Essential Guide for Organic Chemistry Paper 1 and Paper 2

A. Reaction Mechanisms
1. Free Radical Substitution
Alkanes undergo free radical substitution reaction with chlorine and bromine in the presence
of ultraviolet radiation.
CH4 (g) + Cl2 (g)
CH3Cl (g) + HCl (g)
There are three steps in the mechanism of this reaction, namely initiation, propagation and
termination.
Mechanism

Remarks

INITIATION
Cl2
2Cl

Homolytic cleavage* of Cl-Cl bond forming chlorine

radicals. This step is induced by UV light or heat (250400C).

PROPAGATION
CH4 + Cl
CH3 + Cl2

TERMINATION
2Cl
Cl2
CH3 + Cl
CH3 + CH3

CH3 + HCl
CH3Cl + Cl

CH3Cl
CH3CH3

The chlorine radical abstracts a hydrogen atom from the

CH4 molecule, resulting in another reactive intermediate,
a methyl radical, H3C. The methyl radical then reacts with
a Cl2 molecule to produce CH3Cl and a new chlorine
radical, and so on. CH3Cl can undergo further substitution
to form further substituted products like CH2Cl2, CHCl3 and
CCl4.
The propagation steps may continue until all the hydrogen
atoms are substituted. However, they do not go on
forever. The reaction slowly diminishes as the
concentrations of the reactants run out and also because
of the occurrence of chain termination steps.

*Note
Homolytic fission
Eg: in free radical reaction
shows the movement of a single
electron

Heterolytic fission
Eg: Breaking of Br2 bond in electrophilic addition
of alkenes
shows the movement of an electron pair

Note: The free radical substitution of alkanes can be controlled by using a large excess of CH4
to yield monosubstituted chloromethane as the major product.

Essential Guide for Organic Chemistry Paper 1 and Paper 2

2. Elimination Reaction
Other than cracking, an alkene can be formed by the elimination of a hydrogen halide from a
halogenoalkane or elimination of H2O (dehydration) from an alcohol. Alkyl halides
(halogenoalkanes), RX when heated with alcoholic sodium hydroxide undergo an elimination
reaction. This elimination reaction can occur via two mechanisms, either by a carbocation
intermediate (mainly for 3o alkyl halides (halogenoalkanes)) or a concerted step reaction (mainly
for 1o alkyl halides (halogenoalkanes)).
Via carbocation (E1 Mechanism)

OH
R
H3C

H
R

R
+

H
X
Via a concerted step (E2 Mechanism)

H
C

X is the leaving group.

In E2 elimination reaction, the hydroxide ion abstract a H+ from the CH3 group and pulls it off.
This leads to a cascade of electron pair movements resulting in the formation of a carboncarbon double bond, and the loss of the halogen as X.

Essential Guide for Organic Chemistry Paper 1 and Paper 2

3.Nucleophilic Substitution
Nucleophilic substitution reactions occur by either SN1 or SN2 mechanism, depending on the
types of halogenoalkanes involved in the reaction.

SN1 Reaction Mechanism (Two steps)

Tertiary halogenoalkanes with bulky groups usually undergo nucleophilic substitution via the
unimolecular nucleophilic substitution (SN1) mechanism. The reaction happens in two stages.
Firstly, the polarised C-X bond undergoes heterolytic fission, forming an X ion and a highly
reactive trigonal planar carbocation intermediate. This is the rate determining step. Tertiary
halogenoalkanes react via an SN1 mechanism as tertiary carbocations are relatively stable
compared to the secondary or primary ones.
Once the carbocation is formed, it will react immediately with a nucleophile, Nu-. The lone pair
on the nucleophile is strongly attracted to the positive carbon and forms a new bond with it.
Two Steps:
CH3

CH3

slow
Cl

R'

Cl

R'

R"

R"
CH3

Nu-

CH3

Nu

R'
R"

fast

CH3

R'
R"

Nu

Nu

R'
R"

Energy Profile Diagram

Kinetics of the mechanism:
Rate determining step of the above mechanism
involves one reacting species, the tertiary
halogenoalkane. The mechanism is termed
unimolecular nucleophilic substitution. The rate
equation is rate = k [RX] where k = rate
constant. The overall order of reaction is 1.

Essential Guide for Organic Chemistry Paper 1 and Paper 2

SN2 Reaction Mechanism (One step)

Primary halogenoalkanes usually undergo nucleophilic substitution via the bimolecular
nucleophilic substitution (SN2) mechanism. The nucleophile attacks the partially electron
deficient + C atom of the polarised C-X bond to form a pentacoordinate transition state in a
single step. This is the rate determining step.
In the transition state, both the nucleophile and halogen are partially bonded to the same C
atom. The departure of the leaving group (X-) occurs simultaneously with the backside attack
by the nucleophile.
One Step:
H3C
C

Nu-

Br

Nu

H3C

Br
H

Nu

CH3
H
C

Br

transition state
Energy Profile Diagram

Kinetics of the mechanism:

Rate determining step of the mechanism
involves two reacting species, R-X and Nu .
The above mechanism is termed bimolecular
nucleophilic substitution. The rate equation is
rate = k [RX] [Nu ], where k = rate
constant. The overall order of reaction is 2.
The rate of nucleophilic substitution depends on:
a) Type of halogeoalkanes and the mechanism
b) Type of halogen/ leaving group
c) Type of nucleophile
a)
Type of halogenoalkanes and the mechanism
The type of mechanism for nucleophilic substitution is determined by the structure of the
halogenoalkanes:
Structure of halogenoalkane
10
20
30

Type of mechanism
SN2
SN2 or SN1
SN1

The inductive and steric effects of substituents can help to explain why primary
halogenoalkane tend to undergo SN2 while tertiary halogenoalkanes tends to undergo SN1
reactions. In both cases it is helpful to consider the intermediate or transition state formed.
Tertiary halogenoalkanes form a more stable/lower energy carbocation ion intermediate in the
SN1 process. The stability of carbocation intermediate depends on the number of R groups
bonded to positively charged (electron deficient) carbon atom.
4

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Stability of carbocation: 30 > 20 > 10
In a tertiary carbocation, the three electron-donating R-groups bonded to the carbocation will
inductively stabilise the positive charge on the carbocation.
The differences in stability of the different carbocation has been confirmed by gas phase
measurements of the heterolytic C-Br bond dissociation energies of CH3Br, CH3CH2Br,
(CH3)2CHBr, and (CH3)3CBr. The figure below presents the relative stabilities of these four
carbocations in quantitative terms.

Extracted from: J. Amer. Chem. Soc. 96, 7552 (1974)

The SN2 mechanism involves five groups surrounding the central carbon atom in the transition
state. With primary halogenoalkanes, two of these groups are hydrogen atoms so there is
room for the other three groups. Tertiary halogenoalkanes cannot proceed by this mechanism
as there is no room to accommodate five bulky groups around the carbon atom. This is an
example of steric hindrance.

Substitution reactions involving the ionic SN1 mechanism are generally faster than those
proceeding via the SN2 mechanism. Thus the hydrolysis of a tertiary chloroalkane with water
or hydroxide ions is faster than the hydrolysis of a primary chloroalkane under the same
conditions.
CH3

CH3
H3C

C
CH3

Cl

>

H3C

C
H

Cl

H
Cl

>

Cl

>

CH3

Essential Guide for Organic Chemistry Paper 1 and Paper 2

10b.5 Elimination reaction of Halogenoalkane
In the presences of OH ions, which is dissolved in alcohol, one of the () hydrogen of the
halogenoalkane is eliminated with the halogen (e.g. bromine) to form alkenes according to
the following equation:

Elimination versus Nucleophilic Substitution Reaction

The same reagent is used for both substitution and elimination the halogenoalkane and either
sodium or potassium hydroxide solution. In all cases, you will get a mixture of both reactions
happening - some substitution and some elimination, depending on a number of factors.
1) The type of halogenoalkane is the most important factor.
- Tertiary halogenoalkanes tend undergo mainly the elimination reaction,
- Primary halogenoalkanes tend to undergo mainly substitution reaction.
2) The proportion of water to ethanol in the solvent. Water encourages substitution while
ethanol encourages elimination.
3) Higher temperature encourages elimination.
4) Higher concentration of NaOH favors elimination.

Essential Guide for Organic Chemistry Paper 1 and Paper 2

B. Chemical Reactions
Alkenes

Reduction (Hydrogenation)

In general, alkenes react with hydrogen gas at high temperature (~150 oC) in the presence of
finely divided heterogeneous nickel catalyst to form the corresponding alkanes.
Example:
Ni

1. CH3CH=CH2 + H2

CH3CH2CH3

heat
Ni

2.

+ H2
heat

Electrophilic Addition

The main chemistry of alkenes revolves around the C=C double bond. The C=C bond is an
electron-rich region with the -electrons susceptible to attack by electrophiles. Alkenes tend
to undergo electrophilic addition reaction which involves the breaking of the -bond and the
two electrons in the -bond are used to form bonds with other atoms.

1. Addition of Halogen (Halogenation)

General equation for halogenation in non-polar organic solvent like CCl4:
r.t.p
where X2 can be Cl2, Br2 or I2
Observation: For bromine: reddish brown bromine decolourises.
Note: This test is often used to distinguish alkanes and alkenes.

2. Addition of water (Hydration)

Industrially, when heated at 300 oC in the presence of concentrated phosphoric(V) acid,
H3PO4, at high pressure of 70 atm, alkenes react with steam to form the corresponding
alcohols. This is an important industrial process to produce ethanol; a very common
and essential raw material.
C2H4 + H2O

CH3CH2OH

In the laboratory the same hydration reaction can also take place when an alkene is
mixed with concentrated sulfuric acid followed by heating with water.

H
C C

H H

+ H2O

H2SO4

C C
H OH

H
7

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Halogenoalkanes

Nucleophilic Substitution Reaction

In halogenoalkane, the carbon (+), which is bonded to the halogen (-), is susceptible to
attack by nucleophiles. Nucleophiles are species (an ion or a molecule) which are strongly
attracted to region of positive charge. Nucleophiles are either negatively charged ions or
neutral molecules with an available lone pair, imparting a strongly - charge on a molecule.
Examples of nucleophiles in the IB syllabus are the hydroxide ion (OH), cyanide ion (CN)
or the ammonia molecule (:NH3). In a nucleophilic substitution reaction, the halogen will be
substituted by the nucleophile.
a) Formation of alcohol
Alcohol is produced when halogenoalkane is warmed with the aqueous hydroxide ion.
Example: In 1-bromopropane, a bromide ion in the halogenoalkane is substituted by
an -OH group to form propan-1-ol.
CH3CH2CH2Br + OH

CH3CH2CH2OH + Br

warm

b) Formation of amine
Amine is produced when halogenoalkane is heated with ammonia in a sealed tube
which serves to prevent the gaseous ammonia from escaping during the reaction.
Example,
CH3CH2CH2Br +

NH3

CH3CH2CH2NH2 + HBr

Heat in
sealed
tube

c) Formation of nitrile
Nitrile is produced when halogenoalkane is heated under reflux with the alcoholic
cyanide ion like alcoholic potassium cyanide.
Example,
CH3CH2CH2Br + CN

Alcoholic
reflux

CH3CH2CH2CN + Br
(one more carbon atom added to chain)

When the nitrile product of the above reaction undergoes reduction, amine is produced.
CH3CH2CH2CN

H2(g)/ Ni(s)
Heat

CH3CH2CH2CH2NH2

Acidic Hydrolysis of Nitriles

When nitrile is hydrolysed using aqueous acid, then a carboxylic acid is produced.
O
H3C

CH2
CH2 C

H+

heat
2H2O

H3C

C
CH2
CH2

OH

+ NH4+

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Alcohols

Reaction With Sodium

Alcohols undergo redox reactions with reactive metals like sodium at room temperature to
form a salt and hydrogen gas. Sodium reacts with ethanol, according to the equation below,
to form sodium ethoxide and hydrogen gas. Effervescence is observed and gas collected will
produce a pop sound with lighted splint.
Example:
2CH3CH2OH (l) + 2Na (s) 2CH3CH2O-Na+ (aq) + H2 (g)
Being a weak acid in nature (weaker than water), alcohols do not react with sodium hydroxide
and sodium carbonate under room temperature.

Oxidation Of Alcohols

Alcohols can be oxidised to form carbonyl compounds or carboxylic acids, depending on the
class of alcohol and the oxidation conditions employed. Generally, primary and secondary
alcohols can be easily oxidised but not tertiary alcohols.
- Primary alcohols are readily oxidised to aldehydes under controlled conditions, the
aldehydes can be further oxidised to form carboxylic acids.
- Secondary alcohols are oxidised to ketones
- Tertiary alcohols do not undergo oxidation.
Ethanol, CH3CH2OH, a primary alcohol, can be oxidised to ethanoic acid. Common oxidising
agents used are acidified aqueous potassium dichromate(VI) or potassium manganate(VII)
solution. The orange dichromate(VI) ion (Cr2O72) is reduced to form the chromium (III) ion
(Cr3+), which is green in colour. Purple manganate (VII) ions will be reduced to form colourless
Mn2+ ions. For oxidation of primary alcohols, strong reaction conditions like refluxing with
strong oxidising agent like MnO4- will favour the formation of the carboxylic acid. Distillation
and the use of a milder oxidising agent like Cr2O72- will favour the formation of aldehyde. The
aldehyde formed must be collected via distillation immediately; otherwise oxidation reaction
will carry on forming carboxylic acid.

Example of oxidation of alcohol using KMnO4:

1o alcohol eg: ethanol
CH3CH2OH + 2[O] CH3COOH + H2O
2o alcohol eg: propan-2-ol
CH3CH(OH)CH3 + [O] CH3COCH3 + H2O
3o alcohol eg: 2-methylpropan-2-ol
(CH3)3COH + [O] No reaction
9

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Condensation/Esterification (Alcohols and Carboxylic Acids)

Alcohols undergo esterification or condensation reaction with carboxylic acids under reflux
to form sweet-smelling esters. he reaction is slow and reversible, taking hours to reach
equilibrium. The reactant mixture is refluxed and concentrated sulfuric acid catalyst is
added to speed up the reaction. The concentrated sulfuric acid also acts as a dehydrating
agent, removing water from the equilibrium mixture to favour the forward reaction.

Example: Esterification of ethanol with ethanoic acid

CH3CH2OH + CH3COOH
CH3COOCH2CH3
conc
H2SO4

O
H3C

CH2
OH

ethanol

C
H3C

OH

ethanoic acid

+ H2O
O
C

H3C

reflux

O
CH2 CH3

H2O

ethyl ethanoate

Carboxylic Acids

Neutralisation Reaction with Bases

Carboxylic acids undergo neutralisation with sodium hydroxide and carbonates.

RCOOH + NaOH
RCOO-Na+ + H2O
RCOOH + NaHCO3
RCOO-Na+ + H2O + CO2
2RCOOH + Na2CO3
2RCOO-Na+ + H2O + CO2
Eg:
CH3COOH + NaHCO3
CH3COO-Na+ + H2O + CO2
sodium ethanoate

Reduction

Carboxylic acids can be reduced by strong reducing agent such as LiAlH4 in ether (as a solvent)
followed by the addition of aqueous acid to products to form primary alcohols. LiAlH4 acts as a
source of hydride ions, H-, a powerful nucleophile (electron pair donor).
(1) LiAlH4/ether

RCOOH

RCH2OH
(2)H2O/H+

Note: H2/Ni cannot be used to reduce carboxylic acids to alcohols. The reduction of a carboxylic
acid to an aldehyde cannot be achieved.

Amines
Reaction of amines with acids (neutralisation)
Amines (and ammonia) act as bases by accepting a proton (H+) from acids. The basic nature of
an amine depends on the availability of its lone pair on the nitrogen atom for accepting a proton
from an acid via dative bond formation.
When primary, secondary or tertiary amines react with acids at room temperature, they are
converted to amine salts. They are named by changing 'amine' to 'ammonium' and by adding
the name of the negative ion (anion).
10

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Eg:

CH3NH3+Cl-

CH3NH2 + HCl

methylammonium chloride

Ammonium salts will yield the free amine when warmed with aqueous sodium hydroxide.
CH3CH2NH3+Cl- (aq)

NaOH(aq) CH3CH2NH2(g) + NaCl(aq) + H2O(l)

Reactions of amines with carboxylic acids

Amines react with carboxylic acids when heated to form amides that contain the

group.

heat

This condensation reaction is particularly important in biological systems, because amino acids
are bifunctional molecules: they contain both an amine functional group and a carboxylic acid
functional group. There are 20 naturally occurring amino acids that function as the monomers
of proteins in cells.
Eg:

The two amino acids can react (in the presence of enzymes) to form two different condensation
products containing an amide functional group. The amide linkage formed in condensation
reactions of amino acids is also called a peptide bond. It can undergo acid hydrolysis to release
amino acids.

11

Essential Guide for Organic Chemistry Paper 1 and Paper 2

C. Isomerism
Isomerism refers to the existence of two or more compounds having the same molecular
formula but different structural formula or different spatial arrangements of atoms. There are
2 main types of isomerism: structural isomerism and stereoisomerism.

Structural Isomerism
Structural Isomerism Compounds having the same molecular formula but different structural
formula. These isomers arise because of the possibility of branching in carbon chains. For
example, there are two isomers of butane, C4H10. In one of them, the carbon atoms lie in a
"straight chain" whereas in the other the chain is branched.

There are 3 types of structural isomerism:

a) Chain isomerism
b) Positional Isomerism
c) Functional Group Isomerism

12

Essential Guide for Organic Chemistry Paper 1 and Paper 2

a) Chain Isomerism
Compounds having the same molecular formula but a different arrangement of the carbon
chain
Eg: Draw all the possible structural isomers of hexane, C6H14.

b) Positional Isomerism
Compounds having the same molecular formula but different position of a functional group
on a carbon chain or ring
Eg C3H7OH

H H H

H H H

H C C C H

H C C C O H

Eg

H O H

H H H

propan-1-ol
C6H4Cl2

propan-2-ol

Cl
Cl

Cl
Cl

Cl
1,2-dichlorobenzene

1,3-dichlorobenzene

Cl
1,4-dichlorobenzene

c) Functional Group Isomerism

Compounds having the same molecular formula but different functional groups

13

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Stereoisomerism
Stereoisomers have the same structural formula, i.e. their position and type of functional group
are identical, however they differ in the way the atoms are arranged in 3-dimensional space.
The two types of stereoisomerism are:
a) Geometrical Isomerism
b) Optical Isomerism.

a) Geometric Isomerism
Recall from hybridisation theory about the restricted rotation about the C=C double bond in
alkenes.

Because of this restriction to rotation, isomers can be formed when there are two non-identical
groups attached to the carbon atoms at each end of the double bond. The smallest alkene
that can show geometric isomerism is but-2-ene.

Cis isomer : same or similar substituents on same side of double bond.

Trans-isomer: same or similar substituents on opposite sides of double bond
Geometrical isomerism can also occur in disubstituted cycloalkanes. The rotation of bonds is
restricted because the C-C single bond is part of a ring system.
Examples : 1,2-dichlorocyclopropane and 1,3dichlorocyclobutane.

Sometimes geometric isomerism can result in a marked difference in both chemical and
physical properties in disubstitued cycloalkanes. This tends to occur when there is some sort
of chemical interaction between the substituents. Cis-but-2-ene-1,4-dioic acid melts with
decomposition at 130-131C. However, trans-but-2-ene,1,4-dioic acid does not melt until
286C.

14

Essential Guide for Organic Chemistry Paper 1 and Paper 2

In the cis-isomer, the two carboxylic acid groups are closer together so intra-molecular
hydrogen bonding is possible between them. In the trans-isomer, the two carboxylic acid
groups are too far apart to attract each other, resulting in stronger intermolecular forces of
attraction between different molecules and higher melting point. The cis-isomer also reacts
when heated to lose water and form a cyclic acid anhydride. However, the trans-isomer cannot
undergo this reaction.
Consider the compound, 1,2-dichloroethene, ClCH=CHCl. There are two possible
stereoisomers for this compound.

In the cis-isomer, the two Cl-atoms lie on the same side of the C=C bond while in the transisomer, they lie on the opposite sides.

cis-1,2-dichloroethene

trans-1,2-dichloroethene

As a result of geometric isomerism, the physical properties like the melting and boiling points
of the cis-isomer and trans-isomer are different. The cis-isomer of 1,2-dichloroethene has an
overall dipole moment and is polar. However, in the trans-isomer, the two dipole moments
cancel each other and the molecule is non-polar.

cis-1,2-dichloroethene

trans-1,2-dichloroethene

Assigning cis-trans configuration

In assigning a cis-trans configuration for alkenes with four different substituents, the relative
molecular masses of the substituents attached to the two C-atoms in the C=C bonds will be
the main consideration. Consider the molecule BrClC=CFI, the assignment of cis-trans
isomerism is determined by the relative positions of the heavier substituents Br and I.

15

Essential Guide for Organic Chemistry Paper 1 and Paper 2

b) Optical Isomerism
Molecules that are non-superimposable with their mirror images are said to be chiral. Optical
isomerism is exhibited by stereoisomers that are chiral. The two mirror images of such a
molecule are non-superimposable and they are referred to as enantiomers.
Example of enantiomer:

By contrast, if we carry out the same transformations on 1,1-dichoroethane, we find that its
mirror image is superimposable on the original.

A chiral molecule does not have a plane of symmetry. Most commonly the molecule contains
a chiral centre: the presence of a carbon atom bonded to four different groups. A plane of
symmetry is defined to be a plane that cuts through the middle of an object (or molecule) so
that one half of the object is a mirror image of the other half. A molecule that has a plane of
symmetry in any of its possible conformations must be identical to its mirror image. For
example, benzene, propanoic acid, CH3CH2CO2H and methylcyclohexane have planes of
symmetry and so they must be achiral.

As enantiomers contain the same groups attached to the same atoms, with the same angles
between each group (unlike geometric isomers), they have exactly the same chemical
properties. They undergo similar chemical reactions, reacting with reagents at identical rates
as long as the reagents are not themselves chiral.
16

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Their physical properties density, refractive index, colour, melting and boiling points are
also identical except their effects on plane-polarised light. Enantiomers rotate the plane of
polarised light in opposite directions (but to an equal degree). Plane polarised light differs from
normal light in that electromagnetic waves vibrate in a single plane rather than in multitude of
planes. Passing light through a polariser such as a polarized filter produces polarised light. If
a beam of plane-polarised light is passed through a solution of one enantiomer, when light
emerges, the plane of polarisation is rotated either clockwise or anti-clockwise- this is
measured using a polarimeter. This is the phenomenon of optical activity, and is the reason
they are called optical isomers.

If we have a solution that contained equal concentrations of the two enantiomers, the
clockwise rotation caused by one enantiomer will be exactly cancelled by the anticlockwise
rotation caused by the other enantiomer, resulting in zero net rotation. This equimolar mixture
of two enantiomers is called the racemic mixture, and is usually formed when a chiral
compound is synthesised from non-chiral starting materials.

17

Essential Guide for Organic Chemistry Paper 1 and Paper 2

D. Polymerisation
Addition Polymerisation
Polymerisation is the chemical process where smaller molecules (monomers) react to form
chemical bonds to form macromolecules (polymers). Typically a polymer molecule is made up
of 104-106 monomers.
There are mainly two types of polymerisation process: addition polymerisation and
condensation polymerisation.
Alkenes or substituted alkenes tend to undergo addition polymerisation.
Addition polymerisation is an important process where plastics are formed. Some common
addition polymers are shown in the table below.
Polymer / Common
name
Polyethene or
polyethylene, PE

Monomer

General Formula

Ethene,
H

H
C

Chloroethene,

Cl

F
C

H
C

Styrene,
H
C
H

lab equipments,
automobile parts

n
CH3

coating for nonstick pans

Propene,

plastic pipes,
artificial leather,
wire insulation

Tetrafluoroethene,

plastic bottles,
toys, plastic bags,
film wrap

n
H

Cl

Polystyrene, PS

Polypropene, PP

Polytetrafluoroethene,
PTFE

Polychloroethene or
polyvinyl chloride, PVC

Uses

CH3

foamed packaging,
disposable cups
and plates

18

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Polyesters and Condensation Reactions
A condensation reaction is a reaction in which two molecules react together to produce a single
molecule, with the elimination of a small molecule such as water and hydrogen chloride.
Esterification is an example of an acid-catalysed condensation reaction.
General reaction: ROH + RCOOH

conc H2SO4
RCOOR
reflux

+ H2O

If two functional groups are present in the molecules, it will be possible to form a condensation
polymer.

The most widely used condensation polymers are polyesters and polyamides. Polyesters are
useful for forming fibres for making clothes, for example, it has been used extensively in the
production of trousers and skirts. Polyesters can also be used for packaging films. In addition
a polyester resin polyethylene terephthalate (PET) has low permeability to carbon dioxide and
so is used extensively in the bottling of carbonated drinks.

Importance of Condensation Reaction and Nylon synthesis

Polyamides such as nylon and terylene (a polyester) are important condensation polymers.
The formation of a polyamide follows the same procedure as in the synthesis of a simple
amide. The only difference is that both the amine and the carboxylic acid monomer units each
have two functional groups - one on each end of the molecule. In nylon, every other repeating
unit is identical.
Nylon was originally made by the reaction of a diamine (1,6-diaminohexane) with a
dicarboxylic acid (hexane-1,6-dioic acid). The polymer chain is made up from the two
monomers reacting alternately and a simple representation of nylon is -[A-B-A-B-A-B]-. The
link formed repetitively between the monomers is an amide linkage and nylon is also known
as a polyamide.
For example, the polymerization of 1,6-diaminohexane and hexane-1,6-dioic acid to form
nylon. This reaction occurs at the interface of the two liquids.

19

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Because the two monomers each contain a six-carbon chain, this form of nylon is known as
nylon-6,6. The commercial formation of nylon-6,6 requires high temperature, high pressure
and presence of catalyst.
The molecular chains of nylon fibres interact by hydrogen bonding between the hydrogen
atoms of N-H groups of the amide linkage of one polymer chain with the >C=O groups on the
adjacent polymer chain.
Nylons are used in engineering applications and in making fibres. A combination of strength
and resistant to abrasion makes nylon good for making bearings and gears. As a fibre, nylon
is used to make clothing to mountaineering ropes.

20

Essential Guide for Organic Chemistry Paper 1 and Paper 2

E. Physical Properties
A homologous series is a series of organic compounds that have the same functional groups
but differ in formula by a fixed group of atoms. In the example below, each alkane differs from
the next in the series by a -CH2- unit.

Members of a homologous series have similar chemical properties and they may be prepared
by the same methods. However, they have different physical properties eg. melting points and
density. As the chain length (numbers of carbons) increases, the melting and boiling points of
the homolog gradually increases. The longer chain molecules have higher boiling points as
they have greater intermolecular forces (van Der Waalss forces).Branching present within

the molecule will lower its boiling point. Branched molecules are more compact and
have a smaller surface area for Van der Waals forces of attraction to operate. Thus,
less thermal energy is required to overcome the weaker intermolecular forces.
The physical properties of alkenes are quite similar to alkanes.Some key physical properties.
The melting point and boiling point of alkenes increases with increasing size of electron
cloud. Example: ethene, propene and butene are gases at r.t.p. while the rest of the
alkenes are liquids or solids.
Due to geometric isomerism in some alkenes which results in difference in the overall
polarity of the molecule, the melting and boiling points of a pair of geometric isomers
may be different.
All alkenes are insoluble in water due to lack of favourable interactions with water
molecules.

Halogens are more electronegative than carbon. The carbon-halogen bond will be polarised

with the partial positive charge residing on the carbon atom as shown below. The polarisation
of the carbon-halogen -bond is most pronounced in the C-F bond and the least in the C-I
bond. Halogenoalkanes are usually polar molecules as the dipole moments do not cancel out
(except in some like CCl4). Despite being polar molecules, halogenoalkanes are generally
insoluble in water except for the short chain fluoroalkanes.

X= F, Cl, Br or I

21

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Halogen
F

Cl

Br

195
235
276
306

249
285
320
351

277
312
344
374

316
345
376
403

Parent alkane
methane
ethane
propane
butane

Increasing
Boiling
Point
(in K)

Increasing Boiling Point (in K)

As illustrated by the previous table , the boiling point of halogenoalkanes increases with
increasing alkyl chain length and increasing molecular mass of the halogen atom. They have
higher boiling points than their corresponding alkanes due to their larger electron cloud and
permanent dipole-permanent dipole interactions present between molecules.

Alcohols have much higher boiling points compared to alkanes of similar Mr.
CH3CH2CH2CH2CH3
CH3CH2OCH2CH3
CH3CH2CH2CH2OH

Mr
72
74
74

bp oC
36
35
117

The much higher boiling point of alcohol is due to the stronger intermolecular hydrogen bonds
in alcohols compared to the weak intermolecular van der Waals forces in alkanes.

Branched alcohols have lower boiling points compared to straight-chain isomers as a highly
branched isomer has a lower surface area. Hence the extent of intermolecular Van der Waals
forces of attraction is smaller for branched isomers, resulting in the lower boiling points.

(CH3)3COH
CH3CH2CH2CH2OH

Mr
74
74

Bpt oC
82
117

Phenols exist as crystalline solids with low melting point of 34C. As a liquid, phenol has
relatively high boiling point as compared to other organic compounds (e.g. alkanes) of the
same molecular mass. This is because a large amount of thermal energy is needed to
overcome strong hydrogen bonds between phenol molecules
Similar to water, the oxygen atom on the hydroxyl group has two lone pairs which are capable
of forming hydrogen bonds with water molecules. However, the extent of solubility of alcohols
in water is dependent on the chain length of the alkyl group. Alcohols up to three carbons long
are completely miscible with water. Alcohols with four carbons or more are partially miscible
or immiscible with water due to their lower polarity.
22

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Phenols are usually insoluble in water due to the large hydrophobic phenyl group

Carboxylic acids have higher boiling points than most organic compounds of similar Mr as
they are able to form strong intermolecular hydrogen bonds. More thermal energy is required to
overcome the stronger hydrogen bonds than permanent dipole-permanent dipole interactions
and van der Waals forces.
Carboxylic acids have higher boiling points than alcohols of similar Mr. This is due to the stronger
hydrogen bonding found in carboxylic acids due to the presence of the electron-withdrawing
carbonyl group.
e.g.
CH3COOH
bp = 118 oC
Mr = 60
CH3CH2CH2OH
bp = 97 oC
Mr = 60
Carboxylic acid molecules can also pair off to form dimers via intermolecular hydrogen bonds,
a dimer consists of two identical molecules interacting together:
Structure of a dimer:

Carboxylic acids with four carbon atoms or less are soluble in water due to the formation
hydrogen bonds with water molecules. Water solubility decreases (since molecular polarity
decreases) as the carbon chain (alkyl) length of the carboxylic acid increases.

Esters cannot form hydrogen bonds with one another as no hydrogen is attached directly to
oxygen of the ester group. Esters are polar in nature; their molecules are held together by
permanent dipole- permanent dipole interactions. They have higher boiling points than non polar
hydrocarbons but lower boiling points than carboxylic acids and alcohols of similar molecular
mass.

23

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Esters can form hydrogen bonds with water molecules. Therefore esters chains of up to four
carbon atoms are soluble in water.

Amides are neutral molecules. Amides (except for those with no hydrogen atom attached to
nitrogen) form strong intermolecular hydrogen bonds. Consequently, such amides have high
boiling points. Their boiling points are even higher than those of carboxylic acids of
comparable molar mass.
For example, the boiling point of methanamide is 210 C while the boiling point of methanoic
acid is 101 C. Methanamides ability to form an extensive network of hydrogen bonds
accounts for its high boiling point:

24

Essential Guide for Organic Chemistry Paper 1 and Paper 2

F. NOMENCLATURE

Displayed/
Full Structural
Examples:
Formula

3D Full Structural
Formula

Condensed/
structural
formula

Skeletal
structure

Displayed formula or full structural formula is a more complete way of showing which atoms
are bonded to which and it also shows ALL the type of bonds (e.g single, double) present in
the molecule.
In condensed formulae, all the bonds are removed. Brackets e.g. (CH3), (OH) are introduced
to signify a branch in the main chain. When interpreting condensed formula, take note that
each carbon atom should have four bonds (whether single, double or triple). Usually, CO refers
to the carbonyl group C=O and CHO refers to the aldehyde functional group
IUPAC system of nomenclature is to establish an international standard of naming compounds
to facilitate communication. The goal of the system is to give each structure a unique and
unambiguous name, and to correlate each name with a unique and unambiguous structure.
IUPAC nomenclature is based on naming a molecules longest chain of carbons that includes
the functional group. All deviations, either multiple bonds or substituent atoms other than
carbon and hydrogen, are indicated by prefixes or suffixes according to a specific set of
priorities.
The name of an organic molecule is made up of 3 parts: the Prefix, the Stem and the Suffix.

The stem part of the name refers to the longest possible continuous carbon chain that includes
the functional group*, if there are any. Referring to the table below, functional groups of
highest priority is indicated by suffix; the others are indicated by prefix. Functional groups are
organised below in order of increasing priority.

25

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Steps to naming:

Examples of naming organic compounds:

1. Find the highest priority functional group.

2. Determine and name the longest
continuous carbon chain that includes
this functional group.
3. Number the chain so that the highest
priority functional group is assigned the
lowest number.
4. Replace the last e with the suffix of the
highest priority functional group, and
include its position number.
5. The names of the substituent prefix are
arranged alphabetically, followed by the
stem and suffix. If there are 2 or more
similar substituents: di, tri etc will be
used.
(e.g. 3,3-dimethylpropane).
6. Numbers are use to indicate the position
of any substituent. Each substituent gets
a unique number assigned to it.
Comma is used to separate numbers
in the name
Dash is used to separate numbers
from alphabets in the name
(e.g. 3,3-dimethylpropane).

5-chlorohex-2-ene
2,3-dimethylpentane

3-methylbutan-2-ol

3-bromobutanoic acid

26

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Amides
An amide contains the following structure:
In naming amide, use the alkane name for that chain but replace -e with amide. More complex
names are the amides that have one or two alkyl groups attached to the nitrogen atom in place
of hydrogen atoms. In such cases, continue the naming process by naming the alkyl groups
as attachments to the front of the name using N- to show their location.
Eg:
O

H3C

CH3

CH3

N,N-dimethylethanamide

Eg.
methanamide

ethanamide
2-methylpropanamide

Amines
Amines are classified into primary, secondary and tertiary amines, according to the number of
hydrogen atoms replaced by alkyl (R) or aryl (Ar) groups.
R-NH2

Primary amines (1o) have 1 hydrogen atom being replaced.

R-N-R'
|
H

Secondary amines (2o) have 2 hydrogen atoms being replaced.

R-N-R'
Tertiary amines (3o) have 3 hydrogen atoms being replaced.
|
R"
Primary amines are named with the NH2 group as the prefix - amino. For secondary and
tertiary amines, the alkane name is used for the longest amine chain but replace -e with-amine.
More complex names are the amines that have one or two alkyl groups attached to the
nitrogen atom in place of hydrogen atoms. In such cases, continue the naming process by
naming the alkyl groups as attachments to the front of the name using N- to show their location.
Eg:

H
H C
H

H
C
H

H
C
H

H
N
H

C H

H
N-methylpropanamine
The alkyl groups attached to the nitrogen atom are named in alphabetical order, prefixes like 'di'
or 'tri' are used for naming identical alkyl groups.
27

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Eg:
Structure

IUPAC Name

CH3CH2CH2NH2

propanamine/ 1-aminopropane

CH3-CH-CH2CH3
|
NH2

2-aminobutane

ClCH2CH2NH2

2-chloroethanamine/ 1-amino-2chloroethane

NH2

phenylamine/aniline

CH3CH2-N-CH2CH3
|
CH2CH3

N,N-diethylethanamine

CH3-CH2-CH2-CH2-N-CH2-CH3
|
CH3

N-ethyl-N-methylbutanamine

Nitriles
In naming nitrile, select the longest carbon chain starting with the carbon in the nitrile group.
Then use the alkane name for that chain and add in the word nitrile.

Esters

In naming esters, name the alcohol part first then the acid part, replacing oic acid with oate.
For example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the propanoate group.
The acid is named by counting up the total number of carbon atoms in the chain - including
the one in the -COOH group.

Carboxylic Acids
The longest continuous carbon chain containing the carboxyl group is selected as the suffix.
Replace the terminal 'e' from the corresponding hydrocarbon name with oic acid.

28

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Eg:

HCOOH
methanoic acid
CH3COOH
ethanoic acid
For substituted acids, the parent chain is numbered beginning with the carboxyl group.

When a compound contains both a carboxyl group and a hydroxyl group, the hydroxyl group
has a lower priority. The hydroxyl group is treated as a prefix and is named as hydroxy.

H3C

CH3

HO

Eg:

O
C
OH

CH3

3-hydroxy-2,2-dimethylbutanoic acid

Carboxylic acids containing 2 carboxyl (-COOH) groups are named as a dioic acid.
Eg:
HOOCCH2COOH
1,3-propanedioic acid
The simplest aromatic acid is benzoic acid (benzene carboxylic acid); other substituents are
named as derivatives of benzoic acid.

Alkenes
Similar to alkanes, the alkene parent chain is the longest continuous carbon chain that
contains the C=C bond. The position of the C=C bond is given priority in numbering and is
indicated by the smaller of the two number labelling the carbon atoms.
Example

but-1-ene

CH3

CH3

CH3
CH3

CH3

3,3-dimethylbut-1-ene
CH3

1,3,3-trimethylcyclohexene

CH3

CH2

H3C

CH3

C
H

C
CH3

CH3

29

Essential Guide for Organic Chemistry Paper 1 and Paper 2

Halogenoalkanes
Halogenoalkanes are classified as primary (1), secondary (2) or tertiary (3)
halogenoalkanes, depending on the number of R groups attached to the carbon atom bonded
to the halogen atom.
H
H

R
R

X
0

primary
No R groups

X
0

1
primary

2
secondary

1 R group

2 R groups

30

tertiary

3 R groups

The naming of the halogenoalkanes is similar to that of alkanes with the addition of a prefix to
indicate the position of the carbon atom to which the halogen is attached to. The numbering
of the carbon should be the smallest possible. If there is more than one type of halogen, the
order of naming will follow the alphabetical order.
Examples
H H H

H H H H
Cl

C C

C C

2-iodobutane
2-iodobutane

chlorobutane
1-chlorobutane
Cl H H H

H C C C C
H

H H H H

H C C

C C C H
H Br H H H

2-bromo,1-chloropentane
2-bromo-1-chlorobutane

Cl F

H H

H C C C C

H Cl H H
1,2-dichloro,
2-fluorobutane
1,2-dichloro-2-fluorobutane

30