A Level Organic Chemistry Notes

Most General Advanced level texts do not address all the objectives spelt in the syllabus
especially in Organic chemistry therefore it requires the consultation of a number of

dedicated Organic Chemistry textbooks to cover all the objectives, most of which are
unavailable in High School libraries and are also quite reader unfriendly.
This handbook is aimed at helping both pupils and teachers in Organic chemistry for
Advanced level. Its main focus is to give Advanced Level and College students a complete
focused overview of the main principles underlining the chemistry of Organic molecules.
Though the main emphasis is on helping pupils pass their courses, effort has also been made
to make organic chemistry have a more organic or socio look in terms of its applications in
industries, homesteads, warfare life-processes, etc.
MUKANDA S.M
(BSc. Hons. Chemistry)
e-mail: lsmichael2005@yahoo.co.uk
cell: +263778494504
COMPILED BY MUKANDA S.M (BSc. Hons.Chemistry) Page i

1. INTRODUCTION 1
Homologous series 1
Nomenclature 3
Formula of Organic compounds 4
Isomerism in Organic Compounds 5
Terms used in Organic Chemistry 9
2. ALKANES 11
Nomenclature of Alkanes 11
Physical Properties of Alkanes 11
Isomerism in alkanes 11
Reactions of alkanes 12
3. ALKENES 15
Isomerism in Alkenes 15
Reactions of Alkenes 16
Electrophilic Addition reactions 16
Polymerisation Reactions of Alkenes 21
4. AROMATIC HYDROCARBONS (ARENES) 22

Structure of Benzene 22
Nomenclature of Benzene Derivatives 23
Physical properties of Benzene 23
Reactions of Benzene 23
Electrophilic Substitution Reactions of Benzene 24
Effect of Substituent Groups on Benzene Ring 26
Methylbenzene (Toluene) 26
Reaction of benzene Ring 27
Reaction of Methyl group 28
5. HALOGENO-ALKANES AND HALOGENO-ARENES 29

Nomenclature of Organo-halogens 29
Physical Properties Organo-halogens 29
HALOGENO-ALKANES 30
Chemistry of Halogeno-alkanes 30
Nucleophilic Substitution Mechanisms 30
Elimination Reactions in Halogeno-alkanes 33
Uses of Halogeno-alkanes 35
Pollution problems of CFC’s 34
HALOGENO-ARENES 34
Reactivity of halogeno-arenes 34
6. HYDROXYL COMPOUNDS 35
ALCOHOLS 35
Physical properties 35
COMPILED BY MUKANDA S.M (BSc. Hons.Chemistry) Page ii
Reactions of Alcohols 35
PHENOLS 39
Chemistry of Phenols 39
Acidity of Phenol (Compared to ethanol and water) 39
Reactions of the –OH group in Phenol 40
Reactions of Benzene ring 40
7. ORGANIC CARBONYL COMPOUNDS 42

Preparation of carbonyl compounds 42
Chemistry of carbonyl compounds 43
Reactions of Carbonyl Compounds 43
Distinguishing Aldehydes from Ketones 45
8. CABOXYLIC ACIDS AND THEIR DERIVATIVES 46

Chemical properties 46
Acidity of Carboxylic acids 46
Preparation of Carboxylic acids 47
Reactions of Carboxylic acids 48
ACYLCHLORIDES 50
Chemistry of acyl chlorides 50
Reactions of acyl chloride 50
ESTERS 51
Reactions of Esters 51
9. NITROGEN COMPOUNDS 53
AMINES 54
Preparation of amines 54
Basicity of amines 54
Reactions of Amines 55
Reactions of Phenylamines 56
Formation of diazonium salts and azo dyes 56
AMIDES 58
Preparation of Amides 58
AMINO ACIDS 59
Chemical properties of Amino acids 59
Formation of Proteins 60
Electrophoresis 61
10. POLYMERISATION 62
Addition Polymerisation 62
Condensation Polymerisation 63
COMPILED BY MUKANDA S.M (BSc. Hons.Chemistry) Page iii

INTRODUCTION
Organic chemistry: - this is the study of carbon containing compounds. These carbon-containing
compounds are called organic compounds. Generally organic compounds are classified into two broad
groups; Hydrocarbons (compounds which contain compounds the elements carbon and hydrogen only),
Non-Hydrocarbons (compounds which contain carbon, hydrogen and other elements)
Why Carbon so special?

Carbon has the ability to form strong covalent bonds with itself and with other atoms (H, O, N, S,
Halogens) forming an immense variety of structures. Carbon can also form multiple bonds, that is,
double and triple bonds readily. This allows carbon to form an enormous variety of chains and rings, and
this is the reason for the diversity of organic compounds. There are more than 10 million compounds
listed in Chemical Abstracts, and most of these are organic. Fortunately, we can classify them into a few
dozen families. This classification is based on structural entities, which have a chemical reactivity that is
roughly predictable - so-called functional groups. We will not cover them all, but by the end of the
course, the principles will be well apparent to you.
HOMOLOGOUS SERIES
It is a group or family of organic compounds with the same functional group.
A functional group is a reactive part of a compound, which characterises a group.
The organic compounds of the same homologous series also possess:
 The same general formula
 The same chemistry due to the same functional group
 Almost similar physical properties due to the consecutive member differing by —CH2— group
HOMOLOGOUS FUNCTIONAL GROUP GENERAL FORMULA EXAMPLE

SERIES
Alkanes
CnH2n+2
Ethane
Alkenes
CnH2n
Ethene
Halogeno-
alkanes
CnH2n+1X
Chloro-ethane
Arenes -C6H5
Methyl-benzene
Alcohols
-OH CnH2n+1OH
Hydroxyl group
Ethanol
COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

Phenols
*Benzene ring and O—H bond Phenol

Carboxylic Acids
CnH2nO2
Carboxyl group Ethanoic acid
Aldehydes CnH2nO
Aldose group
Ethanal
Ketones
Keto group Propanone

Amines —NR2
Amine group
R- alkyl group or H
R- alkyl/aryl group Ethyl amine
R1 and R2 maybe alkyl (Primary amine)
group or H
Esters
R-alkyl group
R- alkyl groups Ethyl propanoate
Ester group
Acyl-chlorides
Acyl chloride group R-alkyl/aryl group Ethanoyl chloride

Amino acids
Circled: the 2 functional R-alkyl groups Amino propanoic acid

groups
Amides
R1:maybe H or alkyl groups R: alkayl group Ethanamide

R1:maybe H or alkyl
group
Nitriles —CΞN R—CΞN CH3—CΞN ethane nitrile
CH3CH2—CΞN propano nitrile
PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS

 Molecules of organic compounds are bonded together by weak Van Der Waals forces; therefore,
they are usually gases or volatile liquids at room temperature.
 Boiling point increases with increase in molecular size or mass and decrease in branching.
 Organic compounds with hydrogen bonds have high boiling point than those of equivalent mass.

CHEMICAL PROPERTIES OF ORGANIC COMPOUNS
 The chemical properties of the organic compounds depend on the functional group present in
the compound.
NOMENCLATURE (NAMING OF ORGANIC COMPOUNDS)

 The IUPAC (International Union of Pure and Applied Chemistry) system of naming organic
molecules is used for naming organic molecules.
 When naming organic molecules the following information should be given out by the name of
the molecule :
Family to which the molecule belong.
The number of carbon atoms in the chain.
Whether the chain is branched or straight or ring.
Additional atoms/molecules present/functional groups.
 The name of the organic compound gives considerable amount of information about the
structure of the molecule and how it is likely to react.
 RULES OF NAMING ORGANIC COMPOUNDS
The Prefix: denotes the number of carbon atoms in the longest continuous or
unbranched carbon chain present in the molecule and is used as the parent name of that
organic molecule.
For example:
Prefix Number of C—atoms in the main chain
Meth- 1
Eth- 2
Prop- 3
But- 4
Pent- 5
Hex- 6
The suffix: denotes the functional group or the organic family to which it belong.
For example:
Suffix Organic Family to which it belong
-ane alkane
-ene alkene
-ol alcohols
-al aldehydes
-one ketones
-oic carboxylic acid
Position of the Functional group: numbers are used to indicate the whereabouts of the
functional group in the carbon chain. The functional group should be numbered from
whichever end that gives the lowest locant (number) from the first carbon.
For example:

Prefix: - But- (longest chain has four carbon atoms)
Suffix: - ene (due to the present of the double bond or unsaturation)
Position of functional group: - Carbon number 2 (not 3)
Name of Organic molecule: - 2-Butene or But-2-ene
Side Chains or Branches: these are substituent groups found in the organic molecule and
should also appear in the name of the organic molecule. The position of these side groups
is shown using numbers which appear in the name of the organic molecule. The side
group or branch should be numbered from whichever end that gives the lowest locant
(number) from the first carbon.
Side groups of general formula CnH2n+1 are called alkyl groups and those containing
aromatic hydrocarbons are called aryl
For example
Methyl CH3—
Ethyl CH3CH2—
Propyl CH3CH2CH2—
Butyl CH3CH2CH2CH2—
The symbol R is often used to represent a general alkyl group.
Prefix: - Hept- (longest chain has 7 carbon atoms)

Suffix: - ene (due to the present of the double bond or unsaturation)
Position of functional group: - Carbon number 2 (not 3)
Side group:-Propyl on carbon number 3
Name of Organic molecule: - 3-propyl-2-heptene or 3-propyl hept-2-ene.
NB: A hyphen is used to separate numbers and the group name.
Use of the Alphabetical order:-the side groups are listed in alphabetical order e.g ethyl
before methyl
Name of Organic molecule :- 5-ethyl-3-methyl octane
FORMULAE OF ORGANIC COMPOUNDS
The formulae of organic compounds can be expressed in several ways, which are:
 Molecular Formula: - the formula shows all the atoms of each element contained in one
molecule. The formula does not show how the atoms are connected e.g C5H12O
 Displayed Formula: - clearly shows how all the atoms are joined together and also shows all the
bonds.

For example: Pentan-1-ol
 Structural Formula: - shows the abbreviated displayed formula and how the atoms are joined
together.
For example: Pentan-1-ol
CH3CH2CH2CH2CH2OH or CH3—CH2—CH2—CH2—CH2—OH
SHORT HAND (SKELETAL) FORMULAE
 This is a formula that omits all C and H atoms showing only carbon atoms at every bend and
functional groups.
For example:
QUICK QUESTIONS
1. Name the following alkanes:
a. b.
c. d.
2. Write the formulae of the following organic compounds.

a. 2,2,4-trimethylhexane b. 2,4,6-tribromo phenyl amine
c. 2-hydroxyl-4-methyl cyclohexene d. 3-methylpentanone
3. (a) Write the displayed formula of the organic compounds in question 2 above.
(b) Give the skeletal formula of the organic compounds given in question 1 above.

 Isomerism is the existence of different compounds with the same molecular formula but differ in
their structural formula or their arrangement in space resulting in different physical and/or
chemical properties.
TYPES OF ISOMERISM
1. Structural Isomerism
 Exists in compounds with the same chemical formula but differ in the way the atoms are joined
to each other.
 Structural isomers can be members of the same or different homologous series.
For example:
Butane 2-methylpropane
Both compounds belong to alkane group.
Propanone Propanal
Members of different homologous series.
FACTORS GIVING RISE TO STRUCTURAL ISOMERISM
Chain Isomerism
 This is shown by isomers belonging to the same homologous series, possessing the same
functional group but differ only in the carbon chain.
For Example:
2-Methyl-1-butanol Pentanol
Positional Isomerism
 Exhibited by molecules belonging to the same homologous series with the same carbon
skeleton and differ in the position of the functional group.
For example:

Functional Group
 Exhibited by molecules with the same molecular formula but differ in their functional
groups thus resulting in the molecules belonging to different homologous series.
For example:
 Also very common to carbonyl compounds.

For example:
QUICK QUESTIONS
1. Give three structural isomers of each of the following molecular formulae.
a. C5H12 b. C4H10O c. C4H8Cl2
2. Five unbranched molecules have the formula C5H10O2.Write their structural formulae.
2. Stereo Isomerism
 Occurs when 2 or more molecules have both the same molecular and structural formula but
differ in the spacial arrangement of atoms.
 Stereo isomerism can be:
 Geometrical (cis-trans) Isomerism or
 Optical Isomerism
 Geometrical (Cis-trans) Isomerism

 Arises as a result of restricted rotation about a C=C double bond giving rise to cis-trans
isomerism.
 The two groups attached to each carbon atom at the double bond must be different in order
to have different geometrical isomers.
 In Cis-, the identical groups are on the same side of the double bond.
 In Trans-, the identical groups are on opposite side of the double bond.
 Cis-trans isomers have different melting and boiling points (physical properties) but same
chemical properties.

For example: Consider a compound 1,2-dichloroethene ClCH=CHCl
Or 2-Butene CH3CH=CHCH3
 Optical Isomerism
 Occurs when molecules have the same molecular and structural formula but differ in the
way they rotate plane polarised light.
 Light when emitted from normal source has different electric field light waves
(electromagnetic radiation) which are arranged in many planes, which are perpendicular to
the direction of travel of the light ray. Polarisers are used to remove all these planes of light
leaving only one.
 Optically active substances are able to rotate this plane polarised light when it is passed
through them.
 Optical isomers rotate plane polarised light in different directions that is in:
Clockwise (+) direction (D-isomer or (+) isomer) i.e D-Dextrorotatory
Anti-clockwise (-) direction (L-isomer or (-) isomer) i.e L-Levorotatory
 Compounds which are optically active are chiral, due to the presence of a carbon atom that
is bonded to four different groups (chiral centre). Their molecules have no plane or axis or
centre of symmetry (asymmetrical) and are non-superimposable mirror images of each other
(Enantiomers).
 An equimolar mixture of (+) and (—)-enantiomers is optically inactive and is called a racemic
mixture or racemate.
For example: Consider an organic compound H2N—CH(CH3) —COOH
* —chiral centre
 The number of chiral centres in a molecule helps to determine the number of optical
isomers, which can be resolved from a given molecule. The number of optical isomers is
given by 2n where n is the number of chiral centres.

QUICK QUESTIONS
1. (a) State what is meant by a chiral centre.
(b) Explain how such a centre gives rise to optical isomerism.
(c) Which of the following compounds has optical isomers? Show using an asterisk (*) the chiral
centre.
2. Determine the number of optical isomers which can be resolved from the following molecules. Show
using an asterisk (*) the chiral centre.
TYPES OF ORGANIC REACTIONS
Substitution reaction: occurs when an atom/ group of atoms replaces another in an organic
molecule e.g CH3CH2Cl + OH— CH3CH2OH + Cl—
Addition reaction: occurs when two or more molecules reacts to form only one molecule as the
product e.g CH2=CH2 + Br2 BrCH2CH2Br
Elimination Reaction: occurs when one molecule undergoes a reaction in which a small molecule
is removed from it to form more than one molecule. Usually results in the formation of a double
bond e.g CH3CH2OH CH2=CH2 + H2O
Hydrolysis: is a reaction in which a molecule is broken down into smaller molecules using water
e.g
Redox reaction: these occur in organic reactions where oxygen (from an oxidising agent) and
hydrogen (from a reducing agent) are used to oxidise and reduce an organic compound.

Rearrangement: this occurs in a reaction where the atoms or group of atoms shift to occupy
different positions in the molecule from the initial ones e.g
CH3CH(Cl)CH=CH2 CH3CH=CHCH2Cl
TYPES OF ORGANIC REAGENTS
Nucleophiles: these are ions or molecules that are attracted to positively charged centres. They
attack the electron deficient end of a polar bond. They can also be referred to as nucleus
seeking/loving species. They comprise of negative ions and molecules in which an atom has a
lone pair of electrons e.g OH—, Cl—, Br—, I—, CN—, NH3, H2O.
Electrophiles: these are ions or molecules that are attracted to negative centres or region where
electron density is high e.g H+, NO2+, CH3+, SO3.
TYPES OF BOND FISSION
 Bond fission: is the breaking up of a covalent bond

Homolytic Fission: this refers to the cleavage of a covalent bond in such a way that both bonded
atoms each acquire one electron of the bond. This results in the formation of free radicals.
A half curly arrow ( ) is used to indicate the movement of a single electron with the tail
showing where the electron is coming from and the half arrow head where the electron is going.
Heterolytic Fission: this refers to the cleavage of a covalent bond in such a way that one of the
bonded atoms acquires both electrons of the bond. The resultant species are ions which are very
reactive in nature.
A fully curly arrow ( ) is used to indicate the movement of the pair of electrons.
Organic reactions may involve:

Substitution by nucleophile (Nucleophilic Substitution reaction)- SN reaction
Substitution by electrophile (Electrophilic Substitution reaction)- SE reaction
Addition by nucleophile (Nucleophilic addition reaction)- AN reaction
Addition by electrophile (Electrophilic addition reaction)- AE reaction

 Alkanes are saturated hydrocarbons with the general formula CnH2n+2 and consisting entirely of the
elements carbon and hydrogen. The carbon and hydrogen atoms are joined only by single C—C
bonds and single C—H bonds.
 To minimise repulsions between the bonding pairs, the arrangement of substituents around each
carbon atom is tetrahedral with a bond angle of 104.5:.
 In alkanes each carbon atom forms four sigma (δ) bonds with four other atoms. This is the
maximum number of substituents that can be carried by a carbon atom thus are termed saturated
hydrocarbons as they carry the maximum number of hydrogen atoms possible.
NOMENCLATURE OF ALKANES
 As mentioned earlier on, the key to naming of alkanes is to recognise the longest hydrocarbon
chain. After this assign numbers to the carbon atoms in the hydrocarbon chain such that lower
numbers are used to denote the position of substituents.
For example:
The compound show is 2-methylhexane not 5-methylhaxane.
PHYSICAL PROPERTIES
 Alkanes are non-polar hydrocarbons, which are insoluble in polar solvents such as water but
soluble in non-polar solvents such as ether.
 Generally alkanes have low boiling and melting points due to the presence of weak Van der Waals
force of attraction which operates between molecules, however melting and boiling points
increases with increase in molecular size as well as decrease in branching as branching reduces the
distribution of the electron cloud due to increase in surface area and reduced close packing.
 Volatility decreases as shown by the hydrocarbons methane to butane which are gases at r.t.p
while hexane to pentadecane C15H32, are liquids at r.t.p, due to increase in Van der Waals’ forces
strength as the number of electrons increases with increasing molecular size.
ISOMERISM IN ALKANES
 All undergo structural isomerism (chain isomerism
For example: Isomers of pentane CH3CH2CH2CH2CH3
CH3CH(CH3)CH2CH3 2-methylbutane
CH3C(CH3)2CH3 2,2-dimethylpropane
CH3CH(C2H5)CH3 2-ethylpropane

CRACKING OF ALKANES
 This is the process whereby high molecular mass alkanes are converted to low molecular mass
alkanes and alkenes. There are two types of industrial cracking namely:
Thermal Cracking
Catalytic Cracking
 Thermal Cracking
 High molecular mass (HMM) alkane is heated at high temperatures (about 900:C) in the
absence of air and catalyst breaking up to give smaller molecules, which are more easily
vaporised.
Δ 900:C
HMM alkane LMM alkane + alkene
Δ 900:C
For example: C10H22(g) C4H10(g) + 3C2H4(g)
alkane alkene
 Catalytic Cracking
 High molecular mass alkanes are heated at high temperatures in the presence of a catalyst
in a vacuum to breaking up to give smaller molecules of alkanes, alkenes and sometimes
hydrogen gas.
 Using a catalyst allows cracking to occur at fairly low temperatures about 450 :C.
For example:
2CH3CH2CH4(g) CH4(g) + CH3CH=CH2(g) + CH2=CH2(g) + H2(g)
CHEMICAL REACTIONS
Un-reactivity of Alkanes
 Alkanes are generally unreactive. Their inertness arises from non-polar nature of the C—H
bond due to almost equal electro-negativities of C, 2.5 and H, 2.4.
 Alkanes are saturated hence cannot add on any other atoms.
 All the electrons and orbitals of carbon (2s and 2p) are used in bonding, thus there are no
empty orbitals available to form dative bonds with other molecules and ions.
 However alkanes undergo a few reactions under special conditions.
 COMBUSTION
 Alkanes react on heating with excess oxygen to give CO2, H2O and large amount of energy.
This has resulted in the wide spread use of alkanes as fuels.
Alkane + O2 CO2 + H2O + Energy
 Products are energetically stable than the alkane.
 In excess supply of oxygen, the alkane combust according to the following general equation:

CxHy + (x + )O2 xCO2 + H2O
e.g C4H10 + O2 4CO2 + 5H2O ΔH= positive
 In limited supply of oxygen they burn producing soot (unburnt carbon), carbon monoxide,
little carbon dioxide and water.
Combustion of Alkanes in motor car engines

 Combustion of alkanes in excess supply of oxygen produces CO2, H2O and large amount of
heat energy that is reaction is very exothermic.
 Petrol used in combustion engine consists of a mixture of C 5 to C10 alkanes. A typical
example is octane C8H18.
 The efficiency of petroleum mixture is dependent upon the nature of the alkanes in the
mixture. Straight chain or unbranched alkanes, burn quickly and spontaneously such that
they causes knocking of the engine pistons.
 Branched chain alkanes burn more smoothly such that the energy produced can easily be
harnessed to cause movement of the piston. However, an obstacle is that petroleum
mixtures with branched chain alkanes are more expensive than straight chain alkanes.
 As a solution to this, petroleum companies have produced petroleum mixtures of straight
chain alkanes mixed with a compound of lead, lead tetraethyl Pb(C2H5)4 and 1,2-
dibromoethane, BrCH2CH2Br i.e leaded petrol
 The Pb(C2H5)4 decomposes at the high temperatures in the combustion engine producing
ethyl radicals,(C2H5•) and lead (II) oxide.
 The ethyl radicals ensure smooth combustion of petroleum mixture. The 1,2-
dibromoethane reacts and removes PbO(s) which would otherwise accumulate in the
piston walls by forming PbBr2 which is volatile and is evolved in the exhaust fumes.
 The use of leaded petrol has raised concerns of environmental and health safety. Lead is
itself poisonous and can cause brain damage.
 Other pollutants evolved from the combustion engine includes:
Unburnt hydrocarbons- they participate in the formation of photochemical smog
(haze which usually precipitates just above the ground in cities and it irritates
eyes)
Nitrogen oxides- produced from the reaction of atmospheric nitrogen and oxygen
at high temperatures in the engine. Lead to production of acid rain and participate
in ozone layer depletion.
Carbon monoxide-produced from incomplete combustion of fuel, combines with
haemoglobin reducing oxygen carrying capacity of red blood cells leading to
suffocation at high partial pressures.
Removing pollutant gases from car exhaust
 Using oxygenated fuels: Oxygenates are fuels containing oxygen in their molecules e.g
alcohol. Adding these oxygenates to petrol makes combustion more complete and
reduces the quantities of CO and CxHy that are produced.
 Using lean burn engines: these increase the proportion of air in the petrol-air mixture for
complete combustion of petrol, thus producing less CO and CxHy.

 Using catalytic converters: A catalytic consists of Platinum-Rhodium embedded on a
ceramic material fitted in the exhaust pipe so as to remove pollutant gases from exhaust
by oxidising or reducing them. NOx’s oxidises CO to CO2, and itself reduced to harmless
N2(g).
NO(g) + 2CO(g) N2(g) + 2CO2(g)
CO and CxHy are oxidised by air:
2CO(g) + O2(g) 2CO2(g)
 REFORMING
 Converts unbranched chain alkanes into aromatic compounds.
For example:
 HALOGENATION (FREE RADICAL SUBSTITUTION) OF ALKANES

Alkanes undergo free radical substitution reaction with halogens in the presence of a flash of UV
light and not in the dark. The reaction is a chain reaction initiated by UV light. UV light is used to
initiate the reaction by breaking the X—X bond to produce free radicals, which are extremely
reactive. UV light also provides the reaction with adequate activation energy for reaction to
start.
Mechanism of Free Radical Substitution Reaction with Cl2
Initiation (Photochemical Homolysis of Cl2)

 This involves the homolytic fission of the Cl—Cl bond (BE-242KJmol-1) caused by energy
from UV light to form Cl• radicals.
UV
Cl—Cl Cl• + Cl•
Propagation stage
 The chlorine free radicals so formed are very reactive and they react with methane
molecules to form methyl radical and HCl.
CH4 + Cl• •CH3 + HCl
 Like the chlorine radical the methyl radical is also very reactive and will react with
chlorine gas molecules to form a chlorine radical and chloromethane.
•CH3 + Cl2 H3CCl + Cl•
NB: The propagation stage “keeps the reactor going” since each reaction in this stage results in the
formation of another free radical, which will react with more molecules of the reactants. The reaction
continues until the amount of chlorine and methane molecules in the reaction mixture are very low
compared to the amount of •CH3 and Cl• radicals.

Termination stage
 As the amount of radicals in the reaction vessel increases chances of collisions
between free radicals become more.
Cl• + Cl• Cl2
•CH3 + Cl• CH3Cl
•CH3 + •CH3 CH3CH3
 The termination stage kills the reaction since it removes the reactive species (free
radicals) in the reaction mixture.
 Free radical reactions are extremely fast and the random collisions occurring result in a
mixture of products, however by controlling certain parameters, one molecule can be
made the major product.
 Poly-substitution occurs if halogen is in excess or alkane is in limited supply.
 Free radical reactions due to their explosiveness are also employed in nuclear fission
and bomb detonation.
Bromination of Alkane: during bromination, Br2 is decolourised producing fumes of HBr. The
yield per photon of light is less for bromination than chlorination because the stage:
Br• + CH4 •CH3 + HBr is endothermic than the corresponding
stage in chlorination because of weaker H—Br bond than H—Cl bond.
More energy is evolved in formation of H—Cl than H—Br. Iodination reaction does not go to
completion due to weak H—I bond.
 Alkenes are aliphatic hydrocarbons with the general formula CnH2n.

 They contain at least one C=C double bond. Since they do not contain the maximum number of H-
atoms they are called unsaturated hydrocarbons.
 Alkenes which contain more than one C=C double bond are called conjugated alkenes. E.g
CH2=CH—CH=CH2 But-1,3-diene
ISOMERISM IN ALKENES
 They undergo:
Carbon Chain Isomerism: both branched and unbranched chain isomers of alkenes exist.
Positional Isomerism: Position of double bond should be given in the name of the alkene e.g
But-2-ene CH3CH=CHCH3
But-1-ene CH2=CHCH2CH3
Geometrical Isomerism (Cis-Trans Isomerism): e.g

 Alkenes are generally reactive because of the double bond which makes them unsaturated.
 The cloud of electrons which forms the bond lies above and below the plane of the three sp 2
hybrid bonds formed by each of the unsaturated carbon atoms forming a region of high electron
density, therefore the electrons are more susceptible electrophilic attack.
 Alkenes undergo Electrophilic Addition with the following reagents:

Halogens
Hydrogen halides
Hydrogen
Steam
 They also undergo Oxidation with acidified KMnO4
HALOGENATION
 Alkenes react with halogens under ordinary conditions forming halogenoalkanes.
 The reaction occurs rapidly even in the dark.
For example: bromination of ethene/ethylene where bromine is decolourised in the reaction.
MECHANISM OF REACTION

Stage 1:
 As halogen molecule approaches the ethene molecule it becomes polarised by its
negative charge due to the π-electron cloud i.e generation of an electrophile.
Stage 2:
 The halogen then undergoes heterolytic fission s the π electrons attack the positive end of
Br2 molecule forming a C—Br bond and breaking the Br—Br bond producing a Br— anion
and an unstable bromo-carbocation intermediate.
Stage 3:
 The bromo-carbocation ion is immediately attacked by a bromide ion to form the product
1,2-dibromoethane. This reaction is fast compared with the other stages.
Structure of intermediate:
 This is because there is an electrostatic interaction between the positive charge on the
carbon atom and the lone pair of electrons on Br.
If aqueous Br2(aq) is used
 The anion to attack the carbocation depends on the bond energy which results in more
energy being released hence the C—O bond (BE 360KJmol-1) formation is favoured to the
C—Br bond (BE 280KJmol-1) formation.
ADDITION OF HYDROGEN HALIDES (HX): where X Cl, Br, I

 Aqueous solutions of hydrogen halides readily react with alkenes under ordinary conditions
(r.t.p) to yield halogenoalkanes. A molecule of H—X is permanently polar as Hδ+—Xδ—.

 The hydrogen ions act as electrophiles attacking the C=C double bond and forming an
intermediate carbocation which react with halide ion X— to form the product.
 Higher alkenes produce more than one product when they react with hydrogen halides.
Reaction of Propene with hydrogen halide (HBr)
 Propene reacts with HBr producing two possible products; 2-bromopropane and 1-
bromopropane.
 When the hydrogen ions attack the double bond in propene, two different carbocations A and B
are formed.
 The carbocation produced in the formation of 1-bromoethane is called a primary carbocation (1:
carbocation) because the carbon carrying the positive charge is attached to one alkyl group
(CH3CH2), while the carbocation for the formation of 2-bromoethane is called a secondary
carbocation (2: carbocation) since it is attached to two alkyl groups (2 CH3— groups).
 Alkyl groups has a tendency to donate bonding electrons towards positively charged centres
(positive inductive effect) and thus the carbocation with more electron donating groups
(secondary carbocation) has its positive charge on the carbon atom partially neutralised and
therefore is more stable than the primary carbocation with only one electron donating group.
 The secondary carbocation being more stable has higher chances of being formed in the course
of the reaction and also can survive for a longer period than the primary carbocation in the
reaction mixture giving it more chances of reacting with the Br—. The reaction pathway is also of
lower activation energy.
 This phenomenon was first observed by Vladimir Markovnikoff, a Russian chemist in 1869.
Markovnikoff’s Rule
It state that when a molecule HA adds to asymmetric alkene, the major product is the one in
which the hydrogen atom attaches itself to the carbon atom already carrying the larger
number of hydrogen atoms.
For example:

HYDRATION (ADDITION OF STEAM)
 Alkanes can be hydrated to produce alcohols. A strong acid (H3PO4) or SiO2 catalyst is required in
the addition reaction at a temperature of 300 :C and pressure of 60atm.
 The same product can also be obtained by reacting the alkene with concentrated H 2SO4 followed
by addition of H2O with warming hydrolyse the ethyl hydrogensulphate to ethanol.
The first step involves the addition of alkene on an H+ from the acid at the same time being
attacked by the HSO4— anion.
The second step is to warm the mixture with water.
HYDROGENATION
 An alkene can be converted into its corresponding alkane by addition of hydrogen to the double
bond in the presence of a nickel or platinum catalyst.
CH2=CH2 + H2 CH3—CH3
ethene ethane
 The reaction can be used to determine the degree of saturation in a compound by measuring the
number of moles of hydrogen absorbed by one mole of the compound hence the number of
double bonds can be established (number of moles of H2 absorbed is equivalent to the number
of double bonds in the molecule).
 The process is also used to convert edible oils (especially vegetable oils) which are unsaturated
into margarine.
 Alkenes are not used as fuels for motor vehicles because they burn producing more soot and
they react with air and water producing solids which block fuel engines hence are converted to
alkanes.
OXIDATION OF ALKENES
 Alkenes can be oxidised by strong oxidising agents such as KMnO4. The oxidation products vary
depending on the oxidising conditions- strong, mild oxidation with or without heating.

REACTION WITH COLD, DILUTE OR ALKALINE KMnO4 (Mild Oxidation)
 Alkenes are oxidised by cold dilute KMnO4 to produce diols. This reaction as well as that of
alkenes with Br2 can be used to test for the presence of a C=C double bond in an organic
compound. Ethene will decolourise cold dilute KMnO4 (from purple to a pale pink).
CH2=CH2 + 2H2O HOCH2 —CH2OH + H+ + 2e— (x5)
MnO4— + 8H+ + 5e— Mn2+ + 4H2O (x2)
Overall equation
5CH2=CH2 + 2MnO4— + 2H2O + 6H+ 5 HOCH2 —CH2OH + 2Mn2+
Purple colourless almost colourless
OR CH2=CH2 + H2O + [O] HOCH2 —CH2OH
Ethan-1,2-diol
The [O] shows oxygen from the oxidising agent. An acid instead of an alkali can be used as long
as the KMnO4 is cold.
REACTION WITH HOT AND CONCENTRATED KMnO4 (Strong Oxidation)
 Under more oxidising conditions e.g hot, concentrated acidified KMnO4, the diol produced is
further oxidised to produce carboxylic and/or carbonyl compounds. The overall result is the
rapture of the C=C double bond and the terminal carbon atoms bearing the double bond are
oxidised to the maximum extent possible without breaking the other C—C single bonds.
For example: Oxidation of pent-2-ene
 The products produced in the complete oxidation of alkenes vary depending on the position
of the double bond.
 If the carbon carrying the double bond is bonded to one alkyl group and hydrogen atom,
that part will give a carboxylic acid.
For example: Oxidation of but-2-ene
 If the carbon carrying the double bond is bonded to 2 alkyl groups, the carbon will be
oxidised to a ketone.
For example: Oxidation of 2,3-dimethylpent-2-ene

 If the double bond occurs terminally in the hydrocarbon chain, the terminal carbon will be
oxidised to CO2 and H2O.
For example: Oxidation of But-2-ene
POLYMERISATION
 Polymerisation is the joining of small molecules to form a larger molecule.
 These small molecules which join together are termed monomers, while the large molecules
which are formed are termed polymers.
 Alkenes when heated to about 200 :C under high pressure of about 1200 atm in the presence
of trace oxygen undergo a form of polymerisation called addition polymerisation to produce
polyethene or polythene.
 Addition Polymerisation: is when monomers add up to each other producing a single product.
The π- bond in the alkene raptures under these conditions, enabling free bonds to link to one
another, forming a chain. Reaction mechanism is thought to occur through a free radical
pathway.
 Repeat unit show the basic part of the molecule and is used to represent the structure of the
polymer.
 Polyethene is used in making plastic bags, films, wrappers, etc.
Other examples of addition polymers:
PVC (Polyvinyl chloride or Poly (chloroethene)
PVC is used to make waterproof plastic sheets, insulating electric cables, etc.
PVC is much stronger than polyethene.
Polystyrene or Poly (phenylethene)

Polystyrene is used for packaging and heat insulation. Polystyrene is much stronger than
PVC and Polyethene due to increase in molecular size, which increases intermolecular
attractions of polymer chain.
POLLUTION PROBLEMS OF POLY (ALKENES)

 Poly (alkenes) are non-biodegradable
 Incomplete combustion of the polymers produce soot and CO causing more pollution
 PVC releases HCl during degradation which is poisonous and adds to the increase in acidity of
the soil.
 Produces halogenoalkanes which initiates chain reactions leading to the depletion of the
ozone layer
 Aromatic compounds have highly conjugated ring systems, based on benzene ring. The simplest of
these aromatic compounds is benzene itself (C6H6). Other examples are:
STRUCTURE OF BENZENE
KEKULE STRUCTURE 1865

 In 1865 Kekule proposed a hexagonal structure with three double bonds for benzene. In 1872 he
further proposed (incorrectly) that benzene is a mixture of two six-membered-ring compounds,
each with three double bonds, in equilibrium with each other.
 Kekule’s equilibrium proposal by itself does not explain all the unusual properties of benzene.
However experimental evidence shows that benzene is not an alkene as:
Benzene does not decolourise bromine water in the dark (a simple test of alkenes).
Benzene does not decolourise KMnO4
The carbon to carbon bonds in benzene are all equivalent. Data from X-ray diffraction
showed that the carbon to carbon bond in benzene are all intermediate between a C=C
double bond and C—C single bond hence is a partial double bond.
C—C single bond in cyclohexane = 0.154nm
bond in benzene =0.139nm
C=C double bond in cyclohexene = 0.133nm
PAULING’S MODEL
 Pauling model of molecular orbital suggested that the electrons are delocalised in the π bonds of
the benzene ring stabilising the benzene thus lack of reactivity.
 In this model all, the atoms in the ring are planar with each carbon atom forming three sigma
bonds (one to a hydrogen atom and two to its adjacent carbon atoms).
 This leaves one electron in a 2p-orbital of each carbon atom that is perpendicular to the plane of
the ring.

 Because benzene is planar and symmetrical, the p orbitals do not overlap to form three pi bonds.
Instead, each p orbital overlaps equally with each of its neighbours. This results in six molecular
orbitals, which together form two doughnut-like π-clouds, one on each face of the benzene
skeleton (above and below). Because the electronic charge is evenly distributed, therefore the
molecular orbital is referred to as an aromatic pi cloud.
 The electrons in the pi ring system are delocalised within the pi electronic cloud and can be as far
apart as possible minimising repulsions between themselves.
NOMENCLACTURE OF BENZENE DERIVATIVES

 The term phenyl is used to relate to the C6H5— group and is used frequently in naming benzene
derivatives.
 The name of benzene derivatives containing two or more substituent groups is done by giving
the group which has a common name the number 1 position in the benzene ring. Other groups
are numbered by counting from position 1 in the manner that gives them the lowest locants.
For example: Common benzene derivatives
PHYSICAL PROPERTIES OF BENZENE

 Benzene is a colourless toxic liquid of boiling temperature 80 :C and melting temperature 5.5
:C. It is immiscible with water but soluble in other organic solvents.
 Benzene burns with a smoky luminous flame due to high carbon content.
 Benzene does not undergo addition reactions under ordinary conditions thus does not react with
reagents such as Br2. Addition reactions for benzene would require large amounts of energy than
is available under ordinary conditions and would result in the disruption of the delocalised pi
ring.
 Therefore, benzene would rather undergo substitution reactions than addition to maintain its pi
electron ring intact.

ELECTROPHILIC SUBSTITUTION REACTIONS OF BENZENE
 The benzene ring is electron rich and thus is prone to attack by electrophiles. During the
substitution reaction, an intermediate cation is formed in which there is partial disruption of the
delocalised π-ring. Loss of an H+ ion from the intermediate restores the delocalised π-ring system
from the product.
REACTIONS WITH HALOGENS

 Benzene reacts with halogens in the presence of a catalyst (halogen carrier).
 The catalyst used is a Lewis acid or halogen carrier e.g AlX3, FeX3 (where X is a halogen), which
polarises the halogen molecule forming the electrophile.
 The halogen carrier catalyst accept a pair of electrons from the halogen atom at one end of
the halogen molecule
 The molecule is polarised by the transfer of some electron density and the X—X bond splits
producing positively charged bromonium ion that act as the electrophile.
 The electrophile generated is then attacked by the π-electrons of the aromatic ring leading to
the formation of a carbocation
 The intermediate carbocation then loses a proton to form the substituted product.
 Regeneration of the catalyst:

FeBr4— + H+ FeBr3 + HBr
 With Chlorine AlCl3 or FeCl3 is used.
 Poly-substituted products can be obtained if the halogen is in excess.
NITRATION OF BENZENE
 Benzene reacts with a mixture of concentrated HNO3 and concentrated H2SO4 acid (nitrating
mixture) to produce nitrobenzene. The reaction takes place at about 50 :C, at temperatures
higher than 60 :C large amounts of dinitrobenzene are produced.

STEP 1: GENERATION OF AN ELECTROPHILE
 Aid-base reaction occurs between concentrated H2SO4 and concentrated HNO3 where HNO3 is
a weaker acid than H2SO4 hence act as a base for the formation of nitronium cation (NO2+).
H2SO4 being stronger acid, removes OH— from HNO3 forming the electrophilic species.
HNO3 + 2H2SO4 NO2+ + 2HSO4— + H3O++
STEP 2: ELECTROPHILIC ATTACK

 NO2+ (electrophile) attacks the electron π-ring system of benzene to from an unstable
carbocation (Wheland intermediate) which loses a proton by reacting with HSO4— ion to
regain its aromatic character.
 Formation of dinitrobenzene under these conditions is hindered due to the fact that, the nitro
group draws electrons towards itself making the ring less susceptible to further electrophilic
attack.
FREIDEL-CRAFTS ALKYLATION
 Alkyl groups substitute onto the benzene ring using a reaction similar to halogenation of
benzene. The reaction employs halogen carrier molecule (catalyst) and an alkyl halide. The
Lewis acid halogen carrier accepts a pair of electrons from the halogen on the alkyl halide
polarising the C—Hal bond and leaving the partially positive carbon atom prone to attack by
nucleophiles like the benzene ring. In some instance the C—Hal bond raptures forming a
carbocation.
For example:
NB: Formation of free methyl cation is thought to be unlikely as the cation is instable (no electron
donating groups attached to the +ve carbon atom to stabilise it). Attack by the benzene ring on the
+ve carbon atom is thought to occur simultaneously with the cleavage of the C—Cl bond.
FREIDEL-ACYLATION
 Benzene can be acylated using an acyl chloride, RCOCl and an acid chloride in the presence of
a Freidel-craft catalyst at 60 :C. The mechanism is similar to Freidel-craft alkylation.

EFFECT OF SUBSTITUENT GROUPS ON THE BENZENE RING
 When substituted benzene undergoes electrophilic attack, substituent groups on the benzene ring
affect both the rate of reaction and site of attack (position in which further substitution occurs) as
substituent groups affect the reactivity of the ring.
TYPES OF SUBSTITUENT GROUPS:
Activating Substituent Groups:

 These groups releases electrons onto the π-ring system of the benzene (by +ve inductive
effect), increasing the electron density making it more reactive/easily attacked by
electrophiles and direct further substitution on the 2, 4 and 6 position (2 and 6-ortho, 4-
para).
 The CH3—, CH3O—, OH—, C6H5— groups are electron donating hence they are ortho –para
directors and in practice a mixture of the ortho and para isomers are produced (Positional
Isomers).
For example: Phenol is more reactive towards electrophiles than benzene. When bromine is
added to a solution of phenol in the absence of a catalyst, there is immediate precipitation of
white 2, 4, 6-tribromophenol. The lone pair of electrons on the oxygen is partially delocalised
into the pi-ring system increasing the electron density of the benzene ring making phenol more
susceptible to electrophilic attack.
Deactivating Substituent Groups:

 These groups withdraw electrons from the π-ring system of benzene (by —ve inductive
effect), making it less reactive and electrophilic substitution reactions occur more slowly.
 These groups direct further substitution at the 3 and 5 positions (meta-position).
Examples of electron withdrawing groups:
Halogens, CN—, —COOH, —COR, —NH3+ (protonated amine), NO2+
NB: Halogens are weak deactivating groups hence they direct substitution on the ortho-para position.
All the other deactivating groups are meta-directors.
METHYLBENZENE (TOLUENE)
 The benzene ring and the CH3 group contribute to the properties of methylbenzene hence
methylbenzene undergoes two types of reactions which are:
 Electrophilic substitution in the ring just like benzene
 Side chain reactions similar to alkanes because it’s aliphatic
NB: The conditions determine which reactions take place.

REACTIONS OF BENZENE RING
 The benzene ring undergoes electrophilic substitution reactions.
 Methylbenzene is more reactive than benzene towards electrophiles as the methyl group has
a positive inductive effect. Electrophiles attack methylbenzene at the 2, 4 and 6 position.
 Milder conditions are employed than in the reactions of benzene and it proceeds faster.
Substitution reactions with halogens (Chlorination/Bromination)

 Reagents: Freidel craft catalyst AlCl3/AlBr3
 Conditions: in the dark @ room temperature
 In both cases a mixture of 2 geometric isomers are produced.
MECHANISM:
 Same as for benzene but the reaction proceeds faster than the one involving pure
benzene as the aromatic ring is activated.
Nitration of Methylbenzene
 Reagents: conc HNO3, conc H2SO4
 Conditions: at 30 :C
 A mixture of 1,2 and 1,4-substituted methylbenzene is obtained in each case.
If the HNO3 or halogen is in excess polysubstitution at the 2, 4 and 6 position occurs.

For Example:
MECHANISM:
 Same as for benzene but the reaction proceeds faster than the one involving pure benzene as
the aromatic ring is activated.
Alkylation:
 Reagents: RCl, AlCl3 catalyst
 Conditions: 20 :C
MECHANISM:

Acylation:
 Reagents: RCOCl, or (RCO)2O, AlCl3 catalyst
 Conditions: warm
MECHANISM:
REACTIONS OF THE METHYL GROUP

 Show reactions that resembles alkanes and it is also slightly modified by the benzene ring such
that some of its reactions does not resemble that of alkanes.
Radical Halogenation
 In the presence of UV light methylbenzene undergoes free radical substitution on the
methyl group
Oxidation of the methyl group

 The methyl group is oxidised to an aldehyde using dilute KMnO4
 The methyl group is oxidised to a carboxylic acid using hot acidified KMnO4 or K2Cr2O7
Alkyl groups of any lengths attached to the benzene ring are oxidised by acidified hot KMnO 4 to
give a carboxylic acid. The alkyl group is lost except the carbon attached to the benzene ring.

 Are organo-halogens with a hydrocarbon skeleton in which at least one hydrogen atom has been
substituted by a halogen atom. The hydrocarbon skeleton may be aliphatic or aromatic and the
halogen atom may be F, Cl, Br or I.
 The properties of the organo-halogen are influenced by:
 The type of hydrocarbon skeleton
 The position of the halogen atom(s) in the hydrocarbon skeleton
 The halogen(s) attached
 The three main types of organo-halogens are:
 Halogenoalkanes
 Halogenoarenes
 Acyl halides
NOMENCLATURE OF ORGANO-HALOGENS
 Changing the position of halogen atom in the hydrocarbon skeleton greatly affects the properties
of the molecule and it is thus important to state the position of the halogen correctly when
naming these compounds e.g.
PHYSICAL PROPERTIES OF ORGANOHALOGENS

 The electronegativities of halogens are high (F=4.0, Cl=3.0, Br=2.8, I=2.5 and C=2.5),
consequently the C—Hal bond is polar giving rise to dipole-dipole attractions with neighbouring
molecules. Halogenoalkanes therefore have high melting and boiling points than alkanes of
similar Mr.
For example: Boiling points of ethyl halides
Ethyl halide Boiling point/:C
CH3CH2Cl +12.4
CH3CH2Br +38.5
CH3CH2I +72.5
The boiling points of ethyl halides increases due to increase in the molecular size of the ethyl
halides from CH3CH2Cl to CH3CH2I resulting in an increase strength of Van der Waals’ forces of
attraction between the molecules.
 Halogenoalkanes unlike alkanes are slightly soluble in water due to interaction between the
polar molecule and water molecules. The attractive forces are not as strong as hydrogen bonds
in water.
 The compounds have a sweet, slightly sickly smell.

CHEMISTRY OF HALOGENOALKANES
 The C—X bond (where X—F, Cl, Br or I) is the reactive part of the halogenoalkane.
 Two factors which govern the reactivity of the C—X are:
 The C—X bond energy
 The C—X bond polarity
(a) C—X bond Energies:
C—F 467 KJmol-1
C—Cl 340 KJmol-1
C—Br 280 KJmol-1
C—I 240 KJmol-1
 The strength of the C—X depend on the size of the halogen atom, the bigger the halogen
atom the weaker the C—X bond as the shared electrons are further from the nuclei.
(b) Bond Polarity:

 The C—X bond is polarised (all the halogens are more electronegative than carbon giving
the halogens a δ—and the carbon a partial δ+ charge.
 Cδ+ Xδ— , the halogen has a negative inductive effect drawing electrons to itself.
 The C—X bond becomes more polarisable from C—Cl to C—Br to C—I
 Bond polarity predicts the natue of reagent that will attack the halogen.
 Halogenoalkanes are attacked by nucleophiles at the +ve centre of the Cδ+.
Order of reactivity: Iodo > bromo > chloro compounds, since C—X bond strength is increasing.
 In the reaction with nucleophiles the halogen is replaced by another nucleophile and the
reaction follows Nucleophilic Substitution (SN)
NUCLEOPHILIC SUBSTITUTION MECHANISMS

 The halogen molecule is replaced by an electron rich species (nucleophile) seeking a
positive centre. The rate of nucleophile substitution reaction is not very fast since the
halide ion is itself a nucleophile so the reaction mixture has to be refluxed (mixture heated
and the vapour cooled back in a stoppered condenser).
General mechanism of nucleophilic substitution reactions:
FIRST ORDER NUCLEOPHILIC SUBSTITUTION REACTION (SN1)

For example: Hydrolysis of a Tertiary halogenoalkane (2-bromo-2-methylpropane)

STEP 1: The halogen leaves the halogenoalkane leaving a reactive carbocation intermediate, which is then
attacked by nucleophile OH—.
STEP 2: The nucleophile attacks the carbocation intermediate.
 Step 1 is slow step since energy is needed to break the bond therefore the rate depends on the
concentration of the halogenoalkane thus reaction is of first order.
Rate= k[halogenoalkane]
SECOND ORDER NUCLEOPHILIC SUBSTITUTION REACTION (SN2)

For example: Hydrolysis of a Primary halogenoalkane (bromoethane)
 The reaction proceeds via a single step in which the nucleophile OH— attaches itself to the Cδ+
at the same time as the halogen Br leaves.
Mechanism:
 Rate depends on the [OH—] and [bromoethane]

Rate= k[OH—] [bromoethane]
 To minimise repulsion the nucleophile attacks from the side with the δ+.
REACTIONS OF HALOGENOALKANES AS EXAMPLIFIED BY BROMOETHANE
HYDROLYSIS (with H2O or NaOH/KOH)

Water being a polar molecule can act as a nucleophile replacing the halide atom with OH
forming an alcohol.
Hydrolysis with water on its own is slow and has little effect on the halogenoalkane.
However, the rate of the reaction can be increased by refluxing in the presence of an alkali
such as KOH, thus the reaction is called alkaline hydrolysis e.g
reflux
CH3CH2Br + OH— CH3CH2OH + Br—
Mechanism: same as for SN2 reaction
FORMATION OF NITRILES (Reaction with CN—)

Reagents: KCN or NaCN in ethanol
Conditions: reflux
The reaction involves refluxing a mixture of halogenoalkane and KCN/NaCN in ethanol to
give nitriles. The reaction is carried out in a non-aqueous condition to avoid hydrolysis of the
nitrile.
CH3CH2Br + CN— CH3CH2CN + Br—

Mechanism:
The reaction is used to increase the length of the carbon chain.
REACTIONS AMMONIA (Formation of Amines)

Reagents: conc NH3 in ethanol
Conditions: heat in a sealed tube
Ammonia acts as a nucleophile due to the lone pair of electrons on the nitrogen atom.
RCH2Br + NH3 RCH2NH2 + HBr
Mechanism:
When a primary halogenoalkane is used, a primary amine is produced. However, the primary
amine formed possesses a lone pair of electrons like NH3 and is even a much stronger
nucleophile than ammonia due to the electron donating nature of the alkyl group.
It will therefore react with free bromoethane molecules to form diethylamine (secondary
amine/ 2:amine).
In turn, diethylamine is even stronger nucleophile than ethylamine and goes further through
two further steps.
The result of such a reaction is a mixture of primary (1:), secondary (2:) and tertiary (3:) amines together
with an ammonium salt. For this reason, the reaction is not used in the laboratory preparation of
amines, although it is sometimes used in industries.

ELIMINATION REACTIONS IN HALOGENOALKANES
 This is the removal of a small molecule from a compound using a nucleophile (nucleophilic
elimination reaction).
 Under aqueous conditions, halogenoalkanes undergo nucleophilic substitution reaction with
hydroxide ions. However, under non-aqueous conditions, the hydroxide ion acts as a typical
base. In concentrated ethanolic solution, KOH removes a HX molecule from a halogenoalkane
forming an alkene.
Reagents: NaOH/KOH in ethanol (ethanolic solution)
Conditions: heat/reflux
FIRST ORDER ELIMINATION MECHANISM (EN1)

The reaction occurs in tertiary halogenoalkanes when they first ionise in ethanolic solution to
give an unstable carbocation and halide ion.
The unstable carbocation loses a hydrogen atom resulting in the formation of a double bond.
The rate of reaction depends on the concentration of the halide ion in solution, which initiate
the nucleophilic elimination reaction by attacking the hydrogen bonded to the carbon next to
the carbocation.
Rate= k[Br—]
SECOND ORDER ELIMINATION MECHANISM (EN2)
The reaction occurs in primary halogenoalkane when the OH— attacks the hydrogen atom
attached to the acidic alkyl group next to the carbon atom bonded to the halogen.
If the halogen is at the end of the chain, a poor yield will result which will be about 1%.
TESTS OF HALOGEN COMPOUNDS

Boil a little of the compound with NaOH for a few minutes, cool and acidify with HNO3 to
neutralise the reactants and add AgNO3:
 White ppt of AgCl shows the presence of a chloride in the halogenoalkane
 Pale yellow ppt shows the presence of bromide in the halogenoalkane
 Yellow ppt shows the presence of iodide in the halogenoalkane
USES OF HALOGENOALKANES (Fluoro-alkanes and Chlorofluoroalkanes)

Used as coolants in air conditions and refrigerators.
Used in fire extinguishers as they are heavier than O2 thus seclude O2.
Used in the manufacture of plastics.
Used as propellants in aerosol spray cans.
Used in the synthesis of pharmaceutical products and agrochemicals.

POLLUTION PROBLEMS OF CFC’s
CFC’s are non-biodegradable therefore their molecules rise up into the atmosphere
(stratosphere), where they interfere with natural ozone cycle and causing the depletion of the
ozone layer.
In the stratosphere the amount of radiation is high and this will cause CFC’s to break up
liberating Cl• radicals which react with ozone (O3).
Ozone forms a blanket in the stratosphere, which reduces the amount of radiation reaching the
surface of the earth by absorbing much of it. In the process ozone decomposes to O 2 and O•
radicals which then combine with O2 back to O3 thus maintaining a constant level of ozone in the
stratosphere.
UV
O3 O2 + O•
O2 + O• O3
The Cl• radicals produced during the decomposition of CFC’s by UV radiation interfere with
natural ozone cycle.
UV
CF2Cl2 •CF2Cl + Cl•
Cl• + O3 ClO• + O2
ClO• + O• Cl• + O2
ClO• + O3 ClO2 + O2
This leads to the formation of the ozone hole where UV will pass causing skin cancer, brain
tumours, mutations and damage of vegetation.
To reduce pollution problems substitutes of CFC’s have been established which contain no
chlorine.
REACTIVITY OF HALOGENOARENES
 Halogenoarenes have a halogen atom attached directly attached to the benzene ring.
where X is a halogen atom (F, Cl, Br, I)

 The halogen atom on halo-benzene is chemically unreactive as the C—X bond is exceptionally
strong (especially in C—Cl) due to the overlap of halogen lone pairs of electrons being drawn into
benzene delocalised pi-ring of electrons thus making the C—X bond a partial double bond hence
difficult to remove.
 The δ+ charge on the carbon atom bonded to the halogen is reduced, as it is partially neutralised
by the delocalised π-electron hence nucleophilic attack is difficult.
 This suggests that the C—X bond in halogenoarenes is less reactive compared to the same bond
in halogenoalkanes thus halogenoarenes do not undergo nucleophilic substitution reactions with
reagents like NaCN, NH3 as observed with halogenoalkanes.
 Harsh conditions are needed for the replacement of the halogen atom e.g alkaline hydrolysis of
chlorobenzene using a temperature of 350 :C and pressure of 150atm.

C6H5Cl + 2NaOH C6H5O-Na+ + NaCl + H2O
 The benzene ring undergoes the usual reactions although halogenoarenes are less reactive than
benzene as the halogen has a negative inductive effect thus direct substitution on the position
2/4.
 These are organic compounds, which contain the hydroxyl group as the main functional group.
 There are two types: (a) alcohols
(b) phenols
 They are classified as primary, secondary and tertiary alcohols.
PRIMARY ALCOHOLS 1o:

 Are alcohols in which the carbon atom carrying the —OH group is bonded to one alkyl group e.g
ethanol, CH3CH2CH2OH
SECONDAY ALCOHOLS 2O :
 Are alcohols in which the carbon atom carrying the —OH group is bonded to two alkyl groups e.g
propan-2-ol, butan-2-ol
TERTIARY ALCOHOLS 3O :
 Are alcohols in which the carbon atom carrying —OH group is bonded to three alkyl groups e.g
2-methylpropan-2-ol.
PHYSICAL PROPERTIES OF ALCOHOLS

 Alcohols are molecular structures where H-bonds are the major forces binding them together.
 Because of H-bonding, they have high boiling points than alkanes of equivalent mass or size.
 They are soluble in H2O because of H-bonding
CHEMISTRY OF ALCOHOLS
 Alcohols are weak acids with very low Ka values. The RO—H bond fission is involved in some
reactions as the alcohol dissociates in water. Other reactions involve fission of the R—OH bond.
REACTIONS OF ALCOHOLS
COMBUSTION
 They burn in air with a non-luminous flame e.g
CH3CH2OH + 3O2 2CO2 + 3H2O
RECTION WITH SODIUM (Acid –Metal reaction)

 Alcohols behave like typical acids in the presence of an electropositive element like sodium
giving off hydrogen gas and sodium alkoxide salt (white ppt). The reaction is much slower than
the reaction of water and sodium as water is more acidic than alcohols.

2CH3CH2OH(l) + 2Na(s) 2CH3CH2O—Na+ (s) + H2(g)
(sodium ethoxide)
The sodium alkoxide salt can undergo hydrolysis by water to give an alcohol and NaOH.
CH3CH2O—Na+ + H2O CH3CH2OH + NaOH
ESTERIFICATION
Alcohols reacts with carboxylic acids to form esters:

Reagents: carboxylic acid , H2SO4 acid catalyst
Conditions: heat
The RO—H bond cleave resulting in the elimination of H2O
The reaction is termed esterification reaction, which produces esters. The esters are volatile
organic compounds with a characteristic smell and for this reason; they are used as food
flavouring.
Reaction with acyl chlorides (Acylation) to form esters:

Reagents: Acyl chloride,
Conditions: at r.t.p
Acyl chlorides are much more reactive towards nucleophilic substitution than carboxylic
acids thus the reaction between an acyl chloride is rapid goes to completion and does not
require heating or acid catalyst.
NB: In the esterification reaction, the oxygen on the alcohol with its lone pair of electrons acts as the
nucleophile attacking the partially positive carbon atom on the acid halide.
NUCLEOPHILIC SUBSTITUTION OF —OH BY HALOGEN TO GIVE HALOGENOALKANES
Reaction with HX (X= Cl, Br, I)

Reagents: NaX/KX(solid), conc H2SO4/ H3PO4
Conditions: heat
The HX is prepared insitu by mixing NaX/KX with H2SO4 or H3PO4 in the presence of the
alcohol so that the HX produced reacts with the alcohol immediately. H3PO4 is used for the
preparation of HI as H2SO4 is a strong oxidising agent hence oxidises I— to I2.
NaX + H2SO4 HX + NaHSO4
ROH + HX H+ catalyst RX + H2O
NaI, H3PO4
ROH RI + H 2O
distil
Mechanism of reaction:
The —OH group in alcohols is polar (—Oδ——Hδ+ ) and in the presence of a strong acid, the
—OH group becomes protonated.

The protonated oxygen atom now carries a positive charge and it attracts electrons in the
C—O bond causing a large positive charge on the carbon atom, making it more prone to
attack by nucleophiles
Order of reactivity of HX is HI > HBr > HCl

Order of reactivity of alcohols 3o > 2o > 1o
Reaction with Phosphorus halides (PX3 or PX5)

Reagents: PX3 or PX5
Conditions: reflux/heat
The reaction of alcohols with PX5 is used to test for the presence of the —OH group in
alcohols.
reflux
3R—OH + PX3 3RX + H3PO4
e.g 3CH3CH2OH + PI3 3CH3CH2I + H3PO4
heat
R—OH + PX5 RX + POX3 + HX (white fumes)
e.g CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl (white fumes)
To make iodo- and bromo- compounds, PI3 and PBr3 are used respectively which are generated
insitu by reacting red phosphorus with iodine or bromine in the presence of the alcohol.
DEHYDRATION OF ALCOHOLS
 Alcohols are dehydrated to give alkenes by eliminating a H2O molecule. This is done by passing
the alcohol over hot Al2O3 at 300 oC.
e.g dehydration of ethanol Al2O3
CH3CH2OH o
300 C CH2CH2 + H2O
 When an alcohol is heated to 170 oC in the presence of concentrated H2SO4, it loses a water
molecule to form ethene. The acid firsts protonate the —OH group of the alcohol and the
water molecule is then lost since there is no nucleophile to attack the partially positive carbon
atom.
Overall reaction: Conc H2SO4

CH3CH2OH o
170 C
CH2CH2 + H2O
H2SO4 is not a good dehydrating agent as it will oxidise the alcohol to aldehydes and then to
carboxylic acids.

TRIIODOMETHANE REACTION (IODOFORM)
 The reaction is used to classify alcohols and occur with alcohols containing the group
.
Reagents: NaOH , I2 solution
Conditions: warm/heat
Alcohols with the group above are oxidised by alkaline iodine form a yellow ppt of
triiodomethane, CHI3.
 Alcohols which give a positive test:

a) For primary alcohols, only ethanol gives a positive test.
b) For secondary alcohols, all secondary alcohols with the group above give a positive test
e.g propan-2-ol, butan-2-ol.
c) For tertiary alcohols, none of them gives a positive test.
OXIDATION OF ALCOHOLS
 Oxidation reactions of alcohols can be used to distinguish whether an alcohol is a primary,
secondary or tertiary since each type of alcohol gives a different product from the others with
respect to oxidation.
Reagents: acidified conc K2Cr2O7/KMnO4
Conditions: Mild oxidation (r.tp/cold)
Strong Oxidation (heat)
a) Primary alcohols: are oxidised to aldehydes (mild oxidation), which can be further oxidised
to a carboxylic acid (strong oxidation).
e.g
The propanal so formed is further oxidised to produce propanoic acid.
The colour change is due to the orange dichromate (VI) being reduced to green Cr 3+ ions.
All primary alcohols produce aldehydes on mild oxidation (alkaline, cold K 2Cr2O7) and
carboxylic acids on strong oxidation (acidified, hot K2Cr2O7).
b) Secondary alcohols: are readily oxidised to give ketones, however the ketone formed is
resistant to further oxidation as keto- group carries no hydrogen atoms.

c) Tertiary alcohols: have no hydrogen atoms on the carbon atom carrying the —OH group
and cannot be oxidised by common oxidising agents. Prolonged treatment of a tertiary
alcohol with stronger oxidising conditions causes the molecule to break-up into a mixture
of oxidation products.
TEST FOR ALCOHOLS:

Add PCl5 to the compound, if alcohol is present white fumes of HCl gas are observed.
Carboxylic acids also give the same result but unlike alcohols they also give a pH less than 7
with universal indicator.
Add a carboxylic acid/acyl chloride , a little conc H2SO4 to the compound and boil the mixture
for a minute, if alcohol is present an ester is produced which gives off a sweet smell/scent.
Boil the compound with a little acidified K2Cr2O7, 1oand 2o alcohols reduce orange dichromate
(VI) to green Cr3+ ions.
 Has an —OH group directly attached to an arene/benzene ring e.g.
PHYSICAL PROPERTIES:
 They have relatively high melting and boiling points due to H—bonding, therefore they are
moderately soluble in water since the benzene ring is hydrophobic but the —OH group
dissolves.
CHEMISTRY OF PHENOLS:
 Phenols are less prone to attack by nucleophiles as compared to alcohols.
 The C—O bond is stronger than in an alcohol, since one of the lone pair of electrons on the
oxygen atom overlaps with the delocalised π-orbital giving C—O bond in phenol some double
bond character hence making it difficult to break than in alcohols.
 Therefore reactions of phenol mainly involve the cleavage of O—H bond and electrophilic
substitution on the benzene ring.
ACIDITY OF PHENOLS (Compared to Ethanol and water):

 Alcohols and phenols resemble water in a number of ways e.g they all form hydrogen bonds,
solvents for polar solvents and they are amphoteric like water.
 The three (phenol, ethanol and water) reacts with Na liberating H2 gas. The reactions suggest
that ethanol and phenol contain H+ ions and to some degree ionise in solution giving H+ ions.

Relative acidities in decreasing order: Phenol > water > ethanol
Explanation:
 The greater the Ka value the greater the degree of dissociation and hence the stronger the acid.
The relative acidities of these molecules can be understood by looking at the conjugate base
formed in the acid dissociation equilibrium.
 The more stable the conjugate base formed, the greater the extent of dissociation.
 Ethanol: is the weakest acid than water and phenol because the alkyl group attached to the
negatively charged oxygen atom donates electrons (+ve inductive effect) towards the negatively
charged oxygen atom, increasing its affinity for H+ ions and hence the equilibrium lies more to the
left in favour of un-dissociated ethanol.
 Water: is more acidic the ethanol but less than phenol as the H-atom on the OH— has no effect on
the hydroxide ion thus comparatively stable.
 Phenol: is a stronger acid than both H2O and ethanol because the negative charge on the oxygen
atom in phenol can be delocalised into the π-ring system reducing its charge density making it less
willing to accept H+ ions, therefore the equilibrium lies more to the right than in water and
ethanol. Electron withdrawing groups like —NO2 or —Cl increase the acidity strength of phenol by
further delocalising the negative charge on the oxygen atom into the benzene π-ring thus
derivatives of phenol with electron withdrawing groups are used as antiseptics.
Electron donating groups make phenol less acidic e.g —CH3.
REACTIONS OF THE —OH GROUP IN PHENOL
REACTION WITH Na
REACTION WITH NaOH
Phenols react with NaOH but alcohols do not react with NaOH.
ESTERIFICATION
Phenols react with acyl chlorides and not with carboxylic acids because the lone pair of electrons
on the oxygen are partially delocalised into the benzene ring making it a weaker electrophile,
therefore the phenol is first converted into phenoxide ion (which is a stronger nucleophile) by
reaction with NaOH.
REACTION WITH FeCl3

Phenols produce a purple complex with FeCl3 in which the phenol is acting as a ligand. This is
often used as a test of phenols or an —OH group bonded to an unsaturated system.
REACTIONS OF BENZENE RING
 Phenol is much more reactive towards electrophilic substitution reactions than the benzene
ring due to the net electron releasing effect of the —OH group (oxygen attracts electrons than
through the C—O sigma bond but the is outweighed by the release of electrons from oxygen
lone pair onto the benzene ring through the p-orbital —π overlap).

 The —OH activates the ring and is a 2, 4 and 6 director.
BROMINATION OF PHENOL
Phenol reacts at r.t.p with aqueous Br2 to give 2, 4, 6-tribromophenol. Brown colour of bromine
is discharged giving a white ppt of 2, 4, 6-tribromophenol and white fumes of HBr gas.
NITRATION OF PHENOL
Phenol can be nitrated by dilute HNO3 at room temperature to give a mixture of mixture of 2-
nitrophenol and 4-nitrophenol.
Nitration of phenol under more vigorous conditions of concentrated HNO 3 and concentrated
H2SO4 yields 2,4,6-trinitrophenol.
2,4,6-trinitrophenol is highly explosive and decompose spontaneously and exothermically

producing large volumes of CO2, steam and N2 which expand to produce an explosive shock.
Phenols:
 Do not react with PX3/PX5
 Do not undergo dehydration
 Are not oxidised to carboxylic acids

 Are organic compounds containing the carbonyl group . These are aldehydes and
ketones. They have the general formula CnH2nO.
ALDEHYDES
 Have the carbonyl group C=O at the end of the hydrocarbon chain. The have the
functional group and the general formula where R is an alkyl group or H

atom.
Examples: ethanal, propanal, butanal.
KETONES
 Have the carbonyl group C=O within the hydrocarbon chain. The position of the C=O
group may vary giving rise to positional isomers.
 Ketones have the general formula where R1 and R2 are alkyl or aryl groups e.g
propanone. phenylathanone
PREPARATION OF CARBONYL COMPOUNDS:
Oxidation of primary or secondary alcohols using acidified K2Cr2O7 (no refluxing)

For example:
CH3CH2OH + [O] CH3CHO + H 2O
The aldehyde produced must be distilled out as soon as it is formed otherwise it will be oxidised
to an organic acid. Secondary alcohols will be oxidised to ketones, which do not undergo further
oxidation.
CH3CH(OH)CH3 + [O] CH3COCH3 + H 2O
Catalytic dehydrogenation of alcohols

When primary alcohol vapour is passed over copper at a temperature of about 300 oC
dehydrogenation takes place and aldehyde is produced.
CH3CH2OH CH3CHO + H2(g)
If secondary alcohols are used ketones will be produced.
CH3CH(OH)CH3 CH3COCH3 + H2 (g)
Hydrolysis of Dihalides
A nucleophilic substitution hydrolysis occurs when a dihalide is heated under reflux with aqueous
NaOH.
CH3CHCl2 + 2OH— REFLUX CH3CH(OH)2 + 2Cl— dehydration
CH3CHO + H2O

CHEMISTRY OF CARBONYL COMPOUNDS
 Most of the reactions of the carbonyl compounds involve the which is strongly polar
, however the electron density lies more electronegative oxygen atom making the
C more positive. This means that nucleophilic reagents may attack the Cδ+.
δ+
 Since there is a double bond most reaction of the carbonyl compounds are nucleophilic
addition reactions which results in the breaking up of the π-bond.
REACTIONS OF CARBONYL COMPOUNDS
Nucleophilic Addition with HCN

 Aldehydes and ketones react with HCN to form hydroxyl nitriles. The CN— add to the
carbonyl group.
 Since HCN is a weak acid which ionises partially in aqueous solution, the reaction is usually
done in the presence of trace NaCN (catalyst) to provide CN— to initiate the reaction or little
NaOH to react with HCN to liberate CN— to start the reaction.
Reagents: HCN, trace NaCN (catalysts)/little NaOH
Conditions: @ r.t.p
Mechanism of Reaction:
R1 and R2 may be alkyl or aryl or H atom

e.g
NaCN
CH3COCH3 + HCN CH3C(CH3)(OH)CN (2-hydroxyl-2-methylpropanonitrile)
NaCN
CH3CHO + HCN CH3CH(OH)CN (2-hydroxylpropanonitrile)
Benzaldehydes do not give nitriles with KCN/NaCN/HCN but rather undergoes a condensation
reaction catalysed by the CN— ion due to presence of the π electron system of the benzene
which neutralises the δ+ charge on the carbon atom of the carbonyl group thus less prone to
nucleophilic attack.
Addition Elimination (Condensation) Reaction

 Carbonyl compounds undergo addition-elimination reactions with derivatives of
ammonia with general formula NH2—X.
 The NH2—X group is first added and then a water molecule is eliminated from
intermediate formed.

Mechanism of reaction

e.g Reaction with 2,4-dinitrophenylhydrazine/ Brady’s Reagent
Carbonyl compounds react with Brady’s reagent to produce an orange crystalline solid of 2,4-
dinitrophenylhydrazone with well-defined melting point. This reaction is used to test for the
presence of carbonyl compounds.

Reduction
 Aldehydes and ketones can be reduced to give alcohols. Aldehydes are reduced to
primary alcohols while ketones yield secondary alcohols.
 Suitable reducing agents include:
a) H2 with a catalyst of Ni/Pt or Pd
b) Na/Zn in ethanol (H2 gas liberated act as a reducing agent)
c) Lithium tetrahydridoaluminate (III), LiAlH4 in ethoxy ethane followed by water
d) Sodium tetrahydridoborate (II), NaBH4 in aqueous solution
e.g CH3CHO + 2[H] CH3CH2OH

CH3COCH3 + 2[H] CH3CH(OH)CH3
The Triidomethane Reaction
 Aldehydes and ketones which contain the group give a positive

triidomethane test i.e yellow ppt of CHI3 when warmed with I2 and NaOH in aqueous
solution.
 The reaction is used to test for aldehydes and ketones whose carbonyl group is attached to
a terminal CH3— group.
 In aldehydes only ethanal gives a positive test of triidomethane.
e.g
CH3CHO + 3I2 + 4NaOH WARM CHI3 + HCOO—Na+ + 3NaI + 3H2O
(yellow ppt)
 All ketones with the group gives a positive of triidomethane test.

e.g propanone, butanone, phenylethanone
CH3COCH3 + 3I2 + 4NaOH WARM CHI3 + CH3COO—Na+ + 3NaI + 3H2O
(yellow ppt)

Oxidation
 Aldehydes are oxidised to carboxylic acids by oxidising agents such as K2Cr2O7/KMnO4 in
H2SO4 under refluxing or even by mild oxidation.
e.g K2Cr2O7/ KMnO4
CH3CHO H2SO4, reflux CH3CO2H
 The oxidation of ketones requires the breaking of the C—C bond therefore resistant to
oxidation and will only react after prolonged treatment with very strong oxidising agent.
DISTINGUISHING ALDEHYDES FROM KETONES

 Aldehydes and ketones show a number of similarities in most of the reactions but they can
however be easily distinguished by using oxidising agents.
 Weak or mild oxidising agents can oxidise aldehydes to carboxylic acids but not ketones.
The mild oxidising agents are:
a) Tollen’s reagent(Silver mirror Test)
 Tollen’s reagent consist of AgNO3 dissolved in aqueous ammonia resulting in the
formation of the diamine silver (I) complex ions [Ag(NH3)2]+.
 When Tollen’s reagent is warmed with an aldehyde, the aldehyde is oxidised to a
carboxylic acid while the complex silver (I) ions are reduced to grey metallic silver atoms,
which are deposited on the walls of the test tube as a silver mirror.
R—CHO(aq) + 2[Ag(NH3)2]+ (aq) + 3OH— warm

R—COO— + 2Ag(s) + 4NH3 + 2H2O
colourless grey silver metal
b) Fehling’s reagent
 This is a solution containing alkaline Cu2+ ions, complexed by 2,4-dihydroxybutanedioate
ions. When aldehyde is warmed with Fehling’s solution, the aldehyde is oxidised by the
Cu2+ ions to give a carboxylic acid while blue Cu2+ ions are reduced to a brick red/red-
brown precipitate of Cu (I) oxide.
R—CHO(aq) + 2Cu2+(aq) + 4OH—(aq) warm

R—COO—(aq) + Cu2O(s) + 2H2O(l)
 Ketones do not react with Tollen’s reagent or Fehling’s reagent.

 Aromatic aldehydes (benzaldehyde) do not react with Tollen’s or Fehling’s reagents.

 Are organic compounds which contain the functional group (carboxyl group).
 General formula:
PHYSICAL PROPERTIES
 Carboxylic acids have high melting and boiling points. This is because the molecules can form
hydrogen bonds between themselves using the —OH and C=O groups.
 Due to the formation of hydrogen bonds, carboxylic acids are soluble in in water.
 The formation of hydrogen bonds in carboxylic acids occur to a greater extent, such that the
molecules can exist as hydrogen bonded dimers in the pure acid vapour, liquid and solid state.
CHEMICAL PROPERTIES
 The carboxyl group consists of a hydroxyl group (—OH) and a carbonyl group (C=O) attached to the
same carbon atom.
 These two functional groups modify each other such that carboxylic acids have chemicals properties
which are distinct from alcohols and carbonyl compounds e.g the —OH is more acidic than an
alcohol or phenol.
 The greater acidity of carboxylic acids compared to alcohols is because the polar—C=O group is
electron withdrawing, attracting electrons away from the —OH (electron donating group) making it
easier for the H-atom to ionise than in the case of the —OH bond in alcohols.
ACIDITY OF CARBOXYLIC ACIDS

 Carboxylic acids are weak organic acids, they partially ionise in water to form a carboxylate anion.
The above equilibrium lies to the left as carboxylic acids are weak acids.

The two C—O bond in the carboxylate anion are equivalent, thus the negative charge is delocalised
between the two oxygen atoms to stabilise the carboxylate anion.
EFFECT OF SUBSTITUENT GROUPS ON ACIDTY

 Electron withdrawing groups like halogens in the R— group of RCO2— further stabilise the
carboxylate anion (by displacing the negative charge) and increase acid strength, thus halogen
substituted acids are stronger acids than ethanoic acids.
 The strength of substituted acids depends on:
a) Number of substituent group- the greater the number of electron withdrawing groups the
greater the inductive effect and the greater the acid strength (and the vice versa).
e.g CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H
pKa 4.8 2.86 1.3 0.7
b) Position of substituent group- the further away the electron-withdrawing group it is from
the —CO2H group the weaker the acid.
e.g CH2ClCH2CO2H < CH3CHClCO2H
pKa 4.1 2.8
c) Type/Electronegativity of substituent group- the more the electronegativity of the
substituent the stronger the acidity e.g chloro substituted carboxylic acids are stronger acids
than brono and iodo substituted acids.
e.g CH2BrCO2H < CH2ClCO2H < CH2FCO2H
pKa 2.9 2.86 2.6
 Benzoic acid is stronger acid than ethanoic acid because the negative charge on the carboxylate ion
is delocalised over the benzene ring.
PREPARATION OF CARBOXYLIC ACIDS
FROM ALCOHOLS
 Primary alcohols are oxidised via aldehydes to carboxylic acids.
Reagents: K2Cr2O7/KMnO4 in H2SO4
Conditions: reflux/ heat
K2Cr2O7/ KMnO4
CH3CH2OH H2SO4, reflux CH3CHO CH3CO2H
FROM ALDEHYDES
 Aldehydes are oxidised to carboxylic acids.
Reagents: K2Cr2O7/KMnO4 in H2SO4
Conditions: reflux/ heat
K2Cr2O7/ KMnO4
CH3CHO H2SO4, reflux CH3CO2H

HYDROLYSIS OF NITRILES
 Nitriles are hydrolysed to carboxylic acids by refluxing with aqueous solution of a mineral acid
or base
 Acid Hydrolysis H
+
RCΞN + 2H2O reflux RCO2H + NH4+

e.g. +
H
CH3CΞN + 2H2O reflux CH3CO2H + NH4+
 Base Hydrolysis —
OH
RCΞN + H2O reflux RCO2— + NH3
e.g —
OH
CH3CΞN + 2H2O reflux CH3CO2— + NH3 followed by adding an acid to
protonate the carboxylate anion.
CH3CO2— + H+ CH3CO2H
 Nitriles can be obtained from acylation of halogenoalkanes
R—X RCN + 2H2O RCO2H + NH4+
REACTIONS OF CARBOXYLIC ACIDS
FORMATION OF SALTS
 Carboxylic acids form salts by reaction with alkalis, metals carbonates or more reactive
metals.
 The ionic salts have crystalline structures which dissolve in water.
a) Reaction with Na or Mg (acid-metal reaction)
2RCOOH(aq) + 2Na(s) 2RCO2—Na+ (aq) + H2 (g)
— 2+
2RCOOH(aq) + Mg(s) (RCO2 )2Mg (aq) + H2 (g)
b) Reaction with Na2CO3(acid –base reaction)

Since carboxylic acids are stronger acids than phenols, they displace CO2 from solutions of
carbonates. This test is used to distinguish carboxylic acids from alcohols and phenols.
2RCO2H(aq) + Na2CO3 2RCO2—Na+ (aq) + H2O(l) + CO2 (g)
c) Reactions oxides
2RCO2H + CuO (RCO2)2Cu + H2O
d) Reaction with NH3

RCO2H + NH3 RCO2— + NH4+ heat
RCONH2
ESTERIFICATION
 Carboxylic acids react with alcohols in the presence of a strong acid catalyst e.g H2SO4 to form
esters.
R1CO2H + R2OH R1COOR2 + H 2O

 In esterification of secondary and tertiary alcohols, there is fission of the R—OH, therefore the
yield of the ester is very low.
NUCLEOPHILC SUBSTITUTION (Formation of Acyl chlorides)

 Carboxylic acids react with PCl5 or SOCl2 to form acyl chlorides. The Cl— liberated from
PCl5/SOCl2 acts as the nucleophile which replaces the OH— group.
RCO2H + PCl5 RCOCl + POCl3 + HCl (white fumes)
RCO2H + SOCl2 RCOCl + SO2 + HCl (white fumes)
Mechanism:
REDUCTION
 NaBH4/LiAlH4 in ethoxyethane (ether) will reduce carboxylic acids to primary alcohols.
ethoxyethane
RCO2H + 4[H] RCH2OH + H2O
DEHYDRATION
 P2O5 will remove a molecule of water from 2 molecules of carboxylic acids to yield an
anhydride.
 Anhydrides react with alcohols to give an ester and carboxylic acid.

 These are derivatives of carboxylic acids with the —OH group substituted by a Cl-atom.
 They contain the functional group

General formula:
CHEMISTRY OF ACYL CHLORIDES

 Acyl chlorides are very reactive because of the carbonyl carbon that is highly electron deficient
due to the electron withdrawing effects of the highly electronegative O and Cl atoms; hence, it
acts as positive centre for nucleophilic attack.
 Acyl chlorides generally react by losing a Cl— ion in nucleophilic substitution reactions.
 Aromatic acyl chlorides are less reactive than aliphatic acyl chlorides.
REACTIONS OF ACYL CHLORIDES
HYDROLYSIS
 They are hydrolysed rapidly to give a carboxylic acid, HCl and heat.
RCOCl + H2O RCO2H + HCl (white fumes)
e.g CH3COCl + H2O CH3CO2H + HCl (white fumes)
Mechanism of reaction
 A solution of the product gives an immediate precipitate of AgCl with a solution of AgNO3.
ESTERIFICATION
 Acyl chlorides react with alcohols to form esters in the presence of pyridine (base which
removes the HCl produced).
pyridine
RCOCl + ROH RCO2R + HCl
pyridine
e.g CH3COCl + CH3CH2OH CH3CO2CH2CH3 + HCl

AMIDE FORMATION
 Acyl chlorides react with primary amines or ammonia to produce amides.
room temperature
RCOCl + R’NH2 RCONHR’ + HCl
e.g CH3COCl + CH3CH2CH2NH2 CH3CONHCH2CH2CH3 + HCl
Mechanism: similar to hydrolysis of acyl chlorides.
KETONE FORMATION (Freidel crafts reaction AlCl3 /FeCl3)

Acyl chlorides react with electron rich species such as benzene to form ketones in electrophilic
substitution reactions
 They are colourless volatile liquids with a pleasant fruity smell.

 Lower members are moderately soluble in organic solvents.
General formula:
 The bridging oxygen is from the alcohol thus the parent name is of the carboxylic acid with suffix
–ate and the alkyl or aryl group from the alcohol becomes the side group.
e.g
FORMATION OF ESTERS
a) Reactions of carboxylic acids with alcohols
b) Reaction of alcohols with acyl chlorides
c) Reactions of phenols with acyl chlorides
REACTIONS OF ESTERS
Hydrolysis
Esters can be hydrolysed by warming them with dilute acid or alkali to produce acid and
alcohol. The reaction is essentially the reverse of esterification
Acid hydrolysis
+
H2O, H
e.g CH3COOCH2CH3 warm CH3CO2H + CH3CH2OH

Base hydrolysis
—
H2O, OH
e.g CH3COOCH2CH3 CH3CO2— + CH3CH2OH
warm
USES OF ESTERS
Esters are used for manufacture of polyesters like terylene.
a) Polyester (Terylene)
 These are synthetic polymer fibres which are used to substitute cotton and wool.
 They are formed when diols react with dicarboxylic acid to give polyester during a
condensation polymerisation reaction.
 In the polyester, ester linkages join the monomers together.
b) Used as solvents, as they are good organic solvents e.g in paints and varnishes
c) Used in production of soap through saponification reactions
d) Used in perfumes and flavouring material as they have a sweet scent/aroma.

 There are three main types of organic nitrogen containing compounds namely:
1) AMINES
 These are regarded as organic derivatives of NH3 in which one or more H-atoms in NH3 has been
substituted by an alkyl or aryl group.
Classes of Amines:
a) Primary amines: have only one hydrocarbon skeleton joined to the nitrogen atom
General Formula:
b) Secondary amines: have two hydrocarbon groups attached to the nitrogen atom
General Formula:
c) Tertiary amines: have three hydrocarbon skeletons attached to the nitrogen atom
General Formula:
2) AMIDES
 Amides are derivatives of the carboxylic acids in which the —OH group of the —COOH group is
substituted by the —NH2 group.
 There are two classes of amides :
i. Simple amides of general formula
General formula:
ii. Substituted amides
3) AMINO ACIDS
 These are organic molecules consisting of an amine group and a carboxylic acid group attached
to the same carbon atom.
 Alpha (α) amino acids are the building units or monomers of proteins.

General Formula:
PHYSICAL PROPERTIES
 Amines have a relatively high boiling point, but not as high as the alcohols since the HN...H bond is
much weaker than the HO...H bond since nitrogen is less electronegative than oxygen. Tertiary
amines bear no N—H bonds and cannot hydrogen bond to themselves, so their boiling points are
lower e.g
CH3CH2CH2NH2 bp: 48 :C
CH3CH2NHCH3 bp: 37 :C
CH3 N(CH3)CH3 bp 3 :C
 Primary amines with chain length up to C4 are very soluble in water as they can easily form
hydrogen bonds (solubility of amine decreases with increase in the hydrophobic chain).
 Di- and Tri- substituted amines are less soluble as there is less hydrogen bonding.
 Phenyl amine is slightly soluble in water due to the unavailability of the lone pairs of electrons on
the nitrogen atom, as they will have been delocalised onto the benzene ring.
PREPARATION OF AMINES
REDUCTION OF NITRILES
 Nitriles are reduced to primary amines by LiAlH4 or NaBH4 e.g
LiAlH4 , NaBH4
CH3CΞN Dry ether, reflux CH3CH2NH2
HEATING HALOGENOALKANE WITH CONC.NH3 IN A SEALED TUBE

e.g
CH3CH2Cl + NH3 CH3CH2NH2 + HCl
AROMATIC AMINES
 Aromatic amines are made by the reduction of aromatic nitro compounds. A variety of
reducing agents can be used including catalytic hydrogenation, NaBH4/LiAlH4 or tin and HCl in
alkali. NaOH is used to remove the residual H+ which would otherwise protonate the —NH2
group.
BASICITY OF AMINES
 Amines are relatively weak bases. They owe their basic nature to the electronegative nitrogen
atom that carries a lone pair of electrons and can accept an H+ ion. Amines react with acids to
form salts.
CH3CH2NH2 + HCl CH3CH2—NH3+ Cl—
Amine salts are soluble crystalline white solids similar to ammonium chloride.

Comparison of the Relative Basicity of NH3, ethylamine and phenylamine
 An amines’ strength as a base; is the ability of the amine to accept a proton which is governed by
the availability of the lone pair of electrons.
Order of Basicity: CH3CH2NH2 > NH3 > Phenylamine

 The base dissociation constants (Kb values) suggest that ethylamine is a stronger base than
ammonia and phenylamine.
 Ethylamine owes its strong basicity to the electron donating nature of the ethyl group. As the
ethyl group donates electrons towards the nitrogen atom of the amine group, it increases the
electron density on the nitrogen atom increasing its affinity for H+.
 The positive inductive effect of the ethyl group also stabilises the conjugate acid formed as it
partially neutralises the positive charge on the nitrogen atom in ethylammonium ion making it
more stable and therefore the equilibrium lies more to the right for ethylamine than for
ammonia where there is no electron-donating group.
 Electron releasing groups increase basicity e.g diethylamine a secondary amine with two alkyl
groups is a stronger base than ethylamine as it has two electron donating groups.
 Phenyl amine is a much weaker base than aliphatic amines. This is because the lone pair of
electrons on the nitrogen atom becomes partially delocalised into the benzene π-ring system
reducing its tendency to accept H+ ions.
REACTIONS OF AMINES
REACT WITH HALOGENOALKANES (ALKYLATION)

 Primary, secondary and tertiary amines react with halogenoalkanes in alcohol solution
through nucleophilic substitution reaction.
Primary amines:
Secondary amine:

Tertiary amine:
ACYLATION
 The hydrogen atoms bonded to the N-atom in primary and secondary amines can be replaced
by the RCO—group in the presence of NaOH under reflux.
e.g
RNH2 + RCOCl RCONHR + HCl
RNHR’ + R”COCl RN(R’)COR”
Tertiary amines have no replaceable H-atoms, therefore they are not acylated.
REACTIONS OF PHENYLAMINES
REACTIONS OF THE —NH2 GROUP

 The —NH2 group in phenyamine can be protonated by acids to form salts e.g
 Phenylamine also reacts with acyl chlorides to give amides
REACTIONS OF THE BENZENE RING
Electrophilic substitution with Br2

The lone pair of electrons on the nitrogen atom tends to be partially delocalised into the ring
increasing the electron density of the ring, making phenyl amine undergo electrophilic
substitution much more readily than benzene.
NH2 is a 2, 4 and 6 director thus phenylamine reacts with Br2 (in the absence of a catalyst) to give
a white precipitate of 2,4,6-tribromophenylamine while the brown colour of Br2 is discharged.
FORMATION OF DIAZONIUM SALTS AND AZO DYES

 Phenylamine reacts with nitrous acid (HNO2) below 5 oC to form benzene diazonium ions
(diazotisatio).
 Nitrous acid is very unstable and it has to be prepared in-situ using sodium nitrous (NaNO2) and
concentrated HCl. The diazonium compounds formed are very unstable hence, they also
require a temperature below 5 oC.

< 5 :C
NaNO2(aq) + HCl(aq) NaCl(aq) + HNO2(aq)
< 5 :C
RNH2(aq) + HNO2(aq) + HCl(aq) R—N+ΞNCl— (aq) + 2H2O(aq)
A slight increase in temperature would result in the dazonuim salt decomposing to a carbocation
and N2 gas.
R—N+ΞN (aq) R+(aq) + N2(g)
+
The presence of the diazonium group —N2 makes the ring susceptible to electrophilic
substitution reactions as the decomposition of the diazonium ion creates a carbocation
Diazo-coupling Reactions
 The positively charged diazonium group (—N2+) is a strong electrophile and will therefore attack
another benzene ring, especially that which already carries an electron donating group such as
NH2, OH.
 The reaction results in the formation of —N=N— bridge between 2 aromatic rings and this is
called azo coupling.
 Azo compounds are brightly coloured due to the extensive delocalisation of electrons extending
from one ring to the next through the —N=N— bridge (the —N=N— is a chromophore, it
absorbs light).
 Due to the thermal instability of the diazonium salts, coupling reactions must be carried out
below 5oC.
Uses of azo compounds
1. dyes for fabrics and food
2. acid base indicators
Common Azo Dyes

 Simple amides have the general formula:
 Substituted amides :
 They contain the group of the amide bond/linkage called the peptide linkage.
PREPARATION OF AMIDES
Reaction of Acyl chlorides with Amine or concentrated NH3
Reaction of primary amines with carboxylic acids(condensation)
HYDROLYSIS AMIDES
 Amides can be hydrolysed in acid or alkaline solution to yield the carboxylic acid derivative and
an amine derivative.
Acid hydrolysis: yields an ammonium salt and carboxylic acid e.g
+
H2O ,H
RCONH2 reflux
RCO2H + NH4+
+
H2O ,H
e.g CH3CONH2 reflux CH3CO2H + NH4+
+
H2O ,H
For substituted: RCONHR’ RCO2H + R’NH3+
reflux
+
e.g CH3CONHC6H5 H2O ,H CH3 CO2H + C6H5NH3+
reflux
Alkaline Hydrolysis: yields an amine and carboxylic acid salt

H2O ,NaOH
RCONH2 reflux RCO2— Na+ + NH3
H2O ,NaOH
e.g CH3CONH2 reflux CH3CO2—Na+ + NH3

For substituted:
H2O ,NaOH
RCONHR’ RCO2—Na+ + R’ NH2
reflux
e.g
H2O ,NaOH
CH3CONHC6H5 CH3 CO2—Na+ + C6H5NH2
reflux
Evolution of NH3 is used as a simple test of simple amides.
DEHYDRATION
Undergo dehydration using P2O5 to give nitriles and H2O e.g
Phosphorus (IV) oxide
CH3CONH2 CH3CN + H2O
REDUCTION
Amides are reduced by NaBH4 to amines and water e.g.
CH3CONH2 + 4[H] CH3CH2NH2 + H2O
 Amino acids are the building units of proteins and consists of 2 functional groups, the amine and
carboxylic acid group attached to the same carbon atom called the alpha (α) carbon hence they
are called α-amino acids.
 Alpha amino acids differ only in the R group. Most amino acids exist as optical isomers having
four different groups around the α-carbon atom except amino ethanoic acid.
CHEMICAL PROPERTIES OF AMINO ACIDS
 Having both an acidic and basic group, amino acids are amphoteric exhibiting both acidic and
basic properties.
 In acidic solution e.g dilute HCl the —NH2 group accepts a proton amino acid existing as a
positive ion.
H2NCH(R)CO2H + H+ H3+NCH
 In alkaline solution e.g dilute NaOH the —CO2H group loses a proton and the amino acid
molecule exist as anions.
H2NCH(R)CO2H + OH— H2NCH(R)CO2— + H2O
 Due to their ability to react with both acids and alkalis, amino acids act as buffers when they are
in aqueous solution.
 In aqueous solution, amino acids exist as dipolar-zwitterions (dipolar ion) which result when the
carboxylic group protonates the amine group (internal acid-base reaction).

 Every amino acid is characterised by a specific pH value at which all the amino acid molecules in
solution exist in the zwitterion form i.e isoelectric point.
 At the isoelectric point, the amino acid will be neutral in terms of charge since the negative and
positive charges in the zwitterion tend to cancel each other.
 Bonding between zwitterions is ionic, since there are positive and negative ions therefore amino
acids have high melting and boiling points and, dissolve well in water.
 Amino acids are white solids at room temperature, resembling ionic salts in many of their
properties.
FORMATION OF PROTEINS
 Proteins are formed when 2 or more amino acids join together in an acid base reaction resulting
in the formation of polypeptides.
 The amine end of one amino acid and the carboxylic end of another amino acid react in acid-base
reaction forming a dipeptide in which the two amino acid molecules are linked by an amide bond
or a peptide bond.
 Proteins are polypeptides made by condensation of a large number of amino acids in

polymerisation reaction.
 A protein may contain one or more polypeptide chains associated together e.g haemoglobin (has
4 polypeptide unites associated to make the protein molecule.
Structure of proteins:
Primary Structure: is the sequence/order of amino acids in the peptide chain. The —NH2 group is called
the N-terminal and the —COOH group is the C terminal. In the polypeptide, the—NH2 group is always
written on the left.
Secondary Structure: is the coiling or folding of chains into a helical structure. The helical structure is
bound by H-bonds.
Tertiary structure: is the folding of the helices into particular shape. The tertiary structure of protein is
held by: 1. Hydrogen bonds
2. Permanent dipole and induced dipole attractions.
3. Ionic attractions between COO—and NH3+
4. disulphide (—S—S—) bridges.
Hydrolysis of proteins
 The peptide bond in proteins can be split in the presence of a suitable enzyme (biological
catalyst) or by heating the protein in an acidic or alkaline solution.

Acid Hydrolysis:
Alkaline Hydrolysis:
ELECTROPHORESIS
 Electrophoresis is the separation of charged molecules by placing them in an electric field.
 Polyacrylamide or agarose gel an electrolyte is applied on a thin glass plate on which the amino
acid mixture will be spotted.
 In electrophoresis, the separation of the amino acids is carried out either below or above the
isoelectric point of the amino acids; hence pH has to be considered.
 In a solution with a pH above the isoelectric point, a protein has a net negative charge and
migrates toward the positive electrode (anode) in an electric field. When in a solution below a
protein’s isoelectric point, the protein charge is positive and migrates toward the negative
electrode (cathode).
 For electrophoretic protein separations based on the mobility of the different species, the pH of
the solution must be kept constant to maintain the charge and, hence, the mobilities of the
proteins. Therefore, because electrolysis of water generates H+ at the anode and OH– at the
cathode, the solutions used in electrophoresis must be buffered.
 Rate of migration or separation is based on the mass to charge ratio (m/e), the smaller masses
move faster.
Result analysis
 After the electrophoresis run is complete, the gel must be analysed qualitatively or quantitatively
to answer analytical or experimental questions. Because most proteins and all nucleic acids are
not directly visible, the gel must be processed to determine the location and amount of the
separated molecules.
 The most common analytical procedure is staining. Proteins are usually stained with Coomassie
Brilliant Blue in a fixative solution or, after fixation, with silver by a photographic-type
development.

 Once the gel is stained, it can be photographed, scanned, or dried on a transparent backing or
filter paper for a record of the position and intensity of each band.
POLYMERISATION
 Polymerisation is a process by which many monomers are joined together to form a polymer.
POLYMERISATION REACTIONS
Addition Polymerisation
 Addition Polymerisation: is when unsaturated monomers that contain —C=C— or —CΞC— add
up to each other producing a single product. The π- bond in the alkene raptures under these
conditions, enabling free bonds to link to one another, forming a chain. Reaction mechanism is
thought to occur through a free radical pathway.
 Empirical formula of polymer is the same as that of the monomer. Only one type of monomer is
used in the process.
Examples of Addition Polymerisation
(a). Poly(ethene)/Polythene
Applications of Polyethene
 Low Density Polyethene is used in making packaging plastic bags, films, wrappers, toys etc.
 High Density Polyethene is used for making heavy-duty ware, kitchenware, food boxes, plastic
bottles, raincoats, buckets, etc.
(b). PVC (Polyvinyl chloride or Poly (chloroethene)

Applications of PVC
 PVC is used to make waterproof plastic sheets, insulating electric cables, water pipes,
plastic sheet, etc. PVC is much stronger and tougher than polyethene due to polar C—Cl
bond which results in considerable intermolecular attractions of polymer chain.
(c). Polystyrene or Poly (phenylethene)
Applications of Polystyrene
 Polystyrene is used for fast food packaging, disposal cups and heat insulation. Polystyrene
is much stronger than PVC and Polyethene due to increase in molecular size, which
increases intermolecular attractions of polymer chain.
Condensation Polymerisation
 This is the joining of two different monomers, with each having two functional groups and
the process involve the elimination of a small molecule, usually H2O or HCl (condensation
reaction.)
 Polymerisation reactions that involve two or more different types of monomers are called
co-polymerisation process. The process produce polymers called co-polymers.
Examples of Condensation Polymers
(a). Polyesters e.g Terylene

 These are made by reacting a diol with a carboxylic acid with the elimination of a water
molecule. The two monomers are joined by an ester linkage.
Monomers: ethane-1,2-diol
Benzene-1,4-dicarboxylic acid
Applications of Terylene
 Used to make clothing which is both soft and hard.
It can be melted without decomposition.
(b). Polyamides:
 These are made by reacting an amine with a carboxylic acid with the elimination of a
water molecule.
1. Nylon 6.6
Monomers: hexane-1,6-diamine, H2N(CH2)6NH2
Hexane-1,6-dioc acid, HO2C(CH2) 4CO2H
The numbers ‘6,6’ in nylon 6,6 are number of carbon atoms in the two monomers i.e two
monomer of each having 6 carbon atoms are joining together.

2.Nylon 6.10
Monomers: hexane-1,6-diamine, H2N(CH2)6NH2
Decane-1,10-dioc acid, HO2C(CH2)8CO2H
3. Nylon 6
Monomers: amino hexanoic acid H2N(CH2)5CO2H
Applications of Nylon
 Used for clothing material
 Used for engineering plastics

A Level Organic Chemistry Notes

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A Level Organic Chemistry Notes

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Most General Advanced level texts do not address all the objectives spelt in the syllabus

especially in Organic chemistry therefore it requires the consultation of a number of

COMPILED BY MUKANDA S.M (BSc. Hons.Chemistry) Page i

4. AROMATIC HYDROCARBONS (ARENES) 22

5. HALOGENO-ALKANES AND HALOGENO-ARENES 29

7. ORGANIC CARBONYL COMPOUNDS 42

8. CABOXYLIC ACIDS AND THEIR DERIVATIVES 46

COMPILED BY MUKANDA S.M (BSc. Hons.Chemistry) Page iii

Why Carbon so special?

HOMOLOGOUS FUNCTIONAL GROUP GENERAL FORMULA EXAMPLE

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

*Benzene ring and O—H bond Phenol

Keto group Propanone

Acyl chloride group R-alkyl/aryl group Ethanoyl chloride

Circled: the 2 functional R-alkyl groups Amino propanoic acid

R1:maybe H or alkyl groups R: alkayl group Ethanamide

PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

NOMENCLATURE (NAMING OF ORGANIC COMPOUNDS)

 RULES OF NAMING ORGANIC COMPOUNDS

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

Prefix: - Hept- (longest chain has 7 carbon atoms)

NB: A hyphen is used to separate numbers and the group name.

Name of Organic molecule :- 5-ethyl-3-methyl octane

FORMULAE OF ORGANIC COMPOUNDS

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

SHORT HAND (SKELETAL) FORMULAE

2. Write the formulae of the following organic compounds.

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

Both compounds belong to alkane group.

Members of different homologous series.

FACTORS GIVING RISE TO STRUCTURAL ISOMERISM

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

 Also very common to carbonyl compounds.

 Geometrical (Cis-trans) Isomerism

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

TYPES OF ORGANIC REACTIONS

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

TYPES OF ORGANIC REAGENTS

TYPES OF BOND FISSION

 Bond fission: is the breaking up of a covalent bond

Organic reactions may involve:

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

The compound show is 2-methylhexane not 5-methylhaxane.

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

Combustion of Alkanes in motor car engines

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

 HALOGENATION (FREE RADICAL SUBSTITUTION) OF ALKANES

Mechanism of Free Radical Substitution Reaction with Cl2

Initiation (Photochemical Homolysis of Cl2)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

 Alkenes are aliphatic hydrocarbons with the general formula CnH2n.

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

 Alkenes undergo Electrophilic Addition with the following reagents:

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

If aqueous Br2(aq) is used

ADDITION OF HYDROGEN HALIDES (HX): where X Cl, Br, I

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

COMPILED BY MUKANDA S.M (BSc. Hon. Chemistry)

Polystyrene or Poly (phenylethene)