LECTURE NOTE

GENERAL CHEMISTRY II

DEVELOPED BY

AMEH PETER O. MOSES

Bsc, Msc Phd.
ameh3@yahoo.com

OBODO STUDY CENTRE

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 1. SOLUTIONS
Introduction
1. A solution is a homogenous mixture of two or more substances. It mayalso be
defined as a mixture of two or more substances in a single phase.
2. A sample of matter that is uniform in chemical composition and physical state
constitutes a state of homogeneity and can be describes as being ina single phase;
examples include water (liquid), water (vapour), ice, salt water, etc.
3. If a sample of matter consists of more than one phase, it is conveniently described
as a heterogeneous system, e.g. mixture of ice and water.
4. Types of solutions
a. Solid-solid Solution
e.g. Alloys - a homogeneous mixture of two or more metals.
b. Liquid-liquid solution
e.g. mixture of ethanol and water or any other completelymiscible
liquids.
c. solid-liquid solution
e.g. sodium chloride in water
d. Gas-liquid e.g. soft drink (CO2 in water)
5. When a solution is formed, the component that is in excess is called the solvent
while the other component is the solute. Water is perhaps the most widely used solvent,
and the study of aqueous solutions is of great importance.
6. As solutions are mixtures, they must therefore possess properties which depend
on the properties of their constituents and on the relative quantities of each of the
constituents present. For example, the freezing points of 1M and 2M sugar
solutions in water are different.

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7. In the study of solutions, one of the chief objectives is to ascertain how the
properties of a solution depend on its constitution.
8. Solutions which contain relatively small quantities of solute are said to be dilute.
PROPERTIES OF SOLUTIONS
The properties of solutions are ordinarily those of solvents which have been modified by
the presence of solutes. These properties include vapour pressure, refractive index,
melting point and boiling point. Thus, the study of solution properties is essentially the
study of how the presences of solute molecules modify the properties of the solvent.
IDEAL SOLUTIONS
An ideal solution is defined as one which can be formed from its componentswith no
evolution or absorption of heat, and whose volume is the sum of the volumes of the
individual constituents. These criteria imply that the forces of attraction of solute
particles for solvent particles are equal in magnitude to the forces of attraction of solvent
molecules for each other, and of solute particles for each other. If the attractions
between solute molecules and solvent molecules are larger or smaller compared to the
attractions between like molecules in the mixture, energy is released or absorbed and
such a solution is no longer ideal.
A mixture of benzene and methyl benzene (toluene) form almost an ideal solution.
In general, however, dilute solutions are assumed to have the properties of ideal
solutions.
Ways of Expressing Concentration
There are various ways to express the concentration of a solution. The four most
convenient ways for a chemist are:
1. Gram concentration = Number of grams of solute
1dm3 of solution

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 2. Molarity =Number of moles of solute
1dm3
3. Molality =Number of moles of solute
1kg of solvent
4. Mole Fraction =Number of moles of a component
Total number of moles (solute +solvent)
You are already quite familiar with gram concentration and molarity, however,
the terms molality and mole fraction may be new to you and so their meaning
and importance are discussed in the next section.
3 TEMPERATURE - INDEPENDENT CONCENTRATION UNITS
The term concentration is used to describe the quantity of solute in a given
quantity of solution. Molarity and normality are concentration terms used in specifying
the amounts of solute in a given volume of solution. However, it is known that volume of
solutions change with temperature and therefore the temperature must be specified when
these concentration units are used.
The concentration units which are not affected by temperature are: mole fraction
and molality. They are used in the specification of amounts of both solute and solvent in
a solution. More importantly, they are used in describing the properties of the solution
as a whole or describing how the properties of a solvent are affected by the presence of
dissolved solute.
If a solution is composed of several constituents, A,B,C... the mole fraction of
constituents A is denoted nA and is equal to the number of moles of component A
divided by the total number of moles present. No particular component needbe labelled
solvent in order to use the mole fraction concept. It follows from the

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definition of a mole that the mole fraction of a constituent is also the ratio of the number
of molecules of that substance to the total number of molecules of all species present.
nA= moles A
Total moles
Similarly,
nB = moles B

Total moles etc

It follows from the definition of mole fraction that the sum of the mole fractionsof all
the components of a solution is unity. i.e. nA + nB + nc…………=1
The molality of a solution (m) is defined as the number of moles of solute per
kilogram (1000gm) of solvent. It is important to note that the quantity of solvent is fixed,
and thus the number of moles of solvent is fixed. Molality is used when discussing the
properties of the solvent as affected by the concentration.
Example.1
Calculate the molalities and the mole fractions of acetic acid in the solutions
prepared by dissolving 120gm of acetic acid (CH3COOH)
(a) In 100gms of water and
(b) In 100gms of ethyl alcohol (CH3CH20H)
Molar mass of acetic acid 60; Water = 18; ethyl alcohol = 46
Solution
(a) In water,
Molality = 2.00 moles acetic acid
0.10kg, water =20m
Nacetic acid = 2.00 moles
(2.00+ 5.55) moles =0.265

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(b) In ethyl alcohol
Molality = 2.00 moles acetic acid
0.10kg ethyl alcohol = 20m

Nacetic acid = 2.00 moles

(2.00+ 2.17) moles =0.48

Example.2
The density of a 2.03M solution of acetic acid in water is 1017 gm/ml calculate the
molality of the solution.
Solution
One dm3 of the solution, containing 2.03 moles x 60gm/mole = 122gm of aceticacid, and
also 1017 - 122 = 895gm of water.
Molality =2.03 moles solute = 2.27m.
0.895kg water
3.5 VAPOUR PRESSURE AND BOILING POINT
The vapour pressure of a liquid at a given temperature is the pressure exerted by the
vapour when it is in equilibrium with the liquid. A liquid boils when its vapour pressure
equals the pressure of the atmosphere above the surface of the liquid.
Explanation
The processes of vaporization, condensation and the development of vapour pressure are
better described in terms of the kinetic molecular theory. By this theory, when the
molecules of liquid possessing varying kinetic energies collide

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With one another, there is normally transference of energy within the molecules. Those
molecules close to the surface which posses’ kinetic energy greater than the average will
escape as vapours. This gives rise to vaporization. The molecules of the vapour also
collide with one another. If vapour molecules ‘fly together’ on collision they will
normally liquefy. This gives rise to condensation. Equilibrium is established when the
rate of vaporization equals the rate of condensation. Any pressure due to the vapour of
the liquid at this stage is what is described as the vapour pressure at that particular
temperature. The temperature at which the vapour pressure equals the atmospheric
pressure is the boiling point of that liquid. A typical vapour pressure versus temperature
diagram is given below.

A Typical Vapour Pressure - Temperature Plot

Vapour Pressure of Solution

When a solution is made by dissolving a non-volatile solute in a volatile solvent, the
vapour pressure of the solution is entirely due to the solvent, but it will be less than the
vapour pressure of the pure solvent because of the pressure of the solute molecules.
2. THERMOCHEMISTRY
1. Thermochemistry is the study of the heat changes that accompany physical and
chemical processes.
2. In a thermochemical study, the portion of matter being investigated is referred to as
a system.

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3. All other objects which may interact with the system are called surroundings. Example, 1
dm3 of a 1M aqueous solution of sodium chloride at room temperature and 1 atm
pressure may be under investigation and will therefore constitute the system. The glass
container is then part of the surroundings.
4. A complete description of the system which identifies its parts, its quantity, its
temperature and pressure, and perhaps some other relevant properties, describes the state
of the system.
5. The initial state of a system is its state before it undergoes a change.
6. The final state describes the state after the change has occurred.
7. For a system which undergoes a change described by a chemical equation, the description
of the reactants defines the initial state of the system, while the corresponding
description of the products defines the final state.
8. The energy of system can be expressed in terms of its heat content, or enthalpy
represented by the symbol H.
9. When a reaction is run at constant pressure, the change in enthalpy, designated by the
symbol H, is merely the difference between the sum of the enthalpies of the products
∑Hproducts, and the sum of the enthalpies of the reactants ∑Hreactants, H=∑Hproducts
-∑H reactants. The enthalpy change, H, is the heat of reaction at constant pressure and
specified temperature.
2.2 TYPES OF HEAT CHANGES
1. Endothermic Reaction: An endothermic reaction is a reaction which is accompanied by
absorption of heat. It therefore follows that the final state must be higher in energy than the
initial state. A plot of energy vs reaction path for an endothermic process is as shown in figure
below

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Fig 2.2 - Reaction Path for an Endothermic Reaction.
Therefore, the difference between the energies of the products and reactants has a positive
value. Hence, H is assigned a positive value.
2. Exothermic Reaction: An exothermic reaction is a reaction which is accompanied by
evolution of heat. Since energy is given off in an exothermic reaction, the enthalpies of the
products total less than the enthalpies of the reactants. Hence the sign of H is negative.
Schematically, a plot of the energy vsreaction path for an exothermic reaction is
As shown in fig 2.3

UNITS OF H
Classical Units

1. (a) Calorie per mole (Cal mol-1)

(b) Kilocalorie per mole (Kcal mol-1)

2. S.I. Units

(a) Joules per mole (J mol-1)

(b) Kilo joules per mole (kJ mol-1)

Hence to form I mole of methane, -1656 kJ of energy is the heat change involved. But in a
molecule of methane there are four C-H bonds. This means that the average energy for the
formation of one C-H bond is
H H H H

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C C +H---H H----C---C----- H
H H H H
4.4.2 Calculation of heat of Reaction From Bond Energies
It is often possible to calculate the approximate enthalpy of a reaction from bond energy data: for
example the hydrogenation of ethylene: It can be imagined that first of all, the ethylene and
hydrogen are dissociated into atoms, which will absorb energy equivalent to the four C-H bonds,
one C=C bond, and the H-H bond that has to be broken. If the ethane molecule is then formed
from the separate atoms, the C-C bond energy, plus six times the C-H bond energy, will be
evolved. The enthalpy of reaction is the overall amount of energy absorbed, and is therefore
given by: = 4(C-H) + (C=C) + (H-H) - 6(C-H) - (C-C) C=C + (H-H) - 2(C-H) (C-C).
Using the bond energy values from the Table of bond energies above, H= 611+ 431

-2 x 414 -347= -133 kJ mol-1

SUMMARY: H = B. Ebonds broken — B. Ebonds formed
4.5.1 Heat of Solution and Dilution
The heat of solution of a substance is the heat change when one mole of the substance is
dissolved in a specified number of moles of water. Thus when one mole (58. 5g) of sodium
chloride (NaC1) is dissolved in 10 moles (1 80g) of water (H2O), 2008 J is absorbed:
NaC1 + 10H2O NaC1 (10H2O) H= +2008 Jmol-1
If a Concentrated Solution is diluted, there is a further heat change (the heat of dilution)
depending on the amount of water added. The heat of dilution gradually decreases so that
eventually increasing the dilution produces no further heat change. In practice this occurs when
there is 800 - 1000 mole of water to 1 mole of solute. We then say that the substance is at infinite
dilution and the heat of dilution is expressed thus:

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NaC1 + aq NaC1 (aq) H = + 4980 J mol-1
In general the heat of dilution can only be defined in terms of the heat change between
two different molalities of a Solution. The extent to which a solute will dissolve in a
solvent is governed by the following factors:
(a) The attractive forces between the solute and solvent molecules compared with the
attractions that the solute (or solvent) molecules have for each other.
(b) Solvation of solute, i.e. the attachment of molecules of the solvent to solute
molecules or ions, either by electrical attraction or chemical bonding.
Heat of Neutralization
This term refers to the heat evolved in the reaction between one mole of an acid
and the stoichjometric amount of alkali.
Example: HCI + NaOH NaC1+ H2O H = 57.3 kJ mol-1
By this definition, the heat of neutralization of one mole of dibasic acids is about twice
that of a mono-basic acid. Essentially, the neutralization process involves the reaction
between the hydroxonium ion and the hydroxide ion for the formation of water
molecules. i.e. OH- + H3O+
2H2O Since the overall reaction of neutralization process is the formation of water, it
might therefore be expected that the heat of neutralization should be equal to be heat
change for formation of water from its elements. The heat of formation of water from its
elements is given by:
H2 (g) + O2 (g) H2O (1) H = - 283.5 kJ mol-1
Whereas the heat of neutralization of a strong acid by a strong alkali is: Na +OH-
+ H+Cl- Na+Cl- + H2O
i.e H+(aq) + OH-(aq) H2O(1) H= -56.7kJmol-1
The two heat changes are therefore quite different. In the first reaction, water is formed
from hydrogen and oxygen in their standard states, whereas in the second case, water is
formed from hydrated hydrogen and hydroxide ions. Thus,

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although water is produced in each case, the processes leading to the formation are
different and therefore are expected to evolve different heats of reaction. In fact, the
formation of H and OH requires an absorption of energy resulting in the lowering of the
total energy evolved when water is formed from the ions.
Latent Heats

(a) Molal (Latent) Heat of Fusion (L°)

The amount of heat evolved when one mole of liquid solidifies is called the latent heat of
fusion. It is also defined as the amount of heat absorbed when one mole of a crystalline
solid melts at constant temperature and pressure, as defined by Figure 4.2
(b) Molal (latent) Heat of Vaporization ((L°)
This is defined as the quantity of heat required to vaporise one mole of liquid atits
boiling point at constant pressure.
Examples: Water (40.67 kJ mol-)
Sulphur dioxide (25.44 kJ mol -)
Benzene (30.80 kJ (mol-)
The heat absorbed when a liquid evaporates is equal numerically to the heatliberated
when the same amount of liquid condenses but is opposite in sign.

(c) Molal Heat of Sublimation ((L°)

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This is the amount of heat required to sublime one mole of solid at constanttemperature and
pressure.
ENTHALPY, ENTROPY AND FREE ENERGY
Enthalpy
Enthalpy (H) is a measure of the internal chemical energy of a substance at constant
pressure. There is no way yet to determine the absolute values of enthalpy and so
chemists work mainly with changes in enthalpy ( H). As seen in previously H is the heat
change in a reaction carried out at constant pressure. Reactions are favoured when the
enthalpy of the products is lower than that of the reactants, i.e., when H is negative. This
is why most spontaneous reactions are exothermic. However, some spontaneous reactions
are endothermic and thusthere must be another driving force to the direction of a reaction
besides the enthalpy change. This other driving force is the entropy change.
Entropy
Entropy (s) is a measure of the degree of randomness or freedom of motion of a
substance. There are basically three types of molecular motion: translation, rotation, and
vibration. Translation is the movement from place to place. Rotation is the spining of
the molecule about one of its axes. Vibration is theback and forth movement of atoms
or bond within the molecule. The entropy associated with each type of motion has the
following order of magnitude: Strans>> Srot> Svib. Unlike entralpies, absolute entropies
can be measured because the entropy of a pure crystalline substance goes to zero at
absolute zero(T =0 K). The entropy of a gas is much greater than that of a liquid which is
slightly greater than that of a solid. Chemical reactions are favoured by an increased in
entropy (S = positive).
Interplay of Enthalpy and Entropy: The Free Energy Change

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If the H of a reaction is negative (exothermic) and the entropy is positive, then the
reaction is spontaneously favored to the right. If the H is positive and the S is negative,
the reaction will never spontaneously go to the right. This interplay of enthalpy and
entropy and the direction of reaction is summarized below H has units of kJ/mole where
as S has u nits of J/mol-K. In order to quantitatively determine the spontaneity of a
reaction, H and S are linked as follows: H - T S = G, where T is the temperature in
degrees Kelvin and /.G is called the Gibb’s free energy change. G is a measure of the
energy that is freed (liberated) from the system and is thus capable of doing work. When
G is negative, the reaction is spontaneous and capable of doing work. When G is positive,
the reaction willnot proceed spontaneously and work must be done on the system to make
it go to the right. The following example shows how G can be calculated from AH and S
and how temperature can affect the value of G.
ELECTROLYTES AND IONIC EQUILIBRIUM
Electrolytes are liquids or solutions containing free moving ions (Cations and anions)
and capable of conducting electricity.
Nature of Electrolytes
From the above definition of electrolytes it is evident that an electrolyte must contain
ions. It is known that electrovalent compounds consist of ions, even in the solid state. If
an electrovalent substance (e.g sodium chloride) is melted, the ions will be free to move
and the liquid will therefore conduct electricity. The same will also be true for a solution
of the substance. It is in fact found that many salts are electrolytes both in the fused state
and in solution
There are however, other types of compounds which give conducting “solutions,
i.e. acids, bases and covalent salts (e.g Ai2Cl6). These are all covalent substances, so that
in the pure state they consist of molecules and not ions. The fact that their solutions will
conduct electricity shows that the process of solution

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has caused ionization of the molecules. Hydrogen chloride, for example, is a none-
conducting liquid (when below its boiling point) and if dissolved in dry benzene forms a
non-conducting Solution. When it is dissolved in water, however, the solution
(hydrochloric acid) is strongly conducting and shows the usual acidic properties that we
associate with the presence of hydrogen ions. This is due to ionization, as a result of a
reaction between the HCI molecule and water.
HC1 +H2O —H3O+Cl-
This reaction takes place because of the strong affinity between a hydrogen ion and water
molecule and produces the hydronium ion, H30+. The latter is a chemical entity with the
following electronic structure:
¨ H:
O :H
¨
H
A base (e.g., NH3) will also react with water:
NH3+H2O NH4 ++ OH- forming ammonium and hydroxyl ions.
Covalent salts also tend to ionize in solution because of affinity between the resulting
metal ion and water, e.8., A12C16 + 12H2O 2[Al (H2O6)3+ + 6C1- where the water is
held by dative bonds.
Strong Electrolytes; If a substance is completely (or almost completely) ionized in
solution, it forms a strong electrolyte. Hydrochloric acid is one example, and solutions of
many electrovalent salts are strong electrolytes. Some electrovalent salts, e.g, AgC1,
BaCO3 and PbS are weak electrolytes.
Weak Electrolytes
Substances which show very little ionization in solution form weak electrolytes. Many
acids and bases belong to this class. Since ionization involves a reaction

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between solute and solvent, the extent to which any particular compound is ionized will
depend on the solvent used; a substance which is a strong electrolyte in one solvent may
become a weak electrolyte in a different solvent. Examples of weak electrolyte include
CH3COOH, NH4OH and HgCl2.
Ionic and Molecular Solutions:
Some substances form ions when they dissolve whereas other substances dissolved in the
molecular form. For example, common salt produces ions in solution. Sugar produces
molecules in solution. The former is an ionic solution whereas the later is molecular.
Ionic Equilibrium in Aqueous Solution The Solubility of Sparingly Soluble Ionic
Solids in Water When increasing quantities of a sparingly soluble ionic solid are added to
water, a saturated solution is eventually formed. Ions in the saturated solution are in
equilibrium with the excess undisclosed solute.
MX(s) M+ (aq) + X- (aq)
e.g. AgBrO3(s) Ag+(aq) + BrO-3(aq)
[Ag+(aq)] (BrO-3(aq)]= a constant at a given temperature = 3.39 x 10-5 mole2 dm-6 at 16°C.
This has been measured experimentally.
In other words, the product of the concentration of AgBrO3 is completely independent of
the amount of AgBrO3 present, provided there is some undisclosed AgBrO3 in contact
with the solution. This situation is comparable to other heterogenous systems involving
solid/liquid or solid/gas equilibria.
How can we explain the constant value for the product [Ag+][BrO;]? When equilibrium
between pure AgBrO3 and its solution is reached, we have AgBrO31 Ag + BrO3 Hence
we can write an equilibrium constant expression as Kc [Ag+(aq)][BrO-3(aq)] [AgBrO3(s)]
But [AgBrO3(s)] which represents the concentration of pure solid is constant. Hence,
[Ag+(aq)][BrO-3(aq)]=Kc [AgBrO3(s)]
= a new constant

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 ALCOHOLS, PHENOLS AND ESTERS

There are very many reasons why we should show keen

Interest in the study of alcohols. Ethyl alcohol, for example, it used extensively for
beverage purposes the world over in addition to being a very important industrial raw
material. It also finds wide use as a solvent. Similarly, methanol, the simplest member of
the family is very important industrial chemical that can be used as a solvent and for the
manufacture of formaldehyde.
Scope and Classification
The term alcohols normally refers to those saturated open chain aliphatic (acyclic) and
alicyclic (carbocyclic) compounds which contain the hydroxyl
(-O-H) functional group. In effect alcohols are derived from alkanes by replacing one or
more hydrogen atoms by one or more hydroxyl groups.

The reaction of an alcohol is made possible by the presence of the lonepairs of

electrons on the oxygen atom with which the molecule acts as a Lewis base (electron
donor). In addition to behaving as a Lewis
base, the —O-H- group can also behave as a weak acid (proton donor).

When only one-Oil group is found in the molecule, the compound is referred to as
a monohydric alcohol. Dihydric and trihydric alcohols contain twoand three
-OH groups respectively per molecule, Eg.

Monohydric dihydric trihydric

Alcohol alcohol alcohol

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CH3CH2CH2OH CH2OHÇH2OH CH2(OH)CH(OH)CH2O
H
Propan-1-ol ethane-1,2-diol propane-1,2,3-triol

(1,2-dihydroxy ethane) (glycerol)

ethylene glycol)
This aspect focuses on monohydric alcohols of which there are three kinds viz:primary,
secondary and tertiary alcohols. In primary
alcohols, the —OH functional groups is attached to a primary carbon atom suchas

H H H
H C CH3C-, or (CH3)2)CHC-
H H
H

In secondary alcohols, the —OH group is attached to a secondary carbon atomsuch as

(CH3)2 CH- or

CH2-

CH2

CH2-CH-

In tertiary alcohols, the hydroxyl functional group is attached to a tertiary carbonatom.

Primary Secondary Tertiary

Alcohol alcohol alcohol

CH3-OH H3C CH3

CH3.CH2-OH CH-OH H3C-C-OH

H3 C CH3

(CH3)2CHCH2-OH

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General Molecular Formula

For the aliphatic alcohols,the general molecular formula

is CnH2n +1 OH (n ≥ I) while for the alicyclic alcohols, the

general molecular formula is CnH2n-1 OH(n≥ 3).

Examples:

aliphatic alcohols alicylicalohols

n=l CH3OH n=3

n=2 CH3CH2OH
n=4

I.U.P.A.C. Nomenclature

The I.U.P.A.C. name of each alcohol is’ derived from the

parent alkane or cycloalkane containing the same number of

carbon atoms by replacing the last e in the alkane or

cycloalkane with the suffix ol The compoundsare thus

named as alkanols or cycloalkanols:

alkane =alkanol= CnH2n+1OH.

methane=methanol=CH3OH

ethane=ethanol

CH3CH2OH

cycloalkane cycloalkanol

cyclopropane cyclopropanol
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Cyclobutane cyclobutanol

For the higher molecular weight alkanols, the following

Rules should serve as a guide in naming them by the

I.U.P.A.C system;

(a) The class suffix is —ol.

(b) The number of carbon atoms in the longest carbon chain in the molecule
containing the hydroxyl (-0H) group is used as the parent hydrocarbon.

(c) The locations of any side chains and the hydroxyl group are indicated by
numbers, such that the lowest possible number is given to the carbon atom bearing
the hydroxyl group.

Illustration;

3CH 2CH 1CH OH propan- 1 -ol

3 2 2

OH
3CH -2CH-1CH propan-2-ol
3 3

CH3
1CH -2CH-3CH-4CH3 3 -methylbutan-2-ol
3
OH

Industrial Sources of some Alcohols

Methanol, CH3OH, originally termed wood spirit because of its source from wood,
was derived essentially by the destructive distillation of wood. The distillate, known as
pyroligneous acid, contains about 10% ethanoic acid, l-2%methanol, 0.5% acetone,
among others, which on fractional distillation gives methanol. Most of the world’s
methanol is now obtained by synthetic method

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from water gas.

C+ H2 0 C0+H2 H2 CH3OH
red.hot steam water gas Cu/Al203 cat,

The petroleum industry offers yet another important source of methanol. Natural
petroleum gases contain considerable quantities of methane from which methanol is now
obtained from several commercial plants by oxidation. Oxidationof natural gases gives a
mixture of products in which methanol (CH3OH). methanal (1{CHO) and methanoicacid
(H.CO2H) predominate.
2CH4 +02 Cu cat 2CH3OH

2CH3OH +02 2H.CHO + 2H2O

211.CHO ±02 2H.C02H

In another process, methane is converted into a mixture of carbon (II) oxide and hydrogen
either by a catalytic methane-steam process or by controlled oxidation:

CH4 + H20 cat CO + 3H2

(steam)
Or 2CH4 +02> 2C0 +4H2

At high pressures (200-300 bars) and high temperature (400 500°C)

and in the presence of zinc chromite catalyst, the carbon (II) oxide and hydrogencombine
to form methanol:

CO + 2H2 Cat.
CH3O
H200-300bar, 450°C

Ethanol, C21150H, is another alcohol that is commercially derived from thepetroleum

industry. Ethene is a major component in the gases from
cracking operations. It is directly hydrated to ethanol by passing it and steam inthe vapour
phase at high pressure over a suitable catalyst. In a

related process, the ethane is absorbed in a counter-current tower down which is97.5%
“2504 trick lets, the temperature and pressure being

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80°C and 15-30 bars respectively. The ethyl hydrogen tetratoxosulphate

(VI) ester formed initially is hydrolysed with water and the ethanol isstripped

out by steam and concentrated.

H2C = CH2 + 112 so4 —> C2H5.HSO4

ethyl hydrogen tetraoxosulphate (VI)

C2115.H504 + 11,0 C2H5OH + H1S04

Ethanol is also manufactured on a large scale biotechnologically via

fermentation process by the conversion of starch grains into sugar and hence toethanol.
Four stages are involved: malting, mashing,

fermentation and fractional distillation.

During malting, the grain is moistened and allowed to sprout, developing the

enzyme diastase. During mashing the malt is steeped in water (temperature 5 0-

60°C) and t he diastase acts on t he starch o f the grainchanging it into malt-sugar

(maltose):

2(C5H10O5), -I- nH,O djseC12H,7o11

starch 5 0-60°C malt-sugar (maltose)

At the fermentation stage, the maltose is decomposed by yeast to formglucose

which yields ethanol and carbon (TV) oxide.

C12H22011 + H20 maltasç 2C6H1206

in yeas( glucose

C5H1206 ymas 2C2H50H + 2C02

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in yeast

General Laboratory Methods of Preparation

A number of general methods are available for the preparation ofmonohydric

alcohols, These include:

CARBONYL COMPOUNDS AND CARBOXYLIC ACIDS

Carbonyl compounds are characterized by the presence of

the functional group >C=O in which oxygen is bonded to carbon througha

double bond.

Structure of Aldehydes and Ketones

Although aldehydes and ketones are collectively referred to as carbonyl

compounds, the two families do in fact differ in structure andproperties. In

aldehydes, the carbonyl carbon is bonded to a hydrogen

atom, the remaining bond being linked to an alkyl or aryl group whereas in

ketones the carbonyl carbon is bonded to the two organic groups (alkylor aryl or

both).

H-C-H R-C-H Ar-C-H

methanal (formaldehyde) alkanal aromatic aldehyde Methanal

(formaldehyde) is different from other aldehydes because thecarbonyl carbon

is attached to two hydrogen atoms.

R-C-R R-C-Ar Ar-C-Ar

(aliphatic ketone) mixed ketone aromatic ketone

Nomenclature

23
The simplest aldehydes are known trivially by names derived

from the carboxylic acids to which they may be oxidized,

H—C—H H—e—OH
(formaldehyde) formic acid

CH3—C-H CH3—C—OH
Acetaldehyde Acetic Acid

the ic being removed along with the acid and replaced by aldehyde. Common or

trivial names for certain ketones are derived by naming bothGroup attached to the

carbonyl carbon atom, then adding the word Ketone, although in certain cases

special names which end in —one are

employed.

CH3-C-CH3 CH3-C-CH2CH3 CH3CH2C-

CH2CH3
Dimethyl ketone (acetone) ethyl methyl ketone Diethyl ketone

In the IUPAC system the characteristic ending for aldehydes is —al and that of

ketone is —one. The longest chain including the carbonyl carbon isnamed after

the parent hydrocarbon with the last letter e in the hydrocarbon replaced with al

or — one, as suffix. The Carbonyl carbon atom of an aldehyde is always number

one in the carbon chain and takes precedence over most other functional groups

that may be present. The carbonyl carbon atom of ketone, on the other hand may

appear at any point in the chain and must be located by a number. The following

24
examples illustrate the rule

CH3-CH3 CH3-C-H
Ethane Ethanal (acetaldehyde)

H HH
CH3-C-CH3 CH3-C-C=O
CH3 CH3
2-methylpropane 2-methvlpropanal
(Isobutyraldehyde)

H H
CH3-CH=C-CH3 CH3-CH=CH-C=O
2-butane 2-butenal
(crotonaldehyde)

CH3–CH2–CH3 CH3C-CH3
Propane Propanone
(acetone)

CH3–CH3CH2CH2CH3 CH3-C-CH2CH2CH3 CH3–CH2C CH2CH3

Pentane 1 234 5 3-pentanone
2-pentanone pentan-3 -one
(Methyl n-propyl (Diethyl ketone)
Ketone)

Properties: With the exception of methanal (formaldehyde) which is a gas, the

lower molecular weight aldehydes and ketones are liquids thathave lower boiling

points than alcohols of the same carbon content eg.ethanal CH3CHO has a

boiling point of 20.2°C; while

25
CH3CH2CHO boil at 43.8°C, propanone (acetone) 56.1°C while 1- propanol

CH3CH2CH2OH boil at 97.8°C and propanol at 82.5°C. This is because the

carbonyl compounds lacking hydroxyl groups do not hydrogen bond as the

alcohols, and therefore, are Unassociated liquids. The lower members of the

aldehyde family have sharp, irritating odours, but the higher molecular weight

members, and nearly all members of the ketone family are fragrant, and as such

may be used in perfumery and asflavouring agents.

preparation of Aldehydes and Ketone

(1) By the oxidation of alcohols: Aldehydes and ketone prepared by the

Oxidation of alcohols.

(a) Primary alcohols give aldehydes

RCH2OH RCHO
(b) Secondary alcohols give ketones
RCH(OH)R RCOR
These oxidations can also be achieved by the dehydrogenation of alcohol
vapourover a heated copper catalyst.

H H
R-C-O Cu H2 + R-C=O
HH 250-3000C

R R
R-C-O Cu H2 + R-C=O
HH 250-3000C

The oxidation can be carried out in the presence of airH R

26
2H-Ç-OH + O2 (air) Cu 2H-C=0 + 2H20
H

Note that aldehydes are very susceptible to further oxidation to acids andMust be

removed from the reaction mixture (e.g. by distillation) if Oxidation to acid is to

be avoided.

Chemical oxidation in the laboratory is most frequently

Accomplished using tetraoxochromate (VI) acid H2Cr04) oxidant. This is

Prepared from either sodium heptaoxodicromate (VI) (Na2Cr2O7) or

Chromic oxide (Cr03) and acid (usually tetraoxosulphate (VI) or ethanoic acid)eg.

H
2-
3CH3CH2OH +Cr207 + 8H 5O°C CH3C=O+ 2Cr3++7H20
+

2-propanone (acetone) may be prepared in the same way.

H (O)
CH3-C- → CH3-C-CH3
CH3 O
OH
2—propanol 2-propanone
(Acetone)

Ketones unlike aldehydes are not easily oxidized.

2.(a) By heating a mixture of the calcium slats of methanoic acid andAnyone

of its homologues, aldehydes are produced

(RCO2)Ca + (HCO2)2Ca heat 2RCHO + 2CaCO3

(b) Ketones can be prepared by heating the calcium salt of any fatty

27
acid other than methanoic acid.

(RCO2)2Ca heat R2CO + 2CaCO3

3. Aldehydes can be prepared by the Rosenmund reduction of acid chlorides.

RCOCI + H2 Pd/BaSO4 RCHO + HCl

There is no similar reaction for the preparation of ketones

4. Aldehydes or ketones can be prepared by the method of ozonolysis

of alkene. The product obtained is dependent on thestructure of the

alkene.

O
/ O3 / \ H2
CH=CHR ─> RCH—CHR ─>RCHO + R’CHO
O O Cat
ozonide

(1) O3
2C=CR2 ─> R2C0+R’2CO

(2) H2-Cat2

Oxidation of glycols with lead tetra-aceate can give an aldehyde ketone

depending on the structure of the glycol.

(O)
CH(OH)CH(OH)R’ → RCHO +
R’CHO
(O)
2C(OH)C(OH)R’2 ─> R2CO+R2CO

From Alkyne
HC=CH+H2O Hg2+ SO42- (CH2 =CH0H)→CH3 CHO
H2SO4 unstable intermediate

RC=CH + H20 Hg2+SO42- →RCOCH3

H2SO4

28
Aldehydes, but not ketones may be prepared by the reduction ofCyanides
with stannous chloride in HCl.

HCI H2 O
RC=N → (RC=NH) CI SnCI2(RCH=NH2)2 SnCI 6 →
+ - + 2-
RCHO

8. By the hýdrolysis of gem-dihalides. Two halogen atoms, when positioned onthe

same carbon atom (gem-dihalides) may be hydrolysed easily too the carbonyl group.
This method however is only of preparative importance for aromatic aldehydes.

CH3 CHCI2

+2CI2Sunlight +HCI

Toluene (benzylidene chloride)

H H
─C─CI+H2O NaOH -C=O
GG CI

9. Aromatic aldehydes and ketones are readily prepared by the Crafts reaction.

CH3
CH3 \
+HCI + CO AICI3
\
Toluene CHO
p-tolualdehyde

COCH3
\
+ CH3─COCI AICI3

Acetophenone

29
Reaction of aldehyde and ketones have appreciable dipole momentsindicating
that the carbonyl group is polarized as shown.

8+ 8- + -

>C = O >C = O C-O

unpolarized polarization complete polarization

The presence of the double bond and the difference in electronegativity betweenthe
oxygen and the carbon causes electron polarization towards the oxygen atom, leaving the
carbon atom positively charged. Because of this ability to polarize in this way, carbonyl
compounds undergo a
number of addition reactions with nucleophilic reagents.

(1) With HCN

The reaction is initiated by the attack of the nucleophilic cyanide ion on the
electron deficient carbonyl carbon atom.

(2) With water: Aldehydes and ketones add on water to form

hydrates.

CH3CHO + H2O = CH3CH(OH)2

Acetaldehyde hydrate

CH3CCHO +H2O = CI3CH(OH)2

Chlora or trichloro-
Acetaldehyde bp 98°C chloral hydrate mp 52°C

Chlora hydrate is a sedative but suffers from the disadvantage of having an

unpleasant taste.

(3) With sodium hydrogentrioxosulphate (1V):Aldehydes and ketones react with

sodium hydrogentrioxosulphate (IV) (bisulphate)to give salts(hydrogentrioxosulphate
(IV) compounds by an addition process.

OH O
/ ‖
–
CH3-CH2CHO + NaHSO3 = CH3CH2 -C - S – O S-O Na +
/ ‖
H O

30
 Propanal bisulphite compound

hydrogentrioxosulphate (IV) compounds are crystalline products which can decompose by

dilute acid or base to regenerate aldehyde or ketone. ThereforehydrogntrioxosurPhate (IV)
compounds can be used to purify aldehydes and ketones. In

a mixture of carbonyl compound and any other compound, only the aldehyde or ketone
will form ahydrogensurphate(IV) compound which can then be separatedand
composed to give the pure carbonyl compound.

CH3 OH CH3
C C=0+H2O +SO2
CH3 SO3 Na+ + HCI→ CH3

4. Reaction with ammonia derivatives

(i) CH3CHO+NH2CH2CH3 --------- CH3CH= NCH2CH3 + H2O

(ii) (CH3)2CO + NH2NH2 (CH3)2C=NH.NH2 + H2O

Hydrazine acetone hydrazone

(iii) CH3 NO2 CH3

NO2C = O + NH2NH NO2 + H2O
NO2 = C = NNH
CH2CH3
2,4-Dinitrophenyl- butanone-2,4-dinitro-
hydrazine phenylhydrazone

(iv) (CH3)2 CH.CHO +NH2OH (CH3)2 CHCH=N0H+H2O

hydroxyl- mp 139°
amineOxine

(v) CH3CH2CHO + NH2NHCONH2 = CH3CH2CH=

N,NHCONH2sermicarbazide mp 84°C
Propanal semicarbazide

In all the above reactions, the amino compounds add on to the carbonylcompound with
elimination of water. Most of the products are crystalline solids and are used to

31
characterize aldehydes and ketones.

5. Reduction; Aldehydes are reduced to primary alcohols and ketones to

secondary alcohols

CH3CH2CH2CH0 2H----.> CH3CH2CH2CH2OH

The most convenient reducing agent is lithium aluminium hydride AiAlH4 in dry

ether solution or sodium boronhydride (NaBH4) in water or methanol). The

reduction of ketone with zinc amalgam in strong aqueousacid (clemmertson

reduction) converts the C=O to methylene (-CH2) group.

CH3COCH3 Zn - Hg . ÇH3CH2CH3
HCI, H2O

6. Reactions of a - C-H. Certain reactions of aldehydes and

ketones depend primarily on the reactivity of the C-H bonds of alkyl

groups adjacent to the carbonyl group. The reactions are catalysed by

acids and bases.

(a) Aldol condensation

CH3CHO + CH CHOaq. NaOHCH3 OH

CH CH2CHO
aldol, 3-hydroxybutanal

The mechanism of the base catalysed reaction is as follows:

(i) The base removes a proton from one molecule of the aldehyde.

-∩ H H-H

32
HO - H- Ç-C=O→H2O + C-C=O (or -CH2-CHO)
H HH

(ii) The anion obtained from (j) is a nucleophile and attacks the

polarized carbonyl group in another molecules of aldehyde.

CH3∩ CH3 O-
C=O → C
H H
CH2CH
O
CH2CHO

(iii) The above condensation product now reacts with water tti regenerate

the base OH- and to form the aldol, 3-hydroxybutantanal.CH3 O CH3

OH

C + H2 O C +

OHH CH3 CHO H

CH3 CHO

Similarly: Acetone condenses by the same mechanism

CH3OH
CH3 Ba (OH)2 C

2 C= O
CH3CH3COCH3
CH34-hydroxy-4-methylpentan – 2 – one

Only a -CH bonds are reactive. Compounds such as 2,2- dimethylpropanal

(CH3)3C.CHO and methanal H.CHO do not contain a- hydrogen and hence do

not undergo the aldol reaction. If the product ofthealdol condensation is heated a

molecule of water is lost and an

33
unsaturated compound is formed.

CH3CHOH CH2 CHO CH3CH = CHCHO + H2O

Croton aldehyde or buten-2-al or butenal

Sometimes the unsaturated compound is obtained directly during aldol condensation,

especially if the reaction is carried out under acid analysis.

(b) Halogenation

CH3 COCH3 + Br2 traces of HBr CH3COCH2 Br + HBr Bromoacetone

is often not the final product as more a -hydrogen of theacetone can further be

replaced if more bromine is employed.

Similarly

CH3CHO + CI2 H Cl2 CH2CHO + HCI

CICH2CHO + Cl2 H Cl2CHCHO + HCI etc.

7. Oxidation: Aldehydes are oxidized easily to carboxylic acids

containing the same number of càrbon atoms.

O O
RC=O R – C – OH

The reaction involves the C-H bond that ¡s part of the aldehyde group.Since

ketones do not contain such a C-H bond, they are not oxidized in

this way and this difference is the basis of laboratory tests used to
distinguish between aldehydes and ketones.

34
(i) Aldehyde restore the magenta colour of Schiffs reagent. (Schiff’s

reagent is an aqueous solution of rosaniline hydrochloride whose magenta

colour was discharged by the passage of sulphur (1V) oxide into the

solution).

(ii) Aldehydes are oxidized by Tollen’s reagent (an aqueous solutionof

silver trioxonitrate (V), ammonia and sodium hydroxide) to give a si1ver

mirror’. +

RCHO +2 [Ag (NH3)2] + OH RCO2 NH4 + 3NH3 + H2O + Ag

(iii) Oxidation with cupric salts (often called Fehling’s solution) gives aRed

precipitiate of cuprous oxide Cu20. This test is often used to detect the

presence of reducing sugars (ie carbohydrates containing potential aldehydes

groups) in the urine of diabetic patient.

(iv) All carbonyl compounds containing CH3CO (methyl ketones) or

those that are capable of being easily converted to this group during

oxidation give the haloform reaction with halogens. Iodine is used most

of the time and the test is often known as the iodoform reaction.

CH3 COR + 312 + 4Na OH—>CHI3 + RCO2Na + 3H2O + 3Nal

lodoform

Ketones can be oxidized by strong oxidizing agents eg. KMnO4 in acid, but the

carboxylic acid formed must contain less carbon atoms-than the

35
original ketone.
KMnO4
+
CH3CH2COCH2 CH3 H CH3CH=C-CH2CH3 CH3CO2 H +

HO2CCH2CH3

8. Reaction with Grignard Reagents

Grignard reagents (alkyl magnesium halides) in dry ether usuallyeact

with Carbonyl compounds to give alcohols.

RMgX+>C = O >C – O-M+g + X-

R intermediate addition product

(Magnesium alkoxide)

then R
R + H2 O
-
C-O-Mg+X-+ HCI -C-OH + Mg2+ X-CI-

alcohol

Grignard reagents react with methanal to give primary alcohols O

‖ (1)RMgX
R-C-H RCH2OH
(2)H2O,H +

With any other aldehydes a secondary alcohol is obtainedO

‖ (1)RMgX R
R-C-H CH- OH
+
(2)H2O,H R

36
and with any ketone a tertiary alcohol is obtained

O
‖ (1)RMgX R
R-C-H + R CH-
OH(2)H2O,H R

9. Aldehydes lacking in a-hydrogen undergo reaction to give a mixtureof

alcohol and acid (Cannizaro reaction).

HCHO + HCHO + NaOHHCOONa + CH3OH

2(CH3)3CCHO NaOH (CH3)3C.COONa

2C6H5CHO NaOH C6H5CH2OH ± C6H5COONa

Methanal (Formaldehyde) Methanal is not a typical aldehyde and is not prepared by the

methods used for other aldehydes It is manufactured by

passing a mixture of methanol and air Over Copper or silver catalyst at250-3000c

2CH3OH +O2 Cu or Ag 2HCHO + 2H2O

The products are absorbed in water to give formaline a 35 — 40% of

formaldehyde. The polymeric form, Paraformaldehyde (- CH2O-)n is

obtained by evaporating the aqueous Solution. formaldehyde when

heated gives gaseous formaldehyde

Formaldehyde is very reactive and is used extensively in the synthesis ofOrganic

compounds..
Formaldehyde is used for the preservation of anatomical and biological
Specimens.

37
RADIOACTIVITY

Radioactivity is defined as the emission of particles and electromagnetic rays from the
nucleus of an unstable atom.

Radioactivity is the spontaneous emission of radiation in the form of particles or high

energy photons resulting from a nuclear reaction. It is also known as radioactive decay,
nuclear decay, nuclear disintegration, or radioactive disintegration. While there are many
forms of electromagnetic radiation, they are not always produced by radioactivity. For
example, a light bulb may emit radiation in the forms of heat and light, yet it is not
radioactive. A substance that contains unstable atomic nuclei is considered to be
radioactive.

Radioactive decay is a random or stochastic process that occurs at the level of individual
atoms. While it is impossible to predict exactly when a single unstable nucleus will
decay, the rate of decay of a group of atoms may be predicted based on decay constants
or half-lives. A half-life is the time required for half of the sample of matter to undergo
radioactive decay.

Key Takeaways: Definition of Radioactivity

 Radioactivity is the process by which an unstable atomic nucleus loses

energy by emitting radiation.
 While radioactivity results in the release of radiation, not all radiation is
produced by radioactive material.
 The SI unit of radioactivity is the becquerel (Bq). Other units include the
curie, gray, and sievert.
 Alpha, beta, and gamma decay are three common processes through
which radioactive materials lose energy.

Units

The International System of Units (SI) uses the becquerel (Bq) as the standard unit of
radioactivity. The unit is named in honor of the discoverer of radioactivity, French
scientists Henri Becquerel. One becquerel is defined to be one decay or disintegration per
second.

The curie (Ci) is another common unit of radioactivity. It is defined as 3.7 x 1010
disintegrations per second. One curie equals 3.7 x 1010 bequerels.

Ionizing radiation is often expressed in units of grays (Gy) or sieverts (Sv). Agray is
the absorption of one joule of radiation energy per kilogram of massA

38
 sievert is the quantity of radiation associated with a 5.5% change of cancer eventually
developing as a result of exposure.

Six types of radiation produced during nuclear decay includes:

 alpha (α) decay which is composed of two protons and two neutrons and has a
+2 charge.
 beta (β) decay which is an electron ejected from the nucleus (not from the shells of
electrons about the nucleus) and has a -1 charge and no mass. Within the nucleus a
neutron emits the electron and is converted into a proton in the process.

 gamma (γ) decay which is characterized by the emission of ionizing radiation and does
not contain mass or charge.
 positron (β+) emission which is a positron ejected from the nucleus and has a
+1 charge and no mass. Within the nucleus a proton emits the positron and is converted
into a neutron in the process.
 electron capture occurs when an inner shell electron combines with a proton and is
converted into a neutron. The loss of an inner shell electron leaves a vacancy that will be
filled by one of the outer electrons. As the outer electron drops into the vacancy, it will
emit energy often in the form of X-rays.
 nuclear fission occurs when an atomic nucleus breaks apart into smaller pieces in a
radioactive process that releases excess neutrons.

Each radioactive nuclide has a characteristic, constant half-life (t1/2), the time required for
half of the atoms in a sample to decay. The equation below can be used to determine how
much isotope will remain after the passage of a given number of
half-lives

Radioactive emissions can cause damage to biological systems by causing the breakdown
of proteins and DNA. This can lead to cellular and genetic damage

39
and increase a person’s risk for diseases like cancer. However, when used is small
quantities and in controlled settings, radioactive tracers and treatments have proven to
be revolutionary for the medical field. For example, Radiation therapy is the use of
high-energy radiation to damage the DNA of cancer cells, which kills them or keeps them
from dividing. Radioactive tracers have also been very useful in evaluating heart
disease, thyroid dysfunction, and other blood disorders. Positron emission
tomography (PET) scans use radiation to diagnose and track health conditions and
monitor medical treatments by revealing how parts of a patient’s body function and X-
rays have long been used to visualize breaks in bones and cavities in teeth.

Causes Of Radioactivity

As its name implies, radioactivity is the act of emitting radiation spontaneously. This is
done by an atomic nucleus that, for some reason, is unstable; it "wants" to give up some
energy in order to shift to a more stable configuration. During the first half of the
twentieth century, much of modern physics was devoted to exploring why this happens,
with the result that nuclear decay was fairly well understood by 1960. Too many neutrons
in a nucleus lead it to emit a negative beta particle, which changes one of the
neutrons into a proton. Too many protons in a nucleus lead it to emit a positron
(positively charged electron), changing a proton into a neutron. Too much energy
leads a nucleus to emita gamma ray, which discards great energy without changing any
of the particles in the nucleus. Too much mass leads a nucleus to emit an alpha particle,
discarding four heavy particles (two protons and two neutrons).

How is radioactivity measured?

Radioactivity is a physical, not a biological, phenomenon. Simply stated, the
radioactivity of a sample can be measured by counting how many atoms are
spontaneously decaying each second. This can be done with instruments designed to
detect the particular type of radiation emitted with each "decay" or disintegration. The
actual number of disintegrations per second may be quite large. Scientists have agreed
upon common units to use as a form of shorthand. Thus, a curie (abbreviated "Ci" and
named after Pierre and Marie Curie, the discoverers of radium is simply a shorthand way
of writing "37,000,000,000 disintegrations per second," the rate of disintegration
occurring in 1 gram of radium. The more modern International System of Measurements
(SI) unit for the same type of measurement is the becquerel ( abbreviated "Bq" and
named

40
after Henri Becquerel, the discoverer of radioactivity), which is simply a shorthand for
"1 disintegration per second."

What is radioactive half-life?

Being unstable does not lead an atomic nucleus to emit radiation immediately. Instead,
the probability of an atom disintegrating is constant, as if unstable nuclei
continuously participate in a sort of lottery, with random drawings to decide which atom
will next emit radiation and disintegrate to a more stable state. The time it takes for half
of the atoms in a given mass to "win the lottery"-
-that is, emit radiation and change to a more stable state--is called the half-life. Half-lives
vary greatly among types of atoms, from less than a second to billions of years. For
example, it will take about 4.5 billion years for half of the atoms in a mass of uranium
238 to spontaneously disintegrate, but only 24,000 years for half of the atoms in a mass of
plutonium 239 to spontaneously disintegrate. a

Stability may be achieved in a single decay, or a nucleus may decay through a series of
states before it reaches a truly stable configuration, a bit like a Slinky toy stepping down
a set of stairs. Each state or step will have its own unique characteristics of half-life and
type of radiation to be emitted as the move is made to the next state. Much scientific
effort has been devoted to unraveling these decay chains, not only to achieve a basic
understanding of nature, but also to design nuclear weapons and nuclear reactors. The
unusually complicated decay of uranium 238, for example--the primary source of
natural radioactivityon earth--proceeds as follows:[88]

U-238 emits an alpha Thorium 234

emits a beta Protactinium 234

emits a betaUranium 234 emits an

alpha

Thorium 230 emits an alpha

Radium 226 emits an alpha

Radon 222 emits an alpha

41
Polonium 218 emits an alphaLead

214 emits a beta Bismuth 214

emits a beta Polonium 214 emits

an alphaLead 210 emits a beta

Bismuth 210 emits a beta

Polonium 210 emits an alphaLead

206, which is stable

How can radioactivity be caused artificially?

Radioactivity can occur both naturally and through human intervention. An example of
artificially induced radioactivity is neutron activation. A neutron fired into a nucleus can
cause nuclear fission (the splitting of atoms). This is the basic concept behind the
atomic bomb. Neutron activation is also the underlying principle of boron-neutron
capture therapy for certain brain cancers. A solution containing boron is injected into a
patient and is absorbed more by the cancer than by other cells. Neutrons fired at the area
of the brain cancer are readily absorbed (captured) by the boron nuclei. These nuclei
then become unstable and emit radiation that attacks the cancer cells. Simple in its basic
physics, the treatment has been complex and controversial in practice and after half a
century is still regarded as highly experimental.

Types of Radioactive Decay

The first three types of radioactive decay to be discovered were alpha, beta, and gamma
decay. These modes of decay were named by their ability to penetrate matter. Alpha
decay penetrates the shortest distance, while gamma decay penetrates the greatest
distance. Eventually, the processes involved in alpha, beta, and gamma decay were better
understood and additional types of decay were discovered.

Decay modes include (A is atomic mass or number of protons plus neutrons, Z is atomic
number or number of protons):

42
  Alpha decay: An alpha particle (A =4, Z=2) is emitted from the nucleus, resulting
in a daughter nucleus (A -4, Z - 2).
 Proton emission: The parent nucleus emits a proton, resulting in a daughter
nucleus (A -1, Z - 1).
 Neutron emission: The parent nucleus ejects a neutron, resulting in a daughter
nucleus (A - 1, Z).
 Spontaneous fission: An unstable nucleus disintegrates into two or more small
nuclei.
 Beta minus (β−) decay: A nucleus emits an electron and electron antineutrino to
yield a daughter with A, Z + 1.
 Beta plus (β+) decay: A nucleus emits a positron and electron neutrino to yield a
daughter with A, Z - 1.
 Electron capture: A nucleus captures an electron and emits a neutrino, resulting
in a daughter that is unstable and excited.
 Isomeric transition (IT): An excited nucleus releases a gamma ray resulting in a
daughter with the same atomic mass and atomic number (A, Z),

Gamma decay typically occurs following another form of decay, such as alpha or beta
decay. When a nucleus is left in an excited state it may release a gamma ray photon in
order for the atom to return to a lower and more stable energy state.

MEASUREMENT,CONVERSION AND UNIT

Units of Length

= 39.37 inches (in.)

meter (m)
= 1.094 yards (yd)

centimeter (cm) = 0.01 m (exact, definition)

millimeter (mm) = 0.001 m (exact, definition)

kilometer (km) = 1000 m (exact, definition)

43
 = 39.37 inches (in.)
meter (m)
= 1.094 yards (yd)

= 10–8 cm (exact, definition)

angstrom (Å)
= 10–10 m (exact, definition)

yard (yd) = 0.9144 m

inch (in.) = 2.54 cm (exact, definition)

mile (US) = 1.60934 km

Units of Volume

= 0.001 m3 (exact, definition)

liter (L) = 1000 cm3 (exact, definition)
= 1.057 (US) quarts

= 0.001 L (exact, definition)

milliliter (mL)
= 1 cm3 (exact, definition)

= 10–6 L (exact, definition)

microliter (μL)(μL)
= 10–3 cm3 (exact, definition)

= 32 (US) liquid ounces (exact, definition)

liquid quart (US) = 0.25 (US) gallon (exact, definition)
= 0.9463 L

dry quart = 1.1012 L

cubic foot (US) = 28.316 L

Units of Mass

44
gram (g) = 0.001 kg (exact, definition)

milligram (mg) = 0.001 g (exact, definition)

= 1000 g (exact, definition)

kilogram (kg)
= 2.205 lb

=1000 kg (exact, definition)

ton (metric)
= 2204.62 lb

ounce (oz) = 28.35 g

pound (lb) = 0.4535924 kg

=2000 lb (exact, definition)

ton (short)
= 907.185 kg

= 2240 lb (exact, definition)

ton (long)
= 1.016 metric ton

Units of Energy

4.184 joule (J) = 1 thermochemical calorie (cal)

1 thermochemical calorie (cal) = 4.184 ×× 107  erg

erg = 10–7 J (exact, definition)

electron-volt (eV) = 1.60218 ×× 10−19 J = 23.061 kcal mol−1

liter∙atmosphere = 24.217 cal = 101.325 J (exact, definition)

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4.184 joule (J) = 1 thermochemical calorie (cal)

nutritional calorie (Cal) = 1000 cal (exact, definition) = 4184 J

British thermal unit (BTU) = 1054.804 J1

Units of Pressure

torr = 1 mm Hg (exact, definition)

= N m–2 (exact, definition)

pascal (Pa)
= kg m–1 s–2 (exact, definition)

= 760 mm Hg (exact, definition)

= 760 torr (exact, definition)
atmosphere (atm)
= 101,325 N m–2 (exact, definition)
= 101,325 Pa (exact, definition)

= 105 Pa (exact, definition)

bar
= 105 kg m–1 s–2 (exact, definition)

Fundamental Physical Constants

Name and Symbol Value

atomic mass unit (amu) 1.6605402 ×× 10−27 kg

Avogadro’s number 6.02214076 ×× 1023 mol−1

Boltzmann’s constant
1.380649 ×× 10−23 J K−1
(k)

charge-to-mass ratio
1.75881962 ×× 1011 C kg−1
for electron (e/me)

fundamental unit of
1.602176634 ×× 10−19 C
charge (e)

46
Name and Symbol Value

electron rest mass (me) 9.1093897 ×× 10−31 kg

Faraday’s constant (F) 9.6485309 ×× 104 C mol−1

gas constant (R) 8.205784 ×× 10−2 L atm mol−1 K−1 = 8.314510 J mol−1 K−1

molar volume of an
22.41409 L mol–1
ideal gas, 1 atm, 0 °C

molar volume of an
22.71108 L mol–1
ideal gas, 1 bar, 0 °C

neutron rest mass (mn) 1.6749274 ×× 10−27 kg

Planck’s constant (h) 6.62607015 ×× 10−34 J s

proton rest mass (mp) 1.6726231 ×× 10−27 kg

Rydberg constant (R) 1.0973731534 ×× 107 m−1 = 2.1798736 ×× 10−18 J

speed of light (in

2.99792458 ×× 108 m s−1
vacuum) (c)

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 Specific Heat Capacity for Water

C°(H2O(l)) = 4.184 J∙g-1∙°C-1

C°(H2O(s)) = 1.864 J∙K−1∙g−1

C°(H2O(g)) = 2.093 J∙K−1∙g−1

Table E4

Standard Water Melting and Boiling Temperatures and Enthalpies ofthe

Transitions

Temperature (K) ΔH (kJ/mol)

melting 273.15 6.088

boiling 373.15 40.656 (44.016 at 298 K)

Standard Thermodynamic Properties for Selected Substances

Substance ΔH∘fΔHf° (kJ mol–1) ΔG∘fΔGf° (kJ mol–1)

aluminum

Al(s) 0 0

Al(g) 324.4 285.7

Al3+(aq) –531 –485

Al2O3(s) –1676 –1582

AlF3(s) –1510.4 –1425

AlCl3(s) –704.2 –628.8

AlCl3·6H2O(s) –2691.57 –2269.40

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Substance ΔH∘fΔHf° (kJ mol–1) ΔG∘fΔGf° (kJ mol–1)

Al2S3(s) –724.0 –492.4

Al2(SO4)3(s) –3445.06 –3506.61

antimony

Sb(s) 0 0

Sb(g) 262.34 222.17

Sb4O6(s) –1440.55 –1268.17

SbCl3(g) –313.8 –301.2

SbCl5(g) –394.34 –334.29

Sb2S3(s) –174.89 –173.64

SbCl3(s) –382.17 –323.72

SbOCl(s) –374.0 —

arsenic

As(s) 0 0

As(g) 302.5 261.0

As4(g) 143.9 92.4

As4O6(s) –1313.94 –1152.52

As2O5(s) –924.87 –782.41

AsCl3(g) –261.50 –248.95

As2S3(s) –169.03 –168.62

AsH3(g) 66.44 68.93

H3AsO4(s) –906.3 —

barium

49
Substance ΔH∘fΔHf° (kJ mol–1) ΔG∘fΔGf° (kJ mol–1)

Ba(s) 0 0

Ba(g) 180 146

Ba2+(aq) –537.6 –560.8

50