14

14.1 Formulae, Functional Groups and Nomenclature

14.2 Characteristic Organic Reactions
14.3 Isomerism

14.1 Formulae, Functional Groups and Nomenclature

The Chemistry of Carbon Compounds
 Organic chemistry involves the study of the structure, properties and reactions of hydrocarbons and their
derivatives. All organic compounds contain carbon, and most (but not all) contain hydrogen.

 A hydrocarbon is a compound which is made up of carbon and hydrogen atoms only. The derivatives
contain, in addition to carbon atoms, other elements such as hydrogen, halogens, oxygen, nitrogen,
sulphur, etc.

 The carbon atom has only two shells, making it able to form very strong covalent bonds with itself and
with atoms of other elements. Because of this, an almost infinite variety of carbon compounds is known.

 Catenation is the tendency of identical atoms to form long chains of covalent bonds with each other.
Other Group IV elements such as silicon cannot catenate effectively because their bonds will be long and
therefore not strong enough to sustain a chain.

 The physical properties of organic compounds depend on two factors:

1. The number of carbon atoms in the molecule (chain length)

The longer the carbon chain, the more the number of electrons and the stronger the van der Waals’
forces. Strong van der Waal’s forces result in higher boiling and melting points.
The boiling points of straight-chain alkanes increase with increase in the number of carbon atoms.

Ethane Propane Butane

Structure

Total electrons 18 26 34
Boiling point/˚C −88 −42 0

2. The arrangement of carbon atoms in the molecule.

Straight chain molecules tend to offer a greater surface area for intermolecular forces to act, leading to
higher melting and boiling points than branched chain molecules of the same number of carbon atoms.
The boiling point of normal butane is higher than that of 2-methylpropane. These two molecules have
the same nuber of carbon and hydrogen atoms, and hence the same number of electrons.

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 Butane 2-methylpropane

Structure

Total electrons 34 34
Boiling point/˚C 0 −12

 The chemical properties of organic compounds depend on the functional group present in the
molecule.

Types of Formulae

i) General Formula
 Straight-chain alkanes have the general formula 𝐶𝑛 𝐻2𝑛+2 , where 𝑛 is a positive integer. The first part of
the name indicates the chain length, as below:
1 carbon = 𝒎𝒆𝒕𝒉 − 2 carbons = 𝒆𝒕𝒉 − 3 carbons = 𝒑𝒓𝒐𝒑 − 4 carbons = 𝒃𝒖𝒕 − , etc.

 Cyclic alkanes have the general formula 𝐶𝑛 𝐻2𝑛 , where 𝑛 is a positive integer. This is the same general
formula as the straight-chain alkenes.

 The general formula for monocarboxylic acids is 𝐶𝑛 𝐻2𝑛+1 𝐶𝑂𝑂𝐻, with 𝑛 starting at 0 for methanoic acid,
𝐻𝐶𝑂𝑂𝐻.

ii) Empirical Formula

 It gives the simplest whole number ratio of atoms in the molecule. Empirical formulae are usually
determined from percentage compositions by mass, which would have been obtained by combustion
analysis.

 The organic substance is burnt completely in oxygen, and the masses of carbon dioxide and water formed
can be used to determine the percentages of carbon, hydrogen, oxygen, etc. in a molecule of the
compound.

iii) Molecular Formula

 It gives the actual number of atoms of each element in the molecule. The molecular formula can be
determined from empirical formula if the relative molecular mass, 𝑀𝑟 , is known. The 𝑀𝑟 is determined
by mass spectrometry.

 A single molecular formula may suit several different compounds. For this reason, molecular formulae
are generally not informative enough and are rarely used when writing equations.

iv) Structural Formula

 It gives the precise arrangement of the atoms and groups in the molecule. Structural formulae are much
more informative than molecular formulae, and are thus generally used when writing down equations to
avoid ambiguity.

 Enough information is shown to make the structure clear, but most of the actual covalent bonds are
omitted. Sometimes the important bonds are shown.

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v) Displayed or Graphical Formula
 This shows every bond in its relative position in the molecule, without omission whatsoever.

vi) Skeletal Formula

 This shows all atoms except carbon atoms and any H atoms which are bonded to C atoms. Each covalent
bond is shown by a line; a C atom is at the joining points of the lines.
All the atoms of a functional group must be given fully.

The following table compares the different formulae discussed so far:

Displayed Formula Structural Formula Molecular Formula Skeletal

𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3

𝑜𝑟 𝐶4 𝐻10
𝐶𝐻3 (𝐶𝐻2 )2 𝐶𝐻3

𝐶𝐻3 𝐶𝐻(𝐶𝐻3 )𝐶𝐻2 𝐶𝐻3 𝐶5 𝐻12

𝐶𝐻3 𝐶𝐻 𝐶𝐻2
𝑜𝑟 𝐶3 𝐻6
𝐶𝐻3 𝐶𝐻 = 𝐶𝐻2

𝐶𝐻3 𝐶𝐻(𝑂𝐻)𝐶𝐻2 𝐶𝐻3 𝐶4 𝐻10 𝑂

𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐶𝐻3 𝐶4 𝐻8 𝑂2

𝐶𝐻3 𝐶𝐻(𝐶𝐻3 ) 𝐶𝐻2 𝐶𝑂𝑂𝐻 𝐶5 𝐻10 𝑂2

Functional Groups and Homologous Series

 A functional group is a specific atom, group of atoms or arrangement of bonds which confers certain
properties onto the entire molecule. Organic molecules are classified by the dominant functional group
in the molecule.

 A homologous series is a family of compounds with the same general formula and the same functional
group. Alcohols, carboxylic acids, esters, etc., are examples of some homologous series. The formula of
each successive member in a homologous series increases by −𝐶𝐻2 .

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 Chemical properties tend to be similar in a homologous series. Physical properties tend to change
gradually in a homologous series.

 The following table lists common functional groups and the respective homologous series.

Functional Group Homologous Series Example molecule(s)

Alkene propene

Halogenoalkane 1-bromopropane

Alcohol propan-1-ol

Aldehyde ethanal

Ketone propanone

Phenolic 2,4,6 – tribromophenol

Carboxylic acid ethanoic acid

Acyl chloride ethanoyl chloride

Ester methylethanoate

Nitrile ethanenitrile

Amine ethylamine

Amide ethanamide

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Systematic Nomenclature of Alkanes
 To avoid ambiguity, the IUPAC (international Union of Pure and Applied Chemistry) has a set of rules
used for naming organic compounds. In brief, the rules are:
1. Identify the longest continuous carbon chain;
2. Identify any side-groups attached to the main chain, and the “address” of the C atom to which they
are bonded. The lower “address” value must be used;
3. If there are more than one side-groups, these should be given in alphabetical order.

 Common side-groups are:

Side-Group −𝑪𝑯𝟑 −𝑪𝟐 𝑯𝟓 −𝑶𝑯 −𝑩𝒓 −𝑪𝒍 −𝑵𝑶𝟐

Name -methyl -ethyl -hydroxy -bromo -chloro -nitro

 The names of the following compounds are given. Notice that numbers are separated from words by a
hyphen, and numbers are separated from other numbers by a comma.

Alkane Formula Systematic Name

2-methylpentane

2-methylbutane
Longest chain has 4 C atoms

2,3-dimethylbutane

2,2-dimethylbutane

3-methylpentane
The longest chain has 5 C atoms

2-chloro-2-methylbutane
The –chloro comes before -methyl in the
alphabet

3-ethyl-2-methylpentane
ethyl comes ahead of methyl on the alphabet

Methylcyclopentane

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 Practice 14.1a More Complicated Molecules
Systematic Nomenclature of Alkenes
1. Give the IUPAC names of the following alkanes
and cycloalkanes:

4-ethyl-2-methylhexane

(Lowest sum of addresses plus alphabetical

consideration)

3,4,6-trimethyl-5-propyloctane

(The prefixes di, tri, tetra etc., used to designate several

groups of the same kind, are not considered when
alphabetizing.)

1-ethyl-2-methylcyclohexane

(If there are two groups, assign the number one to the
first alkyl group alphabetically. Then count the shortest
distance to the second substituent.)
the ring, name the ring as a side-
NB. For 1. h): When the alkane chain
is complex or has more carbons than
4-ethyl-2,6-dimethylheptane
2,3,4,6-tetramethylheptane
2,2,3,3-tetramethylbutane
3-ethyl-2-methylheptane

5-ethyl-2-methylheptane
2,2,3-trimethylbutane

3-cyclobutylheptane
2,2-dimethylbutane

group on the alkane chain.

Answers

3-ethyl-1,1-dimethylcyclohexane
h)
a)
b)

d)

g)
c)

e)
f)
1.

Systematic Nomenclature of Alkenes

 The IUPAC system for naming alkenes is as follows:

1. Identify the longest continuous carbon chain containing the double bond;
2. Numbering of the chain is done from the end which gives the lower address for the double bond;
3. Alkene name ends with –ene. Side-groups are generally treated in a similar way to alkanes.

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 Alkene Formula Systematic Name

But-1-ene
(The double bond is between the 1st and 2nd C
atoms, hence address = 1)

4-methylpent-2-ene
(Atoms numbered from the right to give the
double bond a lower address)

Penta-1,3-diene

5-methylhept-3-ene

4,4-dimethylhex-2-ene

3-methylhexene
(Not 2-methylhexene). For cycloalkenes, the
name must be such that the double bond is
between C1 and C2.

3-methyl-penta-1,4-diene

Practice 14.1b
b) 4-ethyl-2,3-dimethylhept-

c) 3,3-dimethylcyclohexene

2. Name the following compounds

a) 4-methylhex-1-ene
Answers

2-ene
B
1.
2.

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14.2 Characteristic Organic Reactions
Bond Fission (Bond Breaking)
 Energy (heat or light) must be supplied to break the bonds in organic molecules. The covalent bonds
break in two possible ways: homolytic fission and heterolytic fission.

1. Homolytic Fission
 If A and B are atoms of elements of similar electronegativity, the bond between
the two atoms is non-polar. The bonding electrons are centrally located.

The C-H bond is considered as non-polar, due to C and H having almost the same electronegativity.

 Homolytic fission occurs when a bond breaks, and each atom takes one of the bonding electrons, forming
free radicals.

 Non-polar bonds are the most likely to undergo homolysis:

UV light
𝑪𝒍𝟐 𝑪𝒍 • + 𝑪𝒍 • ∆𝐻 = +242 kJmol−1
chlorine chlorine radicals

𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑯𝟑 𝑪𝑯𝟑 𝑪𝑯𝟐 • + 𝑪𝑯𝟑 • ∆𝐻 = +350 kJmol−1

propane heat propyl radical methyl radical

 A free-radical is an atom, molecule or ion with unpaired electrons. The availability of unpaired electrons
causes radicals to be highly reactive.

 Metals and their ions or complexes with unpaired electrons are not radicals even if they may have
unpaired electrons. The term ‘radical’ is only applied to specie that can form covalent bonds.

2. Heterolytic Fission
 If A and B are atoms of elements of different electronegativity, the bond
between the two atoms is polar. The bonding electrons are closer to the more
electronegative atom.
If the bond breaks, one of the bonding atoms takes both electrons, forming ions. Examples:

𝐹𝑒𝐵𝑟3
𝑪𝑯𝟑 𝑩𝒓 𝑪𝑯𝟑 + + 𝑩𝒓−
bromomethane methyl cation bromide ion

Types of Organic Reagent

Most organic reactions are activated by electrostatic attraction between opposite charges.

1. Nucleophiles
 A nucleophile is a specie that has a lone pair of electrons and is attracted to
centres of positive charge to form a covalent bond.

 Nucleophiles attack the positive or partially positive end of a polar bond.

 Anions, pi-bonds and atoms with lone pairs are examples of nucleophiles, e.g.
𝑶𝑯− , 𝑯𝟐 𝑶, 𝑵𝑯𝟑 and −𝑵𝑯𝟐 , the amine group.

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2. Electrophile
 An electrophile is a specie that has a positive or partial positive charge and attracts to a centre of negative
charge to form a covalent bond.

 Electrophiles attack the negative end of a polar bond, or a region of electron

cloud density such as a benzene ring or an alkene C=C double bond.

 Examples of electrophiles are 𝑁𝑂2+ , (nitryl cation), 𝐵𝑟 + and 𝐶𝐻3+ .

Types of Organic Reactions

i) Addition
 Two molecules react to form one.

+ 𝑯𝑩𝒓

propene 2-bromopropane

ii) Substitution
 An atom or group of atoms is replaced by another atom or group of atoms.

+ 𝑶𝑯− + 𝑩𝒓−

2-bromopropane propan-2-ol

iii) Elimination
 Two substituents are removed from a molecule in either a one-step or two-step mechanism. One of the
molecules formed is usually 𝐻2 𝑂 or a hydrogen halide molecule such as 𝐻𝐵𝑟.
Example 1: the elimination of 𝐻𝐵𝑟 from halogenoalkanes by the action of ethanolic sodium hydroxide:

+ 𝑯𝑩𝒓

2-bromopropane propene

Example 2: the elimination of 𝐻2 𝑂 from alcohols by the action of concentrated sulfuric acid:

+ 𝑯𝟐 𝑶

cyclohexanol cyclohexene

iv) Oxidation
Common oxidising agents used in organic reactions are:

 Potassium manganate (VII) solution, 𝑲𝑴𝒏𝑶𝟒 (𝒂𝒒)

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- It is strongly oxidising when hot, concentrated and acidified, e.g. when used to oxidise alkenes, leading
to the breaking of the C=C bond;
- It is mildly oxidising when cold, dilute and in alkaline solution, e.g. when used to oxidise alkenes to -diols.

 Potassium dichromate (IV), 𝑲𝟐 𝑪𝒓𝟐 𝑶𝟕 (𝒂𝒒), used in the oxidation of, for example, primary alcohols to
aldehydes and subsequently to carboxylic acids. The solution must be hot and acidified.

 Halogens in the present of an alkali are oxidising agents. For example, a solution of iodine in aqueous
𝑁𝑎𝑂𝐻 acts as an oxidising agent when used in the tri-iodomethane test.

 Metal ions in alkaline solution are oxidising agents. Examples are the silver ions in aqueous ammonia
(also known as the Tollens’ reagent) and the copper ions in ammonia (also known as Fehling’s solution).
Both reagents can oxidise aldehydes to carboxylic acids without attacking carbon-carbon double bonds;
the metal ions reduce to lower oxidation states.

v) Reduction
Common reducing agents used in organic reactions are:

 𝑯𝟐 in the presence of a 𝑵𝒊/𝑷𝒕/𝑷𝒅 catalyst can reduce alkenes to alkanes, and benzene to cyclohexane:

𝑁𝑖
+ 𝑯𝟐
ℎ𝑒𝑎𝑡, 140˚𝐶

propene propane

𝑃𝑡
+ 𝟑𝑯𝟐
ℎ𝑒𝑎𝑡, 300˚𝐶

benzene cyclohexane
 Lithium tetrahydridoaluminate (III), 𝑳𝒊𝑨𝒍𝑯𝟒 or sodium tetrahydridoborate (III), 𝑵𝒂𝑩𝑯𝟒 .
- Sodium borohydride, or sodium tetrahydridoborate, reduces aldehydes and
ketones into alcohols but cannot reduce esters or carboxylic acids.

- Lithium aluminium hydride or lithium tetrahydridoaluminate has a similar

structure as sodium borohydride, but is a stronger reducing agent. This is
due to the 𝐴𝑙 − 𝐻 bond being weaker than the 𝐵 − 𝐻 bond. It reduces
aldehydes, ketones, esters, carboxylic acids, and amides.

- Both the reagents react with water, therefore conditions must be dry.

 A metal, e.g. tin in the presence of concentrated 𝑯𝑪𝒍(𝒂𝒒)

- The tin and hydrochloric acid react to form hydrogen, which then acts as the reducing agent. This
is commonly used in the reduction of nitrobenzene to phenylamine:

𝑆𝑛, 𝑐𝑜𝑛𝑐. 𝐻𝐶𝑙

𝑟𝑒𝑓𝑙𝑢𝑥

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14.3 Isomerism
 Isomerism is the existence of compounds with the same molecular formula but different structures.

 Isomerism is broadly classified into two main forms: structural isomerism and stereo-isomerism.

a) Structural Isomerism
 Structural isomers have the same molecular formula but different precise arrangement of groups. There
are 3 main forms of structural isomerism: positional, chain and functional group isomerism.

i) Positional Isomerism
 The molecules have the same parent name and functional group, but differ in the position of some group
on the carbon chain.
and

2-methylpentane 3-methylpentane

and
but-2-ene but-1-ene
ii) Chain Isomerism
 The molecules possess the same functional group, but differ in the length of the carbon skeleton.

and

2-methylpentane 2,2-dimethylbutane

iii) Functional Group Isomerism

 The molecules have different functional groups but same molecular formulae:

and
propanone propanal

 Example: Consider the 5 isomeric compounds with molecular formula 𝐶6 𝐻14 :

A normal hexane

B 2-methylpentane

C 3-methylpentane

D 2,3-dimethylbutane

2,2-dimethylbutane
E

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 Compound A is a chain isomer of compounds B, C, D and E. Compounds B and C are chain isomers of
compounds D and E. Compounds B and C are positional isomers of each other. Compounds D and E are
also positional isomers of each other.

b) Stereo-Isomerism
 Stereo-isomers have the same molecular formula and same structural formula, but differ in the
arrangement of the groups in space. Thus, stereo-isomers cannot be distinguished from each other by
writing down the structural formulae, as these would look the same. Instead, a displayed formula is used.
There are two main forms of stereo-isomerism:

i) Cis-Trans (Geometrical) Isomerism

 It arises in alkenes due to restricted rotation about the C=C bond. Each of the two C atoms of the C=C
group must have different groups on it.

 In the cis- isomer, identical groups lie on the same side of the double bond. In the trans- isomer, the
identical groups lie on opposite sides of the C=C bond:

cis-but-2-ene trans-but-2-ene
(b.p. 4 ˚C) (b.p 1 ˚C)

 Cis-trans isomers have different properties like dipole moments, and hence different boiling points,
solubility, etc. The tans- isomers tend to be less polar than the cis- isomers because the dipole cancel out
when similar groups are across each other.

 If two similar groups or atoms are attached to the same C atom of the C=C group, the molecule cannot
exist as geometrical isomers.

2-methylpropene

 Thus, a molecule like 2-methylpropene does not exhibit geometrical isomerism. (It is, however, a chain
isomer of cis-but-2-ene and trans-but-2-ene.)

 For alkenes with 𝑛 double bonds, each of which can show cis-trans isomerism, the number of possible
cis-trans isomers is 2𝑛 . This is illustrated using the molecule hepta-2,4-diene, below:

Isomer 1 Isomer 2 Isomer 3 Isomer 4

C2 – C3 trans- trans- cis- cis-
C4 – C5 trans- cis- trans- cis-

Skeletal
structure

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 Retinol (also known as Vitamin A) is a vitamin that is needed by the retina of the eye for color vision. It
is found naturally in many foods such as carrots, broccoli and pumpkin. The structure of its molecule is
given below:

Vitamin A
 A molecule of Vitamin A has 5 C=C bonds, but only those numbered 1 to 4 can result in cis-trans
isomerism. The bond numbered 5 has identical groups on the same carbon of the C=C group).
 Thus, the number of possible cis-trans isomers of Vitamin A is 24 = 16.

ii) Optical Isomerism

 It arises in organic molecules where a C atom is bonded to four different groups. This results in a pair
of non-superimposable mirror images, like the left and right hand palms of humans. No matter how the
two hands are oriented, it is impossible for all the major features of both hands to coincide (Try wearing
a left-handed glove on a right hand!).

imaginary
mirror line

Optical isomers of 2-hydroxypropanoic acid (lactic acid)

 The C atom bonded to four different groups is called a chiral centre or asymmetric atom.
Two mirror images of a chiral molecule are called enantiomers or optical isomers.

 A C atom on a benzene ring, or involved in double or triple-bonding cannot be chiral. The drug Cortisone
is used to give short-term pain relief and reduce the swelling from inflammation of a joint or tendon. Its
structure is given below. Its six chiral centres have been marked with rings.

 Optically active molecules generally have similar chemical physical properties, except that they rotate the
plane of polarized light in different directions.

 Many biologically active molecules are chiral, including the naturally occurring amino acids and sugars.
Enzymes, which are chiral, often distinguish between the two enantiomers of a chiral substrate: one

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 enantiomer will fit inside and be bound, whereas the other enantiomer will have a poor fit and is unlikely
to bind.

Summary: Isomerism

Difference in the Difference in the Difference in the Presence of a chiral Restricted rotation
branching of the position of a functional group, centre, e.g. about a C=C bond.
carbon chain, group on the e.g.
e.g. chain, e.g. Propanoic acid and
Butane and Butan-1-ol and methylethanoate
methylpropane Butan-2-ol

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 1. Pyridine, C5H5N, has the following structure:

Which line in the table shows the correct numbers of σ and π bonds in a molecule of pyridine?

2. Which of the following is the geometric isomer of trans-1,2-dibromopropene?

3. Which of the following is correct for the reaction of propene with hydrogen bromide?
A 1-Bromopropane is the only product.
B 1-Bromopropane is the major product.
C 2-Bromopropane is the only product.
D 2-Bromopropane is the major product.

4. Carbon dioxide has the following structure.

O=C=O
Which line in the table shows the correct numbers of and bonds in a molecule of carbon dioxide?

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5.

Which of the above molecules is/are planar?

A P only
B P and Q only
C Q and R only
D P, Q and R

6. Combustion analysis of hydrocarbon X showed that it contained 82·7% carbon and 17·3% hydrogen.
The molecular formula for X could be

7.

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 The systematic name for the structure shown is

A 1,1-dimethylpropane

B 2-methylbutane

C 3-methylbutane
D 2-methylpentane.

1. C
2. C
3. D
4. B
5. B
6. D
7. B

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