2011

ORGANIC CHEMISTRY
STPM

BY MR CHIA KIN KHEN

SMK SULTAN BADLISHAH
2011
 CONTENT
CHAPTER 1
INTRODUCTION TO THE CHEMISTRY OF CARBON
3 32

CHAPTER 2
HYDROCARBONS
33 71

CHAPTER 3
HALIDES
72 90

CHAPTER 4
AMINES
91 99

CHAPTER 5
HYDROXY COMPOUNDS
100 119

CHAPTER 6
CARBONYL COMPOUNDS
120 - 136

CHAPTER 7
CARBOXYLIC ACIDS AND DERIVATIVES
137 - 161

CHAPTER 8
AMINO ACIDS
162 - 171

CHAPTER 9
POLYMERS
172 - 193

2
CHAPTER 1
INTRODUCTION TO THE CHEMISTRY OF CARBON
1. INTRODUCTION
Organic compounds (except of CO, CO2 and carbonates) are compounds that contain
mainly the elements like carbon and hydrogen. These compounds also contain oxygen, nitrogen,
halogen and sulfur. Organic chemistry is a study of the chemistry of these organic compounds.
Organic chemistry is important because of all living things contain organic compounds. Further
more, many modern products and materials are depending on organic compounds. Until 1980,
the number of known organic compounds is 5.5 million.

2. THE CHEMISTRY OF CARBON

Why it is that carbon can form such a vast array of naturally occurring and synthetic
organic compounds?
Carbon atom is basically showing two very distinct chemical properties compares to
other elements.
2.1 Carbon atom has its unique ability to catenate. In catenation, atoms of the same element
form strong, single covalent bonds. As a result, chains and rings structures of various sizes are
formed. Carbon atoms readily catenate because it forms strong, C C covalent bond.

C C C C C C
Chain structure
C C ring structure

C C

Catenation also occurs between the silicon atoms and the oxygen atoms, forming very strong, Si O
covalent bond.

2.2 Carbon atoms are capable of forming various types of hybrids atomic orbitals like the
sp, sp2 and sp3 atomic orbitals that allows carbon atoms forms single bonds, double bonds and
triple bonds in its compounds.
sp sp2 sp3
single C C bond double C=C bond triple CC bond

2.3 Carbon atom also forms strong covalent bonds with other elements like oxygen, nitrogen
and the halogen in various organic compounds.

CO C=O CN CN CCl CBr CF

2.4 Another reason why carbon forms many organic compounds is that its compounds are
kinetically very stable. The activation energy requires in breaking C C bond is high.

3
3. BONDING AND MOLECULAR STRUCTURE OF ORGANIC MOLECULES.

An orbital is defined as a region or volume of space at certain distance from the

nucleus, within which there is a high probability of finding an electron.

There are four types of atomic orbital, namely the s, p, d and f orbital. These orbitals can
be represented by three dimensional surface boundaries, where within the boundaries; you have
high possibility of finding electron. These orbitals have different shapes and orientations. Below
are shapes of s and p orbitals.

y
z y
z
x
x

s orbital :
only one orbital and p orbital : there are three p orbitals and each has the
has the shape of a sphere. shape of a dumb-bell. Each p orbital lies along its
axes. They are 90o to one another.

Carbon is a Group 14 element. The electronic arrangement of carbon atom is 2, 4. The

valence shell of carbon atom has two types of orbital the 2s and the 2p orbitals. A carbon atom
has 4 valence electrons. At ground state, two of the valence electron is filled into the 2s orbital
while the remaining 2 is filled into the 2p orbitals as follows.

2s 2p

(Boxes are used to represent orbitals)

Carbon atoms also forms various types of hybrids atomic orbitals like the sp, sp2 and sp3
atomic orbitals and use these hybrids atomic orbitals in forming various covalent bonds in
organic molecules. To form hybrid orbitals, a carbon absorbs heat energy and becomes excited.
At the excited state, one of the two electrons in the 2s orbital moves into the 2p orbital, as the
result, the electronic configuration of carbon atom is

2s 2p

These orbital are then involved in various type of hybridization to form sp, sp2 and sp3
hybrid atomic orbitals.

4
3.1 The sp hybrid atomic orbital
One s atomic orbital mixed with one p atomic orbital to form two hybrid sp atomic
orbitals at 180o apart from one another.

y
C,2s C,2py 2py z
+ 2px s+p sp sp x
180o
2pz 2pz

Each sp hybrid orbital has one electron in it, while the other two py and pz orbitals
remain unchanged with one electron in each orbital.

2s 2p sp 2p

Example: ethyne, (C2H2) molecule. Both carbon atoms use sp hybrid orbitals.
y y y z y z
py z py z
H,s sp H,s
x H C C H

pz pz sp s

pi bond at y axis. pi bond at z axis

One s orbital from the hydrogen atom overlaps head on with one of the sp orbital of the
carbon atom. A sigma bonding orbital is formed. This happens to the other carbon atom as well.
The remaining sp orbital from both carbon atom overlaps head on along the x axis to form
another sigma bonding orbital. The other py and pz orbitals overlap side-by side to form two pi
bonding orbitals.
A covalent triple bond is formed between the two carbon atoms and a single covalent bond is
formed between the hydrogen and the carbon atom.

HCCH
180o, a linear C2H2 molecule.

Note that, atoms which bonded directly to the triple bond are in one line or linear.

5
3.2 The sp2 hybrid atomic orbital
One s atomic orbital mixed with two p atomic orbitals. As a result, three hybrid sp2
atomic orbitals are formed. These three sp2 hybrid orbitals laid 120o apart from one another at
the trigonal plane.
y
2py
C,2s 2py 2pz
+ s +2 p sp2
2px
120o

Each sp2 hybrid orbital has one electron in it, while the other py orbital remain unchanged with
one electron in it.

2s 2p sp2 2py

Example: ethane, (C2H4) molecule. Both carbon atoms use sp2 hybrid orbital.

H, 1s 2Py

H H

C C
2 H H
C Csp

Two s orbitals from two hydrogen atoms overlap head on with two of the sp2 orbitals
from a carbon atom, forming two sigma bonding orbitals. This happens to the other carbon atom
as well. The remaining sp2 orbital from both carbon atoms overlap head on along the x axis and
form another sigma bonding orbital. The remaining py orbital overlaps side-by side to form a pi
bonding orbital.
A covalent double bond is formed between the two carbon atoms and two single covalent bonds
are formed between the hydrogen and the carbon atom.

H H

C=C

120o . All C and H atoms in the same plane.
H H
A covalent double bond is formed between the two carbon atoms and two single covalent
bonds are formed between the hydrogen and the carbon atoms.
Note that, atoms which bonded directly to the double bond are in the same plane or planar.
3.3 The sp3 hybrid atomic orbital

6
 One s atomic orbital mixed with three p atomic orbitals. As a result, four hybrid sp3
atomic orbitals are formed. These three sp3 hybrid orbitals laid 109.5o apart from one another in
the shape of a tetrahedron.

C,2s py four hybrid sp3

s+3p
+
px
pz

109.5o
3
Each sp hybrid orbital has one electron in it, no p orbital is remains.
2s 2p sp3

Example: ethane, (CH4) molecule. Carbon atom uses sp3 hybrid orbitals.
H H
H,s
sp3
C C 109.5o

H H H
H
H H
Tetrahedron
Note: At the same plane Front of plane Back of plane

Four s orbitals from four hydrogen atoms overlap head on with four of the sp3 orbitals
from a carbon atom, forming four sigma bonding orbitals.
Four covalent single bonds (sigma bond) are formed between four hydrogen atoms and a carbon
atom.
Note that, two hydrogen atoms and the carbon atom are located at the same plane, while one
hydrogen atom is located at the back of the plane and an atom is located in front of the plane.

In benzene, C6H6 molecule forms each carbon atom in the molecule uses sp2 hybrid atomic
orbitals in forming covalent bonds.
1s,H 1s,H

C1 C2 C1 C2
2 2
sp sp
C3 C3
C6 C6

C5 C4 C5 C4

Structure I Above Structure II

Below 7
The overlapping of adjacent p atomic orbitals toward the right will form localized pi bond as
shown in structure I. If the overlapping of adjacent p atomic orbitals toward the left, it will form
localized pi bond as shown in structure II. These structure I and II is represented as the Kekule
structure I and II as shown in the diagram below.

H H H H

C=C CC
H C CH HC CH
C C C=C

H H H H
Kekule I Kekule II

In the real situation, all six p atomic orbitals overlapped adjacently to the left and to the right and
form delocalized pi-bonding orbitals. Thus, two doughnut ring shape pi electron cloud are
formed. One is at above and the other one is at the bottom, sandwiching the carbon hexagon ring
as shown in the diagram below. All bonds between the carbon atoms are equal in length.

p
H,1s

C1 C2
H H
C3
C6 C C above

C5 C4 H C C H
bottom
C C

H H
Delocalized pi electron cloud

The ring in the hexagon represents the

delocalized pi electron cloud.

8
Draw a diagram of overlapping of orbitals during the formation of the following molecules. State
the types of hybridized atomic orbitals used and determine the shapes of these molecules.
i. CH3CH3 ii. CH3CH2CH3 iii. CH3CH=CH2 and iv. CH3CCH.

Determine whether the carbon atoms in these molecules are located in the same line, in the same
plane or out of the plane.
i. CH3CCH ii. CH3CH2CH3 iii. CH3CH=CH2 iv. CH2CH3

4. VARIOUS TYPES OF FORMULAE

4.1 General formula
It is a formula that is used to represent a group of organic compounds in a particular
homologous series.
Examples:
Alkane is represented by CnH2n +2.
Alkene is represented by CnH2n.

Different homologous series can share the same general formula.

Examples:
Alkene and cycloalkane are represented by a same general formula, CnH2n.
Alcohol and ether are represented by a same general formula, CnH2n +2O.
Aldehyde and ketone represented by a same general formula, CnH2nO.
Carboxylic acid and Esther are represented by a same general formula, CnH2nO2.

4.2 Molecular formula

It is defined as a formula that shows the actual number of atoms of each element that
present in a molecule.
Examples:
C2H6O this molecule has two carbon atoms, six hydrogen atoms and one oxygen atom.
C6H12 this molecule has six carbon atoms, twelve hydrogen atoms.

Molecular formula does not distinguish between organic compounds.

Example:
C2H6O is the molecular formula for both ethanol and dimethylether.
C6H12 is the molecular formula for both cyclohexane and 1-hexene.

Since a molecular formula does not distinguish between organic compounds, thus, the formula is
not appropriate to be use in writing a chemical equation.

4.3 Empirical formula

Empirical formula shows the simplest, whole number mole ratio of all elements in the
formula of an organic molecule.
Examples:
Empirical formula of ethene, C2H4, is CH2.
Empirical formula of glucose, C6H12O6, is CH2O.

9
A multiple unit, n, of the empirical formula produces the molecular formula.
(Empirical formula) n = molecular formula.
Examples:
(CH2) 2 = C2H4 , [ n = 2 ]

(CH2O) 6 = C6H12O6 , [ n = 6 ]

The molecular formula of a molecule can be calculated if the molecular mass of that molecule if
given. The following relation can be use.

(Empirical formula) n = molecular mass.

Example:
The empirical formula of propane is CH2. Determine the molecular formula of propene if the
molecular mass of propene is 42.

(CH2) n = 42
[12 + 2(1)] n = 42
n= 3
molecular formula = (CH2) n
= (CH2) 3
= C3H6

4.4 Structural formula

It is defined as a formula that shows the display of atoms and how atoms are bonded to
each other in the molecule.
Examples: H H

CH3CH2OH or H C C OH are structural formulas for ethanol.

(I) (II)
H H
Structural formula (I) is called the shortened structural formula and structural formula (II) is
called the displayed formula or graphic formula.

Stereochemical formula
shows each atom separately, all bonds and its angles in three dimension display in an attempt to
represent the shape of the molecule.

Example: H at the same plane

H pointed in from the plane
C OH pointed out from the plane.
H C
H H, C atoms are at the same plane
H

10
The structural formula for larger molecules containing rings and long chains of carbon atoms are
tedious to draw out in full. The skeletal formula is often used as representation the structural
formula. To use skeletal formula, the following assumptions are to be follow.
1. Covalent bond is represented by line between carbon atoms.
2. All atoms are represented by their symbols. Carbon and hydrogen atoms are not represented.
3. The ends of all bonds are assumed to be bonded to hydrogen.
Examples:

CH3CH2CH2CH2CH2CH3 is represented as

end elbow
CH3 CH2
*CH3

CH3CH2CHCH2CHCH3 is represented as

*CH2CH3
*CH3 *CH2CH3
Cl

CH3CH2CHCH2CHCH3 is represented as

OH
Cl OH

CH CH

CH2 CH2 is represented as

CH CH

CH3 COOH COOH

Draw the skeletal formula for these molecules.

CH3CH2CH=CHCH3, CH3CCCH2CH3 and
CH3CH(CH3)CH(OH)CH(CH2CH3)CH2CH2NH2

5. ISOMERISMS AND ISOMERS

11
 Isomers are the compounds which have the same molecular formula but different in the
arrangement of atoms in their molecule. This phenomenon is called isomerism. Isomerism is the
existence of different compounds that have the same molecular formula. There are two principal
types of isomerism.

5.1 The structural isomerism

Structural isomers have same molecular formula but have different structural
formulae or arrangement of atoms.

Examples:
C4H10 forms two structural isomers.
They are CH3CH2CH2CH3 and CH3CH(CH3)CH3.

C4H8 forms four structural isomers. CH2 CH2

They are CH3CH2CH=CH2, CH3CH=CHCH3, CH2=C(CH3)CH3 and
CH2 CH2
C2H6O forms two isomers.
They are CH3CH2OH and CH3OCH3.

Write all possible isomers that can be form by C5H12.

5.2 The stereoisomerism

Stereoisomers have the same molecular formula but have different spatial
arrangement of their atoms.
Stereoisomers can be divided into two categories:
Geometrical isomerism and
Optical isomerism.

a. Geometrical isomerism
Geometrical isomers have same structural formula but differ in the geometrical
arrangements of their atoms.
This is due to the present of a double bond, C=C, which hinders the free rotation of C=C bond
(or carbon atoms ring that hinders the free rotation of C C bond). On top of this, the carbon
atoms that form the double bond, C=C, are bonded with two different group of atoms.
Example:
C2H2Br2 forms two geometrical isomers and one structure.
They are Br Br Br H Br H
C=C C=C C=C
H H H Br Br H
(I) (II) (III)
Isomer I and II are geometrical isomers. Both carbon atoms in the C=C double bond are bonded
with two different groups of atoms.
Geometrical isomer I is called the cis isomer. Both bromine (heavier) atoms are located at the
same side of the molecule.
Geometrical isomer II is called the trans isomer. Both bromine (heavier) atoms are located at
the opposite side of the molecule.

12
However, isomer III is a structural isomer to isomer I and II because it has different arrangement
of atoms in the molecule compares to isomer I and II. Further more, the carbon atoms in the
double bond are bonded with two similar atoms.

Write all possible isomer for C4H6Cl2.

b. Optical isomerism
Optical isomers have same structural formula but they rotate plane polarized light at a
different direction. Thus these isomers are optically active
To be optical active, the molecule must be asymmetric or chyral.
Any carbon atom that bonded with four different atoms or groups is called an asymmetric or
chiral carbon atom (C*).

Optical isomers of a compound exist in a pair of enantiomers. These enantiomers are object and
mirror image to one another. Thus, the enantiomers cannot be superimposed on one another.
Example: Lactic acid / 2-hydroxypropanoic acid.

H H

C* C*
HO CH3 CH3 OH

HOOC COOH
Mirror plane

Or can be represented by using the Fischer diagram.

H H

HO * CH3 CH3 * OH

COOH COOH

If one enantiomer rotates the plane of polarized light clockwise (or dextrorotation, +) by xo, then
the other enantiomer will rotate the plane of polarized light anticlockwise (or laevorotation, ) by
xo as well. A mixture of equal numbers of mole of each enantiomer is known as a racemic
mixture. A racemic mixture is not optically active because the rotation of polarized light by an
enantiomer is cancel of perfectly by the other enantiomer.
A pair of enantiomers is chemically and physically identical with each other except their optical
activity.

Draw the enantiomers of this molecule, HOOCCH(NH2)CH3.

13
Identify the chiral carbon in these molecules.

Cl CH2CH3

CH3CH2CHCH2CHCH3 CH3CH2CHCH2CHCH3

OH CH2CH3

CH CH

CH2 CH2 OH

CH CH

CH3 COOH

Types of Structural isomers Stereoisomers

isomerism Positional Functional Geometrical Optical isomers
isomers group isomers isomers
Chemical
properties Identical Different. Identical Identical

Physical Identical
properties Different. Different. Different. (except optical
activity)

6. FUNCTIONAL GROUPS AND THE HOMOLOUS SERIES

What is a functional group?
It is defined as certain bond or group of atoms attached to the main carbon chain of an organic
molecule.

Examples:
CH3CH2OH, the OH group of atoms attached to CH3CH2 is the functional group.
CH3CH2COOH, the COOH group of atoms attached to CH3CH2 is the functional group.
CH3CH=CHCH3, the double bond, C=C in the molecule is the functional group.

A functional group in an organic molecule performs the characteristic chemical reactions that
the molecule can undergo.

Example:

14
Organic molecules with double bond, C=C can only undergo addition reaction. Thus, addition
reaction is said to be the characteristic chemical reaction for all organic molecules that has
double bond.

Organic molecules that have same functional group are grouped together to form a large group
of organic compounds which called the homologous series. In this series, organic molecules are
arranged in the order of increasing molecular mass as going down the series. The table below
shows the classification of organic compounds into various homologous series.

Homologous General formula Functional group Examples.

series and name
Alkane CnH2n +2 C C and C H CH4, C2H6, C3H8,
n = 1, 2, 3,.. Single covalent
bond
Alkene CnH2n C=C. C2H4, C3H6, C4H8, .
n = 2, 3,.. Double covalent
bond
Alkyne CnH2n-2 CC C2H2, C3H4, C4H6, .
n = 2, 3,.. Triple covalent
bond
Cycloalkane CnH2n C C and C H
n = 3, 4, 5,.. Single covalent
bond C3H6, C4H8,
C5H10 C6H12
Arene CnH2n-6 Aromatic
n = 6, 7, 8, ring
Haloalkane CnH2n +1 X X CH3Cl, C2H5Cl, C3H7Cl.
n = 1, 2, 3,.. halide
X = F, Cl, Br, I
Amine CnH2n +1 NH2 NH2 CH3NH2, C2H5NH2, .
n = 1, 2, 3,.. Amino
Alcohol CnH2n +1 OH OH CH3OH, C2H5OH, C3H7OH.
n = 1, 2, 3, hydroxy
Ether (CnH2n +1)2O C O C CH3OCH3, CH3O C2H5, ..
n = 1, 2, 3, ether
Aldehyde CnH2n +1 CHO C=O , aldehyde HCHO, CH3CHO, C2H5CHO, .
n = 0.1, 2, 3,..
H
Ketone (CnH2n +1)2CO C C=O , ketone (CH3)2CO, CH3COC2H5, ...
n = 1, 2, 3,..
C
Carboxylic acid CnH2n +1 COOH COOH, carboxyl HCOOH, CH3COOH, .
n = 0.1, 2, 3, ..
Ester CnH2n +1 COO CmH2m +1 COOC HCOO CH3, CH3COO CH3,
n = 0, 1, 2, . carboxylate
m = 1, 2, 3,
Acyl chloride CnH2n +1 COCl COCl HCOCl, CH3COCl
n = 0.1, 2, 3, Acyl chloride
Amide CnH2n +1 CONH2 CONH2 HCONH2, CH3CONH2
n = 0.1, 2, 3, Amide

Properties of the homologous series are

15
 1. All compounds can be represented by a general formula.
2. The molecular mass of the successive molecule has 14 unit or a CH2 unit higher then
the previous member in the series. Thus, the molecular mass increases steadily as going
down a series. Consequently, as going down the series,
a. The boiling point and the melting point increases.
b. The density and viscosity increases.
c. The solubility decreases.
3. All members performing the identical types of chemical reactions.
4. All members can be prepared by the same reaction methods.

By these applying these properties, we can predict the physical and chemical properties of
certain organic molecule in the same homologous series.

7. OTHER MEANS OF CLASSIFICATION OF ORGANIC COMPOUNDS

7.1 Classification by the structure of the carbon skeleton

Compound Description Examples.

Aliphatic Carbon atoms form open chains CH3CH2CH3 , CH3CH=CHCH3 ,
structures. It can be straight CH3CCCH3 , CH3CH2CH2CH2COOH
chain or branched. CH3CH2CH(CH3)CH(CH3)CH2COOH
Alicyclic Carbon atoms form close rings
structures.
C3H6, C4H8, C5H10 C6H12

Aromatic Carbon atoms form hexagon OH

ring with delocalized
electrons Benzene toluene naphthalene 2-naphtol
Heterocycli Carbon and other atoms form
c close rings structures N-H pyridine. N-H pyrrole

7.2 Saturated and unsaturated compounds

a. Saturated organic compounds.

It means organic compounds in which the carbon atoms are joined together by C C single bond.
Examples:
Alkanes, cycloalkanes, halogenoalkanes, alcohols, amines are saturated organic compounds.

b. Unsaturated organic compounds.

It means organic compounds in which its molecules have double or triple bonds.
Examples:
Alkenes, alkynes, the aromatic compounds, aldehydes, ketones

16
If a molecule has more than one double bond or triple bond, the molecules is said to be
polyunsaturated.

Examples:
CH2 = CHCH = CH2, CH2 = CHCOOH

Hydrocarbons are covalent compounds that consist of carbon and hydrogen only. They are sub
divided into saturated and unsaturated hydrocarbons.
Saturated hydrocarbons are alkanes (CnH2n+2) and cycloalkanes (CnH2n). The alkanes are
hydrocarbons with open chain structured molecules, while the cycloalkanes are close ring
structured molecules.

Examples:
An alkane: CH3CH2CH2CH2CH2CH2CH3 (heptane)

A cycloalkane: (cyclohexane)

Unsaturated hydrocarbons are alkenes, alkynes and arenes. They have double or triple bond in
their molecules.
Alkenes (CnH2n) are open chain structured molecules, while cycloalkenes (CnH2n-2) have close
ring structured molecules.

An alkene: Examples CH3CH2CH2CH2CH2CH=CH2 (heptene)

A cycloalkene: Example (cyclohexene)

Alkynes are hydrocarbons that have a triple bond in its molecules.

Examples: CH3CCH and CH3CH2CCH

Arenes are hydrocarbons that have delocalized pi electrons in a hexagon ring.

Examples:
, CH3,

8. FUNCTIONAL GROUP AND ITS RELATIONSHIP TO PHYSICAL AND CHEMICAL

PROPERTIES
Almost all organic compounds are covalent. They exist as discrete molecules from the
simple to the macromolecule like the polymers. The physical and chemical properties of organic
compounds depend to a great extent on the size, shape, structure, bond polarity, type of
functional group and other atom groups of an organic molecule.

8.1 Melting point and boiling point

17
 In general, organic compounds are gases, liquids of low boiling point or relatively low
melting solid. They are volatile liquid and solid. This is because of the organic molecules are
held together by weak van der waals forces.
Melting point and boiling point increase as going down the homologous series due to the
molecular mass and the van der waals forces increases.
Branched isomers have lower boiling points then the straight chain isomers. Branched isomers
have round shape molecule while straight chain isomers have long shape molecule. Long shape
molecules allowed greater intermolecular interaction, thus develop stronger van der waals forces.
As a result, they have higher boiling points.

8.2 Viscosity
Viscosity increases as going down a series due to the molecular mass and the van der
waals forces increases.

8.3 Density
Density increases as going down a series due to the molecular mass increases.

8.4 Solubility
Organic molecules that has hydrophilic group like COOH, SO3H, OH, and NH2 are
soluble in polar solvent (water) through forming the hydrogen bond with water molecules.
However, the solubility of these molecules decrease as the hydrophobic (hydrocarbon or non-
polar) group increasing in size. Thus, solubility decreases as going down a homologous series.
Non-polar organic molecules are soluble in non-polar solvent like toluene. However, highly polar
organic molecules such as the amino acids are not soluble in non-polar solvent.

9.0 ACIDITY OF ORGANIC COMPOUNDS

Organic compounds alcohols, amines, amides and the carboxylic acids are weak bases or
weak acids.
The acidity of organic acids depends on other atom groups that attached in these organic
molecules.

Alkyl groups like CH3 (Methyl), C2H5 (ethyl), C3H7 (propyl), are electron repelling groups. An
alkyl group repels electron to the neighboring atom and thus shifting the density of electron to
the next neighboring atom. This is known as positive inductive effect (+I).

Example: H

CH3 C Cl

H (I)

The strength of this inductive effect increases as the number of the alkyl groups increases and as
the alkyl group becomes bigger.

H CH3

18
CH3CH2 C Cl CH3 C Cl

H (II) CH3 (III)

Molecule (III) has strongest +I effect while is molecule (I) has weakest +I effect.

+I effect increases
Molecule I ,II , III

Aryl group, Ar or Ph (C6H5, phenyl), is an electrons withdrawing group. It withdraws electrons

from the neighboring atoms and thus shifting the density of electron to itself. This is known as
negative inductive effect ( I).

Example:
CH3

This I effects of aryl is due to the delocalized pi electrons in the aromatic ring.

The inductive effect becomes weaker as the inducting group is located further from the
functional group.

Example:

H H

CH3 C COOH H C CH2 COOH

Cl (I) Cl (II)

The negative inductive effect, ( I), in molecule I is stronger than that in molecule II because in
molecule I, the Cl atom is located closer to COOH.

The inductive effect becomes stronger when there are more inducting groups present in the
molecule or the inducting group is more electronegative.

Cl H

CH3 C COOH CH3 C COOH

Cl (III) Br (IV)

-I effect increases
Molecule II , IV, I, III

19
Most attaching groups like NO2, CN, COOH, COOR, CO, SO3H, OH, OR,
NH2, X(halogen) are having I effects. Note that, these groups are more electronegative than
carbon atom.

Inductive effect and acidity of organic compounds can be explained by the Lowry-Bronsted
Theory of acid-base. According to the Lowry-Bronsted theory for acid and base, an acid is a
substance that donates proton or H+. As a result of donated proton, the acid forms its conjugate
base. A base is a substance that receives proton. As a result of receiving proton, the base forms
its conjugate acid.
Examples:
1. CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)
(Acid) (Conjugate base)

2. CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH(aq)

(Base) (Conjugate acid)

The strength of a weak acid or a weak base is depends on the stability of the conjugate base or
the conjugate acid formed. If the conjugate base or the conjugate acid is stabilized, the
equilibrium () is shifted to the right (forward) which causes more ionization of the weak acid
or the weak base. Thus, the acidity of the weak acid or the weak base becomes stronger.
A positive inductive effect (+I) group reduces the acidity of a weak acid by destabilized the
conjugate base formed. Thus, the equilibrium of reaction (1) is shifted backward. Greater
positive inductive effect (+I) will reduce the acidity of a weak acid further.
A negative inductive effect ( I) group will strengthen the acidity of a weak acid by stabilized
the conjugate base formed. Thus, the equilibrium of reaction (1) is shifted forward. Greater
negative inductive effect ( I) will strengthen the acidity of a weak acid further.
The inductive effect alter the strength of a weak base is the opposite way as it affect the acidity
of a weak acid.
Examples:
1. Compare and explain the acidity of the following organic acids.
CH3CHClCOOH, ClCH2CH2COOH and CH3CCl2COOH

H O H O

CH3 C C O H(aq) + H2O(l) CH3 C C O(aq) + H3O+(aq)

Cl Acid Cl (conjugate base)

The highly electronegative chlorine atom is an electrons withdrawing group. Thus, it exerts a
negative inductive effect over the carboxyl, COOH, group. As a result, it magnifies the polarity
of OH bond in the carboxyl, COOH group, causing it easier to dissociate (ionize). Further
more, the negative inductive effect also stabilized the conjugate base. These effects shift the
equilibrium of the reaction to the right and strengthen the acidity of the organic acid.
ClCH2CH2COOH is weaker acid than CH3CHClCOOH because the chlorine atom is located
further away from the carboxyl group. Therefore it exerts weaker negative inductive effect over
the carboxyl group. Thus, it conjugate base is lesser stabilized.

20
However, CH3CCl2COOH is a stronger acid than CH3CHClCOOH because there are two
chlorine atoms bonded to carbon atom that is adjacently to the carboxyl group. Thus, they exert
stronger negative inductive effect over the carbonyl group and stabilized more its conjugate base.
ClCH2CH2COO < CH3CHClCOO < CH3CCl2COO

Stability of conjugate bases increases

The acidity of these organic acids increases as the following.

ClCH2CH2COOH < CH3CHClCOOH < CH3CCl2COOH

2. Compare and explain the strength of following organic bases.

(CH3CH2)2NH , CH3CH2NH2 and NH2

CH3CH2NH2(aq) + H2O(l) CH3CH2NH3+(aq) + OH(aq)

Base conjugate acid
The ethyl, CH3CH2, is an electron repelling group. Thus, it exerts a positive inductive effect over
the amino, NH2, group. This positive inductive effect magnifies the electron density of nitrogen
atom in the amino group, causing it easier accept proton, H+. Further more, the positive inductive
effect also stabilizes the conjugate acid. These effects shift the equilibrium of the reaction to the
right and strengthen the alkalinity of the organic base.

NH2 is weaker base than CH3CH2NH2 because the phenyl group, the aromatic

ring, has delocalized pi electrons, acts as an electron withdrawing group. It exerts a negative
inductive effect over the amino group.
The negative inductive effect reduces its density of electrons of the nitrogen atom in the amino
group, causing it less capable to accept proton, H+. Further more; the negative inductive effect
destabilizes the conjugate acid. These effects cause the equilibrium of the reaction shifted to the
left and weaken the alkalinity of the organic base.
However, (CH3CH2)2NH is stronger base than CH3CH2NH2 because there are two ethyl, CH3CH2,
groups bonded to the nitrogen atom of the amine group. Thus, they exert stronger positive
inductive effect over the amino group and stabilized more its conjugate acid.

NH3+ < CH3CH2NH3+ < (CH3CH2)2NH2+

Stability of conjugate acid increases

The strength of organic bases increases as the following order.

NH2 < CH3CH2NH2 < (CH3CH2)2NH

Arrange the following organic compounds according to the increasing order of acidity. Explain
your answer.

OH, HOH and CH3 OH

21
10. TYPES OF CHEMICAL REACTION IN ORGANIC CHEMISTRY
10.1 Nucleophilic and Electrophilic
A chemical reaction between two reactants may be regarded as the attack of one species
on the other. In this case the attacking species is called the reagent and the species which is
under attack is called the substrate.
The reagents in organic reactions are classified as nucleophiles or electrrophiles.

a. Nucleophiles
The word nucleophile means nucleus-loving. Thus, a nucleophile is a species which
attack a carbon atom that bears a positive pole, + (low density of electrons) by donating a pair
of electron. Therefore, a nucleophile is a Lewis base. A Lewis base is a negatively charged ion or
a neutral molecule that has a non-bonding pair of electrons.

Examples: Negative ions like OH, CN, CH3O, Cl, Br and I.

Neutral molecules like H2O, NH3, CH3OH, and the organomatellic
compounds.

b. Electrrophiles
The word electrophile means electron-loving. Thus, an electrophile is a species which
attack a carbon atom that bears a negative pole, - (or high density of electrons or bonding
system that rich in electrons) by accepting an electron pair. Therefore, an electrophile is a
Lewis acid. A Lewis acid is a positively charged ion or a neutral molecule that has an empty
orbital.

Examples: Positive ions like H+, CH3+ and NO2+.

Neutral molecules like AlCl3, ZnCl2, FeBr3 and BF3.

In a reaction involved organic molecule, chemical reaction takes at certain reactive site of the
organic molecule. A reactive site is a region of higher or lower electron density. Functional
groups in an organic molecule contain reactive sites that are attacked by incoming reagent
(nucleophile or electrophile).

Reactive sites include:

Electron-deficient (low electrons density) sites are atoms with a partial + charge and positive
ions.
Electron-rich (high electrons density) sites are atoms with a partial - charge, negative ions, the
non-bonding pair of electrons and the double/triple covalent bond.

10.2 Substitution and addition

There are two common types of chemical reactions in organic chemistry. They are the
substitution reactions and the addition reactions.

a. Substitution
In a substitution reaction, an atom or group, X, in a substrate molecule is replaces by
another atom or group, Y from the reagent.
This reaction takes place mainly in saturated organic compounds.

22
The outcomes of the reaction are:
1. An atom or group, X, in a substrate (saturated organic molecule) is replaces by another
atom or group, Y from the reagent.
2. The products formed are saturated.
3. Bonding system at the reaction site remains un-changed.
Example:
H H

H C H + Cl Cl H C Cl + H Cl
(x) (y) (y) (x)
H H

b. Addition
In an addition reaction, the reagent molecule (x-y) is added into the substrate molecule to
form a larger product molecule.
Addition reactions are typical of unsaturated organic compounds.
The outcomes of the reaction are:
1. Only one product is formed.
2. Unsaturated molecule (substrate) becomes saturated (product)
3. Bonding system at the reaction site changes.

Example:
H H H H

HC=CH + BrBr H C CH
(x) (y)
Br Br
(x) (y)

If a nucleophile is substituted in a reaction, the reaction is called the nucleophilic substitution

reaction.
Example:
H H

H C+ Cl + H+ CN H C CN + H Cl
nucleophile
H H

If a nucleophile is added in a reaction, the reaction is called the nucleophilic addition reaction.
Example:
O OH

CH3 C+ CH3 + H+ CN CH3 C CN

nucleophile
CH3

23
Similarly, if an electrophile is substituted in a reaction, the reaction is called the electrophilic
substitution reaction.
Example:
+
H + NO2 NO2 + H+
electrophile

If an electrophile is added in a reaction; the reaction is called the electrophilic addition reaction.
Example:
H H H H

H C = C H + H+ Cl+ H C C H
electrophile

H Cl

The table below shows the summary of the types of reactions.

Type of reaction Type of reagent Name of reaction

Substitution Nucleophile Substitution nucleophilic
Electrophile Substitution electrophilic
Addition Nucleophile Addition nucleophilic
Electrophile Addition electrophilic

Classify the following reactions.

1. CH3CH2OH + HCl CH3CH2Cl + H2O
2. CH2=CH2 + HBr CH3CH2Br
3. CH3CC2H5 + HCN CH3C(CN)C2H5

O OH

4. H + SO3 SO3 + H+

11. BOND BREAKING IN ORGANIC REACTION

A single covalent bond is consists of two electrons shared in between two atoms.
Example:

C C equivalent to C C

Chemical reaction involved breaking of bonds in the molecules of the substrate and the reagent.
They are two ways where a bond can be broken during a chemical reaction. They are Homolytic
fission and heterolytic fission.

24
11.1 Homolitic fission
Homolytic fission involves equally splitting of the two electrons shared in a single covalent
bond.

C C C + C

It produces particle species that bear a single electron which called the radicals. Homolytic
fission normally occurs in reactions take place in the gaseous phase or in non-polar solvent.

Write the equations to show the homolytic fission for CH and ClCl covalent bonds.

11.2 Heterolitic fission

Heterolitic fission involves unequally splitting of the two electrons shared in a single covalent
bond. One of the atoms keeps both electrons and thus, it acquires a negative charge. The other
atom lost the electron and thus, it acquires a positive charge.

C C C +
+ C (or C )

carbocation carboanion
(carbonium ion) (carbanion)
Write the equations to show the heterolytic fission for CH and CCl bonds.

12. VARIOUS TYPES OF CARBON ATOM IN ORGANIC MOLECULES

They are three types of carbon atoms can be found.

Example: CH3

CH3 CH2 CH CH3

1o 2o 3o

The C atoms are called the primary (1o) carbon because the carbon atom has only one immediate
neighboring carbon atom.

The C atom is called the secondary (2o) carbon because the carbon atom has two immediate
neighboring carbon atoms.

The C atom is called the tertiary (3o) carbon because the carbon atom has three immediate
neighboring carbon atoms.

Identify the types of carbon atoms in these organic molecules.

CH3CH(CH3)C(CH3)2CH3, , CH3

25
PAST YEARS QUESTIONS
A. OBJECTIVE
990/21. Which of the following shows the correct match between the organic molecules and the
type of isomerism?
CH3CH=CHCH3 CH3CH(OH)COOH C6H5CH=CHCl
A Optical Geometrical Geometrical
B Optical Geometrical Optical
C Geometrical Optical Optical
D Geometrical Geometrical Optical
E Geometrical Optical Geometrical

1990/37. An organic acid A is represented by the following structural formula.

O
XCH2C
OH
Which of these statements is correctly regarding to acid A if X is Cl or Br or H.
1 The density of electrons at the oxygen atom oh the OH group is the lowest if X is Br.
2 The Cl and Br atom withdraw electrons from the OH group, but the H atom is not.
3 The strength of acid decreases as the following order: ClCH2COOH < BrCH2COOH <
HCH2COOH.

1991/23. Which of the following statements is correct for electrophilic substitution?

A Substituting a hydrogen atom in methane molecule by a chlorine atom.
B Substituting a hydrogen atom in the benzene ring by a NO2+ ion.
C Substituting a chlorine atom in ethanoyl chloride molecule by a CH3O ion.
D Substituting a bromine atom in bromomethane molecule by a OH ion.
E Substituting the OH group in ethanol molecule by a Cl ion.

1994/38. Which of the following statements is correct regarding to the cis-trans isomerism?
1 Alkenes with two same groups bonded to the carbon atom of the C=C double bond do
not exhibit cis-trans isomerism.
2 The C=C double bond hinders free rotation of the carbon atoms.
3 Both cis and trans isomers have different physical and chemical properties.

1995/38. The infra-red spectrum can be used to differenciate the following pair of organic
compounds.
1 Chloroethane and bromoethane
2 Ethanol and chloroethane
3 Ethane and ethene

1996/34. Which of the following statement correctly explain why fluoroethanoic acid is a
stronger acid than the ethanoic acid?
A The relative molecular mass of fluoroethanoic acid is bigger than that of the ethanoic acid.
B The fluoroethanoic acid is more polarized than the ethanoic acid.

C The fluorine atom in the fluoroethanoic acid molecule withdraw electrons from the

26
 COOH functional group.
D Fluoroethanoic acid ionizes easier than ethanoic acid to give fluoride ion and
ethanoate ion.
E Fluorine is more electronegative than oxygen.

1997/32. Which of the following compounds does not show geometrical isomerism?
A CH3CH=CHCH3 B ClCH=CHBr C CCl2=CH2 D ICH=C(Cl)Br E
ClCH=CHCl
1997/33. Which of the following reaction involves electrophilic substitution?
A C2H6 + Cl2 C2H5Cl + HCl
B C3H6 + Br2 C3H6Br2
C C2H5I + KOH C2H5OH + KI
D C2H5COCH3 + HCN C2H5C(CN)(OH)CH3
E C6H6 + CH3Cl C6H5CH3 + HCl

1997/58. Which of the following is true for nucleophilic addition?

1 The reaction involved the addition of a nucleophile to the C=C functional group.
2 The reaction involved the addition of an electrophile to the C=C functional group.
3 The reaction involved the addition of a nucleophile to the C=O functional group.

1998/33. Which of the following compound has two isomers with same structural formula?
A CH3CH2CH2Cl B CH2=CHCH2Cl C CH3CH=CCl2 D CH3CCl=CCl2
E CH3CHClCH2CH3

1998/34. Which of the following is not a nucleophile?

A CN B NO2 C H2O D NH3 E Br2

1998/56. Which of the following is the requirement for an organic molecule to exhibit
geometrical isomerism?
1 Two different groups or atoms to the carbon atoms of the C=C bond.
2 The present of C=C double bond that hindered free rotation.
3 All atoms in the molecule are located at the same plane.

1999/31. Which of the following molecule shows optical isomerism?

A CH3CH=CHCH3 B CH3CH2C(Cl)2CH3 C CH3CH2CH2OH
D CH3CH2CH(OH)CH3 E HOCH2CH(OH)CH2(OH)

1999/32. Given are three organic bases with the following structural formulae.

I CH3NH2 II NH2 III NH2

Cl
Which of the following is the correct sequence of strength of base in the ascending order?
A I, II, III B II, I, III C III, II, I D III, I, II E I, III, II

27
2000/32. Which of the following compounds does not exhibit stereoisomerism?
A 1-butene B 2-butene C 1,2-dichloropropene
D 1-bromo-1-chloroethane E 2-hydroxypropanoic acid

2000/57. The mechanism of reaction between KOH and 2-bromo-2-phenylbuthane is given as

the following.
CH3 CH3 CH3

HO + C Br HO C Br HO C + Br
H5C2 C2H5
C6H5 C2H5 C6H5 C6H5
Which of the following statements is correct in regarding to the above mechanism of reaction?
1 It is a substitution reaction.
2 The alcohol produced is optically active.
3 The OH ion is an electrophile.

2001/30. Which of the following pair of bonding and mechanism of reaction is correctly
matched?
Bonding Mechanism of reaction
A Single Free radical addition
B Single Electrophilic addition
C Double Electrophilic addition
D Double Nucleophilic addition

2001/31. Which of the following reactions involved an electrophile?

A C2H6 + Cl2 C2H5Cl + HCl
B CH3Br + NaOH CH3OH + NaBr
C C3H6 + HBr C3H7Br
D CH3COOH + C2H5OH CH3COOC2H5 + H2O

2001/32. Which of the following pair of reactants would goes through nucleophilic substitution?
A B
and conc. HNO3/H2SO4 and Br2/Fe

C D
CH2Cl and NaOH CHO and HCl

2002/29 Five carboxylic acids are listed as follows.

I. HCOOH
II. CH3COOH
III. FCH2COOH
IV. F2CHCOOH
V. ClCH2COOH

28
Which of the following is the correct order that shows the increase of pKa values of the acids?
A I, II, V, III, IV
B IV, III, V, I, II
C IV, III, V, II, I
D V, III, IV, II, I

2003/38. The structural formulae of three organic compounds are given below.
X CH3CH2CH2OH
Y CH3CH2Cl
Z CH3COOH
Which sequence of compounds shows the order of increasing boiling point?
A X<Y<Z B Y<X<Z C Y<Z<X D
Z<X<Y

2004/48. 4-Hydroxy-2-pentene has stereoisomers. These isomers can be differentiated by using

1. A plane-polarised light
2. An alkaline iodine solution
3. Mass spectrum

2005/40. When C6H5OH, ClC6H4OH and CH3C6H4OH react separately with aqueous NaOH
solution, they form basic sodium salt solution. Which of the following arrangements correctly
shows the ascending order of base strength of the sodium salt?
A C6H5ONa, CH3C6H4ONa, ClC6H4ONa
B CH3C6H4ONa, C6H5ONa, ClC6H4ONa
C ClC6H4ONa, C6H5ONa, CH3C6H4ONa
D ClC6H4ONa, CH3C6H4ONa, C6H5ONa

2005/49. The table below shows the dissociation constant, Ka, for four organic acids at 25oC.

Formula Ka/ mol dm-3

C6H5COOH 6.3 x 105
CH3COOH 1.7 x 105
ClCH2COOH 1.3 x 103
Cl2CHCOOH 5.0 x 102

Which of the following statements is/are the conclusion(s) based on the data?
1. Chlorine substituted ethanoic acid is a stronger acid than ethanoic acid.
2. Cl3CCOOH is expected to be a stronger acid than Cl2CHCOOH
3. ClC6H4COOH is expected to be a stronger acid than C6H5COOH
1990: 21E, 37(2&3) /1991: 23B/ 1994:38 (1&2) / 1995: 38(2&3) / 1996: 34 / 1997: 32C, 33E, 58(3 only)/ 1998: 33E, 34E, 56(1&2)/ 1999: 31D,
32C/ 2000: 32A, 57(1,2 &3) /2001: 30C, 31C, 32C.

29
B. STRUCTURED
1993/2. b. The table below shows the pKb values of several organic bases.

Organic bases pKb

C2H5NH2 3.28
NH3 4.74
C6H5NH2 9.38
NH2CH2COOH 11.70
i. Arrange these bases in the order of increasing strength of base.
ii. Compare and explain the strength of base between C2H5NH2 and C6H5NH2. [3]

2002/4(a) Below is a list of several carboxylic acids.

CH3COOH, COOH, O2N COOH, HO COOH

i. Arrange the carboxylic acid in the order of increasing acid strength

ii. Which of the acid has a strongest conjugate base?
iii. State the effect of nitro, NO2 group on the acid strength of HO COOH [5]

1997/3. a. Write the structural formula for the following organic compounds.

Name Structural
formula
i. 4-bromo-2-methylhexan-1-ol

ii. 2-methylkexan-1,4-diol

iii. 3-methylpenta-1,3-diene

(b) i.
Which of the above compound is able to form geometrical isomers? Draw the
structural formulas for this geometrical isomer and label the cis and trans
isomer.
ii. Which of the above compound is optical active? Mark all the chiral carbon
atoms. [4]

(c) State the reagent and condition of reaction it which 4-bromo-2-methylhexan-1-ol can
be converted to 2-methylkexan-1,4-diol. [1]

30
2003/4 Two organic compounds X and Y have the following structural formulae

X is O2N CH3 Y is H2N COOH

(a). State which of these two compounds has the higher melting point. Explain tour
answer.
(b). Compound X and Y can be distinguished by using hydrochloric acid. State the
observation and write an equation for the reaction which occurs.
(c). Compound X can be prepared from benzene in two steps. State the reagent used and
write an equation for the reaction which occurs in each step.
Step 1: (i). Reagent:
(ii). Equation:
Step 2: (i). Reagent:
(ii). Equation:
(d). (i). Which of the compound X and Y exist as zwitterions?
(ii). Write the structural formula of the zwitterions.

C. ESSAY
1990/6. (a) By referring to ammonia (NH3), ethylamine (CH3NH2) and methylamide (HCONH2).
Discuss the factors that determine the strength of base of these compounds. [6]

1990/7. (d) Explain; why the value of pKa for ethanoic acid, CH3COOH is 1.7 x 10-5 mol dm-3,
while the value of pKa for chloroethanoic acid, ClCH2COOH is 1.3x 10-3 mol /dm3.
[4]
1991/7. (a) By using an appropriate example, explain the following terms
i. Structural isomerism
ii. Optical isomerism
iii. Geometrical isomerism. [12]

1993/8. (a) What do you understand by the terms structural isomerism, geometrical isomerism
and optical isomerism? [6]

1995/8. (b) The table below shows the pKa values of several organic acids in aqueous solution
at room temperature.
acid pKa
Methanoic acid, HCOOH 3.80
Ethanoic acid, CH3COOH 4.80
Chloroethanoic acid, ClCH2COOH 2.90
Arrange these acids in the order of increasing strength of acidity. Explain your answer. [6]

31
1998/7. The table below shows the pKa values of several organic acids.
Benzoic acid 4-methylbenzoic acid 4-nitrobenzoic acid
Aci
d COOH H3C COOH O2N COOH

pKa 4.19 4.36 3.41

Explain; why there are differences in the values of pKa. [6]

1999/7. a. The table below shows the values of dissociation constant, Ka of several alcohol in
aqueous solution at room temperature.

Alcohol Cyclohexanol Phenol 4-methylphenol

OH OH H3C OH

Ka / mol dm- 1.0 x 10-18 1.0 x 10-10 6.8 x 10-11

3

Arrange these alcohols in the order of increasing strength of acidity. Explain your answer. [8]

2000/7. (a) 4-chloro-4-methyl-2-hexene, CH3CH = CHC(CH3)(Cl)CH2CH3 forms both optical

and geometrical isomers.
i. Explain the term optical isomer and geometrical isomer.
ii. Draw and label the geometrical isomers of 4-chloro-4-methyl-2-hexene.
iii. Draw and label the optical isomers of 4-chloro-4-methyl-2-hexene. [7]

2002/9 (a) i. Draw structural formulae of all isomers that can be derived from CH3CH(OH)C3H7
and CH3CH=CHC2H5 [5]

2003/9 (a). 3-Methyl-4-hexen-3-ol shows stereoisomerism which is geometrical isomerism and

optical isomerism. Describe the stereoisomerism present in this compound. [8]

2005/9(a). Explain why 2-butene exist as a pair of cis-trans isomers and 2-hydroxybuthanoic acid
exist as a pair of optical isomers. [4]
(b) The structural formula of compound T is given as below.

CH3COCH2 =O
What are the products expected when T is reacted with each of the following reagents?
(i)
H2/Pt; 200oC
(ii)
LiAlH4, followed by H3O+
(iii)
I2, NaOH; heat [4]

32
CHAPTER 2
HYDROCARBONS
PART A: ALKANES
1. INTRODUCTION
Hydrocarbon means compounds that consist of carbon and hydrogen only.
Saturated hydrocarbons are classified into two groups. They are aliphaticalkanes and
alicyclicalkanes.
Aliphaticalkanes are hydrocarbons with open chain structured molecules. The grouping up of
these alkanes formed the alkane series. All the alkenes in this series can be represented by a
general formula, CnH2n + 2.
Alicyclicalkanes are hydrocarbons with close ring structured molecules. The grouping up of these
cycloalkanes formed the cycloalkane series. All the alkanes in this series can be represented by a
general formula, CnH2n.

2. THE HOMOLOGOUS SERIES OF ALKANE

The molecular formula of each member in the series can be generated from the general
formula, CnH2n + 2 by substituting n with the numerical number 1 for the first member and 2, 3, 4,
5 and so on for the subsequent members in the series.

Example: the first member of the series, n=1.

CnH2n + 2 becomes C(1)H2(1)+2
The molecular formula is CH4

The molecular formulas of the subsequent members in the alkane series can be obtained
by using the same procedure of calculation. The table bellow shows the molecular formulas of
the first ten members in the alkane series.

Number of 1 2 3 4 5 6 7 8 9 10
carbon atom, n
Molecular CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22
formula

3. NOMENCLATUREOF ALKANES
The general name of alkanes is paraffins.
According to the IUPAC naming system, the name of an alkane is made up of two major parts.
The prefix: It indicates the number of carbon atoms in the alkane molecule.
Latin words are used as the prefix to represent the number of carbon atoms.

Number of 1 2 3 4 5 6 7 8 9 10
carbon atom, n

Latin words Meth Eth Prop But Pent Hex Hept Oct non dec

33
The suffix: ane indicates the alkane series.
The name of an alkane is formed by putting together the prefix with the suffix ane.

Number of
carbon atom, n 1 2 3 4 5 6 7 8 9 10
Molecular
formula CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22

Name of
alkane methane ethane propane butane pentane hexane heptane octane nonane decane

Number of
carbon 3 4 5 6
atom, n
Molecular
formula C3H6 C4H8 C5H10 C6H12

Structural
formula

Name of
cycloalkane cyclopropane cyclobutane cyclopentane cyclohexane

4. IUPAC SYSTEM
Rules to follow
a. Identify the longest carbon atoms chain. This gives the basic name of the alkane
molecule.
Example:
CH3

CH3CH2CHCH2CHCH3 or

CH2CH3

The longest carbon atoms chain is consist of seven carbon atoms. The basic name
of the molecule is heptane.

b. Other shorter carbon chain is to be considered as group or branch. Identify the groups of
carbon atoms that become the branches of the longest carbon atoms chain.

Groups CH3 CH3CH2 CH3CH2CH2 (CH3)2CH

Name methyl ethyl propyl isopropyl

Example: there are two CH3 group attached to the longest carbon atoms chain.
CH3 is named as methyl

34
 c. Give numbering to these groups according to the carbon atom at which the groups are
bonded to. The numbering should start from the end of the carbon chain that produces the
smallest (total sum) numbering as possible.
Example: the numbering is started from the left end. The CH3 groups are attached
to the 3rd and the 5th carbon atoms.

d. If two similar groups are bonded to the longest carbon chain, the numbering must
be repeated and a prefix di is added to the groups name.
Example: Two similar CH3 groups attach to the chain. Thus, it is named as
3,5-Dimethyl.

e. Name the groups first as prefix and the basic name as suffix.
If there are different groups attached to the chain, these groups are to be arranged
in the alphabetical order, starting from the smallest alphabet.

The name of the alkane is 3,5-Dimethylheptane.

Name the following molecules:

1. CH3CH2CH(CH3)CH3
2. CH3CH(CH3)CH(CH2CH3)CH3
3. CH3CH2CH(CH2CH3)C(CH3)2CH3
4. CH3CH2CH2CH(CH2CH2CH3)CH(CH3)CH2CH3
5. CH3CH(CH3)CH2C(CH2CH3)2CH(CH3)CH2CH3
6. 7.

5. PHYSICAL PROPERTIES OF ALKANES

The physical properties of alkanes are closely related to the molecular mass and the van
der waals forces between alkane molecules.
Note that, as going down the alkane series, the molecular formula or the molecular mass
of any member in the series is greater than the previous member in the series by a CH2 unit or
by 14 unit of mass. Thus, as going down the series, the alkane molecules become increasingly
larger in size and it molecular mass increases. Consequently the strength of van der waals forces
also became increasing stronger.
As the results, both boiling point and the melting point of alkanes increase as going down
the series. The alkanes with 1 to 4 carbon atoms are all colorless gasses at room temperature and
pressure, while alkanes with 5 to 15 carbon atoms are colorless volatile liquid and those with
more than 15 carbon atoms are solid. All alkanes are insoluble in water but soluble in organic
solvent.

6. CHEMICAL PROPERTIES OF ALKANES

Alkanes are non-polar molecules (carbon and hydrogen have similar electronegativity).
Alkanes are relatively less reactive because of the molecules do not have electron deficient site
where a chemical reaction may take place.

35
 Since the alkane molecules are non-polar, they do not react with polar reagents like
strong acids (like HCl), strong bases (NaOH), strong oxidizing agents (like KMnO4, H2SO4) and
strong reducing agents (Na).
However, alkanes undergo substitution reaction with non-polar reagents like hydrogen, chlorine
and bromine and combustion reaction with oxygen at high temperature due to the high
activation energy of these reactions.

6.1 Combustion reaction

An alkane goes through complete burning in plentiful supply of oxygen to produce
carbon dioxide and water. In burning, the alkane is oxidized to form carbon dioxide and water.

Reagent: O2
Condition: heat
The combustion reaction of alkanes can be represented by this general equation.
CxHy + [x+(y/4)]O2 xCO2 + (y/2)H2O
Examples: CH4 + 2O2 CO2 + 2H2O
2C2H6 + 7O2 4CO2 + 6H2O

Under limited supply and low supply of oxygen, the incomplete combustion of alkanes forms
carbon monoxide and carbon black as the product of reaction instead of carbon dioxide.
Limited supply of oxygen: 2CH4 + 3O2 2CO + 4H2O
Low supply of oxygen: CH4 + O2 C + 2H2O

Write an equation to show the combustion of octane, C8H18, under the condition of
i. Excess of oxygen
ii. Limited supply of oxygen
iii. Very low supply of oxygen

The molecular formula of an alkane can be determined through analyzing the volumes of gases
required and produced in a combustion reaction.

Examples:
1. 20 cm3 of a gaseous alkane, CxHy, was completely burned in 170 cm3 of excess oxygen. After
that the gaseous mixture is allowed to cold until the room temperature, the volume of the mixture
is reduced to 120 cm3. Some dilute sodium hydroxide is added into the gaseous mixture in order
to absorb carbon dioxide from the mixture. The volume gas is further reduced to 40 cm3.
Calculate the molecular formula of the alkane.

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

From this equation, the mole ratio of CxHy : O2 : CO2
1 : [x+(y/4)] : x
3
Volume analysis: Volume of CxHy is 20 cm
Volume of O2 is (170-40) = 130 cm3
Volume of CO2 is (120-40) = 80 cm3
According to the Avogadros principle, at a fixed temperature; the volume of a gas is
proportional to its mole. Thus, the mole ratio of these gases can be written as the following.

36
 CxHy : O2 : CO2
1 : [x+(y/4)] : x.
20 : 130 : 80
Thus,
The mole ratio of CxHy : CO2 is 1 : 4 and is equals to 1 : x.
Hence, 20/40 = 1/ x
x = 4.
The mole ratio of O2 : CO2 is [x+(y/4)] : x and is equals to 13 : 8
Hence, 130/80 = [x+(y/4)] / x
13/8 = [4+(y/4)] / 4
y = 10
The molecular formula of the alkane is C4H10.

2. 0.72g of an alkane, P, is completely burned in excess of oxygen. 2.20g of carbon dioxide and
1.08g of water are formed. Calculate the molecular formula of P.

The number of moles of carbon atom = the number of moles of carbon dioxide.
= 2.20/ 44.0
The number of moles of hydrogen atom = 2 x the number of moles of water.
= 2 x (1.08/18.0)

If the mole ratio of carbon atom to hydrogen atom in alkane P is x : y, hence,

x / y = (2.20/44.0) / 2(1.08 / 18.0)
= 5 / 12
Thus, x = 5 and y = 12.
The molecular formula of P is C5H12.

Solve these questions.

1. 20 cm3 of a gas of an alkane, Q, was completely burned in 250 cm3 of oxygen. After mixture
of gases was allowed to cold until the room temperature, the volume of gas became 180 cm3.
Some dilute sodium hydroxide was added into the gaseous mixture in order to absorb carbon
dioxide from it. The volume of the gaseous mixture was further reduced to 60 cm3. Calculate the
molecular formula of Q.

2. 1.00g of an alkane, R, was completely burned in excess of oxygen. 3.08g of carbon dioxide
and 1.51g of water were formed. Calculate the molecular formula of R.

6.2 Substitution reaction

If a gaseous mixture of methane and chlorine is kept in the dark at room temperature, no reaction
will take place. However, if this mixture is exposed to the sunlight or is heated to 200oC, they
undergo a series of vigorous substitution reactions and produce a mixture of substituted
chloromethane.

Why there is no reaction in the beginning?

Chlorine and methane are non-polar molecules. Further more, the C C and the C H bond are
strong. Thus, the activation energy for the reaction is high.

37
Why the sunlight is needed?
The sunlight is the source of energy. It provides the activation energy required for the reaction to
progress.

How does the sunlight help in the reaction?

There are three types of bonds that are possibly being broken in order to initiate the reaction.
They are Cl Cl, C C and C H bonds. Among these bonds, the Cl Cl bond is the weakest of
all. The sunlight is used to break the Cl Cl bond.

The substitution reaction progress according to the mechanism called the free radical
substitution reaction. The mechanism involves three steps.

What is a mechanism of reaction?

Mechanism of a reaction means the detail, in sequent step by step of chemical reactions that show how a
reagent reacts with the substrate to form the reaction products.

Free radical substitution reaction is Consists of three steps:

1. The initiation step
2. The propagation step
3. The termination step

The initiation step

This step involves the homolytic fission of Chlorine molecules, producing chlorine radicals. This
is also called a photolytic reaction.
Cl Cl + hv 2Cl (chlorine radicals)

What is a radical?
It is an atomic or molecule species that bears a single electron. The radical is a highly reactive species.

The propagation step

This involves reactions that bring about the forming of products of reaction and the radical
species that enable the reaction goes on in cycle.

The reactions involve are:

1. CH4 + Cl CH3 + HCl
2. CH3 + Cl2 CH3Cl + Cl
(1st substitution product)
As these reactions go on cycle, it forms a chain reaction.
Overall reaction is CH4 + Cl2 CH3Cl + HCl

The termination step

This occurs when two radicals combine to form a molecule.
Cl + Cl Cl2
Cl + CH3 CH3Cl
CH3 + CH3 CH3CH3

38
Why the reaction can be so vigorous?
This is because the reaction is exothermic and the chain reaction is difficult to control. Thus,
large amount of energy is being released during the reaction, making the reaction to progress in a
very high rate and turns vigorous.

Why and how the mixture of substituted chloromethane is formed?

In the propagation step, chlorine radicals may attack CH3Cl or other product molecules. As a
result, further substitution of a hydrogen atom by a chlorine atom takes place to form a mixture
of multiple substituted chloromethane compounds like CH2Cl2, CHCl3 and CCl4.
Example:
CH3Cl + Cl CH2Cl + HCl
CH2Cl + Cl2 CH2Cl2 + Cl
(substitution product)
Write the mechanisms for the formation of CHCl3 and CCl4.

Note that, a hydrogen atom is substituted by a chlorine atom during the reaction.
H H

H C H + Cl Cl H C H + H Cl

H Cl
Thus, the reaction is called the substitution reaction. The reaction also called chlorination
because it involves chlorine as reagent of reaction.
When involves more complex alkane molecules, substitution of hydrogen atom from an alkane
molecule would takes place at the carbon atom that forms most stable radical as intermediate.
Relative stability of radicals increase as:
1o radical < 2o radical < 3o radical
Preference of hydrogen atom in substitution:
H atom of 1o carbon < H atom of 2o carbon < H atom of 3o carbon
o
1
CH3CH3 + Cl2 CH3CH2Cl + HCl
Ethane chloroethane
o
2
CH3CH2CH3 + Br2 CH3CH(Cl)CH3 + CH3CH2CH2Cl + HCl
Propane 2-bromopropane (main product)
Secondary radical (MORE STABLE)
CH3CHCH3 CH3CH(Cl)CH3

Cl2
CH3CH2CH3 + Cl
Primary radical
CH3CH2CH2 CH3CH2CH2Cl

Cl2

39
 2o
+ Cl2 Cl + HCl

cyclohexane Chlorocyclohexane

Determine the major product of chlorination of (CH3)3CH, (CH3)4C and . Give

explanation to your answers.

CH3 + Cl2 CH2Cl + HCl

Methylbenzene Chloromethylbenzene

Write the major product of chlorination of CH2CH2CH3. Explain your answer.

Fluorination, chlorination and bromination of methane are exothermic reactions but in reducing
rate of reaction. However, iodination is endothermic and it does not occur under this condition.

Question:
Explain why ethane decolorizes bromine if the mixture is exposed to the u-v radiation. Write the
mechanism of the reaction involved. Explain why C2H4Br2 is formed and the write the possible
structural isomers for C2H4Br2.

6.3 Cracking
This is the process where the C C bonds in a long chain alkane molecule are broken,
producing smaller alkanes, alkenes and hydrogen molecules. There are two types of cracking,
namely the thermal cracking and the catalytic cracking.

i. The thermal cracking

It is also known as pyrolysis. The alkane is heated to a temperature between 500 to 700oC.
Thermal cracking of alkanes involve free radicals mechanism.
Examples:

CH3CH2CH2CH2CH2CH2CH2CH2CH3 CH3CH=CHCH3 + 2CH2=CH2 + CH4

CH3CH2CH2CH2CH2CH2CH2CH2CH3 CH3CH=CH2 + 3CH2=CH2 + H2

Usually, thermal cracking forms a mixture of H2, methane, ethene, propene and butene.

ii. The catalytic cracking

The alkane is passed over a catalyst, a mixture of Al2O3and SiO2 or CrO3 at a temperature
between 400 to 500oC. Zeolite also is used as catalyst in catalytic cracking.
Catalytic cracking of alkanes involve carbocation mechanism. This allows the forming of
branched-chain molecules instead of straight-chain molecules as in the thermal cracking of
alkanes.
Question:

40
Write a balanced equation to show the cracking of octane to form butane and ethene.

7. SOURCE OF ALKANES
Petroleum or crude oil is consists of a complex mixture of hydrocarbons of various molecular
sizes. These components of hydrocarbons in the mixture have different boiling points and this
allows them to be separated by mean of fractional distillation.
Through fractional distillation, this complex mixture is separated into simpler mixtures or
fractions that consist of hydrocarbons within a given range of boiling points. Below is a table
showing the fractions produced by fractional distillation of petroleum.

Fraction Number of Percentage of Typical use for Approximate

carbon atoms in fraction fraction demand for
molecules fraction in %
Gas C1-C4 2 LPG and petrol- 4
chemistry
Gasoline C5-C8 12 Petrol 22
Naphtha C8-C10 12 Cracking 5
Kerosene C10-C14 12 Jet fuel 8
Gas oil C14-C19 19 Diesel 23
Fuel oil C19-C35 43 Power station 38

Note that, most of these hydrocarbons are used up as fuel in various means. In order to fulfill the
demand for fuel, cracking of longer hydrocarbon fraction is carried out.
Cracking of longer alkanes like naphtha, (C8-C10), produce shorter molecules like ethene,
propene and butene; thus, increase the percentage of petrol gas fraction (C1-C4).

This is particularly important because these alkenes are very useful for synthesizing other
organic compounds. In addition to this, it also increases the percentage of gasoline fraction (C5-
C8).

Hydrocarbons are extensively used as fuel for combustion.

A good fuel must obviously have a high exothermic enthalpy change of combustion so that it is
an efficient provider of heat. The effectiveness of a fuel is measured by the energy density of a
fuel.
The energy density of a fuel is defined as the amount of heat that can be generated by a unit
mass of a fuel.
An efficient fuel must have high energy density. In addition to this, it must be safe or not easily
catch fire, cheap, easy to be transported and should not contribute to pollution by producing
toxic combustion products.

The extensive use of hydrocarbons as fuel and other organic products in daily living causes
serious pollution problems.
Landfill of organic wastes produces methane gas, which is easily exploded and highly
flammable. Methane is also a green house gas. Toxic liquids produce from landfill also pollute
the underground water.

41
Burning of organic waste products and fuel produce large quantity of green house gas like the
carbon dioxide and toxic gases like carbon monoxide and dioxins along with acidic gases like
sulfur dioxide and nitrogen dioxide.

8. OCTANE NUMBER OF PETROL

The effectiveness of petrol is measure by its octane number.
The combustion of petrol or hydrocarbon in an internal combustion engine usually produces
knocking sound. The extent of this sound is depending on the molecular structure of alkanes
molecules in petrol.
The combustion of 2,2,3-trimetilpentane, CH3C(CH3)2CH(CH3)CH2CH3 produces lowest
knocking sound. Thus, it is refers as the most efficient petrol. The octane number is given as 100
base on the standard of 2,2,3-trimetilpentane.
Highly branched hydrocarbon molecules usually produce lower knocking sound than the straight
chained hydrocarbon molecules. Thus petrol that contains highly branched hydrocarbons has
higher octane number and became more effective fuel.
There are two ways to increase the octane number of petrol.
i. Catalytic cracking of naphtha (fraction C8-C10) produces highly branched
hydrocarbons that contain 5 to 8 carbon atoms.
ii. Adding of petrol additives such as tetramethyllead, Pb(CH3)4. The adding of this
compound increases the percentage of branched molecule in petrol. However, it causes
the air to be polluted by lead particles.

42
PART B: ALKENES
1. INTRODUCTIN
Alkenes are hydrocarbons with open chain structured molecules. This group of hydrocarbons can
be represented by a general formula, CnH2n.

2. THE HOMOLOGOUS SERIES OF ALKENE

The molecular formula of each member in the series can be determine from the general formula,
CnH2n by substituting n with the numerical number 2 for the first member and 3, 4, 5, 6 and so on
for the subsequent member in the series.

Example: the first member of the series, n=2.

CnH2n becomes C(2)H2(2)
The molecular formula is C2H4

The molecular formulas of the subsequent members in the alkane series can be obtained by using
the same procedure of calculation. The table bellow shows the molecular formulas of the first ten
members of the alkane series.

Number of 2 3 4 5 6 7 8 9 10
carbon atom, n
Molecular C2H4 C3H6 C4H8 C5H10 C6H12 C7H14 C8H16 C9H18 C10H20
formula

3. NOMENCLATURE OF ALKENES
The general name of alkanes is olefins.
The names of alkenes according to the IUPAC system are made up of two major parts.
The prefix indicates the number of carbon in the alkane molecule and the suffix ene.
Latin words are used as the prefix to represent the number of carbon atoms.

Number of 2 3 4 5 6 7 8 9 10
carbon atom, n
Latin words Eth Prop But Pent Hex Hept Oct non dec

The name of an alkane is formed by joining the prefix with the suffix ene.

Number of
carbon 2 3 4 5 6 7 8 9 10
atom, n
Molecular
formula C2H4 C3H6 C4H8 C5H10 C6H12 C7H14 C8H16 C9H18 C10H20

Name of
alkane ethene propene butene pentene hexene pentene octene nonene decene

43
4. IUPAC SYSTEM
Rules to follow
a. Identify the longest carbon atoms chain that contains double bond. This gives the basic
name of the alkene molecule and number the double bond with the smaller number.
Example:
CH3

CH3CH=CCH2CHCH3 or

CH2CH3

The longest carbon atoms chain is consist of seven carbon atoms. The basic name
of the molecule is hept and the double bond is located at the second carbon atom
-2- ene. Thus the longest chain is named hept-2-ene.

If the longest chain has two double bonds, the suffix -diene is used and the
numbering for the double bonds are placed in front of the suffix.
b. Identify the groups of carbon atoms that become the branches of the longest carbon atoms
chain.

Groups CH3 CH3CH2 CH3CH2CH2 (CH3)2CH

Name methyl ethyl propyl isopropyl

Example: there are two CH3 group attached to the longest carbon atoms chain.
CH3 is named as methyl

c. Give numbering to these groups according to the number of carbon atom at which
the groups are bonded to, abide to rule 1 above..
Example: the numbering is started from the left end. The CH3 groups are attached
to the 3rd and the 5th carbon atoms.

d. If two similar groups are bonded to the same carbon atom, the numbering must be
repeated and a prefix di is added to the groups name.
Example: Two similar CH3 groups attach to the chain. Thus, it is named as
Dimethyl.

e. Name the groups first as prefix and the basic name as suffix.
If there are different groups attached to the chain, these groups are to be arranged
in the alphabetical order, starting from the smaller alphabet.

The name of the alkene is 3,5-Dimethylhept-2-ene.

CH3CH=CCH=CHCH3 or

CH3

This is named as 3-methylhex-2,4-diene.

44
Name the following molecules:
CH3CH=C(CH3)CH3, CH3CH(CH3)CH=C(CH2CH3)CH3, CH3CH=C(CH2CH3)C(CH3)2CH3,
CH3CH2CH2C(CH2CH2CH3)=C(CH3)CH2CH3,
CH3C(CH3)=CHC(CH2CH3)2C(CH3)=CHCH3.

5. PHYSICAL PROPERTIES OF ALKENES

The physical properties of alkenes are closely related to the molecular mass and the van der
waals forces between alkene molecules.
Note that, as going down the alkene series, the molecular formula or the molecular mass of any
member in the series is greater than the previous member in the series by a CH2 unit or by 14
unit of mass. Thus, as going down the series, the alkene molecules become increasingly larger in
size and it molecular mass increases. Consequently the strength of van der waals forces also
became increasing stronger.
As the results, both boiling point and the melting point of alkenes increase as going down the
series. The alkenes with 2 to 4 carbon atoms are all colorless gasses at room temperature and
pressure, while alkenes with 5 to 15 carbon atoms are colorless volatile liquid and those with
more than 15 carbon atoms are solid. All alkenes are insoluble in water but soluble in organic
solvent.

6. CHEMICAL PROPERTIES OF ALKENES

Alkenes are non-polar molecules, but the molecule has a carbon-carbon double bond, C=C, that
serves as an electron rich site in the molecule. This makes the alkenes molecules easier to be
attacked by an approaching electrophile. Thus, alkenes are more reactive than alkanes.
Alkenes are unsaturated hydrocarbon. During a reaction, the whole electrophile molecule is
added into the double bond and the double bond, C=C becomes saturated. Thus, a saturated
product is produced.

The electrophilic addition reaction mechanism is shown as the following.

C=C C C + X C C
UNSATURATED +

Y a carbocation X Y
- +
X Y ELECTROPHILE SATURATED SINGLE PRODUCT

The product of electrophilic addition is depends on the types of alkene.

Symmetrical alkenes like CH2=CH2, CH3CH=CHCH3 and other alkenes molecule that have a
double bond in the middle of the molecule, the additional of an electrophile in these alkenes only
produce a single product of addition.
However, the additional of an electrophile in non symmetrical alkenes like CH3CH=CH2,
CH3CH2CH=CH2, CH3CH2CH2CH=CH2, CH3CH2CH=CHCH3 alkenes molecule will form two
products of addition. The product that appears in the higher percentage is called the
Markovnikov product and the other product that appears in the lower percentage is called the
anti Markovnikov product.
According the Markovnikovs rule, the more electronegative atom or group always adds to the
carbon atom bound to the least number of hydrogen atoms.

45
Why it is so? The electrophilic addition reaction progress through an intermediate called the
carbocation. If the carbocation that is formed as an intermediate of reaction is more stable, more
of this carbocation will be formed. Thus, it appears at a higher percentage.

Primary, 1o secondary, 2o tertiary, 3o

carbocation carbocation carbocation
H H CH3
1o 2o 3o
CH3 C H CH3 C CH3 CH3 C CH3
+ + +
stability of carbocation increases
as the number of methyl groups, stronger +I effect
Example: H H
2o 1o
CH3CH=CH2 CH3 C C H
+
Y
X - Y+ secondary, 2o, carbocation (more stable)

H H
o o
2 1
CH3CH=CH2 CH3 C C H
+
Y
X - Y+ primary, 1o, carbocation (less stable)

More stable carbocation is form more rapidly and appears in a higher percentage.

Write all the structural formulas of the carbocation that may be formed by CH3CH2C(CH3)=CH2
molecule. Identify the most stable carbocation.

7. REACTIONS OF ALKENES.
7. 1 Hydrogenation of alkenes
A mixture of hydrogen and an alkene is stable at room temperature. However, in the present of a
catalyst such as nickel (of platinum or palladium) and at about 180oC; the hydrogen molecule is
added into the double bond of an alkene molecule.

Reagent: Hydrogen.
Condition: heated and nickel as catalyst.

Example of reaction:
CH2=CH2 + H2 CH3CH3
Ethene ethane

46
 + H2

Cyclohexene cyclohexane

The number of moles of hydrogen requires in the hydrogenation process is equals to the number
of double bond in the alkene molecule involved.

Example:
CH3CH= CH2 + H2 CH3CH2CH3
(one mole of C=C requires one mole of H2)
CH2=CHCH= CH2 + 2H2 CH3CH2CH2CH3
(two moles of C=C require two moles of H2)
The number of moles of hydrogen used in the hydrogenation process indicates the number of
unsaturation or double bond in an alkene molecule.

In the food industry, margarine is produced by hydrogenation process carried out on the
poly-unsaturated vegetable oil. The process is carried out at 200oC in the present of
nickel as catalyze. During this process, hydrogen is added into the double bond in the
oils molecules. The process reduces the number of double bond in the unsaturated
vegetable oil, causes the oil to be harden.

7.2 Halogenations
Halogen reacts readily with alkenes at room temperature. In the reaction, a halogen molecule is
added into the double bond of an alkene molecule. The most frequently used halogen is bromine.

Reagent: Br2 (aq) or Br2 in alcohol

Condition: room temperature
Observation: the reddish-brown color of bromine water becomes decolorized.
Example:
CH2=CH2 + Br2 CH2BrCH2Br (1,2-dibromoethane)
Br
+ Br2
(1,2-dibromocyclohexane)
Br

Bromine water is always used to test or detect the present of double bond in an unsaturated
organic compound.

In research and food industry, the number of double bond in poly-unsaturated

vegetable oil is tested by adding of iodine solution. If a poly-unsaturated vegetable
oil can decolorized more iodine, it means the poly-unsaturated vegetable oil
contain higher number of double bond. The poly-unsaturated vegetable oil is said
to have higher iodine value. Example Sunflower oil has higher iodine value than
the peanut oil. This means, the sunflower oil contains more double bond than the
peanut oil.
47
7.3 Addition of hydrogen halides (HX)
Alkenes react rapidly with hydrogen halides aqueous solution at room temperature.
A HX molecule is added into the double bond of an alkene molecule. The addition of HX to an
alkene obeys Markovnikovs rule.

Reagent: HBr (aq)

Condition: room temperature

Examples:
CH2=CH2 + HBr CH2BrCH3 (bromoethane)

+ HBr Br (bromocyclohexane)

CH3CH= CH2 + HBr CH3CH(Br)CH3 + CH3CH2CH2Br

(2-bromopropane) (1-bromopropane)
a Markovnikov product.

The reaction mechanism of electrophilic addition is shown as the following.

H H
2o 1o
CH3CH=CH2 CH3 C C H + Br
+ CH3CH(Br)CH3
H (2-bromopropane)
Br - H+ secondary, 2o, carbocation main product
(more stable)
H H
o o
2 1
CH3CH=CH2 CH3 C C H + Br
+ CH3CH2CH2Br
H (1-bromopropane)
Br - H+ primary, 1o, carbocation
(less stable)

+ HBr + Br
Br (main product)

7.4 Hydration of alkenes

Alkenes react with water at 140oC at the present of concentrated sulfuric acid as catalyze.
In this reaction, a water molecule is added into the double bond. The addition of H2O to an
alkene obeys Markovnikovs rule.
Reagent: H2O
Condition: Concentrated H2SO4, heating
Examples:
CH2=CH2 + H2O CH2(OH)CH3 (ethanol)

48
 + H2O OH (cyclohexanol)

CH3CH= CH2 + H2O CH3CH(OH)CH3 + CH3CH2CH2OH

Main product

In the industry, ethanol is produced by the hydration of ethene with steam at the
pressure of 60 atm. and at the temperature of 300oC with the present of concentrated
phosphoric acid as catalyze.

CH2=CH2 + H2O CH2(OH)CH3

7.5 Addition of sulfuric acid.

In this reaction, a sulfuric acid is added into the double bond. The addition of H2SO4 to an alkene
obeys Markovnikovs rule.
Reagent: Concentrated H2SO4
Condition: Room temperature.

CH2=CH2 + H2SO4 CH2(OSO3H)CH3 (ethylhydrogensulfate)

+ H2SO4 OSO3H (cyclohexylhydrogensulfate)

CH3CH= CH2 + H2SO4 CH3CH(OSO3H)CH3 + CH3CH2CH2OSO3H

Main product

8. OTHER REACTIONS OF ALKENES

Oxidation of alkenes takes place by adding of oxygen into the double bond. Under strong
oxidation agent, cleavage of double bond takes place.

8.1 Oxidation with potassium manganate (VII)

The purple color of an acidified solution of potassium manganate (VII) becomes decolorized
when the solution is shaken with an alkene. The alkene is hydroxylated to form a diol.

Reagent: KMnO4, H2SO4

Condition: Room temperature
Observation: the purple color of acidified KMnO4 becomes decolorized
Examples:
CH2=CH2 + H2O + (O) CH2(OH)CH2(OH) (ethane-1,2-diol or glycol)

OH
+ H2O + (O) (cyclohexane-1,2-diol)
OH

49
This acidified solution of potassium manganate (VII) is also used to test on the present of double
bond in an alkene molecule.

8.2 Oxidative cleavage

Oxidative cleavage occurs when an alkene is heated with the excess acidified KMnO4 solution.
The cleavage takes place at the double bond, breaking an alkene molecule into two fragments.
These fragments may be of an carboxylic acid, ketone or carbon dioxide, depending on the
location of the double bond in the alkene molecule and the type of alkene itself.

Oxidative cleavage is used to determine the location of the double bond in an alkene molecule.

8.2a. The cleavage of a 1-ene (double bond at the end of an alkene molecule) produces carbon
dioxide and a carboxylic acid or ketone.
Examples:
CH2=CH2 + 6(O) 2CO2 + 2H2O

CH3CH= CH2 + 3(O) CH3COOH + CO2 + H2O

Ethanoic acid

If the carbon of the double bond has two alkyl groups, a ketone is formed during the cleavage.
Example:
(CH3)2C= CH2 + 3(O) (CH3)2CO + CO2 + H2O
Propanone
(a ketone)

8.2b. The cleavage of other than 1-ene (double bond does not located at the end of an alkene
molecule) involved two situations.

i. Cleaving a symmetrical alkene produces single product.

Examples:
CH3CH = CHCH3 + 4(O) 2CH3COOH
But-2-ene ethanoic acid ony
(CH3)2C= C(CH3)2 + 2(O) 2(CH3)2CO
2,3-dimethylbut-2-ene Propanone (ketone) only

ii. Cleaving an asymmetrical alkene produces two products. They are carboxylic acid and
ketone.
Example:
CH3CH = C(CH3)2 + 3(O) CH3COOH + (CH3)2CO
2-methylbut-2-en ethanoic acid propanone

50
iii. Cleaving of a cycloalkene produces two carboxyl (COOH) groups at the ends of an open
chain.
Example:

COOH
+ 4(O)
COOH
Cyclohexene hexane-1,6-dioic acid

Hexane-1,6-dioic acid is one of the monomer used in manufacturing Terylene, a synthetic

polyester used TEXTILE INDUSTRIES.

From the products of oxidative cleavage, the structural formula of an alkene can be determine by
eliminating the oxygen atoms from the end of both products and join the carbon ends of these
products with a double bond.
Examples:
CH3COOH + (CH3)2CO CH3CH = C(CH3)2

CH3COOH + CO2 CH3CH = CH2

8.3 Ozonolysis of alkenes

Alkenes react with ozone to form alkene ozonide. In this reaction, an ozone molecule is inserted
into the double bond to form a ring structure. If the alkene ozonide is hydrolyzed, the molecule
will be broken into two fragments, which is consists of aldehyde and ketone.
Reagent: O3 in CCl4
Condition: Cold (<20oC)
Follow by
Reagent: dilute sulfuric acid
Condition: boil.
Examples: O
CH2=CH2 + O3 H2C CH2 + 2H+ 2 HCHO + H2O
Ethene methanal
O O (an aldehyde)
(ethene ozonide)

O
CH3CH=C(CH3)2 + O3 CH3CH C(CH3)2 + 2H+ CH3CHO +

O O (CH3)2CO + H2O

Note that, the outcome of ozonolysis on alkene is the same as that of the oxidative cleavage.

51
An alkene X reacts with ozone to form an ozonide that after further hydrolysis, it produces
CH3CH2CH(CH3)COCH3 and CH3CH2CH(CH3)CHO. Determine the structural formula and the
name of X.
An alkene Y reacts with ozone to form an ozonide that after further hydrolysis, it produces
(CHO)CH2CH2CH2CH2CHO only. Determine the structural formula and the name of Y.

9. USE OF ETHENE IN INDUSTRY

9.1 Synthesis of glycol
Ag
2CH2=CH2 + O2 250oC, 15 atm. 2CH2CH2 H2O,o H+ 2CH2CH2
200 C
O OH OH
epoxyethane (glycol)etahane-1,2-diol
Glycol is use as coolant or antifreeze is cars radiators and making detergents. It is also use as a
monomer in the manufacturing of polyester like Terylene.

9.2 Synthesis of vinyl chloride or chloroethene

ZnCl2 (or FeCl3)
CH2=CH2 + Cl2 CH2ClCH2Cl ClCH=CH2 + HCl
(Or pumice; 500oC, 3 atm.)
Chloroethene
CuCl2
2CH2=CH2 + 2HCl + O2 2ClCH=CH2 + H2O
500oC
The vinyl chloride is used to manufacture polyvinyl chloride (PVC) polymer. This polymer is use
to make plastic pipes, shoes, rain coat, bags

9.3 Synthesis of polyethene

n CH2=CH2 ( CH2 CH2 )n

polyethene
Polyethene is uses to make plastic bags, plastic for wrapping, plastic bottles.

9.4 Synthesis of ethanol

Hydration of ethene in the present of concentrated phosphorus acid
H3PO4
CH2=CH2 + H2O CH3CH2OH
300oC, 60 atm.
ethanol

Ethanol is use as an organic solvent for lacquers, varnishes and cosmetic.

52
PART C: ARENES
1. INTRODUCTION
Arenes are aromatic hydrocarbons. The molecule of an arene is consists of a hexagon carbon
ring and the delocalized electrons. This hexagon carbon ring is called the aromatic ring. Arenes
can be represented by a general formula, CnH2n-6.

2. THE HOMOLOGOUS SERIES OF ARENES

The molecular formula of each member in this series can be derived from the general formula,
CnH2n-6 by substituting n with the numerical number 6 for the first member and 7, 8, 9, 10 and so
on for the subsequent member in the series.
Example: the first member of the series, n=6.
CnHn becomes C(6)H2(6)-6
The molecular formula is C6H6
The molecular formulas of the subsequent members in the arenes series can be derived by using
the similar procedure of calculation. The table bellow shows the molecular formulas of the first
ten members of the arenes series.

Number of 6 7 8 9 10 11 12 13 14
carbon atom, n
Molecular C6H6 C7H8 C8H10 C9H12 C10H14 C11H16 C12H18 C13H20 C14H22
formula

3. NAMING THE ARENES

Arenes are name differently than alkanes and alkenes. The carbon atoms in the aromatic ring are
numbered by 1, 2, 3, 4, 5 and 6 clockwise or anti-clockwise.
1 1 The 2nd and 6th position is
6 2 2 6 called ortho, the 3rd and
or 5th position is called meta
5 3 3 5 and the 4th position is
4 4 called para.
clockwise anti-clockwise
Alkyl groups attached to the ring are numbered and sum of the numbers must be the smallest as
possible. The alkyl groups are named according to the number of carbon atoms.
CH3 CH2CH3

benzene methylbenzene ethyl benzene

(toluene) phenyl ethane
CH3 CH3 CH3
CH3

CH3
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene
(ortho xylene) (meta xylene) (para xylene)
CH3CHCH3 naphthalene

53
 Isopropyl benzene
2-phenylpropane

4. PHYSICAL PROPERTIES OF ARENES

Arenes are non polar molecules. There are weak Van der Waals forces between the arenes
molecules. Thus, arenes are colorless volatile liquid, immiscible with water but miscible with
non-polar solvent and itself a good solvent for organic compounds.

Benzene, toluene and xylene are components found in petrol. These arenes are
highly toxic to human body. Inhalation of these vapors cause dizziness and
headaches. High concentration can lead to unconsciousness. They irritate the ayes
and mucous and even absorb through the skin. Frequently expose to these vapors
may cause fatal blood disease.

5. CHEMICAL PROPERTIES OF ARENES THE ELECTROPHILIC SUBSTITUTION

REACTION
Although the benzene molecule is non polar, but it has electron rich double bonds or delocalizes
electrons. Thus, the molecule is stabilized by the delocalized -electrons. During a reaction,
the benzene molecule retains its delocalized -electrons by undergoing electrophilic substitution
instead of electrophilic addition reaction like that of the alkenes. In the electrophilic substitution
reaction, a hydrogen atom from the benzene molecule is substituted by an electrophile.
H E
H
+ E+ + E + H+
electrophile
intermediate compound

Toluene reacts more reactively compares to benzene.

The methyl (CH3) group in the toluene molecule poses a positive inductive effect (+I ) on the
aromatic ring and magnified the electron density of the aromatic ring. This makes it more readily
to react with the electrophiles.
Apart from this, the methyl (CH3) group directs the incoming electrophile so that the
electrophilic substitution takes place at the orto and para positions at the aromatic ring.
Thus, the alkyl group is an activator and orto-para director.
CH3 CH3 CH3
E
+ E+ + + H+

orto-substituted E
para-substituted
Both products appear as a mixture of isomers.

54
5.1 Nitration
Benzene can be nitrated using a mixture of concentrated nitric acid and sulfuric acid at 55oC.
Reagent: Con. HNO3 and H2SO4
Condition: Heat.
Mechanism of nitration:
HNO3 + H2SO4 NO2+ + HSO4 + H2O
(base) (acid) (nitronuim ion)
The nitronium ion, NO2+, is an electrophile. It attacks the benzene ring as the following.
H NO2
H
+ NO2+ + NO2 + H+

nitro benzene
H+ + HSO4 H2SO4

The overall reaction is

H NO2

+ HNO3 + H2O

Nitrobenzene is a pale yellowish liquid with a characteristic smell of almonds.

Nitration of toluene takes place with a mixture of concentrated nitric acid and sulfuric acid at
room temperature.
Reagent: Con. HNO3 and H2SO4
Condition: room temperature
CH3 CH3 CH3
NO2
+ HNO3 + + H2O

2-nitrotoluene
NO2
4-nitrotoluene
CH3 CH3
O2N NO2 NO2 Heat
+

2,6-dinitrotoluene
NO2 2, 4-dinitrotoluene
CH3
O2N NO2
Heat
2.4,6-trinitrotoluene (TNT)

TNT is use as explosive. NO2

55
5.2 Halogenation
Benzene reacts with Cl2 or Br2 at room temperature at the present of catalyze such as FeBr3 or
AlCl3.
FeBr3 and AlCl3 are Lewis acids. They polarize Cl2 or Br2 molecules by forming a complex.
+
Cl2 + AlCl3 ClCl AlCl3
Reagent: Cl2, AlCl3
Condition: room temperature
H Cl

+ Cl2 + HCl

Chloro benzene

Halogenation of toluene forms 2,4-dichlorotoluene.

Reagent: Cl2, AlCl3
Condition: room temperature, dark
CH3 CH3 CH3
Cl Cl Cl
+ 2Cl2 + + 2HCl

2,6-dichlorotoluene
Cl 2,4-dichlorotoluene
5.3 Friedel-Craft reaction
There are two types of Friedel-Craft reactions.

a. Alkylation reaction involves crafting an alkyl group into the benzene molecule. As a result, the
product molecule always has higher number of carbon atoms than the substrate. Alkylation takes
place when chloromethane is warmed with benzene in the present of anhydrous (dry) AlCl3 (a
Lewis acid) as catalyze.
Reagent: CH3Cl, anhydrous AlCl3
Condition: warmed
H CH3

+ CH3Cl + HCl

Toluene
Alkylation of toluene takes place at room temperature.
Reagent: CH3Cl, anhydrous AlCl3
Condition: room temperature
CH3 CH3 CH3
CH3
+ CH3Cl + + HCl

2-methyltoluene 4-methyltoluene
CH3

56
b. Acylation reaction involves crafting an acyl group into the benzene molecule.
Acylation takes place when an acylchloride is added into benzene at room temperature in the
present of anhydrous (dry) AlCl3 (a Lewis acid) as catalyze.

Reagent: CH3COCl, anhydrous AlCl3

Condition: room temperature O
H O
C CH3
+ CH3 C Cl + HCl
ethanoylchloride phenyl ethanone (a ketone)
benzene

O
CH3 O CH3 CH3
C CH3
+ CH3 C Cl + + HCl

toluene (2-methyl)phenylethanone
O C CH3
(4-methyl)phenylethanone

5.4 Sulfonation of benzene

Benzene is sulfonated by refluxing it with concentrated sulfuric acid. In this reaction, the
electrophile, SO3 substituted a hydrogen atom from the benzene molecule. The overall reaction
for sulfonation of benzene is shown as the following.
Reagent: Con. Sulfuric acid
Condition: reflux

+ H2SO4 SO3H + H2O

Benzenesulfonic acid
Benzenesulfonic acid is a weak acid and it is widely used to synthesis detergents.

6. OTHER REACTIONS OF ARENES

Although the characteristic reactions of benzene involve electrophilic substitution, benzene also
undergoes certain addition reactions because of the double bonds it has.
6.1 Hydrogenation
Reagent: H2, Pt (catalyze)
Condition: heat. (150-200oC)

+ 3H2

benzene cyclohexane
Three moles of hydrogen molecules are added into the benzene molecule. Hydrogenation of
toluene produces methylcyclohexane under the similar condition of reaction.

57
 CH3 + 3H2 CH3 methylcyclohexane

6.2 Chlorination
Reagent: Cl2
Condition: u-v, heat Cl
Cl Cl

+ 3 Cl2
Cl Cl
Cl 1,2,3,4,5,6-hexachlorocyclohexane
In chlorination of benzene, chlorine molecules are added into the benzene molecule through the
electrophilic addition. However the chlorination of toluene does not only take place at the
benzene ring, but it occurs at the methyl group. The reaction resembles the chlorination of
alkanes (free radical substitution).
Reagent: Cl2
Condition: u-v, boil.

CH3 + Cl2 CH2Cl + HCl

phenyl chloromethane

CH2CH3 + Cl2 CHClCH3 + HCl

1-chloro-1-phenylethane

6.3 Oxidation of arenes.

Benzene is stable under strong oxidation agent. However other arenes are oxidized if they are
heated with strong oxidizing agent. During oxidation, the alkyl group attached to the benzene
molecule is oxidized to form benzaldehyde or benzoic acid.
Reagent: KMnO4, H2SO4 (aq) (for strong oxidation)
Condition: heat

CH3 + 3(O) COOH + H2O

benzoic acid

Reagent: MnO2, H2SO4 (aq) (for mild oxidation)

Condition: heat

CH3 + 2(O) C O + H2O

H benzaldehyde
If there is more than one alkyl groups attached to the benzene molecule, these alkyl groups will
be oxidized to the carboxyl groups.

58
 CH3 CH3 + 6(O) HOOC COOH + 2H2O

4-methyltoluene benzene-1,4-dioic acid

If the alkyl group is consists of more than one carbon atoms, cleavage of C C takes place
between the 1st and the 2nd carbon atoms and produce CO2 and other carboxylic acids as products.

CH2CH3 + 5(O) COOH + CO2 + H2O

carbon dioxide
ethylbenzene

CH2CH2CH3 + 5(O) COOH + CH3COOH + H2O

ethanoic acid
Propylbenzene

7. USES OF BENZENE IN INDUSTRIES

7.1 Synthesis of Cumena
Con.H3PO4
+ CH2=CHCH3 CH(CH3)2 cumena
heat
or 2-phenyl propane

O2,100oC , 6 atm

O OH

OH CH3CCH3
O
H2O, H2SO4
CH3CCH3 + Cumena peroxide.
100oC
propanone
phenol

Propanone is used as organic solvent and phenol is used to make resins and plastic.

59
7.2 Synthesis of phenyl ethene
Con. H3PO4
+ CH2=CHCl CH2CH2Cl
Vinyl chloride heat

ZnCl2
heat

CH=CH2
Phenyl ethene + HCl
(Styrene)

Phenyl ethene is used to make polystyrene polymer. This polymer is widely used as packaging
material.

PAST YEARS QUESTIONS

A OBJECTIVE
1990/22. Which of the following is not true regarding to the ethene and benzene molecules?
A They are planar molecules
B They are non-polarized molecules.
C They are unsaturated molecules.
D All carbon atoms use sp2 hybrid orbitals.
E Their characteristic reaction is electrophilic addition.

1990/24. When excess of chlorine gas is blubbered through boiling methylbenzene at the present
of sun light, an organic product P is formed. Which of the following is the structural formula of
P?
A B C D
Cl CH3 Cl CH2Cl CCl3 CHCl2

E
CH2Cl

1991/25. When benzene is added slowly into a warm mixture of concentrated nitric acid and
sulphuric acid and the reacting mixture is pour into cold water, yellow oily liquid is formed. In
another experiment, benzene is added slowly into a boiling mixture of concentrated nitric acid
and sulphuric acid and the reacting mixture is pour into cold water, yellow crystal is formed.
Which of the following explain the above observations?
A At higher temperature, product of reaction formed is insoluble in water.
B At higher temperature, product of reaction decomposes to form crystal.
C At higher temperature, sulphonification of benzene occurred.
D At higher temperature, double substitution of benzene occurred.
E At lower temperature, nitration of benzene does not occur.

60
1992/18. Explosive trinitrotoluene (TNT), C7H5N3O6, is prepared by heating a mixture of
concentrated nitric acid and toluene. The reaction is as the following.
C7H8 + 3HNO3 C7H5N3O6 + 3H2O
If 0.03 mol of nitric acid is used in the preparation, how much of trinitrotoluene is produced?
[Relative molecular mass of trinitrotoluene is 227]
A 2.27g B 6.81g C 22.70g D 68.10g E 75.67g

1992/22. Given the structural formulae of X, Y and Z.

H

C H

H
X Y Z
Which of the following combination correctly explain the special arrangement of atoms in these
molecules?
All atoms are located at the same plane Only carbon atoms are located at the same
plane
A X and Y X
B X and Z X and Y
C X and Z X and Z
D X and Y X, Y and Z
E X and Z X, Y and Z

1992/23. Which of the following compounds are the major products from the reaction between
cyclohexene and bromine water?
A B

OH and Br Br and OH

Br Br
C D E

Br Br HO OH

OH

1992/24. X and Y are compounds from two different homolog series. X and Y go through
complete combustion in excess of oxygen at 150 oC to give carbon dioxide and water at a ratio of
1 is to 1.
What are the possibility of X and Y?
X Y
A Alkane Alkene
B Alkane Aldehyde
C Alkene Ketone

61
D Alcohol Alkene
E Ketone Alkane

1992/39. C9H12, is a hydrocarbon that does not react with hydrogen halides. Which of the
following statement is correct the hydrocarbon?
1. The molecule has a benzene ring.
2. One of its structural isomer is CH3

CH3 CH3
3. Some of the carbon atom use sp3 hybride orbital in bonding.

1993/23. A series of reactions showing the conversion of benzene to its derivatives is shown as
the following.

CH3 CH3 COOH COOH

I II III IV

NO2
Br Br Br
Which stage of the conversions involved electrophilic substitution?
A. I and III B. I, II and III C I, II and IV D II and IV E IV only

1993/24. A hydrocarbon X contains 85.7% of carbon and 14.3% of hydrogen by mass. X reacts
with hydrogen in the present of nickel as catalyst. The possible structural formula of X is
A CH3CH2CH2CH2CH2CH3 B CH3CH=CHCH2CH2CH3

C D E

1994/22. In which of the following molecule, all carbon atoms use sp3 hybrid atomic orbitals in
bond formation?
A CH3CH=CH2 B CCl2=CCl2 C D E
CH3

1994/23. Which of the following statements is true regarding to the chlorination of methane as
shown by the equation below?
Cl2
CH4 CCl4
uv
A The uv light is required for breaking CH bond.
B Chlorine radicals are produced by homolytic fission.
C The initial step involved reaction between chlorine radical and methane molecule.
D The termination step involved reaction between CCl3 radical and chlorine atom.
E Chlorination of ethene through the same mechanism produces 1,2-dichloroethane.

62
1994/24. A hydrocarbon Z exists as liquid at room temperature and it decolourizes bromine in
the present of iron(III)bromide.

A C2H2 B C2H6 C C6H6 D C6H10 E C6H14

1996/32. State the correct types of hybridized orbitals used in the following carbon atoms
labeled a, b and c in this molecule.
c
CH = bCH a
CH3

a b c
A sp sp2 sp2
B sp3 sp sp2
C sp2 sp2 sp
D sp3 sp2 sp2
E sp2 sp2 sp2

1996/33. Which of the following molecule has empirical formula same as its molecular formula?
A CH2=CH2 B CH2=CHCH=CHCH=CH2 C CH3COOH
D CH2(OH)CH2(OH) E CH2(OH)CH(OH)CH2(OH)

1996/35. The following is the reaction mechanism between methane and bromine in the present
of sun light.
step 1: Br2 + uv 2Br
step 2: CH4 + Br HBr + CH3
step 3: CH3 + Br2 CH3Br + Br
Which of the following statement is true for the reaction mechanism?
A This reaction also takes place in the absent of sun light at the room temperature.
B This reaction can be initiated by CH3 radical.
C This reaction only produce CH3Br.
D This reaction stops after step 3.
E Bromination of ethene is also via the same mechanism.

1996/36. Given are three aromatic compounds with the following structural formulae.

Cl CH3

I II III
These aromatic compounds go through nitration at the aromatic ring.Arrange in the descending
order of the reactivity of these compounds toward nitration.
A I, II, III B I, III, II C II, I, III D III, I, II E III, II, I

1996/55. The following scheme shows the preparation of polyphenylethene from benzene.
Benzene phenylethane phenylethene polyphenylethene

Which of the following statement is true for the process above?

63
1 Phenylethane can be produced by reaction of ethene and benzene in the present of
suitable catalyst.
2 Phenylethene is obtained from the dehydrogenation of phenylethane.
3. The repeating unit of polyphenylethene is C=CH.

1997/31. Which of the following is not due to the delocalization of electrons in the benzene
ring?
A. Same bond length CC in the benzene molecule.
B. Each carbon atom in the benzene molecule used sp2 hybrid orbitals in bonding.
C. Benzene goes through electrophilic addition reaction.
D. The heat of hydrogenation of benzene is three times higher than the heat of
hydrogenation of cyclohexene.
E. Heat of formation of benzene obtained from experiment is higher than its theoretical
value.

1998/35. Which of the organic compound can be obtained from the reaction between ethene and
aqueous solution of bromine?
A CH3CH2Br B CH2BrCH2Br C CH3CH2OH and CH3CH2Br
D CH2BrCH2Br and CH2BrCH2OH E CH2OHCH2OH and CH2BrCH2Br

1998/36. 2.30g of methylbenzene reacts with excess chlorine gas to form an organic compound
X. Hydrolysis of X with hot sodium hydroxide and follow by the addition of excess aqueous
silver nitrate produced 7.18g of white precipitate, silver chloride.
CH3 NaOH and follow by AgNO
3

+ Cl2 X AgCl

Identify compound X.
A CH2Cl B CHCl2 C CCl3 D CH3 E CH2Cl
Cl

Cl
1999/35. Which of the following represents additional reaction?
Cl2 Cl2
A Cl + HCl B Cl + HCl

Cl Cl
Cl2 Cl2
C Cl Cl D CH3 CH3 + HCl

Cl Cl Cl

Cl2

64
E CH3 CH2Cl + HCl

1999/54. Which of the following is true for benzene?

1. Benzene goes through electrophilic addition reaction.
2. Each carbon atom in the benzene molecule use sp hybrid orbital in bonding.
3. The benzene molecule is stabilized by the delocalized electrons.

1999/55. Which of the following compound reacts with aqueous potassium permanganate
solution?

1 2 3 CH3

2000/30. X is an unsaturated hydrocarbon and all carbon atoms in the molecule is in-plan. X
goes through catalytic hydrogenation to produce XH2 according to the following equation.
X + H2 XH2

A CH2=CH2 B CHCH C CHCCH3 D E CH=CH2

2000/31. 240 cm3 of a gaseous hydrocarbon X went through complete combustion in excess of
oxygen. 720 cm3 of carbon dioxide and 0.03 moles of water are formed. If one mole of gas
occupied 24000 cm3 at room temperature, what is the molecular formula of X?
A. C2H4 B C2H6 C C3H6 D C3H8 E C4H8

2000/34. Which of the following compounds is produced when a mixture of ethene and steam is
passed through preheated phosphorus acid as catalyst?
A C2H6 B C2H5OH C CH3COOH D (CH2CHOH)n E C2H4(OH)2

2000/35. Which of the following is correct for benzene?

A Benzene is an odorless compound.
B Benzene appears as gas at room temperature.
C Carbon atoms in benzene molecule use sp3 hybrid atomic orbitals.
D Benzene goes through electrophilic additional reaction.
E Combustion of benzene in excess oxygen produces carbon dioxide and water.

2000/36. Benzene reacts with chloromethane in the present of aluminium chloride. The function
of aluminium chloride is to produce
A Chloride ion B aluminium ion C Free radical
D Electrophile E Nucleophile

2000/54. Excess of chlorine reacts with 0.1 mole of an organic compound X to produce 2.24
dm3 of another organic compound Y with all hydrogen atoms are substituted by chlorine atoms
and 13.44 dm3 of HCl. Determine the structural formula of X.
1. CH4 2. CH3CH3 3. CH3COCH3

2000/56. Ethane is relatively unreactive because ethane

65
 1 is saturated hydrocarbon.
2 is non polar molecule.
3 molecule does not have an electron deficient or high electron density site.

2001/28. Bond length of CC in ethane and ethene is 0.154 nm and 0.134 nm respectively.
Which of the following is true regarding to the bond length of CC in the benzene molecule?
A All CC bond is 0.134 nm.
B All CC bond is 0.140 nm.
C All CC bond is 0.154 nm.
D Some CC bond is 0.134 nm and the others is 0.154 nm.

2001/29. Limonene is found in the skin of lemon and orange. The structural formula is
CH2
CH3 C
CH3
Which of the following is not true for Limonene?
A It has optical isomers.
B It has cis-trans isomers.
C It dissolves in water.
D It is easily oxidized by acidified potassium permanganate.

2002/28. 0.1 mol of a hydrocarbon X underwent complete combustion in excess of oxygen to

produce 17.6g carbon dioxide. It is also found that 0.1 mol of the hydrocarbon underwent
complete reaction with 4.48 dm3 of bromine gas at s.t.p. The structural formula of X could be
A CH3CH2CH2CH3
B CH3CH=CH2
C CH2=CHCH=CH2
D CH2=C=C=CH2

2002/30 Which of the following intermediate species is found in a methane and chlorins mixture
at the presence of the sunlight?
A CH3+ B Cl C CHCl3 D CH2Cl

2002/31. Which of the following is not true for catalytic cracking in petroleum industry?
A To produce petrol with lower octane number
B To produce petrol from kerosene
C To produce useful alkene for prteochemical industry
D To produce hydrocarbon with lower molecular mass

2002/32. Citral is a type of oil extracted from lemongrass. The oil has the following structural
formula.
CH3C(CH3)=CHCH2C(CH3)=CHCHO
Based on the formula, citral is expected to exhibits the following chemical properties, except
A It is easily attack by both nucleophile and electrophile
B Dissolves in both water and organic solvent
C Undergo additional and polymerisation reaction

66
D React with both oxidizing agent and reducing agent

2002/33 Nitrobenzene can be prepared by adding benzene to a hot mixture of concentrated nitric
acid and sulphuric acid. The reaction is as follows.

H2SO4
C6H6 + HNO3 C6H5NO2 + H2O
The function of concentrated sulphuric acid is
A To protonise nitric acid
B To remove water that formed in the reaction
C To prevent further nitration on nitrobenzene
D Tp prevent oxidation of benzene by nitric acid

2002/48 Ethene reacts with hydrogen halide, HX as shown by the equation follows.
CH2=CH2 + HX CH3CH2X
In this reaction
1. the electrons are used to make bond with H atom and X atom of the HX
2. the intermediate species is CH3CH2+ ion
3. the rate of reaction increases in the order of HF < HCl < HBr < HI

2003/49. An organic compound containing 59.7% chlorine is formed when a hydrocarbon X

reacts completely with chlorine without evolving white fumes. Whwt could be the structural
formulae of X? [H=1, C=12, Cl=35.5, X=96]
1. CH3CH=CHCH=CH2CH3
CH3
2.

CH3

3. CH3

2004/28. Which of the following statements is true of the mechanism of nitration of benzene?
A The reaction involves free radicals
B Nitric acid acts as an electrophile
C Nitronium ion, NO2+, is a nucleophile
D Nitronium ion NO2+, is formed from the reaction of concentrated sulphuric acid with
concentrated nitric acid.

2004/29.Dinotrotoluene is an intermediate substance in the production of TNT. Dinotrotoloune

which is formed as the major product of the nitration of toluene is

67
A B
CH3
O2N CH3
NO2 NO2
NO2
CH3
C D
NO2
NO2
NO2 CH3
NO2
2004/30. An organic compound Z undergoes a catalytic hydrogenation reaction. Z also reacts
with hydrogen bromide to form 2-bromopropane. Z could be
A CH2=CH2
B CH3CH=CH2
C CH3CH2CH3
D CH3CH(OH)CH3

2004/49. Which of the following alkenes produces 0.132g ofCO2 and 0.045g of water after
complete combustion? [C=12,H=1, O=16]

1 2 C3H7 3 CH3 C2H5

CH3 C2H5
C3H7

2005/28. The chlorination of toluene is shown as follows.

CH2Cl + HCl
Cl2
CH3
Cl CH3 + HCl

Which of the following statements about the chlorination of toluene is true?

A Substitution reaction occurs
B The reagent for reaction is an electrohile
C The reaction rate increases in the presence of sunlight
D The reaction rate increases in the presence of aluminium chloride catalyst

2005/29. Which of the following compounds is the product obtained when ethane is oxidized by
oxygen at 300oC using silver catalyst?

68
A HOCH2CH2OH B HC CH
|| ||
O O

C H2C CH2 D O

O CH2 CH2

O O

2005/48. The reaction scheme below shows the effect of heat on an alkane X under two different
conditions.
O2,
6CO2 + 7H2O
X
CH3CH2CH3 + CH2=CHCH3

Alkane X may be
1. Hexane
2. 2-methylpentane
3. 2,3-dimethylbutane

B. STRUCTURED
1995/4. Pent-2-ene reacts with oxygen when the mixture is heated at the present of silver, Ag as
catalyze to form a compound, W.
W becomes hydrolyzed when it is heated with dilute sulfuric acid to form X.
X is oxidized when it is heated with acidified KMnO4 to form Y and Z.
(a) Write the structural formula for W, X, Y and Z. [4]
(b) Polymerization of pent-2-ene will produce a polymer, P.
i. Draw the structural formula of polymer P.
ii. State the type of polymerization that takes place. [2]
(c) i. Write a schematic reaction to show the reaction of Y with HCN and follow by the
hydrolysis of the reaction product.
ii. Write an equation to show the reaction between Z and NH2OH. State the name of
the reaction. [4]

2005/4(a). Benzene, toluene and nitrobenzene each undergoes chlorination reaction in the
presence of iron(III) chloride.
(i) Write an equation for the cholorination of nitrobenzene.
(ii) State the fuction of iron(III) chloride in the reaction.
(iii) Write the mechanism of chlorination of nitrobenzene.

69
 (iv) Arrange the three compounds in the increasing order of reactivity towards
the chlorination. Explain your answer. [7]

C. ESSAY
1990/7. Explain the following observation and write related equation to support your argument.
(a) Methylbenzene reacts with chlorine at the present of u-v light, while benzene does not react
under the same condition. [3]

1991/7. (b) i. Describe the nitration of benzene. In your answer, state the reagent, the
condition of reaction used and the type of mechanism of reaction involved.
ii. Write an equation to show the nitration of methylbenzene and name the reaction
products. [8]

1992/7. (d) Suggest a test to be used to differentiate benzene and methylbenzene. In your answer,
state the observation and write an equation involved. [4]

1994/6. a) Explain what it meant by the following terms.

i) Free radical ii) Electrophile iii) Nucleophile [8]
b) By suitable example, explain each of the following types of reaction. Your answers should
include suitable equations and conditions for reactions.
i) Free radical reaction
ii) Electrophilic addition reaction
iii) Electrophilic substitution reaction
iv) Friedel-Craft reaction [8]

1995/6. (a) Suggest the reagents, conditions of reaction and write equations of reaction to
show how the following organic compounds can be prepare, starting form the
methylbenzene.
i. ii. iii.
CONH2 H3C NH3 CH2OH

Give a simple test to show the present of OH group in the CH2OH molecule.
Write a balance equation involved. [12]

1997/8. (a) In an experiment, chlorine gas is bubbled through liquid methylbenzene at the
present of sun light.
i. Draw the structural formulas of two of the organic products formed as the result of the
above reaction. Name these products according to the IUPAC system.
ii. Write the mechanism of reaction in which one of these products is formed. [10]
(b) Benzene goes through substitution reaction with chlorine while cyclohexene goes through
additional reaction with chlorine. Explain these phenomena by giving appropriate equations
involved. [10]

2001/9. (a) State the reagent and condition of reaction used in order to differentiate
methylcyclohexane and methylbenzene. Write the observation and reaction involved. [3]
70
2002/9(a)iii. Write an equation for the reaction between CH3CH=CHC2H5 and H2 in the presence
of Ni as catalyst at 150oC. [1]

2004/9(a). Alkene undergoes addition reactions according to the Markovnikovs rule. State the
markovnikons rule.
Write the structural formulae of the major products from the following addition reaction.

(i) CH3 + HCl

(ii) CH3CH2C=CHCH3 + Bromine water

H2O
(iii) =CH2 + Conc. H2SO4
[4]

(b). Write the mechanism for the following chlorination reaction.

hv
CH3CH2CH3 + 2Cl2 CH3CHCH2Cl + 2HCl
|
Cl
Explain the formation of (CH3)CHCH(CH3)2 as a side product in the chlorination reaction above.
[5]

Answers:
1990:22E, 24C.
1991:25D
1992:18A, 22E, 23B, 24C, 39D
1993:23C, 24B
1994:22E, 23B, 24C
1996:32D, 33E, 35B, 36D, 55B
1997:31A
1998:35C, 36B
1999: 35C, 54(3), 55(2,3)
2000:30A, 31C, 34B, 35E, 36D, 54(2,3), 56(2,3)
2001:28B, 29B.

CHAPTER 3
ORGANIC HALOGEN COMPOUNDS

71
1. INTRODUCTION.
Organic halogen compounds are compounds formed by substituting a hydrogen atom(s) in
alkanes molecules with a halogen atom(s).
They are classified into haloalkanes, haloalkenes and haloarenes.

2. HALOALKANES.
Haloalkanes are represented by a general formula CnH2n+1X, where X represents F, Cl, Br and I.

The table below shows the chloroalkane series.

CnH2n+1X n Molecular formula Name

1 CH3Cl Chloromethane
2 CH3CH2Cl Chloroethane
3 CH3CH2 CH2Cl Chloropropane
4 CH3CH2CH2CH2Cl Chlorobutane
5 CH3CH2CH2CH2CH2Cl Chloropentane 3. NAMING THE
HALOALKANES
The name of a haloalkane is derived from the name of the corresponding alkane molecule by
adding the prefix- Flouro, Chloro, Bromo and Iodo to the respective alkane (refers to the table
above).

Naming of other haloalkanes

Examples:
Haloalkanes:
Cl

Cl 5-bromo-3,3-dichloroheptane
Br
Br

4,4-dibromo-2-chlorohexane

Br Cl
Cl

2,3-dichloro-5-iodohexane

Cl I
Halocycloalkanes:

72
 Cl Cl Br

Chlorocyclohexane Br
1,2-dibromo-4-chlorocyclohexane

Haloarenes:

Cl Cl Cl CH2Cl
Phenylchlorometane
Chlorobenzene Br
2-bromo-1,4-dichlorobenzene

4. CLASSIFICATION OF HALOALKANES
Haloalkanes are classified into primary, secondary and tertiary haloalkanes.

H H C

C C X C C X C C X

H C C

Primary (1o) Secondary (2o) Tertiary (3o)

One neighboring C Two neighboring C Three neighboring C

5. PHYSICAL PROPERTIES
The halogen atom (X) has higher electronegativity than the carbon atom. Thus, the C X
bond is polar and the molecule becomes polarize.

C+ X

Haloalkanes are colorless and volatile liquid. These properties made them good organic solvent.
They have higher density and boiling point than their corresponding alkanes due to the present of
heavier halogen atom and stronger van der waals forces between molecules. They are not soluble
in water because their molecules do not have hydrophilic group.

6. CHEMICAL PROPERTIES
Since the halogen atom (X) has higher electronegativity than the carbon atom and the
C X bond is polarized,

C+ X

The carbon atom attached to the halogen atom, X has a + pole and thus serve as an electron
deficient site, which is easily attack by an incoming nucleophile. During the reaction, the halogen

73
atom (leaving group) in a haloalkane is substituted by the nucleophile. This reaction is called the
nucleophilic substitution reaction (SN).

LEAVING GROUP is the species that becomes displaced from the carbon atom and leaves the
substrate molecule. In the nucleophilic reactions, the halogen atom is the leaving group.

The reaction mechanism of nucleophilic substitution reaction defers according to the class of
haloalkane.

a. Tertiary haloalkanes go through the unimolecular nucleophilic substitution (SN1) reaction. In

this reaction, the compound becomes ionized first, to produce a carbocation. Then, the
carbocation is then attacked by the in coming nucleophile to form the substituted product.

The mechanism of SN1

Example:

Step 1: The tertiary haloalkane molecule becomes ionized. The ionization takes place in a very
low rate. Thus, this step is called the rate determining step.

CH3 CH3

CH3 C+ X CH3 C+ + X

CH3 CH3
3o carbocation

Step 2: Then, the carbocation is then attacked by the in coming nucleophile to form the
substituted product. Since the reaction involves ionic species, the reaction progress in a very high
rate.

CH3 CH3

CH3 C+ + Y CH3 C Y

CH3 CH3

The overall reaction is

(CH3)3CX + Y (CH3)3CY + X

The rate of this reaction is control by the slowest step in the reaction mechanism that is the rate
determining step.

74
Since the rate determining step only involves one (CH3)3CX molecule, the reaction is said to be
first order to the concentration of (CH3)3CX.

Thus, the rate equation is

Rate of reaction = k [(CH3)3CX]1

This means, the reaction rate of SN1 reaction is only depending on the concentration of
(CH3)3CX.

b. Primary haloalkanes go through the bimolecular nucleophilic substitution (SN2) reaction. In

this reaction, the compound is attacked by the nucleophile first to form a five bonding
intermediate complex and then the unstable complex decomposes to form the substituted
product.

The mechanism of SN2

Example:

Step 1: The primary haloalkane is attacked by the in coming nucleophile first, to form a five
bonding intermediate complex. This step progress in a very low rate, thus, it is called the rate
determining step.

CH3 CH3
Nucleophile attacks from the back

C [X C Y ]
+ Y
H H H H
X five bonding intermediate complex

Step 2: The unstable five bonding intermediate complex decomposes to form the substituted
product.

CH3 CH3

[X C Y] C + X

H H H Y (at the reverse side of X)

H
The overall reaction is

CH3CH2X + Y CH3CH2Y + X

The rate of this reaction is control by the slowest step in the reaction mechanism that is the rate
determining step.

75
Since the rate determining step involves one CH3CH2X molecule and one Y ion, the reaction is
said to be first order to the concentration of (CH3CH2X and first order to the concentration of
Y. The overall order of reaction is (1+1) = 2; that is second order.

Thus, the rate equation is

Rate of reaction = k [CH3CH2X]1 [Y]1

This means, the reaction rate of SN2 reaction is depending on the concentration of CH3CH2X
and Y.

7. NUCLEOPHILIC SUBSTITUTION REACTION OF HALOALKANE

7.1 Hydrolysis of haloalkanes

Hydrolysis of haloalkanes form alcohols. This is carried out by refluxing the haloalkanes with
dilute aqueous potassium hydroxide.

Reagent: KOH (aq)

Condition: Reflux.

CH3CH2Cl + OH CH3CH2OH + Cl
Ethanol
The rate of hydrolysis of the haloalkanes is depends on the type of compound used in the
reaction.
The rate of hydrolysis increases as the following:

i. Tertiary haloalkanes > secondary haloalkanes > primary haloalkanes

ii. Iodoalkanes > bromoalkanes > chloroalkanes

The rate of hydrolysis of the halogenoalkanes can be investigated by adding aqueous silver
nitrate solution into the reaction mixture. The Ag+ ion reacts with the halide ion, X produced
from the hydrolysis reaction to form precipitate of AgX.

Example: CH3CH2Cl + OH CH3CH2OH + Cl

Ag+ + Cl AgCl

The table below shows the different in the rate of reaction as various types of haloalkane are
hydrolyzed with dilute KOH solution and how halorgano compounds are differentiated from
each other.

76
 Type of Color of Duration required
haloalk precipitate
ane
CH3CH2I Yellowish A short while
CH3CH2Br Creamy (beige) Slightly longer
CH3CH2Cl White Longest
(CH3)3CI (3o) Yellowish Almost immediately
(CH3)2CHI (2o) Yellowish Very short while
CH3CH2I (1o) Yellowish A short while

Cl No change No reaction
Haloarenes are relatively
unreactive to nucleophilic
reagents. CH2Cl White Longest They usually
do not hydrolyzed
by KOH under the
condition used for the haloalkanes. This is due to the compounds have strong C X bond than the
haloalkanes. The delocalization of non-bonding pair of electron from the halogen atom into the
aromatic ring causes the C X bond to be stronger and less polarized.
delocalization of non-bonding pair of electron from
the halogen atom into the aromatic ring
X

However the haloarenes is hydrolyzed by concentrated NaOH at 300OC and 200 atm.

Cl + 2NaOH ONa + NaCl + H2O

HCl

OH Phenol

On the contrary, if the halogen atom is attached to the side chain of the haloarenes, the
compounds is as reactive as the haloalkanes. They are easily hydrolyzed when the compounds
are refluxed with dilute KOH.

CH2Cl + KOH CH2OH + KCl

77
7.2 Reaction with cyanide, (CN)
Haloalkanes react with KCN (nucleophile) to produce nitrile.
The halogen atom in the haloalkane is replaced by the nitrile ion. On top of this, the product has
one carbon atom more than the substrate.

Reagent: KCN in ethanol

Condition: Heating (reflux)

CH3CH2Br + KCN CH3CH2CN + KBr

Propanonitrile

Nitrile compounds are very useful, especially for synthesizing other organic compounds.

The nitrile group can be converted to other useful organic compounds like amine
(-NH2) and carboxylic acid (-COOH).

Reduction of nitrile to form amine

Reagent: LiAlH4, in ether
Condition: Room temperature

CH3CH2CN + 4(H) CH3CH2CH2NH2 (Propylamine)

Hydrolysis of nitrile to form carboxylic acid

Reagent: H2O, H2SO4 (aq)
Condition: Heat

CH3CH2CN + 2H2O + H+ CH3CH2COOH + NH4+

Propanoic acid

7.3 Reaction with ammonia, NH3

Haloalkanes react with ammonia (nucleophile) to form amine.
The halogen atom in the haloalkane is replaced by the NH3 molecule.

Reagent: NH3 excess, in ethanol

Condition: Heated

CH3CH2Br + NH3 CH3CH2 NH3Br (ethyl ammonium bromide)

Base is added to liberate amine from the ammonium salt.

CH3CH2 NH3Br + NaOH CH3CH2 NH2 + NaBr + H2O

Ethyl amine
(a primary amine)

78
Usually the reaction will form a mixture of primary, secondary, tertiary amine and the quaternary
ammonium salt. This is due to the CH3CH2 NH2 produce during the reaction is also a nucleophile
like ammonia and it can further react with the substrate to form secondary amine.

CH3CH2Br + CH3CH2 NH2 (CH3CH2)2 NH + HBr

Primary amine Diethyl amine
(a secondary amine)
CH3CH2Br + (CH3CH2)2 NH (CH3CH2)3 N + HBr
Secondary amine Triethyl amine
(A tertiary amine)

CH3CH2Br + (CH3CH2)3 N (CH3CH2)4 N+Br

Tertiary amine Tetraethyl ammonium bromide
(a quaternary ammonium salt)

8. OTHER REACTIONS OF HALOALKANE

8.1 Elimination reaction.
Elimination of HX molecule from the haloalkenes molecules takes place when the haloalkanes is
heated with KOH in ethanol. As a result, alkenes are formed.

Reagent: KOH, ethanol

Condition: Heat.

If a primary or a symmetrical haloalkane is used, only one alkene if formed as the result of
elimination reaction.
CH3CH2Br + KOH CH2 = CH2 + KBr + H2O

CH3CH(Br)CH3 + KOH CH3CH= CH2 + KBr + H2O

However, if an asymmetry secondary or tertiary haloalkane is used in the reaction, a mixture of

alkene isomers is formed. The alkene with most branches attach to the C=C is the main product.

CH3CH(Br)CH2CH3 + KOH CH3CH=CHCH3 + CH2 =CHCH2CH3

( 2o haloalkane) but-2-ene
(main product)
KBr + H2O

(CH3)2CBrCH2CH3 + KOH CH2=C(CH3)CH2CH3 + (CH3)2C=CHCH3

(3o haloalkane) 2-methylbut-2-ene
(main product)
KBr + H2O

79
8.2 Grignard reagent
Grignard reagents are organometallic compounds that have the general formula RMgX, where R
is alkyl of phenyl and X is a halogen. The reagent can be prepared by adding magnesium powder
into the haloalkane in dry ether at room temperature.

Reagent: Mg,
Condition: dry ether at room temperature
Example: CH3CH2I + Mg CH3CH2 MgI (ethyl magnesium iodide)

The C Mg bond is a highly polarized covalent bond, with the carbon atom bears a - pole. Thus
the Grignard reagents are strong nucleophiles.

Grignard reagents are very useful tool for the synthesis of more complex organic molecules.
They can add more than one carbon atom to the carbon chain of the substrate molecules.
The synthesis process is carried out in two steps. First, the Grignard reagent is added into the
substrate molecule, and then followed by hydrolysis in acid solution.

Examples: synthesis of various alcohols

H2O , H+
CH3MgI + HCHO CH3CH2OMgI heat CH3CH2OH + Mg(OH)I
(aldehide) (ethanol)
H2O ,H+
CH3MgI + CH3COCH3 (CH3)3COMgI heat (CH3)3COH + Mg(OH)I
(ketone) 2-methylprop-2-ol
H2O ,H+
CH3MgI + CO2 CH3COOMgI heat CH3COOH + Mg(OH)I
Ethanoic acid

Apart from the Grignard reagents, there are several important organometallic compounds.

i. Organolithium compounds
Example: Dry ether
CH3CH2I + 2Li CH3CH2Li + LiI
Ethyllithium
Ethyllithium compounds have similar uses as the Grignard reagents.

Examples:
Dry ether
2CH3CH2Li + SiCl4 (CH3CH2)2SiCl2 + 2LiCl
Diethyldichorosilicon
Diethyldichorosilicon is used in synthesizing silicone, a synthetic inorganic polymer that is
widely used as lubricant oil, surfacetant and car shampoo.
Dry ether
4CH3CH2Li + SnCl4 (CH3CH2)4Sn + 4LiCl
Tetraethylstanum
Tetraethylstanum and related compounds are used as fungicide. They are usually mixed in paint.

80
ii. Triethylaluminium
Dry ether
3CH3CH2Cl + 2Al (CH3CH2)3Al + AlCl3
Triethylaluminium is one of the component in the Ziegler-Natta catalyze used in polymerization
of alkenes.

iii. Tetraethyllead.
Dry ether
4 CH3CH2Cl + 4Na/Pb (CH3CH2)4Pb + 4NaCl
Tetraethyllead was added to some petrol to improve its octane number. Its use has now been
stopped due to the fear about the adverse effects of high levels of lead in the environment.

9. USES OF HALOGENO ORGANIC COMPOUNDS

The table below shows the uses and the physical properties of halogeno organic compounds.

USE AS EXAMPLES PHYSICAL PROPERTIES

Refrigerants for air Freon 11: CFCl3 Odorless, non-toxic, easily compress and
conditionals and Freon 12: CF2Cl2 easily evaporate.
refrigerators Freon 113: CFCl2CF2Cl
Propellants for Freon 12: CF2Cl2 Odorless, non-toxic, easily compress and
aerosol of paints, easily evaporate.
insecticides, and
perfumes.
Solvents for dry CCl4, CCl3CH3 and Freon 113. Odorless and easily evaporate.
washing and grease.
Fire extinguisher BCF: CBrClF2 Higher density than air and highly
inflammable.
Inhibit combustion by blanketing a fire in a
dense, non-flammable, oxygen-excluding
vapor. Bromine radicals help to inhibit
combustion.
Insecticide DDT: Highly stable to decomposition and
unreactive.
(Cl ) )2CHCCl3 A very effective insecticide. It remains
unchanged and thus, accumulated in the
Dichlorodiphenyltrichloroethane bodies of organisms. The DDT accumulated
is passed on to the organisms in the higher
order of the food chain and causes DDT
poisoning.
Polymers Teflon Anti stick layer:
The polymer is usually coated on cooking
utensils.

Polyvinylchloride (PVC) Strong and resistant to chemical:

Anaesthetics Halothane: CF3CHBrCl
Isoflurane: CF3CHClOCHF2
Sevoflurane: (CF3)CHOCHF2
It is use for making plastic containers,
pipes, plastic cloths and shoes.
Odorless, non-toxic and chemically stable.

81
10. EFFECTS OF CFCs.
CFCs are compounds in which some or all of the hydrogen atoms of an alkane have been
replaced by chlorine or fluorine atoms. CFCs are even less reactive than alkanes because the C
F bond is extremely strong. However, at the stratosphere, they decompose to form radicals under
the influence of u-v radiation. These radicals react with the ozone formed at this altitude and
break it down, producing the hole in the ozone layer. This phenomenon is called the depletion
of ozone layer.

Ozone shields the earth from harmful and excess of u-v radiation. At the stratosphere, oxygen
and ozone coexist in equilibrium as below.
O3 O2 + O + heat

Thus, ozone changes the u-v radiation into heat.

The C Cl bond is the weakest in the CFC molecule. As the molecule absorbs u-v radiation, the
CFC molecule decomposes and producing a chlorine radical, Cl through holytic fission.

Initiation: CF3Cl + u-v CF3 + Cl

The chlorine radicals react with ozone molecules to produce other radicals and oxygen.

Propagation: Cl + O3 OCl + O2

The OCl radicals react further with O radicals from the stratosphere to form chlorine radicals,
Cl.
OCl + O Cl + O2

The overall reaction: O + O3 2O2

As a result, ozone is converted to oxygen.

As the concentration of ozone decreases, it reduces its abilities to absorb u-v radiation. Thus,
more u-v radiations pass through the stratosphere and enter into the atmosphere. Hence, the
temperature of the atmsphere rises and causes global warming.

HFCs such as CH2FCF3 have similar physical properties as the CFCs. Thus, the HFCs are good
replacement for CFCs as afford to minimize the bad effects of CFCs to the environment.

82
PAST YEARS QUESTIONS
PART A: OBJECTIVE
1990/25. Compound X has the following structural formula

Cl CH2CH(Cl)CH2COCl
(I) (II) (III)
Which of the following show the correct sequent of increasingly easier for the chlorine atoms to
be substituted during hydrolysis by dilute alkali solution?
A I, II, III B II, I, III C I, III, II D II, III, I E III, II, I

1992/25. A reaction scheme shows the conversion of a bromoalkane to an amine is given as the
following.
I II
CH3CH2CH(Br)CH3 X CH3CH2CH(CH2NH2)CH3

State the reagents use in stage I and II in the reaction scheme.

Stage I Stage II
A Gaseous ammonia Hydrogen gas
B Hydrogen cyanide Gaseous ammonia
C Potassium cyanide Lithium tetrahydridoaluminate(III)
D Aqueous sodium hydroxide Gaseous ammonia
E Aqueous sodium hydroxide Concentrated nitric acid

1993/25. A haloalkane, RX is hydrolyzed when reflux with aqueous sodium hydroxide. The rate
equation for hydrolysis is
rate = k[RX][OH]
What is the possible structural formula of RX?
A CH3CH2CH2Br B CH3CH2CHBrCH3 C (CH3)3CBr

D Br E C(CH3)2Br

1994/25. Below is the scheme of reaction to show the conversion of a bromoalkane, Z to a

carboxylic acid.
KCN, Akohol. H+, H2O
Z NCCH2CH2CN HOOCCH2CH2COOH
Heat
Z is
A CH3CH2Br B BrCH2CH2Br C BrCH2CH2CH2Br D CH3CH(Br)CH(Br)CH3
E BrCH2CH2CH2CH2Br

1995/23. The reaction between bromoethane and aqueous sodium hydroxide to produce ethanol
is
A Free radical reaction B Electrophilic substitution reaction
C Electrophilic addition reaction D Nucleophilic substitution reaction

83
E Electrophilic substitution reaction

1995/25. A haloalkane X is hydrolyzed by aqueous solution of sodium hydroxide to form an

organic compound Y that does not decolourize the acidified aqueous solution of potassium
permanganate. X is
A CH3CH2CH2Br B CH3CHBrCH3 C (CH3)3CBr D (CH3)3COH
E BrCH2CH2COBr

1996/37. Which of the following compounds does not react with bromoethane?
A Water B Ammonia C Potassium cyanide D Sodium hydroxide
E Potassium permanganate

1996/38. Which of the following compounds reacts with silver nitrate in ethanol to form 1 mole
of silver chloride?
A Cl B Cl C Cl

Cl CH3 Cl CH2Cl Cl CHCl2

Cl Cl Cl

D Cl E Cl

Cl CH3 Cl CH2Cl

Cl Cl

1997/35. In industry, ethane-1,2-diol is prepared through the following reactions.

Ag 2H2O
2CH2=CH2 + O2 X 2CH2(OH)CH2(OH)
300oC 200oC
A CH3CHO B CH3CH2OH C CH3COOH D (COOH)2 E O
CH2 CH2

1997/36. Depletion of ozone in the stratosphere is cause by the reaction of chlorine free radical
and ozone molecule.
Cl + O3 ClO + O2
ClO + O O2 + Cl
Which of the following molecules went through photolytic fission to produce the chlorine
radical?
A Cl2 B CCl4 C CH3Cl D CFCl3 E HOCl

1997/37. An amine is produce through bromoalkane through the following scheme of reaction.
I II
CHBrCH3 Y CH(CH2NH2)CH3

What are the suitable reagents to be used in step I and II of the preparation of the amine?

84
 Step I Step II
A Gaseous ammonia Hydrogen gas
B Hydrogen cyanide Gaseous ammonia
C Potassium cyanide Lithium tetrahydridoaluminate(III)
D Aqueous sodium hydroxide Gaseous ammonia
E Aqueous sodium hydroxide Concentrated nitric acid

1997/56. In the preparation of 1-bromopropane, a mixture of propan-1-ol, sodium bromide and

concentrated sulphuric acid is refluxed for some time and the mixture is let to cold. The mixture
than is distilled until droplets of oily liquid (distillate) is formed. Which of the following is to be
added in order to purify 1-bromopropane?
1. Ether
2. Concentrated hydrochloric acid
3. Aqueous sodium hydrogen carbonate

1997/60. When bromoethane is heated with a mixture of sodium and aluminium, an

organometallic compound, (C2H5)3Al, is formed. Which of the following is true to the
compound?
1. The compound contains 23.7% of aluminium by weight.
2. The compound is one of the components in the Ziegler Natta catalyst.
3. The compound is uses together with TiCl4 as catalyst to produce high density polyethene.

1998/38. Which of the following is not true about ozone?

A In atmosphere, ozone is formed during lightning.
B In stratosphere, ozone is formed by photochemical reaction.
C Ozone filters off part of the ultra violet radiation of the sun light.
D It is used for the purification of drinking water.
E It is used for the analysis of molecular structure of alkene through the formation of
ozonide.

1998/43.
CH3CH2CH(Br)CH3 + X CH3CH2CH(NH2)CH3
Reagent X in the reaction above is
A Ethanamide B Methylamine C Aqueous ammonia
D Ammonium chloride E Ammonia in alcohol

1999/36. Which of the following compounds do not react with CH3O?

A CH3CH2CHClCH3 B CH2Cl C CH3CH2Br D (CH3)3CBr

E Br

1999/37. Which of the reagent can be used to convert ROH to RCl in the laboratory?
A Cl2 B CHCl3 C NaCl D HCl E SOCl2

85
1999/53. Hexachlorophene, a bactericide, is used as mouth cleansing agent. The structural
formula of hexachlorophene is
OH OH
Cl CH2 Cl

Cl Cl
Cl Cl
Which of the following is true for hexachlorophene?
1. Molar mass of hexachlorophene is 407g.
2. 72 dm3 of chlorine gas is required to produce 1 mole of hexachlorophene.
3. 3 dm3, 2 mol dm-3 of NaOH is needed to react with 1 mole of hexachlorophene.

1999/56. Methylbenzene reacts with chlorine in the present of sun light to produce X, C7H7Cl.
When X is hydrolyzed with sodium hydroxide, Y is produced. Which of the following is true
about Y?
1. It is oxidized to benzoic acid.
2. It is neutral.
3. It does not produce purple colour with neutral iron(III)chloride solution.

2000/33. A mixture of chlorine and excess of ethane is exposed to the sun light. Which of the
following compounds is the major product of the reaction?
A CH3CH2Cl B CH3CHCl2 C CH3CCl3 D ClCH2CH2Cl
E Cl2CHCHCl2

2000/41.
Cl2
Cl Cl
AlCl3
Cl
The reaction is
A. Free radical reaction B Electrophilic substitution C Electrophilic addition
C Nucleophilic substitution E Nucleophilic addition

2001/41. Tetramethyl ammonium chloride is formed when ammonia in ethanol is heated with
excess of chloromethane in a concealed vessel. Which of the following statement is true for
tetamethyl ammonium chloride?
1. Tetramethyl ammonium chloride has high melting point and boiling point.
2. Tetramethyl ammonium chloride has both ionic and covalent bonds in it.
3. The shape of cation is tetrahedron.

2001/49. An organic liquid Y decolourizes bromine water and reacts with silver nitrate solution
to form white precipitate. Y could be

86
 1. CH2=CHCH2Cl

2. CH2CH2Cl

3. CH=CH2

Cl

2003/32. When chlorine gas is bubbled through methylbenzene under certain conditions, a
compound Q with the molecular formula C7H7Cl is produced. Compound Q forms a white
precipitate on warming with ethanolic silver nitrate solution.
Which of the following about the conditions of the reaction of methylbenzene
chlorination and the structural formula of compound Q is correct?

Condition of reaction Compound Q

A AlCl3, room temperature CH2Cl

B Sunlight/ reflux CH2Cl

C Sunlight/ reflux CH3

Cl

D AlCl3, room temperature CH3

Cl

2003/35. The table below shows the boiling point of some haloalkanes.

Haloalkane Boiling point oC

CH3CH2Cl 12
CH3CH2 Br 38
CH3CH2I 72

Which of the following statements explain the difference of boiling point of the haloalkanes?
A The strength of bond increases in the order CCl < CBr < CI
B The polarity of bond increases in the order CCl < CBr < CI
C The size of the haloalkanes increases in the order CH3CH2Cl < CH3CH2Br < CH3CH2I
D The reactivity of the haloalkanes increases in the order CH3CH2Cl < CH3CH2Br <
CH3CH2I

87
2004/35. Which of the following reaction takes place especially through SN1 mechanism?
A C6H5CH2Br + NH3 C6H5CH2 NH2 + HBr
B (CH3)3CBr + NaOH (CH3)3COH + NaBr
C CH3CH2CH2Br + KOH CH3CH2CH2OH + KBr
D CH3CHBrCH3 + KCN CH3CH(CN)CH3 + KBr

B. STRUCTURED
1990/5. (a) A haloalkane X has the following composition: 14.1% carbon, 2.4% hydrogen and
83.5% chlorine by mass.
i. Determine the empirical formula of X.
ii. 0.1 g of X is evaporated to produce 34.2 cm3 of vapor at 350K and at a pressure of 100
kPa. Calculate the molecular mass of X and determine the molecular formula of X.
iii. X and other organic compounds are formed if excess of chlorine is added into CH4
during a reaction at the present of sun light. Write the structural formulas of these organic
compounds formed. [6]
(b) i. The boiling point if dichlorodifluoromethane, CCl2F2 is 303K. State one use of this
compound and explain; how the use of this compound is related to its property.
ii. Dichlorodifluoromethane can cause serious damage to the environment. Explain this
statement. [4]

2004/3(a). Freons were used as coolants in air conditioners and refrigerators. One example of
freons is trichlorofluoromethane.
(i). Write the chemical formula of a Freon other than trichlorofluoromethane.
(ii). State a property of Freon that justifies its use as a coolant.
(iii). Name two reagent that can be used to prepare trichlorofluoromethane.
(iv). Write an equation for the decomposition of trichlorofluoromethane into species
which are responsible for the destruction of ozone layer in the stratosphere. [5]

2004/4(a). Starting with 1-bromopropane, CH3CH2CH2Br, show the reaction schemes to

synthesise the following carboxylic acids.
(i) CH3CH2COOH
(ii) CH3CH2CH2COOH

2005/4(b). Draw the structure of the major product of each of the following reactions.
Ethanol
(i) Br + NH3
Excess

(ii) (CH3)2CBr2 + 2NaOH

[2]

C. ESSAY
1993/6. (b) B, C7H7Br reacts readily with dilute sodium hydroxide, NaOH. By giving
appropriate reasons, suggest the structural formula of B. Write an equation involved to support
your answer. [5]

88
1994/6. b) By suitable example, explain nucleophilic substitution reaction. Your answers should
include suitable equations and conditions for reactions. [2]

1994/7. (a) Compound A and B are isomers of C7H7Cl. A is readily reacts with dilute NaOH
while B does not react with dilute NaOH. Determine the structural formula of A and B by giving
appropriate reason. Write the equation for the reaction involved. [5]

1996/7. (a) Suggest a chemical test that can be use to compare the reactivity of the following
compounds.
1-bromobutane , 2-bromobutane and 2-bromo-2-methylpropane.
State the reagent that is used, the observation and write an equation for the reaction involved. [5]
(b) Both 1-bromobutane and 2-bromo-2-methylpropane go through nucleophilic substitution
reactions with the same reagent. State the reagent that is used, the type of nucleophilic
substitution reactions involved. Write the mechanism of reaction of these reactions. [8]
(c) The Grignard reagent is an organometallic compound that is widely used to synthesis other
organic compounds.
i. Suggest one method of preparation of the reagent, starting with bromoethane. State the
reagent that is used, the condition of reaction and write the equation for the reaction involved.
ii. Write the equations for the reaction between the Grignard reagent and ethanal, then
follow by hydrolysis and the reaction between the Grignard reagent and silicon tetrachloride. [7]

1997/7. (a) State the reagent and the condition of reaction that is used to differentiate the
following compounds.

Br and CH2Br

State the observation and write the equation for the reaction involved. [3]

1999/8. (a) P, C4H10Br reacts readily with dilute NaOH aqueous solution to form Q, C4H10O. Q
decolorizes an acidified potassium permanganate solution to produce a compound R, C4H8O that
form yellow precipitate when 2,4-dinitrophenylhydrazine is added. Both Q and R produce
yellowish precipitate respectively when they are heated with alkaline iodine solution.
P also reacts with magnesium to form an organometallic compound S, C4H9MgBr. R reacts with
S and then, follow by hydrolysis to produce T, C8H18O that reacts with PCl5 to produce white
fume.
Determine the structural formula of P, Q, R, S and T. Write the equations for all reactions
involved. Give the IUPAC name of T. [17]

2000/7. (b) W, C7H7Cl is an aromatic compound that reacts with NaOH aqueous solution to
form a compound X. X is oxidized to form another compound Y that in turn can be oxidized
further to form Z. Y produces yellow precipitate when it is added 2,4-dinitrophenylhydrazine,
while Z produces carbon dioxide when sodium carbonate is added.
Determine the structural formula of W, X, Y, and Z. Write the equation for all reaction involved.
Write also the reaction mechanism in which W is converted to X. [18]

89
2002/10 a. A haloalkane P, which relative molecular mass is 126.5 has the following
composition: 66.4% carbon, 28.1% chlorine and 5.5% hydrogen.
i. Determine the molecular formula of P
ii. P, when reflux with aqueous potassium hydroxide solution, produces organic
compound Q. Compound Q can undergo mild oxidation to form R, which reacts
with 2,4-dinitrophenylhydrazine to form a yellow precipitate S. Further oxidation
of R would produce a white solid T. Determine the structural formulae of
compound P, Q, R, S and T.
b. 2-Bromo-2-methylpropane goes through hydrolysis when heated with aqueous potassium
hydroxide.
i. Describe the mechanism of hydrolysis.
ii. State how the concentration of potassium hydroxide would affect the rate of
hydrolysis.

2004/9 (c). Organometallic compounds such as organolithium and organomagnesium are very
important in organic syntheses.
(i) Give the reaction equation for the preparation of butyllithium.
(ii) Show the reaction sequence in the preparation of 2-phenyl-2-hexanol from butyllithium.
(iii) Compare the reactivity between Grignard reagent and organolthium. [6]

Answers:
1990: 25A 1992: 25C
1993: 25A 1994: 25B
1995: 23D, 25C 1996: 37E, 38B
1997: 35E, 36A, 37C, 56(3), 60(1,2,3) 1998: 38D, 43E
1999: 36E, 37A, 53(1), 56(1,2,3) 2000: 33A, 41B
2001: 41(1,2,3), 49(1)

90
CHAPTER 4
AMINES
1. INTRODUCTION
Amines are organic compounds that have amino, NH2, functional group in their
molecules. Amines are represented by a general formula, RNH2 or CnH2n+1NH2 , where R
represents alkyl.

2. THE HOMOLOG SERIES OF AND PHYSICAL PROPERTIES OF AMINE

Members in the homolog series are generated from the general formula, CnH2n+1NH2 by
substituting n begins with 1.

n CnH2n+1OH Name Physical properties

1 CH3NH2 Methanamine Amines are colorless liquid with fishy smell. They less
2 C2H5NH2 Ethanamine volatile than hydrocarbons due to the present of hydrogen
3 C3H7NH2 Propanamine bond between amines molecules. This also account for higher
4 C4H9NH2 Butanamine boiling point for amines than alkanes.
5 C5H11NH2 Pentanamine Amines are soluble in water because the NH2 group is
6 C6H13NH2 Hexanamine hydrophilic and forms hydrogen bond with water molecules.
7 C7H15NH2 Heptanamine However, the solubility decreases when molecular mass
8 C8H17NH2 Octanamine increases or hydrophobic group becomes bigger.
9 C9H19NH2 Nonanamine
1 C10H21NH2 Decanamine
0

3. IUPAC NOMENCLATURE OF AMINES

Amines are named according to it equivalent alkanes by dropping ane of alkane and replaced
by an amine. However, the position functional group of NH2 has to be predetermined first.
Examples:
CH3CH2CH2NH2 is propanamine (NH2 is attached to the first carbon atom)
CH3CH(NH2)CH3 is propan-2-amine (NH2 is attached to the second carbon atom)

CH3CH2CH2CH2NH2 is butanamine (NH2 is attached to the first carbon atom)

CH3CH2CH(NH2)CH3 is butan-2-amine (NH2 is attached to the second carbon atom)
CH3C(CH3)(NH2)CH3 is 2-methylpropan-2-amine (Both NH2 and CH3 are attached to the
second carbon atom)
NH2

NH2
NH2
3,5-dimethylheptan-3-amine 3-ethyl-5-methylhexan-3-amine Cyclohexanamine

NH2 is Phenylamine or aniline (The NH2 functional group is attached to the aromatic

91
 ring)

4. CLASSIFICATION OF AMINES
Amines are classified as primary (1o), secondary (2o) and tertiary (3o) amines.

Primary amine Secondary amine Tertiary amine

Examples: Examples: Example:
CH3NH2 CH3NCH3 CH3
CH3CH2NH2
(CH3)2CHNH2 H CH3 N CH3
(CH3)2CNH2 CH3NCH2CH3
CH2CH3
NH2 H
NH2 CH3 N CH3
NH2 is attached to only one NCH2CH3
group of alkyl. CH2CH3
H
NH is attached to two CH3 N
groups of alkyls / phenyls.
N is attached to three
groups of alkyls / phenyls.

5. BONDING OF AMINE
Nitrogen atom is much electronegative than carbon and hydrogen. The CN and NH bonds are
polarized, where nitrogen atom has a - pole while carbon and hydrogen atom have a + pole.
Example: Ethanol molecule
H

H C+ N H+

H H +
Effects of bonding to
5.1 Physical properties
Amine molecules form hydrogen bond between molecules
H

CH3NH NCH3

H H
Hydrogen bonding
* See section: Homolog series and physical properties of amines

5.2 Chemical properties

92
The reactions of amines depend on the nature of NH2 functional group. The nitrogen atom of
the NH2 has a non bonding pair of electrons. Thus, amine is nucleophile and Lewis base.
5.2a Acid and base reaction
Amines are weak bases. The strength of base is affected by the nature of the neighboring group.
The relative strength of base is

O2N NH2 < NH2 < NH3 < CH3NH2 < (CH3)2NH < (CH3)3N

electron withdrawing electron repelling

Strength of base increases

CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH(aq)

Amines dissolve in acids by forming soluble salts. This a test for amines.
CH3CH2NH2 + HCl CH3CH2NH3Cl

NH2 + HCl NH3Cl

5.2b Amines are nucleophiles

5.2bi. Reaction with haloalkanes:
NaOH
CH3CH2NH2 + CH3Cl [CH3CH2NH2(CH3)]+Cl CH3CH2NH(CH3) + NaCl + H2O
Primary amine secondary amine
NaOH
(CH3)2NH2 + CH3Cl [(CH3)3NH]+Cl [(CH3)3N + NaCl + H2O
Secondary amine tertiary amine

N(CH3)2 + CH3Cl [ N(CH3)3]+Cl

Tertiary amine Quantanary ammonium salt

5.2bii. Reaction with acylchloride:

O O
C + 2CH3NH2 C
+ CH3NH3Cl
Cl Primary amine NHCH3
Secondary amide
O O
CH3C + 2(CH3)2NH CH3C + (CH3)2NH2Cl
Cl secondary amine N(CH3)2
Tertiary amide

93
6. DIFFERENTIATION OF AMINES
Reagent: NaNO2, dilute HCl
Condition: Cold (<5oC)
Primary amines form diazonim ion that decomposes further to give nitrogen. One mole of amino
group, NH2 per molecule gives one mole of nitrogen gas. Secondary amines give yellowish oily
liquid,while tertiery amines give ammonium salt that soluble.

NaNO2 + HCl HNO2 + NaCl

CH3CH2NH2 + HNO2 + HCl [CH3CH2N2]+Cl + 2H2O
Primary amine ethyldiazonium chloride (highly unstable)

Decomposes Cl H2O

CH2=CH2 CH3CH2Cl CH3CH2OH

+ N2 + N2 + N2

NH2 + HNO2 + HCl [ N2]+Cl + 2H2O

Primary amine Benzenediazonium chloride (stable)

Benzenediazonium salt is very useful for synthesis of other aromatic organic compounds.
Examples:
N2+

H2O CuCl CuBr KI CuCN

OH Cl Br I CN

Phenol Chloribenzene Bromobenzene Iodobenzene Cyanobenzene

Benzenediazonium for dyes

Diazo coupling reaction:

N2+ + O N=N O ( diazo compound or dye)

Azo dyes are coloring used in textile and food industry.

NO2
NaSO3
OCH3
N=N CH3 N SO3Na N=N N=N N(CH3)2

94
 OH N
HO OH (butter yellow)
(red) (allura red) (para red)
7. TEST FOR ANILINE
Reagent: Bromine water
Condition: room temperature
Observation: Decolorizing the brown color of bromine water and forming a white precipitate

NH2 NH2
Br Br
+ 3Br2 + 3HBr

Br white precipitate

8. PREPARATION OF AMINE
Reduction of nitrobenzene
Reagent and conditions: Sn and dilute HCl solution; followed by adding of dilute NaOH solution

NO2 NH3Cl

+ 6H+ + HCl + 2H2O

NaOH

NH2

+ H2O + HCl

NO2 NH2
Overall :
+ 6H+ + + 2H2O

Selective reducing agent: Add H to a specific double bond

Examples: Sn, HCl for NO2
Na, ethanol for NO2, C=O and CN
LiAlH4 for NO2, C=O and CN

Non selective reducing agent: Add H to any of the double bond

Example: H2, Pt or Ni with heating

LiAlH4
Example: CH3CH=CHCCH2 CN CH3CH=CHCHCH2 CH2NH2
O OH
H2, Pt; Heat

95
 CH3CH2CH2CHCH2 CH2NH2
PAST YEARS QUESTIONS OH
OBJECTIVE
1991/29. A diazonium salt is formed when sodium nitrite in hydrochloric acid is added into an
acidic solution of an organic compound X at low temperature.
X is
A B C
NH2 CH2NH2 CONH2

CH3

D CH3CH2CONH2 E CH3CH2NH2

1991/40. Putresine , H2NCH2CH2CH2CH2NH2, a diamine formed during the decomposition of

protein. Which of the following statements is true of putresine?
1. Releases nitrogen when react with nitrous acid.
2. Forms a soluble salt when react with hydrochloric acid.
3. Can be prepared by NCCH2CH2CN.

1993/29. X and Y are produced from the following reaction.

COCl
H2/Pt
CN X Y

Y is
A B
CONHCH2 CH2NH COCl

C D
CH2NHCH2 CONHCH2

E
CONHCH2CH2

1994/40. Which of the following compound dissolves in nitrous acid at 0 oC to give nitrogen
gas?
1 2 3
CONH2 NO2 N2Cl

1996/43. Which of the following compound releases nitrogen gas when added into sodium
nitrite in dilute hydrochloric acid?

96
A CH2=CH2 B CH3CH2OH C CH3COOH D CH3COOCH3 E CH3CH2NH2

1998/59. Which of following pairs of compounds, when added together will go through acid-
base reaction?
1. Propanol and ethanoyl chloride
2. Phenylamine and hydrochloric acid
3. Phenol and sodium hydroxide

1999/41. Which of the following pairs of compounds react to form benzenediazonium chloride
salt at low temperature?
A Phenol and H2SO4/HCl B Toluene and HNO3/HCl
C Nitrobenzene and Sn/HCl D Phenylamine and NaNO2/HCl
E Phenylamine and NaNO3/HCl

1999/44. Which of the following reagent is not reacting with H2N(CH2)2COOH?

A CH3CH2OH B HNO2 C NaHCO3 D NaOH E Br2

1999/59. Z, with molecular formula C2H5NO2, reacts with nitrous acid, HNO2 to release nitrogen
agas. 10 cm3 , 0.75g dm-3 of Z required 10 cm3, 0.01 mol dm-3 of NaOH for complete
neutralization. Which of the following is true for Z?
1. An amino acid 2. A monobase 3. An amide

2000/42. A mixture of NaNO2 and HCl is added to X at low temperature. Solution contains Y is
formed. If some phenol is added, orange precipitate is firmed. X is
A B C D
NH2 NH2 NO2 CONH2

E
CH2NH2

2001/38. Organic compound X releases white fumes, HCl when reacted with ethanoyl chloride.
X also react with nitrous acid at low temperature follow the adding of 2-naphthol to produce an
azo dyes. X is
A B C D
OH CH2OH NH2 HO CH=CH2

2001/39. Y has the following properties.

i. React with nitrous acid at low temperature to form nitrogen gas.
ii. Dissolve in hot sodium hydroxide solution.
Y is
A H2NCHCOOH B H2NCHCH2OH C H2NCHCOOH D COOH

CH2COOH CH2OH CONH2

NH2

97
2002/38 When benzenediazonium chloride reacts with phenol, a compound X with the
following structural formula is produced.

N=N OH

Which of the following is incorrect for X?

A X has bright color
B X is an azo compound
C The reaction that form X is called coupling reaction
D X can be produced through reaction between benzene, nitrogen and phenol

2003/34. An amine is produced in two steps as shown below.

KCN, ethanol Na, ethanol

2-Bromopropane X Amine

The structural formula of this amine could be

A CH3CH(NH2)CH3
B CH3CH2CH2NH2
C (CH3)2CHCH2NH2
D CH3CH2CH(CH3)NH2

2005/50. Amine can be prepared by the following.

1. NO2 + Sn + HCl

2. Cl + NH3

3. CN + LiAlH4, followed by H3O+

ESSAY
1990/8. e) Both phenylamine and ethylamine react with cold hydrochloric acid and sodium
nitrate(III). Phenylamine forms yellow precipitate but nitrogen gas is liberated with
ethylamine. Explain these observations. [4]

1991/8. d) Ethylamine reacts with nitrous acid to produce ethene, ethanol and nitrogen gas.
Explain this observation with the help of suitable chemical equations. [5]

1994/7. c) Compound I, C6H7N, reacts with bromine water than followed by ethanoylchloride to
give J, with the molecular formula C8H6NOBr3. However, if compound I, is added with
ethanoylchloride than follow by bromine water, a compound K, with the molecular formula

98
C8H8NOBr. Determine the structural formulae of I, J and K and write all chemical equations of
the reactions involved. [5]

2001/9 b) i) Explain why aniline dissolves in aqueous solution of hydrochloric acid. [2]

Answer:

1991:29A, 40A(all) 1993:29A 1994:40D(1) 1996:43E 1998:59C(2,3)

1999:41D, 44E, 59D(1) 2000:42A 2001:38C, 39C

99
CHAPTER 5
HYDROXY COMPOUNDS
1. INTRODUCTION
Alcohols are organic compounds that have hydroxyl, OH, functional group in their molecules.
Alcohols are represented by a general formula, ROH, where R represents alkyl or CnH2n+1OH.

2. THE HOMOLOG SERIES OF AND PHYSICAL PROPERTIES OF ALCOHOL

Members in the homolog series are generated from the general formula, CnH2n+1OH by
substituting n begins with 1.

n CnH2n+1OH Name Physical properties

1 CH3OH Methanol Alcohols are colorless liquid. They are volatile, but less volatile
2 C2H5OH Ethanol than hydrocarbons due to the present of hydrogen bond between
3 C3H7OH Propanol alcohol molecules. This also account for higher boiling point for
4 C4H9OH Butanol alcohols than alkanes.
5 C5H11OH Pentanol Alcohols are soluble in water because the OH group is hydrophilic
6 C6H13OH Hexanol and forms hydrogen bond with water molecules. However, the
7 C7H15OH Heptanol solubility decreases when molecular mass increases or
8 C8H17OH Octanol hydrophobic group becomes bigger.
9 C9H19OH Nonanol
1 C10H21OH Decanol
0

3. IUPAC NOMENCLATURE OF ALCOHOL

Alcohols are named according to it equivalent alkanes. However, the position functional group of
OH has to be predetermined first.
Examples:
CH3CH2CH2OH is propan-1-ol (OH is attached to the first carbon atom)
CH3CH(OH)CH3 is propan-2-ol (OH is attached to the second carbon atom)

CH3CH2 CH2CH2OH is butan-1-ol (OH is attached to the first carbon atom)

CH3CH2CH(OH)CH3 is butan-2-ol (OH is attached to the second carbon atom)
CH3C(CH3)(OH)CH3 is 2-methylpropan-2-ol (Both OH and CH3 are attached to the
second carbon atom)
HO

OH
OH
3,5-dimethylheptan-3-ol 3-ethyl-5-methylhexan-3-ol Cyclohexanol
HOCH2CH2OH is ethane-1,2-diol or glycol
HOCH2CH2CH2OH is propane-1,3-diol
HOCH2CH(OH)CH2OH is propane-1,2,3-triol or glycerol

100
 OH Phenol: A transparent crystalline solid with smell of antiseptic.
(The OH functional group is attached to the aromatic ring)

CLASSIFICATION OF ALCOHOL
Alcohols are classified as primary (1o), secondary (2o) and tertiary (3o) alcohols.

Primary alcohol Secondary alcohol Tertiary alcohol

Examples: Examples: Example:
CH3CH2OH CH3CH(OH)CH3 CH3
CH3CH2CH2OH CH3CH(OH)CH3
CH3 C CH3
* OH
OH

OH is attached to CH2. The OH is attached to CH. The OH is attached to C. The

molecule has CH2OH group. molecule has CHOH group. The molecule has COH group.
The carbon attached to OH carbon attached to OH The carbon attached to OH
has 1 immediate carbon atom. has 2 immediate carbon atom. has 3 immediate carbon
atom.

Classify the following alcohols.

CH3CH(OH)CH2CH3
CH3C(OH)(CH3)2

OH

CH3CH2CH2CH2(OH)

HO
OH

HO OH

4. ISOMERISM
Isomerism is defined as the existence of compounds with same molecular formula but different
structural formulae. The compounds are called isomers.
Alcohol shows three major types of isomerism
1. Location of OH
CH3CH2CH2OH (propan-1-ol) and CH3CH(OH)CH3 (propan-2-ol) are isomers of C3H7OH.

2. Branched molecules CH3

CH3 C CH3

OH 101
CH3CH2CH(OH)CH3 (butan-2-ol) and (2-methylpropan-2-ol) are isomer of
C4H9OH.

3. Different functional groups

Alcohols and ether are isomers of the same molecular formula
CH3CH2OH (ethanol) CH3OCH3 (diethylether) are isomers of C2H5OH.

Construct possible structural formulae for alcohols from the following molecular formulae.
i) C4H9OH.
ii) C5H11OH.
Construct possible structural formulae for ethers from C3H7OH and C4H9OH.

5. BONDING OF ALCOHOL
Oxygen atom is much electronegative than carbon and hydrogen. The CO and OH bonds are
polarized, where oxygen atom has a - pole while carbon and hydrogen atom have a + pole.
Example: Ethanol molecule H

H C+ O H+
Effects of bonding to H
5.1 Physical properties
Alcohol molecules form hydrogen bond between molecules

CH3OH OCH3
H
Hydrogen bonding
* See section: Homolog series and physical properties of alcohols

5.2 Chemical properties

The reactions of alcohols are divided into two major types depending on how bond is broken at
the OH functional group.
H

H C+ O H+

a. Cleavage of CO bond b. Cleavage of OH bond

Neucleophilic substitution Displacement
of OH Neutralization
Esterification

102
6 CHEMICAL PROPERTIES OF ALCOHOL

6.1 Cleavage of OH bond

6.1a Displacement (Redox) reaction
Proton, H+, in the OH functional group can only be displaced by strong reducing agent like
sodium and potassium at room temperature to give hydrogen gas.
Reagent: Sodium
Condition: room temperature
Observation: Colorless gas is liberated. The gas catches fire to give pop sound when a
lighted splinter is inserted into it.
2CH3CH2OH + 2Na 2CH3CH2ONa + H2
Ethanol

2 OH + 2Na 2 ONa + H2

Phenol

6.1b Neutralization reaction

Alcohol and Phenol are extremely weak acids. Phenol is stronger acid than alcohol due to the
aromatic ring has delocalized pi electron that weaken the OH bond and causes it easier to
dissociate to give H+ ion. Thus phenol reacts with aqueous solution of strong alkali like sodium
hydroxide and potassium hydroxide to give soluble salt and water but not with alcohols. This is
how phenol can be differentiated from alcohol.
Reagent: Aqueous NaOH solution
Condition: Room temperature
Observation: phenol, but not with alcohol, dissolved in aqueous NaOH solution.

OH + NaOH ONa + H2O

Sodium phenoxide (soluble)

However, the acid strength of phenol is weaker than the carbonic acid. Therefore phenol does
not react with sodium carbonate to give carbon dioxide.
The relative strength of acids:
Alcohol < water < phenol < carbonic acid < carboxylic acid
*Refer to the chemistry of carbon for the effect of neighboring group on the acidity of alcohol.

6.1c Esterification
Alcohol, but not phenol forms ester when reacts with glycial ethanoic acid in the present of
concentrated sulphuric acid as catalyst. Ester is produced in the reaction gives sweet fragrant of
fruits.
Reagent: Glycial ethanoic acid and con. sulphuric acid as catalyst
Condition: Heat

103
Observation: Sweet fragrant of fruits is given out
CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O
Ethanoic acid ethylethanoat
Phenol, however reacts with ethanoylchloride to give ester

OH + NaOH ONa + H2O

CH3COCl + NaO CH3COO + NaCl

Ethanoyl
chloride phenylethanoate

Construct the structural formula of esters formed from the following pair of reagents.
CH3CH2COOH + CH3CH(OH)CH3
CH3CH2COOAg + CH3CH2Br
CH3CH2COCl + CH3CH2OH

CH3CH2COCl + OH

6.2 Cleavage of CO bond

Nucleophilic substitution involved breaking of CO bond and OH functional group is
substituted by another nucleophile.
The OH functional group of the alcohol is easily substituted by other nucleophiles. However, the
OH functional group of phenol is not easily substituted. Thus, phenol is assumed no reactive
with nucleophile reagents.

6.2a Chlorination
Reagent: SOCl2 (or PCl5)
Condition: Room temperature ( or heat, when PCl5 is used)
Observation: White fume is given out.
CH3CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl
Ethanol Chloroethane white fumes
CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl

This is a test for the present of OH functional group in alcohols (not phenol)

Lucas test: To differentiate primary, secondary and tertiary alcohol based on the rate of
chlorination.
Reagent: Conc. HCl + ZnCl2
Condition: Room temperature
Observation: Primary alcohol:- No change
Secondary alcohol:- Solution turns cloudy after some time.
Tertiary alcohol:- Double layers is formed almost immediately.
(CH3)3COH + HCl (CH3)3CCl + H2O
(CH3)3CCl is insoluble in water, thus causes the solution to be cloudy or forming two layers.

104
6.2b Formation of ether
Reagent: CH3ONa, in alcohol.
Condition: Heat
Methoxide nucleophile substitutes OH functional group to give ether.
CH3CH2OH + CH3ONa CH3CH2OCH3 + NaOH
Sodium ethylmethyl ether
methoxide
Also:
Concentrated sulfuric acid is added to excess of ethanol and the mixture is heated to 140oC.
2CH3CH2OH CH3CH2OCH2CH3 + H2O
diethylether

6.3 Other reactions involve alcohol

6.3a Oxidation
6.3ai By combustion
Alcohols burnt in excess of oxygen to give carbon dioxide, water and large quantity of heat.
CH3CH2OH + 3O2 2CO2 + 3H2O

6.3aii By potassium permanganate

Oxidation of alcohols by acidified potassium permanganate give different products depends on
the type of alcohols.
Primary alcohol is easily oxidized to carboxylic acids through aldehyde as intermidiate.
Secondary alcohol is oxidized to ketone.
Tertiary alcohol is not oxidized.
This is an important test to differentiate the types of alcohols.

Primary alcohol
Reagent: KMnO4, dilute sulphuric acid
Condition: Heat
Observation: Decolorisation of purple color of potassium permanganate

CH3CH2OH + 2[O] CH3COOH + H2O

1o carboxylic acid
Secondary alcohol
Oxidation of secondary alcohol involved the same reagent, condition of reaction and gives
similar observation as the primary alcohol.

CH3CH(OH)CH3 + [O] CH3COCH3 + H2O

2o ketone
Tertiary alcohol
it is not oxidized. Thus, it does not decolorlized the purple color of potassium permanganate.

105
Oxidation of a primary alcohol involves two steps.
The first step of oxidation takes place at the carbon atom (C*) that attached to the OH
functional group by removing one H atom from this carbon (C*) and one hydrogen from OH.
The hydrogen atoms combine with oxygen atom to give water, H2O.
The second step is followed by adding of one oxygen atom to CH bond at the same carbon (C*)
to give a carboxylic acid.
H H OH
Step 1 Step 2
CH3 C* O + [O] CH3 C O + [O] CH3 C O
aldehyde carboxylic acid
H H + H2O
Primary alcohol

However, the oxidation of secondary alcohol terminates after the first step. Ketone is not
oxidized further because it does not have CH bond at first carbon (C*).
CH3 CH3
Step 1
CH3 C* O + [O] CH3 C O
ketone
H H
Secondary alcohol

Tertiary alcohol is not oxidized because it does not have H atom at the carbon (C*) atom attached
with OH.

Which of these alcohols decolourises solution of potassium permanganate? Write the structural
formula of the product of oxidation.
CH3CH(OH)CH2CH3
CH3C(OH)(CH3)2

OH

CH3CH2CH2CH2(OH)

6.3aiii By aqueous Iodine solution in sodium hydroxide

Only alcohols with this structure, CH3CH(OH)R (R can be H or alkyl) is oxidized to give yellow
precipitate, CHI3 or iodoform and carboxylic acid.

CH3CH(OH)R (R can be H or alkyl)

R = H: The alcohol is ethanol, CH3CH2OH.
R = C6H5: 1-phenyl ethanol, C6H5CH(OH)CH3

106
R = alkyls: All -2-ol alcohols.
Examples of -2-ol are:
CH3CH(OH)CH3 (propan-2-ol), CH3CH(OH)CH2CH3 (butan-2-ol) .

Reagent: I2 in aqueous NaOH

Condition: Heat
Observation: yellow precipitate (iodoform, CHI3) is formed
During the reaction CH3 is converted to iodofrom, CHI3 to give yellow precipitate and the
remaining of the molecule is oxidized to carboxylic acid.

CH3CH2OH + 4I2 + 6NaOH CHI3 + HCOONa + 5NaI + 5H2O

yellow carbocylate
precipitate
CH3CH(OH)CH3 + 4I2 + 6NaOH CHI3 + CH3COONa + 5NaI + 5H2O

CH(OH)CH3 + 4I2 + 6NaOH CHI3 + COONa + 5NaI + 5H2O

Phenol does not give yellow precipitate with I2/NaOH solution when heated.

Alcohol D reacts with alkaline iodine solution to give CHI3 and (CH3)2CHCOONa.
Determine the structural formula of alcohol D.

Given three alcohols with the following formulae

A = CH3CH2CH(OH)CH2CH3 B = CH3CH2CH2CH(OH)CH3 C = (CH3)3COH
Identify the alcohols by giving suitable tests.

6.3b Dehydration
Elimination of water molecule from alcohol molecule is called dehydration. Hydrogen atom
from the adjacent carbon atom is eliminated together with the OH functional group to from a
C=C double bond and lead to the formation of alkene.
H H H H

H C C H H C C H + H2O

H OH
Reagent: Conc. sulphuric acid (or Al2O3)
Condition: Heat
CH3CH2OH CH2=CH2 + H2O

Dehydration of symmetrical and 1 ol alcohols give only one alkene.

Examples:
Symmetrical alcohols:
CH3CH(OH)CH3 CH3CH=CH2 + H2O
CH3CH2CH(OH)CH2CH3 CH3CH2CH=CHCH3 + H2O
(CH3)3COH (CH3)2C=CH2 + H2O

107
 OH

+ H2O

1- ol alcohols:
CH3CH2CH2OH CH3CH=CH2 + H2O
(CH3)3CCH2OH (CH3)2CCH=CH2 + H2O

Dehydration of non-symmetrical alcohols and alcohols other than 1 ol give more than one
alkenes, where alkene with more alkyl groups attached to the C=C double bond is the major
product.
Examples:
CH3CH(OH)CH2CH3 CH3CH=CHCH3 + CH2=CHCH2CH3 + H2O
major product
CH3CH2CH2CH(OH)CH3 CH3CH2CH=CHCH3 + CH3CH2CH2CH=CH2 + H2O
major product

Phenol is not dehydrated by concentrated sulphuric acid while methanol is oxidized to CO2 and
H2

7. OTHER REACTION OF PHENOL

The OH group attached to the aromatic ring activates the ring toward electrophilic substitution
at the orto and para possition.

7.1 Nitration NO2

dilute HNO3, r.t.
OH + HNO3 OH + O2N OH + H2O

2-nitrophenol 4-nitrophenol
If concentrated HNO3 is used, double substitution to form 2,4-dinitrophenol and 2,6-
dinitrophenol. Triple substitution 2,4,6-tirnotrophenol is formed when heat is applied.

7.2 Halogenation
Bromine water or Br2/CCl4 is added to phenol at room temperature would give immediate effect
of decolorization of brown bromine water to form white precipitate. This indicates that phenol is
very reaction to bromination than benzene and toluene.
OH
Br Br
OH + 3Br2(aq) + 3HBr

Br 2,4,6-tribromophenol (white precipitate)

This is a quick test for phenol.

7.3 Formation of complex

Phenol forms purple complex with neutral aqueous FeCl3 solution.

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6 OH + FeCl3 [Fe( O)6]3- + 6H+ + 3Cl
purple complex

8. PREPARATION OF ALCOHOL
8.1 Fermentation
Zymase, r.t.
C6H12O6 2CH3CH2OH + 2CO2

8.2 Hydration of alkenes

Conc. H2SO4, r.t. H2O, heat
CH2=CH2 CH3CH2OSO3H CH3CH2OH + H2SO4

Overall: CH2=CH2 + H2O CH3CH2OH

+ H2O OH

8.3 Hydrolysis of haloalkanes

CH3CH2Br + KOH(aq) CH3CH2OH + KBr

Br + KOH(aq) OH + KBr

8.4 Reduction of carbonyl compounds

Reduction is carried out by LiAlH4 in ether at room temperature or by H2, Pt or nickel with
heating.
Reduction of aldehyde to give primary alcohol
LiAlH4
CH3CHO + 2[H] CH3CH2OH

Reduction of ketone to give secondary alcohol

LiAlH4
CH3CO CH3 + 2[H] CH3CH(OH)CH3

8.5 From Grignard reagent

Grignard reagent is added to the carbonyl the compound and followed by hydrolysis.

8.5a With aldehyde, it gives primary and secondary alcohol

H2O, H+(aq)
HCHO + CH3MgBr HCH(OMgBr)CH3 CH3CH2OH + Mg(OH)Br
Methanal 1o alcohol

Other aldehydes than methanal form 2o alcohol.

H2O H+(aq)

109
CH3CH2CHO + CH3MgBr CH3CH2CH(OMgBr)CH3 CH3CH2CH(OH)CH3 +
Other aldehyde 2o alcohol
Mg(OH)Br
CH3CHO + CH3 CH2MgBr
8.5b With ketone, it gives tertiary alcohol
H2O,H+(aq)
CH3COCH2CH3 + CH2MgBr CH3(CH3CH2)C(OMgBr)CH2

CH3(CH3CH2)C(OH)CH2 +
3o alcohol

Mg(OH)Br

9 PREPERATION OF PHENOL
9.1 The cumene process
H3PO4
+ CH3*CH=CH2 *CH(CH3)2 cumene
30 atm, 250oC

O2, Heat

H2O, H2SO4(aq)
OH + (CH3)2*CO *C(CH3)2OOH cumeneperoxide
Phenol Propanone Heat

9.2 The Dow process

300oC
Cl + 2NaOH ONa + NaCl
150 atm
HCl(aq)
OH + NaCl

Phenol
9.3 Hydrolysis of benzenediazoniumchloride salt
Heat
N2Cl + H2O OH + N2 + HCl

Phenol

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PAST YEAR QUESTIONS
OBJECTIVE:
1990/26
Which of the following sequential steps is used for the preparation of 1,2-dibromobutene from
butane -1-ol?
A Dehydration and than followed by addition
B Dehydration and than followed by oxidation
C Oxidation and than followed by hydrolysis
D Addition and than followed by hydrolysis
E Hydrolysis is followed by addition

1991/27
Organic compound P is not oxidized by potassium permanganate but is dehydrated to form
compound Q that decolourises bromine water. Q reacts with hydrogen bromide, HBr, to produce
2-bromi-2-methylpropane.P is
A Butan-2-one B Propan-2-ol C Butan-2-ol
D 2-methylpropan-1-ol E 2-methylpropan-2-ol

1992/26
An organic compound X is with this following properties.
i. X is neutral
ii. X reacts with sodium to give hydrogen gas
iii. X forms sweet smelling compound when reacts with ethanoic acid
Compound X is
A Propanal B Propan-1- ol C Propanoic acid
D Ethyl cynide E Propanoyl chloride

1993/22
The schematic diagram for the conversion of C2H5OH, W to compounds X and Y is given as the
following.
KMnO4/H+ Cl2/uv
C2H5OH, W X Y
Heat Heat
Which of the following is the correct order of pKa values of compounds W, X and Y in the
descending order?
A W, X, Y B W, Y, X C X, W, Y D X, Y, W E Y, X, W

1993/26
Oxidation of an organic compound X forms another organic compound that has the following
properties.
i. form orange precipitate with 2,4-dinitrophenylhydrazine

111
 ii. does not produce silver mirror with Fehlings solution
iii. does not produce yellow precipitate when heated with alkaline iodine solution.
X is

A. CH3CH2CH2CH2CH2OH B CH3CH2CH2CH(OH)CH3
C CH3CH2CH(OH)CH2CH3
D CH(OH)CH3 E CH2CH2CH2OH

1994/26
Which of the following compounds does not give positive iodoform test?
A CH3CH2OH B CH3CH2CH2CH(OH)CH3 C CH3CH2CH(OH)CH2CH3
D C6H5CH(OH)CH3 E CH3OCH3

1995/26
Compound Z has the following properties.
i. React with sodium to form hydrogen gas.
ii. React with benzoyl chloride to form a precipitate with sweet smell.
iii. React with sodium hydroxide to form salt and water.
Z could be
A OH B OH C CH2OH D CHO E COOH

1996/40
X produces yellow precipitate when heated with alkaline iodine solution. X could be
A CH3CH2CH2CH2CH2OH B CH3CH2CH2CH(OH)CH3
C CH3CH2CH(OH)CH2CH3 D (CH3)2C(OH)CH2CH3
E (CH3)3CCH2OH

1997/34
Below is the mechanism for a reaction.
Step 1: (CH3)3COH + HCl (CH3)3CO+H2 + Cl (Fast)
Step 2: (CH3)3CO+H2 (CH3)3C+ + H2O (Slow)
+
Step 3: (CH3)3C + Cl (CH3)3CCl (Fast)
Which of the following statement is not true about the mechanism?
A (CH3)3COH and (CH3)3CO+H2 are conjugate acid-base pair.
B The nucleophile is HCl.
C The rate equation is, r = k[(CH3)3CO+H2].
D The overall reaction is (CH3)3COH + HCl (CH3)3CCl + H2O
E The overall reaction is nucleophilic substitution.

1997/38
Which of the following reagents reacts with ethanol and phenol?
A Ethanoic acid B Bromine water C Ethanoyl chloride
D Sodium hydroxide solution E Acidified potassium dichromate solution.

112
1998/37
Below is the schematic diagram for the synthesis of Z.

X
(CH3)2CHOH (CH3)2CHBr
CrO3 Mg H2O/H+
Y + (CH3)2CHMgBr Z
X, Y and Z are
X Y Z
A Br2 CH3COCH3 (CH3)2CHC(CH3)2OH
B Br2 CH3COCH3 (CH3)2CHCH2CH2CH2OH
C PBr3 CH3COCH3 (CH3)3CCH(OH)CH3
D PBr3 CH3COCH3 (CH3)2CHC(OH)(CH3)2
E AlBr3 CH3CH2CHO (CH3)2CHC(OH)(CH3)2

1998/39
Which of the following alcohols can be oxidized to ketone?
A CH3CH2CH2CH2CH2OH B CH3CH2CH2CH(OH)CH3
C CH3CH2C(CH3)2OH D (CH3)2CHCH2CH2OH
E (CH3)3CCH2OH

1998/40
Compound W has the following properties.
i. Releases HCl fumes when reacts with PCl5
ii. Optically active
W could be
A HOCH2CH2 COCH3 B HOCH2 COCH2CH3
C COCH(CH3)CH2OH D CH3O CH(CH3)CHO

E HO COCH(CH3)2

1998/57
Adrenaline has the following structure.
HO

HO CH(OH)CH2NHCH3

Which of the following is true to adrenaline?

1. Dissolve in water

113
 2. React with PCl5 to release white fumes.
3. React with HNO2 to release N2
1999/34
Chlorine water is decolourized when added into phenol and a white precipitate, 2,4,6-
trichlorophenol is formed. This reaction involves
A electrophilic substitution B nucleophilic substitution
C electrophilic addition D nucleophilic addition
E free radical reaction

1999/57
Q is a substituted group in phenol molecule. The acidity of phenol is higher of Q is
1. NO2 2. Cl 3. CH3

2001/34
Organic compound Z has the following structure.
HO

CH3CH CH2COOH

OH
Z dissolves in aqueous sodium hydroxide to form a soluble salt whit the following formula
A HO B HO

CH3CH CH2COONa CH3CH CH2COONa

OH ONa

C NaO D NaO

CH3CH CH2COONa CH3CH CH2COONa

OH ONa

2002/34 When an optically active compound Y is heated with chromic acid, a compound
produced is not optically active and does not give yellow precipitate with hot alkaline iodine
solution. Y could be
A (CH3)2CHCH2OH
B CH3CH2CH2CH(OH)CH3
C CH3CH2CH(OH)CH2CH3

D CH(OH)CH2CH3

114
2002/35 Given is a schematic transformation of phenol to CH3COOC6H5 via intermediate
compound X.
Reagent I Reagent II
C6H5OH X CH3COOC6H5

What could be reagent I and reagent II?

Reagent I Reagent II
A PCl5 CH3COCl
B Na CH3COCl
C NaOH CH3COH
D PCl5 CH3COH

2003/36.Iodoethane can be prepared from the reaction of ethanol with

A iodine
B Sodium iodide
C phosphorous triiodide
D potassium iodide with concentrated sulphuric acid

2003/50. In industry, phenol is produced by either the cumene process or the hydrolysis of
chloribenzene, namely the Dow process. What are the advantages that the cumene process has
over the Dow process?
1. The use of inexpensive raw material
2. The production of useful by products
3. The production of purer phenol

2004/33. The cleavage of the CO bond in ethanol involves specific reagents and reaction
conditions. Which of the following reagents and reaction conditions is true of the cleavage
reaction?
A K2Cr2O7 , H2SO4 ; Heat
B Na, room temperature
C Concentrated H2SO4, excess; Heat
D CH3COOH, concentrated H2SO4; reflux

2004/40. Which of the following reactions produces ethanol?

A Ethyl ethanoate and lithium tetrahydridoaluminate
B Methyl ethanoate and hot concentrated sulphuric acid
C Ethene and dilute aqueous potassium manganate(VII)solution
D Choroethane and ethanolic sodium hydroxide solution

2004/50. Propanone reacts with acidified potassium cyanide solution to form a compound. When
this compound is hydrolysed in acidic solution, it becomes compound Y. Which of the following
is true of compound Y?
1. Reacts with hot concentrated sulphuric acid

115
 2. Changes the orange colour of acidified aqueous potassium dichromate(VI) to green
3. Shows optical isomerism
2005/32. A compound has the following chemical properties?
i. It gives positive iodoform test
ii. It ecolourises acidified aqueous potassium manganate(VII)
iii. It reacts with phosphorus pentachloride to produce hydrogen chloride gas

A CH3CH2OH
B CH3OCH3
C (CH3)3COH
D (CH3CH2)2CHOH

2005/36. 2-chloro-2-methylbutane and 1-chlorobutane are separately reacted with aqueous

potassium hydroxide. The reagent that can be used to distinguish the product of the reaction is
A Na
B Br2, CCl4
C Concentrated H2SO4
D Concentrated HCl, ZnCl2

STRUCTURED
1990/3
(a) J (C4H10O) has three isomers K, L and M. These isomers are heated with excess of
concentrated sulphuric acid respectively. Isomers K and L produce a same compound, N,
whereas M produces compound O that has geometrical isomers. Determine the structural
formulae of J, K, L, M, N and O. [6]
(b) Which isomer among K, L and M shows optical isomerism?
(c) Draw structural formulae for the compounds produced when geometrical isomers of O react
with bromine in chloroform.

1991/1
(a) Q gives ethene when heated with concentrated sulphuric acid.
i. Identify Q.
ii. State the function of concentrated sulphuric acid. [2]

1993/5
(a) i. Determine the structural formulae of 3-chloro-3-methyl pentane, alcohol W and alkene
X in the following schematic diagram.

NaOH I Alcohol W
3-chloro-3-methylpantane
II
Alkene X

116
 ii. Sate the condition of reaction for reaction I and reaction II. [5]
(b) i. Alcohol W reacts with certain reagents under specific conditions to give alkene
Y and ether Z. State the reagents and conditions of reaction involved in producing the alkene and
ether respectively.
ii. Identify the structural formula of ether Z. [5]

ESSAY
1990/7
Explain the observation and write equation for the following reactions
(a) Propan-2-ol turns acidified potassium dichromate (VII) from orange to green, while 2-
methylpropane-2-ol is not.
(c) Butan-1-ol is not soluble in aqueous sodium hydroxide solution, while phenol dissolves.

1991/8
Explain the following observation and write the equation of reaction involved.
(c) Phenol dissolved in dilute NaOH but does not dissolve in Na2CO3 solution. [4]

1992/6
(i) An organic compound A contains 59.95% of carbon, 13.42% of hydrogen and
26.63% of oxygen. Determine the molecular formula of A if the relative molecular mass of A is
60.
(ii) When A is heated with concentrated sulphuric acid, it produces water and ether B. If A is
heated with aluminium oxide, it gives gas C that decolorized bromine water. When gas C is
bubbled through hot dilute sulphuric acid, it produces D, which is an isomer to A. mild oxidation
of A gives compound E that is able to produce red precipitate with Fehlings reagent. Explain the
observations; determine the structural formulae of A, B, C, D and E and write equations for all
reactions involved.
(iii) State a chemical test to differentiate A from D. [20]

1992/7
Give a chemical test to differentiate the following pairs of compounds. State the observations and
write all equation for all reactions involved.
(a) Phenylmethanol and phenol
(b) Butan-2-ol and 2-methylpropan-2-ol

1993/8
(b) (i) Four compounds W, X, Y and Z have the following composition: 64.88% of carbon,
13.49% of hydrogen and 21.63% of oxygen and their relative molecular mass is 74. Determine
the molecular formula for the compounds.
X, Y and Z react with sodium to give hydrogen gas while W is not. X and Y are easily oxidized
by acidified potassium permanganate, while Z is not. X gives yellow precipitate when heated
with Iodine in aqueous sodium hydroxide solution, while Y is not.

117
Explain the observations; determine the structural formulae of W, X, Y and Z and write equations
for all reactions involved.
(ii) Among the compounds W, X, Y and Z, which one is optically active? Dehydration of
this optically active compound gives a compound V that appears to be the major product and has
a geometrical isomer. Write the equation of reaction, draw and name the geometrical isomers.
[14]

1994/7
(b) C and D share the same molecular formula C4H10O. Dehydration of C gives a mixture of
three alkenes E, F and G. Dehydration of D gives only alkene H. Alkenes E, F, G and H share the
same molecular formula H4H8.
Determine the structural formulae of C, D, E, F, G and H and write equations of all reactions
involved. State the types of isomerism between E, F, G and H. [10]

1994/8
b) Ethane-1,2-diol, C2H6O2 is a useful compound for manufacturing polyester. Explain the
preparation of ethane-1,2-diol.

1995/6
(b) Give one chemical test to differentiate butan-1-ol and butan-2-ol. Your answer should
include the reagent and condition of reaction; observations and write the equation of reaction
involved. [4]

1996/8
(b) Give an alcohol that is used for the preparation of phenylethane. State the reagent and the
condition of reaction used and write the equation involved. State one used of phenylethane.

1997/7
State reagent and condition of reaction used for the differentiation of 1-phenylethanol from 2-
phenylethanol. Your answer should include observations and the equation of reaction involved.
[4]

1998/7
Suggest; how the benzoic acid is prepared from a suitable alcohol. Write a chemical equation for
the reaction involved and state one use of benzoic acid in industry. [4]

1999/7
State reagent used for the differentiation of the acidity of cyclohexanol and phenol. Your answer
should include the observations and the equation of reaction involved. [4]

2001/9
(a) (ii) State reagent and condition of reaction used for the differentiation of 1-phenylethanol
from 2-phenylethanol. Your answer should include observations and the equation of reaction
involved. [4]

118
(b) (ii) Phenol dissolves in aqueous sodium hydroxide but not in aqueous sodium carbonate.
[3]

2001/10
Z, a monobasic carboxylic acid contains 54.5% carbon, 9.1% hydrogen and 36.4% oxygen. An
aqueous solution that contains 0.100 g of Z required 11.4 cm3, 0.100 mol dm3 of aqueous sodium
hydroxide solution for complete neutralization.
Z can be syntheses from 1-propanol according to the following scheme of reaction.
I II III
CH3CH2CH2OH X Y Z
(a) Determine the empirical formula and the molecular of Z [6]
(b) Suggest the reagent and the condition of reaction fro steps I and III. [3]
(c) Predict the structural formulae of X, Y and Z. [3]
(d) Give a chemical test to differenciate Z from 1-propanol. [3]

2002/9 a (ii) Write an equation to show the reaction between CH3CH(OH)C3H7 with hot and
acidified potassium dichromate (VI). [1]

Answer:
1990:26A 1991:27E 1992:26B 1993:22E, 26A 1994:26C 1995:26B 1996:40B 1997:34B,
38C 1998:37D, 39B, 40C, 57B(1,2) 1999:34A, 57B(1,2) 2001:34C

119
CHAPTER 6
THE CARBONYL COMPOUNDS
1. INTRODUCTION
Carbonyl compounds are organic compounds that have carbonyl, C=O, functional group in
their molecules. Carbonyl compounds are represented by a general formula, CnH2nO.
Carbonyl compounds are sub-divided to two homolog series
a. Aldehyde: CnH2n+1C=O.

H
The carbonyl functional group is bonded with one or two hydrogen atoms.

b. Ketone: CnH2n+1C=O.

CnH2n+1
The carbonyl functional group is bonded with two carbon atoms.

Aldehydes and ketone share the same molecular formula, CnH2nO.

2. HOMOLOG SERIES OF ALDEHYDE AND KETONE

Aldehyde Ketone
n Formula Name Formula Name
0 H2CHO Methanal - -
1 CH3CHO Ethanal - -
2 C2H5CHO Propanal CH3COCH3 Propanone
3 C3H7CHO Butanal C2H5COCH3 Butanone
4 C4H9CHO Pentanal C3H7COCH3 Pentanone
5 C5H11CHO Hexanal C4H9COCH3 Hexanone
6 C6H13CHO Heptanal C5H11COCH3 Heptanone
7 C7H15CHO Octanal C6H13COCH3 Octanone
8 C8H17CHO Nonanal C7H15COCH3 Nonanone

3. NOMENCLATURE AND ISOMERISM OF ALDEHYDES AND KETONES

Aldehydes are named according to it equivalent alkanes by replacing the subscribe of
ane of the alkane by anal in the aldehyde. Since the CHO group is always at the first carbon,
its position usually is not stated.
Ketones are also named according to it equivalent alkanes by replacing the subscribe of
ane of alkane by one in ketone. The CO group cannot be placed at the first carbon.

120
Examples:
CH3CH2CHO and CH3COCH3 are isomers.
Propanal Propanone
CH3CH2CH2CHO and (CH3)2CHCHO and CH3CH2COCH3 are isomers
Butanal 2-methylpropanal butan2-one

CH3CH2CH2CH2CHO: Pentanal
CH3CH(CH3)CH2CHO: 3-methylbutanal
CH3CH2CH(CH3)CHO: 2-methylbutanal
CH3C(CH3)2CHO: 2,2-dimethylpropanal they are isomers
CH3CH2CH2COCH3: Pentan-2-one
CH3CH(CH3)COCH3: 3-methylbutan-2-one
CH3CH2COCH2CH3: Pentan-3-one

CHO : benzaldehyde CH2CHO: Phenylethanal

(or phenylmethanal)
Benzaldehyde is an aromatic aldehyde, the CHO functional group is attached directly to the
benzene ring.
Phenylethanal is not an aromatic aldehyde.

COCH3: Phenylethanone CO : Diphenylmethanone

They are both aromatic ketones, the CO functional group is attached directly to the benzene
ring.

=O cyclohexanone, a cyclic ketone

4. BORN PROPERTIES OF FUNCTIONAL GROUPS, PHYSICAL PROPERTIES AND

CHEMICAL PROPERTIES

The CHO and CO functional groups are polarized.

+ - + -
C=O C=O

H
Aldehydes and ketones are colorless and volatile liquids. They have low boiling points
due to weak Van der Waals forces between molecules.
Aldehydes have pungent smell while ketones have sweet and pleasant smell.

The carbon atom of the carbonyl functional group is easily attacked by the incoming
nucleophiles. In the reaction, the whole nucleophile molecule is added into the C=O functional

121
group. Thus, the reaction is called nucleophilic addition. As the result, saturated product is
formed.

Nucleophilic addition:
+ - + -
C=O + H Nu C O + H+ C O
Nucloephile
Carbonyl Nu Nu H saturated product

The reactivity of the carbonyl functional group, C=O, is depending on the types of
neighboring groups attached to it and the size of the groups.
Electrons repelling group reduces the polarity of the carbonyl group causes it to be less
reactive. Larger group attached to the carbonyl causes strong steric effect that hinders the attack
of the incoming nucleophile, causes it to be less reactive.

The following is the reactivity of carbonyl compound in the descending order

HC =O > HC =O > CH3C =O > HC =O > CH3C =O > C =O

H CH3 CH3

Stronger electron repelling effect

Stronger steric effect

5. REACTIONS OF CARBONYL COMPOUNDS

Four types of reactions

1 Nucleophilic addition
2 Reduction
3 Oxidation
4 Condensation

5.1 Nucleophilic addition

5.1a. Addition of hydrogen cyanide to carbonyl compounds forms cyanohydrins.
Reagent: NaCN, dilute H2SO4
Condition: Room temperature
R R CN
C=O + HCN C
R R OH cyanohydrin
R and R = H, alkyls or phenyls.

When heated, cyanohydrin is easily hydrolized under acidic or alkaline condition to give 2-
hydroxy carboxylic acid.

122
Under acidic condition:
R CN R COOH
C + 2H2O + H+ C + NH4+
R OH R OH
2-hydroxi-carboxylic acid
Under alkali condition:
R CN R COONa
C + H2O + NaOH C + NH3*
R OH R OH
sodium 2-hydroxi-carboxylate
*NH3 is leberated indicate the compound has a CN functional group.
Cyanohydrin is reduced to amine with LiAlH4 in ether.
H CN H CH2NH2
C + 4[H] C
R OH R OH

5.1b. Addition of Grignard reagent (RMgX) to give alcohol

Reagent: RMgX, dry ether
Condition: Room temperature

Addition of Grignard reagent to methanal to give primary alcohol

H H R H2O, dilute H2SO4 H R
C=O + RMgBr C C + Mg(OH)Br
H H OMgBr heat H OH
Intermediate a primary alcohol
R = alkyls or phenyls.

Addition of Grignard reagent to aldehyde to give secondary alcohol

R R R H2O, dilute H2SO4 R R
C=O + RMgBr C C + Mg(OH)Br
H H OMgBr heat H OH
Intermediate a secondary alcohol
R and R= alkyls or phenyls.

Addition of Grignard reagent to ketone to give tertiary alcohol

R R R H2O, dilute H2SO4 R R
C=O + RMgBr C C + Mg(OH)Br
R R OMgBr heat R OH
Intermediate a tertiary alcohol
R, R and R = alkyls or phenyls.

Given an alcohol A is
CH2CH3

CH3 C OH

123
State the combination of Grignard reagent and carbonyl compound that can be used to synthesis
alcohol A.

5.1c. Addition of alcohol to form hemiacetal

Reagent: C2H5OH, dilute H2SO4
Condition: Heat
Condition: Room temperature

R R OC2H5
C=O + C2H5OH C
R R OH hemiacetal
R and R = H, alkyls or phenyls.

5.2 Reduction
Hydrogen is added to the C=O double bond, converting the carbonyl compound to alcohol.
Reagent: LiAlH4 in dry ether*
Condition: Room temperature
*Reduction also can be accomplished by NaBH4/ether or Na/ethanol or Zn/HCl or H2/Pt with
heating.

Reduction on aldehydes gave primary alcohol.

R R

HC=O + 2(H) H C OH
Aldehyde primary alcohol (R= H, alkyl or phenyl)
H
Reduction on ketones gave secondary alcohol.
R R

R C = O + 2(H) R C OH
Ketone secondary alcohol (R and R=alkyl or phenyl)
H

Determine the alcohols resulting from the reduction of the phenyl ethanone by
i. LiAlH4 in ether
ii. H2, Pt ; Heat.

124
5.3. Oxidation of carbonyl compounds
Only aldehydes are easily oxidized to carboxylic acids. An oxygen atom is inserted into the CH
bond, changing the carbonyl, C=O to the carboxylic, COOH functional group.

5.3a Acidified KMnO4

Reagent: KMnO4 in dilute sulphuric acid
Condition: Heat
Observation: The purple color of potassium permanganate is decolorized.
R

HC=O + (O) RCOOH

Aldehyde carboxylic acid (R= H, alkyl or phenyl)

Write the equation of oxidation for

i. Ethanal
ii. Benzaldehyde
Reactions of aldehyde with Tollens reagent, Fehlings reagent and the iodoform test are
oxidation reactions.
These reagents are used for the identification of aldehydes and ketones.

5.3b Tollens Reagent

Tollens reagent for aldehydes only:
Reagent: AgNO3 in ammonia solution
Condition: Heat
Observation: Silver mirror is formed
RCHO + 2Ag(NH3)2+ + OH RCOO + 2Ag(s) + NH3 + 2NH4+
Aldehyde silver mirror
(R= H, alkyl or phenyl)

5.3c Fehlings reagent

Fehlings reagent for aliphatic aldehydes only:
Reagent: CuSO4 in sodium hydroxide
Condition: Heat
Observation: Red precipitate
RCHO + 2Cu2+ + 5OH RCOONa + Cu2O(s) + 3H2O
Aldehyde Red precipitate
(R= H or alkyl)

5.3d Alkaline NaOH solution

Iodoform test only for ethanal and ketones that with CH3C=O molecular structure.
Reagent: I2 in dilute NaOH
Condition: Heat
Observation: Yellowish precipitate

125
 CH3

HC=O + 3I2 + 4NaOH HCOONa + CHI3 + 3NaI + 3H2O

Ethanal yellow
Precipitate
R

CH3 C = O +3I2 + 4NaOH RCOONa + CHI3 + 3NaI + 3H2O

Ketone Yellow
Precipitate
(R= H, alkyl or phenyl)

Write the equations of reaction for ethanal, benzaldehyde and propanone with
i. Tollens reagent
ii. Fehlings reagent

5.4. Condensation reaction

Condensation reaction means a reaction involves two molecules combine to form a larger
molecule and at the same time a small molecule is eliminated.
Carbonyl compounds react with derivatives of primary amine (H2NX) in condensation reaction
to give imines (C=NX) and water molecule is eliminated.

R R
C=O + H2N X C=N X + H2O
R R
(R and R = H, alkyl and phenyl)

H2N X C = N X
Types of primary amine derivatives imines
Hydroxyamone H2N OH C = N OH
oxime
Hydrazine H2N NH2 C = N NH2

hydrazone
Phenylhydrazine H2N NH C = N H

Phenylhydrazone
2,4-dinitrophenylhydrazin H2N NH C=N NH
or 2,4-DNPH or Bradys reagent NO2 NO2

NO2 NO2
2,4-dinitrophenylhydrazone
Orange precipitate

126
Reagent: 2,4-dinitrophenylhydrazin
Condition: Room temperature
Observation: Orange precipitate is formed

R R
C=O + H2N N H C=N N H + H2O
R NO2 R NO2

Orange precipitate
NO2 NO2
(R and R = H, alkyl and phenyl)
Bradys reagent is the test for the present of the carbonyl, C=O in organic molecules.

Write equation for the reaction between phenylethanone and 2,4-dinitrophenylhydrazin.

6. PREPARATION OF CARBONYL COMPOUNDS

6.1. Oxidation of alcohols
Reagent: KMnO4, dilute H2SO4
Condition: Warm (for aldehyde)
Heat (for ketone)

Primary alcohol gives aldehyde:

CH3CH2OH + [O] CH3CHO + H2O
Aldehyde
Secondary alcohol gives ketone:
(CH3)2CHOH + [O] (CH3)2CO + H2O
Ketone

Use Cu, heat for preparing aldehyde from primary alcohol.

CH3CH2OH CH3CHO + H2
Aldehyde
Suggest the alcohols used for the preparation of benzaldehyde and phenylethanone. Write
equations involved.

6.2. Friedel-Craft acylation of benzene to give aromatic ketone

Reagent: CH3COCl, AlCl3
Condition: Heat

CH3COCl + CH3C=O + HCl

127
7. CARBOHYDRATES
Monosaccharide
7.1. Glucose
Molecular structure: C6H12O6 H

H H OH H H C CH2OH
HO C O*
HOCH2 C C C C C = O HO H H
C C H
HO* OH H OH C
H OH
Straight chain glucose OH
Cyclic glucose (a cyclic hemiacetal)
Glucose is a monosaccharide, an aldose and a reducing sudar. In solution, straight chain glucose
exists in equilibrium with the cyclic glucose. The straight chain glucose molecule has an
aldehyde (-CHO) functional group. Thus, it functions as a reducing agent. The cyclic glucose
does not have an aldehyde functional group. Thus, it does not function as reducing agent.
The present of the aldehyde group in the straight chain glucose molecule enable the aqueous
solution of glucose to be a reducing sugar. It gives red precipitate (Cu2O) when heated with
Fehlings reagent.

HOCH2[CH(OH)]4CHO + 2Cu2+ + NaOH + H2O HOCH2[CH(OH)]4COONa + Cu2O

+ 4H+

7.2. Fructose
Fructose is a monosaccharide and structural isomer of glucose. Fructose is a ketose and has a
ketone functional group in the straight chain molecule.
In aqueous solution the straight chain fructose exists in equilibrium with the cyclic fructose.
H H H OH H
HOCH2 O OH
HCCCCCCH C H HO C
H CH2OH
HO *OH OH H O OH C C
Straight chain fructose
OH H
Cyclic fructose (a cyclic hemiacetal)
In aqueous solution, straight chain fructose also exists in equilibrium with glucose as the
following.
H H H OH H H H H OH H

HCCCCCCH HCCCCCCH

HO HO HO H O OH HO OH OH H OH O

128
 Fructose (Ketose) glucose (Aldose)

Since the ketone functional group is converted to the aldehyde functional group, therefore
fructose is also a reducing sugar and gives red precipitate with Fehlings reagent.

Disaccharide
1. Sucrose consisting one unit of cyclic glucose and one unit of cyclic fructose.
H
Sucrose is not a reducing sugar. The
C CH2OH molecule does not have free aldehyde
HO C O group. The acetal linkage (OCO) is
HO H H broken during the hydrolysis of sucrose by
C C H dilute HCl or invertase. The aqueous
Cyclic glucose C solution now contains free reducing sugar
H OH glucose and fructose that form red
O precipitate when heated with Fehlings
O reagent.
CH2OH
C OH H C
HOCH2 H
C C
Cyclic fructose
H OH

Sucrose

PAST YEAR QUESTIONS

A. OBJECTIVE
1990/27. The composition of Q by weight is 64.3% carbon, 7.1% hydrogen and 28.6% oxygen.
Q reacts with Fehlings reagent to form red precipitate. 0.1 mol of Q required 4480 cm3 of
hydrogen for hydrogenation.
Q is
A CH3CH=CHCHO B CH3CH=CHCH=CHCHO
C HOCH=CHCH=CHCHO D CH2=CHCH=CHCH2COOH
E CHCCH2OH

1991/26. Which of the following compounds does not form yellow precipitate when it is
warmed with alkaline iodine solution?
A CH3CH2OH B CH3CH(OH)CH2CH3
C CH3COCH2CH3 D CH3CH2COCH2CH3
E C6H5COCH3

129
1991/28. The following equation represents the oxidation of propan-2-ol to propanone.
KMnO4/H+
CH3CH(OH)CH3 CH3COCH3
Which of the following reagents can be use as to indicate the reaction is already taken place?
A Sodium B Tollens reagent C NaOH D 2,4-dinitrophenylhydrazine
E I2/NaOH

1992/27. Which of the reagents give positive identification test for propanone and
phenylethanone?
A I2/NaOH B K2Cr2O7/H+ C Fehlings reagent D Tollens reagent
E Bromine water

1992/38. Compound S has empirical formula C2H4O and the relative molecular mass is 88.0.
Hydrolysis of S produces two compounds.
1. CH3COOCH2CH3
2. CH3CH(OH)CH2CHO
3. CH3COCH2CH2OH

1993/27. Calculate the mass of propanone used in the reaction with alkaline iodine solution to
produce 20.4 g of iodoform, CHI3.
A. 0.3 B 1.5 C 3.0 D 6.0 E 8.5

1993/39. Which of the following species attack the carbon atom of the carbonyl functional
group in propanone, CH3CCOH3?
1. H+ 2 Br2 3 CN

1993/40. Which of the following compounds form yellow precipitate with alkaline iodine
solution?
1. C6H5COCH3 2. C6H5CHO 3. C6H5CONH2

1994/27. X has the following properties.

i. Forms white precipitate with silver nitrate solution.
ii. Forms yellow precipitate with 2,4-dinitrophenylhydrazine solution.
X is Cl
A B C
COCH2Cl CH3 CHO Cl COCH3

D E Cl
HOCH2 CH2Cl
CH3 CH2OH

1994/39. Which of the following compounds form yellow precipitate with alkaline iodine
solution?
1. CH3CH2COCH2CH3 2. CH3CH2COCH3 3. C6H5COCH3

130
1995/24. Compound X decolourized potassium permanganate solution when reflux. The mixture
is let cold and followed by acidified with dilute sulphuric acid to produce white precipitate. X is
A ethanol B ethanal C propanone D propan-2-ol E toluene

1995/27. Y is warmed with acidified sodium dichromate solution. The colour of the reacting
mixture changes from orange to green. Further adding of acid to the mixture causes the forming
of white precipitate.
Y is

A NH2 B OH C COCH3 D CHO

E COCl

1995/39. Which of the following compounds is oxidized by potassium permanganate solution at

room temperature?
1. CH3CH2CH2OH 2. CH3CH(CH3)CHO 3. CH3CH(CH3)OH

1996/39. Q has the following properties.

1. Neutral
2. Form red precipitate with fehlings reagent.
3. Form white fumes with PCl5.
Q is HOOC
A OH B HOCH2 C
CH2OH
CH2OH CHO
H3C
D H3COCO CHO E HOCH2

CH2CHO

1996/56. Compound X is made up of 62.1% carbon, 10.3% hydrogen and 27.6% of oxygen by
weight. Which of the following statements is true for X?
1. The empirical formula of X is C3H6O.
2. X has a hydroxyl functional group.
3. X has a carbonyl group.

1997/39. Which of the following methods can not be used for the differentiation of CH3CHO and
CH3COCH3?
A Mass spectrometer B Tollens reagent C Iodoform test
D Fehlings reagent E Oxidation

131
1997/57. X reacts with 2,4-dinitrophenylhydrazine to form yellow precipitate. Evaporation of
0.218 g of X at 50 oC produces 0.10 dm3 of vapour X at the standard pressure of 101.1 kPa.
Which of the following statements is true for X?
1. X is an aldehyde.
2. X is a ketone.
3. The empirical formula of X is C3H6O.

1998/41. Below are structural formulae of glucose and fructose.

H H H OH H H H H H H O H

HC C C C CC=O HC C C C C C H

HO HO HO H OH HO HO HO H HO
Glucose Fructose

Which of the following is not true for glucose and fructose?

A Glucose is isomer for fructose.
B Glucose has more chyral carbon than fructose.
C Fructose is the only product of hydrolysis of sucrose.
D Glucose and fructose have different functional group.
E Glucose and fructose are reducing sugar.

1998/58. Which of the following pair of compounds react to form an alcohol with the following
structure?
C(CH3)2OH

1. MgBr and CH3COCH3 2. COCH3 and CH3MgBr

3. COCH3 and CH3Li

1999/38. X has the following properties.

i. It forms yellow precipitate with 2,4-dinitrophenylhydrazine.
ii. It gives yellow precipitate with alkaline iodine solution.
X is
A C6H5CHO B C6H5CH(OH)CH3 C C6H5COCH3 D C6H5COCl
E C6H5COOCH3

1999/58. Below is the mechanism of reaction between hydrogen cyanide and ethanal.
O O OH
+
H
CH3 C H + CN [ CH3 C H ] CH3 C H

CN CN

132
In this reaction
1. The carbon atom of the carbonyl functional group has low electron density.
2. The temperature for the reaction is higher than the room temperature.
3. The nitrogen atom in the cyanide ion donated one non-bonding electron in bond
formation.

2000/38. X decolourizes the purple colour of acidified potassium permanganate and also form
yellow precipitate with alkali iodine solution.
X is
A CH3COCH3 B (CH3)3COH C CH3CH(OH)CH3 D CH3CH2CHO
E C6H5CHO

2000/39. Which of the following compounds would go through nucleophilic addition reaction?
A CH3CH3 B CH3CH2Br C CH3CH2OH D CH3CHO E C6H6

2000/58. X has the following properties.

i. It forms yellow precipitate with 2,4-dinitrophenylhydrazine.
ii. It gives yellow precipitate with alkaline iodine solution.
iii. It forms silver mirror with Tollens reagent.
X is
1. benzaldehyde 2. propanone 3. ethanal

2001/33. X is oxidized to Y, a compound that does not give a positive test when treated with
Fehlings reagent. X is
A CH3COCH3 B CH3CH(OH)CH3 C CH3CH2CH2OH D (CH3)3COH

2001/35. X has the following properties.

i. Form yellow precipitate with alkali iodine solution
ii. Oxidized by acidified potassium permanganate to an acid
iii. Releases hydrogen when react with sodium.
X is
A CH3CH2CH(OH)CH3 B (CH3)3COH C CH3CH2OH D C6H5COCH3

2002/36 A compound Q reacts with hydrogencynide to form an organic compound, which can
be further hydrolyzed when reflux with dilute hydrochloric acid to produce final product Q with
the following structural formula RCH2COOH.
Q could be
A Aldehide
B Ketone
C Carboxylic Acid
D Ester

133
2003/28. The compound 2-(phynylmethyl)-2-butanol, CH3CH2C(OH)CH3 can be
|
CH2

prepared from the reaction between the Grignard reagent, X, and compound Y below except for
X Y

A CH3MgBr CH2COCH2CH3

B CH3CH2MgBr CH2COCH3

C CH3CH2CH2MgBr COCH3

D CH2MgBr CH3CH2COCH3

2003/48. The disgram below shows a set of apparatus for the reaction between a compound X
and an acidic solution of potassium dichromate(VI).

Condenser
Water

X + potassium dichromate (VI) +

Concentrated sulphuric acid
If the colour of the solution changes from orange to green, compound X could be
1. C6H5OH
2. C6H5CHO
3. C6H5CH2OH

2005/34. The structural formula of progesterone, a sex hormone, is shown as follow

134
 CH3 COCH3
CH3

Which of the following statements is true of progesterone?

A It has a planar ring structure
B It has three chiral carbon atom
C It reacts with Fehling solution
D It reacts with aqueous potassium manganate(VII).

B. STRUCTURED
1995/5. a) Draw structural formulae for all isomers of ester with molecular formula C5H10O2. [3]
b) The product of hydrolysis of one of these isomers of the ester gives a positive iodoform test.
i) Write the structural formula for the isomer.
ii) Write the structural formulae for the products formed when the ester is reduced by
using LiAlH4. [3]
c) Salicylic acid reacts with ethanoylchloride to give an ester.
i) Write an equation for the reaction.
ii) State a test to be use for the identification of the ester. Explain your answer. [4]

2005/4(b) Draw the structure of the major product of each of the following reactions.
i. CH3CH2MgBr
(iv) CHO
ii. H3O+ [1]

C. ESSAY
1991/8. Explain the following observations and write equations for the reactions involved.
(a) Both ethanol and propanone form yellow precipitate in the iodoform test. [6]
(b) Both ethanal and propanone form orange precipitate when added 2,4-
dinitrophenylhydrazin solution, but only ethanal forms silver mirror when heated with
Tollens reagent. [5]

1992/7. b) Differenciate pentane-2-one and pentane-3-one by giving the suitable reagent,

observation and write reagent involved. [4]

1992/8. b) Explain what it meant by condensation reaction by using an aldehyde as example.

1993/6. a) A, C3H6O forms orange precipitate when reacts with 2,4-dinitrophenylhydrazin.

Compound A also turns yellowish solution of acidified chromic acid to green.

135
b) B, C4H8O, reacts with LiAlH4 to form compound D, C4H10O. Both compounds B and D form
yellow precipitate with alkaline iodine solution.
Determine the structural formulae of B,C and E by giving reasons and write suitable equations of
reaction involved. [10]

1994/6. b) By suitable example, explain Nucleophilic addition reaction. Your answers should
include suitable equations and conditions for reactions. [2]

1998/7. a) Compound X, C5H10O form orange precipitate with 2,4-dinotrophenylhydrazin and

yellow precipitate with iodine in aqueous sodium hydroxide solution. However, it does not form
silver mirror with Tollens solution.
Determine the structural formula of X and its name by giving reason and suitable equations
involved.

1999/8. b) X and Y have the following structural formulae.

O O
X is C Y is C
H OCH(CH3)2
State the reagent and the condition of reaction, give observation and write suitable equation of
reaction for
i) preparation of X and Y
ii) a chemical test to differentiate X from Y.

2003/9 (b). Glucose, C6H12O6, is a monosaccharide which is an important source of energy.

(i). Draw the structural formula of glucose.
(ii). Blood glucose can be detected by using the Fehling reagent. Based on the
structural formula of glucose, explain the reaction between glucose and the Fehling reagent.
(iii). Sorbitol is a sweetener which is used by diabetics to replace glucose. Sorbital can
be prepared by reduction of glucose. Write an equation for the reaction involved in the
preparation of sorbitol from glucose. [7]

Answer:
1990:27A 1991:26D, 28D 1992:27A, 38D(1) 1993:27C 39E(3), 40D(1)
1994:27A, 39C(2,3) 1995:24E, 27D, 39B(1,2) 1996:39E, 56(1,3) 1997:39C, 57A(All)
1998:41C, 58A(All) 1999:38C, 58D(1,2) 2000:38C, 39D, 58E(3) 2001:33B, 35C

136
CHAPTER 7
CARBOXYLIC ACIDS AND DERIVATIVES
1. INTRODUCTION
Carboxylic acids are organic compounds that have a carboxyl, COOH, functional group in their
molecules. Carboxylic acids are represented by a general formula, CnH2n+1COOH.

2. HOMOLOG SERIES OF CARBOXYLIC ACID

n Formula Name
0 H2COOH Methanoic acid
1 CH3COOH Ethanoic acid
2 C2H5COOH Propanoic acid
3 C3H7COOH Butanoic acid
4 C4H9COOH Pentanoic acid
5 C5H11COOH Hexanoic acid
6 C6H13COOH Heptanoic acid
7 C7H15COOH Octanoic acid
8 C8H17COOH Nonanoic acid

3. NOMENCLATURE OF CARBOXYLIC ACIDS

Carboxylic acids are named according to it equivalent alkanes by replacing the sub-scribe of
ane of the alkane by oic acid in the carboxylic acid. Since the COOH functional group is
always at the first carbon, its position usually is not stated.

Examples:
CH3CH2CH2COOH is buthanoic acid
(CH3)2CHCOOH is 2-methylpropanoic acid

CH3CH2CH2CH2COOH is pentanoic acid

CH3CH2CH(CH3)COOH is 2-methylbutanoic acid
CH3CH(CH3) CH2COOH is 3-methylbutanoic acid
CH3C(CH3)2COOH is 2,2-dimethylpropanioc acid
HO
COOH COOH

OH
2-hydroxi-2,4-dimethylhexanoic acid
4-ethyl- 4-hydroxi-2-methylhexanoic acid
HOOCCOOH is ethanedioic acid
HOOCCH2COOH is propane-1,3-dioic acid COOH

HOOCCH(NH2)COOH is 2-aminopropane-1,3-dioic acid Cyclohesanoic acid

137
 COOH is Benzoic acid (White crystalline solid)
(The COOH functional group is attached to the aromatic ring)
OH

COOH is 2-hydroxibenzoic acid

4. BONDING OF CARBOXYLIC ACID

Oxygen atom is much electronegative than carbon and hydrogen. The CO and OH bonds are
polarized, where oxygen atom has a - pole while carbon and hydrogen atom have a + pole.
The carboxyl group:
O

C O H
+ +
Effects of bonding to
4.1. Physical properties
Carboxylic acid molecules form hydrogen bond between molecules.

CH3COOH OOCCH3
H
Hydrogen bonding
Carboxylic acids are liquids with high boiling point due to the formation of hydrogen bond
between molecules of acid.
Carboxylic acids dissolve in water by forming hydrogen bond with water molecules. However,
the solubility decreases as the size of the hydrocarbon (hydrophobic) becomes bigger.
Dimerization of carboxylic acid molecules in organic solvent through forming of inter molecular
hydrogen bond.
O------- HO
CH3C CCH3
OH -------O

4.2. Chemical properties

The reactions of carboxylic acid are divided into two major types, depending on how bond is
broken at the OH functional group.
O

H C+ O H+

a. Cleavage of CO bond b. Cleavage of OH bond

Neucleophilic substitution Examples: Displacement
Examples: Chlorination Neutralization
Esterification

138
5. CHEMICAL PROPERTIES OF CARBOXYLIC ACID
5.1 Cleavage of OH bond
5.1a Displacement reaction
Carboxylic acids and Benzoic acid are weak acids. However, they are stronger than the acidity
of alcohol and phenol. Proton, H+, in the COOH functional group can only be displaced by
reactive metals like sodium and potassium at room temperature to give hydrogen gas.
Reagent: Sodium
Condition: room temperature
Observation: Colorless gas is liberated and gives pop sound when ignited.
2CH3COOH + 2Na 2CH3COONa + H2
Ethanoic acid

2 COOH + 2Na 2 COONa + H2

Benzoic acid

5.1b Neutralization reaction

Carboxylic acids are stronger acid than water and carbonic acid.
The relative strength of acids:
alcohol < water < phenol < carbonic acid < carboxylic acid
Carboxylic acids readily dissociate in water to give H+ ion.
RCOOH(aq) + H2O(aq) RCOO(aq) + H3O+(aq)
*Refer to the chemistry of carbon for the effect of neighboring group to the acidity of carboxylic
acid.

Thus, the aqueous solution of carboxylic acid is acidic and neutralizes aqueous solutions of
strong alkali like sodium hydroxide or potassium hydroxide and to give soluble salt and water.
The solution also liberates carbon dioxide when added to carbonate salt.

Acid conjugate base

ROH RO
Acid H2O HO Base
Strength C6H5OH C6H5O strength
Increase H2CO3 CO3 increase
RCOOH RCOO
HCl Cl
Reagent: Aqueous NaOH solution
Condition: Room temperature
CH3COOH + NaOH CH3COONa + H2O

COOH + NaOH COONa + H2O

Sodium benzoate (soluble)

Reagent: Aqueous Na2CO3 solution

Condition: Room temperature

139
Observation: Colorless gas, changing lime water chalky.
2CH3COOH + Na2CO3 2CH3COONa + H2O + CO2

2 COOH + Na2CO3 2 COONa + H2O + CO2

5.2 Cleavage of CO bond

Nucleophilic substitution involved breaking of CO bond and OH functional group is
substituted by another nucleophiles.
5.2a Esterification
Carboxylic acids forms ester when reacts with alcohols in the present of concentrated sulphuric
acid as catalyst. Ester is produced in the reaction gives sweet fragrant of fruits.
Reagent: Ethanol and concentrated sulphuric acid as catalyst
Condition: Heat
Observation: Sweet fragrant of fruits is given out
CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O
Ethanoic acid ethylethanoat

COOH + CH3CH2OH COOCH2CH3 + H2O

Benzoic acid Ethylbenzoat

5.2b Chlorination
Reagent: SOCl2 (or PCl5)
Condition: Room temperature (or heat, when PCl5 is used)
Observation: White fume is given out.
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
Ethanoic acid Ethanoyl chloride white fume

COOH + PCl5 COCl + POCl3 + HCl

Benzoyl chloride
This is a test for the present of OH functional group in carboxylic acids.

5.3 Other reaction of carboxylic acids

5.3a. Reduction of carboxylic acids
Reagent: LiAlH4, dry ether
Condition: Room temperature
Reduction of carboxylic acids gave primary alcohols.
CH3COOH + 4[H] CH3CH2OH + H2O
Ethanoic acid Ethanol

COOH + 4[H] CH2OH + H2O

Phenylmethanol

5.3b. Decarboxylation of carboxylic acid

140
Reagent: NaOH(s)
Condition: Heat
Decarboxylation involves eliminating the carboxyl group from the carboxylic acid to give
hydrocarbon.
CH3COOH + 2NaOH CH4 + Na2CO3 + H2O
Ethanoic acid methane

COOH + 2NaOH + Na2CO3 + H2O

Benzene

6. METHANOIC ACID
Methanoic acid, HCOOH, is the strongest carboxylic acid.
It has reducing property as aldehydes.
6.1 Tollens reagent:
Reagent: AgNO3 in ammonia solution
Condition: Heat
Observation: Silver mirror is formed
HCOOH + 2[Ag(NH3)2]+ 2Ag(s) + CO2 + 2NH4+ + 2NH3
Silver mirror

6.2 Fehlings reagent:

Reagent: CuSO4 in sodium hydroxide
Condition: Heat
Observation: Red precipitate
HCOOH + 2Cu2+ + 4OH Cu2O(s) + CO2 + 3H2O
Red precipitate

6.2 Decolorizing the purple color of acidified potassium permanganate

Reagent: KMnO4 in dilute sulphuric acid
Condition: Heat
Observation: The purple color of potassium permanganate is decolorized.
HCOOH + [O] CO2 + H2O

6.4 Methanoic acid dehydrates when heated with concentrated sulphuric acid.
Reagent: Con. sulphuric acid
Condition: Heat
HCOOH CO + H2O
Flame test: When lighted at the open end of a delivery tube fitted to the test tube, CO burns and
gives a blue flame.

7. ETHANEDIOIC ACID

141
Ethanedioic acid, (COOH)2, is crystalline solid at room temperature. It also has reducing
property as the methanoic acid. However, it is a weaker reducing agent than methanoic acid.

7.1 Ethanedioic acid decolorizes the purple color of acidified potassium permanganate
Reagent: KMnO4 in dilute sulphuric acid
Condition: Heat
Observation: The purple color of potassium permanganate is decolorized.
(COOH)2 + [O] 2CO2 + H2O

7.2 Ethanedioic acid dehydrates when heated with concentrated sulphuric acid.
Reagent: Con. sulphuric acid
Condition: Heat
(COOH)2 CO + CO2 + H2O
Flame test: When lighted at the open end of a delivery tube fitted to the test tube, CO burns and
gives a blue flame.
It also produces CO2, and turns lime water chalky.

8. PREPARATION OF CARBOXYLIC ACIDS

8.1. Oxidation of primary alcohols or aldehydes by acidified potassium permanganate with
heating.

CH3CH2OH + 2[O] CH3COOH + H2O

CHO + [O] COOH

8.2. Hydrolysis of cyanide or amide under acidic or alkali condition.

Under acidic condition:
H2O, H+
CH3CH2CN + H2O CH3CH2CONH2 CH3CH2COOH + NH4+
Cyanide amide Propanoic acid

Under alkali condition:

CONH2 + NaOH COONa + NH3*

Benzalmide Sodium benzoate

HCl(aq)

COOH(s)
Benzoic acid

9. TEST OF CARBOXYLATE ANION

142
9.1. Reagent: Aqueous FeCl3 solution
Condition: Heat
Observation: Brown solution turns to brown precipitate upon heating.

3CH3COO + FeCl3 + 3H2O Fe(OH)3 (s) + 3CH3COOH + 3Cl

9.2. Reagaent: Aqueous CaCl2 solution

Condition: room temperature
Observation: white precipitate

C2O42 + Ca2+ CaC2O4(s)

10. FATTY ACIDS

Fatty acids are organic acids obtained from the hydrolysis of fats or oils.
Fats and oils are triglycerides (ester). When hydrolyzed, they give glycerol and fatty acids.
CH2OOCR CH2OH + HOOCR

CHOOCR + 3H2O CHOH + HOOCR

CH2OOCR CH2OH + HOOCR

Triglyceride Glycerol Fatty acids

R, R and R are straight chain alkyls. Naturally occuring fatty acids have even number of carbon
atom range from 12 to 20 carbon atoms. They can be saturated or unsaturated alkyl with one or
two or three C=C double bond.
If R (R or R) is consists of saturated alkyl, the fatty acid is called saturated fatty acid.
Example:
CH3(CH2)10COOH is Lauric acid
CH3(CH2)12COOH is Myristic acid
CH3(CH2)14COOH is palmitic acid
CH3(CH2)16COOH is stearic acid
If R (R or R) is consists of unsaturated alkyl with C=C double bond, the fatty acid is called
unsaturated fatty acid.
Unsaturated fatty acid with only one C=C bond is called monounsaturated fatty acid.
Example:
CH3(CH2)5CH=CH(CH2)7COOH is palmitoleic acid
CH3(CH2)7CH=CH(CH2)7COOH is oleic acid
Unsaturated fatty acid with two or three C=C bonds is called polyunsaturated fatty acid.
Example:
CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH is linoleic acid
CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH is linolenic acid

10. DERIVATIVES OF CARBOXYLIC ACIDS

143
10.1 INTRODUCTION
Derivatives of carboxylic acid are organic compounds derived from the carboxylic acids. The
genaral formula is RCOX.
O
RC
X (X = Chlorine in acylchloride; X = OR in ester, R is alkyl or phenyl; X = NH2 in
amide)

10.2 THE HOMOLOG SERIES AND NOMENCLATURE

Acylchlorides Esters Amides

O O O
RC (or RCOCl) RC (or RCOOR, OR RC (or RCONH2)
Cl is from alcohol) NH2
OR
Drop oic acid from the name Write the name of alkyl of Drop oic acid from the name of
of carboxylic acid and replace alcohol in front. Drop oic carboxylic acid and replace by
amide.
by oyl chloride. acid from the name of Examples:
Examples: carboxylic acid and replace by Primary amide: with NH2.
HCOCl is methanoylchloride oate. HCONH2 is methaamide
CH3COCl is ethanoylchloride Examples: CH3CONH2 is ethanamide
CH3CH2COCl is HCOOCH3 is CH3CH2CONH2 is propanamide
propanoylchloride methylmethanoate CONH2 is benzamide
CH3COOCH3 is
COCl is methylethanoate Secondary amide: with NHR
CH3CH2COOCH3 CH3CONHCH3 is N-
benzoylchloride methylpropanoate methylethanamide
N indicate the methyl is attached to
HCOOCH2CH3 nitrogen atom
ethylmethanoate
CH3CH2CONH is N-
COOCH3 phenylpropanamide
methylbenzoate
Tertiary amide: with NRR
CH3CH2CON(CH3)2 is N,N-
dimethylpropanamide
COO
CON(CH3)CH2CH3
phenylbenzoate
is N-ethyl-N-methylbenzamide
Alkyl groups are name according to
the alphabetical order.

10.3 BONDING, PHYSICAL AND CHEMICAL PROPERTY

Acylchlorides Esters Amides

144
 O O
+ +
RC
Cl-
C Cl bond is polarized and
the molecule is polar
molecule.
Physical properties:
Volatile liquid with low
boiling point. Highly soluble
in water due to hydrolysis
producing highly acidic
solution accompanied by the
release of white fume.
Chemical properties:
Cl is good leaving group.
Thus Cl is easily substituted by
other nucleophiles and the
compound is highly reactive in
reactions.
Reactions are non-reversible
and occur at the room
temperature.
RC
-
OR
C O bond is polarized and
the molecule is polar
molecule.
Physical properties:
Volatile liquid with low
boiling point. The compound
has distinctively sweet
fragrant of fruits. Insoluble in
water. It is a good solvent.
Chemical properties:
RO is not a good leaving
group. Thus, RO is not
easily substituted by other
nucleophiles and the
compound is relatively less
reactive in reactions.
Reactions are reversible and
needed the assistant of
catalyst and heating
O
+
RC
-
NH2
C N bond is polarized and
the molecule is polar molecule.
Molecules form intermolecular
hydrogen bond.
Physical properties:
The liquid is less volatile with
relatively high boiling point.
Slightly soluble in water
through forming hydrogen
bond with water molecule.
Chemical properties:
NH2 is not a good leaving
group. Thus, NH2 is not
easily substituted by other
nucleophiles and the
compound is relatively less
reactive in reactions. It is a
weak base.
Reactions are reversible and
needed the assistant of catalyst
and heating

10.4 PREPARATION AND CHEMICAL REACTIONS

10.4.1 Acylchlorides
O
+
RC
Cl-

10.4.1a Preparation
r.t
CH3COOH + SOCl2 CH3COCl + HCl + SO2
Ethanoyl chloride
COOH+ SOCl2 COCl + HCl + SO2

Benzoyl chloride

10.4.1b Reactions
10.4.1b.i Hydrolysis with water.
Produce related carboxylic acid and white fume.

145
CH3COCl + H2O CH3COOH + HCl
White fumes

10.4.1b.ii Formation of ester.

CH3COCl + C2H5OH CH3COC2H5 + HCl
Ethylethanoate

COCl + ONa COO + NaCl

Phenyl benzoate

10.4.1b.iii. Formation of amides

CH3COCl + 2NH3 CH3CO NH2 + NH4Cl
Ethaneamide (1o amide)

COCl + 2CH3NH2 CONHCH3 + CH3NH3Cl

N- methylbenzamide

10.4.1b.iv Friedel-Crafts acylation in the present of catalyst, AlCl3, with heating.

Forming aromatic ketones.

CH3COCl + + COCH3 + HCl

Phenyl ethanone

COCl + CO + HCl

Diphenyl methanone

10.4.2.Esters
O
R C+
O-R

10.4.2a Preparation:
CH3COCl + C2H5OH CH3COOC2H5 + HCl
Ethyl ethanoate

COCl + ONa COO + NaCl

Phenyl benzoate

10.4.2b Reaction

146
10.4.2b.i. Hydrolysis
Reactions:
RCOOR + H2O RCOOH + ROH 1
NaOH + RCOOH RCOONa + H2O 2
The hydrolysis can be conducted with heating in alkali or acidic condition.

Alkali condition
Hydrolysis of ester in alkali solution is irreversible or a complete reaction.
Under alkali condition, the second reaction used up RCOOH and shifted the equilibrium position
of the first reaction to the right continuously. Thus, the overall process is irreversible and
hydrolysis of ester in alkali solution is more effective.
RCOOR + NaOH RCOONa + ROH

Acidic condition
Hydrolysis of ester in acidic solution is reversible and incomplete. The second reaction is not
exist.

The products of carboxylic acid and alcohol can be used for the identification of the molecular
structure of the ester.
CH3COOC2H5 + H2O + NaOH CH3COONa + H2O
Phenol

COO + C2H5OH + H2O COOH + OH

10.4.2b.ii. Reduction of ester by LiAlH4, at room temperature

Produces alcohols.
CH3CO OC2H5 + 4[H] 2CH3CH2OH
Pt
COO + 9H2 CH2OH + OH

10.4.3 Amides
O
R C+

147
 O-R

10.4.3a Preparation

CH3COCl + 2NH3 CH3CONH2 + NH4Cl

Ethaneamide (1o amide)

COCl + 2CH3NH2 CONHCH3 + CH3NH3Cl

N- methylbenzamide

10.4.3b Reaction

10.4.3b.i Hydrolysis
The hydrolysis can be conducted by heating in acidic or alkali condition.
RCOONH2 + H2O RCOOH + NH3 .1
HCl + NH3 NH4Cl ..2

Acidic condition
Hydrolysis of amide in acidic solution is irreversible or a complete reaction.
The second reaction used up NH3 and shifted the equilibrium position of the first reaction to the
right continuously. Thus, the overall process is irreversible and hydrolysis of ester in acidic
solution is more effective. In addition to that, the process does not produce ammonia gas.
RCOONH2 + HCl RCOOH + NH4Cl
Hydrolysis of amide in acidic solution is irreversible and a complete reaction. Thus is more
effective.

Alkali condition
Hydrolysis of amide under alkali solution is reversible and produces salt and ammonia (amines).
RCOONH2 + H2O RCOOH + NH3
NaOH + RCOOH RCOONa + H2O
Overall: RCOONH2 + NaOH RCOONa + H2O
The products of carboxylic acid and ammonia or amine can be used for the identification of the
molecular structure of the amide.
Hydrolysis of primary amide gives ammonia, that follow by the releases of gas with pungent
smell.

CH3CONH2 + NaOH CH3COONa + NH3

148
Primary amide ammonia CH3
CO
Hydrolysis of secondary amide gives primary amine that forms an oily layer on top of the
aqueous solution.

CONH + NaOH COONa + NH2

Secondary amide Primary amine

Hydrolysis of tertiary amide gives secondary amine that forms an oily layer on top of the
aqueous solution.

N(CH3)2+ NaOH Tertiary amide

amide
CH3CO ONa + (CH3)2NH
Secondary amine

10.5 FAT AND OIL AND USES OF ESTER

Fat and oil are ester of glycerol and fatty acids. Fat is solid at room temperature and oil is liquid.
Fats and oils are triglycerides (ester). When hydrolyzed, they give glycerol and fatty acids.
CH2OOCR CH2OH + HOOCR

CHOOCR + 3H2O CHOH + HOOCR

CH2OOCR CH2OH + HOOCR

Triglyceride Glycerol Fatty acids

R, R and R are straight chain alkyls. Naturally occurring fatty acids have even number of
carbon atom range from 12 to 20 carbon atoms. They can be saturated or unsaturated alkyl with
one or two or three C=C double bond.
Triglycerides with all saturated fatty acids form saturated fat and appear to be solid at room
temperature. On the other hand, triglycerides with any of the fatty acids are not saturated form
unsaturated oil and appear to be liquid at room temperature.

Unsaturated oil is converted to saturated fat or margarine by a process called hydrogenation. This
process is catalyzed by Nickel at 200oC.
CH2OOC(CH2)14CH3 CH2OOC(CH2)14CH3

CHOOC(CH2)7CH=CH(CH2)7CH3 + 2H2 CHOOC(CH2)16CH3

CH2OOC(CH2)7CH=CH(CH2)7CH3 CH2OOC(CH2)16CH3
Unsaturated oil saturated fat / margarine
Hydrolysis of triglycerides in fat or oil by concentrated NaOH solution with heating in the
process called saponification produce sodium carboxylate that called soap.

149
 CH2OOC(CH2)14CH3 CH2OH + CH3(CH2)14COONa

CHOOC(CH2)16CH3 + 3NaOH CHOH + CH3(CH2)16COONa

CH2OOC(CH2)14CH3 CH2OH + CH3(CH2)14COONa

Fat Glycerol soap

Esters give good fragrant of fruits and they are used as food flavoring.
Examples:
Methyl butanoate (apple flavor), pentyl ethanoate (banana flavor), octyl ethanoate (orange
flavor) and pentyl buthanoate (apricot flavor).

Ester also used as food preservative.

Example: ethyl-4-hydroxibenzoic acid

Ester for synthetic polyester.

Examples: PET, Terylene, Mylar and fortrel.

Ester for medical purposes:

Examples:
OH OH OOCCH3
COOH COOCH3 COOH
Salicylic acid methyl salicylate Aspirin
(analgesic)
Wintergreen oil.

150
PAST YEARS QUESTION
OBJECTIVE
1990/28. Compounds Y (C2H4O2) and Z (C4H8O2) are produce when compound X is refluxed
with ethanol. X, Y and Z could be
X Y Z
A CH3CH2CH2COOH HOCH=CHOH CH3CH2COOCH3
B CH3CH2COCH3 CH3COOH CH3CH2CH2COOH
C CH3CH2CH2CHO HCOOCH3 CH3CH2COOCH3
D CH3CH2COOCH3 CH3COOH CH3COOCH2CH3
E (CH3CO)2O CH3COOH CH3COOCH2CH3

1990/29. N-phenylethananide, CH3CONH is prepared by

A CH3CONH2 and Cl B CH3CHO and NH2

C CH3COCl and NH2 D CH3Cl and NHCOH

E CH4 and NHCOCl

1990/39. Which of the following statement is true for ethyl ethanoate?

1. Ethyl ethanoate is coloules liquid.
2. Ethyl ethanoate is produce by the reaction of ethanol and ethanoyl chloride.
3. Ethyl ethanoate reacts with HCl to produce ethanoyl chloride.

1991/39. Ethanoyl anhydrous, (CH3CO)2O, is used for the synthesis of

1. CH3COOCH2CH3 3. CH3CH2OH
2 COOH
CH3COO

1992/28. Hydrolysis of ethyl ethanoate is prefer to be carried out in sodium hydroxide solution
followed by addition of hydrochloric acid than hydrolysis carried out in hydrochloric acid
solution because
A Hydrolysis of ethyl ethanoate in acidic condition required more heat.
B The OH ion is better catalyst than the H+ ion.
C Hydrolysis of ethyl ethanoate in alkaline solution is non reversible.
D Ethyl ethanoate need to be neutralized with NaOH first before it can be hydrolyzed.
E Hydrolysis of ethenoate in alkaline solution form gaseous products.

1992/30. 25.0 cm3, 10.0 g dm-3 of solution of acid Z (C4H6O3) requires 24.5 cm3, 0.10 mol dm-3
of NaOH for complete neutralization. Acid Z is
A monobasic acid B dibasic acid C tribasic acid D anhydrous acid

151
E ester

1993/28. Which of the following pairs of compounds is most likely not to produce an ester?
A Ethanoic acid and propan-1- ol B Ethanoyl chloride and propan-1-ol
C Benzoic acid and propan-1-ol D Ethanoyl chloride and phenol
E Benzoic acid and phenol

1994/28. Hydrolysis of X produces a white precipitate. 1.0 mole of the white precipitate requires
2.0 moles of potassium hydroxide for complete reaction. X is
A CH3COCl B C6H5CH2Cl C C6H5CCl3 D (CH3CO)2O
E NCC6H4CN

1995/28. X contents 38.4% chlorine and it reacted actively with water to produce white fumes.
X is
A CH3COCl B CH3CH2COCl C CH3CH2Cl D CH3CH2CH2Cl
E CH3CH2CH2CH2Cl

1995/31. X contains carbon, hydrogen and oxygen. The molecular mass of X is 60. Combustion
of 1.20 g of X produces 1.76g of CO2 and 0.72g of H2O. Which of the following statements ix
true of X?
1. X contains 0.64g of oxygen
2. X contains 0.04 moles of carbon
3. Molecular formula of X is C2H4O2

1995/40. Which of the following pairs of compounds will react to form CH3COOCH2CH3?
1. CH3COCl and CH3CH2OH 2. CH3CH2I and CH3COOAg
3. CH3CH2OH and (CH3CO)2O

1996/41. A monobasic organic acid Z contents 40.0% carbon, 6.7% hydrogen and 53.3%
oxygen. 0.9g of Z is completely neutralized by 10 cm3, 1.0 mol dm-3 of NaOH. What is the
structural formula of Z?
A CH3COOH B CH3CH2COOH C CH3COCH2OH D CH3COOCH2OH
E HOCH2CH2COOH

1996/42. X is insoluble in water and has empirical formula C7H6O. Hydrolysis of X produces Y
and Z. Compound Y can be oxidized to Z. X, Y and Z could be
X Y Z

A COOCH2 OH CH2COOH

B COOCH2 CH2OH COOH

C COOOCH2 CH2OH COOH

152
D CO CHO COOH

E COOCO CHO COOH

1996/57. Study the following diagram.

KMnO4 / acid KMnO4 / acid
X (C2H4O3) Y(C2H2O3) Z(C2H2O4)
PCl5 PCl5 PCl5
2 mole of HCl 1 mole of HCl 2 mole of HCl
Which of the following statements is true for X,Y and Z?
1. X has COOH and CH2OH functional groups.
2. Y gives yellow precipitate with 2,4-dinitrophenylhydrazine.
3. Z is ethandioic acid.

1996/58. Compound X has the following properties.

i. X reacts with LiAlH4 to form a weak acid.
ii. X decolourized acidified KMnO4
X is
CH3

1. COO 2 COO

3. COOCH2

1997/40. Reaction between the ethanoic acid and LiAlH4 will produce
A CH3CH3 B CH2=CH2 C CH3CHO D CH3CH2OH E CH3COOLi

1997/41
CH3CONH2 and CH3CH2NH2 can be differentiated by using
A Acidified potassium permanganate solution.
B 2,4-dinitrophenylhydrazine solution
C Sodium hydroxide solution
D Alkaline iodine solution
E Tollens reagent

1997/42. Which of the following is true for oil and fat?

A Oil and fat are ester of glycerol
B Oil and fat are products from the hydrolysis of ester
C Fat is unsaturated ester while oil is saturated ester
D Fat is ester from animals and oil is ester from plant

153
E Oil and fat are represented by the following general formula
CH2COOR

CHCOOR (R, R and R are alkyl and alkenyl)

CH2COOR

1998/37. How many acyl chloride isomers can be formed by C5H9OCl?

A 2 B 3 C 4 D 5 E 6

1998/42. Y, C4H8O2 is not oxidized but forms ester. Y is

A CH3CH2COOCH3 B CH3CH2CH2COOH C HOCH2CH=CHCH2OH
D CH3CH(OH)CH2CHO E CH2 CHCH2CH2OH

O
1999/39. Which of the following compounds reacts with PCl5 to form white fumes and is
reduced to primary alcohol?
A CH3CHO B CH3COCH3 C CH3COOH D CH3COOCH3
E (CH3)3COH

1999/40. Which of the following compounds when hydrolyzed, does not form benzoic acid?
A B C
CN COCl COOCH2CH3

D E
COOCH2 CH2COO

1999/42. Y dissolve in water without reacting and is not easily reacts with sodium carbonate. Y
is
A CH3CH(OH)CH2COCl B CH3CH(Cl)CH2COOH
C D E
Cl OH Cl COOH OH

CH2COCl
1999/43. When L, C5H10O2 is hydrolyzed with NaOH followed by the addition of dilute acid, an
organic liquid M, C2H4O2 and N, C3H8O are formed. N form yellow precipitate with alkaline
iodine solution. L is
A CH3CH2COOCH2CH3 B (CH3)2CHCOOCH3 C HCOOCH(CH3)CH2CH3
D CH3COOCH(CH3)2 E CH3COOCH2CH2CH3

1999/48. R, C3H6O2 has the following properties.

i. Dissolve in water and react with Mg to form an inflammable gas.
ii. Dissolve in benzene and form molecule with molecular mass 148.
Which of the following statements id true for R?
1. R has COOH functional group.

154
 2. R forms hydrogen bonding with water molecule.
3. R forms hydrogen bond with each other to produce dimmer in benzene.

2000/40. Which of the following statements is true for ethanoic acid?

A Its acid strength is stronger than the benzoic acid.
B Its boiling point is lower than ethanol
C It is produced by the hydrolysis of ethanitrile in acidic solution.
D It reacts with ethanal to form ester.
E It does not produce hydrogen gas when react with Mg.

2000/59. Ethanoic acid reacts with PCl5 or SOCl2 to form ethanoyl chloride. Which of the
following explain why SOCl2 is more commonly used than PCl5?
1. Percentage of yield is higher.
2. The reaction is easier to be controlled.
3. The side products are gases that easier to be isolated from the reaction mixture.

2001/36.Which of the following carboxylic acid decolourlised potassium permanganate solution?

A HCOOH B CH3COOH C CH3CH2COOH D C6H5COOH

2001/37. Z has the following properties.

i. Reacts with water.
ii. Reacts with alcohol and phenol to form ester
Z is
A CH3CH2Cl B CH3COOH C CH3COCl D C6H5Cl

2002/37 An optically active compound Z, C5H9OCl producing white fumes in moist air and it
also reacts with cold water to produce an acidic solution.
Z could be
A CH3CH2CH2CH2COCl
B CH3CH(CH3)CH2COCl
C CH3COCH2CH2CH2Cl
D CH3CH2CH(CH3)COCl

2002/49 An ester, Ethyl buthanoat is an artificial pineapple flavouring used in food industry.
Which of the following pair of compounds can be used to prepare the ester?
1. CH3CH2CH2COOH and CH3CH2OH
2. CH3CH2CH2COCl and CH3CH2OH
3. CH3CH2COOH and CH3CH2CH2OH

2003/29. What could X and Y be in the following reaction?

H2O C2H5OH
X X CH3CH2COOC2H5
Conc. H2SO4

X Y
A CH3CH2CH2Cl CH3CH2COCl

155
B CH3CH2CH2Cl CH3CH2COOH
C CH3CH2COCl CH3CH2COOH
D CH3COCl CH3COOH

2003/37. Ethanoic acid has a variety of uses. Which of the following is not one of its use?
A As food flavouring
B As solvent in dry cleaning
C For making cellulose acetate polymer
D in the coagulation of latex

2004/31. Aspartame is an artificial sweetener which is used to replace sugar for diabetics. The
structural formula of the sweetener is as follows
O O O
|| || ||
HO C CH2CH C O N CH C OCH3
| | |
NH2 H CH2

Which of the following statements is not true about aspartame?

A Optically active
B A methyl ester
C Has one peptide linkage
D Form two different amino acids when hydrolysed

2004/32. Which of the following compounds reacts easily with cold water?

A Cl B CH2Cl

C CH3CH2Cl D CH3CH2COCl

2004/36. N- Acetylglucosamine, NAG, ia a major component of the crustacean skin. Its

structural formula is
Given as follows.
O
||
CH3C N CHCH(OH)CH(OH)CH(OH)CH2OH
| |
H CHO
What is the name of the functional group of NAG which undergoes hydrolysis?
A Amino B Carbonyl C Hydroxyl D Carboxamide

2004/37. An amount of 2.25g of a monobasic carboxylic acid with empirical formula CH2O
requires 25.00cm3 of 1.00 mol dm-3 aqueous NaOH solution for neutralization. The number of
structural isomers of this acid which undergo dehydration to become alkene and react with
aqueous Na2CO3 solution is [C=12, H=1, O=16]
A 1 B 2 C 3 D 4

156
2004/38. The scheme below shows the cycle of formation of an oily compound X
NaOH(aq),
C8H9NO Oily compound X + CH3COONa

HCl(aq),
SOCl2
CH3COCl CH3COOH

The oily compound X is

A NH2 B NHCH3

C CH2NH2 D CH2CH2NH2

2005/30.What is the product formed when Cl Y CH2CH=CHCl reacts with water at room
temperature?

COCl

A CH2CH=CHCl B CH2CH=CHCl

COOH COCl
Cl Cl

C CH2CH=CHCl D CH2CH2CH(OH)Cl

COOH COOH
OH OH

STRUCTURED
1991/2. a) i) Construct all possible structural formulae of ester from C4H8O2.
ii) Write one equation of reaction for the formation of one of these esters from a
carboxylic acid and alcohol.
iii) Write the structural formula of the products formed by the reduction of
phenylbenzoate. [6]

157
b) X is one of the ester of in a) (i). When X is hydrolysed, it forms Y and Z. When Y is heated
with iodine in aqueous sodium hydroxide, it gives yellow precipitate. When PCl5 is added to Z, it
produces white fume and ethanoylchloride is formed.
i) Identify the structural formulae of X, Y and Z.
ii) Write an equation for the formation of ester X without using any carboxylic acid. [4]

1993/2. a) Y is an amide with relative molecular mass is 149 and it composes 72.5% of carbon,
7.4% of hydrogen, 9.4% of nitrogen and 10.7% of oxygen. Determine the molecular formula of
Y.
b) When Y is boiled with dilute sulphuric acid for a few hours and the mixture is allowed to
cold, no white precipitate is formed. However, an oily primary amine is formed when ammonia
is added. Determine the structure of Y and give explanation to your answer.
Write an equation to show, how the primary amine is formed when ammonia is added to the
mixture.

1994/4. During the preparation of phenylbenzoate, aqueous solution of sodium hydroxide is

added to phenol and is followed by benzoylchloride.
i) Write an equation to show the formation of the ester.
ii) What is the function of sodium hydroxide in the preparation of the ester?
iii) Name the process that can be use for purification of the ester.
iv) State one physical property of the ester that can be use to determine it purity.
v) What is the by product from the preparation of phenylbenzoate.
vi) Is ethanol a suitable solvent to be used during the preparation of the ester? Explain your
answer.
vii) Write equations to show the formation of benzoylchloride from methylbenzene.

2001/3. a) In an aqueous solution, the ethanoate ion reacts with dihydrogenphophate ion
according to the following equation.
CH3COO(aq) + H2PO4(aq) CH3COOH(aq) + HPO42(aq)
Write formulae of acid and its conjugate base for the forward reaction. [2]
b) 4-aminobenzoic acid is one of the ingredient contain in a type of sun block lotion. An aqueous
solution with 0.03 mol dm3 of 4-aminobenzoic acid contains 8.1 x 10-4 mol dm-3 of hydrogen
ions.
i) Write the structural formula of 4-aminobenzoic acid.
ii) Write an equation to show the dissociation of 4-aminobenzoic acid in an aqueous solution.
iii) Calculate the pH value of the aqueous solution of 4-animobenzoic acid.
iv) State the reagent used the condition of reaction and write equation for preparing ethyl-4-
aminobenzoate from 4-aminobenzioc acid. [8]

2004/4(b). Write equation for the reaction between benzoyl chloride, C6H5COCl, and the
following compounds and name the organic products according to the IUPAC nomenclature.
(i) CH3NH2
(ii) CH6H5OH
(c). Aspirin has the following structure

OOCH3

158
 COOH
Give the products formed when aspirin is heated with aqueous potassium hydroxide solution. [4]

ESSAY
1990/8. a) A with relative molecular mass 138, composed of 60.87% of carbon, 4.35% of
hydrogen and 34.78% of oxygen. Compound A reacts with ethanol in the present of concentrated
sulphuric acid to form B, which molecular formula is C8H10O3. Compound A also reacts with
ethanoylchloride to produce C, which is aspirin.
Determine the structural formulae of A, B and C by giving your explanation and write equations
for the reaction involved. Give the IUPAC name of compound A. [15]
b) Give a chemical test to differentiate benzoic acid from phenol. [5]

1991/6. b) Compound A, C6H12O2 is neutral and optically active. Hydrolysis of A gives B,

C2H2O2 and an alcohol C. B reacts with aqueous sodium carbonate solution to give colourless gas
the turns lime water to chalky. Alcohol C is optically active and produces yellow precipitate
when heated with alkaline iodine solution. Oxidation of C by acidified potassium permanganate
gives compound D, which gives orange precipitate with 2,4-dinitrophenylhydrazin.
Determine the structural formulae of A, B, C and D by giving your explanation and write
equations for the reaction involved. [12]

1992/7. e) Give a chemical test that differentiate ethanoylchloride and ethanoic acid. In your
answer, state the reagent, observation and write equation that involved. [4]

1992/8. a) State reagent and condition of reaction required for the following transformations A,
B, C, D, E, F, G and H.
A B
RCONH2 RCOCl RCOOH
C
D E F G
RCOOCH3 RCH2OH RCH2Br RCH2COOH
H
RCH2NH2 [8]

1993/6. c) C, C5H9ClO is optically active. It produces white fume on exposed to moist air and
reacts with ethanol to give D, that give sweet fragrant of fruits.
Determine the structural formulae of C and D by giving your explanation and write equations for
the reaction involved.

1993/7. b) Compound X, C10H12O2, which has sweet fragrant of fruits is hydrolysed under acidic
condition to produce alcohol Y and a carboxylic acid. The alcohol Y reacts with bromine solution
to give a white precipitate. Reduction of X produces alcohol Y and alcohol Z. Dehydration of
alcohol Z by concentrated sulphuric acid to give 2-methylprop-1-ene.
Determine the structural formulae of X, Y and Z by giving your explanation and write equations
for the reaction involved. Give the IUPAC name of compound X.

159
1995/7. Compound A, which molecular mass is 120.5 and it composes 49.8% of carbon, 7.5% of
hydrogen, 29.5% of chlorine and 13.2% of oxygen. Calculate the molecular formula of A.
Compound A is optically active. It forms white fume when expose to moisture in the air. With
this information, determine the structural formula of C. Write all structural formulae for the
isomers of A.

1995/8. a) Compounds B and C share the same molecular formula, C3H6O2. Hydrolysis of B
produces an alcohol D that gives yellow precipitate when heated with alkaline iodine solution. C
reacts with methanol to give E, that has sweet fragrant of fruits. Identify the structural formulae
of B, C, D and E by giving your explanation and write the related equations for the reactions
involved. [10]
c) Methylmethanoate and methanoic acid have same molecular mass. However, the boiling point
of methylmethanoate is 32 oC, while the boiling point of ethanoic acid is 118 oC. Explain this
statement. [4]

1997/7. (a) Compounds X and Y have the following structural formulae.

CH3 CH3
COOH OH
X: Y:

State the reagent and the condition of reaction that can be use for the differentiation of
compounds X and Y. In your answer, include observation and write equation for the reaction
involved.
(b) i) Hydrolysis of butanenitrile, CH3CH2CH2CN under acidic condition forms compound A. A
reacts with phosphorus pentachloride to give an organic compound B. B reacts with ethanol to
give a compound C, that has sweet fragrant of fruits. Determine the structural formulae and state
the IUPAC name of compounds A, B and C.
ii) Write equation of reaction and state the condition of reaction for the preparation of 1-
propaneamine from C.

1998/8. a) Aspartame is an artificial sweetener with the following structural formula.

O O O

HOCCH2CH(NH2)CNCHCOCH3

H CH2

Upon hydrolysis, aspartame produces compounds X, Y and an alcohol. When excess of sodium
carbonate is added to aqueous solution contain equal molar of X and Y respectively, they
produces colourless gas that turns lime water to chalky in the ratio of 2 is to 1.
i) Name all functional groups that present in the molecule of aspartame.
ii) Explain the solubility of aspartame in water.
iii) Determine the structural formulae of X and Y and write the equations involved.

160
2001/9. b) iii) Explain why methanoic acid decolourised the purple colour of potassium
permanganate. [2]

2003/10 (a). Isopentyl ethanoate, CH3COOCH2CH2CH(CH3)2, is a banana flavouring used in the

food industry. State one carboxylic acid which is an isomer of isopentyl ethanoate. Describe the
differences in boiling point and solubility in water between these two isomers. [5]

2005/9(c). Both naphthalene and benzoic acid are aromatic compounds which exist as white
solids. Their molecular structures are given as below.

COOH
Benzoic acid Naphthalene

(i) Based on their physical and chemical properties, describe how you could separate the
mixture of these two compounds without using any organic solvent.
(ii) State one use of each of the above compounds. [7]

2005/10(a) Two isomers M and N have structural formulas as follows.

COOH CONH2

NH2 OH
(M) (N)
(a). Predict the solubilities of M and N in hydrochloric acid and aqueous solution of
sodium hydroxide at room temperature. Write equation for the reactions where appropriate. [5]
(b). State what happened when N is heated gently in hydrochloric acid. [2]
(c). By giving reagents and reaction conditions, show the synthesis of M from 2-
nitrotoluene. Hence show how M can be converted to N. [8]

Answer:
1990: 28E, 29C, 39B(1,2) 1991:39b(1 ,2) 1992:28C, 30A 1993:28E 1994:28E 1995:28B,
31A(1,2,3), 40A(1,2,3) 1996:41E, 42B, 57A(1,2,3), 58C(2,3)
1997:40D, 41C, 42A 1998:37C, 42B 1999:39C, 40E, 42B, 43D, 48A(1,2,3)
2000:40C, 59E(3) 2001:36A, 37C

161
CHAPTER 8
AMINO ACIDS AND PROTEINS
1. INTRODUCTION
Amino acids are organic compounds that have amino, NH2, functional group attached to the
second or carbon of the carboxylic acid. Amino acids are represented by a general formula,
RCH(NH2)COOH, where R represents hydrogen or alkyl.

2. NOMENCLATURE AND EXAMPLES

HCH(NH2)COOH CH3CH(NH2)COOH (CH3)2CHCH(NH2)COOH
2-amino ethanoic acid 2-amino propanoic acid 2-amino-3-methylbutanoic acid
(Glycine) (Alanine) (Valine)

CH2CH(NH2)COOH HO CH2CH(NH2)COOH

2-amino-3-phenyl propanoic acid 2-amino-3-(4-hydroxy) phenyl propanoic acid

(Phenylalanine) (Tyrosine)

H2NOCCH2CH2CH(NH2)COOH HOOCCH2CH2CH(NH2)COOH
(Glutamine) (Glutamic acid)

H2NCH2CH2CH2CH(NH2)COOH HOCH2CH(NH2)COOH
2,5-diamino pentanoic acid 2-amino-3-hydroxypropanoic acid
(Lysine) (Serine)

3. BONDING, ACID-BASE AND PHYSICAL

3.1. Bonding
The amino, NH2 group has a non-bonding electron pair at the nitrogen atom and enable the
amino group to accept proton. Thus, -NH2 is basic.
The carboxyl, COOH has very polar OH bond that easily dissociate to give away H+ ion. Thus,
-COOH is acidic.

3.2. Chemical properties

3.2a. acid-base
Both amino and carboxyl groups exhibit their respective acid-base properties.
Example:
Glycine: H2NCH2COOH
The -COOH functional group as proton donor
H2NCH2COOH(aq) H2NCH2COO(aq) + H+(aq)

The NH2 functional group as proton acceptor

162
H2NCH2COO(aq) + H+(aq) +
H3NCH2COO(aq)
Zwitterion
A zwitterion of glycine is formed.
A zwitterion of an amino acid has a negatively charged end that is the carboxylate ion, COO,
and a positively chargd end that is the ammonium ion, -NH3+ in the same amino acid molecule.
The zwitterion of glycine is isoelectric.
The zwitterion of amino acid exists in both solid and aqueous solution of amino acids.

However, the overall acid-base propertiy of an amino acid depends on the relative number of
group of amino and carboxyl in the amino acid molecule.
Neutral amino acids have equal number of amino and carboxyl group in its amino acid
molecule.
Examples:
Glycine, Alanine, Serine, Valine, Phenylalanine and Tyrosine have one -NH2 and one COOH in
their respective amino acid molecule.
H2NCH2COOH(aq) +H3NCH2COO(aq)

Acidic amino acids have more carboxyl group than the amino group in its amino acid molecules
Examples:
Glutamic acid has two COOH and one NH2 in its amino acid molecule.
HOOCCH2CH2CH(NH2)COOH(aq) [OOCCH2CH2CH(NH3+)COO ](aq) + H+(aq)

Basic amino acids have more amino group than the carboxyl group in its amino acid molecules.
Examples:
Glutamine and Lysine have two NH2 and one COOH in its amino acid molecule.
H2N(CH2)3CH(NH2)COOH(aq) + H2O(l) [H3N+(CH2)3CH(NH3+)COO](aq) + OH(aq)

3.2b. Buffer property

Aqueous solution of amino acid is a buffer solution. The aqueous solution of amino acid contains
zwitterions.
Example: Aqueous solution of glycine
H+ OH
H3N+CH2COOH(aq) H3N+CH2COO(aq) H2NCH2COO(aq) + H2O(l)
(1) Zwitterions (2)

The COO in the zwitterions of amino acid is the conjugate base for acid, COOH. When some
acid is added to an aqueous solution of glycine, the COO of the zwitterions of amino acid
accept a proton and neutralize the acid added.
H3N+CH2COO(aq) + H+(aq) H3N+CH2COOH(aq)
The equilibrium (1) is shifted left. Thus, cancel off the effect due to the addition of the acid.

The NH3+ in the zwitterions of amino acid is the conjugate acid for base, NH2. When some
alkali is added to an aqueous solution of glycine, the NH3+ of the zwitterions of amino acid
donate a proton to neutralize the alkali added.
H3N+CH2COO(aq) + OH(aq) H2NCH2COO(aq) + H2O(l)
The equilibrium (2) is shifted right. Thus, cancel off the effect due to the addition of the alkali.

163
3.3. Physical property
Amino acids are crystalline solid at room temperature with high melting point. This is due to the
present of zwitterions in the ionic crystal lattice of crystals amino acids. Between zwitterions is
strong electrostatic attractive force.
They are soluble in water but insoluble in organic solvent because zwitterions form strong
electrostatic attractive force with water molecules.

4. CHEMICAL REACTIONS
Chemical reactions of amino acids resemble the reactions of carboxylic acids and amines which
have discuss in the previous chapters.

4.1 TESTS FOR AMINO ACIDS

4.1a. The present of -COOH
Reagent: Aqueous Na2CO3 solution
Condition: Room temperature
Observation: Colorless gas, changing lime water chalky.
2H2NCH2COOH + Na2CO3 2H2NCH2COONa + H2O + CO2

4.1b. The present of NH2

Reagent: NaNO2, dilute HCl
Condition: Cold (<5oC)
Observation: Colorless gas is liberated.
Amino acids are primary amines, form diazonim ion that decomposes further to give nitrogen
gas.
H2NCH2COOH + HNO2 + H+ HOCH2COOH + 2H2O + N2

4.1c. Forming of complex

Reagent: CuSO4 solution
Condition: room temperature
Observation: Light blue solution turns dark blue
Amino acids are chelate agent that form complex ion with transitionmetal ion.
2H2NCH2COO (aq) + Cu2+(aq) [Cu(H2NCH2COO)2]2+(aq) + 2H+(aq)

4.2 DIPEPTIDE, TRIPEPTIDE AND PEPTIDE LINKAGE

Two amino acid molecules go through condensation reaction to give dipeptide. The amino acid
molecules are linked togather by an amide functional group, CONH , or the peptide linkage.
Examples:

O O

164
H2NCH2 C OH + H N CH2COOH H2NCH2 C N CH2COOH + H2O
Glycine
H H Peptide linkage / amide group
Glycinylglycine dipeptide
O O Peptide linkage / amide group

H2NCH(CH3)C OH + H N CH2COOH H2NCH(CH3)C N CH2COOH + H2O
Alanine
H H
Alanylglycine dipeptide

Three amino acid molecules go through condensation reaction to give tripeptide.

Examples:
O O

H2NCH2 C OH + H NCH(CH3)C OH + H NCH(CH2OH)COOH
Serine
H H
O O

H2NCH2 C NCH(CH3) C N CH(CH2OH)COOH

H H Glycinylalanylserine tripeptide
Peptide linkage

4.3 POLYPEPTIDE AND PROTEINS

If more amino acids molecules are linked together with the peptide linkage, a straight chain
polymer is formed. The polymer is called polypeptide or protein.
Proteins are classified into three main group based on their shapes or structures.

4.3a Primary proteins:

They are single polypeptide chain. Amino acid monomers are linked together with peptide
linkage.
O O O

(NCH2 C NCH(CH3) C N CH(CH2OH)C)

H H H
4.3b Secondary proteins:
The present of C=O and NH groups in the peptide link that present along the polypeptide chain
enable the formation of intra molecular and inter molecular hydrogen bonds between these
groups. These hydrogen bonds fixed the twists and bends along the polypeptide to form -helix
and -pleated sheet.

165
 Polypeptide chains
Intramolecular
hydrogen bond
-helix

4
polypeptide chains

Intermolecular
hydrogen bond
Pleated sheet

4.3c Tertiary proteins:

In addition to the characteristics of the secondary proteins, tertiary proteins have intermolecular
hydrogen bonds formed at certain position of the -helix or pleated sheet that causes it to twist,
turn and fold at a specific angle to give a specific spheroidal shapes.

-helix twisted and folded at specific

angles to give a spheroidal shape of
tertiary protein
Intermolecular
hydrogen bond

4.4 HYDROLYSIS OF PROTEINS

Polypeptides are strong polymers due to strong peptide linkage. Thus, polypeptide can withstand
pH change and organic solvents.
However in the present of enzine or under vigorous acidic or alkaline conditions, hydrolysis of
proteins takes place to produce amino acids.During hydrolysis, the peptide links are broken up
by the insertion of water molecules.
Example: Hydrolysis of tripeptide
O O Peptide linkage O O
2H2O

H2NCH2C NCH(CH3)C NCH(CH2OH)COOH H2NCH2 C OH + HNCH(CH3)COH

Glycine alanine
H H H
Glycinylalanylserine tripeptide + H NCH(CH2OH)COOH
Serine
H

166
PAST YEARS QUESTIONS
OBJECTIVE
1992/29. The simplest amino acid is glysine, H2NCH2COOH. It dissolves in dilute acid and
alkali solution. What is the ion present when glysine is dissolved in an acid solution at pH 2.5?
A H3N+CH2COO B H2NCH2COO C H3N+CH2COOH
D H2NCH2COOH E H2NCH2CONHCH2COOH

1994/29. Some dilute HCl is added into 2-aminopropanoic solution until the pH of the solution
is 2.0. The particle species present in the solution is
A CH3CHCOOH B CH3CHCOO C CH3CHCOO

NH2 H3N+ NH2

D CH3CHCOOH D CH3CHCOOH

H3N+ NH3Cl

1995/22. Below are structural formulae of amino acids Alanine and leusine.
CH3 (CH3)2CHCH2
H2NCHCOOH H2NCHCOOH
Alanine Leusine
Which of the following statements is true for the compounds?
A Alanine is optically active
B Leusine has geometrical isomers
C Alanine and leusine produces the same mass spectrum
D Alanine and leusine have same dissociation constant
E Alanine and leusine show the same absorption in their respective IR spectrum

1995/29. Which of the following statements is not true for aminoethanoic acid?
A The aqueous solution of the acid conduct electricity
B It has high boiling point
C It forms zwiterion
D It is optically active
E Dissolve in water

1996/59. Which of the following reactions involved when a peptide link is formed between
amino acids or the peptide link is broken during the breaking down of protein?
1. Condensation 2. Hydrolysis 3. Elimination

1997/43. Q has high melting point, dissolves in water to form a neutral solution. Q self
-polymerized to form condensation polymer. Q is
A CH3CONH2 B CH3CONHCH3 C CH3CH2CN
D H2NCH2COOH E H2NCH2CH2OH

167
1997/59. Below is the structural formula of serine.
CH2OH

H2NCHCOOH
Which of the following statement is true for serine?
1. React with nitrous acid to give nitrogen gas.
2. Release ammonia when react with sodium hydroxide.
3. From polypeptide with the following repeating unit.
H O

[O CH2 C C ]

NH2

1998/44. Below is the structural formula of an amino acid.

CH2

H2NCHCOOH
Which of the following statements is true for the amino acid?
A It has geometrical isomers B It forms diazonium ion
C It form zwiterion D It has two chiral carbons
E It forms dimer.

2000/43. Which of the following is true for aminoethanoic acid?

A It relative molecular mass is 150
B It form cation in alkaline solution
C It form zwiterion in aqueous solution
D It dissolves easily in CCl4
E The amino group and the carboxylic group react with sodium hydroxide to form salt.

2001/50. Give is the structural formula of a molecule.

H H O H O

H N C C N C C OH

H H CH3
Which of the following statement is true for the molecule?
1. It can function as a buffer
2. It has peptide link
3. It is amphoteric

168
2002/50. Alanine is an amino acid, with the following structural formula.
H2NCH(CH3)COOH
Which of the following statements is correct with regard to the amino acid?
1. It forms an zwiterion in neutral solution
2. It forms an anion in aqueous solution with pH lower then 7
3. It dissolves in eter

2005/33. The structural formula of a peptide is as follows.

O O O
|| || ||
H2N CH C N CH C N CH C OH
| | | | |
CH2OH H CH2 H CH2CH2CH2NH2
Which of the following is true of the peptide?
A A tripeptide
B Neutral
C Insoluble in water
D Opticllly inactive
2005/39. Compound Z has composition percentage by mass: 40% carbon, 6.7% hydrogen and
53.3% oxygen. Z has a chiral carbon atom and its relative molecular mass is 90.0. Which of the
following stataments is not true of compound Z?
A It can be prepared from propenenitrile
B It prodices effervescence with aqueous NaHCO3
C It produces yellow precipitate when heated with alkaline iodine solution
D It decolourlised acidified potassium manganate(VII) solution when heated

STRUCTURED
1994/5. a) Glycine is the simplest amino acid.
i) Draw the structural formula of glycine.
ii) Write balance equations for the reactions of glycine with aqueous sodium hydroxide and with
ethanol in the present of concentrated sulphuric acid. [4]
b) Alanine, CH3CH(NH2)COOH, and serine, HOCH2CH(NH2)COOH, are two other amino acids
like glycine. They are basic units for protein.
i) Write the structural formula for a tripeptide produced by these amino acids according to the
sequence of glycine, alanine and serine.
ii) What is expected to take place if this tripeptide is dissolved in cold aqueous solution of
sodium hydroxide?
iii) Hydrolysis of protein produces a mixture of amino acids. Give two separating techniques
where by these amino acids in the mixture can be separated.
iv) Draw structural formulae for the enantiomers of alanine. [6]

2000/3. Three structural formulae of amino acids are given as the following.
Lysine: H2NCH2CH2CH2CH2CH(NH2)COOH
Serine: HOCH2CH(NH2)COOH

169
Glutamic acid: HOOCCH2CH2CH(NH2)COOH
These amino acids dissolve in water may produce acidic or alkali solution that depending on the
functional groups present in the particular molecule of the amino acid.
a) Name the functional groups that present in these amino acids. [2]
b) Which of these amino acids form alkali solution when it is dissolves in water. [2]
c) i) Draw two structural formulae of dipeptide formed by lysine and serine.
ii) Name the chemical process where by the dipeptide is converted to it amino acids. [3]
d) Glutamic acid form a type of food flavouring, monosodium glutamate, when it reacts with
dilute aqueous sodium hydroxide. Write an equation for the formation of this food flavouring. [1]

ESSAY
1990/6. b) Write equations for the reactions involved
i) Synthesis of 2-aminoethanoic acid from ethanoic acid.
ii) Formation of dipeptide from 2-aminoethanoic acid. [6]
c) Write structural formulae for the organic products formed as 2-aminoethanoic acid reacts with
i) Aqueous sodium hydroxide
ii) Sulphuric acid
iii) Nitrous acids
iv) Ethanol and concentrated sulphuric acid.
State the acid-base property of the organic products. [8]

1995/7. b) i) What are the functional groups present in the molecule of an amino acid?
ii) Draw structural formula and state the acid-base property of the zwitterion of
2-aminoethanoic acid. [5]
c) Give one chemical test that can be used for the differentiation of a primary amine from an
amino acid. [3]

1998/8. b) Glycine (2-aminoethanoic acid) and alanine (2-aminopropanoic acid) are amino
acids.
i) Draw structural formula of zwitterion of glycine.
ii) Write the equations of reactions for the formation of two different dipeptides from glycine
and alanine. State the name of the dipeptides.
iii) Explain what would happen if alanine reacts with hydrochloric acid. Write the equation for
the reaction.

2002/9b (i) State the functional group that found in an amino acid molecule.
(ii) Glycine or 2-aminoethanoic acid is solid with high melting point and high solubility in water
but insoluble in eter. Explain the statement with the help of the appropriate structural formula the
amino acid.
(iii) Write an equation to show the formation of peptide kink between two glycine molecules.
(iv) Write equations to show the reaction of glycine with hydrochloric acid and sodium
hydroxide solution respectively. [8]

2004/10 (a). Compound A is a phenylalanine which is an essential amino acid that must be
provided in the diet for healthy growth. A can be synthesised from the 3-phenylpropanoic acid.
The structural formula of A is given as follows.

170
 CH2CH(NH2)COOH

(i) Name A according to the IUPAC system.

(ii) Draw the structure of A at isoelectric point. State the direction of the movement of A
when a potential difference is applied to an aqueous solution A at the isoelectric point.
(iii) Draw the structure of A at pH 2.
(iv) Give the reaction equation for the following.
a. The formation of a tripeptide only from A
b. The formation of an amide using A and the 3-phenylpropanoic acid by a two step
reaction
(v) Give a chemical test to differentiate the 3-phenylpropanoic acid from A. [12]

(b). What is meant by the following?

(i) The structure of primary protein.
(ii) The structure of secondary protein. [3]

Answer:
1992/29 C 1994/29 D 1995/22 A 1995/29 A 1996/59 B (I and II) 1997/43 D 1997/59 D (I
only) 1998/44 C 2000/43 C 2001/50 D(I, II and III)

171
CHAPTER 9
POLYMERS

1. INTRODUCTION
POLY means many, MER means monomer units.
Polymers are long chain molecules produced by joining together many monomers through
polymerization reaction.
Monomer is a simple molecule that has at least a C=C double bond or two different functional
group the can be polymerized.
Polymerization is the reaction between monomers to produce a polymer.

2. CLASSIFICATION OF POLYMERS

2.1 By means of existence

2.1a. Natural polymer
Polymers produced naturally by plant or animal.
Examples:
Proteins, carbohydrates, natural rubber, cotton, Silk, wool, DNA and celulose

2.1b Synthetic polymer

Polymers produced by man-made chemical reactions
Examples:
Polyethene, polypropene, polystyrene, PVC, perspex, teflon, nylon, polyester, bakelite,
vulcanized rubber and SBR.

2.2. By means of polymerization

2.2a Additional polymer
Polymer produced by additional polymerization. Monomer has at least one C=C double bond.
Examples:
Natural rubber, polyethene, polypropene, polystyrene, PVC, perspex, teflon, vulcanized rubber
and SBR

2.2b Condensation polymer

Polymer produced by condensation polymerization. Monomers hves two polymerizeable
functional groups
Examples:
Proteins, carbohydrates, cotton, silk, wool, DNA, celulose, nylon, polyester and bakelite.

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3. SYNTHTIC ADDITIONAL POLYMERS

3.1. Polyethene (PE)

Polyethene is produce by additional polymerization of ethene monomers.
H H H H
During the reaction, the C=C bond of monomer is breaking
n C=C ( C C )n up. New CC bond is formed between monomers that link
the monomers into the polymer chain.
H H H H The additional polymerization can be initiated by means of a
Ethene Polyethene radical or Ziegler-Natta catalyst.

3.1a. Additional polymerization by

3.1a. i. Free radical chain growth polymerization

Conditions for polymerization: Peroxide as catalyst, 1000-2000 atm and 200oC.
Polymerization involves three major steps:
Initiator: Dialkyl peroxide (ROOR)
Dialkyl peroxide (ROOR) is heated to give alkoxy radical (RO).
ROOR 2RO
Initiating step:
CH2=CH2 + RO ROCH2CH2 (alkyl radical)

Propagating step:
The alkyl radical grows longer as ethene monomers are adding on it.
ROCH2CH2 + CH2=CH2 ROCH2(CH2)2CH2
ROCH2(CH2)2CH2 + CH2=CH2 ROCH2(CH2)4CH2

Termination step:
Alkyl radicals combine to from long polyethene polymer.
ROCH2(CH2)xCH2 + CH2(CH2)yCH2OR (CH2)n
Polyethene

Polyethene produced by free radical polymerization is consists of short and highly branched
polymer chains.

Side-chains cause the polymer chains to coil and entangle together. Thus, prevent orderly
arrangement of the polymer into its crystal lattice and lead to lower density. Thus, the polymer is
called low density polyethene, LDPE.
LDPE has low softening temperature; it is soft, waxy, low density, transparent, flexible and
appears as amorphous solid.

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LDPE is widely used for film-wrap, bread and garment bags.
3.1a.ii. Coordination polymerization
Conditions for polymerization: Al(C2H5)3 and TiCl4 as catalyst, 60oC and 30 atm.
Forming of octahedron titanium complex with a vacant d orbital
Al(C2H5)3 + TiCl4 [TiCl4(C2H5)][Al(C2H5)2]+
The initiator of polymerization is the transition metal that has vacant d orbital as reactive site.
Cl
CH2CH3
Cl Ti vacant d orbital as reactive site
Cl
Cl
Initiating step:
Coordination of ethene molecule
Ethene acts as ligand and donates the pi electron into the vacant d orbital.
Cl Cl
CH2CH3 CH2CH3
Cl Ti + CH2=CH2 Cl Ti CH2
Cl Cl CH2
Cl Cl

Rearrangement and insertion of ethene into the growing polymer and recovering of the active
site again
Cl Cl
*
CH2CH3 CH2CH2*CH2CH3
Cl Ti CH2 Cl Ti
Cl CH2 Cl
Cl Cl
Propagating step:
Further coordination of ethene molecule, rearrangement, insertion and recovering of the reactive
site take place.

Cl Cl
*
(CH2)x CH2CH3 (CH2)y*CH2CH3
Cl Ti CH2 Cl Ti
Cl CH2 Cl
Cl Cl

Termination step:
Polyethene is released when the complex is hydrolyzed.
Cl
(CH2)y*CH2CH3
Cl Ti O2H TiCl4OH + (CH2)n
Cl Polyethene
Cl

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In the polymerization, the insertion of ethene into the growing polymer is coordinated by the
catalyst. Thus, the polymer produce is stereoregular straight chain polymer.

The polymer chains produced are long and can be orderly arranged into it crystal lattice to form
crystal with higher density. Because of that the polymer is called high density polyethene, HDPE.

HDPE has high softening temperature, it is hard, tough, and resilient, has high density and appears as solid crystal.

HDPE is wide used for producing containers, bottles and toys.

3.2. Polypropene (PP)

Polypropene has similar structure as PE, but has CH3 group on alternate carbon atom along the
chain.
CH3H CH3H

nC=C (C C)n

H H H H
Propene Polypropene

PP is more brittle than PE, but has higher softening temperature than PE. PP is light weight, has
high abrasion resistance and high impact strength, no toxic, can be spin into fibers with low
absorbance and high stain resistance.

PP is widely used as interior part for automobile, home furnishings, carpet, rain-coat, lab
equipments, table cloth and curtain.

Additional polymerization of propene can be carried out through free radical or through
coordination polymerization as that of ethene.

3.2a Cationic chain-growth polymerization

Cationic polymerization involves the carbocation as intermediate of reaction. The
polymerization is initiated by a strong acid (HClO3) or a Lewis acid containing trace of water
(BF3/H2O).

Initiator: HClO3 H+ + ClO3

or BF3 + H2O [BF3OH] + H+
The H+ ion initiates the polymerization reaction.

Initiating step:
CH3CH=CH2 + H+ CH3CH+CH3 (carbocation)

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Propagation step:
Propene molecules are added into the carbocation and the carbocation grows longer.
CH3CH+CH3 + CH2=CHCH3 (CH3)2CHCH2CH+(CH3)

(CH3)2CHCH2CH+(CH3) + CH2=CHCH3 (CH3)2CHCH2CH(CH3)CH2CH+(CH3)

Termination step:
The polymerization is terminated by adding a base, like H2O.
(CH3)2CH(CH2CH(CH3))xCH2CH+(CH3) + H2O H(CH2CH(CH3))nH
Polypropene

Only monomers with electron repelling group, which stabilizes the carbocation intermediate, like
alkyl can be polymerized by the cationic additional polymerization.

3.3 Polyvinyl chloride (PVC)

Polymerization of vinyl chloride produces polyvinyl chloride, which is similar to PP with Cl
atom attached at alternate carbon atoms along the chain. The reaction involved is the same as
ethene and propane.
Cl H Cl H

n C = C (C C )n
Polyvinyl chloride
H H H H
There two types of PVC.
3.3a Flexible PVC:
It is Soft, flexible and has high porosity to absorb plasticizers.
It is widely used for producing shower curtains, rain coats, artificial leather and insulation for
wires and cables.
3.3b Rigid PVC:
It is hard, strong and has high resistance to heat, u-v radiation and chemicals.
It is used for producing clear bottles, pails, baskets, containers, water tanks, drums, pipes and
door panel.

3.4. Polystyrene (PS)

Polymerization of styrene produces polystyrene, which is similar to PP and PVC with phenyl
group attached at alternate carbon atoms along the chain. The reaction involved is the same as
ethene and propane.

H H

n C=C (C C)n

H H H H
Styrene Polystyrene

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Polystyrene has different properties depends on how it is produces.
Pure PS:
Pure PS is hard, brittle, transparent, non-toxic, excellent thermal insulator and resistance to most
chemicals
Pure PS is used for producing transparent CD, audio cassette box and inner lining of
refrigerators.
Expanded PS or Styrofoam:
Expanded PS is soft, light weight, non-toxic, excellent thermal insulator, excellent cushion
properties, limitless design possibilities.
ESP is used for home insulator, containers for hot or cold food and drinks, protective packaging
in various electrical, chemical and retail produces.

3.4a Anionic chain-growth polymerisation

Anionic polymerization involves the carbanion as intermediate of reaction. The polymerization
is initiated by a strong base like NaNH2 and Alkyl lithium.

Initiator: C4H9Li C3H7CH2 + Li+

or NaNH2 Na+ + NH2
The C3H7CH2 and NH2 anions are initiator of the polymerization reaction.
Initiating step:

CH=CH2 + C3H7CH2 C3H7CH2CH2CH (carbanion)

Propagation step:
Syrene molecules are added into the carbanion and the carbanion grows longer.

C3H7CH2CH2CH + CH2=CH C3H7CH2CH2CHCH2CH

Termination step:
The polymerization is terminated by adding an acid, like H2O.

C3H7CH2(CH2CH)xCH2CH + H2O H(CH2CH)nH + OH-

Polystyrene
Only monomers with electron withdrawing group, which stabilizes the carbanion intermediate,
like chlorine, phenyl, cyano and carbonyl can be polymerized by the anionic additional
polymerization.

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3.5. Polyacrylonitrile (PA)
H CN H CN

n C=C (C C )n
Polyacrylonitrile
H H H H
Acrylonitrile
Polyacrylonitrile is strong, tough has high impact strength, can be spin into fibers.
It is used for producing plastic thread or string and bottles.

3.6. Polymethylmethacrylate or Perspex.

H COOCH3 H COOCH3

n C=C (C C )n

H CH3 H CH3
Methylmethacrylate Polymethylmethacrylate
Polymethylmethacrylate is transparent, hard, tough has high reflection index.
It is used for producing lenses optical equipments and artificial glass.

3.7. Polytetrafluoroethene or Teflon

F F F F

n C=C (C C )n
Teflon
F F F F
Tetrafluoroethene

Teflon is non-toxic and has high non-stick resistance.

It is used for inner coating of non-stick cooking utensils.

3.8. Styrene-Butadiene Rubber (SBR)

SBR is the most widely use synthetic rubber. It is a copolymer produced by polymerizing two
different monomers, namely styrene and butadiene at the ratio of 1 is to 3.

CH2= CHCH=CH2 + n CH2=CH (CH2CH=CHCH2CH2CH)n

Butadiene styrene SBR

Other synthetic rubbers are Isoprene-Isobutene Rubber and Acrylonitrile-Butadiene-Styrene

Rubber (ABS). They are also copolymers.
SBR is flexible, tough, resistance to most chemicals and oxidation.
SBR is widely used for producing tyres, inner tube of tyres, footwear, carpet backing and
adhesives.

ABS is tough and strong. It is used for making suitcases and childrens toy bricks.

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4. SYNTHETIC CONDENSATION POLYMERS
4.1. Polyetheneterepthalate (PET) or Polyetheneterepthalic Ester (PETE)
O O O O

n HOC COH + n HOCH2CH2OH (C COCH2CH2O)n + 2nH2O

Terephthalic acid ethan-1,2-diol PET

PET is called polyester because the ester, (CO) functional group that links the two
monomers is repeated along the polymer chain.
PET is non-toxic, high impact strength, transparent, tough and can be spin into fibers.
It is widely used for producing bottles, textile fibers, X-ray film, and floppy disk, audio and
video tapes.

4.2. Nylon 6 and Nylon 6.6

O O

n ClC(CH2)5NH2 (C(CH2)5N)n + nH2O

Nylon 6
H
The polymer is called nylon 6 because the monomer has six carbon atoms. Like proteins, nylon
is a polyamide because the amide functional group, (CONH) links the monomer along the
polyester chain.

Nylon 6.6
O O

n HOC(CH2)4 CCl + n H2N(CH2)6NH2

Hexan-1,6-dioic acid Hexan-1,6-diamine
O O

(C(CH2)4 CN(CH2)6N)n + 2nH2O

Nylon 6.6
Nylon 6.6 is a copolymer, where both monomers have 6 carbon atoms.
Nylon is strong, has high tensile strength and can be spin into fibers.
It is mainly used for producing textile fibers and sewing threads.

5. POLYMER AND THE REPEATING UNIT

The repeating unit refers to the simplest structural section of the polymer that has the same
composition of the polymer.

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Additional polymer Repeating unit
Polyethene CH2
Polytetrafluoroethene CF2
Polyvinylchloride CH2CHCl
Polypropene CH2CH(CH3)
Polyacrylonitrile CH2CH(CN)
Polymethylmethacrylate CH2C(CH3)(COOCH3)
Polystyrene CH2CH

SBR CH2CHCH2CH=CHCH2

Condensation polymer Repeating unit

PET O O

C COCH2CH2O

Nylon 6.6 O O

C(CH2)4 CNH(CH2)6NH

6. THERMOPLASTIC AND THERMOSETTING PLASTIC

6.1. Thermoplastic
Thermoplastics can be melted and reshaped. Thermoplastic comprised of linear polymer with
weak Van der Waals forces between molecules. When heated, Van der Waals forces are
weakened and the polymer molecules can slide past on another. Thus, the thermoplastic turn soft
when heated.

Molecules of Polymer

Van der Waals forces

When melt, thermoplastic can be shaped into moulds, spun or dissolved in suitable solvent for
fashioning. Thus, thermoplastic is recyclable. Examples of thermoplastic are PE, PP, PVC, PS,
Perspex, PET and Nylon.

6.2. Thermosetting plastic

Thermosetting plastics can only be molded once, before the polymers is set (harden). They retain
their shapes once they have been manufactured. Thermosetting plastic comprised of cross-link
polymers that form a net-work three dimensional giant structure. With these cross links, the

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molecules of polymer are prevented from slipping past on one another. Thermosetting plastics
are hard, rigid or inflexible, can not be melted or mould again.
Example: Bakelite for making 3-pin plugs and electrical switches.

Polymer
Chains

Cross
Links*

Net-work 3-D structure of thermosetting plastic

*Cross links are short polymer chains (or group of atoms) the link two other longer polymer
molecules.

Comparison of thermoplastic and thermosetting plastic:

Thrmoplastic Thermosetting plastic

1. Composed of linear polymer molecules with weak 1. Composed of cross link polymers that
Van der Waals forces between molecules. form 3-D net work structure.

2. Can be melted, reshaped and fashion again.

Recyclable.
3. Soft, flexible, permanently deform when heated
and become hard and brittle when cold.
2. Can not be melted, reshape and
fashion again. Not recyclable
3. Hard, inflexible and not soften when
heat.

7 NATURAL RUBBER
The monomer of rubber is isoprene or 2-methylbuta-1,3-diene.
Thus, rubber is polyisoprene.

n CH2=C(CH3)CH=CH2 (CH2C(CH3)=CHCH2)n
Isoprene Polyisoprene

Natural rubber is cis-polyisoprene and a thermoplastic.

CH3 H
C=C
(CH2 CH2)n
Cis-polyisoprene

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Natural rubber is soft, low elasticity, easily oxidized by oxygen, become sticky when in contact
with heat and organic solvent.
Natural rubber is used for making rubber cement and adhesive tapes.

Vulcanization helps to improve on its physical and mechanical properties. Vulcanization involves
heating a mixture of natural rubber and sulphur under high pressure. The hardness of vulcanized
rubber depends on the amount of sulphur added. Higher percentage of sulphur may produce
harder vulcanized rubber. This is due to more sulphur-bridges (cross links) are formed between
the molecules of the polymer of natural rubber when more sulphur is used. (Similar structure as
thermosetting plastic)

Structure of vulcanized rubber

CH3 H
C=C
(CH CH2)n

S S sulphur link

(CH2 CH)n
C=C
CH3 H
Vulcanized rubber is an elastomer (Elastomers are elastic polymers). It is elastic, rigid, strong,
not become sticky when expose to heat or chemicals, not become harden when cold nor soften
when heat.
Vulcanized rubber is widely used for making tyres, window blades, radiator hosts, car mat, seals,
suspension mountings, conveyor belts, rubber soles, elastic bands and disposable surgical gloves.

Trans-polyisoprene is the geometrical isomer of cis-isoprene

CH3 CH2)n
C=C
(CH2 H
Trans-polyisoprene

The trans isomer is not elastic and can not be vulcanized. It is used for insulate marine and
underground cables, dental fillings, golf-ball covering and adhesives.

8. STEREOREGULAR OF POLYMERS
A polymer chain can have groups, branches and linkages attached to it.

Group = functional group attached along the polymer chain

Example: PVC Cl
Cl Cl Cl

Cl Cl Cl
Cl

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Branches = short polymer chains attached to a much long polymer chain
Example: LDPE
Branch

Long chain

Linkage = very short polymer chain that link neighbouring polymer chains together.
Example: Thermosetting plastic
Neighbouring chain
Linkage
Long chain polymer
Linkage
Neighbouring chain

Tactics of groups along a polymer chain

1. Isotactic: Groups are arranged at the same side along a polymer chain.

1. Isotactic: Groups are arranged at the same side along a polymer chain.

H CH3 H CH H CH
H CH3 H CH H CH H CH3 3 3
3 3

2. Syndiotactic: Groups are arranged in alternately at both side along a polymer chain.

H CH3 CH3 H H CH3

H CH3 CH H H CH3 CH3 H
3

3. Atactic: Groups are arranged at random at both sides along a polymer chain.

CH3 H H CH3 CH3 H

H CH3 CH H H CH3 H CH3
3

Isotactic and syndiotatic polymers are stereo=specific or stereo-regular polymers. They are
produced through catalytic polymerization using the Zeigle-Natta catalyst. These polymers
usually have higher density, have higher softhening point and crystaline because the polymers
can packed closer and in regular packing.

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Atactic polymer is non stereo-specific and having lower density and lower softening point. It is
produced by non catalytic polymerization

Branched polymer is even more non stereo specific than the atactic polymer. This is due to the
branch usually longer than the group. Thus, branched polymers are even lower density and
softening point than the atactic polymer. The polymer is produced through free radical
polymerization.

PAST YEARS QUESTIONS

OBJECTIVE
1990/30. Below is the repeating unit of a polymer.
O O

[ C C O CH2 CH2 CH2 O ]

Which is the following pair of monomers can be used for the preparation of the polymer?
COOH COOH

A and HOCH2CH2CH2OH B and CH3CH2CH2OH

COOH COOH

COOH CHO

C and HOCH2CH2OH D and CH2 (COOH)2

COOCH3 CHO

CHO

E and (COOH)2

CHO

1991/30. Which of the following molecules reacts with HOOC COOH to form a
polymer?

A CH3CH(OH)CH(Cl)CH3 B HOCH2CH2CH2CH2CH3
C CH3CH(OH)CH2COOH D HOCH2CH2CH2OH
E
HO CHO

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1992/40. Which of the following pairs of compounds reacts to form polymer?

1. HOOC COOH and CH3CH2OH

2. NH2CH2CH2CH2CH2CH2CH2NH2 and ClOCCH2CH2CH2CH2COCl

3. HOOCCH2CH2COOH and HOCH2CH2OH

1993/30. Nylon 66 is produced from the polymerization of hexanedioic acid and

1,6-diaminehexane according to the following scheme of reaction.

NH2CH2CH2CH2CH2CH2CH2NH2 + HOOCCH2CH2CH2CH2COOH
O

[HNCH2CH2CH2CH2CH2CH2NCCH2CH2CH2CH2CO ] + H2O

H
If 100 hexanedioic acid molecules and 100 1,6-diaminehexane molecules are polymerized
according to the equation, what is the number of water molecules formed?
A 99 B 100 C 199 D 200 E 201

1994/30. Given are structural formulae of polymer P and polymer Q.

P: Q:
H CH3 H H O O

[ C C]n [C C O C C O]n

H COOCH3 H H
Which of the following statements is true for polymer P and Q?
P Q
A Polyseter Polyseter
B Condensation polymer Condensation polymer
C Additional polymer Additional polymer
D Condensation polymer Additional polymer
E Addition polymer Condensation polymer

1995/30. Below is given the structural formula of a polymer.

CH3 H

[ C C]n

H COOCH3
The monomer of the polymer is
A CH3CH=CHCOOH and CH3Cl B CH3CH=CHCOOH
C CH3CH=CHCOOCH3 D CH3CH2CH2COOH and CH3OH
E CH3CH2CH2COOCH3

185
1996/44. Which of the polymers is produced by condensation polymerization?
A Polyethene B Polystyrene C Synthetic rubber D Polyvinylchloride
E Poliamide

1996/45. Isoprene, CH2=C(CH3)CH=CH2 is monomer of the natural rubber. The structural

formula of natural rubber is
A [CH2C(CH3)=CHCH2]n B [CH2=C(CH3)CHCH2]n
C [CH2CH=CHCH2]n D [CH2C(CH3)CHCH2]n
E [CH2C(CH3)=CH]n

1997/44. Which of the following substances has peptide linkages?

A Polypropenamide B Natural rubber
C Polystyrene D Carbohydrate
E Terylene

1997/45. Natural rubber is made up of units of isoprene, CH2=C(CH3)CH=CH2. Which of the

following is not true?
A IUPAC name of isoprene is 2-methylbutane-1,3-diene
B Natural rubber is unsaturated molecule.
C Natural rubber becomes soft and melts when heated.
D Natural rubber contains a mixture of cis polymer and trans polymer.
E Natural rubber becomes harden when vulcanized.

1998/45. X is transparent polymer used as packaging material. Monomer of polymer X is

hydrocarbon. Polymer X is
A Nylon 6.6 B Terylene C Polyethene D Polystyrene E PVC

1998/60. Below is part of the structure of a polymer.

H Cl H H Cl H

CC=CCCC=CC

H Cl H H Cl H
Which of the following statement is true for the polymer?
1. The monomer is CH2=CHCl
2. The empirical formula is C2H2Cl
3. The polymer has geometrical isomers

1999/45. Which of the following compounds function as monomer in condensation

polymerization?
A CH3CH3 B CH3COOH C CH3COCH3 D CH2=CHCl E HOCH2CH2OH

186
1999/60. Which of the following is true regarding to polymerization process using Ziegle-Natta
as catalyst?
1. Polymerization involves free radical
2. Polymerization is additional polymerization
3. Polymerization produces high density polymer

2000/44. Which of the following pairs of compounds forms condensation polymer?

A H2NCH2CH2CH2CH2NH2 and HOCH2CH2OH
B HOOCCH2CH2CH2COOH and ClCH2CH2Cl

C HOCH2CH2CH2CH2OH and HOOC COOH

D ClOC COCl and HOOC COOH

E CH2CH2CONH2 and CH2CH2COOH

2000/45. Below is part of the structural formula of insulin.

O O O O

[HN CH2 C NH CH C NH CH C NH CH C]

CH2 CH2 CH2

OH
Which of the following is correct if the insulin is hydrolyzed?
A 1 mole of H2NCHCOOH , 2 moles of H2NCHCOOH and 1 mole of H2NCHCOOH

CH3 CH2 CH2

OH

187
B 1 mole of H2NCH2COOH , 1 moles of H2NCHCONHCHCOOH and

CH2 CH2

1 mole of H2NCHCOOH

CH2

OH

C 1 mole of H2NCH2COOH , 1 moles of H2NCHCOOH and 2 mole of H2NCHCOOH

CH2 CH2

OH
D 1 mole of H2NCHCOOH , 1 moles of H2NCHCOOH and 1 mole of H2NCHCOOH

CH2OH CH2 CH2

CH2CONH2

OH

E 1 mole of H2NCHCOOH and 2 moles of H2NCHCOOH

CH2CH2CH(OH)CONH2 CH2

2000/60. Which of the following statements is true for natural rubber and vulcanized rubber?
1. Both rubbers contain cis polymer.
2. Natural rubber is easier to be oxidized than vulcanized rubber.
3. Natural rubber is stronger than vulcanized rubber.

188
2001/40. Which of the following represents condensation polymerization?
A nCH2=CHCH3 [CH2CH]n

CH3
B nCH2=CHOCOCH3 [CH2CH]n

OCOCH3
O

C nH2N(CH2)5COOH [HN(CH2)C]n + nH2O

D CHO + H2NNH NO2 CH=NNH NO2 + H2O

NO2 NO2

2002/39. Polyvinylchloride or PVC, is produced through free radical mechanism reaction by

heating chloroethene or vinyl chloride at high pressure in the presence of benzoyl peroxide
(C6H5COO)2. Which of the following is the propagation step of the mechanism?
A 2C6H5 + CH2=CHCl C6H5CH2CHClC6H5
B C6H5CH2CHCl + C6H5CH2CHCl C6H5CH2CH(Cl)CH(Cl)CH2 C6H5
C C6H5CH2CHCl + C6H5 C6H5CH2CH(Cl) C6H5
D C6H5CH2CHCl + CH2=CHCl C6H5CH2CH(Cl)CH2CH(Cl)

2002/40. Which of the following is made of thermosetting polymer?

A Fabric B Tyre C Fire Jacket D Wire Insulator

2003/30. The following scheme of reaction shows the production of nylon - 6.6 from benzene.

X (i) O2 H2, Ni
CH CH3 Y OH
| (ii) H2SO4
CH3 Conc. HNO3
H H O O
| | || || Z
[NCH2CH2CH2CH2CH2CH2NCCH2CH2CH2CH2C]n COOH
COOH
What could be X, Y and Z?

X Y Z

A CH3CH=CH2/ H+ COOH H2N NH2

B CH3CH2CH3 OH H2N NH2

C CH3CHClCH3 COOH H2NCH2CH2CH2CH2CH2CH2NH2

189
D CH3CH=CH2/ H+ OH H2N CH2CH2CH2CH2CH2CH2NH2

2003/33. The structural formula of natural rubber is given below.

H H CH3 H
| | | |
[ C C = C C ]n
| |
H H
The presence of double bonds in the structure of natural rubber makes this substance
A elastic B hard
C resistant to heat D easy to oxidise

2003/39. When 1 mol of compound X is heated with a concentrated solution of potassium

manganate(VII), 2 mol of compound Y with the moleculae formula C2H4O2 is produced.
Compound X undergoes polymerisation in the presence of Al(CH3)3 and TiCl3 to form
compound Z. The structure of Z could be

CH3 CH3 CH3 CH3 CH3 CH3 H CH3 H CH3

| | | | | | | | | |
A C C C C C B C C C C C
| | | | | | | | | |
H H H H H H H H H H

CH3 H CH3 H CH3 CH3 H CH3 CH3 CH3

| | | | | | | | | |
C C C C C C D C C C C C
| | | | | | | | | |
CH3 H CH3 H CH3 H CH3 H H H

2004/34. A pokymer has a glass transition temperature (Tg) of -5oC and a melting point (Tm) of
162oC. The table below shows the properties of the polymer at various temperatures.

Temperature / oC Properties
-10 Brittle solid
0 Flexible and Mouldable
200 Viscous liquid

What type of polymer is this?

A Fibre B Thermoset
C Elastomer D Thermoplastic

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2004/39. Which of the following pairs of polymer and its repeating unit is true?

Polymer Repeating unit

A Polypropene CH2CH2CH2

B Nylon 6.6 CO(CH2)5NH

C Terylene OCH2CH2OCO CO

D Polystyrene CHCH2CHCH2

2005/31. Which of the following monomers has the same empirical formula as its polymer?
A CH2=CHCN B CH2(OH)CH2()H)

C HOOC(CH2)5NH2 D HOOC COOH

2005/37. Which of the following pairs of monomers can undergo condensation polymerization?
A HOCH2CH2OH and H2NCH2CH2NH2
B HOCH2CH2OH and HOOCCH2CH2COOH
C CH2=CHCH=CH2 and HOOCCH=CHCOOH
D H2NCOCH2CH2OCNH2 and HOOCCH2CH2COOH

2005/38. The following reactions involve free radicals except

A n CH2=CH2 [ CH2CH2]n
B CH3Cl + Cl2 CH2Cl2 + HCl

C + Cl2 Cl + HCl

D CH3 + Br2 CH2Cl + HBr

STRUCTURED
1996/3. a) Natural rubber is cis-poly(2-methylbuta-1,3-diene). Its physical properties are altered
by vulcanization.
i) Draw the repeating unit of natural rubber.

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ii) What characteristic does the molecule of polymer must have so that it can be vulcanized?
iii) State two changes in the physical properties of natural rubber after it is vulcanized.
iv) What would happen to the physical properties of natural rubber if excess of vulcanizing agent
is added?
v) Draw the structure of vulcanized rubber. [6]

1998/3. a) Polymers are classified as thermosetting plastic, thermoplastic and elastomer.

i) What it meant by thermoplastic?
ii) Give one example of thermoplastic.[2]
b) Natural rubber is an elastomer.
i) What it meant by elastomer?
ii) Draw structural formula for natural rubber.[2]
c) Synthetic rubber is made up of a mixture of geometrical isomers of poly(buta-1,3-diene),
which is sticky and not useful. What is the catalyst used for preparing an elastic synthetic rubber?
[1]
b) SBR is another type of important synthetic rubber used in automobile industry. Name the
monomers used for preparing SBR. [2]

2002/1 (c). Propene is the monomer for polypropene.

(i) Draw the repeating unit of polypropene.
(ii) State one use of the polymer and one physical property that related to its uses. [3]

2002/4 (b) An acid HO COOH can form a polymer.

(i). State the type of polymerisation that would take place for the acid.
(ii) Draw the structural formula of the polymer that would produce.
(iii) State the functional group that appeared in the polymer. [3]

ESSAY
1992/8. c) Write balance equations for the following reactions.
i) Formation of nylon 6.6 from 1,6-diaminohexane, H2N(CH2)6NH2, with hexanedioic acid,
HOOC(CH2)4COOH.
ii) Preparation of 1,6-diaminohexane, H2N(CH2)6NH2, and hexanedioic acid,
HOOC(CH2)4COOH from Br(CH2)6Br.
iii) Formation of polyester (terilene) from ethane-1,2-diol and benzene-1,4-dioic acid.

1994/8. a) Explain what it meant by additional polymerisation and condensation polymerisation.

State an example for each of the types of polymerisations. [8]
c) In an experiment, 5.60g of ethene and 2.60g of a gaseous catalyst with molecular mass is
51.90 are placed in an enclosed container and polymerisation takes place at 1.00 atm. After 20.0
minutes, pressure in the container reduced to 0.60 atm. If the vapour pressure of polyethene is
negligible and the rate of polymerisation is constant, calculate the time required for the
polymerisation to be completed. [8]

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2000/8. a) By using suitable examples, state the differences between additional polymer and
condensation polymer. [8]
b) Polyethene is an example of polymer that produced by free radical addition. Discuss this
statement. [8]
c) Explain the differences between polyethene produced by free radical polymerisation and
polyethene produced by the Ziegler-Natta catalyst. [9]

2001/9. b) Styrene, C6H5CH=CH2, is liquid at room temperature. It forms transparent solid when
exposed to air. [2]

2003/10 (b). 2-Hydroxy-2-methylpropanoic acid can be used to prepare methyl-2-

methylpropanoate, a monomer of Perspex.
(i). Write the chemical equation and state the suitable reagent and conditions for the
conversion of 2-methylpropanoic acid into methyl-2-methylpropanoate.
(ii). The initial step of the polymerisation mechanism in the formation of Perspex is
shown as follows.
CH3 CH3
| |
CH3(CH2)3Li+ + CH2=CCOOCH3 CH3(CH2)3CH2C + Li+
|
COOCH3
Describe the mechanism of this polymerisation.

Answer
1990:30A 1991:30D 1992:40C(2,3) 1993:30D 1994:30E 1995:30C
1996:44E, 45A 1997:44A, 45D 1998:45C, 60C(2,3) 1999:45E, 60E(2,3)
2000:44C, 45C, 60B(1,2) 2001:40C

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