chains to pair perfectly side by side, linked by
hydrogen bonds. Separate chains therefore stack together like sheets in a book, as shown in the following
diagram.The resulting fibre is therefore very strong.

C C N C C N N

C C N C C N N

hydrogen bond

C C N C C N N

3.2. 3 Specialized polymers

Some polymers have been developed which have unusual but useful properties. These include plastics that
can conduct electricity, and which can emit light

Conducting plastics
Plastics are usually associated with insulating properties.
Polyethyne is an example of a plastic that can conduct electricity, but it must be doped with certain
impurities such as iodine to convert it from an insulator to a conductor.
The monomer for polyethyne is ethyne

C C
ethyne
Polymerization results in the breaking of one of the π bonds. The polymer contains alternating double and
single bonds. Such a molecule is said to beconjugated.

C C C C C C ... C C C C C C C C C C

n
 875

In conjugated systems, the π electrons of the double bonds occupy one continuous π orbital which extends
throughout the molecule. Such a molecule retains insulating properties until it is doped with an impurity
such as iodine. Iodine is an oxidizing agent; it removes some electrons from the polymer, creating
‘positive holes’. When connected to a source of voltage such as a battery, electrons are pushed into the
polymer. When an electron moves into a hole, it fills it (neutralizes the positive charge represented by the
hole). A positive hole develops where the electron originally was. In this way, positive holes appear to be
moving in a direction opposite to the flow of electrons. The flow of electrons in the conductor is therefore
made possible by the presence of positive holes as electrons move to neutralize the positive charges in the
conducting material.
A plastic that can conduct electricity has great potential since it combines the desirable properties of the
plastic with the conductivity of a metal. The desirable properties of the plastic include resistance to
corrosion, low weight, and malleability. Possible uses of such plastics could include the manufacture of
low weight rechargeable batteries and in computer displays.

Organic light emitting diodes (OLEDS)

Polymers that can conduct electricity can also be used as light emitting diodes (OLEDS). A diode is an
electronic component that allows electricity to flow in one direction only. Conducting polymers can be
modified so they have a very high resistance to the flow of current in one direction, and a very low
resistance in the other direction. In this way they can be used as diodes. OLEDS have great potential in
the field of electronics. They can be used in the displays of cameras and computers and they can replace
the conventional traffic lights which make use of a light bulb protected inside coloured glass. The main
challenge so far is to find OLEDS that can emit different colours. Scientists have developed the following
polymers , which can emit blue light.

n
n
(a)
(a)

(b)
(b) n
n

11.3.3 NANOTECHNOLOGY
Nanotechnology is the application of science at a nanometre scale. It involves manipulation of
individual molecules or atoms.

The nanometre has the magnitude of 10⁻⁹m. This is equal to the total diameter of 12 hydrogen atoms. The
width of the DNA molecule is about 2nm. Cells in higher organisms (eukaryotes) have an average
 876

diameter of up to 40 µm( micrometres). A nanospherehas a diameter of from 10 to 500nm. Buckmins-

terfullerene, an isotope of carbon, has a diameter of about 1nm.

Fig 11.91 Some types of particle and their dimensions

Table 11.7shows the scientific scale of length based on the metre . Notice the position of the nanometre
relative to familiar lengths such as the centimetre and the metre.

Unit Symbol magnitude in metres.

picometre pm 0.000000000001m = 1 x 10 -12m

nanometre nm 0.000000001m = 1 x 10 -9m

micrometre m 0.000001m = 1 x 10-6m

millimetre mm 0.001m = 1 x 10 -3m

metre m 1m = 1 x 10 0m

decametre dm 10m = 1 x10 1m

hectometre hm 100m = 1 x 10 2m

kilometre km 1000m = 1 x 10 3m

megametre Mg 1000 000m = 1 x 10 6m

gigametre Gm 1 000 000 000m = 1 x 10 9m

Terametre Tm 1 000 000 000 000m = 1 x 10 12m

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3.3.1 Nanomolecular chemistry

This involves the manipulation of particles at the atomic, molecular and super molecular levels (from
about 1 nm to about 100 nm). Nanosynthesis involves synthesizing substances by joining together atom
by atom or molecule by molecule. Using appropriate technology, this synthesis involves auto assembly of
small particles, at the nanometer level, to form a product of larger dimensions. Table 11.8compares this
method of producing substances with the traditional method of production.

Nanosynthesis Conventional methods of production

Raw materials are used as nonosized particles Raw materials are used in bulk

Reaction vessels are of nanometer Reaction vessels are big, often with a capacity
dimensions, for example, nanotubes of several tones

The joining of atoms or molecules is closely Atoms or molecules collide randomly during
controlled the reaction.

The product may not need to be purified The product has to be purified further and
further since only the required molecules or this may involve crude methods of grinding
atoms are assembled during the synthesis and crushing.
stage.

Table 11.8 Comparison of nanosynthesis and traditional methods of synthesis

Producing a substance at the atomic and molecular levels has obvious advantages.
 It prevents wastage of materials since atoms combine in specific quantities.
 It is possible to design a substance so that it has exactly the desired properties. Nanotechnology
can therefore produce materials with superior qualities, such as conductivity, refractive
index, hardness and flexibility.
 Large vessels such as fermenters are not necessary. This cuts down on costs.

However, synthesis at the nanometer level has possible draw backs:

 High levels of expertise are required
 The use of very fine particles poses a risk to health since the particles may enter the blood
through the skin or through the respiratory pathways.
 Processes which manipulate very small particles pose a risk of explosions. This is because very
small particles have a large total surface reaction, which makes chemical reactions very fast.

How nanomolecular chemistry began

Interest in nanomolecular chemistry was triggered by the discovery in 1985 of a third allotrope of
carbon,Buckminsterfullerene, with the formula C₆₀. This substance was produced when an electric spark
was discharged between two graphite electrodes. The aim of the investigation was to find out if soot could
be formed from carbon in outer space. In this experiment, soot was produced, together with another
substance which had peculiar properties. X-ray crystallography revealed that the substance was made of
pure carbon, that is, it was an allotrope of carbon. Before this discovery, it was thought that pure carbon
 878

existed only in two allotropic forms, namely graphite and diamond (allotropes are pure and different
forms of the same element).

The structure of C₆₀

Several analytical techniques, including UV spectroscopy, X-ray crystallography and C-13 NMR spectros-
copy were used to determine the structure of Buckminsterfullerene. X-ray crystallography revealed that
the substance contained carbon only. C-13 NMR spectroscopy gave only one peak on the spectrum,
showing that all of the carbon atoms are in equivalent electronic environments. The problem was now to
determine how the carbon atoms were arranged relative to each other. Kroto, one of the researchers,
recalled the geodesic dome designed by the designer Buckminster Fuller, and suggested that the new allo-
trope could have a similar shape. After several attempts, they worked out that the 60 carbon atoms could
be fitted into a sphere made of 20 hexagons and 12 pentagons. The structure would be spherical, resem-
bling a soccer ball. Experimental techniques have long since verified that the structure of C₆₀ is indeed
spherical, and does consist of carbon atoms connected in 20 hexagons and 12 pentagons, and it resembles
a modern soccer ball(Fig 11.92). This molecule was named Buckminsterfullerene, after the famous
designer. The molecule was soon dubbed ‘bucky ball’ and this name soon became popular among
scientists.

Molecules similar to C₆₀ were soon discovered. These molecules, like C₆₀,
are pure allotropes of carbon, and they all have a spherical and hollow
structure. These allotropes of carbon, now known as the
Buckminsterfullerenes, or bucky balls, have the formulae, C₂₈, C₃₂, C₅₀,
C₆₀ and C₇₀. Scientists soon realized that bucky balls, as small as they
were, could be put to use in new ways that would revolutionize science
and its applications. Thus developed the concept of nanotechnology.

Fig 11.92 Structure of

buckminsterfullerene, C60

Bonding in a bucky ball

The carbon atoms in a bucky ball are connected together in hexagons and pentagons. This implies that
each carbon atom is sp2 hybridized, that is, one valence s orbital is hybridized with two valence p orbitals,
to form three hybrid orbitals. This leaves the pzvalence orbital unhybridized. The three hybrid orbitals are
each occupied by a single electron and are spaced out in a trigonal planar geometry around each carbon
atom. This is the geometry that will minimize repulsion between the orbitals. The unhybridized pz
orbitals on the carbon atoms are oriented at 90⁰ to each other, so they overlap sideways to form one
delocalized π bond, just as in benzene.

Physical properties of bucky balls

 Solubility – the bucky balls are soluble in organic solvents, unlike
the other allotropes of carbon, diamond and graphite. Solubility
of the bucky balls can be explained in terms of the very small size
of the particles. Compare with graphite and diamond which have
giant molecular structures and are therefore insoluble.
Fig 11.93Each carbon atom  Slippery - bucky balls can be more slippery than Teflon®. The
in C60 has three hybrid slipperiness of bucky balls is caused by the very small size of the
orbitals (sp2 hybridization), individual particles and their spherical nature. The particles act
each containing a single like very tiny ball bearings. Their very small size increases surface
electron area when they are applied between moving parts which
experience friction.
 879

 They are insulators. Although delocalized electrons are present in each molecule, a bucky ball
does not have the sheet form which would allow electrons to flow from one point to another. This
is similar to the situation in benzene, which is an insulator despite the presence of delocalized
electrons.

Are bucky balls rigid, like diamond, or are they slippery like graphite?
This question should be answered with care. It all depends on whether we are referring to individual mo-
lecules, or we are referring to the bulk substance. If we think in terms of individual molecules, then the
answer is that bucky balls are rigid and hard like diamond. This is because of the large number of strong
carbon to carbon covalent bonds in the molecule. However, when we consider the bulk material, it is
found to be slippery, because the spherical shape of the molecules allows them to act as ball bearings.

Uses of Bucky balls

Some uses have been found for bucky balls, and scientists continue to investigate other ways in which they
can be used.

 Protecting reactive atoms. Suppose that a certain chemical

species must be protected during a reaction, so that it only
reacts when it is supposed to. The species must therefore be
protected during the course of the reaction, only being
released when it is required to participate in the reaction.
Bucky balls, being hollow, have been used to protect
reactive species such as the lanthanum atom. Fig11.94
shows a reactive atom protected inside a bucky ball.
 Plugging nanotubes. Nanotubes are rolled up sheets of
Fig11.94 A reactive atom graphite. Half a bucky ball can be used to plug (cap) one or
protected in a bucky ball both ends of a nanotube.

3.3.2 Carbon nanotubes from graphite

The discovery of bucky balls was immediately followed by the discovery of structurally related forms of
graphite, of which nanotubes are probably the most remarkable and most promising in terms of possible
applications.

The relationship between graphite and a nanotube

A nanotube is a rolled up sheet of graphite. This results in the formation of a hollow cylindrical structure.
One or both ends of the cylinder can be plugged by half a bucky ball. Nanotubes can have a diameter of
1 nm or slightly more. Nanotubes in which one end is closed by a bucky ball can be used as nano test
tubes. Fig 11.95 shows the relationships that are possible between the different forms of carbon.
 880

Fig111.95 The relationship between some forms of graphite

Properties of nanotubes
 Good electrical conductors. This property is expected since the nanotubes are based on the
structure of graphite. Graphite conducts electricity because it has π electrons delocalized along a
layer of hexagonally arranged carbon atoms.
 High tensile strength. Nanotubes are stronger than steel. It is difficult to break the strong and
numerous carbon to carbon bonds.
 Mechanically stiff. Ordinary graphite is slippery because it contains many layers which can slide
over each other. A nanotube is made of only one layer of graphite, which is rigid due to the large
number of strong covalent bonds.

These properties allow nanotubes to have a wide range of applications. Current applications include
 Carrying out of controlled reactions in nano test tubes.
 Electrical fibres and cables with nanometre dimensions. Such cables can be packed within a very
small volume, thus allowing production of low weight gadgets and enabling miniaturization ( a
miniature is a much smaller version of something, for example, a battery.)
 As electrodes in batteries. Nanotubes are found in the electrodes of lap top batteries.
 881

Use of nano test tubes in controlled reactions

The very small width of a nano test tube makes it useful in the synthesis of certain substances.
 Oxford scientists have used a nano test tube to polymerize fullerene oxide, C₆₀O. An ordinary test
tube is not useful here because it provides much space to allow the polymer to form branches. In a
nano test tube there is restriction of space, so that the desired product, a linear polymer, is
formed.
 By using a nano test tube it is possible to exert greater control on the course of reaction
(Fig 11.96). In ordinary reaction vessels, formation of a product depends on chance encounters
between reactant molecules, and the formation of side products becomes a problem. In a nano
test tube, the small width allows the reaction to occur by connecting atom to atom or molecule to
molecule. Chances of forming side products are greatly reduced. Control on the course of reaction
can also be exerted by attaching certain agents such as catalysts to the walls of the test tube. One
possible technique is to attach enzymes to the walls of the test tube. The enzymes are said to be
immobilized. Reactant particles move over the catalyst in a controlled way, and the product
formed is not contaminated by enzymes. In this way, the enzymes can be used over and over
again.
The use of nanotubes in synthesis will greatly increase the yield of product and minimize wastage.
This is because all reactants are able to react, and no reactant molecules are wasted in forming
side products.

Fig11.96 Computer generated model depicting formation of poly (fullerene

oxide) in a nano test tube.

The use of nanotubes in miniature batteries

A tiny battery has been developed which can easily be mistaken for a tiny piece of black paper. Among its
unusual properties is its flexibility; it can be folded like a note and be carried in the breast pocket like a
tiny handkerchief!
Fig 11.97compares such a battery to a conventional battery.
 882

 In a conventional battery, a redox reaction occurs between the electrolyte and a metal, resulting in
a flow of electrons from the anode to the cathode. In the miniature paper battery above, the redox
reaction is between the electrolyte and the carbon nanotubes. This reaction results in a flow of
electrons when an external circuit is included.
 The carbon nanotubes are made of graphite, which is a conductor of electricity. The fact that
graphite exists in a layered (sheet) form allows it to be rolled into tubes.
 The carbon nanotubes are so small that they do not break when the paper is folded. This allows
the battery to be very flexible. It can be rolled up or be folded.
 The paper battery also works as a capacitor. It is able to store current and can therefore allow the
steady flow of current in circuits.

The major advantages and possible applications of the paper battery are
 It is very light. It can be used as a steady source of current in portable devices such as wrist
strapped intelligence surveillance gadgets and medical implants.
 Because of their very small size, the nanotubes in the battery present a very large surface area
over which electrochemical reactions take place. The batteries could be designed to give a large
and steady voltage.
 The battery can be disposed safely when it reaches the end of its life. This is because the battery
does not contain toxic metals such as cadmium.
 Because of their very small size, the batteries can be stacked like pages of a book, without any
significant increase in mass. Such a stack could be useful in gadgets in which lightness and a large
and steady source of current is a requisite.
 Its flexibility will allow it to have very wide applications. It can be folded to fit into a particular
gadget. It can even be resized by cutting.

3.3.3Nanospheres and nanoparticles

Nanoparticles are very tiny particles which are either less than a nanometre in size, or are in the
nanometre range, for example, atoms and simple molecules. A nanosphere is a spherically shaped
nanoparticle with a diameter of between 10 and 500nm.
 883

The use of nanoparticles in sunscreen lotions

A sunscreen lotion is designed to minimize the amount of ultraviolet radiation absorbed by the skin, for
example during sunbathing, as this would lead to problems such as skin cancer. A good sunscreen lotion
should reflect as much of the UV radiation as possible. Some sunscreens contain nanoparticles in the form
of TiO₂.The very small size of these particles is similar to the wavelength of ultraviolet radiation. As a
result, the particles do not absorb the radiation. Rather, they reflect it from the surface of the skin. The
small size of the particles also prevents whitening of the skin when the cream is applied. Whitening of the
skin is associated with lotions that contain relatively large particles.

The use of nanoparticles in medicine

The medicinal importance of silver was known to the Greeks. Scientists continue to research on the
possible uses of nanoparticles in modern medicine. Silver particles can be applied to wounds where the
atoms act as an antibiotic. The major advantage of silver is that it does not easily rust. Using very fine
particles of silver has the advantage of increasing total surface area for antibacterial action.
One major disadvantage of using nanoparticles, for example, on wounds, is that they may be absorbed
into the blood, leading to possible poisoning. For instance, silver is a well known enzyme inhibitor, and it
may disrupt vital metabolic processes. Research will enable the development of nanoparticles with the
correct dimensions for surface applications, such as on the surface of the skin. These particles would be
small enough to have the desired effects, e.g. reflection of UV, and yet large enough not to be taken into
the body through the skin.

The use of nanoparticles in sport

Some golf sticks have been developed in which the shaft is impregnated with nanoparticles. This gives
extra strength to the stick since the very small size of the particles allows them to pack closely. The golf
sticks are therefore less prone to fracturing. At the same time, density is reduced because the particles are
very light.

The use of nanoparticles in nanocomposites

A nanocomposite is a material made by mixing nanoparticles of two or more substances. The resulting
material has properties that are superior to those of the individual materials of which it is made.
Nanocomposites have been developed by combining nanoparticles of a ceramic or clay with molecules of a
polymer. The resulting nanocomposite is many times stronger, tougher and heat resistant than either of
the individual material present. Nanocomposites can be used to construct electric furnaces where
temperatures can be astronomically high.

Use of nanospheres in medicine

Researchers have designed a method of oral drug delivery which makes use of nanospheres. The drug
molecules are packed inside nanospheres, and the nanospheres themselves are in turn packed inside
time - release capsules. The capsules dissolve gradually in the digestive tract, releasing the nanospheres.
The walls of the nanosphere contain a hydrogel, a type of condensation polymer which has the ability to
absorb water. When the nanospheres are released from the capsule they do not release their drug
contents suddenly. First they absorb water, which causes them to swell. The water results in the hydrogel
coat dissolving slowly by hydrolysis, so that the drug molecules are gradually released. Major advantages
of this method of drug administration are

 the drug is protected from the hydrolytic environment of the digestive tract.
 the drug is released gradually, so that the body is not suddenly flooded by drug molecules, as this
would cause side effects.
 884

 the hydrogel coat can be modified to control the rate of release of the drug. This modification may
involve choosing a correct type of hydrogel for a particular drug, and including perforations in the
hydrogel coat.

Supramolecules - an unusual form of nanoparticles

Supramolecules are molecules with unusual properties. Conventional methods of synthesis may not be
able to produce supramolecules. It is possible to synthesize supramolecules at the nanometre level by
carefully assembling atoms and chemical groups. Examples of supramolecules include crown ethers,
molecular motors and quantum dots. Supramolecules have potential in catalysis, ion identification and
separation, in electronics and in light harvesting processes.

Crown ethers
An ether is an organic compound that contains the ether
linkage, -C-O-.
A crown ether is a crown shaped polyether that has
the ability to recognize and bind certain types of
metals ions. The importance of crown ethers is their
selectivity. Different forms of crown ethers can be
developed that have a selective affinity for different
metal cations.
Fig 11.98shows the structure of a typical crown ether,
bonded to a metal cation. The ether acts as a
polydentate ligand. In this case, the ether forms a
complex with a co-ordination number of five.

Fig 11.98A crown ether. Note that

the ether acts as a polydentate ligand

Possible applications of crown ethers

 Identification of ions
 Separation of ions
 Purification by removing certain ions from solution.
 Quantitative determination of certain ions, for example as pollutants in a water source.
 Removal of heavy metal ions in contaminated soils.
 885

Supramolecules that can identify specific molecules

Interest in supramolecules continues, and chemists are synthesizing supramolecules that can identify and
bind to other molecules. Possible applications of such molecules include drug targeting. Supramolecules
can be synthesized which mimic the action of antibodies. An antibody is a protein molecule that is
produced in response to an infection. This protein has an affinity for a specific molecule, known as an
antigen. The body therefore produces a different antibody for each type of antigen that may enter the
body. The antibody ‘seeks’ the antigen and binds to it, allowing defense cells to destroy the pathogen
before it causes harm to the body.
Supramolecules could be engineered to act just like antibodies. When introduced into the body, they are
attracted to the right sites, where they may bind, for example, to poisons produced by bacteria. The
supramolecules can be used as a vehicle to direct drugs to affected tissues, where they bind with certain
molecules in the tissue, allowing the drug molecules to be discharged directly to the affected part of the
body.
This is an example of targeted approach to drug delivery. Supramolecules that can identify other
molecules can also be developed into catalysts. Such catalysts would mimic the high specificity of enzymes
by attracting only a particular type of reactant molecule.

Quantum dots
A quantum dot is a very tiny chip, in the nanometre or micrometre range, that is capable of emitting
photons one at a time.
Toshiba has developed a device that contains quantum dots and can be used to produce the required
number of photons when excited by short pulses of light energy. The functional unit in the quantum dot is
actually a giant molecular substance such as silicon. The material contains trapped electrons, which can
be excited by optical pulses to higher energy levels. When the electrons fall back to their ground state
energy levels, they give out the energy they had absorbed in the form of photons. The device can be tuned
to give the required number of photons.
Before the invention of the Toshiba photon emitter, it was extremely difficult to control the number of
photons that could be given out by a semiconductor material. It is hoped that the development of the
quantum dot device will allow the production of optical computers that are so fast they will render the
current version of the computer obsolete.

3.3.4 Nanotechnology - promise and possible challenges

Some people have described nanotechnology as the science of the future and the ambitious.
Nanotechnology will have a large impact in all most all fields of scientific endeavour and production,
including medicine, agriculture, space navigation and environmental remediation. The quality of human
life will greatly improve as new methods of drug delivery and disease diagnosis are developed using
nanotechnology.In fact, nanotechnology will make possible the things we currently associate with science
fiction movies.

…. just to exercise your imagination

Imagine a nanorobot that could be introduced into the body. The robot, because of its small size, is
carried in blood. The robot is engineered to bypass certain tissues and go only to specific areas of the
body. Once it gets there, it carries out what it was engineered to do, for example, it administers a certain
drug in predetermined quantities. When done, it can even collect a few sample cells and move to a
certain point where it can easily be removed from the body.
 886

This probably sounds like science fiction, but scientists are optimistic that nanotechnology will turn
today’s ‘impossibles’ into tomorrow’s ‘possibles’.
However, nanotechnology generates unease among some people. Just the mention of some terms like
biological or chemical warfare raises dread in many people. Could nanotechnology lead to nanowarfare;
for example, including nanorobots that can be inhaled into the body and target certain organs such as the
heart or the kidneys?
Another potential problem associated with nanotechnology is the risk associated with the use of very
small particles. This may lead to explosions, due to the large surface area presented by the particles.
Moreover, very tiny particles can be absorbed into the blood through the skin, and this may lead to
poisoning.

11.3.4ENVIRONMENT AND ENERGY

3.4.1 Using chemistry to overcome environmental problems

Chemical knowledge can be used in environmental remediation, which involves reducing the levels of
pollutants in the atmosphere, water bodies and in soils.

Cleaning up oil spills

Oil can be spilled on land or in water bodies, deliberately or by accident. The most recent crisis in oil
spillage is the massive BP shell oil leak into the Gulf of Mexico. Deliberate spilling of oil in the seas and
oceans is illegal, and where an accidental spillage occurs, it often has to be determined if the accident was
actually a result of negligence. Penalties for oil spillages could be stiff.
Once an oil leak has occurred, it has to be cleaned. Oil is immiscible with water. It forms a very thin layer
on the surface of the water (oil is less dense than water) which is easily spread by water currents. A very
thin layer of oil on the surface of water is known as an oil slick.

Effects of oil slicks

Oil pollution of water bodies is one of the most serious forms of pollution because of the difficulties asso-
ciated with its removal. Oil contains compounds (hydrocarbons) which are generally unreactive and so
can stay in the water for a very long time. Some of the effects of oil pollution are
 sea birds, seals and other animals can be killed by the oil. Sea birds are typically vulnerable to oil
slicks, which results in their feathers being coated with a film of oil. This causes the feathers to
stick together and lose their insulating properties. The birds may die from cold. They may also
ingest the oil when they preen their feathers, leading to kidney damage and death. Other animals,
such as the seals are affected by oil in the same way.
 oil washed up to the shores makes beaches unsightly. This repels tourists, and so has a direct eco-
nomic impact.
 death and contamination of fish by oil has a negative impact on the fishing industry.
 0il enters the food chain and ends up being taken up by man. This occurs like this: oil is taken up
by plankton, which is then fed upon by fish. Fish take up large quantities of the plankton, so they
concentrate the oil in their bodies. Humans then eat the fish and so take up the oil into their own
bodies. The effects of oil in the human body include kidney damage, nervous disorders, and can-
cers caused by carcinogens found in oil, for example, benzene.
 887

Possible solutions
 Mechanical methods can be used to contain the oil in a specific area. The oil can then be siphoned
out.
 Mechanical methods such as high pressure water washing and wiping of rocks and surfaces can be
employed.
 Sorbent materials(booms) can be used to absorb the oil.
 The use of biological methods. Investigations are under way on the feasibility of the large scale
useof certain bacteria that can digest oil or convert it to more reactive compounds.

The use of sorbents in cleaning up oil spills

Sorbents are porous materials which can absorb particles of another substance. The first sorbents which
where used in cleaning up oil spills were not so effective, because they absorbed both water and oil. As a
result, they sunk due to the increase in mass.
A porous fibre glass sorbent has been developed which allows oil to pass though it, but repels water. This
property of the sorbent material is caused by fluorinated molecules trapped in the structure. The fluorine
atoms have hydrophobic properties, so it repels water but attracts oil, letting it in. The sorbent materials
can take up to 200times their weight in oil, and they do not sink. The major advantage of using sorbents is
that the precious oil is recovered.

Bioremediation of contaminated water

Certain bacteria can convert the relatively inert hydrocarbons in oil spills into compounds that are more
reactive. One such type of bacteria can insert an O atom between a carbon and a hydrogen atom. This
results in hydrocarbons such as alkanes being converted to alcohols, which are more reactive and can
therefore be easily degraded by natural environmental processes.
Bacteria and fungi could also be employed to feed directly on the oil spills. The advantages of
bioremediation include
 low cost since no sophisticated machinery are required.
 no noise pollution is generated

Remediation of contaminated soils

Soil can be polluted in a number of ways
 By heavy metal ions such as mercury (II) and silver (I). These ions can enter food chains, for
example via plants. The ions can also be washed into water bodies, where they are taken up by
fish and other water animals. In this way, the ions end up being taken by humans. Mercury and
silver are well known metabolic poisons, and they can lead to death or long term health disorders.
Heavy metal pollution in soil is often traced to mining activities. Other industrial processes, such
as electrolysis, may release heavy metal ions into the environment. At one time, electrolysis of
brine (concentrated sodium chloride solution), made use of mercury as the cathode. This led to
serious environmental pollution by mercury.

 Oil spillages can occur on land, for example due to burst oil pipes. A well known case is the Niger
Delta oil leaks from deliberately damaged pipes.

 Acid pollution can also occur in soil. Possible sources of acids in soil are acid rain and mining
activities. Acids in the soil may lead to direct death of plants and soil dwelling organisms. Acids
also mobilize toxic ions such as Al3+ ions. These ions are often present in soils, but they do not
 888

usually pose a threat to plant life because they are usually trapped in insoluble compounds, for
example, Al2O3, and composite materials such as clays. A low pH in the soil may dissolve these
solids and thus free the metal ions. The ions are said to bemobilized because they can now move
freely in solution. In this way they enter water bodies and food chains. Such ions can be taken up
by humans, directly through drinking water, or indirectly through food chains. Aluminium has
been associated with Alzheimer’s disease (a serious nervous disorder, especially affecting the
old)which is characterized by brain malfunction, loss of memory and loss of articulation skills)

 Polyaromatic hydrocarbons (PAHs) are pollutants which may also enter the soil. PAHs are pro-
duced during the incomplete combustion of complex organic compounds, for example during
plastic disposal. PAHs are thought to be carcinogenic, and they may be taken up by humans
through food chains. These compounds, being of a hydrophobic nature, are not easily taken up by
plants, but they may enter water bodies where they are taken up by aquatic animals such as fish.
They are then accumulated in the hydrophobic fatty tissues of the animals. In this way, the chemi-
cals enter the food chain and are eventually taken up by man.
Some examples of PAHs are shown below.

 Polychlorinated biphenyls (PCBs)were once used as coolants in electrical transformers. They had
the advantages of being inert, resistant to burning and good electrical insulators. The use of PCBs
has been discontinued because they pose a serious threat to human life when they accumulate in
the environment. PCBs are also hydrophobic in nature, and they enter the food chain mainly
through aquatic animals which concentrate them by absorbing them into their fatty tissues. PCBs
are potential carcinogens. An example of a polychlorinated biphenyl is shown below.

Possible measures to counter soil pollution

 Biological methods. Certain bacteria take up and accumulate heavy metal ions, for example,
bacteria of the genus Pseudomonas are known to accumulate mercury ions. These bacteria can be
used to clean up contaminated soils.
Even without human intervention, biological processes involving bacteria and fungi will even-
tually destroy some pollutants, but the process is very slow. The process can be speeded up by
pumping air into the soil and by supplying the micro-organisms with nutrients.

 Physical methods can be used. For instance, the contaminated soil is treated with a suitable
solvent to dissolve contaminants such as diesel oil. The contaminants can then be pumped out of
the soil. This method is of course suitable for cleaning up small tracts of land. The solvent itself
must not be a pollutant, and must be volatile enough so that it can be driven out of the soil by
 889

flushing it with air or by warming the soil. Another physical method is to use electrodes. This
method is suitable for charged pollutant species such as heavy metal ions. The ions are attracted
to the oppositely charged electrode where they accumulate and are removed. This method is
physical in the sense that it involves the physical process of movement of ions towards the
electrode. The method can, however, also be considered as being chemical as it may involve
electrolysis at the electrodes.
The major disadvantage of using electrodes is that the process is not selective, so important ions
end up being removed from the soil.

 Chemical methods can also be employed. Chemicals can be pumped into the soil to react with the
pollutants. For instance, ozone can be used to destroy PAHs. However, ozone is poisonous and it
should be handled with care. Another disadvantage of ozone is that it is quite unstable and so
easily decomposes to form oxygen.

Soil as a source of underground water

Many people depend on underground water sources for domestic and agricultural activities. The water
can be tapped by sinking wells and boreholes. Presence of impurities in the water, such as metal salts,
cannot be avoided.

The presence of calcium ions in ground water

Water obtained from limestone (calcium carbonate) landscapes is particularly rich in calcium ions. The
concentration of these ions is particularly high if the landscape becomes acidic, for example due to acid
rain. Limestone on its own is poorly soluble in water. However, if the water is acidic, it dissolves faster,
releasing carbon dioxide and liberating calcium ions.
Presence of calcium ions in drinking water is beneficial. It is an important nutrient, required for teeth and
bone development, and also for the transmission of nerve impulses.However, calcium ions are a well
known nuisance in water which has to be used for laundry or for bathing. Such water, containing calcium
ions, is described as hard water. It forms precipitates with the carboxylates of fatty acids present in soap.
This precipitation reaction reduces the effectiveness of soap in removing dirt, and it forms white scum on
clothes, hair and the skin. Hard water also causes formation of scales (calcium carbonate) on the elements
of water heaters, kettles and geezers. This increases the resistance to the flow of current. Heating time
increases and energy is wasted.

Poisonous metal ions in ground water

A well known poisonous metal that can be found in water from underground sources is arsenic. Arsenic
poisoning was once a major health concern in Bangladesh when boreholes were sunk to provide drinking
water. A notorious water weed, the hyacinth, was found to be effective at removing arsenic ions from
water. The weed can be used as a whole living organism, or the dried and crushed roots can be added to
the water. It has been found that the weed is able to reduce the levels of arsenic in water to those matching
the WHO guideline.

3.4.2 Green Chemistry

Although the knowledge of chemistry has enabled the production of products and processes that improve
the quality of human life, there has been a cost to pay in terms of environmental degradation. This term
implies the decrease in the quality of resources such as soil and air. One major cause of this loss of quality
is pollution. Chemists have taken the challenge of minimizing the negative impact on the environment
 890

associated with chemical processes. To this end, chemists are developing products and processes thathave
minimal effects on the environment in terms of pollution and depletion of resources. The theme of green
chemistry has been developed to help as a guideline to chemists and producers of goods and processes
that involve chemical processes. This theme has twelve principles, the so called principles ofgreen
chemistry. A few of the principles are listed below.

 Where ever possible, reactions should be catalyzed. The use of a catalyst reduces the amount of
energy used. An uncatalyzed reaction might need very high temperatures. The heat is obtained by
burning fuels such as coal. This leads to pollution and depletion of resources which could be put
to more profitable uses such as the manufacture of petrochemicals. However, the catalysts
themselves must be chosen with care, because some of them, especially the heavy transition
metals and their compounds,are poisonous to both plants and animals.

 It is better and cheaper to prevent formation of waste products that may pollute the environ-
ment, than trying to clean up waste after it has been formed.

 The synthesis of a chemical product must ensure that there is maximum use of raw
materials. Wastage of resources should be avoided, or it should be kept at a minimum.
Nanotechnology is offering promises towards the efficient use of resources. It ensures that only
the particles needed to assemble the product react. Nanotechnology also prevents side reactions
which use the raw material to produce an unwanted substance.

 Products should be relatively non toxic. Toxic products currently on the market should be
replaced by new products which are not a threat to animal or to plant life.

 The use of organic solvents should be avoided wherever possible. Most organic solvents are
pollutants with life threatening effects on plants and animals.

How green has chemistry gone so far?

Research continues towards the development of green chemistry. The examples below show how some of
the 12 guidelines towards green chemistry have been applied so far.

Use of supercritical CO2 as a solvent

Compressing a gas (increasing pressure) causes its particles to come close to each other. The gas deviates
from ideality and approaches liquid behaviour. If the compressed gas is heated its particles gain kinetic
energy, and they start moving rapidly in a random order, that is, it begins to show some properties of a
gas. It therefore follows that at a certain temperature and pressure, a gas will exhibit both liquid and
gaseous behaviour. Its particles will be close enough to give it properties of a liquid, and yet the kinetic
energy of the particles will be high enough to give it properties of a gas. A gas which shows properties of a
gas and a liquid at the same time is known as a supercritical fluid. Carbon dioxide becomes a
supercritical fluid at a temperature of 31⁰C and a pressure of 7 290 KPa. A supercritical fluid can be used
as a solvent. Its liquid nature allows it to dissolve substances and its gaseous nature allows it to move
rapidly, thus reducing the time required to complete the separation. Supercritical carbon dioxide has
been used as a solvent in the synthesis of thymol.
 891

Thymol is commonly used as a disinfectant and as a perfume. It is the starting material for the synthesis
of menthol by catalytic hydrogenation of the benzene ring.

The advantages of using carbon dioxide as a solvent

 It does not have the toxicity associated with most organic solvents.
 Carbon dioxide is a renewable gas which is obtained from the atmosphere. It is therefore
relatively cheap and it is always available.
 It is non-polluting since it is a natural component of the atmosphere.
 It is easily separated at the end of the process. Separation can be achieved by simply altering the
conditions of pressure and temperature, so that the fluid escapes as a gas. After being separated,
the gas can be recycled.
 The carbon dioxide can be obtained from processes that produce it as waste gas, for example,
during the manufacture of ethanol by fermentation. The use of a waste product is one of the
guidelines for green chemistry.
 It is possible to control temperature and pressure so that production of side products is
minimized. This reduces the wastage of raw materials.

However, there is a potential hazard associated with the use of supercritical carbon dioxide. The use of a
highly compressed gas poses a risk of explosion of gas tanks. The use of supercritical carbon dioxide can
be expensive in terms of setting up plants. Specially designed vessels and pipes would be required to
contain the pressurized carbon dioxide.
Other potentially green solvents are being developed which do not have the drawback associated with the
use of carbon dioxide. Ionic liquids show great potential as such solvents.

Ionic Liquids
Ionic liquids are organic salts which are liquid at room temperature, or can be easily turned to liquids by
temperatures well below 100⁰C. Ionic liquids are versatile; they can dissolve a wide range of compounds,
both organic and inorganic. Scionix, a USA company, has developed an ionic liquid, choline
chloridechromium (III),using chromium (III) chloride and choline chloride. The structure of the ionic
liquid is shown in Fig 11.99.

3 +
O Cr
+
HO-CH2 CH(OH)CH2-O-P-O-CH2CH2N (CH3)3Cl
Fig 11.99Structure of the
O ionic liquid choline chloride
chromium (III)
choline chloride(vitamin B4)
An ionic liquid made from choline chloride( anion)
and Cr3+
 892

The ionic liquid above was designed to replace the toxic chromic acid, which is used as the electrolyte
during chromium plating. The advantages of using the ionic liquid as the electrolyte include
 reduced health risk to workers. However, the risk factor still remains because of the presence of
Cr (III) ions, which are themselves poisonous.
 the major advantage of this method is that it increases the efficiency of the electrolytic process
about five fold. This saves on energy (electrical) consumption.

Although ionic liquids will meet the requirements of green chemistry in terms of efficiency of the process
and energy conservation, their use might be limited because they could be potentially toxic.

Rock-munching bacteria: a green solution to mining

Mining is one of the most serious sources of pollution and environmental degradation. Not only does
mining scar the land and make it unsightly, it also results in pollution of water, air and soil. A new method
of mining has been introduced which overcomes some of the challenges of conventional mining. This
method, known as bioleaching, makes use of bacteria.
Some types of bacteria are described as chemoautotrophs. Such organisms obtain energy for living from
inorganicsources, such as metal ores. They obtain energy through redox reactions which cause the ore to
dissolve. The bacteria thus appear to be eating the rocks, and so they have been dubbed ‘rock munching’
bacteria. This is beneficial in two ways:
 The ore is concentrated
 The metal can now be obtained fairly easily from solution by redox displacement reactions

The ability of these bacteria to concentrate metal ions in solution means they can be used to recover the
metals in old mines, which were discarded when the concentration of the metals in the ores dropped to
uneconomic levels. The rocks at these mines, especially those which are wet, are often blue- green
coloured due to a mixture of iron (II) and copper(II) sulphates formed when the bacteria dissolve the
rocks. The use of bacteria in mining is now routinely used in countries such as the USA. Metals which can
be mined in this way include copper, silver, gold, lead and uranium. These metals have one thing in
common. They are low in the electrochemical series, that is, they are rather unreactive. For this reason, it
is possible to obtain them by reducing their ions. Reactive metals such as aluminium cannot be obtained
by this method. The negative electrode potential for aluminium
Al3+(aq)+ 3e⁻⇌ Al(s) Eθ = -1.66V
Shows that the conversion of Al3+ ions is very unlikely under standard conditions.

Mining of copper by bioleaching: bacteria at work

Bacteria of the genus Thiobacillus have an unusual metabolism which enables them to extract energy from
inorganic materials such as mineral ores. Two species of the bacterium often co-exist in wet rocks;
Thiobacillus thio-oxidans and Thiobacillusferro-oxidans. As the first part of their names suggest, these
bacteria utilize sulphur containing ores such as iron pyrites(FeS) and copper iron pyrites(CuFeS) for
energy.

The work of Thiobacillus thio - oxidans

The last part of the name of this bacterium tells that it oxidizes sulphides (‘thio’ = sulphur).
This bacterium oxidizes the sulphide component of iron pyrites and copper iron pyrites to sulphate:
S2-(aq) + 2O₂→ SO₄2⁻(aq)
 893

This reaction results in the conversion of insoluble FeS (black) to soluble FeSO₄ (aq), which is light green
in colour. Similarly, it converts the insoluble CuFeS to a mixture of CuSO₄ (aq) and FeSO₄ (aq). The bacte-
ria uses the energy released in these conversions to run its own life processes. In this way, the bacterium
dissolves the rocks to a solution containing transition metal cations. The solutions containing CuSO₄ and
FeSO₄ drain into shallow ponds, in which scrap iron is now added. The iron reacts with Cu 2+ ions in a re
dox displacement reaction.
Cu2+ (aq)+ Fe(s) → Fe2+ (aq) + Cu(s) (I)

Q
Extract relevant reduction potential data from the Data Booklet and use them to
construct the equation for the reduction of copper (II) ions by iron. Calculate the
electrode potential for this reaction.

A consideration of electrode potentials shows that iron metal does reduce copper (II) ions to copper
metal. In the process, iron is oxidized to iron (II).The pure copper sinks to the bottom of the ponds whilst
the scrap iron objects dissolve to iron (II) sulphate.

The work of Thiobacillus ferro-oxidans

The last part of the name of this bacterium tells that it oxidizes an iron species. The bacterium oxidizes the
iron (II) present in sulphide ores to Fe (III).
Fe2+→Fe3+ + e⁻
This reaction provides the bacterium with the energy needed to sustain its life processes. The reaction is
also useful in the extraction of copper from insoluble copper (I) sulphides. The iron (III) ions produced in
the reaction above oxidize copper (I) in the rocks to copper (II) ions.
Fe3+ + Cu+ → Fe2+ + Cu2+
The copper (II) ions are then reduced to copper metal as before.

Advantages and disadvantages of using bacteria in mining

Extraction of metals by bioleaching has more advantages than disadvantages, and it is now used routinely
for mining in some countries. 10% of the copper mined in the USA is by this method.

Advantages
 Economic in the sense that it recovers the metals in mine dumps.
 Saves energy. Compare with conventional methods of mining which burn fuels such as coal to
drive the metal extraction process.
 More environmentally friendly: pollution caused by the combustion of fuels is avoided. Conven-
tional methods of mining are largely blamed for the accumulation of some pollutants such as
sulphur dioxide in the atmosphere.
 Saves on labour.
 Relatively cheap with respect to capital investments since very little machinery is needed.
 Occupational hazards are reduced since there is no or little use of heavy machinery.
 Bioremediation is achieved. This refers to the removal of pollutants such as heavy metals from the
environment. Some metal ions such as copper are toxic to plants. Bioleaching results in the
removal of such metals from discarded mines.
 894

 The process is quite, that is, there is no noise pollution.

 Waste iron is put to use. This results in reduction of pollution by metal litter and recovers the
economic value of the metal.
 The use of poisonous chemicals such as cyanide in the extraction of gold is avoided. Cyanide ions
are poisonous to all life forms.

Notice that the use of bacteria in mining meets a number of the requirements of green chemistry.

This method of mining has its own drawbacks.

 Large and continuous supplies of water are required.
 The mining sites are unsightly, that is, they are not so appealing to the sense of sight.
 There is increased risk of contamination of water bodies by acids. This can result in the death of
aquatic life.
 Bioleaching results in the immobilization of toxic metal ions such as mercury and aluminium.
These ions are usually locked up in insoluble compounds, so they cannot move easily from one
point to another. Bioleaching dissolves metal ores, and in the process toxic metal ions may be re-
leased. These may then move in solution with water. Such ions may end up in rivers and dams,
leading to the death of aquatic life.
 The use of bacteria in mining could be a source of unemployment. This method of mining is less
labour intensive than conventional mining.
 Bacteria are living organisms and so they need certain optimum conditions for maximum growth.
These conditions are not always achievable because different geographical locations have differ-
ent climates. The bacteria discussed above thrive well at 30⁰C. In very cold climates such as near
the poles, the bacteria cannot thrive. Similarly, the bacteria may not thrive in very hot climates
such as deserts.

3.4.3Alternative sources of Energy

Biofuels
A biofuel is a fuel derived from a plant or an animal source.
Ethanol is probably the best known biofuel. Some biofuels are termed biodiesels. These biofuels have
relatively high Mr values and therefore tend to have relatively high boiling points. Biodiesels also have low
volatility because of the presence of relatively strong Van der Waals forces that operate between the
molecules. A biodiesel is most suitable for use in diesel engines which generates powerful compressions
which are necessary for the ignition of the fuel. Ethanol and biodiesels are examples of liquid biofuels.
Bagasse is an example of a solid biofuel.

BIOFUEL

ETHANOL BIODIESEL BAGASSE

Source sugarcane the jatropha plant sugarcane
grain crops such as rape seeds
maize and sorghum.
Beetroot
 895

Ethanol
A large number of countries are using ethanol as an alternative to fuels obtained from petroleum, such as
petrol and diesel. However, ethanol has not completely replaced fossil fuels in any country. Ethanol has
been used to power cars in Brazil for many years. In African countries such as Zimbabwe, the cost of
petrol is cut by blending it with ethanol. In Zimbabwe, the fuel known as blended petrol contains 80%
ethanol and 20% petrol by volume. For a long time, the government has always had plans to increase the
acreage of sugarcane plantations to meet the growing energy needs of the country. Recently, a major
sugarcane project has been initiated and it is hoped that this will make the cost of fuel cheaper in the next
few years.
Ethanol is produced from the fermentation of glucose by enzymes present in yeast. The yeast obtains its
energy by respiring anaerobically on the sugar.

enzymes in yeast
C6H12O6 2C2H6O + 2CO2
Glucose ethanol

The glucose can be obtained insitu from carbohydrate rich sources such as sugarcane, beetroot and grain
crops such as maize.
Here are some reasons why some countries may wish to switch to the use of ethanol as an alternative
source of fuel.

 Sustainability
The supply of fuel will always be available as long as the crop is being produced.

 Economic
Most countries have to import petroleum based fuels. It would be cheaper to use a fuel which is
produced locally.

 Conservation
Like all fossil fuels, petroleum is a finite resource. World deposits of petroleum are dwindling, and
it would be wise to conserve the resource by using alternatives. The use of other forms of fuel will
also imply that petroleum is used in the production of petrochemicals such as plastics and in the
manufacture of many useful products such as pharmaceuticals.

 Versatility
Ethanol can be used as a general purpose fuel, for example, for lighting in the home and for spirit
burners in school labs. Some oil based products such as petrol would not be suitable or safe for
such applications.

 Less polluting
When used in homes, it is found that ethanol burns with a cleaner flame than most fuels. Smaller
amounts of soot and carbon monoxide are produced. This can be explained in terms of the rela-
tively small number of bonds that must be broken during the combustion process. A fuel with a
large number of C-H and C-C bonds would have a higher demand for oxygen. Consequently,
combustion is largely incomplete, resulting in the production of large amounts of the pollutants
carbon monoxide and soot.
When ethanol is used in the internal combustion engine, no sulphur dioxide is produced, as
would be the case with fossil fuels. Ethanol is therefore a greener fuel than oil based fuels.
 896

 Economic use of surplus

Some countries such as the USA have in some years experienced over - production of grain crops
such as maize. This has resulted in very low prices for such commodities. One way that has been
used to get rid of the surplus is to convert the grains to ethanol at plants constructed in the agri-
cultural regions.

 Efficient use of resources

Very little waste is thrown away in the production of ethanol. For instance, bagasse, obtained
after squeezing out the juices from sugarcane, can be used as a solid fuel, for example in
generating electricity. The electricity so generated can be used to run production processes at the
ethanol plant. Even the tops from the sugarcane can be used as fuel. An ethanol plant can
therefore be self - sufficient, with no strong dependence on other utilities, for example those
which provide power. In this respect, the production of ethanol may be considered to be a green
process, as there is little wastage of resources.
A process has been investigated which could result in the cellulose in bagasse being converted to
glucose, which would then be used to produce ethanol. This process is not yet commercially avail-
able, but when it does, it will make the production of ethanol from sugarcane an even more
efficient process. One consequence of the process would be the production of ethanol even when
the crop is out of season. This is because the bagasse can be stored relatively easily and in large
amounts.

During fermentation of glucose, carbon dioxide is produced as a by product. This gas is collected and sold
for use in fire extinguishers, as dry ice refrigerants, as a solvent( in the form of supercritical carbon
dioxide) and in the production of fizzy drinks.

Further considerations in the use of ethanol as a fuel

 Some people claim that the use of ethanol as a fuel is not as energy efficient as most people think.
They say that the energy used to produce the crop and to convert the crop to ethanol is almost
equal to the energy yield that would be produced when the ethanol is used as a fuel. However,
analysts counter by noting that ethanol is a versatile chemical. It has many other possible uses,
including in the manufacture of alcoholic beverages and drugs.
 With the increasing incidences of droughts in some countries, especially African countries, the
development of sugarcane plantations might prove to be a challenge.

Fuel cells: a green method of solving the energy problems?

A fuel cell is an electrochemical device that produces a continuous supply of electrical current from a
feed stock of a fuel and an oxidizing agent.
The most common fuel cell uses hydrogen gas as the fuel, and oxygen as the oxidizing agent. The reaction
that takes place in the fuel cell is essentially oxidation of hydrogen by oxygen. Like in all redox reactions,
the reducing agent loses electrons, that is, it is oxidized. The electrons are then accepted by the oxidizing
agent, which is therefore reduced. In an electrochemical cell, there is a path for electrons to flow from the
reducing agent to the oxidizing agent. As the electrons flow in the external circuit, they can do useful
work, such as lighting a bulb.
The main difference between a battery and a fuel cell is that the chemicals in a battery soon get used up,
and the battery stops working, but a fuel cell works continuously for a long time. This is because raw
materials are introduced as a continuous supply in the cell.
 897

The hydrogen/oxygen fuel cell is one of the greenest sources of electrical current. Levels of pollution are
very low, since the only product is water. Conventional batteries such as the nickel/cadmium battery pose
a disposal problem when they come to the end of their life. The heavy metals contained in the batteries are
toxic to both plant and animal life and so they must be disposed of with care.
One potential source of pollution from the fuel cell is the acid or base that is used as an electrolyte. If the
acids or alkalis leak into water bodies or into the soil, this may result in the death of soil and water
organisms. Productivity of agricultural land is also adversely affected by the lowering or increasing of soil
pH.
Despite the great potential of fuel cells to act as clean sources of electrical energy, there are challenges
which prevent their widespread use. Here are some of the challenges.

 Storage of hydrogen
Hydrogen is an explosive gas and it must be handled with care.

 Sourcing hydrogen
Methods used to obtain hydrogen are not so environmentally green. One possible source is the
electrolysis of water, but this uses huge quantities of electricity. In fact, more energy is used than
would be stored as chemical energy in the hydrogen produced. In other words, the use of
hydrogen (from the electrolysis of water) in fuel cells is not an energy efficient process. This goes
against the guidelines of green chemistry.
Another source of hydrogen is methane gas. However, this makes use of a natural and infinite
resource which could be put to other more important economic uses such as the manufacture of
pharmaceuticals. This process is also not so green because it produces greenhouse gases.

 Cumbersome nature of the fuel cell

Because of their cumbersome nature, fuel cells are not as versatile as conventional batteries. The
applications of fuel cells are therefore limited.

Because of the challenges outlined above,the fuel cell still has limited applications, but it has been used to
provide a steady supply of current in spacecrafts.

The use of hydrogen in the internal combustion engine

Combustion of hydrogen produces large amounts of heat energy. Combustion of 1 mole of hydrogen gas,
under standard conditions, produces about 286Kj of heat energy.
H₂(g) + 1/2O₂(g) → H₂O(l) ∆Hθc = -285.8Kj/ mol
This energy could be used to propel a motor vehicle. Notice the difference between the combustion of hy-
drogen in the internal combustion engine and its reaction with oxygen in the fuel cell. Both reactions are
redox, and they involve the oxidation of a fuel, hydrogen, by oxygen. However, in the fuel cell, the energy
of the reaction is tapped as electrical energy. In the internal combustion engine, the energy of the reaction
is released as heat energy.
Prototype cars have been designed and tested which run on hydrogen gas. The major advantage is that no
pollutants are released. However, the major challenges associated with the use of hydrogen as a fuel is its
explosive nature and the problem of finding an energy efficient and green source of the gas.

Solving the storage problem

Hydrogen is potentially explosive, and so it must be stored with care. The risk of explosion in some early
versions of the prototype hydrogen powered cars was worsened by the fact that the hydrogen had to be
compressed to very high pressures so that it would occupy a small volume.
 898

Researchers are investigating the use of NaAlH₄ as a solution to the storage problem. NaAlH₄ reversibly
absorbs and releases hydrogen. The absorption process involves reaction between the NaAlH₄ and hydro-
gen gas. This reaction is reversed at high temperatures, so that the hydrogen is made available once more.
NaAlH₄ has the advantage of being light (the three elements in the compound are very light) so its contri-
bution to the net mass of the car is very small. The major drawback of NaAlH₄ is that it can only store a
very small amount of hydrogen and it is very sensitive to water, in which it decomposes rapidly. Research
has shown that doping NaAlH₄ with titanium increases its ability to absorb and release hydrogen. The
titanium metal acts as a catalyst, catalyzing both the ‘absorption’ and the ‘release’ reactions.
Investigations are also being undertaken on the possible use of porous materials that can absorb hydrogen
and release it when needed. Such a material should have molecular sized pores, and nanotechnology may
eventually help in finding one such material.

Nuclear energy
The energy locked in the nucleus of radioactive atoms, such as uranium, can be released as heat energy.
Albert Einstein proposed that matter and energy could be interconverted, as summarized by his famous
equationE = mc2, where m is mass (matter), E is energy and c is the speed of light. This conjecture by
Albert Einstein led to the development of the nuclear bomb. Governments have of course realized that the
energy of the nucleus can be put to good use, for example, nuclear plants have been set up in industrially
advanced countries to generate electricity. About 80% of France’s electric power is generated in nuclear
plants. A few other countries also generate electricity using nuclear energy. Iran has been in the headlines
for its uranium enrichment programme, which it claims, is for the benign reason of producing electricity.
However, the USA and her allies fear that this project might be a cover for producing nuclear weapons or
nuclear propelled devices that can be used maliciously against other countries.

Advantages of nuclear power

 It does not produce toxic and greenhouse gases.
 It is energy efficient. A small amount of the radioactive fuel (element) produces a very large
amount of energy.
 It allows petroleum and other fossil fuels to be put to more environmentally friendly uses, such as
the manufacture of drugs, dyes fibres.

Despite these advantages, certain issues about nuclear energy have been preventing its widespread use.

World politics
The development of nuclear power stations may be retarded by the influence of the UN and world powers
such as the USA.

The terrorism threat

The threat of terrorism, especially against targeted countries such as the USA is very real. Perhaps the
USA and the UN are justified in regarding with suspicion the development of nuclear power stations by
some countries.

Threat of a holocaust
Just mentioning the word ‘nuclear’ is enough to send shivers among some people. There are people who
believe strongly that nuclear power is the means by which the earth may be destroyed one day in the fu-
ture. Such people therefore dread anything that has to do with nuclear energy. Even if nuclear power is
put to benign uses such as the generation of electricity, the knowledge of nuclear enrichment will spread,
 899

and will eventually get into the hands of rogue countries. The Bible predicts that wars at a scale never seen
before are imminent on earth. Some Bible scholars think that the descriptions of the wars given in the Bi-
ble actually point to the use of nuclear weapons.

Threat of nuclear accidents

The Chernobyl nuclear disaster is well remembered by most people. There are fears that accidents at
nuclear power stations would release radioactive fallout that would have both short and long term effects
on human health. Nuclear radiation from such accidents would lead to death, cancers and birth deformi-
ties. Countries which are currently running nuclear power stations claim that they have designed them to
be fail-safe, but the question is, can anything designed by man be fail safe? Recently, a major nuclear
plant in Japan was destroyed by a Tsunami, a natural disaster which no no-one could adequately prepare
for.

The problem of waste disposal

The solid waste from nuclear stations is radioactive, and so it has to be disposed of with great care.

Prohibitive costs
It will be a long time before developing countries begin to explore the potential of nuclear energy. This is
because of the prohibitive costs associated with setting up a nuclear plant and hiring an appropriately
skilled labour force.
 900

Questions, solutions and discussions

Q1 (a) Graphiteand buckminsterfullerene are two structural forms of carbon. By referring to

diagrams of their structures, suggest three differences in their properties.

(b) Nano-sized ‘test-tubes’ can be formed from carbon structures.

What is the relationship between the parts of these ‘test tubes’ and the two structural
forms of carbon shown above?

(c)Many modern sunscreens contain nano-sized particles of titanium dioxide. This substance does
not absorb ultraviolet radiation.

Suggest how these nano-particles are able to protect the skin from ultraviolet radiation.
9701/04/M/J/07

Solutions /key points

(a)
• graphite is a conductor of electricity
• graphite is slippery because layers can slide against each other
• buckyballs are more slippery because they act as molecular ball bearings
• graphite is less soluble
• graphite has higher melting point
• buckyballs are hollow and so can trap atoms /particles .
 901

Questions, solutions and discussions

(b) The nano-sized test tube consists of a sheet of graphite rolled into a hollow cylinder
of graphite .
The ends are half a buckyball .

(c) Dimensions of the particlesis similar to the wavelength of UV light and reflect/scatter the
harmful radiation .

Q2Read the following article about the use of bacteria in mining and then answer
the questions that follow it.

The discovery that bacteria could ʻmineʼmetals for us was made in Spain. The Rio Tinto mine, in the
Southwest corner of Spain was originally mined for copper by the Romans some 2,000 years ago.
In 1752, some mining engineers looked over the mine to see if it could possibly be re-opened. They
noticed streams of a blue-green liquid running from spoil heaps of the processed rock that lay around
the mine. When this blue-green liquid ran over iron, it coated the iron with a brown film. The brown
film was metallic copper.
There was still some copper left in the spoil heaps. At the time, everybody thought that the copper
was being dissolved in the liquid through a simple chemical reaction. But in 1947, US scientists
discovered that the copper was being ʻminedʼby a bacterium called Thiobacillus ferrooxidans.
The bacterium Thiobacillus ferrooxidans lives off the chemical energy trapped in metal sulphides.
In the ore, the copper exists as copper sulphide. The bacteria gain energy by converting the copper
sulphide to copper sulphate, which is then excreted. At the same time, they absorb the difference in
energy in the chemical bonds. These bacteria can also obtain energy in similar reactions with ores of
zinc, lead and uranium.

(a) Use the Data Booklet to explain why the blue-green liquid coated the iron with copper.
Write an equation for the reaction.

(b) Suggest two reasons why this method of extracting copper might be useful for ore containing only a
small percentage of copper.

(c)Suggest one disadvantage of using bacteria rather than traditional mining and smelting
methods.

(d)In conventional copper mining, the ore will typically contain 0.5 – 2.0% copper, which gives an idea
of what a valuable resource copper is.

(i)The ore from a particular mine contains 0.75% copper, and 150 000 tonnes of ore are mined
each year. From this ore about 60% of the copper is extracted, and the remainder is left in the
‘spoil heaps’ of processed ore.

What mass of copper is extracted each year?

 902

(ii)If the use of bacteria can recover a further 17% of copper from the spoil heaps, what is the
extra mass of copper produced?

(e)Suggest why bacteria are unlikely to be used in the extraction of aluminium.

(f) Metals like copper and zinc from abandoned mines can contaminate ground-water.
Suggest one way of removing these contaminants.
9701/04/O/N/07

Solutions /key points

(a) Iron is higher in the reactivity series than copper

Cu2+(aq) + Fe(s) → Cu(s) + Fe2+(aq) E θ/V = 0.34 + 0.44 = +0.78 V
Reaction takes place since cell potential is positive

(b) Refer to main text

(c) Refer to main text

(d) (i) 0.75% implies that every tonne of ore contains 7.5 kg of copper
7.5 x 150 0000
Therefore 150,000 tonnes of ore produces = 1 125 tonnes of copper
1 000
Amount of Cu extracted = 1 125 x 0.6 = 675 tonnes

(ii) 1125 x 0.17 = 191.25 tonnes

(e) Aluminium is very reactive since it is high in the reactivity series

(f) Use special plants which absorb these ions/use ion exchange/chelating agents

Q3Read the passage about the production of ethanol for fuel, and then answer the
questions.

Sugar cane is the world’s largest source of fermentation ethanol. Ethanol can be produced by converting
the starch content of biomass feedstocks, such as sugar cane, into alcohol. Yeast is used to break down the
complex sugars of starch into simpler sugars, which are fermented to form ethanol. A further advantage is
that bagasse, the remains of the cane after the sugar is extracted, and the tops and leaves of the sugar cane
can be used as a fuel for electricity production. An efficient ethanol distillery using sugar cane by-products
can therefore be self-sufficient and also generate a surplus of electricity.There is a second process that
utilizes biomass feedstocks to produce ethanol. The main carbohydrate constituent of these feedstocks is
cellulose, which, like starch, is a sugar polymer that can be broken down by hydrolysis into simpler sugars.
 903

The new process uses enzymatic hydrolysis or acid hydrolysis of cellulose to produce simple sugars for
fermentation. The use of bagasse as the cellulose source in the new process could allow off-season
production of ethanol with very little new equipment. This process is relatively new and is not yet
commercially available, but potentially can use a much wider variety of abundant, inexpensive feedstocks.
Alcohol fuels have been developed in a number of African countries – Kenya, Malawi, South Africa and
Zimbabwe – currently producing sugar, with others, including Mauritius, Swaziland and Zambia also
having great potential.
Ethanol has different chemical properties from gasoline. Although one litre of ethanol has about two-
thirds of the energy of a litre of gasoline, tuning the engine for ethanol can make up as much as half the
difference. Furthermore, should there be a spill, ethanol can be dealt with more quickly and easily than
gasoline. Using ethanol even in low-level blends (e.g. E10 – which is 10% ethanol, 90% gasoline)
can have environmental benefits. Tests show that E10 produces less carbon monoxide, sulphur dioxide
and carbon dioxide than gasoline. Higher blends (E85 – 15% gasoline), or even neat ethanol burn with less
of almost all these pollutants.

(a)Explain two ways in which bagasse can be used to reduce the cost of ethanol production.

(b)In addition to ethanol, what other product is formed in the fermentation of sugars by yeast?

(c)Suggest an equation to show the hydrolysis of cellulose in bagasse to form fermentable sugars with
the molecular formula C6H12O6.

(d) Using your knowledge of chemical bonding, suggest why a spill of ethanol is more easily dealt with
than a spill of gasoline.
9701/04/SP/2007

Solutions /key points

10 (a)Fuel, for example for the generation of electricity

Can be hydrolyzed to produce sugars

(b) Carbon dioxide

(c)(C6H10O5)n+ nH2O →nC6H12O6

(d) - Ethanol has an –OH group so it easily dissolves in water by forming hydrogen bonds. In this way
it is easy for the ethanol to be washed away.
- Gasoline (a hydrocarbon) has no polar group, so it is insoluble in water
- Being more reactive, ethanol can easily be degraded by micro - organisms
 904

Q4 (a) A number of drugs, such as insulin for diabetics, are delivered by injection rather than by
mouth (oral delivery). Suggest two reasons why this might be necessary.

(b) Many patients prefer oral delivery to injection, and a number of methods for overcoming the
problems of oral delivery are being investigated. Several of these use nanotechnology.

Study the passage and diagram and then answer the questions that follow.

At a 2004 meeting, engineers from the University of Texas described their research into nanospheres for
oral drug delivery. Nanospheres can transport a drug safely through the hostile environment of the
stomach. The nanospheres are created from hydrogels which are stable, organic materials formed
from a network of polymer chains. Hydrogels have a variety of uses including disposable nappies, soft
contact lenses, dressings for burns and, more recently, drug delivery. The drug is contained in the
hydrogel nanosphere as shown in the diagram below. Hydrogels absorb water and swell at a rate
dependent on the pH of their environment. As the hydrogel swells, the drug is released.

(i)What is a nanosphere?

(ii) Suggest why the stomach might be a particularly hostile environment for drugs.

(iii)Suggest two ways in which the nanosphere shown in the diagram can be modified to change the rate
of drug release.

(c) Hydrogels may be formed as homopolymers (using a single monomer), or heteropolymers

(using two or more different monomers).
By using the monomers below, you are to draw sections of both a homopolymer and
a heteropolymer. Each of your drawings should show a three-monomer section of the polymer.

HOCH2CH2OH HO2CCHRNH2 HO2CCH(OH)CH2CO2H

9701/04/M/J/08
 905

Solutions /key points

(a)
• to speed delivery of drug to target organ/tissue
• to avoid hydrolysis of drug by enzymes/acids
• to avoid over dosage

(b) (i) spherical particles with a diameter in the range 10 nm t0 500 nm

(ii)Low pH of the stomach/strongly acidic environment causes hydrolysis of drugs

(iii) Alter :
- thickness of hydrogel walluse hydrogels
- chemical composition of the wall
- use a wall with perforations

(c) Left as an exercise to the reader.

Q5The nature and variety of drugs that are available to treat diseases or life-threateningconditions has
never been greater. At the same time, we are much better able to deliverdrugs to their targets in
the body.

(a)Some drugs have to be given by injection, rather than by mouth.

Name a functional group in a drug molecule that might be broken down by the acid in the
stomach.

(b)The anti-cancer drug Taxol could be broken down if taken by mouth.

Circle two bonds, each in a different functional group, that could be hydrolyzed in the
digestive system.
 906

(c) One way of protecting drug molecules that are taken by mouth is to enclose them in liposomes.
These are artificially created spheres made from phospholipids which have an ionic phosphate
‘head’ and two hydrocarbon ‘tails’.

(i) State in which area of the liposome, A, B or C, each of the following types of drug would be
carried.

(ii) For the remaining position, A, B or C, explain why this would not be a suitable area for
carrying a drug.

(d)One way of carrying drugs in the bloodstream is to attach them by a chemical bond to a polymer.
One such polymer is polyethylene glycol or PEG.
HO – (CH2 – CH2 – O)n – H

(i)Where would a drug be attached to a molecule of PEG?

(ii) Suggest why a liposome can carry more drug molecules than a molecule of PEG.
9701/41/M/J/2010

Q3
 907

[Type a quote from the document or the summary of an interesting point. You can position the text
Exercise 11.1in the document. Use the Text Box Tools tab to change the formatting of the pull quote
box anywhere
text box.]
1 (a)Silk from silkworms, used as a fabric shows a different secondary structure to thatproduced by
spiders.

(i)What sort of bonding would you expect to occur between adjacent parts of theprotein
chains in each form of silk?

(ii)Suggest two differences in properties that these forms of silk could have. Explain
your answer.

(iii) Spider dragline silk contains large amounts of the amino acid glycine. How doesthis
affect the properties of the silk?

(b) Both forms of silk are condensation polymers.

(i)Explain what is meant by a condensation polymer.

(ii) Another type of polymer is called an addition polymer. Name an example of anaddition
polymer.

(iii) Suggest why condensation polymers such as proteins show a wider range ofproperties
than addition polymers.
9701/41/O/N/2008

2The technology of DNA fingerprinting has enormously advanced scientific identification

techniques in medicine, crime detection and archaeology in recent years.
 908

(i)In order to prepare a DNA sample for analysis, the DNA is treated with restriction
enzymes.

What do restriction enzymes do?

(ii)What is the next stage in DNA analysis, after the treatment with restrictionenzymes?

(iii) How are the DNA fragments made visible?

9701/41/O/N/2008

3(a)Spider silk is a natural polymer which has an exceptional strength for its weight. Kevlaris a
man-made polymer designed to have similar properties. It has a wide variety ofuses from
sporting equipment to bullet-proof vests.

(i)In Kevlar, the polymer strands line up to form strong sheets with bonds between
the strands.

On the diagram above, draw part of a second polymer chain showing how bondscould be
formed between the chains.

(ii)Suggest what type of bonds these are.

(iii) Draw two possible monomer molecules for making the polymer Kevlar.

(b) The transportation of oil by sea has resulted in a number of oil spills in recent years. As wellas a
waste of a valuable resource, these have caused major environmental problems.Traditional
sorbent materials absorb water and sink. Researchers have developed newsorbent materials to
help collect the spilled oil. The sorbent consists of a material called‘hydrophobic aerogels’. This
is a network of silicon(IV) oxide with some of the siliconatoms attached to fluorine-containing
groups.

—O—Si—CH2—CF3
 909

The introduction of these fluorine-containing groups allows the oil to be absorbed but notthe
water. Tests show that these materials can absorb more than 200 times their mass of oilwithout
sinking.

(i)Suggest what the word hydrophobic means.

(ii) Suggest why the fluorine-containing groups allow oil to pass through but not water
molecules.

(iii) Suggest another important fluorine-containing polymer that repels water-containing

materials.
9701/41/M/J/2009

4 (a)Put the following items in order of increasing size. Use the number 1 to indicate thesmallest
and 3 to indicate the largest.

Length of DNA in a Nanosphere diameter Cell diameter

chromosome

(b) Nanotechnology has an increasing range of uses across a number of fields includingsport. For
example, golf clubs are now being made using nanomaterials.

Use the diagrams above and your knowledge of nanomaterials to suggest two properties
of the new shafts. Explain your answers.
9701/42/M/J/2009
 910

5 A possible source of energy for the road vehicles of the future is hydrogen. One of the problems
still to be solved is the storage of the hydrogen in the vehicle. A conventional tankholding liquid
hydrogen would have to be pressurized and refrigerated. In a crash, this typeof tank could break
resulting in the rapid release of hydrogen and an explosion.One alternative is to use a fuel tank
packed with carbon nanotubes. The hydrogen in the tankwould be adsorbed onto the surface of
the nanotubes at a pressure of no more than a fewatmospheres.

(a) (i)What is the approximate width of a carbon nanotube?

(ii)In what structural form is the carbon in a nanotube?

(iii)What forces could be responsible for holding the hydrogen on the surface of the
nanotubes? Explain your answer.

(b) The hydrogen atoms in a fuel tank packed with nanotubes are closer together than in
liquid hydrogen. Suggest one advantage of this.

(c)When a nanotube-packed fuel tank is full of hydrogen there is a steady pressure of

hydrogen in the tank. While hydrogen gas is being removed from the fuel tank to power
the car, the pressure in the fuel tank drops very little for some time. State Le Chatelier’s
principle and suggest how it explains this observation.

6 In today’s world, many traditional materials have been replaced by different sorts of polymers.
This includes rigid polymers such as those used in car bodies to replace steel and flexiblepolymers
like those used in textiles to replace cotton or wool.

(a) (i) To form a polymer, what is the minimum number of functional groups that the
monomer must possess?

(ii)Illustrate your answer to (i) with the structure of a possible monomer.

(b) State two differences between addition and condensation polymerization.

(c)The polymer formed from the co-polymerization of the two monomers shown is known
as Terylene.

(i) The two monomers react by condensation polymerization. What other molecule is
formed in this reaction?

(ii)Draw the structure of one repeat unit of Terylene.

 911

(iii) What is the name given to polymers containing the same functional group asTerylene?
(d) The monomers ethene and but-1-ene can also co-polymerise to form a polyalkene, but
this does not produce a regular alternating structure like Terylene. Explain why this is
the case, drawing diagrams if you wish.
9701/41/M/J/2011

7. In today’s world we make use of a wide range of different polymers. These polymers are often
substitutes for traditional materials, but may have more useful properties.

(a) Complete the table identifying one traditional material that has been replaced by each
polymer.

Traditional Modern polymer and its use

material

PVC in packaging

Terylene in fabrics

Polycarbonate bottle

(b) Throwing away articles made from polymers after use is a major environmental concern for
two main reasons. Identify each of these reasons and suggest a strategy that has been adopted
to try to overcome each of these.

(c) One suggestion for the disposal of polymers is to use them as a fuel for small-scale power
stations or district heating schemes.
Identify one polymer which would be unsuitable for this use, explaining the reason behind
this.

(d) Polymers can be either thermoplastic or thermosetting.

Name a thermoplastic polymer

State which type of polymerization produces thermoplastic polymers, explaining your answer
in terms of the structure of the polymer.
9701/41/O/N/2011

[Type a quote from the document or the summary of an interesting point. You can position the text
box anywhere in the document. Use the Text Box Tools tab to change the formatting of the pull quote
text box.]
 912

Optional Topics

FURTHER TRANSITION CHEMISTRY

In section, we discussed the physical and chemical properties of transition elements. In this section, we
study the chemistry of individual elements from the first row of the transition elements, from vanadium
to copper (Table)

Vanadium Chromium Manganese Iron Cobalt Nickel Copper

3d 3 5 5 6 7 8 10

4s 2 1 2 2 2 2 1

Tv 5 6 7 8 9 10 10

Ho +5 +6 +7 +6 +5 +4 +2

Table Electronic structure of the transition elements, from

vanadium tocopper.
Tv = total valence electrons, H0 = maximum possible
oxidation state

Recall the following facts about the electronic structure of the transition elements

 The 4s and the 3d shells are so close in energy that in chemical reactions they behave as one shell.
Electrons can therefore be lost from both shells. This is why the total number of valence electrons
for each of the elements is equal to the sum of the 3d and the 4s electrons.
 The elements have the general configuration [Ar] 3d n4s2, except for chromium and copper which
have a 4s1 configuration. One of the 4s electrons is transferred to the a 3d orbital,
resulting in the formation of an exactly half filled d sub shell for chromium and an exactly filled d
sub shell for copper. These configurations are energetically stable because of the symmetric
distribution of electrons in the orbitals.
 Manganese achieves the highest possible oxidation state of +7 in its compounds, corresponding to
the loss of the five 3d and the two 4s electrons. After manganese, the highest possible oxidation
state that can be achieved becomes smaller by one. This is caused by the pairing of electrons in
the 3d sub shells. Only unpaired electrons may be lost during chemical reactions, for example, in
iron the total number of unpaired valence electrons is six. This is equal to the highest oxidation
state that can be achieved.
 913

Vanadium

Atomic number: Z= 23

Configuration:[Ar] 3d³4s²

Possible oxidation states in compounds: +2,+3, +4 and +5

Most stable oxidation state: + 4

paramagnetism : all oxidation states except +5 are paramagnetic

Redox chemistry
The five oxidation states of vanadium may be represented by the aqueous ions shown in Table below

Ion Oxidation Colour

number

VO₂⁺ +5 yellow

VO²⁺ +4 blue

V³⁺ +3 green

V²⁺ +2 violet (lilac)

Table Ions representing the fivestable oxidation

states of vanadium

Inter conversion between these species can be done using suitable redox reagents.

Reduction half equation (E0/V) Notes

1 VO2+ + 2H+ + e-Ý H2O + VO2+ +1.00 Conversion of vanadium (V) to

vanadium (IV)

2 VO2+ + 2H+ + e-Ý H2O + V3+ +0.34 Conversion of vanadium (IV) to

vanadium (III)

3 V3+ + e-Ý V2+ -0.26

 914

4 V2+ + 2e-Ý V -1.18

Table Some reduction potentials involving vanadium

Reaction 1 one involves vanadium in its highest possible state(+5). The vanadium (V) species is shown as
VO₂⁺. In aqueous solution, this ion is complexed to water molecules, forming the species [VO₂ (H₂O)₅]⁺.
Being positively charged, it will be attracted to counter ions such as chloride, so the full formula would be
that of a salt, for example, [VO₂ (H₂O)₅] Cl.
The vanadic ion, VO₂⁺,can be prepared from ammonium vanadate, NH₄VO₃. In water, this solid dissolves
to give the vanadate ion, VO₃⁻, in which vanadium has the +5 oxidation state. Upon
addition of an acid, the vanadate ion is converted to the vanadic ion.

VO₃⁻(aq) + 2H⁺(aq) → VO₂⁺(aq) +H₂O(l)

The vanadic ion can be converted by metallic zinc in stages until the +2 state is achieved. The formation
of lower oxidation states is accompanied by the change of colour. At first, the colour changes from yellow
to lime green. This yellowish green colour is actually a mixture of two
colours, the yellow of VO₂⁺ and the blue of the lower oxidation state, the vanadous ion, VO²⁺. When all of
the vanadic ions have been reduced, the colour turns blue due to the presence of VO²⁺. Further reduction
of the +4 state results in the formation of [V (H₂O) 6]³⁺, causing the solution to turn green. Zinc is
powerful enough to bring about the lower +2 state,which is purple. There is no further change in colour,
showing that zinc can not reduce vanadium (II) to vanadium metal
(vanadium (0)).

Q
(a)Use a Data Booklet to construct an equation for the conversion of VO2+ to VO2+ by zinc.
Calculate the cell potential for this reaction

(b) Explain clearly whether or not Fe2+ can be used in place of zinc metal for the conversion
in (a) above.

Vanadium metal is prone to attack by dilute acids, forming the purple V(II) salt. The +2 salt undergoes
further oxidation by the acid to form the +3 salt. This shows that the +3 state is more stable than the +2
state. Use the Data Booklet to verify the following outcomes.

i.V(s) + 2H⁺ (aq) → V²⁺ (aq) + H₂ (g) Eѳ cell = +1.20V

ii.V(s) + 2H⁺ (aq) → V³⁺ (aq) + H₂ (g) Eѳ cell = +0.26V

iii.V²⁺ (aq) + 2H⁺ (aq) → V³⁺ (aq) + H₂ (g) Eѳ cell = +0.26

 915

Vanadium can also be attacked by a mixture of oxygen and water to form vanadium (II) in the form of
V(OH)2(s), which undergoes further oxidation in air to form V(OH)3.

iv.2V(s) + O₂(g) + 2H₂O(l) →2V²⁺(aq) + 4OH⁻(aq) (= 2V(OH)₂)

Reactions i to iv might not be observed in practice because of the presence of a tough and impermeable
surface layer of vanadium (III) oxide, V2O3, which protects the metal from chemical agents. Vanadium is
therefore rendered kinetically stable by the superficial oxide layer, just like most of the transition metals.
It is resistant to attack by oxygen, water and dilute acids.

Uses of vanadium and its compounds

 Vanadium is added to steel to make a very strong alloy which is also resistant to corrosion.
Vanadium improves the strength of steels by reacting with carbon present in the steel,
forming vanadium carbide, which is a very strong substance.

 Vanadium pentoxide is used as a catalyst in the contact process for the manufacture of
sulphuric acid.During the catalysis, vanadium pentoxide is decomposed by heat, producing
oxygen:

2V2O5(s) → 2V2O4(s) + O₂ (g)

The oxygen then oxidizes sulphur dioxide to sulphur trioxide.

2SO2(g) + O2(g) ⇋2SO3(g)

The unstable V2O4 is oxidized back to V2O5 by atmospheric oxygen.

Chromium

Atomic number: 24

Configuration:[Ar] 3d54s1

Possible oxidation states in compounds: +2, +3, +4, +5and +6

Stable oxidation states: +3 and +6

Paramagnetism: all oxidation states are paramagnetic except Cr(VI)

Redox Chemistry
The redox chemistry of chromium is dominated by the +3 and the +6 oxidation states, which are the most
stable. Table below shows important reduction potentials involving chromium.
 916

Reduction half Equation E0/V

1 Cr2O72- + 14H++ 6e-Ý 2Cr3++ 7H2O +1.33 Conversion of Cr (VI) to Cr3+

2 Cr3+ + 8OH-ÝCrO42- + 4H2O+ 3e- -0.13 Conversion of Cr3+ to Cr (VI)

3 Cr3+ + e-Ý Cr2+ -0.41

4 Cr3+ + 3e-Ý Cr -0.74

5 Cr2+ + 2e-Ý Cr -0.91

Table Some reduction potentials involving chromium

The +6 oxidation state

The dichromate and chromate ions are well known species in which chromium has an oxidation state of
+6. In the lab, these ions can be obtained from the crystalline salts potassium dichromate (orange) and
sodium chromate (yellow). High oxidation states of a transition metal (+4 and higher) can not exist as
simple (aqua) ions in solution. Having a large charge density, such ions would easily undergo hydrolysis
and extract the oxygen atoms from water, forming ions that contain oxygen (oxo anions).

Oxo anion Ion Oxidation State Colour Dominant in

Cr2O72-(aq)

1090
2-
+6 orange Acidic solution

CrO42-(aq)

+6 yellow Alkaline solution

 917

1090
2-

In aqueous solution, the oxo anions can be interconverted by changing pH. The dichromate ion is
orange in neutral aqueous solution. Upon addition of a strong alkali such as OH -, the solution turns
yellow due to the conversion of dichromate to chromate ions.

Cr2O72-(aq)+ 2OH-(aq) Ý 2CrO42-(aq) + H2O (l) ... (i)

dichromate chromate
(orange) (yellow)

The yellow chromate can be converted back to the dichromate by adding a strong acid.

2CrO42-(aq) + 2H+(aq) Ý Cr2O72-(aq)+ H2O(l) ... (ii)

Note that reactions (i) and (ii) areneutralization reactions (not redox). In (i), dichromate acts as an acid.
In (ii), chromate acts as a base.
The interconversions of dichromate and chromate ions can be explained in terms of Le Chatelier’s
principle. When dichromate ions are added to water, the following equilibrium is established.

Cr2O72- (aq) + H2O (l) Ý 2CrO42-(aq) + 2H+ ... (iii)

This equilibrium lies well to the left hand side, that is, dichromate is the dominant species, so the
solution appears orange. Upon addition of an alkali, hydrogen ions are removed from the right hand side
of the equilibrium through neutralization.

2H+(aq) + 2OH-(aq)  2H2O(l)

Concentration of hydrogen ions in (iii) therefore decreases, and by Le Chatelier’s principle, the
equilibrium shifts to the right, so that more hydrogen ions are produced. The concentration of chromate
ions thus increases, and this causes the solution to turn yellow.
Now consider the effect of adding a strong acid to equilibrium (iii). The concentration of H+ ions
increases, and by Le Chatelier’s principle, the equilibrium should shift in the direction that removes the
added hydrogen ions. In other words, the equilibrium shifts to the left, thus converting chromate ions
dichromate ions.

Now, suppose that you start by dissolving yellow crystals of sodium chromate in water. Some of the
chromate ions are converted to dichromate, according to the equilibrium
 918

2CrO42-(aq) + 2H+(aq) Ý Cr2O72-(aq)+ H2O(l) ... (IV)

The solution appears yellow, showing that CrO42- is the predominant species. Adding a strong acid
increases the concentration of hydrogen ions on the left hand side of the equilibrium. By Le Chatelier’s
principle, the equilibrium responds by shifting to the right, so that the excess hydrogen ions are neu-
tralized by chromate to form water. This is accompanied by an increase in the concentration of di-
chromate ions, so the solution turns orange.

Q
Explain whyadding aqueous barium chloride to an orange solution of sodium
dichromate (VI) causesa yellow solid to be precipitated, and an acidic solution
to remain.

AThe following equilibrium is established when dichromate is added to water.

Cr2O72- (aq) + H2O (l) Ý 2CrO42-(aq) + 2H+

Upon addition of BaCl2, a precipitation reaction occurs between Ba 2+ and chromate ions.

Ba2+(aq) + CrO4-(aq)  BaCrO4(s)

(yellow precipitate)

This reaction removes CrO4- ions from the right-hand side of the equilibrium. This forces the
equilibrium to shift to the right (Le Chatelier’s principle), thus producing more hydrogen
ions. This explains why an acidic solution is formed.

Redox reactions involving the +6 oxidation state

A compound of a transition element in which the metal has a high oxidation state is usually a good
oxidizing agent. This is because the transition element has a tendency to be reduced to lower oxidation
states. While it is being reduced, it acts as an oxidizing agent. The dichromate ion is a well known
oxidizing agent, for example, it can oxidize light green Fe2+ (aq) to yellowish brown Fe3+(aq). Meanwhile,
the dichromate is reduced to the dark green Cr3+ ions.

Q Use relevant equations from the Data Booklet to construct a balanced equation
for the reaction between dichromate and Fe2+. Calculate the cell potential of
the reaction.

The reaction between Cr2O72- and Fe2+ is quantitative and can be used to determine the concentration of
Fe2+ in a solution by titration.
Another application of potassium dichromate as an oxidizing agent is in the detection of sulphur dioxide.
When a strip of filter paper is soaked in potassium dichromate and exposed to sulphur dioxide, the paper
 919

turns green. This shows that dichromate is reduced to Cr 3+ by sulphur dioxide. Meanwhile, the sulphur
dioxide is oxidized to sulphate. The relevant half equations for this reaction are shown below.

Eθ/V
Cr2O72- + 14H+ + 6e-Ý 2Cr3+ + 7H2O +1.33
oxidizing agent

SO42- + 4H+ + 2e-Ý SO2+2H2O +0.17

reducing agent

The net (ionic) equation for the reaction between potassium dichromate and sulphur dioxide is therefore

3SO2 + 6H2O + 2H+ + Cr2O72-Ý 3SO42- + 8H+ + 2Cr3+ + 7H2O Eθcell = +1.16V

Dichromate ions can also be reduced to Cr3+ by acidified hydrogen peroxide. When you choose the
relevant half equations from the data booklet, make sure that

 the half equation involving hydrogen peroxide has an E θ value which is less than that of
dichromate (+1.33V). This allows dichromate to act as an oxidizing agent (more positive E θ) and
hydrogen peroxide to act as a reducing agent.
 the half equation you select for hydrogen peroxide contains hydrogen ions. This is because
hydrogen peroxide is a reducing agent in an acidic medium (In an alkaline medium it is a
reducing agent).

Eθ/V
Cr2O72- + 14H+ + 6e-Ý 2Cr3+ + 7H2O +1.33
oxidizing agent

O2+ 2H+ + 2e-Ý H2O2+0.68

reducing agent

Net equation :
Cr2O72-+ 8H+ + 3H2O2Ý 2Cr3+ + 7H2O + 3O2Eθcell = +0.65V

During the reaction

 the orange colour of dichromate changes to the green colour of Cr 3+
 bubbles of oxygen gas are liberated

The +3 oxidation state

The +2 and + 3 oxidation states of a transition metal ions exists as simple aqua ions in water. However,
due to their large density, the + 3 ions undergoes hydrolysis, resulting in the formation of an acidic
solution. Consider what happens when the green coloured salt CrCl3. 6H2Ois added to water.
 920

6H2O 6H2O
CrCl3.6H2O (s) Cr3+(aq) [Cr(H2O)6]3+ (aq)
(i) (ii)

[Cr[(H2O)5 (OH)]2+(aq) + H+(aq)

(iii)

(i)As the salt dissolves, Cr3+ and chloride ions are hydrated, that is, they form ion-dipole attractions with
water molecules. This is a physical process which releases large amounts of heat energy (enthalpy change
of hydration) due to the large charge density of Cr3+ ions.

(ii)Dative covalent bonds are established between water molecules (ligands) and Cr 3+ ions, resulting in
the formation of an octahedral hexa-aqua complex, [Cr (H2O)6]3+. Due to the large density of the Cr3+ ion,
a water ligand undergoes hydrolysis, releasing H+ and OH- ions. The hydroxide ion, being a strong ligand,
immediately forms a covalent dative bond to the metal ion.

(iii) This results in the formation of an octahedral complex which contains two types of ligands; H 2O and
OH-. Notice that the charge on the complex has changed from +3 to +2 due to the uptake of a negative
ligand which neutralizes one of the positive charges.
The presence of hydrogen ions in the solution results in an acidic solution being formed. This solution is
acidic enough to

turn blue litmus paper red

produce effervescence (bubbles of carbon dioxide) with carbonates

Redox reactions involving Cr3+

Aqueous Cr3+ is often reported as being green in colour. This is the colour usually observed when the ion
is formed in a chemical reaction. However, when Cr3+ ions are prepared by dissolving a Cr (III) salt in
water, the colour may appear violet at first but changes to green over time. This change is caused by ligand
exchange in the chromium (III) aqua complex. When the salt is dissolved in water, the violet complex [Cr
(H2O) 6]3+ is formed, but some of the water ligands are soon replaced by negative ions from the salt. This
results in a change of colour.
We have said that the higher oxidation states of transition metals tend to act as oxidizing agents. The
lower oxidation states of the transition metals tend to act as reducing agents, that is, in redox reactions,
they tend to lose electrons and are thus oxidized to higher oxidation states.

Consider what happens when a solution of hydrogen peroxide containing an excess of NaOH is added to a
green solution of Cr3+ ions. A green precipitate is formed which settles at the bottom of a yellow solution.
When the mixture is filtered and the yellow filtrate is acidified with a strong acid, an orange solution is
formed. This observation can be explained in this way:
Since the solution is alkaline (rich in OH - ions), a portion of the Cr3+ ions is precipitated as green
chromium (III) hydroxide, Cr(OH)3(s). Some of the precipitate is converted to [Cr(OH)6]3- (colourless
solution) through complexation with OH- ions. This colourless complex, containing Cr(III), is then
oxidized by hydrogen peroxide to form the yellow chromate ion. Acidifying the yellow solution results in
the conversion of chromate ions to dichromate, which is orange.

2[Cr(OH)6]3- + 3H2O2 2CrO42- + 2OH- + 8H2O

 921

However, it may be noticed that the orange dichromate is soon converted to a green solution. This is
because upon addition of an acid, unreacted hydrogen peroxide in the reaction vessel is converted to a
reducing agent. It immediately reduces dichromate back to Cr3+, as discussed earlier

Cr2O72-+ 8H+ + 3H2O2Ý 2Cr3+ + 7H2O + 3O2Eθcell = +0.65V

To avoid this reaction, it is necessary to drive out the excess hydrogen peroxide by boiling the reaction
mixture. Heat causes hydrogen peroxide to decompose to oxygen and water.

Non redox reactions involving Cr3+

Apart from participating in redox reactions, the Cr3+ (aq) undergoes the following reactions

 precipitation by NaOH(aq) and NH3(aq)

(i) When dilute NaOH (aq) is added gradually to Cr3+ (aq), a green precipitate is formed
which dissolves in excess NaOH to form a colourless solution. There are two types of
reactions involved here. First, precipitation occurs, forming Cr (OH)3(s), which is green
in colour. When an excess of NaOH is added, complexation occurs, causing the
precipitate to dissolve.

3OH- xs OH-
Cr[(H2O)6]3+ Cr[(H2O)3(OH)3](s) [Cr(OH)6]3- + 3H2O
green solution green precipitate colourless solution

Note that the full formula of the precipitate is Cr [(H 2O)3(OH)3]. Written in this way, you
can easily see that the complex is a neutral and basic octahedral complex containing two
types of ligand (H2O and OH-). This neutral complex dissolves in excess NaOH (aq)
because the H2O ligands are replaced by more OH- ligands, resulting in the formation of
a charged complex.

(ii)When dilute NH3 is added to Cr3+(aq), a green precipitate of Cr [(H2O)3(OH)3] is formed,

which is insoluble in excess of the NH3 . However, if concentrated ammonia is
used, the precipitate does dissolve, forming the violet complex [Cr(NH 3)6]3+. Recall that
aqueous ammonia contains OH- ions, and so it can precipitate metal ions from solution.

 reaction with sodium carbonate

An aqueous solution of Cr3+ effervesces when sodium carbonate is added. Bubbles of carbon
dioxide are produced and a green precipitate of chromium (III) hydroxide is formed. The fact that
Cr3+(aq) reacts with sodium carbonate shows that it is acidic. The following equilibrium exists in
water due to the ability of Cr (III) to hydrolyze water.

Cr[(H2O)6]3+ Ý Cr[(H2O)5(OH)]2+ + H+ ... (i)

When sodium carbonate is added to this acidic solution, it neutralizes the hydrogen ions,
resulting in the formation of carbon dioxide and water.

CO32- + 2H+  CO2 + H2O

 922

Removal of hydrogen ions from equilibrium (i) promotes further hydrolysis in the complex on the
right hand side, so that more hydrogen ions are produced to replace those that have been
removed from the equilibrium.

Cr[(H2O)5]2+ Ý Cr[(H2O)4(OH)2] + + H+ ... (ii)

Once more, the H+ ions are removed by carbonate ions, promoting further hydrolysis in the
complex shown on the right hand side of equilibrium (ii). This results in the formation of a
neutral complex (precipitate)

Cr[(H2O)4(OH)2] + Ý Cr[(H2O)3(OH)3](s)
(green precipitate)

Isomerism in compounds of chromium

Different forms of isomerism are shown by complexes of transition elements. Here we use chromium to
illustrate how some forms of isomerism may arise in compounds of the transition elements. The ability of
chromium to form a large number of complexes can be explained in terms of the kinetic stability of the Cr-
ligand dative bonds. These bonds do not easily break. If it was easy for these bonds to break, then one
isomer would easily be converted into the other.

 Stereoisomerism

(i)Geometric (cis - trans) isomerism

(ii) optical isomerism

 co-ordination isomerism
 ionization (hydrate ) isomerism

Stereoisomerism
Stereoisomers are compounds that share the same molecular formula but differ in the spatial (‘in space’)
arrangement of groups. There are two types of stereoisomerism , geometric (cis -trans) and optical
isomerism.

(i) Geometric isomerism

This occurs in octahedral complexes of the general formula MA 4B2 , where M is the central
metal ion and A, B are ligands or in square planar complexes of the general formula MA 2B2. The complex
[Cr (NH3)4Cl2]+ can be used to illustrate geometric isomerism in an octahedral complex (Fig)
 923

.. ..

.. .. .. ..

.. ..
.. ..
.. ..

Fig An example of cis - trans isomerism

 In the trans isomer, similar ligands occupy positions which are on opposite sides of the central
metal ion. In the cis isomer, similar ligands are on the same side of the central metal ion.
 Cis-trans isomers usually have different colours
 The isomers also differ in polarity. The trans isomer is non - polar because it has equal dipole
moments that operate in opposite directions. The dipole moments therefore cancel out, so that
the molecule is overally non - polar. The cis isomer is polar.

(ii) Optical isomerism

This occurs in octahedral complexes which contain three bidentate ligands. Optical isomers lack a centre
of symmetry and so their mirror images are non-superimposable. Consider the octahedral complex
formed between Cr3+ and oxalate, which is a bidentate ligand. The three oxalate ions can bond to the
metal ion in two different ways, giving rise to two stereoisomers that are mirror images of each other, as
shown in Figure

= C C

Fig Optical isomerism in an octahedral complex

 924

Co-ordination isomerism
Co-ordination isomers are salts in which both the cation and anion are complexes. Co-ordination
isomerism arises when it is possible to interchange ligands between the cation and the anion. The two
compounds shown below are examples of co-ordination isomers.

[Cr(NH3)6]3+[Co(CN)6]3- and [Co(NH3)6]3+[Cr(CN)6]3-

Hydrate isomerism
This occurs when a hydrated salt can exist in different forms. A typical example is exhibited by the salt
CrCl3. 6H2O(s). There are three different solid forms that share this molecular formula. One of the forms is
greenish blue, and the other two are green. It is possible to distinguish between the three solid isomers by
dissolving them separately in water and then determine the amount of free chloride ions in each solution
by adding AgNO3 (aq). Table shows the formula of each isomer and the effect of adding AgNO 3 (aq).

 The isomers differ in how many chloride ions are directly bonded to the central metal (acting as
ligands). The chloride ions that are bonded to the metal ion via covalent dative bonds are said to
be part of the co-ordination sphere.
 Chloride ions outside the co-ordination sphere act as counter - ions to neutralize the positive
charge on the co-ordination complex. In solution, these ions are dispersed in water and so can be
precipitated as AgCl when aqueous AgNO3 is added.
 Note that each chloride ion that is taken into the co-ordination sphere causes the positive charge
on the co-ordination complex to decrease by 1. This is because the chloride ion is a negatively
charged ligand.

Isomer Colour Effect of Remark

in adding
solution AgNO3(aq)

[Cr(H2O)6]3+(Cl-)3 blue-violet All chloride The three chloride ions are outside
ions are the co-ordination sphere. That
precipitated is, they are not directly bonded to
as AgCl the central metal ion. The ions are
therefore free in solution and so
can be precipitated by Ag+.

[Cr(H2O)5Cl]2+(Cl-)2 green Only 2/3 of One of the chloride ions is directly

the chloride bonded to the central metal ion by
ions are strong covalent dative bonds. This
precipitated. ion is not available in solution to
react with Ag+

[Cr(H2O)4Cl2] +Cl- Darker Only 1/3 of Two of the chloride ions are part of
Green the chlorides the co-ordination sphere.
 925

is
precipitated.

When the three aqueous solutions are dried, they all take up six water molecules of crystallization, so
they will all share the formula CrCl3. 6H2O. However, they crystallize as different compounds due to
the fact that they differ in the number of chloride ions that are directly bonded to the
central metal ion by dative covalent bond.

NB Hydrate isomerism is often referred to as ionization isomerism.

Relative stabilities of the +2 and the +3 oxidation states

Just as in vanadium, the +2 oxidation state is less stable than the +3. The sky blue Cr 2+ (aq) can be
prepared by dissolving chromium metal in an acid. However, the red Cr 2+ solution formed immediately
turns green as it is oxidized to Cr 3+ by oxygen in air. This is supported by relevant redox data in Table

Reduction half equation Eθ/V

1 Cr2+ + 2e-Ý Cr -0.91

2 Cr3+ + 3e-Ý Cr -0.74

3 Cr3+ + e-Ý Cr2+ -0.41

4 O2 + 4H+ + 4e-Ý 2H2O +1.23

 926

5 2H+ + 2e-Ý H2 0.00

Table

 combining equations (1) and (5)

Cr + 2H+Ý Cr2+ + H2Eθcell = +0.91V

This shows that chromium metal can be oxidized by an acid to Cr2+(aq)

 Combining equations (3) and (5)

2Cr2+ + 2H+Ý 2Cr3+ + H2Eθcell = +0.41V

This shows that Cr2+ is further oxidized by the acid to Cr3+. In other words, Cr3+ is more stable
than Cr2+.

 Combining equations (3) and (4)

4Cr2+ + 4H+ + O2Ý 4Cr3++ 2H2O Eθcell = 1.23 +0.41 = 1.67V

This shows that when prepared by dissolving chromium metal in an acid, Cr 2+ is also oxidized by
atmospheric oxygen to form Cr3+.

It can therefore be concluded that Cr2+ is a powerful reducing agent since it is readily oxidized to Cr 3+. In
other words, Cr2+ easily loses an electron to become Cr3+. This observation canbe explained in terms of
theelectronic configurationof Cr2+:

Cr2+ : [Ar] 3d44s1

3d

In aqueous solution, Cr2+ exists as a hexa - aqua complex with water ligands. As you may recall from
section, the effect ligands is to split the d-orbitals into two energy sets. Since Water is a weak field ligand,
the energy difference between the lower and the higher d-orbital set is relatively small. This implies that
the fourth d electron in Cr2+ canafford to occupy an orbital in the higher energy set. This prevents pairing
of electrons in the lower set, since this would bring about instability.
Oxidation of Cr2+ to Cr3+ involves loss of the single electron in the higher 3d orbital set. This electron is
relatively easy to remove since it is high in energy, that is, it is a large distance from the nucleus.

Uses of chromium metal

 In chrome plating
Chrome plated objects, for example, car bumpers, are strong, resistant to corrosion and
attractive.

 Manufacture of stainless steel

 927

Chromium and other transition metals are added to iron during the manufacture of steel. The
presence of chromium hardens (strengthens) steel and increases resistance to corrosion.
Although a consideration of reduction potentials indicates that chromium is very reactive
towards atmospheric agents (O2 and water vapour), in practice chromium shows resistance to
corrosion. This is because it forms a tough and impermeable surface layer of chromium (III) oxide
is formed, protecting the rest of the metal from attack by oxygen and water. This oxide layer helps
to protect steel from corrosion.

Summary : the chemistry of chromium

 Main oxidation states : +2, +3, +6
 The +2 state is a powerful reducing agent. It is easily oxidized in air to form Cr 3+. The +6 state is a
good oxidizing agent and can be converted to Cr3+ by a suitable reducing agent.
 The colours of the aqueous ions are

Cr2+sky blue
Cr3+bright green
CrO42- yellow
Cr2O72- orange

 The complexes of chromium are usually octahedral.

Manganese

Atomic number: 25

Configuration: [Ar] 4s23d5

Possible oxidation states: +2, +3, +4, +5, +6, +7

Most stable oxidation states: +2, +4 and +7

Paramagnetism:all oxidation states except +7 are paramagnetic

Representative species

Oxidation number
compounds aqueous ions,

+2 MnCl2 Mn2+(aq) = [Mn(H2O)6]2+pale pink

 928

Pink salt

+3 Mn2O3 Mn3+(aq)red, unstable

Dark brown
solid when
freshly
prepared

+4 MnO2

Black solid

+5 MnO43-

+6 MnO42-

+7 KMnO4(s) MnO4-purple

Purple
crystals

Redox chemistry

Manganese is a very electropositive metal, a fact which is supported by its large and negative reduction
potential (equation, Table ). In other words, it is a good reducing agents and it is readily oxidized by water
and dilute acids, forming Mn (II) compounds and liberating hydrogen gas in the process. Check to see
that you can construct equations for the reactions of manganese with dilute acids and water, and calculate
the corresponding Eθcell values (refer to equations 10, 12 and 14). Manganese metal is also readily
oxidized by chlorine gas to form manganese (II) chloride, which is a pink salt (equations 10 and 11).

Stable oxidation states of manganese

Reduction half equation Eθ/V
 The +2 state
1 MnO42- + 4H+ + 2e-Ý MnO2 + 2H2O +2.26
It is found in salts such as MnCl2,
which is a pink solid. In aqueous
2 MnO4- + 4H+ + 3e-Ý MnO2 + 2H2O +1.67
solution, the hexa-aqua complex
[Mn(H2O)6]2+ has a very faint pink
3 MnO4- + 8H+ + 5e-Ý Mn2+(aq) + 4H2O +1.52
colour, so faint that it caneasily be
missed if the solution is dilute. The
4 Mn3+ + e-Ý Mn2+ +1.49
cation M2+(aq) canbe obtained by
dissolving manganese metal in an
5 MnO2 + 4H+ + 2e-Ý Mn2+(aq) + 2H2O +1.23
acid or by reducing higher oxidation
states of manganese.
6 +o.60
 The +4 state
This is found in the black solid,
MnO2. This compound can be
formed from the oxidation of Mn2+
in an alkaline environment, or from
 929

MnO42- + 2H2O + 2e-Ý MnO2 + 4OH-

7 MnO4- + 2H2O + 3e-Ý MnO2 + 4OH- +0.59

8 MnO4- + e-Ý MnO42- +0.56

9 MnO42- + e-Ý MnO43- +0.27

10 Mn2+ + 2e-Ý Mn -1.18

Other systems

11 Cl2 + 2e-Ý 2Cl- +1.36

12 O2 + 4H+ + 4e- Ý 2H2O +1.23

13 Fe3+ + e-Ý Fe2+ +o.77

14 2H+ + 2e-Ý H2 +0.00

15 2CO2 + 2H+ + 2e-Ý H2C2O4 -0.49

Table Reduction potentials for manganese

and other systems

MnO42- MnO4- + e-Eθ/V = -0.56V

A third of the MnO42- is reduced to MnO2(s) (equation 1)

MnO42- + 4H+ + 2e-Ý MnO2 + 2H2O Eθ/V = +1.26V

Combining the two equations gives the net equation for the disproportionation of MnO42- in acidic
medium. Multiply the first equation by 2 to balance the number of electrons, then simply add together the
two equations (do not reverse any equation; remember that the first equation is already reversed).

3MnO42-(aq) + 4H+(aq) 2MnO4-(aq)+MnO2(solid)+ 2H2O(aq)

Eθcell = -0.56V + 1.26V = 1.70V

In this reaction, the green MnO42- is simultaneously oxidized to the deep purple MnO4- and reduced to
the black solid MnO2.

Disproportionation of MnO42- can still take place in aqueous

Oxidation solution, but the reaction is somewhat energetically
Oxo state colour unfavourable and is slow, as indicated by the very small
anion value of the cell potential. You can obtain this equation by

2MnO42- 2MnO4- + 2e-Eθ/V = -0.56V

MnO42- + 2H2O + 2e-Ý MnO2 + 4OH-Eθ/V = +0.60V

Adding the two equations gives the net cell reaction

 930

of Mn

MnO43- +5 Bright
blue

MnO42- +6 Green

MnO4- +7 purple

The disproportionation of MnO42- does not take place when the solution is made strongly alkaline. This is
because an increase in concentration of OH - ions on the right hand side of equation (i) causes the
equilibrium to shift to the left hand side (Le Chatelier’s principle). In other words, the forward
disproportionation reaction becomes unlikely. The effect of pH on stability of MnO 42-is therefore clear.

 In an acidic medium MnO42- is unstable and readily disproportionates to MnO4- and MnO2
 In neutral solution, the disproportionation occurs slightly and slowly. MnO 42- is therefore more
stable in aqueous solution than in an acidic environment
 In the presence of a strong alkali, MnO42- is stabilized against disproportionation.

These observations give us a way of preparing manganate (VI). A mixture of MnO 4-, MnO2 and a
strong concentrated alkali such as NaOH is heated. Formation of MnO 42- occurs according to the
reverse of reaction (i) above.

2MnO4- + MnO2 + 4OH-Ý 3MnO42-(aq) + 2H2O Eθcell = +0.04V

The reaction occurs despite the fact that it has a negative cell potential. This is because the conditions
employed are non-standard (concentrated alkali and heat) and the redox potential is a small negative
number.

Manganate (VII) as an oxidizing agent

Manganese achieves its highest oxidation state in the manganate (VII) ion, MnO 4-. This ion is a good
oxidizing agent and can be used in the quantitative and qualitative determination of some reducing
agents, for instance,

 It can oxidize Cl- ions (in concentrated HCl) to chlorine gas. This is a good method for preparing
chlorine in the lab
 It can oxidize the light green Fe2+(aq) to the yellow brown Fe3+(aq)
 It oxidizes ethanedioate ions (C2O42- = oxalate) to carbon dioxide

Make sure you can construct balanced equations for these reactions using appropriate redox data in
table.MnO4-can also easily oxidize some organic compounds

 Primary alcohols and aldehydes are oxidized to carboxylic acids

 alkenes are oxidized to diols under ice cold conditions
 931

Complexes of manganese
Manganese has only one stable cationic form, Mn2+ which is found in solid salts. In aqueous solution, the
octahedral hexa-aqua complex, [Mn (H2O)6]2+ has a very faint pink colour. The reason for this faint colour
can be explained in terms of the d5 configuration of Mn (II). Recall that colour in
transition metal compounds is usually explained in terms of absorption of photons of light energy, which
causes d-d transitions of electrons from the lower energy set to the higher energy set.

Mn2+ : [Ar] 3d54s2

3d

 the d5 configuration is exactly half-filled and is therefore stable due the symmetric distribution of
electrons. Any rearrangement of electron distribution is therefore not energetically
favourable.
 If an electron were to be promoted into the higher set of d orbitals, one orbital in this set would
contain paired electrons. This leads to instability due to inter - electronic repulsion between the
paired electrons.

d-d transitions of electrons in Mn(II) therefore occur very infrequently. In other words, very little light
energy is absorbed and so the solution appears almost colourless.

Mn(II) forms a very small number of complexes compared with other +2 cations of the first row transition
elements, for example, it does not form any complexes with ammonia or with hydroxide ions. The
explanation lies in the kinetic instability associated with many complexes of Mn (II).

Relative stabilities of the +2 and the +3 oxidation states of manganese

For chromium, you probably recall that the +2 state is very unstable and is easily oxidized to the +3 state.
For manganese, the +2 state is very stable in acidic or neutral solution with respect to oxidation to the +3
oxidation state, as shown by the large and negative electrode potential for the oxidation
reaction

Mn2+  Mn3+ + e-Eθ = -1.49V

Remember that Mn(II) has a d5 configuration which is very stable because of the symmetric
distribution of electrons in the orbitals. Mn (II) therefore resists oxidation to the +3 state because this
conversion would be accompanied by a loss in the stable symmetric distribution of electrons. However, in
alkaline solution, it Mn (II) is easily oxidized in air to Mn (III). In the presence of an alkali, Mn2+ is exists
as solid [Mn(H2O)3(OH)3]. Being neutral, this compound can easily lose an electron to oxygen, resulting
in oxidation to from manganese (III) hydroxide. This conversion is difficult for Mn 2+(aq) because an
electron is not willing to leave a positively charged ion.

Tests for some compounds or ions of manganese

 932

Mn2+(aq)
 Add dilute NaOH or NH3 gradually until in excess. An off white (buff) precipitate is formed which
is insoluble in excess NaOH or NH3, but it is possible to miss this observation because the
precipitate immediately turns to brown in air.

OH- O2
Mn[(H2O)6]2+(aq) Mn(OH) 2(s) Mn(OH) 3

Mn2O 3 .xH2O

 MnO2(black powder)
Add cold dilute hydrogen peroxide. There is brisk effervescence and the reaction mixture becomes
warm. The gas produced relights a glowing splint. During the reaction, no visible change occurs to
the MnO2.
Manganese dioxide catalyzes the decomposition of hydrogen peroxide to oxygen and water.

 KMnO4 (aq)
KMnO4 is decolourized by a number of reducing agents, including Fe2+ (aq).

Summary: chemistry of manganese

 Most stable oxidation states are +2, +4 and +7
 The +3, +5 and +6 oxidation states also exist but they are unstable through disproportionation
 In aqueous solution, the cations and oxo anions have the following colours

Mn+2pale pink
Mn+3red
MnO43-(Mn(IV))bright blue
MnO42- (Mn(VI)) green
MnO4- (Mn(VII)) deep purple
 933

Iron

Atomic number: 26

Configuration: [Ar] 4s23d6, 3d

Maine oxidation states: +2, +3and +6

Most stable oxidation states: +2, +3

Paramagnetism: +2 and +3 statesareparamagnetic, except some low spin complexes of iron

(II)

Redox chemistry
The redox chemistry of iron in aqueous solution is predominated by the +2 and the +3 states. Iron has
only one oxo anion, FeO42-, which is very unstable and is easily reduced by many reducing agents to Fe 3+.

Ion Colour in Remarks

aqueous solution

Fe2+ Pale green Slowly oxidizes in air to Fe3+. For this reason, Fe2+
solutions to be used inquantitative and qualitative
analysis should be used soon after being prepared

Fe3+ Yellowish brown More stable. The solution is acidic due to the hy-
drolysis.

Table The cationic forms of iron

Table shows some reduction potentials involving iron and other systems. You should particularly note the
effect of pH and different ligands on the relative stabilities of the +2 and the +3 oxidation states of iron.

 Comparing equations (2) and(5)

If you read these equations in reverse, you have the oxidation reactions for the conversion of
Fe(II) to Fe(III). The more positive the redox potential for the oxidation reaction, the easier it is
for Fe(II) to be converted to Fe(III). Equation (5) has the most positive electrode potential,
showing that it is very easy to convert iron (II) hydroxide to iron (III) hydroxide. In other words,
Fe(II) is very unstable in alkaline environment. Adding NaOH(aq) to a light green solution of
Fe2+(aq)results in the formation of a green precipitate, which immediately turns brown in air due
to oxidation
 934

oxidation in air
Fe2+(aq) Fe(OH) 2(s) Fe(OH) 3 (s)

Fe2O 3 .xH2O

In neutral or acidic solution, Fe2+ is

Reduction half equations involving Eθ/V
not so easily oxidized to Fe3+ because
iron
an electron is unwilling to leave a
1 +2.20 positively charged ion. In the
FeO42- + 8H+ + 3e-Ý Fe3+ + 4H2O
presence of an alkali, Fe(II) exists as
2 +0.77 Fe(OH)2. Being neutral, this
Fe3+ + e-Ý Fe2+
compound can lose an electron
3 +0.36 relatively easily, to form iron (III)
[Fe(CN)6]3- + e-Ý [Fe(CN)6]4-
hydroxide.
4 Fe2+ + 2e-Ý Fe -0.44
 Using equations (2) and (8)
5 -0.56 These equations can be used to
Fe(OH)3 + e-Ý Fe(OH)2 + OH-
predict the effect of oxygen on an
acidified solution of Fe2+. Combining
Other systems the two equations gives the net cell
reaction (remember to reverse
equation (2) and multiply it by 4 to
6 MnO4- + 8H+ + 5e-Ý Mn2+ + 4H2O +1.52 balance electrons)

7 Cl2 + 2e-Ý 2Cl- +1.36 4Fe2+ + O2 + 4H+Ý 4Fe3+ + 2H2O

8 +1.23 Eθcell = 1.23 - 0.77 = +0.46V

O2 + 4H+ + 4e-Ý2H2O
The positive cell potential shows that from an
9 I2 + 2e-Ý 2I- +0.54 energetic point of view, even in acidic
solution, Fe2+ can still be oxidized to Fe3+.
10 O2 + 2H+ + 4e-Ý 4OH- +0.40 The resistance of Fe2+ to be converted to Fe3+
in acidic medium is therefore caused by
11 2H+ + 2e-Ý H2 0.00 kinetic factors. As already explained, it is
difficult for an electron to leave the positively
Table charged Fe2+.

 Comparing equations (2) and (3)

If you read these equations in reverse, you should be able to see that the aqua Fe 2+ complex, in
which the ligands are water molecules, is not so easily oxidized to Fe 3+ (Eθ/V = -0.77). In the
presence of CN- ligands, the electrode potential for the oxidation of Fe (II) to Fe (III) is more
positive (-0.36V). In other words, the effect of cyanide ligands is to destabilize the +2 state of iron,
 935

so that it is relatively easily oxidized to Fe3+. In the presence of CN-, Fe3+ is therefore more stable
than Fe2+

 Using equations (2) and (9)

These two equations can be used to predict the outcome of mixing Fe 3+ (aq) with iodide ions.
Reversing equation (9), multiplying equation (2) by 2 and combining the two equations gives the
net cell for the reaction between iodide ions and Fe3+.

2Fe3+(aq) + 2I-(aq)  2Fe2+(aq) + I2(aq) Eθcell = +0.23V

The positive cell potential shows that Fe3+(aq) is indeed reduced by iodide ions to Fe2+.
Meanwhile iodide ions are reduced to brown iodine.

Using equations (3) and (9)

You can use these two equations to see if iodide ions can oxidize Fe (II) to Fe (III) in the presence
of cyanide ligands. Reverse equation (9) to put iodide ions on the reactant side, multiply equation
(3) by 2, then combine the two equations.

2[Fe(CN)6]3- + 2I - I 2(aq) + 2[Fe(CN) 6]4- Eθ/V = -0.18V

The negative cell potential shows that iodide ions can not reduce Fe(III) to Fe(II) in the presence
of cyanide ligands. This is further proof that CN- ligands stabilize Fe(III) with respect to
reduction. In fact, Fe(II) can be oxidized by iodine to Fe(III) in the presence of cyanide ligands
(equations (2) and (9)).

2[Fe(CN)6]4- + I 2(aq) 2[Fe(CN) 6]3- + 2I - E θ/V = +0.18V

This reaction can easily be followed because it is accompanied by decolourization of the brown
iodine solution.

More reactions of Fe2+ and Fe3+

We have already discussed some reactions of Fe2+ and Fe3+ which illustrate the effect of pH and ligands on
the relative stabilities of these two oxidation states. More reactions of Fe2+ and Fe3+ are discussed below.

Reactions of Fe2+(aq)

Reaction with Observations Notes

NaOH(aq) Green precipitate formed, Please refer to main text above

insoluble in excess NaOH.
Precipitates turns red brown in
air.

NH3(aq) Same observation as above Please refer to main text above

 936

Reaction with Observations Notes

CN-(aq) White precipitate formed, Fe2+(aq) + 2CN-(aq)  Fe(CN)2(s)

soluble in excess cyanide to white ppt
form a yellow solution.
The precipitate dissolves due to complexation

Fe(CN)2(s) + 4CN-(aq)  [Fe(CN)6]4-(aq)

yellow complex

NB cyanide is poisonous and may not be used

in the school lab.

KMnO4-(aq) in KMnO4 is decolourized. Light Fe2+ oxidized to Fe3+ and MnO4-reduced to

acidic medium green colour of Fe2+ changes to Mn2+.
yellowish brown

CO32-(aq) white ppt formed Fe2+(aq) + CO32-(aq)  FeCO3(s)

white ppt

Cl2(g) Light green colour of Fe2+ Cl2 oxidizes Fe2+ to Fe3+

changes to yellowish brown
2Fe2+(aq) + Cl2(g)  2Fe3+(aq) + 2Cl-

[Fe(CN)6]3-(aq) A Turnbull’s blue precipitate is An insoluble dye (complex) is formed, with a

(complex of formed blue colour described as Turnbull’s blue.
Fe(III) with
cyanide This reaction cab be used to distinguish
ligands) between Fe2+ and Fe3+

Reactions of Fe3+(aq)
 937

Reaction with Observations Notes

NaOH(aq) or Red - brown precipitate Iron (III) hydroxide precipitated

NH3(aq) formed, insoluble in excess
NaOH or NH3(aq)

Reaction with Observations Notes

KI(aq) solution turns brown Fe3+ oxidizes colourless I-(aq) to brown iodine
solution. Meanwhile, Fe3+ is reduced to Fe2+

2Fe3+ + 2I-(aq)  2Fe2+ + I2(aq)

CN-(aq) Orange brown solution Hexa cyano complex , [Fe(CN)6]3-(aq), formed

formed

CO32-(aq) Red - brown precipitate Iron (III) hydroxide is formed, not iron (III)
formed carbonate. This is due to the acidic nature of
Fe3+(aq) (please refer to main text).

SCN-(aq) Blood - red solution formed aqua - thiocyanato complex is formed

(thiocyanate
ions) Fe3+(aq) + SCN-(aq)  [Fe(H2O)5SCN]2+
blood - red complex

NB: This is a good and sensitive test to

distinguish between Fe2+(aq) and
Fe3+(aq).

[Fe(CN)6]4-(aq) Prussian blue precipitate An insoluble dye (complex) is formed, with a

complex of formed blue colour described as Prussian blue.
Fe(II) with
cyanide NB Prussian blue and Turnbulls’ blue are only
different in their impure forms. When purified,
they are found to be identical.

Complexes of Fe2+ and Fe3+

 Most of the complexes are octahedral.
 938

 The aqua complex of iron (II) is the pale green [Fe(H2O)6]2+.

 The corresponding aqua complex for Fe(III) does not exist because the large charge density on the
Fe3+ polarizes a water molecule, takes up an OH- ligand and releases H+ in solution (recall that
Cr3+(aq) behaves in a similar way).

[Fe(H2O)6]3+(aq)  [Fe(H2O)5(OH)]2+(aq) + H+(aq) ... (i)

 A solution of Fe3+ in water is therefore acid. In fact, it is acidic enough to turn blue litmus
paper red and liberate carbon dioxide from a carbonate. The carbonate ions combine with H+ ions
in equilibrium (i), forming carbon dioxide and water. This induces the complex
[Fe(H2O)5(OH)]2+ to polarize another water molecule, releasing H+ ion to replace the one
 removed by carbonate. The new complex formed now has the formula [Fe(H2O)4(OH)2]+. Con-
tinued removal of H+ ions by carbonate results in the formation of the neutral complex
[Fe(H2O)3(OH)3]. This is the precipitate (iron (III) hydroxide) responsible for the muddy brown
colour observed when sodium carbonate is added to Fe 3+(aq).
 Fe(II) forms a reasonably stable complex, [Fe(NH3)6]2+ with concentrated ammonia. The complex
is not formed when dilute ammonia is used. Fe(III) does not form a complex with ammonia.
 Complexes of Fe2+ and Fe3+ are paramagnetic, except some low spin complexes of Fe2+(d6). These
complexes contain strong field ligands which cause an extremely high separation in
energy between the lower and the higher 3d orbital sets. As a result, electrons can not be distrib-
uted into the higher energy set because they would require a very large amount of energy would
be required to move from the lower set. This causes the six electrons to pair up in the lower
energy set, leading to diamagnetism. Compare the two complexes of Fe(II) in Fig.

very large ΔE
ΔE is small

3d 3d

[Fe(CN)6 ]4- [Fe(H2O)6 ]2+

low spin complex. high spin complex with

All electrons are paired four unpaired electrons
(diamagnetic) (paramagnetic)

FigThe hexacyano complex of Fe(II) is low spin

and diamagnetic. The hexaaqua complex is
high spin and paramagnetic.

Catalytic roles of iron and its ions

Most transition metals, or their ions or compounds are catalytically active.

 Iron metal (or iron (III) oxide) is used as a heterogeneous catalyst in the Haber process
for the manufacture of ammonia from hydrogen and nitrogen gases. The metal uses its
 939

partially filled d orbitals to attract electron density in the reactant molecules. This causes
the
reactant molecules to adsorb onto the surface of the catalyst. As a result

(i)the bonds in the reactant molecules are weakened. Activation energy of the
reaction is therefore lowered.
(ii)reactant molecules are brought closer together on the surface of the catalyst.
New bonds can easily be formed and the reaction no longer depends on random
collisions of reactant molecules. The rate of reaction is thus increased.

 Fe2+(aq) or Fe3+(aq) can be used to speed up the reaction between peroxodisulphate and
iodide ions.

S2O82-(aq) + 2I-(aq)  2SO42-(aq) + I2(aq)

This reaction involves particles of the same charge. Such ions do not have a tendency to
collide, but instead, they repel each other. The reaction therefore has a very high
activation energy and is therefore very slow. Fe2+(aq) or Fe3+(aq) creates an alternative
reaction pathway with a very low activation energy since the reacting ions are of opposite
charge.
Please revisitSection, page for details of this reaction.

The chemistry of metallic iron

Most metals, including iron, have large negative reduction potentials. In other words, most metals are
highly electropositive, that is, they have a high tendency to lose electrons during chemical reactions. The
reduction potential for iron is -0.44

Fe2+ + 2e-Ý Fe Eθ = -0.44V

Iron is therefore subject to oxidation by oxidizing agents such as chlorine and a mixture of oxygen and
water. Most transition metals do not corrode in oxygen and water because they are protected by a tough
and impervious oxide layer. Iron is not protected in this way because iron (III) oxide that forms on the
surface of the metal is non-tenacious (does not stick firmly to the metal) and it is porous. It allows further
entry of oxygen and water, causing the rest of the metal to rust.
Metallic iron is also easily oxidized by strong acids, for example, iron fillings dissolve gradually in the acid,
with a steady liberation of bubbles of hydrogen gas.

Fe(s) + 2H+ (aq)  Fe2+ (aq) + H2 (g) Eθ= +0.44V

The rusting of iron

Rusting is the name given to the corrosion (oxidation) of iron by a combination of water and oxygen. It is
an electrochemical process, that is, it involves anodic regions where iron isoxidized and cathodic regions
where oxygen and water are reduced(Fig). Electrical circuits are set on the surface of the metal, which
allow electrons to flow through water from the anodic to the cathodic sites.
Formation of anodic and cathodic sites is a result of inconsistencies on the surface of the metal, which
cause some sites to become deficient in oxygen (anodic sites) and others to be well aerated (cathodic
sites).
 940

moist metal

cathodic site
anodic site
O2 + 2H2O + 4e- 4OH-
2Fe 2Fe2+ + 4e-

The OH- ions formed at cathodic sites and Fe2+ ions formed at anodic sites attract each other and combine
to form a precipitate of iron (II) hydroxide.

Fe2+(aq) + 4OH-(aq)  2Fe(OH)2(s)

The iron (II) hydroxide is immediately oxidized in oxygen to form iron (III) hydroxide, which is a
yellowish brown solid. Dehydration of iron (III) hydroxide results in the formation of rust (hydrated iron
(III) oxide).

O2
Fe(OH)2(s) Fe(OH) 3 (s) Fe2O 3 .xH2O
rust
(red - brown)

Rusting of iron can be rapid because a large number of electrochemical cells are simultaneously formed
on the surface of the metal. Some conditions can accelerate the rusting of iron.

(i)Salty water (e.g sea water) rapidly increases the rate of reaction by acting as a good electrolyte
for the transfer of electrons from anodic to cathodic sites.
(ii)Differential exposure of iron to air initiates rusting by creating regions that are deficient in
oxygen ( anodic sites). This results in the oxidation of Fe2+ to Fe3+. The electrons produced at the
anodic site then flow to the oxygen rich (cathodic) sites.
The rusting of iron is therefore faster when one part of the metal is exposed to and the other is
partially hidden from air.

Methods of preventing rusting

Rusting is undesirable because it weakens iron objects and makes them unsightly. Several methods can be
used to prevent or reduce the rate of rusting.

Barrier methods
These methods involve covering the surface of the metal with a tough impermeable substance which
prevents entry of oxygen and air. Barrier methods include painting and electroplating, in which an
electrolytic process is used to introduce a thin layer of a second metal on the surface of the iron object.
The metal used for electroplating must be resistant to attack by oxygen and water, for example copper and
chromium.
 941

Alloying
Stainless steel is an alloy of iron whose resistance to corrosion is due to the presence of chromium.
Formation of a tough and impermeable layer of Cr2O3 (chromium (III) oxide) on the surface of the steel
object prevents entry of oxygen and water. This method is therefore similar to the barrier
methods discussed above. The difference is in how the barrier is introduced onto the surface of the metal.

Sacrificial protection
In this method, the iron or steel object is brought into contact with a more reactive metal (one which is
higher than iron in the electrochemical series). It is this reactive metal which is attacked by oxygen and
water instead of iron. Two commonly used methods of sacrificial protection are galvanizing and cathodic
protection. Galvanizing is achieved by dipping a steel object into molten zinc. If a break in the zinc coat
exposes the steel to the atmosphere, it is the zinc which will corrode, not the iron. Steel roofing sheets are
protected in this way.
Cathodic protection involves attaching the iron or steel object to a block of a reactive metal, for
example magnesium. The oxidation of iron to iron (II) is prevented since this anodic reaction now takes
place on the more reactive metal.

Use of chemical inhibitors

These are chemicals which stop or slow the anodic or cathodic reactions that take place on the surface of
an iron object. Hydrogen carbonate can be used as a cathodic inhibitor. It removes OH - ions that are
generated in cathodic reactions, resulting in the formation of an insoluble carbonate.

HCO3-(aq) + OH-(aq)  CO32-(aq) + H2O(l)

Formation of an insoluble layer of metal carbonate prevents further entry of oxygen and water, and in
turn this stops the cathodic reaction. Inhibition of the cathodic reaction also stops the anodic reaction.
This is because oxygen and water are not available any more to accept electrons that are produced at the
anodic sites.

The biochemical importance of iron

Iron is one of the major metals found in the human body. It is found in the form of Fe(II) in haemoglobin
and cytochrome oxidase.

Haemoglobin, found in red blood cells, is responsible for the transportation of oxygen from the lungs to
the rest of the body. The basic functional unit in haemoglobin is a molecule known as haem(Fig ). This is a
complex which contains Fe (II) at its centre. It is this iron which binds oxygen ligands at the lungs,
allowing them to be carried to the tissues. The Fe-O2 dative bond is weak and its formation in is favoured
by the high partial pressure of oxygen in the lungs. In the tissues, where the concentration of oxygen is
low, the bond breaks, thus allowing oxygen to be delivered to the cells. Each haemoglobin molecule
contains four haem groups and therefore can transport four molecules of oxygen.
 942

.. .O.2

.. .. .. ..
O2 oxygen atoms labelled
1 to 4 come from a
single ring shaped
.. .. .. .. non-protein molecule

Nitrogen 5 comes from

a protein chain

.. ..

At the lungs, oxygen At the tissues, oxygen is released

is picked up and water and water is picked up
is released

As you can see from the diagram above, haem has five permanent dative bonds and a sixth co-ordination
site which can bond reversibly to oxygen and water. Unfortunately, this site is not so selective, and it can
bind other types of ligands. Cyanide and carbon monoxide, well known respiratory poisons, can bind
strongly to this site, thus preventing transportation of oxygen.

Cytochrome oxidase is an enzyme that is involved in electron transfer during respiration in the
mitochondrion. Respiration is essentially an oxidation process, involving loss of electrons from the
respiratory intermediates. Respiration only works if the electrons lost by the intermediates can flow along
the respiratory chain. Electron transfer agents such as cytochrome oxidase are therefore important in
respiration. The haem group is also found in cytochrome oxidase, and it is iron (II) at the centre of the
haem group that gives cytochrome oxidase its ability to act as an agent of electron transfer.

Summary of the chemistry of iron

 There are three main oxidation states, +2, +3 and +6. The +6 state is the least stable and it is
easily reduced to Fe(III).
 The +3 state is the most stable oxidation state. In aqueous solution it has a yellowish brown
colour and it is acidic due to hydrolysis.
 The +2 state, which has a light green colour in solution, is quite unstable with respect to
oxidation to the +3 state. This oxidation is rapid in alkaline medium. However, in acidic
medium, Fe2+ is significantly stabilised through kinetic factors.
 All oxidation states of iron exhibit paramagnetism except in some low spin complexes of iron
(II).
 Rusting is the oxidation of iron by a mixture of water and oxygen. This process is
electrochemical in nature and it is caused by inconsistencies on the surface of the iron object.
 943

Cobalt

Atomic number: Z= 27

Configuration: [Ar] 3d74s²

Stable oxidation states: +2and +3

More stable oxidation state :+2

The chemistry of cobalt is dominated by the +2 and the +3 oxidation states, with the +2 being by far more
stable.

Ion Colour in Remarks

aqueous
solution

Co2+ pink Stable in aqueous solution and not easily oxidized to Co(III), but is
destabilized by addition of ligands such as ammonia and oxalate, and by
increasing pH. Under such conditions, Co(II) is easily oxidized in air to form
Co(III).

Co3+ blue Very unstable in aqueous solution. Easily reduced by water to Co(II).
However, it can be stabilized by the presence of ligands such as ammonia
and oxalate.

Electrode potentials given in Table give some useful insights into the chemistry of cobalt(II) and Co(III).

Consider what happens when aqueous ammonia is gradually added to a solution of Co(II) until in excess.
A blue precipitate of Co(OH)2 is formed which dissolves in excess ammonia to form a pale brown
solution. On standing in air, the solution becomes darker brown. What happens is that as soon as cobalt
(II) is complexed to ammonia ligands, it becomes unstable and is easily oxidized by oxygen to form the +3
amine complex.
 944

NH3 (aq) xsNH3 (aq)

[Co(H2O)6]2+(aq) Co(OH) 2(s) [Co(NH 3 )6]2+(aq)

pink blue golden brown

O2

[Co(NH3 )6]3+(aq)

dark brown

Comparing equations (1) and (2)

Reduction potentials involving Eθ/V Reading equation (1) reverse gives you the half
cobalt equation for the oxidation of Co(II) to Co(III) in
aqueous solution. The electrode potential for this
1 [Co(H2O)6]3+ + e-Ý [Co(H2O)6]2+ +1.81 conversion, -1.81V, shows that Co(II) is much more
stable in aqueous solution than Co(III). You can
2 [Co(NH3)6]3+ + e-Ý [Co(NH3)6]2+ +0.11 verify that oxygen can not oxidize a solution of
Co2+(aq) to Co3+(aq)(refer to equation 5 or 6).
3 Co2+ + 2e-Ý Co -0.29 It can also be said that since the +3 state is much
more unstable than Co(II), there is a strong
tendency for Co(III) to be reduced to the stable
Co(II). In other words, Co(III) is strongly oxidizing
Other systems in aqueous solution. This is exactly what you expect
in view of the large and positive reduction potential
4 Cr2O72- + 6e- + 14H+Ý 2Cr3+ + 7H2O +1.33
for Co3+/Co2+ (equation 1).
In the presence of ammonia ligands (equation 2),
5 O2 + 4H+ + 4e-Ý 2H2O +1.23
the electrode potential for the conversion of Co(II)
to Co(III) is -0.11V. This value is much more
6 O2 + 2H2O + 4e-Ý 4OH- +0.4
0 positive, showing that the effect of ammonia
ligands is to destabilize Co (II) with respect to
7 CoO(OH) + e-Ý Co(OH)2 +0.17 oxidation.

Table Electrode potentials for cobalt

8 2H+ + 2e-Ý H2 0.00
and for other systems

The stability of Co (II) is also affected by pH. If the pH is made alkaline by adding NaOH (aq) or a limited
amount of NH3(aq), [Co(H2O)6]2+ is converted to Co(OH)2(s), but on standing in air this off white
precipitate immediately turns blue due to oxidation to cobalt (III) hydroxide.
Co(III) as an oxidizing agent
In aqueous solution, Co(III), which is almost colourless, is so strongly oxidizing that it can easily be
reduced by water and by Cr3+ ions. Consider what happens when green Cr3+(aq)is added to a solution
containing Co3+ ions. The green colour of the reaction mixture immediately changes to orange, showing
that Cr3+ is oxidized by Co3+ to dichromate. Using equations (1) and (4) in Table gives the net reaction
and cell potential.
 945

6Co3+(aq) + 2Cr3+(aq)+ 7H2O(l) Ý 6Co2+(aq) + Cr2O72-(aq) + 14H+(aq)

Eθcell = 1.81 - 1.33 = +0.48V

Also note that a strongly acidic solution is formed.

Preparation of Co(III) complexes

Early attempts to prepare such complexes were met with difficulty due to the fact that in water Co(III) is
very unstable and is easily reduced by water to form the more stable Co(II).
Using equations (1) and (5):

4[Co(H2O)6]3++ 2H2O  4[Co(H2O)6]2+ +O2 + 4H+

Eθcell = 1.81 - 1.23 = +0.58V

When Co(III) is added to water, its blue colour disappears and is replaced by the pink of Co(II). Bubbles
of oxygen are also produced and the solution becomes acidic. This shows that Co(III) is strongly oxidizing
in aqueous solution.
Despite this difficulty, Co(III) complexes are now fairly easy to prepare for two reasons:

(i)Co(II) can easily be oxidized in air to Co(III) by replacing water ligands with other ligands such
asammonia.
(ii)Cr(III) is stabilized by replacing water ligands with other ligands such as ammonia.

A chromium (III) complex can therefore be prepared by adding the ligand of choice to Co 2+(aq). As soon
as Co(II) takes up these ligands, it becomes unstable with respect to oxidation. It is then easily oxidized to
Co(III), for example, by hydrogen peroxide or by simply leaving it in air. Once formed, the Co(III)
complex is stabilized by the presence of non-water ligands, so it does not revert back to Co(II). Consider
the preparation of the Co(III) oxalate complex [Co(C2O4)3]3-.

3C2O 42-
[Co(H2O)6 ]2+(aq) Co(C 2O 4)3]4- [Co(C 2O 4)3]3-

stable aqua complex unstable oxalato complex stable oxalato complex

The kinetic stability of non aqua Co(III) complexes has made it possible to prepare a wide range of
octahedral Co(III) complexes exhibiting different forms of isomerism, just as seen for Cr(III). Here are
examples
 946

[Co(NH3 )4Cl2]+

.. ..

.. .. .. ..

.. ..
.. ..
.. ..

green deep violet

FigCis - trans isomerism

[Co(C2O 4)3 ]3-

Fig Optical isomerism

Cobalt(II) complexes

Cobalt (II) forms pink octahedral and blue tetrahedral complexes. An good illustration is the conversion
of the pink hexaaqua [Co(H2O)6]2+ to the blue tetrachloro [CoCl4]2- complex. A dilute solution of cobalt
(II) chloride has a pink colour, showing that the predominant species is [Co(H 2O)6]2+. Increasing
 947

concentration of Cl- ligands (by heating or by adding concentrated HCl) causes the solution to change to
blue. This shows that the predominant species is now [CoCl 4]2-. Diluting the blue solution (adding more
water ligands) reverses the change and the solution becomes pink once more.

.. 2+
.. 2-

.. .. conc HCl
or heat

H2O

.. .. .. ..
..
..

octahedral tetrahedral
pink blue

This conversion is the basis for the chloride paper test for water. This paper is impregnated with
cobalt(II) chloride. The Co(II) in the paper is complexed to chloride ligands and so appears blue. In the
presence of water, the hexaaqua complex is formed by ligand exchange, and this causes the colour to
change to pink.

Commercial uses of cobalt and its compounds

(i)Ores of cobalt are used in the manufacture of pigments for use in ceramics and paints.
(ii) Cobalt metal is used in the manufacture of heat resistant alloys gas turbines.
(iii) Cobalt metal is also used in the manufacture of an alloy known as ALNICO (Aluminium, Nickel,
Cobalt). This alloy is used in the manufacture of very powerful permanent magnets.

The biological importance of cobalt

Co(III) is required for the formation of vitamin B12, an extremely important nutrient required for the
formation of blood. It is also an important co-enzyme (enzyme helper) in many metabolic processes,
including respiration.

Summary of the chemistry of cobalt

 The main oxidation states are +2 and +3

 The +2 state is very stable in aqueous solution and shows no tendency to be oxidized in air to
the +3 state. However, an alkaline pH or presence of other ligands such as oxalate and
ammonia greatly destabilizes the +2 state with respect to oxidation.
 The +3 state is highly oxidizing and very unstable in aqueous solution. It is easily reduced by
water to form Co(II). Oxygen is liberated in the process.
 948

 The +3 state is stabilized by other ligands such as ammonia and oxalate. Such complexes are
only weakly oxidizing and can stay unchanged for a long time. However, simple ligands such
as F- can not stabilize Co(III).
 Complexes of Co(II) are either pink and octahedral or blue and tetrahedral.
 Many non-aqua complexes of Cr(III) are octahedral and kinetically stable. This inertness of
the Co-Ligand bond in such complexes gives rise to different forms of isomerism.
 Cobalt (as Co(III)) is biologically important as it is required for the formation of vitamin B 12

Nickel

Atomic number: Z= 28

Configuration:[Ar] 3d84s²

Stable oxidation state in aqueous solution: +2(green)

Paramagnetism: octahedral complexes of Ni2+ are paramagnetic, whereas square planar

complexes are diamagnetic

Nickel occurs in the earth’s crust in the form of sulphide ores. The stages involved in the extraction of
nickel metal from the sulphide ore are

(i)Roasting of the oxide in air. This converts the sulphide ore into the metal oxide.

(ii)Reduction of the metal oxide by carbon. This results in the formation of impure nickel metal.

(iii) Purification of the metal. This can be achieved electrolytically or by the Mond process.

Electrolytic purification involves making the impure nickel metal the anode in an electrolytic
cell containing pure nickel cathodes and an electrolyte of nickel (II) sulphate. The anodes
dissolve in the process, liberating Ni2+ ions, which then migrate to the cathodes. At the cathode,
Ni2+ ions are reduced to pure nickel metal, which is deposited on the cathodes.

Purification of nickel by the Mond process

(i) Nickel is heated at 600Cin the presence of carbon monoxide. This results in the formation of a
volatile neutral complex, tetracarbonyl nickel (0), in which the metal has an oxidation state of
zero.

Ni(s) + 4CO(g)  Ni(CO)4(l)

(ii)Ni(CO)4 is distilled out and then heated at 2000C. This causes it to decompose back to pure
nickel and carbon monoxide. Impurities are lost during the decomposition process, so the nickel
formed is very pure.

The tetrahedral complex Ni(CO)4 is unusual in that the central metal is neutral (oxidation state 0).

Redox chemistry
Ni2+ (aq) is very stable and can not be oxidized in air. You can use a relevant data from the Data Booklet to
verify this.
The reduction potential for Ni2+(s)/Ni(s) is negative
 949

Ni2+(aq) + 2e-Ý Ni(s) Eθ/V = -0.25V

Nickel metal is therefore oxidized by dilute acids, resulting in the formation of green solutions containing
Ni2+, and liberating hydrogen gas in the process.

Complexes
Ni2+ forms both six co-ordinate (octahedral) and four co-ordinate complexes. The four co-ordinate
complexes usually have a square planar geometry, but a few tetrahedral complexes are known. Here are
examples.

Complex Shape and bond angle colour

[Ni(H2O)6]2+ octahedral, 900 green

[Ni(NH3)6]2+ octahedral, 900 blue

[Ni(CN)42- square planar, 900 yellow

[NiCl4]2- tetrahedral, 1090 blue

Some four co-ordinate complexes of nickel show a form of isomerism which is unusual among transition
elements. This form of isomerism, known as structural isomerism, occurs when two compounds share
the same molecular formula but differ in their geometry. An example is provided by complexes with the
molecular formula Ni(Cl)2(R3P)2 (Fig ), where R3P is an organic phosphorous compound.

..

.. ..

.. .. .. ..
..

square planar tetrahedral

diamagnetic paramagnetic

Note that the square planar complex itself exhibits cis - trans (geometric) isomerism. The diagram shows
the non-polar trans isomer.
 950

Tests for nickel (II)

The reactions of nickel with NaOH (aq) and NH3 (aq) are predictable. With sodium hydroxide, a green
precipitate of nickel (II) hydroxide is formed, which is insoluble in excess of the reagent. With ammonia, a
green precipitate is formed which dissolves in excess of the reagent to give blue hexamine complex.
The most reliable and sensitive test for the presence of Ni2+ involves adding dimethylglyoxime. A bright
red precipitate indicates the presence of nickel (II).

Uses of nickel metal

(i)in alloys
Important alloys that contain nickel include
 Nichrome (60% Ni and 40% Cr), which is used for making high resistance wires.
 ALNICO which is used in the manufacture of powerful permanent magnets. The alloy also
contains aluminium and cobalt.
 Stainless steel. Ni is strong, resistant to corrosion and high temperatures. It imparts these
properties to steel.
 Cupronickel (20% Ni and 80 % Cu) which is used to make ‘silver coins’.

(ii) Industrial catalyst

Ni is commonly used in reactions which involve addition of hydrogen to a raw material, for
example, hydrogenation of oils in the manufacture of margarine. This process involves addition
of hydrogen to the double bonds in the liquid oil molecules. Nickel uses its d - orbitals to attract
electron density from the reactant molecules. Adsorption of the reactants on the surface of the
catalyst brings them closer and also weakens their bonds. This weakening of bonds lowers
activation energy and makes the reaction faster.

Summary of the chemistry of nickel

 The main oxidation state is +2, which is green in aqueous solution.
 Most complexes are square planar or octahedral, but a few tetrahedral complexes are known.
 Octahedral and tetrahedral complexes are paramagnetic whereas square planar complexes are
diamagnetic.

Copper

Atomic number: Z= 29

Configuration:[Ar] 3d104s1

Possible oxidation states in compounds: +1 and +2

Stable oxidation state in aqueous solution:+2

Paramagnetism: Cu (I) compounds are diamagnetic (d10), copper (II) compounds are
usually paramagnetic.
 951

Copper occurs in the earth’s crust in the form of copper (I) sulphides, copper (I) oxides and copper (II)
carbonates. The sulphide ores are the major sources of copper. The extraction of copper from the
sulphide ores is similar to the extraction of nickel. The sulphide ore is roasted in air, which drives out
sulphur as sulphur dioxide and results in the formation of copper (I) oxide.

2Cu2S + 3O2 2Cu2O + 2SO2

Further reaction between copper (I) oxide and unconverted copper (I) sulphide causes reduction to of
Cu(I) to form an impure form of copper known as blister copper.

Cu2S + 2Cu2O  6Cu + SO2

Purification of blister copper is achieved by electrolysis. The impure copper is made the anodes in an
electrolytic cell containing pure copper cathodes and an electrolyte of copper (II) sulphate. During the
process, the impure copper anodes dissolve, liberating Cu 2+ ions which are attracted to the cathodes. At
the cathodes, the copper (II) ions are reduced to pure copper, which sticks onto the cathodes. The
cathodes therefore become thicker with pure copper whilst the anodes are gradually dissolved.
Some impurities that are removed by this method include silver and zinc.

 The reduction potential for Ag+/Ag is +0.80 and that for Cu2+/Cu is +0.34. In other words, silver
is lower in the electrochemical series than copper. As a result, silver present in impure copper is
not oxidized to Ag+ at the anode. It can not therefore enter the solution, but it sinks to the bottom
of the cell as metallic silver.
 Zinc is higher up in the electrochemical series (its reduction potential is more negative). Since it is
above hydrogen, it is easily oxidized at the anode to form Zn 2+. However, zinc, being a very
reactive metal, can not be discharged at the cathode, so it remains in solution.
If you find yourself somewhat lost, you should revisit section, page

Aqueous ions
The +1 state is very unstable in water, in which it would be colourless due to its d 10 configuration. Since all
of the d - orbitals are exactly filled; d-d transitions which are responsible for absorption of light energy
and formation of colour are not possible. Cu(I) is unstable in water through disproportionation. It rapidly
undergoes simultaneous oxidation to Cu2+ and reduction to copper metal. The +1 state of copper is only
stable in insoluble copper (I) compounds such as Cu2S and Cu2O.
The +2 state is very stable in aqueous solution, in which it has a sky blue colour due to the hexaaqua
complex [Cu (H2O) 6]2+.

Redox chemistry
Table provides useful insights into the chemistry of copper. Copper is unique among the first row
transition elements in that it forms a large number of stable compounds containing the +1 state. These
compounds have one thing in common; they are all insoluble in water. In fact, it is this insolubility which
stabilizes the +1 state. In aqueous solution, Cu(I) is very unstable and rapidly disproportionates to copper
metal and Cu2+. Most Cu(I) salts are white in colour, which is expected since Cu(I) has a an exactly filled
d10 configuration which does not allow absorption of light through d -d transitions.

Reduction potential Eθ/V

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1 Cu+(aq) + e-Ý Cu(s) +0.52

2 Cu2+(aq) + 2e-Ý Cu(s) +0.34

3 Cu2+(aq) + e-Ý Cu+ (aq) +0.15

Table Redox potentials
involving copper

 The positive reduction potential of Cu2+/Cu shows that is below hydrogen in the electrochemical
series. Metals that are above hydrogen have negative reduction potentials. Such metals are good
reducing agents and can be oxidised by dilute acids to form stable positive ions. Copper has no
reaction with dilute acids, as shown by the negative cell potential for the oxidation process

Cu(s) + 2H+(aq)  Cu2+(aq) + H2(g) Eθ = -0.34V

However, concentrated nitric acid can oxidize copper metal to a blue solution containing copper
(II) nitrate. During the process, some nitrate ions are reduced to brown fumes of NO 2. The other
product of the reaction is water.

 Inspection of reactions (2) and (5) shows that Cu(I) is unstable in aqueous solution due to
disproportionation. Reversing reaction (5), which has the less positive reduction potential, and
adding it to reaction (2):

2Cu+(aq) Ý Cu(s) + Cu2+(aq) Eθ = 0.52 - 0.15 = +0.37V

For example, dissolving the white solid copper (I) sulphate in water does not produce the
expected colourless solution. Instead, a blue solution of Cu 2+ and a pink deposit of copper metal
are produced.

Cu2SO4(s)  Cu(s) + CuSO4(aq)

Redox reactions involving copper (II)

(i) A metal which is higher in the electrochemical series can be used to reduce Cu(II) to copper metal.
Such metals have negative reduction potentials, that is, they are unstable elative to their ions. Such metals
are said to electropositive since they readily form positive ions. Thus Cu2+ ions are reduced by adding iron
metal.

Cu2+(aq) + Fe(s)  Cu(s) + Fe2+(aq)

Using a Data Booklet, it can be shown that the cell potential of the reaction is +0.78V.
This is an example of a redox displacement reaction. Ions of the less reactive metal (copper) act as an
oxidizing agent, whilst the more reactive metal (iron) acts as a reducing agent. You can easily check out
this reaction in the lab by putting an iron nail in a solution of CuSO 4. After some time, the nail is coated
pink, showing that copper metal has been deposited on it. Meanwhile, the blue colour of CuSO 4 (aq) fades
is and may assume a greenish colour due to the presence of Fe 2+(aq). You can confirm the presence of Fe2+
at the end of the experiment by using KMnO4(aq).
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(ii)Copper (II) can be reduced to insoluble copper (I) compounds. A well known example is the reduction
of Cu2+ in Fehling’s solution by aldehydes. Fehling’s solution contains copper (II) complexed to tartrate
ions in the presence of NaOH (aq). During the reaction, the aldehyde group is oxidized by Cu 2+ to form a
carboxylate. Meanwhile, Cu2+ is reduced to Cu(I) which is converted to the insoluble brick red copper (I)
oxide, Cu2O by the alkaline environment and by heating.
The Fehling’s solution test is routinely used to test for the presence of a reducing sugar, for example
glucose. Such sugars are known as aldoses because they contain an aldehyde group. Ketoses are sugars
that contain a ketone group. Such sugars give a negative test with Fehling’s solution. An example of such a
sugar is fructose, which is an isomer of glucose.

Another interesting reaction in which Cu (I) is stabilized by formation of an insoluble compound is the
reduction of Cu2+by iodide ions. I-ions reduce Cu2+ ions to copper (I). Meanwhile some of the iodide ions
are oxidized to iodine.

2Cu2+(aq) + 2I-(aq) Ý 2Cu+(aq) + I2 (aq) ... (i)

If you calculate the cell potential for this reaction, you will find that it is 0.15 - 0.54 = -0.39V. In other
words, we do not expect the reaction to take place since it has a negative cell potential. In practice the
reaction occurs without any difficulty because as soon as the unstable Cu +(aq) ions are formed, they are
stabilized through precipitation with unreacted iodide ions.

2Cu+(aq) + 2I-(aq)  2CuI(s) ... (ii)

Removal of Cu+ from equilibrium (i) causes the equilibrium to shift to the right (Le Chatelier’s principle).
In this way, the reduction of Cu2+ goes to completion. The net reaction between Cu2+(aq) and iodide ions
is often conveniently expressed as one equation by combining reactions (i) and (ii).

2Cu2+(aq) + 2I-(aq) Ý2Cu+ (aq) + I2 (aq) ... (i)

2Cu+ (aq) + 2I-(aq)  2CuI(s) ... (ii)

net reaction 2Cu2+(aq) + 4I-(aq)  2CuI(s) + I2 (aq) ... (iii)

Reaction (iii) shows us the key facts at a glance. When Cu2+ reacts with iodide ions, a white precipitate of
insoluble copper (I) iodide and a brown solution of iodine is formed. However, this reaction masks very
important details about the reaction:
 It does not make it apparent that the reaction proceeds via formation of an unstable Cu +(aq)
intermediate.
 It hides the fact that two types of reactions are involved, a redox reaction in which Cu2+ is reduced
to Cu+ and a precipitation reaction in which iodide ions combine with Cu + to form the stable and
insoluble copper (I) iodide.

The amount of iodine produced in reaction (iii)can be estimated quantitatively by titration with sodium
thiosulphate. In this reaction, iodine acts as an oxidizing agent, converting thiosulphate ions, S2O32-, to
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tetrathionyl, S4O62-. .Meanwhile, the iodine is reduced back to iodide. This reaction forms the basis for the
quantitative estimation of Cu (II) ions by back titration.

2Cu2+ (aq) + 4IÈ(aq) 2CuI(s) + I2(aq)

2S2O32- (aq) + I2 (aq) 2IÈ(aq) + S4O62- (aq) … reduction of iodine back to iodide

Q
A 0.250 g sample of a copper-containing alloy was converted into an aqueous
solution of Cu2+ ions, and an excess of I–(aq) ions was added. The iodine
liberated required20.0 cm3 of 0.100 moldm–3 thiosulphate to react
completely.

What is the percentage of copper in the alloy?

Solution :
50.8%

ligand exchange and precipitation reactions of Cu2+ (aq)

The common geometry for Cu(II) complexes is octahedral and tetrahedral. A well known example of a
tetrahedral Cu(II) complex is the yellow [CuCl4]2-.
Cu2+(aq) can be prepared by dissolving black copper oxide in a strong acid or by dissolving a soluble
copper (II) salt such as copper (II) sulphate. In aqueous solution, Cu 2+ has a sky blue colour. Table
summarizes some reactions of Cu2+(aq).

Reaction with Observations Notes

dil HCl followed by Solution turns from light blue to Warming drives out some
warming yellowish- green. water and thusincreases
concentration of Cl- ligands,
resulting in the formation of the
yellow complex CuCl42-by ligand
exchange. The greenish-yellow
colour is caused by the mixing of
colours, the blue of Cu2+(aq) and
the yellow of CuCl42 -.
[Cu(H2O)6] 2++ 4Cl-CuCl42 -

conc HCl Same as above. Ligand exchange occurs

[Cu(H2O)6] 2++ 4Cl-CuCl42 -
No warming is required.
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dilute NaOH(aq) Pale blue precipitate formed, Precipitation of Cu2+ by OH-

insoluble in excess NaOH. ions.
Cu2+ + 2OH-Cu(OH)2(s)
No soluble complex is formed
upon addition of excess NaOH.

dilute NH3(aq) A pale blue precipitate isformed, [Cu(H2O)4(OH)2](s) is first

soluble in excess NH3 to give a precipitated. The precipitate then
deep blue solution. reacts further with NH3
molecules in a ligand exchange
reaction, to form the deep blue
complex [Cu(NH3)4(H2O)2]2+.
[Cu(H2O)4(OH)2](s) + 4NH3
[Cu(NH3)4(H2O)2]2+(aq) + 2H2O

Na2CO3(aq) A blue -green precipitate is CO32- ions precipitate Cu2+ as the

formed insoluble CuCO3.

Followed by a dilute Brisk effervescence. A colourless

acid The precipitate is decomposed by
gas is produced which turns lime
acid.
water from clear to milky. A light
blue solution is formed. CuCO3(s) + 2H+(aq) Cu2+(aq)
+ CO2(g) + H2O(l)

Reaction with Observations Notes

Concentrated HCl Solution turns greenish - yellow CuCl42- is formed.

followed by The greenish - yellow colour is Ammonia is a stronger field

concentrated ammonia immediately replaced by a deep ligand than chloride. Therefore
blue colour. Cl- ligands in CuCl42- are replaced
by ammonia, resulting in the
formation of a more stable
complex. The new complex
formed has a higher stability
constant, so its formation is
favoured.
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[CuCl4]2- + 4NH3 + 2H2O

yellow

 [Cu(NH3)4(H2O)2]2+ + 4Cl-
deep blue

followed by EDTA4- The blue colour becomes lighter.

EDTA4-is a stronger field ligand
than ammonia. EDTA4-ligands
therefore replace NH3 in the
complex [Cu(NH3)4(H2O)2]2+ ,
resulting in the formation of the
light blue complex [CuEDTA]2-.
This complex has a very large
stability constant which favours
its formation.

Uses of copper

 Being a relatively cheap metal which is also resistant to corrosion, it is used in electrical cables.
 It is used in the manufacture of alloys, including brass and bronze.
Bronze is an alloy of copper and tin. It has greater tensile strength than copper. It can also be
cast into moulds more easily. For this reason, it is used to make sculptures. Other uses of bronze
include

1.For electrical connectors (it is a better conductor than most steels)

2. Boat and ship propellers (It is resistant to corrosion)

Brassis an alloy of copper andzinc. It is harder and stronger than copper. Its colour makes it
decorative. The uses of brass include

1. Making musical instruments (brass has excellent acoustic properties)

2. In ornaments

 Copper is used in car radiators because it is resistant to corrosion and it is also a goon conductor
of heat.
 Complexed Cu(II) is used in alkaline solution in the Fehling’s and Benedict’s test for aldehydes,
for example, reducing sugars.

Summary of the chemistry of copper

 The main oxidation states of copper are +1 and +2.
 The + 2 state is the more stable in aqueous solution. The +1 state is unstable in water through
disproportionation. However, it can be stabilized by being incorporated into insoluble compounds
such as copper (I) iodide , copper (I) sulphide and copper (I) oxide.
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 Copper (I) compounds are diamagnetic whereas copper (II) complexes are paramagnetic
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