Anic Chemistry

ADVANCED LEVEL
ORGANIC CHEMISTRY 2020
N O
cocaine
FOR ONLINE LESSONS APP OR CALL SIR LAYAN ON 0774372589
SIR LAYAN
EXTRATERRESTRIAL
CONTENT
Table of Contents
CHAPTER 1: Introduction to Organic Chemistry ................................................. 10
1.1 HOMOLOGOUS SERIES .............................................................................................................. 10
1.2 FUNCTIONAL GROUP ................................................................................................................ 10
1.2.1 Common Functional Groups in Organic Chemistry ................................................................10
1.3 FORMULAE OF ORGANIC COMPOUNDS ............................................................................... 11
1.3.1 Empirical formula .............................................................................................................................11
1.3.2 Molecular formula ............................................................................................................................11
1.3.3 Structural formula ............................................................................................................................11
1.3.4 Displayed formulas ...........................................................................................................................11
1.3.5 Skeletal formula ................................................................................................................................12
1.4 ISOMERISM .................................................................................................................................. 12
1.4.1 Difference between Structural and Stereoisomerism ...........................................................12
1.4.2 Structural Isomerism .......................................................................................................................13
1.4.3 Stereoisomerism ................................................................................................................................14
1.5 ORGANIC REACTIONS ............................................................................................................... 17
1.5.1 Homolytic and heterolytic bond fission ......................................................................................17
1.5.2 Curly Arrows .......................................................................................................................................18
1.5.3 Nucleophiles ........................................................................................................................................18
1.5.4 Electrophiles .......................................................................................................................................19
CHAPTER 2: Alkanes ....................................................................................................... 20

2.1 STRAIGHT-CHAIN ALKANES .................................................................................................... 20
2.2 BRANCHED-CHAIN ALKANES .................................................................................................. 20
2.3 PHYSICAL PROPERTIES ............................................................................................................ 22
2.3.1 Melting and Boiling Points .............................................................................................................22
2.3.2 Solubility ..............................................................................................................................................22
2.3.3 Density ..................................................................................................................................................22
2.4 REACTIONS OF ALKANES ......................................................................................................... 23
2.4.1 Free Radical Substitution ...............................................................................................................23
2.4.2 HALOGENATION OF HIGHER ALKANES .......................................................................................25
2.4.3 COMBUSTION OF ALKANES .............................................................................................................27
2.4.4 CATALYTIC CRACKING ......................................................................................................................27
1|Page
COMPILED AND EDITED BY SIR LAYAN 0774 372 589
2.4.5 CATALYTIC RE-FORMING .................................................................................................................28
CHAPTER 3: Alkene Chemistry.................................................................................... 29

3.1 NOMENCLATURE AND ISOMERISM OF ALKENES .............................................................. 29
3.2 CHEMICAL PROPERTIES OF ALKENES.................................................................................. 30
3.2.1 Reduction of Alkenes ........................................................................................................................30
3.2.2 Addition of steam, H2O (Hydration) ............................................................................................31
3.2.3 Addition of halogen, X2 In Inert Solvent (Halogenation).......................................................32
3.2.4 Addition of halogen, X2 In Aqueous Solution .............................................................................33
3.2.5 Addition of hydrogen halide, HX ...................................................................................................34
3.2.6 Oxidation of Alkenes .........................................................................................................................35
3.3 Assignment.................................................................................................................................. 37
CHAPTER 4: ARENE CHEMISTRY ................................................................................ 38

4.1 PHYSICAL PROPERTIES OF BENZENE .................................................................................. 38
4.2 NOMENCLATURE OF ARENES ................................................................................................. 39
4.3 REACTIONS OF ARENES ............................................................................................................ 40
4.3.1 Combustion .........................................................................................................................................40
4.4 ELECTROPHILIC SUBSTITUTION IN BENZENE RING ........................................................ 40
4.4.1 Halogenation of Benzene ................................................................................................................41
4.4.2 Nitration of Benzene.........................................................................................................................42
4.4.3 Alkylation (Friedel Crafts Reaction)............................................................................................43
4.5 ADDITIONS REACTIONS OF BENZENE RING ....................................................................... 45
4.6 ELECTROPHILIC SUBSTITUTION ON SUBSTITUTED ARENES ....................................... 45
4.6.1 Inductive Effect...................................................................................................................................45
4.6.2 Resonance Effect ................................................................................................................................46
4.6.3 Activating Groups ..............................................................................................................................46
4.6.4 Deactivating Groups .........................................................................................................................47
4.6.5 ORDER OF ACTIVATING THE RING ................................................................................................47
4.6.6 Oxidation of Substituted Aromatic Rings ..................................................................................48
4.6.7 Free radical Substitution on Side Chains ...................................................................................48
4.8 ADDITIVITY EFFECTS EXAMPLES .......................................................................................... 49
Chapter 5: Organohalides ............................................................................................ 50

5.1 HALOGENOALKANES ................................................................................................................. 50
2|Page
5.2 PHYSICAL PROPERTIES OF HALOGENOALKANES ............................................................. 50
5.2.1 Boiling point .......................................................................................................................................50
5.2.2 Solubility in water .............................................................................................................................50
5.3 ISOMERISM AND NOMENCLATURE ....................................................................................... 51
5.4 CHEMICAL PROPERTIES OF HALOGENOALKANES ........................................................... 51
5.4.1 Order of Reactivity ............................................................................................................................52
5.4.2 The SN2 mechanism...........................................................................................................................52
5.4.3 The SN1 mechanism...........................................................................................................................54
5.5 REFLUX CONDITION .................................................................................................................. 55
5.6 CHEMICAL REACTIONS OF HALOGENOALKANES .............................................................. 56
5.6.1 Reaction of Halogenoalkane with NaOH(aq) ...........................................................................56
5.6.2 Reaction of Halogenoalkanes with CN- ions ..............................................................................56
5.6.3 Reaction of Halogenoalkane with NH3........................................................................................57
5.6.4 Reaction of Halogenoalkane with alcoholic NaOH .................................................................58
5.7 USES OF HALOGENOALKANES ................................................................................................ 58
CHAPTER 6: HALOGENOARENES ................................................................................ 61

6.1 NAMING OF HALOGENOARENES ............................................................................................ 61
6.2 CHEMICAL REACTIONS ............................................................................................................. 62
6.2.1 Reaction of Halogenoarenes with NH3........................................................................................62
CHAPTER 7: Hydroxyl Compounds ............................................................................ 63

7.1 NOMENCLATURE AND ISOMERISM OF ALCOHOLS ........................................................... 63
7.1.2 Assignment Questions .....................................................................................................................63
7.2PHYSICAL PROPERTIES OF ALCOHOLS ................................................................................. 64
7.2.1 Melting and Boiling Points .............................................................................................................64
7.2.2 Solubility ..............................................................................................................................................65
7.3 Acid Base Nature of Alcohols ................................................................................................. 65
7.4 CHEMICAL REACTIONS ............................................................................................................. 66
7.4.1 Combustion .........................................................................................................................................66
7.4.2 Dehydration ........................................................................................................................................66
7.4.3 Reaction with sodium metal, Na ...................................................................................................67
7.5 NUCLEOPHILIC SUBSTITUTION TO GIVE HALOGENOALKANES .................................... 67
7.5.1 Reaction with hydrogen halide, HX .............................................................................................67
3|Page
7.5.2 Reaction with phosphorus halide, PCl5/PCl3/PBr3/PI3 ..........................................................67
7.5.3 Reaction with thionyl chloride, SOCl2..........................................................................................68
7.5.4 Oxidation..............................................................................................................................................68
7.5.5 Esterification ......................................................................................................................................69
7.6 TEST FOR ALCOHOLS ................................................................................................................ 70
7.6.1 Lucas Reagent ....................................................................................................................................70
It constitutes of anhydrous ZnCl2 and concentrated HCl ........................................................70
7.6.2 Triiodomethane reaction................................................................................................................71
CHAPTER 8: Phenol ......................................................................................................... 72

8.1 NOMENCLATURE OF PHENOL ................................................................................................ 72
8.2 PHYSICAL PROPERTIES OF PHENOL .................................................................................... 72
8.2.1 Melting and Boiling Point ...............................................................................................................72
8.2.2 Solubility ..............................................................................................................................................73
8.2.3 Acid and Base nature of Phenols ..................................................................................................73
8.3 CHEMICAL REACTIONS OF PHENOL...................................................................................... 73
8.3.1 Reaction with sodium metal, Na ...................................................................................................73
8.3.4 Reaction with sodium hydroxide, NaOH.....................................................................................74
8.3.5 Esterification ......................................................................................................................................74
8.4 Substitution into the benzene ring of phenol ................................................................... 74
8.4.1 Bromination of Phenol.....................................................................................................................75
8.4.2 Nitration of Phenol............................................................................................................................75
8.4.3 Coupling ...............................................................................................................................................76
8.5 A SPECIFIC TEST FOR PHENOLS ............................................................................................ 76
Chapter 9: Carbonyl Chemistry .................................................................................. 77

9.1 Identification of Aldehydes and Ketones ........................................................................... 77
9.2 Physical properties of carbonyl compounds..................................................................... 77
9.2.1 Melting and Boiling Point ...............................................................................................................77
9.2.2 Solubility ..............................................................................................................................................78
9.3 CHEMICAL REACTIONS OF ALDEHYDES AND KETONES.................................................. 78
9.3.1 Preparation of aldehydes and ketones .......................................................................................78
9.4 Reactions of Aldehydes and Ketones ................................................................................... 79
9.4.1 Reduction .............................................................................................................................................79
4|Page
9.4.2 Oxidation..............................................................................................................................................81
9.4.3 Reaction with hydrogen cyanide, HCN ........................................................................................81
9.5 TESTS FOR ALDEHYDES AND KETONES .............................................................................. 83
9.5.1 Test for carbonyl group using 2,4-dinitrophenylhydrazine ................................................83
9.5.2 Test for aldehydes using Tollens' reagent (silver mirror test) ...........................................84
9.5.3 Test for aldehydes using Fehling's solution ..............................................................................84
9.5.4 Reactions to form tri-iodomethane .............................................................................................85
CHAPTER 10: Carboxylic acids ................................................................................... 86

10.1 NAMING CARBOXYLIC ACIDS................................................................................................ 86
10.1.1 Assignment .......................................................................................................................................86
10.2 PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS ............................................................. 87
10.2.1 Melting and Boiling Points...........................................................................................................87
10.2.3 Solubility ............................................................................................................................................87
10.2.4 Acidity of carboxylic acids ............................................................................................................88
10.3 Chemical Reactions of Carboxylic acids ........................................................................... 89
10.3.1 Formation of Carboxylic Acids ....................................................................................................89
10.3.2 Acidic hydrolysis of nitrile ...........................................................................................................89
10.3.3 Alkaline hydrolysis of nitrile .......................................................................................................90
10.3.4 Reaction with bases .......................................................................................................................90
10.3.5 Reaction with metals .....................................................................................................................90
10.3.6 Reaction with carbonates and hydrogen carbonates .........................................................91
10.4 CONVERTING CARBOXYLIC ACIDS TO ACYL HALOGENS............................................... 91
10.4.1 Reaction with phosphorus (III) halide, PX3 ............................................................................91
10.4.2 Reaction with phosphorus(V) halide, PX5 ...............................................................................91
10.4.3 Reaction with thionyl chloride, SOCl2 .......................................................................................91
10.4.4 Reduction of the -COOH .................................................................................................................92
CHAPTER 11: CHEMISTRY OF ESTER ........................................................................ 93

11.2 NOMENCLATURE OF ESTERS................................................................................................ 93
11.3 PHYSICAL PROPERTIES OF ESTERS ................................................................................... 93
11.3.1 Melting and Boiling Points...........................................................................................................93
11.3.2 Solubility ............................................................................................................................................93
11.4.3 Acid Base Nature of Esters ...........................................................................................................93
5|Page
11.5 CHEMICAL REACTIONS OF ESTERS ..................................................................................... 93
11.5.1 Preparation of esters .....................................................................................................................93
11.5.2 HYDROLYSIS OF ESTERS................................................................................................................94
11.5.3 Reduction of Esters .........................................................................................................................95
11.7 USES OF ESTER ......................................................................................................................... 95
11.7.1 As solvents .........................................................................................................................................95
11.7.3 As perfumes and flavourings ......................................................................................................95
CHAPTER 12: ACYL HALIDES ....................................................................................... 96

12.1 NOMENCLATURE OF ACYL HALIDES .................................................................................. 96
12.2 Physical Properties of Acyl Halides ................................................................................... 96
12.2.1 Melting and Boiling Points of Acyl Halides .............................................................................96
12.2.2 Solubility ............................................................................................................................................96
12.2 CHEMICAL PROPERTIES OF ACYL HALIDES ..................................................................... 96
12.3 CHEMICAL REACTIONS OF ACYL HALIDES ....................................................................... 97
12.3.1 Reactions of acyl halide with water ..........................................................................................97
12.3.2 Reaction with amines ....................................................................................................................98
12.3.4 Reaction of acyl halide with Alcohol .........................................................................................99
12.3.5 Reaction of acyl halide with phenol ..........................................................................................99
12.3.6 Reaction of Acyl halide with NaOH(aq).......................................................................................99
CHAPTER 13: AMINES .................................................................................................. 100

13.1 CLASS OF AMINES ..................................................................................................................100
13.2 NOMENCLATURE AND ISOMERISM ..................................................................................100
13.2.1 ASSIGNMENT.................................................................................................................................. 101
13.3 Physical Properties of Aliphatic amines ........................................................................102
13.3.1 Melting and Boiling Point ......................................................................................................... 102
13.3.2 Solubility of Amines..................................................................................................................... 102
13.4 ACIDS AND BASE NATURE OF AMINES ............................................................................102
13.4.1 Strength of basicity in amines ................................................................................................. 103
13.4.2 Assignment .................................................................................................................................... 103
13.5 PREPARATION OF AMINES .................................................................................................104
13.5.1 Reaction of Halogenoalkane with NH3 (Recap) .................................................................. 104
13.5.2 Reduction of Nitriles ................................................................................................................... 104
6|Page
13.6 CHEMICAL REACTIONS OF ALIPHATIC AMINES ............................................................104
13.6.1 Reaction of amines with nitrous acid .................................................................................... 104
13.6.2 Reactions of Amines with acyl Halides .................................................................................. 105
13.6.3 Reactions of Amines with Halogenoalkanes ....................................................................... 106
CHAPTER 14: Aromatic Amines................................................................................ 107

14.1 PHYSICAL AND CHEMICAL PROPERTIES ........................................................................107
14.1.1 Melting and Boiling Points........................................................................................................ 107
14.1.2 Solubility ......................................................................................................................................... 107
14.2 Acid-Base Nature of Aromatic amines ...........................................................................107
14.3 PREPARATION OF PHYNYLAMINE ....................................................................................108
14.3.1 Reduction of Nitrobenzene........................................................................................................ 108
14.3.2 Reaction of halogenoalkane with ammonia ....................................................................... 108
14.4 CHEMICAL REACTIONS OF PHENYLAMINE ....................................................................109
14.4.1 Phenylamine with aqueous bromine ..................................................................................... 109
14.4.2 Reaction with Nitrous acid........................................................................................................ 109
14.4.3 Reaction of phenylamine with Acyl Halides ........................................................................ 109
14.4.4 The reaction of phenylamine with halogenoalkanes ....................................................... 110
Chapter 15: Amides ...................................................................................................... 111

15.1 NOMENCLATURE OF AMIDES .............................................................................................111
15.2 PHYSICAL PROPERTIES .......................................................................................................111
15.2.1 Melting and Boiling Points........................................................................................................ 111
15.2.2 Solubility of amides ..................................................................................................................... 112
15.2.3 Acid Base Nature of Amides ...................................................................................................... 112
15.3 Preparation of Amides ........................................................................................................113
15.3.1 Making amides from acyl chlorides ....................................................................................... 113
15.4 CHEMICAL REACTIONS OF AMIDES ..................................................................................113
15.4.1 HYDROLYSIS OF AMIDES ............................................................................................................ 113
15.4.5 REDUCTION OF AMIDES ............................................................................................................. 114
Chapter 16: Azo Compounds ..................................................................................... 115

16.1 Stage 1: REACTIONS OF DIAZONIUM SALTS ..................................................................115
16.2 STAGE 2: COUPLING REACTIONS OF DIAZONIUM IONS..............................................115
16.2.1 The reaction with phenol .......................................................................................................... 115
7|Page
16.2.2 The reaction with naphthalen-2-ol ........................................................................................ 116
16.2.3 The reaction with phenylamine (aniline) ............................................................................ 116
16.3 THE USE OF AN AZO DYE AS AN INDICATOR - METHYL ORANGE ............................117
16.4 SUBSTITUTION REACTIONS OF DIAZONIUM IONS.......................................................117
CHAPTER 17: Amino Acids ......................................................................................... 118

17.1 IDENTIFICATION OF THE FUNCTIONAL GROUP: ..........................................................118
17.1.1 Alpha Amino acids ....................................................................................................................... 118
17.1.2 Beta Amino Acids ......................................................................................................................... 118
17.2 NOMENCLATURE OF AMINO ACIDS ..................................................................................118
17.3 PHYSICAL PROPERTIES .......................................................................................................119
17.3.1 Zwitterions ..................................................................................................................................... 119
17.3.2 Melting and Boiling Point ......................................................................................................... 119
17.3.3 Solubility ......................................................................................................................................... 120
17.4 THE ACID-BASE BEHAVIOUR OF AMINO ACIDS ............................................................120
17.4.1 They are amphoteric................................................................................................................... 120
17.4.1 Adding an alkali to an amino acid solution......................................................................... 120
17.4.2 Adding an acid to an amino acid solution............................................................................ 120
17.5 Electrophoresis......................................................................................................................121
17.5.1 Paper Electrophoresis ................................................................................................................ 121
17.6 Chemical Reactions of Amino Acids ................................................................................121
17.6.1 Amino acids are nucleophilic ................................................................................................... 121
17.6.1 Peptide Formation ....................................................................................................................... 122
17.7 ASSIGNMENT ..........................................................................................................................122
CHAPTER 18: Polymerisation ................................................................................... 123

18.1 Terms used in Polymerisation ..........................................................................................123
18.1.1 Polymer ........................................................................................................................................... 123
18.1.2 Monomer......................................................................................................................................... 123
18.1.3 Repeating Unit .............................................................................................................................. 123
18.1.4 Homopolymer................................................................................................................................ 123
18.1.5 Copolymer ...................................................................................................................................... 123
18.2 Properties of Polymerisation ............................................................................................123
18.2.1 Advantages of Addition Polymerisation ............................................................................... 124
8|Page
18.2.2 Disadvantages of addition polymerisation ......................................................................... 124
18.3 TYPES OF POLYMERISATION .............................................................................................124
18.3.1 ADDITION POLYMERISATION ................................................................................................... 124
18.4 TACKLING QUESTIONS ON ADDITION POLYMERS .......................................................125
18.5 CONDENSATION POLYMERISATION ................................................................................126
18.6 Properties of Condensation Polymers ............................................................................126
18.6.1 Advantages of Condensation Polymerisation ..................................................................... 127
18.6.2 Disadvantages of Condensation Polymers........................................................................... 127
18.7 EXAMPLES OF POLYAMIDES ..............................................................................................127
18.7.1 Nylon 6............................................................................................................................................. 127
18.7.2 Nylon-6,6......................................................................................................................................... 128
18.7.3 Nylon-6,10 ...................................................................................................................................... 128
18.7.4 Kevlar .............................................................................................................................................. 129
18.8.5 Uses of Polyamides ...................................................................................................................... 130
18.8 POLYESTER .............................................................................................................................130
18.7.1 Monomers of Terylene ................................................................................................................ 130
18.7.2 Hydrolysis of Polyester............................................................................................................... 131
18.7.3 Uses of Polyester .......................................................................................................................... 131
18.8 Disposal of Polymers ...........................................................................................................131
9|Page
CHAPTER 1: Introduction to Organic Chemistry
• Organic chemistry is the study of carbon compounds excluding simple compounds like (CO,
CO2, CO3²⁻, HCO3⁻).
1.1 HOMOLOGOUS SERIES

• A homologous series is a series of compounds with the same functional group, and the
adjacent members differ in the number of carbon atoms.
1.2 FUNCTIONAL GROUP

• A functional group is a group of atoms within a molecule that has a similar characteristic
physical and chemical behaviour.
• Chemically, a given functional group behaves in nearly the same way in every molecule in
the homologous series.
1.2.1 Common Functional Groups in Organic Chemistry
10 | P a g e
1.3 FORMULAE OF ORGANIC COMPOUNDS
There are five ways in which organic compounds/molecules can be presented:
i. Empirical formula
ii. Molecular formula
iii. Structural formula
iv. Displayed formula
v. Skeletal formula
1.3.1 Empirical formula

• It gives the simplest ratio of the number of atoms of each element present in the compound.
1.3.2 Molecular formula

• It gives the actual number of atoms of each element present in the compound. These two
formulae are least useful and rarely used in organic chemistry because they do not reveal
much information about the compounds e.g. the molecular formulae of Dodecane is C12H26.
1.3.3 Structural formula

• It shows the order of the atoms joined together in an organic compound and it gives more
detail about a molecule e.g.
a) Ethane - CH3CH3
b) Ethene - CH2=CH2 (only double and triple carbon bonds are shown)
c) Ethanoic acid - CH3COOH
d) 3-ethyl-2-methylpentane
1.3.4 Displayed formulas

• shows the order of the atoms joined together, as well as the orientation of the atoms and
bond angles.
Examples:
• Remember to show the correct orientation of atoms of benzene and hydroxyl

functional group
11 | P a g e
1.3.5 Skeletal formula
• It shows only the functional groups. The carbon and hydrogen atoms are simplified and
hidden. In a skeletal formula:
• There is a carbon atom at each junction and at the end of the bond, there is no carbon atom
at a place occupied by another functional group.
• There are enough hydrogen atoms bonded to each carbon so that each carbon has four
bonds only.
1.4 ISOMERISM
• It is the existence of molecules with the same molecular formulae but different structural
arrangement.
• Isomerism exists between isomers
• Isomers are two or more compounds with the same molecular formula but a different
arrangement of atoms in space.
• This excludes any different arrangements which are simply due to the molecule rotating as
a whole, or rotating about particular bonds. For example, both of the following are the same
molecule. They are not isomers, both are butane.
• Isomers must have different names. A good way to identify isomers is by naming the
molecules, molecules with the same name are not isomers.
• There are two types of isomerism which are structural and stereoisomerism isomerism.
1.4.1 Difference between Structural and Stereoisomerism

Structural Isomerism Stereoisomerism
They have the same molecular formula but They have the same molecular formula and
different structural formula. structural formula.
They differ in structural arrangement of atoms The differ in spatial arrangement i.e. 3D
arrangement of atoms in space
Examples of structural isomerism are chain, Examples of stereoisomerism are geometrical
positional and functional group isomerism and optical isomerism
12 | P a g e
1.4.2 Structural Isomerism
• The chemical properties of isomers are the same because they contain the same functional
group.
• The physical properties of isomers may vary.
1.4.2.1 Chain Isomerism

• arises due to the different arrangement of carbon atoms in a chain. The carbon atoms may
be arranged in a straight chain or branched chain.
1.4.2.2 Positional isomerism

• arises due to different positions of functional group in the carbon chain.
1.4.2.3 Functional Isomerism

• This exist in organic molecules with the same molecular formulae but different functional
groups.
• It exists in carbonyl compounds i.e. ketones and aldehydes of corresponding carbon atoms
e.g.
13 | P a g e
• It also exists in alcohol and esters of corresponding number of carbon atoms.
• It also exists in carboxylic acids and esters of corresponding number of carbon atoms e.g
CH3CH2COOH (Propanoic acid)and CH3COCH3 (methlyethanoate).
1.4.3 Stereoisomerism
1.4.3.1 Geometrical Isomerism
• Geometrical isomerism arises because the rotation about a bond is restricted. It is common
in compounds containing carbon-carbon double bond(C=C bond)and certain ring systems.
• A C=C bond cannot be rotated due to the presence of πbond. A πbond will break if a rotation
occurs. Conversely, a carbon-carbon single bond is rotatab
• In ring systems, rotation about a bond is restricted due to the linkage of the ring because the
C-C bond is now part of the ring system.
• Geometrical isomers occur in pairs, differing from each other in the positioning of the two
groups across the double bond.
i. A cis-isomer has the two groups on the same sideof the double bond.
ii. A trans-isomer has the two groups on the opposite sidesof the double bond.
• To identify geometrical(cis-trans) isomers, it is essential to draw the groups around the

double bond showing the correct bond angles(120°).
14 | P a g e
• Geometrical(cis-trans)isomerism cannot exist if either carbon carries identical groups. In
short, to have geometrical isomers, it is essential to have two different groups on the left
and two different groups on the right.
Physical Properties
• Geometrical isomers have similar(not identical) chemical properties but different physical
properties.
• cis-isomer generally has a higher boiling point than trans-isomer. This is because dipoles in
a cis-isomer do not cancel out each other, causing the entire molecule to have a net dipole
moment and it is polar. Permanent dipole- dipole forces exist and more energy is required
to overcome it.
• trans-isomer generally has a higher melting point than cis-isomer because of steric strain
between the two larger substituents on the same side of the double bond of the cis isomer.
• Steric Strain is the increase in potential energy of a molecule due to repulsion between
electrons in atoms that are not directly bonded to each other.
Draw the isomers of the following compounds
15 | P a g e
1.4.3.2 Optical Isomerism
• Optical isomerism arises due to the ability of compounds to rotate the plane of polarisation
of a plane-polarised light.
• A compound is said to be optically-active(optical isomerism exists) if it rotates the plane of
polarised light. If it does not, it is said to be optically-inactive.
• A chiral centre is shown on organic molecules using a esterics.
• Optical isomers can also be reffered to as enantiomers.
For a compound to be optically active:

a) It needs to have an asymmetrical carbon with four different groups attached to it so that
there is no plane of symmetry. The carbon atoms with four different groups attached to it is
called the chiral carbon or chiral centre.
b) The isomers must be mirror-images of each other and are non-superimposable. That is, no
matter how the molecules are rotated, they never fully resemble each other.
Represents a bond sticking out in front of the plane of the paper

Represents a bond lying on the plane of the paper
Represents a bond sticking out behind the plane of the paper
➢ Benzene is planar hence it does not have a chiral
Other Compounds which exhibit optical Isomerism
16 | P a g e
1.5 ORGANIC REACTIONS
Reactions that organic compounds undergo
Organic reactions are classified using two ways:
a) By the type of reagent used:
i. Nucleophilic
ii. Electrophilic
b) By what happens during the reaction:
i. Addition
ii. Substitution
iii. Elimination
1.5.1 Homolytic and heterolytic bond fission

• Organic reactions involve the breaking of covalent bonds. There are two ways in which a
covalent bond can be broken, by homolytic or heterolytic fission.
• Homolytic fission is the breaking of a covalent bond in such a way that one electron goes to
each atom, forming free-radicals.
• A free-radical is an atom or a group of atoms with an unpaired electron formed from the
homolytic fission of a covalent bond and is very reactive.
• Heterolytic fission is the breaking of a covalent bond in such a way that both electrons go to
the same atom, forming cation and anion.
17 | P a g e
1.5.2 Curly Arrows
• Curly arrows are used in organic chemistry to represent the movement of electron(s). It is
often used in the presentation of an organic mechanism.
• The tail of the arrow shows where the electron(s) originates from while the head shows the
place where electron(s) is/are moved to. The electrons can either originate from a lone pair
or from a bond.
• Half arrows show the movement of one electron while a full arrow shows the movement of
two electrons. In the diagram above, the first is a half arrow while the second is a full arrow.
• Curly arrows can only be used to represent the movement of electron(s), they may not be
used for other purposes to avoid ambiguity.
1.5.3 Nucleophiles
• A nucleophile is a species which contains a lone pair of electrons and is attracted to regions
of positive charge or electron-deficient sites. They are often negatively-charged or carry a
partial negative charge.
• Some examples of nucleophiles are NH3, CN⁻, OH⁻, Cl⁻, Br⁻ and H2O.
1.5.3.1 Functional groups with Electron Deficient Carbon
18 | P a g e
1.5.4 Electrophiles
• An electrophile is an electron-deficient species which can accept electrons and is attracted
to regions of negative charge or electron-rich sites. They are often positively-charged or
carry a partial positive charge.
• Some examples of electrophiles are H⁺, Br⁺, Cl⁺ and NO2⁺.
[ Note: A benzene ring is an electron-rich region]
19 | P a g e
CHAPTER 2: Alkanes
2.1 STRAIGHT-CHAIN ALKANES
2.2 BRANCHED-CHAIN ALKANES

1. Name the longest possible straight chain
➔ give the parent name for the alkane
2. Name the substituent groups – the branches

20 | P a g e
CnH2n+1– Alkyl groups (derived from alkanes)
CH3 – methyl
C2H5 – ethyl
3. Number the positions of the substituent groups with the smallest possible
numbers
4. If more than one substituent group of the same kind exist, the numbers are denoted by
prefixes.
2 → di ,3 → tri ,4 → tetra ,5 → penta and 6 → hexa
5. If two or more different substituent groups exist, they are named in alphabetical
order but NOT in numerical order of their positions.
21 | P a g e
2.3 PHYSICAL PROPERTIES
2.3.1 Melting and Boiling Points
• Alkanes generally have a low mp and bp due to the presence of weak Van der Waals
forces.
• The boiling point of straight-chain alkanes increases as we go down the homologous
series with increase in the size of molecule. This is because the number of electrons
in each molecule increases, resulting in the increased strength of Van der Waals'.
Thus, more energy is required to break these forces.
Consider the boiling points of the following isomers
• Butane is a long chain molecule while 2-methypropane is more spherical (more compact).
This causes the number of contact point between butane molecules to be more than in 2-
methypropane.
• Therefore, the van der Waals' forces of attraction in butane is stronger than in 2-
methypropane. This causes the boiling point of butane to be higher.
2.3.2 Solubility
• Alkanes are generally insoluble in polar solvents like water because they can not form
hydrogen bonds or ionic polar interactions with water.
• Alkanes are non-polar therefore they are soluble in non-polar solvents like CCl4 i.e. they
have the same intermolecular forces which are dispersion forces. They are, in general,
insoluble and less dense than water.
2.3.3 Density
• The density of liquid alkanes increases slightly. The mass of each succeeding molecule
increases but due to the increased strength of van der Waals' forces, the molecules are
closer together. This results in higher ratio of mass/volume.
22 | P a g e
2.4 REACTIONS OF ALKANES
• Alkanes are saturated and generally unreactive because they are non-polar, hence they are
unattractive towards nucleophiles and electrophiles.
• Alkanes will only react with non-polar reagents in the presence of heat or ultraviolet light.
As a result, alkanes a few chemical reactions and these are

i. Free Radical Substitution
ii. Combustion
iii. Cracking
iv. Catalytic Reforming
2.4.1 Free Radical Substitution

• Alkanes undergo halogenation via free-radical substitution to give a range of products. In
free-radical substitution, hydrogen atoms in the molecule are gradually substituted by
halogen atoms.
Reagent: Chlorine gas, Cl2 or bromine gas, Br2

Condition: The presence of ultraviolet (UV) light or sunlight
Product: Halogenoalkanes (alkanes with halogens)
• Free-radical substitution proceeds via a chain reaction. During a chain reaction, for every
reactive species you start off with, a new one is generated at the end, and this keeps the
process going.
• When methane reacts with chlorine in sunlight, the greenish-yellow colour fades and
steamy acidic fumes of hydrogen chloride can be observed.
• However, this is a chain reaction and does not end here. More hydrogen atoms will be
substituted as long as there are sufficient chlorine atoms.
23 | P a g e
2.4.1.1 The Mechanism of Free-Radical Substitution:
Step 1: Initiation Step
• The reaction is initiated by the homolytic fission of chlorine molecule in the presence of
UV light, forming chlorine free radicals.
Step 2: Propagation step

➢ The free radicals then attack the methane molecules, leading to a chain reaction
Step 3: Termination step

➢ The reaction ends with the free radicals joining up with each other.
• [ Note: All other alkanes react in a similar manner but the reactions involved are getting
more and more complicated.]
• To produce mainly tetrachloromethane, an excess of chlorine gas is used so that all the
hydrogen atoms eventually get substituted.
• Bromine gas reacts in a similar manner but the reaction is slower.
24 | P a g e
2.4.2 HALOGENATION OF HIGHER ALKANES
• A useful way of classifying organic halides, alcohols, carbocations is to place them in one of
the three categories primary, secondary and tertiary
• When alkanes react with halides, a mixture of monohalogenoalkanes compounds is formed

e.g. When propane reacts with chlorine.
2.4.2.1 The Inductive Effect of Alky Groups

• An inductive effect is the withdrawal or donating of electrons through a sigma bond due to
electronegativity.
• C-C bonds are essentially non-polar, owing to the equal electronegativities of the carbon
atom at each end
• If one of the carbon atoms is electron deficient in some way (for example, by being
surrounded by only seven electrons as in a radical), the other carbon atoms can partially
compensate for the deficiency by acting as an electron reservoir.
• This reservoir effect is not so apparent with C-H bonds, because the bonding electrons are
much closer to the hydrogen nucleus.
25 | P a g e
methyl radical ethyl radical Prop-2-yl radical
The 2-methylprop-2-yl radical:
(The arrow on the bond represents the drift of the electrons away from the CH3 group)
• Methyl radical is much less stable than the ethyl radical which in turn is less stable than the
prop-2-yl radical.
• The 2-methylprop-2-yl radical experiances even greater stabilisation to positive inductive
effect of three alkyl groups.
26 | P a g e
2.4.3 COMBUSTION OF ALKANES
• Alkanes are very good fuels hence they release energy when they burn.
• When alkanes burn, complete or incomplete combustion occurs.
2.4.3.1 Complete Combustion

• Alkanes undergo complete combustion under excess oxygen gas to give carbon dioxide and
water e.g.
2.4.3.1 Incomplete Combustion

• When the supply of oxygen is limited, alkanes undergo incomplete combustion. The
possible products are carbon monoxide, carbon and water e.g.
• Other hydrocarbons are not good fuels
2.4.4 CATALYTIC CRACKING

• Catalytic cracking involves heating the alkane mixture to a temperature of about 5000C and
passing it under a slight pressure over a catalyst made from a porous mixture of aluminium
and silicon oxides (Zeolites).
• These catalyst causes the carbon chains to go internal arrangements before forming the
final products which are useful components of high-octane fuel.
• Short chain alkanes fuels are more efficient than long chain fuel alkanes.
• During the process an alkene is also produced.
27 | P a g e
2.4.5 CATALYTIC RE-FORMING
• It occurs when a catalyst converts straight alkane chains to cyclic alkanes without loss of
any carbon atoms but often with the loss hydrogen atoms.
• This process occurs in the presence of a platinum - coated aluminium oxide (Alumina),
temperature of 5000C and moderately high pressure of 50atm.
28 | P a g e
CHAPTER 3: Alkene Chemistry
• Alkenes are unsaturated hydrocarbons which contain at least one carbon-carbon double
bond(C=C) bond. They form the homologous series with the general formula of CnH2n.
• The physical properties of alkenes are similar to that of alkanes.
• Alkenes can exhibit both structural and stereoisomerism. This is due to the rotation-
restricting double bond. The isomers of C4H8 are:
3.1 NOMENCLATURE AND ISOMERISM OF ALKENES

• Geometric and Positional isomerism exists in alkenes.
Trans Pent-2-ene Cis Pent-2-ene
3-methylbut-1-ene
29 | P a g e
3.2 CHEMICAL PROPERTIES OF ALKENES
• Unlike alkanes, alkenes are more reactive because they are unsaturated and contain a C=C
bond. A C=C bond contains a σ bond and a π bond. A π bond is a region of high density of
electron which is open to attack by something that carries an amount of positive charge,
electrophiles.
• Alkenes mainly undergo electrophilic addition. An electrophilic addition reaction is the
addition of an electrophile across the C=C bond.
Reactions that alkenes undergo
1. Addition of hydrogen, H2 (Hydrogenation)
2. Addition of steam, H2O(Hydration)
3. Addition of halogen, X2(Halogenation) where X = A halogen
4. Addition of hydrogen halide, HX where X= A halogen
5. Oxidation by cold and hot potassium manganate (VII), KMnO4
6. Addition polymerisation
3.2.1 Reduction of Alkenes

Reagent: Hydrogen gas, H2
Condition: Heat in the presence of nickel, Ni catalyst at 150 °C and Pressure of 10atm
Product: Alkanes
Other Common Reducing Reagents
i. H2 and Pd/C in ethanol
ii. LiAIH4 in dry Ether at r.t.p (sometimes reflux at 350C)
iii. NaBH4 in alkaline aqueous Methanol at r.t.p/warming
• In hydrogenation of ethene, two hydrogen atoms are added across the C=C double bond.
Ethane is produced.
• In this case, although hydrogen molecule has no polarity, it is still able to behave as an
electrophile. This is because as the hydrogen molecule approaches the double bond, a dipole
is induced due to the repulsion between the two-bond pair of electrons (one from the C=C
bond, another from the H-H bond).
30 | P a g e
3.2.2 Addition of steam, H2O (Hydration)
Reagent: Steam, H2O
Condition: Heat the gaseous alkene at 330 °C and 60 atm in the presence of phosphoric(V)
acid, H3PO4 as catalyst
Product: Alcohols (compounds that -OH group)
• In the hydration of alkene, steam, H-OH is added across the double bond. Ethanol is
produced.
3.2.2.1 Mechanism of The Reaction is as Follow:
31 | P a g e
3.2.2.2 Consider Unsymmetrical Alkene (Propene)
3.2.3 Addition of halogen, X2 In Inert Solvent (Halogenation)

Reagent: Halogen, X2 (in tetrachloromethane)
Condition: Room temperature in dark
• When ethene is bubbled into Br2 in CCl4 at room temperature in dark, Br-Br is added across
the C=C bond. The brown colour of bromine is decolourised. 1,2-dibromoethaneis produced.
3.2.3.1 Reaction Mechanism
32 | P a g e
3.2.4 Addition of halogen, X2 In Aqueous Solution
Reagent: Halogen, X2 (in aqueous)
Condition: Room temperature
• When ethene is bubbled into aqueous Br2 at room temperature in dark, two products are
obtained:
• With Bromine aqueous, 2-bromoethanol is the major product and the reaction is very fast
because OH- is a stronger nucleophile than Br- to attack the carbocation ion.
• Br2 in CCl4 is used as a test to differentiate alkanes and alkenes as they both are colourless.
Alkene will decolourise the brown colour of bromine whereas alkane will not.
33 | P a g e
3.2.5 Addition of hydrogen halide, HX
Reagent: Hydrogen halide, HX(g)
• When an alkene reacts with H-X the Markovnikov'srule is followed. It states that when an
alkene reacts with H-X the H from the HX molecule is going to be added on the carbon atom
in the C=C with more hydrogen atoms directly attached to the carbon atom.
• The richer Carbon becomes richer and the poor Carbon becomes poorer, in terms of
hydrogen atoms.
• When ethene reacts with hydrogen bromide, 1-bromoethane, a halogenoalkane is produced.
• The type of reaction is electrophilic addition.
The addition of unsymmetrical alkene is as follow. Take propene as an example:
34 | P a g e
Deduce the Mechanism
3.2.6 Oxidation of Alkenes

3.2.6.1Oxidative Addition
Reagent: Cold and dilute potassium Manganate (VII) solution, KMnO4
Product: Alcohols(diols)
• When ethene is reacted with cold, dilute acidified KMnO4solution, the purple colour of
KMnO4 is decolourised. Ethane-1,2-diol is produced.
• This is a redox reaction; the carbon species is oxidised while the oxidising agent is reduced.
• This is another test used to differentiate alkanes and alkenes. Only alkene will decolourise
the purple colour of KMnO4 whereas alkane will not.
35 | P a g e
3.2.6.2 Oxidative Cleavage
Reagent: Hot and concentrated acidified Potassium, Manganate (VII) solution, KMnO4
Condition: Reflux
Product: Carbon dioxide/carboxylic acids/ketones
• When an alkene is reacted with hot and concentrated acidified KMnO4 solution, the C=C
bond in the alkene ruptures. The purple colour of KMnO4 is also decolourised. The product
formed will differ according to the position of the C=C bond.
a. If there are two alkyl groups at one end of the bond, that part of the molecule will give a
ketone. For example:
b. If there are one alkyl group and one hydrogen at one end of the bond, that part of the
molecule will give a carboxylic acid. For example:
• Ethanal (an aldehyde) is further oxidised to ethanoic acid (a carboxylic acid)
• The net effect is as such:
c. If there are two hydrogens at one end of the bond, that part of the molecule will give carbon
dioxide and water. For example:
36 | P a g e
• This reaction is useful in determining the position of C=C bond in an alkene molecule. This
can be done by examining the product(s) formed.
Predict the products formed when the following compound react with Hot Acidified
KMnO4
3.3 Assignment
37 | P a g e
CHAPTER 4: ARENE CHEMISTRY
• Organic hydrocarbons containing one or more benzene rings are called arenes e.g. benzene,
naphthalene and anthraxene.
• Benzene is cyclic, conjugated and contains an electron π system which is rich in electrons
• The six-centre delocalised π bond is responsible for the following physical and chemical
properties of the benzene.
It causes all C-C bonds to be equal, creating a planar, regular hexagonal shape and all
bond angles are 120°, all carbon atoms are sp2-hybridized.
It prevents benzene undergoing any of the normal addition reactions that alkenes show
• carbon–carbon bond lengths is 0.139 nm.
• Benzene is unusually stable, having a heat of hydrogenation 150 kJ/mol less negative than
we might expect for a conjugated cyclic triene.
• Benzene undergoes substitution reactions that retain the cyclic conjugation rather than
electrophilic addition reactions that would destroy the conjugation.
• Benzene can be described as a resonance hybrid whose structure is intermediate between
two line-bond structures.
4.1 PHYSICAL PROPERTIES OF BENZENE

• Benzene and most alkyl-benzenes are strongly oily-smelling colourless liquids, immiscible
with, and less dense than water.
• They are non-polar and the only intermolecular bonding is due to the induced dipole of Van
Der Waals Forces.
• Their boiling points are similar to those of equivalent cyclohexane and increase steadily
with relative molecular mass as expected.
38 | P a g e
4.2 NOMENCLATURE OF ARENES
• Mono-substituted benzenes are named systematically in the same manner as other
hydrocarbons, with -benzene as the parent name.
• Thus, C6H5Br is bromobenzene, C6H5NO2 is nitrobenzene, and C6H5CH2CH2CH3 is
propylbenzene.
• Alkyl-substituted benzenes are sometimes referred to as arenes and are named in different
ways depending on the size of the alkyl group.
• If the alkyl substituent is smaller than the ring (six or fewer carbons), the arene is named as
an alkyl-substituted benzene
• If the alkyl substituent is larger than the ring (seven or more carbons), the compound is
named as a phenyl-substituted alkane. The name phenyl is used when the benzene ring is
considered as a substituent. Although they are unsaturated, they do not show typical
reactions of alkenes.
• In addition, the name benzyl is used for the C6H5CH2 – group
• Disubstituted benzenes are named using one of the prefixes ortho (o), meta (m), or para (p).
• An ortho-disubstituted benzene has its two substituents in a 1,2 relationship on the ring, a
meta-disubstituted benzene has its two substituents in a 1,3 relationship, and a para-
disubstituted benzene has its substituents in a 1,4 relationship.
• If the two substituents are different, one of them is defined as the root group, in the
following order of precedence e.g.
39 | P a g e
4.3 REACTIONS OF ARENES
4.3.1 Combustion
• Benzene and methylbenzene are components of many brands of unleaded petrol. In
sufficient oxygen, they burn completely to carbon dioxide and steam.
• Just as with hydrogenation, the enthalpy change of combustion of benzene is less

exothermic as expected, because of the stability due to the delocalised pi electrons.
4.4 ELECTROPHILIC SUBSTITUTION IN BENZENE RING

• The delocalised electrons in the benzene ring is an area of high electron density. Therefore,
benzene react with electrophiles.
• Because of the extra stability of the delocalised electrons, however, the species that react
with the benzene have to much more powerful electrophiles than those that react with
alkenes. (Bromine water and acids have no effect on the benzene)
• In alkenes, an anion adds on to the carbocation intermediate. In benzene, carbocation
intermediate loses a proton so as to reform the ring of π electrons and this demonstrate
how stable the system is.
40 | P a g e
4.4.1 Halogenation of Benzene
• Benzene will react with non-aqueous bromine on warming in the presence of anhydrous
aluminium chloride or aluminium bromide or iron (III) chloride or even iron metal.

• Anhydrous aluminium or iron (III) halides contain electron deficient atoms. They can react
with bromine molecule by accepting one of the lone pairs of electrons on bromine.
• This causes strong polarisation Br-Br bond, weakening it and eventually leading to
heterolytic fission.
• The Bromine cation formed is a powerful electrophile and it is attracted to the π bond of
benzene. It eventually breaks the ring of the electrons and forms a sigma bond to one of the
carbon atoms of the ring.
• The intermediate carbocation then loses a proton, to reform the sextet of π electrons
• The final stage regenerates the catalysts, by the reaction between the proton formed with
the [AlBr4]- formed above.
H+ + [AlBr4]- HBr + AlBr3

• Further substitution can occur with an excess of Bromine, to form dibromo benzene, even
tribromo benzene.
41 | P a g e
• Iodine itself is unreactive toward aromatic rings, so an oxidizing agent such as or a copper
salt such as CuCl2 must be added to the reaction
4.4.2 Nitration of Benzene

• Benzene does not react with Nitric acid even concentrated, but a mixture concentrated
nitric acid and concentrated sulphuric acid produces Nitrobenzene.
• The role of sulphuric acid in this reaction is to produce the powerful electrophile
(Nitronium ion) needed to nitrate the benzene ring.
• Further nitration to dinitrobenzene can occur unless the temperature is controlled below
550C.
4.4.2.1 The Mechanism of Nitrobenzene

• Sulphuric acid is a strong acid than nitric acid. It is so strong that it donates a proton to
nitric acid and in this reaction nitric acid is acting as a base.
• The protonated nitric acid then loses a water molecule, and the water molecule is
protonated by another sulphuric acid molecule.
Overall Reaction
42 | P a g e
• The nitronium ion then attacks the benzene ring, forming the carbocation intermediate ion
which subsequently loses a proton.
• H+ combines with the HSO4- to form H2SO4 which is acting as a catalyst.

• The nitration of benzene and other arenes as in an important reaction in the production of
explosives.
4.4.3 Alkylation (Friedel Crafts Reaction)

• When Benzene is heated with a chloro-alkane in the presence of aluminium chloride, the
alkyl group attaches to the benzene ring.
• The reaction goes with the formation of a carbocation ion. Anhydrous aluminium contains
electron deficient atoms. They can react with chlorine atom by accepting one of the lone
pairs of electrons on chlorine
• The carbocation is the electrophile
• The final stage regenerates the catalysts, by the reaction between the proton formed with
the [AlCl4]- formed above.
H+ + [AlCl4]- HCl + AlCl3
43 | P a g e
4.4.3.1 Limitations of Friedel-Crafts Reactions
• Despite its utility, the Friedel–Crafts alkylation has several limitations. For one thing, only
alkyl halides can be used.
• Aromatic (aryl) halides and vinylic halides don’t react because aryl and vinylic carbocations
are too high in energy to form under Friedel–Crafts conditions.
• Another limitation to the Friedel–Crafts reaction is that a skeletal rearrangement of the
alkyl carbocation electrophile sometimes occurs during reaction, particularly when a
primary alkyl halide is used.
• The carbocation rearrangements that accompany Friedel–Crafts reactions are like those
that accompany electrophilic additions to alkenes and occur either by hydride shift or alkyl
shift.
• If an acyl chloride is used instead of a chloroalkane in the FRIEDEL CRAFTS reaction, a

phenyl ketone is produced.
• The reaction between an acyl chloride produces the acylium ion. The intermediate is
formed from the attack of the acylium ion on the benzene ring.
44 | P a g e
4.5 ADDITIONS REACTIONS OF BENZENE RING
• Benzene can be forced to undergo addition of hydrogen under certain harsh conditions as
shown by the reaction below.
• Benzene being more stable, it requires more elevated temperature and pressure.
4.6 ELECTROPHILIC SUBSTITUTION ON SUBSTITUTED ARENES

• The orientation of the incoming group (NO2 or Br) depends on the substituent already on
the ring and not on the electrophile.
• The substituent groups either activate the ring by donating electrons to the ring or
deactivate the ring by withdrawing electrons.
• The withdrawal or donation of electrons by a substituent group is controlled by an interplay
of inductive effects and resonance effects.
4.6.1 Inductive Effect

• An inductive effect is the withdrawal or donating of electrons through a sigma bond due to
electronegativity.
• The effect is most pronounced in halobenzene and phenols, in which the electronegative
atom is directly attached to the ring, but is also significant in carbonyl compounds, nitriles,
and nitro compounds.
45 | P a g e
4.6.2 Resonance Effect
• A resonance effect is the withdrawal or donation of electrons through a pi bond due to the
overlap of a p orbital on the substituent with a p orbital on the aromatic ring.
• Carbonyl, cyano, and nitro substituents, for example, with-draw electrons from the aromatic
ring by resonance. The pi electrons flow from the ring to the substituent, leaving a positive
charge in the ring. Y.
• There are two types of substituent groups which can be substituted on the benzene ring and
these are
Activating groups
Deactivating groups
4.6.3 Activating Groups

• These are groups which make the benzene ring more reactive by donating electrons to the
benzene ring.
• Activating groups are said to be ortho and para directing.
Examples of Activating Groups
Hydroxyl, alkoxyl, and amino groups
• Hydroxyl, alkoxyl, and amino groups are also ortho and para activators.
• Hydroxyl, alkoxyl, and amino groups have a strong, electron donating resonance effect that
outweighs a weaker electron withdrawing inductive effect.
Alkyl groups
• Alkyl groups, on the other hand, inductively donate electrons (Positive Inductive Effect).
46 | P a g e
4.6.4 Deactivating Groups
• These are groups which make the benzene ring less reactive by withdrawing electrons from
the benzene ring.
• Deactivating groups are generally said to be meta directing groups.
Examples of Deactivating Groups
C=O, CN, NO2

• The groups have got a strong negative inducting and a strong resonance effect which are
meta directing.
Halogens
• Halogens are deactivating because their stronger electron withdrawing inductive effect
outweighs their weaker electron donating resonance effect.
• Although weak, that electron donating resonance effect is nevertheless felt only at the ortho
and para positions and not at the meta position
• The incoming electrophile is more likely to attack these positions but because of steric
hindrance at the ortho position, the para product usually predominates over the ortho
product.
4.6.5 ORDER OF ACTIVATING THE RING
47 | P a g e
4.6.6 Oxidation of Substituted Aromatic Rings
• Despite its unsaturation, the benzene ring is inert to strong oxidizing agents such as KMnO4
and Na2Cr2O7, reagents that will cleave alkene carbon–carbon bonds.
• It turns out, however, that the presence of the aromatic ring has a dramatic effect on alkyl
side chains. Alkyl side chains react rapidly with oxidizing agents and are converted into
carboxyl groups, COOH.
• The mechanism of side-chain oxidation is complex and involves reaction of C-H bonds at the
position next to the aromatic ring to form intermediate benzylic radicals, tert-Butylbenzene
has no benzylic hydrogens, however, and is therefore inert.
4.6.7 Free radical Substitution on Side Chains

• Alkylbenzene readily undergo free radical substitution with chlorine or bromine in the
presence of U.V light.
48 | P a g e
4.8 ADDITIVITY EFFECTS EXAMPLES
49 | P a g e
Chapter 5: Organohalides
• These are compounds that contain one or more halogen atoms (Halogen-substituted
organic compounds)
There are three types of Organohalides compounds:

1. Halogenoalkanes
2. Halogenoarenes
3. Acyl halides
5.1 HALOGENOALKANES
• Halogenoalkanes (or alkyl halides) are compounds in which one or more hydrogen atoms in
an alkane have been replaced by halogen atoms (fluorine, chlorine, bromine or iodine).
• Halogenoalkanes can be classified as primary, secondary or tertiary depending on the
number of alkyl groups (R groups) attached to the carbon atom holding the halogen atom.
5.2 PHYSICAL PROPERTIES OF HALOGENOALKANES

5.2.1 Boiling point
• Generally, the boiling points of halogenoalkanes are low but higher than that of alkanes due
to the existence of permanent dipole moments.
• The main intermolecular force in halogenoalkanes are the Van Der Waals Forces.
• Boiling point of the halogenoalkanes increases as the molecular size increases. This is
because there are more electrons in larger molecules and more temporary dipoles can be
set up, resulting in stronger van der Waal's forces.
• Primary halogenoalkanes have higher boiling point compared to secondary and tertiary
halogenoalkanes of the same molecular weight. This is because the surface area of primary
halogenoalkanes is higher, more temporary dipoles can be set up, resulting in stronger van
der Waal’s forces
5.2.2 Solubility in water

• Halogenoalkanes are insoluble in water but soluble in organic solvents.
• This is because when dissolved in water, the energy needed to break the hydrogen
bonds between water molecules is too high. The energy released when
halogenoalkane-water attraction is set up is not enough to compensate it.
• While when it is dissolved in organic solvents, the halogenoalkane-solvent
attraction is strong enough to compensate the energy needed to break the weak van
der Waal’s forces between organic molecules.
50 | P a g e
5.3 ISOMERISM AND NOMENCLATURE
• Halogenoalkanes show chain, positional and optical isomerism e.g. There are 5 isomers of
C4H9Br.
1. Give IUPAC names for the following halogenoalkanes.
2. State the type of isomerism that exist in each of the compounds shown below
5.4 CHEMICAL PROPERTIES OF HALOGENOALKANES

• The carbon–halogen bond in an alkyl halide is polar and that the carbon atom is electron-
poor. Thus, alkyl halides are electrophiles, and much of their chemistry involves polar
reactions with nucleophiles and bases.
• The signature reaction of halogenoalkanes is nucleophilic substitution. Nucleophilic
substitution is the substitution of an atom by a nucleophile.
Examples of Nucleophile
51 | P a g e
5.4.1 Order of Reactivity
• The strength of halogenoalkanes is governed by the strength of C-X bond in the
molecule.
• The strength of the C-X is measured using bond energy values.
• Fluoroalkanes are the least reactive while iodoalkanes are the most reactive. This is
because the carbon-halogen bond strength decreases from fluorine to iodine as the size
of the halogen atoms increases.
• Since reactions of halogenoalkanes involve the breaking of the carbon-halogen bond, it
follows that carbon-iodine bonds are the easiest to break, making them the easiest to
react.
• Nucleophilic substitution is done via two mechanisms, the SN1 or SN2 mechanism.
5.4.2 The SN2 mechanism

• In SN2 mechanism, the 'S' stands for substitution, the 'N' stands for nucleophilic and the '2'
stands for bimolecular (Bimolecular means that two molecules, nucleophile and alkyl
halide, take part in the step whose kinetics are measured).
• The general mechanism of an SN2 reaction, using bromoethane, CH3CH2Br as a typical
primary halogenoalkane and Nu⁻ as a general nucleophile:
1. The carbon-bromine bond in bromoethane is polarised due to the electronegativity
difference between the two atoms. Carbon carries a partial positive charge while
bromine carries a partial negative charge.
2. The nucleophile Nu⁻ uses its lone-pair electrons to attack the positive alkyl halide
carbon 180° (from the backside of alkyl halide carbon) away from the departing halogen
being repelled further due to the approaching nucleophile
3. This leads to a transition state with a partially formed C–Nu⁻ bond and a partially
broken C–Br bond. The transition state has five groups attached to the central carbon
atom.
4. The stereochemistry at carbon is inverted as the C–Nu⁻ bond forms fully and the
bromide ion departs with the electron pair from the former C–Br bond (the product has
a configuration opposite to the reactant).
52 | P a g e
5.4.2.1 Steric Effects in the SN2 Reaction
• It is unlikely for tertiary halogenoalkanes to react by SN2 mechanism.
• SN2 mechanism involves the nucleophile approaching and forming bond from the opposite
side of the halogen.
• In the case of tertiary halogenoalkane, it is unlikely because the opposite of the halogen is
hindered and the bulky substrate prevent easy approach of the nucleophile, making bond
formation difficult.
a) b)
a) Bromomethane is readily accessible, resulting in a fast SN2 reaction

b) 2-bromo-2-methylpropane (tertiary) are successively more hindered, resulting in
successively slower SN2 reaction
5.4.2.2 Energy Pathway Diagram (SN2)
• The rate of a chemical reaction is determined by the activation energy Ea the energy
difference between reactant ground state and transition state.
Compare the Ea of Primary ,Secondary and Tertiary of similar halogenoalkanes
53 | P a g e
5.4.3 The SN1 mechanism
• In SN1 mechanism, the '1' stands for unimolecular which is the initial step (rate-determining
step) that involves one specie only (the halogenoalkane). The overall rate of reaction is
governed by the rate of the first step.
• The general mechanism of an SN1 reaction, using 2-bromo-2-methylpropane,
(CH3)3Br as a typical tertiary halogenoalkane and Nu⁻ as a general nucleophile:
1. The reaction happens in two stages. In the first stage, a small proportion of the
halogenoalkane ionises to give a carbocation and a bromide ion.
2. Once the carbocation is formed, it will react immediately when it comes into contact
with a nucleophile, Nu⁻. The lone pair of the nucleophile is strongly attracted towards
the positive carbon, and moves towards it to create a new bond.
3. Tertiary halogenoalkanes react via SN1 because the tertiary carbocation intermediate
formed is relatively stable. If primary halogenoalkanes were to react in the same
manner, the primary carbocation formed would be relatively unstable, resulting in high
activation energy of the reaction.
• Secondary halogenoalkanes can react using both SN1 and SN2mechanisms
because:
1. The opposite of the halogen is not hindered by bulky substrates only CH3 group(s).
2. The secondary carbocation formed is more stable than primary carbocation.
54 | P a g e
5.4.3.1 Energy Pathway Diagram (SN1)
• The activation energy Ea1 of the first step is high owing to the energy required to break to
bonds and this I why this is a slow step.
• The activation energy Ea2 of the second step is low because the oppositely charged ions
attract each other more strongly.
• Multiple step reactions will produce a stable intermediate.
5.5 REFLUX CONDITION

• Heating under reflux means to heat a flask so that the solvent boils continually.
• A condenser is placed vertically in the neck of the flask condense the solvent vapour.
• This method allows the temperature of the mixture to kept at the boiling point of the
solvent so that slow organic reactions can be speeded up as much as possible without the
solvent evaporating away.
55 | P a g e
5.6 CHEMICAL REACTIONS OF HALOGENOALKANES
5.6.1 Reaction of Halogenoalkane with NaOH(aq)
Reagent: Aqueous sodium hydroxide, NaOH or water
Condition: Heat under reflux
Product: Alcohols
• When aqueous sodium hydroxide, NaOH is heated with bromoethane under reflux, the
bromine is substituted by hydroxide ion, OH. Ethanol is produced.
• Water can also be used as the nucleophile in this reaction. However, hydrolysis using water
occurs much slower. This is because the negatively-charged OH⁻ is a more effective
nucleophile than water.
• The mechanism of this reaction is the same as the ones mentioned before for primary
halogenoalkanes, the nucleophile here is hydroxide ion, OsH⁻ or H2O
5.6.2 Reaction of Halogenoalkanes with CN- ions

Reagent: Potassium cyanide, KCN in ethanol
Product: Nitriles
• When ethanolic potassium cyanide, KCN is heated with 2-bromo-2- methyl pentane under
reflux, the bromine is substituted by cyanide ion, CN⁻.2-methyl-2-propanenitrile is
produced.

• The mechanism of this reaction is the same as the ones mentioned before for tertiary
halogenoalkanes, the nucleophile here is cyanide ion, CN⁻.
56 | P a g e
This is a very useful reaction in organic synthesis because:
It serves as a means of increasing the length of carbon chain (a step-up reaction).

The nitrile produced can be converted to carboxylic acid by heating under reflux with
acid or alkali (hydrolysis reaction)
5.6.3 Reaction of Halogenoalkane with NH3

Reagent: Excess ammonia, NH3 in ethanol
Condition: Heat in sealed tube under high pressure
Product: Amines
• If a halogenoalkane is heated with an excess of ammonia dissolved in ethanol under

pressure, an amine is formed.
• If the ammonia used is not in excess, a complicated mixture containing secondary and
tertiary amine is obtained. This is because ethylamine is a good nucleophile and it can
attack the unreacted bromoethane.
• Since ammonia is in excess it removes one hydrogen atom from the positive ion to form a
primary amine in a reversible reaction.
57 | P a g e
The salt decomposes to salt and HBr due to high temperatures
NH4 + Br- NH3 + HBr

5.6.4 Reaction of Halogenoalkane with alcoholic NaOH
Reagent: Sodium hydroxide, NaOH in ethanol
Product: Alkenes
Type of reaction: Base Induced Elimination
• In this alcoholic condition, the hydroxide ion, OH⁻ acts as a base rather than a nucleophile.
Hence it will accept a proton (hydrogen ion) from the carbon atom next door to the one
holding the bromine.
• The resulting re-arrangement of the electrons expels the bromine as a bromide ion and
produces ethene.
Zaitsev’s Rule
• In the elimination of HX from an unsymmetrical alkyl halide, the more highly
substituted alkene product predominates.
• In unsymmetrical halogenoalkanes, a mixture of products of different isomers is

produced due to the choice of hydrogen being removed.
5.7 USES OF HALOGENOALKANES

• Tetrachloromethane (CCl4) is used as a solvent in some organic chemical reactions.
• 1.2-dibromoethane is used in leaded petrol as an anti-knock additive so as to react with lead
residues to generate volatile lead bromides thereby preventing fouling of the engine with
lead deposits.
Types of CFCs
58 | P a g e
• CFCs are chlorofluorocarbons, compounds containing carbon with chlorine and fluorine
atoms attached. Two common CFCs are CFC-11(CCl3F) and CFC-12(CCl2F2).
Properties of CFCs
➢ Chemically unreactive or inert

➢ Non-flammable
➢ Low toxicity
➢ Odourless and tasteless
➢ Volatile (low boiling point)
Uses of CFCs
➢ As refrigerants (Cooling fluids) e.g. in refrigerators and air conditioners

➢ As aerosol propellants e.g. in perfume
➢ As foam blowing agents e.g. to make expanded polystrenes packaging
➢ As flame retardant in fire extinguishers e.g. CClBrF2
CFCs and the environment
• CFCs have many uses in our daily life. However, due to their stability and inertness, they are
also large responsible for the destruction of the ozone layer. Ozone layer prevents harmful
ultraviolet radiation from reaching us
Equations Involved in Ozone Destruction
• Although the C-F is very strong, the C-Cl is weak enough to be split by ultraviolet light
forming chlorine radicals.
• Chlorine radicals disrupts the equilibrium balance of the ozone by acting as a homogeneous
catalyst for the destruction of the ozone
• Chlorine radicals are then regenerated and this involves the destruction of more oxygen
atoms responsible for the formation of ozone by natural ozone formation.
59 | P a g e
Possible solutions to protect the ozone layer:
➢ Reduce the use of CFCs. For example, replace aerosol spray with manual pump spray.
➢ Collect and recycle CFCs for future use.
➢ Find alternatives for CFCs.
Possible alternatives for CFCs:
➢ Use HCFCs (CFCs with at least one hydrogen atom, for example, CF3CHCl2)
➢ Use LPG (liquid petroleum gas) as propellant in aerosol sprays.
➢ Use air-blowing agent in packaging and building industries.
➢ Use water-based cleaning system in electronic industries.
60 | P a g e
CHAPTER 6: HALOGENOARENES
• A Halogenoarene is only formed when a halogen is directly attached to the an arene.
6.1 NAMING OF HALOGENOARENES

• Mono-substituted benzenes are named systematically in the same manner as other
hydrocarbons, with -benzene as the parent name.
• Thus, C6H5Br is bromobenzene, C6H5NO2 is nitrobenzene, and C6H5CH2CH2CH3 is
propylbenzene.
Consider the following Examples
Give IUPAC names for the following halogenoalkanes.
a) b)
61 | P a g e
6.2 CHEMICAL REACTIONS
• Halogenoarenes are generally unreactive because:
The C-X bond experiences a partial double bond (Double bond Character). Halogen
donate electrons to the aromatic ring by resonance. Lone pair of electrons flow from the
halogens to the ring, placing a negative charge in the ring and forming a partial double
bond.
Halogenoarenes without electron withdrawing substituents don’t react with

nucleophiles under most conditions. At high temperature and pressure, chlorobenzene
can be forced to react e.g.
6.2.1 Reaction of Halogenoarenes with NH3

Reagent: Concentrated NH3
Condition: Copper Catalysts, 2000C and 50atm
Product: Phenylamine
62 | P a g e
CHAPTER 7: Hydroxyl Compounds
• Alcohols are compounds in which one or more hydrogen atoms in an alkane have been
replaced by an -OH group.
• Organic hydroxyl group compounds can be divided into three i.e. alcohol, phenol and enol.
• Alcohols can be classified as primary, secondary or tertiary depending on the number of

alkyl groups (R groups) attached to the carbon atom holding the -OH group.
7.1 NOMENCLATURE AND ISOMERISM OF ALCOHOLS

• Simple alcohols are named by the IUPAC system as derivatives of the parent alkane, using
the suffix -ol.
• Alcohols show chain, positional, optical isomerism and functional isomerism with ethers.
7.1.2 Assignment Questions
63 | P a g e
7.2PHYSICAL PROPERTIES OF ALCOHOLS
• Alcohols have higher boiling points than the alkanes with similar Mr due to the presence of
intermolecular hydrogen bonding in addition of van der Waals' forces of attraction.
• The boiling point increases as the number of carbon atoms increases. This is because there
are more electrons, hence more temporary dipoles (Van Der Waals forces) can be set up.
• More energy is required to overcome these forces.
7.2.1.1 Questions
i. Compare the boiling point of butanol and 2-methyl propanol.
ii. Compare the boiling point and melting point of 1.4-butanediol and 2.3-butanediol.
7.2.1.1 Solutions
i. Butanol is a long chain molecule while 2-methypropanol is more spherical (more compact).
This causes the number of contact point between butanol molecules to be more than in 2-
methypropanol. Therefore, the van der Waals' forces of attraction in butane is stronger than
in 2-methypropane. This causes the boiling point of butane to be higher.
ii. Butan-1.4-diol has intermolecular hydrogen bonding and butan-2.3-diol has intramolecular
hydrogen bonding. Intermolecular bonding results in association of molecules hence it
increases the melting point and boiling point. Intramolecular hydrogen bonding results in
the cyclisation of the molecules thus preventing association of molecules. Hence the boiling
and melting point does not change significantly.
64 | P a g e
7.2.2 Solubility
• Alcohols are soluble in water because they can form hydrogen bonds with water molecules.
• However, the solubility decreases as the number of carbon atoms increases. This is because
the presence of long hydrocarbon tail which disrupts the effectiveness of hydrogen bonding.
7.2.2.1 Questions
i. Compare the solubility of 1.4-butanediol and 2.3-butanediol.
7.3 Acid Base Nature of Alcohols

• Alcohols are weakly acidic, weaker than water except for methanol. It is because the extent
at which an alcohol dissociates to form H+ is less than the extent to which water can
dissociate to form an H+.
• Alcohols contain an alkyl group with a positively inductive effect (electron donating
properties). Therefore, the alkyl groups donate electrons thereby strengthening the O-H
bond and this makes it difficult for the O-H to easily release the H+.
65 | P a g e
7.4 CHEMICAL REACTIONS
7.4.1 Combustion
Reagent: Oxygen supply
Condition: Heat
Product: Carbon dioxide (and carbon monoxide) and water
Type of reaction: Combustion
• Alcohols undergo complete combustion under excess oxygen to give carbon dioxide and
water. Example:
• When oxygen is limited, carbon monoxide and carbon soot might be formed.
7.4.2 Dehydration
Reagent: Excess concentrated sulfuric acid, H2SO4 or hot Catalyst aluminium oxide, Al2O3
Condition: Heat at about 170 °C
Product: Alkenes
Type of Reaction: Dehydration
• When ethanol is heated with concentrated sulphuric acid, the alcohol is dehydrated, a water
molecule is removed from the alcohol. Ethene is produced.
• During dehydration, the -OH group gets removed together with a hydrogen atom from the
next-door carbon atom.
• For more complicated alcohols, be careful of the possibility of more than one product being
formed and also the possibility of geometric isomers in the alkenes. This is due to a different
hydrogen being removed from the alcohol. An example is butan-2-ol.
66 | P a g e
7.4.3 Reaction with sodium metal, Na
Reagent: Sodium metal, Na
Product: Alkoxides and hydrogen gas
Type of reaction: Displacement reaction
• Acids react with metals to produce hydrogen gas and a salt. Alcohols are very weak acids, so
they undergo this reaction as well.
• When sodium metal is added to ethanol, the sodium metal dissolve in ethanol and bubbles
of hydrogen gas are released. The ionic salt formed is sodium ethoxide, a white solid.
• This reaction can be used as a test for hydroxy, -OH group. Bubbles of hydrogen gas is
released if a hydroxy group is present.
• Remember, in order to produce a hydrogen gas molecule, H2, two hydrogens from two
molecules of alcohols must be used.
7.5 NUCLEOPHILIC SUBSTITUTION TO GIVE HALOGENOALKANES

• The -OH group of the alcohol can be substituted by a halogen to produce a halogenoalkane.
The halogen can be obtained from three sources:
Hydrogen halide, HX; where X= Cl/Br/I
Phosphorus halide, PCl5 or PBr3 or PI3
Thionyl chloride (or sulphur dichloride oxide), SOCl2
7.5.1 Reaction with hydrogen halide, HX

• The alcohol is refluxed with sodium halide, NaX and concentrated sulphuric acid, H2SO4 to
produce the hydrogen halide, HX.
• For iodine, phosphoric(V) acid, H3PO4 is used instead of sulphuric acid at r.t.p.
• The hydrogen halide at r.t.p, HX is the reacted with the alcohol. Take ethanol as an example:
7.5.2 Reaction with phosphorus halide, PCl5/PCl3/PBr3/PI3

• Alcohols react with phosphorus(V) chloride at r.t.p, to produce a halogenoalkane, white
fumes of hydrogen chloride gas are also observed. Take ethanol as an example:
• This can be used as a test for the hydroxy, -OH group. White fumes of hydrogen chloride gas
are observed if hydroxy group is present.
67 | P a g e
• For phosphorus (III) halides, a halogenoalkane is also obtained. The phosphorus halides are
prepared in situ by mixing red phosphorus and the halogen.
7.5.3 Reaction with thionyl chloride, SOCl2

• Alcohols react with thionyl chloride to produce a halogenoalkane. Sulphur dioxide and
hydrogen chloride are given off as well.
• This reaction is useful in obtaining pure halogenoalkane. This is because the other two
products are gases, and they can be separated from the mixture easily.
7.5.4 Oxidation
Reagent: Acidified potassium dichromate (VI), K2Cr2O7 or acidified potassium manganate
(VI), KMnO4
Product: Primary alcohol - Aldehydes and carboxylic acids
Secondary alcohol - Ketones
Tertiary alcohol - Will not be oxidised
• Different class of alcohols (primary, secondary or tertiary) will behave differently during
oxidation. Therefore, it is a very useful test to distinguish them.
• For primary alcohols, if the alcohol used is in excess and the product formed is distilled off
as soon as possible, aldehydes are formed. Take ethanol as an example, ethanal is formed.
• If the alcohol used is limited and heated under reflux, the primary alcohol will be oxidised to
aldehyde then to carboxylic acid. Take ethanol as an example, from the aldehyde formed,
ethanoic acid is formed.
68 | P a g e
• For secondary alcohols, the secondary alcohol will be oxidised to a ketone. Take propan-2-
olas an example, propanone is formed.
• For tertiary alcohols, they will not be oxidised. This is because there is no hydrogen atom
from the carbon atom holding the -OH group can be removed.
Observation
1) If K2Cr2O7 is used as oxidising agent: colour of solution changes from orange to green.
2) If KMnO4 is used as oxidising agent: colour of solution changes from purple to colourless.
7.5.5 Esterification
Reagent: Carboxylic acid
Conditions: Heat under reflux with concentrated sulphuric acid, H2SO4 as catalyst
Product: Esters
• Esters are derivatives of carboxylic acids. In an ester, the hydrogen from the -COOH group of
carboxylic acid is replaced by an alkyl group.
• The alkyl group came from the alcohol. Some common esters and their naming:
69 | P a g e
• Alcohol and carboxylic acids/acyl halides mixture is heated with little concentrated acid
sulphuric acid.
• Sulphuric acid serves two purposes
➢ It supplies H+ to act as catalysts.
➢ It absorbs the water produced in the reaction and increases the yield of the ester.
• For example, to make methyl benzoate, methanol and benzoic acid are used. Both of them
are heated under reflux with the presence of catalyst and strong acid HCl.
• Esters can be detected from a sweet-smelling odour.
7.6 TEST FOR ALCOHOLS

• In organic chemistry, it is very important to distinguish primary, secondary and tertiary. It
can be achieved by using a Lucas Reagent.
7.6.1 Lucas Reagent

• It constitutes of anhydrous ZnCl2 and concentrated HCl
• Zn acts as a catalyst for the following reaction.
R-OH + HCl R-Cl + H2O

• The insoluble halogenoalkane is responsible for the cloudy or white ppt observed.
Observations
1. In the presence of a tertiary alcohol there is an immediate production of white ppt.
2. In the presence of secondary alcohol, a cloudy or white ppt is observed after 5-10mins.
3. In the presence of primary alcohol, no cloudy or white ppt is observed. The solution
remains clear.
70 | P a g e
7.6.2 Triiodomethane reaction
• Alcohols which contain the group below react with iodine and aqueous sodium hydroxide to
produce triiodomethane, CHI3. The reaction is used as a test for the group shown below in
organic compounds.
• The alcohols which gives a positive test are:

a) Primary alcohols – ethanol only
b) Secondary alcohols – all secondary methyl alcohols
c) Tertiary alcohols – none
d) Some aldehydes and ketones will give a positive triiodomethane reaction.
• The reaction takes place at r.t.p though it is necessary to warm the reactants.
Observations
• The CHI3 is seen as a yellow precipitate for a positive test.
71 | P a g e
CHAPTER 8: Phenol
• Identification of the functional group.
8.1 NOMENCLATURE OF PHENOL

• Note that -phenol is used as the parent name rather than -benzene.
8.2 PHYSICAL PROPERTIES OF PHENOL

8.2.1 Melting and Boiling Point
• Phenols have higher boiling points than the alkyl benzenes with similar Mr due to the
presence of intermolecular hydrogen bonding in addition of van der Waals' forces of
attraction.
• The boiling point increases as the number of substituent alkyl group atoms increases. This
is because there are more electrons, hence more temporary dipoles (Van Der Waals forces)
can be set up.
Compare the boiling point of o-nitrophenol and p-nitrophenol
• p-nitrophenol has intermolecular hydrogen bonding and o-nitrophenol has intramolecular

hydrogen bonding. Intermolecular bonding results in association of molecules hence it
increases the boiling point.
• Intramolecular hydrogen bonding results in the cyclisation of the molecules thus
preventing association of molecules. Hence the boiling and melting point does not change
significantly. Therefore p-nitrophenol has a higher boiling point than o-nitrophenol.
72 | P a g e
8.2.2 Solubility
• Phenols are partially soluble in water because it contains a polar -OH group which forms
hydrogen bonds with water molecules and a non-polar bulky benzene which is immiscible
with water.
Compare the solubility of o-nitrophenol and p-nitrophenol

• p-nitrophenol is more soluble in water because it forms more intermolecular hydrogen
bonds with water whereas o-nitrophenol forms fewer intramolecular hydrogen bonds with
water due to the cyclisation of the molecules thus preventing association with water
molecules.
8.2.3 Acid and Base nature of Phenols

• Phenols are weakly acidic, stronger than water. It is because the extent at which phenol
dissociates to form H+ is greater than the extent to which water can naturally dissociate to
form an H+.
• There is going to be delocalization of lone pair of electrons from the oxygen atom into the
benzene electron π system. This weakens the O-H bond realizing an H+ easily compared to
alcohols.
8.3 CHEMICAL REACTIONS OF PHENOL

8.3.1 Reaction with sodium metal, Na
Product: Phenoxides and hydrogen gas
Type of reaction: Displacement reaction/Redox Reaction
• Phenols react with vigorously with Na metal giving off hydrogen gas and white solid
phenoxide solid.
Observations
• Bubbles of hydrogen gas observed.
• Effervescence sound of hydrogen is produced
• White solid of phenoxide.
73 | P a g e
8.3.4 Reaction with sodium hydroxide, NaOH
Product: Phenoxides and water
Type of reaction: Neutralisation reaction
• phenol is a weak acid so it will react with an alkali to give a salt plus water. The salt formed,
sodium phenoxide, is soluble in water.
• The reaction does not have clear observations.
8.3.5 Esterification
Reagent: Acyl Halides, NaOH
Product: Esters and HX (small molecule)
Type of reaction: Addition elimination reaction
• Esters can only be formed from phenol by reacting phenol with acyl halides. The formation
of esters from phenol and acyl halides is a good example of an addition elimination reaction.
• Phenols do not react with carboxylic acids to form esters.
• The reaction is carried out under basic conditions.
8.4 Substitution into the benzene ring of phenol

• Compared with benzene, phenol reacts more readily with electrophiles. The overlap of one
of the lone pairs of electrons on the oxygen atom in the OH group with the π bonding system
increases the electron density of the benzene ring in phenol.
• This makes the benzene ring more open to attack from electron-deficient electrophiles. It
‘activates’ the benzene ring, especially at positions 2, 4 and 6.
74 | P a g e
8.4.1 Bromination of Phenol
• However, bromine water reacts readily with phenol to form tribromophenol.
• In inert solvent bromine ionisation is not facilitated that much and phenol is mono substituted.
Observations
• Phenol decolorise the orange solution and forming a white precipitate of 2,4,6-
tribromophenol.
8.4.2 Nitration of Phenol

• This activation of the benzene ring is also shown in the nitration of phenol.
• With benzene, we need a mixture of concentrated nitric and sulfuric acids to reflux with
benzene at about 55 °C for nitration to take place.
• However, the activated ring in phenol readily undergoes nitration with dilute nitric acid at
room temperature.
• If we use concentrated nitric acid, we get 2,4,6-trinitrophenol formed, shown below:
75 | P a g e
8.4.3 Coupling
• Phenols couple with diazonium salts to form azo dyes.
8.5 A SPECIFIC TEST FOR PHENOLS

• When a solution of iron III Chloride is added to a dilute solution of phenol, a coloured
complex is formed. A purple colour coloration is observed.
Phenols Do Not have Similar Reactions as Alcohols.

a) No reaction with phosphorous halides
b) No reaction with HX
c) No Dehydration
d) No Oxidation
e) No esterification with carboxylic acids
f) No reaction with metal carbonates
76 | P a g e
Chapter 9: Carbonyl Chemistry
• Carbonyl compounds are compounds that contain the C=O (carbonyl) group. Examples are
aldehydes and ketones.
9.1 Identification of Aldehydes and Ketones
9.2 Physical properties of carbonyl compounds

• The boiling point of carbonyl compounds is higher than the alkanes with similar Mr.
• The boiling point increases with increasing number of carbon atom. This is because there
are more electrons, hence more temporary dipoles can be setup. More energy is required to
overcome these forces.
• Besides temporary dipoles, permanent dipole-dipole forces are also present due to carbonyl
compounds being polar.
• Methanal and ethanal are gases at room temperature, while others are liquids.
77 | P a g e
9.2.2 Solubility
• Carbonyl compounds are soluble in water. This is because they are able to form hydrogen
bond with water molecules.
• The solubility decreases with increasing number of carbon atoms. This is because the long
hydrocarbon chain disrupts the hydrogen bonding.
9.3 CHEMICAL REACTIONS OF ALDEHYDES AND KETONES
9.3.1 Preparation of aldehydes and ketones
• Aldehydes and ketones can be made by oxidising primary and secondary alcohol
respectively. The oxidising agent used is either acidified potassium dichromate (VI),
K2Cr2O7 or acidified potassium manganite (VII), KMnO4.
Reagent: acidified conc K2Cr2O7/KMnO4
Condition: Reflux
Type of reaction: Oxidation reaction
9.3.3.1 To make an aldehyde:

• The primary alcohol used must be in excess and heated under reflux with acidified dilute
K2Cr2O7/KMnO4. The aldehyde formed must be distilled off as soon as possible.
• Under these conditions, a primary alcohol is oxidised to an aldehyde. Take ethanol as an
example, ethanal is produced.
78 | P a g e
9.3.3.2 To make a ketone:
• The secondary alcohol is heated under reflux with acidified K2Cr2O7/KMnO4.
• Under these conditions, a secondary alcohol is oxidised to a ketone. Take propan-2-ol an
example:
Observations
• Purple KMnO4 is decolorized
• Orange K2Cr2O7 is reduced to Cr3+ which gives a green colour.
9.4 Reactions of Aldehydes and Ketones

• The C=O bond of the carbonyl group is highly polarised due to oxygen atom being more
electronegative.
• This causes the slightly positive carbon atom to be susceptible to nucleophilic attacks.
Nucleophiles are species that carries a negative charge.
• Therefore, carbonyl compounds will undergo nucleophilic addition.
9.4.1 Reduction
Reagent: Lithium tetrahydridoaluminate, LiAlH4 or sodiumtetrahydridoborate, NaBH4
Condition: For LiAlH4 - in dry ether (ethoxyethane) at r.t.p

For NaBH4 – in alkaline aqueous methanol solution at r.t.p/warming.
Type of reaction: Nucleophilic Addition Reaction (Reduction reaction)
Product: Aldehyde - primary alcohol
Ketone - secondary alcohol
• LiAlH4 and NaBH4 are acting as reducing agents as well as providing the nucleophile, H⁻.
This is a redox reaction as well as a nucleophilic addition reaction.
79 | P a g e
• The most preferred reagent for this reaction is this reaction is NaBH4 than LiAlH4 because
LiAlH4 is more hazardous and expensive than NaBH4.
• For aldehydes, primary alcohols are formed upon reduction. Take ethanal as an example:
• For ketones, secondary alcohols are formed upon reduction. Take propanone as an
example:
80 | P a g e
9.4.2 Oxidation
Reagent: Acidified potassium dichromate (VI), K2Cr2O7 or acidified potassium manganate
(VI), KMnO4
Product: Aldehyde - Carboxylic acid
Ketone - Will not be oxidised
• Aldehydes will be oxidised to carboxylic acids.
• Ketones will not be oxidised by acidified K2Cr2O7or KMnO4. The only exception is
phenylethanone.
Observations
Acidified purple KMnO4 is decoulorised or orange K2Cr2O7 is converted to Cr3+ which is green.
9.4.3 Reaction with hydrogen cyanide, HCN

Reagent: Sodium/potassium cyanide, NaCN and a little sulphuric acid, H2SO4 or NaOH(aq)
Product: Hydroxy nitriles
• The hydrogen cyanide acid is too weak to provide enough cyanide ion for the reaction occur
at a reasonable rate. Therefore, a catalyst is used either NaCN(aq) or NaOH(aq)
81 | P a g e
Consider the reaction of ethanal using a trace of base as catalyst
• The hydroxide ion regenerates cyanide ion from the hydrogen cyanide.
• The nucleophile in the reaction is the cyanide ion, CN-.

• The CN- is attracted to the positively charged carbon.
• The O- then reacts with a water molecule in aqueous solution.
• The hydroxide is regenerated back since it is acting as a catalyst.

Consider the reaction of ethanal using a trace of NaCN as catalyst
• NaCN ionizes in aqueous solution to form Na+ and CN-
NaCN + (aq) CN- + Na+

• The CN- is attracted to the positively charged carbon.
82 | P a g e
• The intermediate anion is a strong base, and can abstract a proton from a molecule an un-
ionised HCN.
• The cyanide is regenerated back since it is acting as a catalyst.
9.5 TESTS FOR ALDEHYDES AND KETONES

9.5.1 Test for carbonyl group using 2,4-dinitrophenylhydrazine
Reagent: 2,4-dinitrophenylhydrazine (Brady's reagent)
Condition: Room temperature/warming
Product: 2.4-dinitrophenylhydrazones
Type of Reaction: Condensation/Addition elimination
• 2,4-dinitrophenylhydrazine or 2,4-DNPH can be used to detect the presence of carbonyl

group, C=O. The structure of 2,4-DNPH is shown below:
• When a little aldehyde or ketone is added to the 2,4-dinitrophenylhydrazine (Brady's

reagent), an orange-yellow precipitate is formed.
• A condensation reaction occurs when a carbonyl compound is added to 2,4-DNPH. During

this reaction, a water molecule is lost. The final compound is seen as orange-yellow
precipitate.
83 | P a g e
9.5.2 Test for aldehydes using Tollens' reagent (silver mirror test)
Reagent: [Ag (NH3)2] ⁺, NaOH(aq)
Condition: Gentle Warming
Type of Reaction: Redox
• Tollens' reagent contains diamminesilver(I) ions, [Ag (NH3)2] ⁺. Aldehydes will reduce the
diamminesilver(I) ions to metallic silver, aldehyde itself is oxidised to a salt of carboxylic
acid.
• Since ketones will not be oxidised, it will not reduce it to metallic silver.
• Therefore, when a few drops of aldehyde are added to the freshly prepared Tollens' reagent,
and warmed in a water bath for a few minutes, a grey precipitate or a silver mirror is
observed only if aldehyde is present.
9.5.3 Test for aldehydes using Fehling's solution

• Fehling's solution contains copper (II) ions complexed with tartrate ions in sodium
hydroxide solution. Complexing the copper (II) ions with tartrate ions prevents
precipitation of copper (II) hydroxide. It is a blue solution.
• Only aldehydes will reduce the complexed copper (II) ion to copper(I) oxide. Because the
solution is alkaline, the aldehyde itself is oxidised to a salt of the corresponding carboxylic
acid.
84 | P a g e
• When a few drops of the aldehyde are added to the reagent, and the mixture is warmed
gently in a hot water bath for a few minutes, a red precipitate is observed only if aldehydes
present.
9.5.4 Reactions to form tri-iodomethane

Reagent: NaOH(aq) + I2
Condition: Reflux
Type of Reaction: Redox
• Tri-iodomethane (iodoform) forms as a yellow precipitate with methyl ketones, i.e.

compounds containing the CH3CO group.
The reaction involves two steps

1) the carbonyl compound is halogenated – the three hydrogen atoms in the CH3 group are
replaced by iodine atoms
2) the intermediate is hydrolysed to form the yellow precipitate of tri-iodomethane, CHI3, with
a sweet, antiseptic ‘hospital’ smell.
85 | P a g e
CHAPTER 10: Carboxylic acids
• Carboxylic acids are compounds that contain the -COOH group.
10.1 NAMING CARBOXYLIC ACIDS

• Simple carboxylic acids derived from open-chain alkanes are systematically named by
replacing the terminal -e of the corresponding alkane name with -oic acid.
• Compounds that have a CO2H group bonded to a ring are named using the suffix -carboxylic
acid.
10.1.1 Assignment
86 | P a g e
10.2 PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS
• Carboxylic acids generally have higher melting and boiling points due to the existence of
strong hydrogen bonds which require a lot energy to break.
• The boiling point increases as the number of carbon atoms increases. This is because there
are more electrons, hence more temporary dipoles (Van Der Waals forces) can be set up.
More energy is required to overcome these forces.
10.2.1.1Comparing the Mp and Bp of Carboxylic acids and alcohols

• Carboxylic acids have higher melting and boiling points than the corresponding alcohols
because most pure carboxylic acids exist as cyclic dimers held together by two hydrogen
bonds.
• This strong hydrogen-bonding has a noticeable effect on boiling points and also doubles the
size of the molecule, making the van der Waals' forces stronger.
• Hence more energy is required to overcome these forces of attraction.
• A dimerization reaction is an addition reaction in which two molecules of the same

compound react with each other to give an adduct.
• A dimer is an oligomer consisting of two monomers joined together by bonds that can either
be weak or strong, covalent or intermolecular.
10.2.3 Solubility
• Carboxylic acids are generally soluble in water because carboxylic acids are capable of
forming hydrogen bond with water molecule.
• However, the solubility decreases as the number of carbon atoms increases. This is because
the presence of long hydrocarbon tail disrupts the effectiveness of hydrogen bonding.
• In non-polar solvents the polar ends associate resulting in the formation of dimers which
are predominantly non-polar making it soluble in non-polar as well.
Dissolving ethanoic acid in water Dissolving Ethanoic acid in benzene
87 | P a g e
10.2.4 Acidity of carboxylic acids
• Carboxylic acids are weak acids because they can partially donate a proton to form
carboxylate ion and hydroxonium ion. The presence of hydroxonium ions makes the
solution acidic.
Why are carboxylic acids so much more acidic than alcohols, even though both
contain OH groups?
The carboxylic acids are stronger acids than alcohols because:
1. The O-H bond in the carboxylic acid is weakened by the carbonyl group, C=O which is an
electron withdrawing group (-ve resonance effect).
2. The carboxylate ion is stabilised by the delocalisation of electrons around the COO– group.
This delocalisation spreads out the negative charge on the carboxylate ion, reducing its
charge density and making it less likely to bond with an H+(aq) ion to re-form the
undissociated acid molecule
• In resonance terms, a carboxylate ion is a stabilized resonance hybrid of two equivalent

structures. Since a carboxylate ion is more stable than an alkoxide.
88 | P a g e
10.3 Chemical Reactions of Carboxylic acids
10.3.1 Formation of Carboxylic Acids
There are three ways to produce carboxylic acids:
1. Oxidation of primary alcohol.
2. Oxidation of aldehyde.
3. Acidic/alkaline hydrolysis of nitrile.
For oxidation of primary alcohol and aldehyde, refer back previous chapters.
10.3.2 Acidic hydrolysis of nitrile

Reagent: Dilute acid (dilute HCl(aq)), Nitrile
Condition: Heated under Reflux
Type of Reaction: Hydrolysis
• When nitrile is heated under reflux with a dilute acid such as dilute hydrochloric acid,
carboxylic acid will be formed.
• Using ethane nitrile as an example, ethanoic acid is formed.
89 | P a g e
10.3.3 Alkaline hydrolysis of nitrile
Reagent: Aqueous Alkaline solution e.g. NaOH(aq), Nitrile
• When nitrile is heated under reflux with an alkali such as sodium hydroxide, salt of
carboxylic acid (carboxylate salt) is produced. Using ethane nitrile as an example, ethanoate
ion is formed.
• Ethanoate ion can be converted to ethanoic acid by the addition of acid.
10.3.4 Reaction with bases

Reagent: Aqueous Alkaline solution e.g. NaOH(aq)
Condition: Room Temperature and Pressure
Type of Reaction: Neutralisation Reaction
• Since carboxylic acids are acids, they will react with a base such as sodium hydroxide to
produce a carboxylate salt and water. This is a simple neutralisation reaction.
• Take ethanoic acid and sodium hydroxide as an example:
10.3.5 Reaction with metals

Reagent: Reactive metals e.g. Na metal
Type of Reaction: Redox/Displacement Reaction
• Carboxylic acids will react with reactive metals such as sodium to produce a carboxylate salt
and hydrogen gas.
• Take ethanoic acid and sodium metal as an example:
10.3.5.1 Observation
• Na metal dissolves in acid
• Effervescence sound of hydrogen gas
90 | P a g e
10.3.6 Reaction with carbonates and hydrogen carbonates
• Carboxylic acids will react with carbonates and hydrogen carbonates to produce a
carboxylate salt, carbon dioxide gas and water.
• Take ethanoic acid and sodium carbonate as an example:
• Take ethanoic acid and sodium hydrogen carbonate as an example:
• This is a useful test to distinguish carboxylic acids from alcohols and phenols. This is
because alcohols and phenols are not acidic enough to react with these.
Observations
• Na2CO3 or NaHCO3 dissolves in carboxylic acid.
• Effervescence sound of carbon dioxide gas.
10.4 CONVERTING CARBOXYLIC ACIDS TO ACYL HALOGENS

Type of Reaction: Nucleophilic Substitution
• Acyl halides have the -OH in the -COOH group of the carboxylic acid replaced by a halogen.
• There are three methods to produce acyl chlorides from carboxylic acids
10.4.1 Reaction with phosphorus (III) halide, PX3

• Take ethanoic acid as an example, the equation is:
3CH3COOH + PX3 →3CH3COX + H3PO3

10.4.2 Reaction with phosphorus(V) halide, PX5
CH3COOH + PX5 →CH3COX + POX3+ HCl

10.4.3 Reaction with thionyl chloride, SOCl2
CH3COOH + SOX2 →CH3COX + SO2+ HX

• This method is generally preferred because SO2 and HCl are both gases, and can be
separated from the mixture easily.
Observation
• White fumes of HX are observed
91 | P a g e
10.4.4 Reduction of the -COOH
Reagent: LiAlH4 in dry ethoxyethane (ether)
Condition: Reflux at 350C
Type of Reaction: Reduction Reaction
• Carboxylic acid can be reduced to alcohol by a reaction LiAlH4 in dry ether.

• The reaction requires a strong powerful reducing agent LiAlH4 and neither NaBH4 nor Ni
and H2 are strong enough to reduce carboxylic acids to alcohols.
92 | P a g e
CHAPTER 11: CHEMISTRY OF ESTER
• Esters are derivatives of carboxylic acids.
• In an ester, the hydrogen from the -COOH group of carboxylic acid is replaced by an alkyl
group. The alkyl group came from the alcohol/phenol.
11.2 NOMENCLATURE OF ESTERS

• Note that the name of an ester is 'alcohol + carboxylic acid'.
11.3 PHYSICAL PROPERTIES OF ESTERS

• Esters have lower melting and boiling points than carboxylic acids. This is because they are
not capable of forming intermolecular hydrogen bonding.
• The mp and bp is generally low, it contains weak Van Der Waals forces which are dominant
and a small permanent dipole-dipole contribution.
11.3.2 Solubility
• Esters are insoluble in water and often identified by their strong fruity smell.
• Despite two oxygen atoms, they do not form strong hydrogen bonds with water.
11.4.3 Acid Base Nature of Esters

• Unlike carboxylic acids, esters are neutral.
• This is because they cannot donate or accept a proton.
11.5 CHEMICAL REACTIONS OF ESTERS

11.5.1 Preparation of esters
Reagent: Alcohols and carboxylic acids in the presence of conc H2SO4
Product: Esters and HX (small molecule)
93 | P a g e
Type of reaction: Addition elimination reaction/Condensation
• Esters can be prepared from the reaction between alcohol and carboxylic acid.
• To prepare an ester from carboxylic acid and alcohol, both them are heated under reflux in
the presence of concentrated sulphuric acid as catalyst.
The general equation:
Observations
• Esters can be detected from a sweet-smelling odour.
11.5.2 HYDROLYSIS OF ESTERS

11.5.2.1 Acidic hydrolysis of esters
Reagent: Dilute acid (dilute HCl(aq)), Ester
• The hydrolysis of an ester is a slow process. Therefore, the ester is heated under reflux with
a dilute acid such as dilute hydrochloric acid, the corresponding carboxylic acid and alcohol
will be formed.
• This is just the reverse process of esterification.
11.5.2.2 Alkaline hydrolysis of esters

Reagent: Aqueous Alkaline solution e.g. NaOH(aq), Ester
• The reaction is quicker than in acidic solution because OH- is a stronger nucleophile than
water.
• When ester is heated under reflux with a base such as sodium hydroxide solution, the
corresponding carboxylate salt and alcohol will be formed.
94 | P a g e
• The sodium ethanoate can be converted to ethanoic acid by adding dilute acid.
11.5.3 Reduction of Esters

Reagent: LiAlH4 in dry ethoxyethane (ether)
Condition: Reflux
Type of Reaction: Reduction Reaction
• Esters can be easily reduced using a powerful reducing agent LiAlH4 but not less reactive
NaBH4.
• Reduction of esters results in the formation of 10 alcohol (primary alcohols)
11.7 USES OF ESTER

11.7.1 As solvents
• Small esters such as methyl ethanoate, ethyl ethanoate and butyl ethanoate are very widely
used as solvents.
11.7.3 As perfumes and flavourings

• The smell and taste of fruits such as oranges, apples, pears, raspberries, strawberries, and
so on, are due to naturally occurring esters. Many foods will have those same esters added
to them to simulate the smell and taste of real fruit.
• Flower and other smells are also produced by naturally occurring esters.
• Perfumes will have the same esters added. Benzyl ethanoate, for example, is used to
produce jasmine or gardenia fragrances.
95 | P a g e
CHAPTER 12: ACYL HALIDES
• Identification of the functional group -COX.
12.1 NOMENCLATURE OF ACYL HALIDES

• Acid halides are named by identifying first the acyl group and then the halide.
• the acyl group name is derived from the carboxylic acid name by replacing the -ic acid or -
oic acid ending with -oyl, or the -carboxylic acid ending with -carbonyl.
12.2 Physical Properties of Acyl Halides

12.2.1 Melting and Boiling Points of Acyl Halides
• Acyl halides generally have a low melting and boiling point due to the presence of
permanent dipole-dipole moment and weak Van Der Waals Forces.
• The extra electron withdrawing effect has of the carbonyl group, resulting in extra dipole-
dipole attractions increasing the boiling point compared to halogenoalkanes with similar
shape/mass.
12.2.2 Solubility
• Acyl halides are slightly soluble in water and they can form hydrogen bonds with water.
12.2 CHEMICAL PROPERTIES OF ACYL HALIDES

• Acyl halides are very reactive because they have two electron withdrawing atoms attached
to the same carbon only and this has a dramatic effect on the reactivity of acyl halides.
• This makes the carbon very partially positive thus making it susceptible to nucleophilic
attack.
• The acyl chlorides are very reactive liquids. When they react with nucleophiles the C-Cl
bond breaks and white fumes of hydrogen chloride, HCl, are given off.
• All the reactions are carried out at room temperature because of their reactivity.
96 | P a g e
12.3 CHEMICAL REACTIONS OF ACYL HALIDES
12.3.1 Reactions of acyl halide with water
Reagent: H2O
Condition: R.t.p
Product: Carboxylic acid and HX (small molecule)
Type of reaction: Hydrolysis
• Acyl halides react vigorously with water to produce two acids a carboxylic acid and HX.
• Acyl chlorides hydrolyses the most rapidly, giving an instant result with cold AgNO3 (aq)
• (white precipitate of AgCl).
• As a result of their speed reaction with water, acyl chloride produces steamy white fumes of
HCl(g) when few drops of water are added.
• This is a good test for acyl halides which differentiate them from halogenoalkanes and
Halogenoarenes.
Observations
• Steamy white fumes of HCl are produced within minutes
97 | P a g e
12.3.2 Reaction with amines
Reagent: Conc NH3
Condition: R.t.p
Product: Amide and HX (small molecule)
• Amines contain nitrogen atoms with a lone pair of electrons. This lone pair of electrons is
available to attack the carbonyl carbon atom in acyl chlorides.
• The reaction is vigorous and the organic product is a substituted amide.
Observations
White fumes of HCl are produced
• HCl will react with another molecule of ammonia in an acid-base reaction if ammonia is in
excess
NH3 + HCl →NH4+Cl-

• White smoky fumes of salts (NH4+Cl-)/NH3+Cl- are produced if NH3/Amine is in excess.
98 | P a g e
12.3.4 Reaction of acyl halide with Alcohol
Reagent: Acyl Halides, Alcohol
• Acyl halides reacts readily with alcohols, forming esters
12.3.5 Reaction of acyl halide with phenol

Reagent: Acyl Halides, NaOH/Pyridine, Phenol
Condition: Warming
• Esters can only be formed from phenol by reacting phenol with acyl halides. The formation
of esters from phenol and acyl halides is a good example of an addition elimination reaction.
• Phenols do not react with carboxylic acids to form esters.
• The reaction is carried out under basic conditions because phenols are not so nucleophilic
as alcohols because lone pair on oxygen atom is delocalized into the ring.
12.3.6 Reaction of Acyl halide with NaOH(aq)

Reagent: Acyl Halides, NaOH(aq)
Condition: R.t.p
Type of reaction: Nucleophilic Substitution
• Acyl chlorides generally react rapidly or violently with hydroxide ions solution.
• If the -COX group is directly attached to the ring, the reaction will be slower.
• The reaction of ethanoyl chloride will produce a solution containing sodium ethanoate and
sodium chloride
99 | P a g e
CHAPTER 13: AMINES
Organic Nitrogen Compounds include:
1. Amines
2. Amides
3. Azo compounds
4. Amino Acids
• Amines are organic derivatives of ammonia by replacing one or more hydrogen in ammonia
by hydrocarbon group. They have a fishy smell and become less odorous as the bulky
hydrocarbon increases.
13.1 CLASS OF AMINES

• There are three types of amines which are primary amine (10 amine), secondary amine (20
amine) and tertiary amine (30 amine).
13.2 NOMENCLATURE AND ISOMERISM

• Amines can be either alkyl-substituted (alkylamines) or aryl-substituted (arylamines).
• Primary amines have an NH2 group bonded to an alkyl or aryl group, e.g. ethylamine,
C2H5NH2 or phenylamine, C6H5NH2
• Alternatively, the suffix -amine can be used in place of the final -e in the name of the parent
compound.
• Amines with more than one functional group are named by considering the NH2 as an
amino substituent on the parent molecule.
100 | P a g e
• Symmetrical secondary and tertiary amines are named by adding the prefix di- or tri- to
the alkyl group.
• Unsymmetrically substituted secondary and tertiary amines are named as N-substituted

amines.
• The largest alkyl group is chosen as the parent name, and the other alkyl groups are
considered N-substituents on the parent.
13.2.1 ASSIGNMENT
101 | P a g e
13.3 Physical Properties of Aliphatic amines
• Generally, amines have a higher melting and boiling points because more energy is required
to break the strong hydrogen bonds.
• The boiling point increases as the homologous series of hydrocarbons increases. This is
because there are more electrons, hence more temporary dipoles (Van Der Waals forces)
can be set up.
13.3.2 Solubility of Amines

• Aliphatic amines are generally soluble in water because they can form hydrogen bonds with
water.
• However, the solubility decreases as the homologous series of hydrocarbons increases. This
is because the presence of long hydrocarbon tail which disrupts the effectiveness of
hydrogen bonding.
13.4 ACIDS AND BASE NATURE OF AMINES

• The chemistry of amines is dominated by the lone pair of electrons on nitrogen, which
makes amines both weakly basic and nucleophilic.
• They react with acids to form acid–base salts
• Amines partially dissociate in water to release OH-.
102 | P a g e
13.4.1 Strength of basicity in amines
• The aryl group attached on the amine group has an effect the basicity of amines.
13.4.1.1 Electron Donating Groups

• These have positive inductive effect and can donate electrons through the sigma bonds to
the nitrogen atom e.g. alkyl groups.
• This makes the lone pair electrons on the nitrogen atom more available for donation to
protons to form a dative bond, thus increasing the strength of the basicity of amines.
13.4.1.2 Electron Withdrawing groups

• These have either negative inductive effect or negative resonance effect and the can
withdraw electrons from the nitrogen atom.
• This makes the lone pair of electrons on the nitrogen atom less available for donation to
protons to form a dative bond thus deceasing the strength of the base of the amine.
13.4.2 Assignment
Comment and compare on the decrease or increase in pKa per each class of the following
nitrogen organic compounds.
103 | P a g e
13.5 PREPARATION OF AMINES
13.5.1 Reaction of Halogenoalkane with NH3 (Recap)
Reagent: Excess ammonia, NH3 in ethanol
Product: Amines
• If a halogenoalkane is heated with an excess of ammonia dissolved in ethanol under

pressure, an amine is formed e.g.
• If the ammonia used is not in excess, a complicated mixture containing secondary and
tertiary amine is obtained. This is because ethylamine is a good nucleophile and it can
attack the unreacted bromoethane.
13.5.2 Reduction of Nitriles

Reagent: LiAlH4 in dry ether or Nickel catalyst and H2 gas
Condition: Reflux
Product: Amine
Type of reaction: Reduction
• We can also use LiAlH4 in dry ether to reduce amides to amines. So ethanamide will be
reduced ethylamine.
13.6 CHEMICAL REACTIONS OF ALIPHATIC AMINES

13.6.1 Reaction of amines with nitrous acid
• 10, 20 and 30 amines react with nitrous acid differently.
• Nitrous acid (HNO2) is unstable has to be made as required by reacting together sodium
nitrite (NaNO2) and hydrochloric acid.
• The reaction is used to distinguish 10, 20 and 30 amines.
104 | P a g e
13.6.1.1 Primary Amines
• They react in warm aqueous acidic solution to give nitrogen gas and alcohols.
Observations
• Odourless, colourless nitrogen gas evolution from a clear solution (effervescence)
13.6.1.2 Secondary Amines

• Secondary amines react in warm aqueous acidic solution to produce an insoluble yellow
liquid oil called nitrosamine.
• These compounds are powerful carcinogens therefore great precautions should be
observed.
Observations
• an insoluble yellow liquid oil called nitrosamine.
13.6.1.2 Tertiary Amines

• A tertiary amine reacts with nitrous acid to produce salts which are soluble in water.
(CH3) 3N + HNO2 →(CH3) 3NH+NO2-

Observations
• No visible change is observed because a clear solution remains the same (A soluble salt of
trimethyl ammonium nitrite is produced).
13.6.2 Reactions of Amines with acyl Halides

Reagent: Conc NH3
Condition: R.t.p
Product: Amide and HX (small molecule)
• Amines contain nitrogen atoms with a lone pair of electrons. This lone pair of electrons is
available to attack the carbonyl carbon atom in acyl chlorides.
• The reaction is vigorous and the organic product is a substituted amide.
105 | P a g e
Observations
• White fumes of HCl(g)
Refer the mechanism from acyl halides
13.6.3 Reactions of Amines with Halogenoalkanes

• Ammonia and other amines are good nucleophiles in SN2 reactions.
Reagent: R-X and Excess R-NH2 in ethanol
Product: Amines
CH3CH2NH2 + CH3CH2Br → CH3CH2NHCH2CH3 + HBr

• Bromine is lost as a bromide ion and the intermediate product is a salt which is further
reacted with ammonia to remove one hydrogen atom in a reversible reaction.
106 | P a g e
CHAPTER 14: Aromatic Amines
Identification of the group
14.1 PHYSICAL AND CHEMICAL PROPERTIES

• They have a low mp and bp due to the predominant of Van Der Waals forces in the molecule.
Therefore, less energy is required to break the weak Van Der Waals forces.
14.1.2 Solubility
• Phenylamine is generally insoluble in water because the hydrogen bonds in phenylamine is
hindered due to the delocalisation of the lone pair of electrons which is supposed to form
hydrogen bonds into the benzene electron π system.
• It is soluble in non-polar solvents due to the non-polar bulky benzene which is immiscible
with water.
14.2 Acid-Base Nature of Aromatic amines

• These are weakly basic and they react with acids.
• Phenylamine is a Lewis Base because it donates lone pair of electrons on Nitrogen atom.
107 | P a g e
14.3 PREPARATION OF PHYNYLAMINE
• Phenylamine can be prepared by two different methods.
14.3.1 Reduction of Nitrobenzene

Reagent: Sn (Tin) and Concentrated HCl
Condition: Heat
Product: Phenylamine/Aniline
Type of reaction: Reduction
• Phenylamine is made by reducing nitrobenzene. This reduction is carried out by heating

nitrobenzene with tin (Sn) and concentrated hydrochloric acid.
• The phenylamine is separated from the reaction mixture by steam distillation.
14.3.2 Reaction of halogenoalkane with ammonia

Reagent: Concentrated NH3
Condition: Copper Catalysts, 2000C and 50atm
Product: Phenylamine
• Halogenoarenes without electron withdrawing substituents don’t react with nucleophiles

under most conditions. At high temperature and pressure, chlorobenzene can be forced to
react e.g.
108 | P a g e
14.4 CHEMICAL REACTIONS OF PHENYLAMINE
14.4.1 Phenylamine with aqueous bromine
Reagent: Bromine aqueous
Condition: r.t.p
Product: 2.4.6-tribromophenylamine
Type of reaction: Electrophilic Substitution
• The reaction of aqueous bromine with phenylamine is similar to the reaction of aqueous
bromine with phenol and a white precipitate is also formed.
• The nitrogen in the NH2 group in phenylamine has a lone pair of electrons that can be
delocalised into the benzene ring so that the π bonding system extends to include the C-N
bond.
Observations
• A white precipitate is also formed
14.4.2 Reaction with Nitrous acid

• Aryl amines form fairly stable diazonium salts at very low temperatures. Under these
conditions Nitrogen is not evolved but a solution of diazonium salt is formed.
• Aryl diazonium salts are unstable and explosive when dry, but can be kept for several days
in refrigerator.
14.4.3 Reaction of phenylamine with Acyl Halides

• Phenylamine reacts vigorously in the cold with acyl halides to form amides.
109 | P a g e
14.4.4 The reaction of phenylamine with halogenoalkanes
• This is another reaction of phenylamine as a nucleophile, and again there is no essential
difference between its reactions and those of aliphatic amines.
• Taking bromoethane as a typical halogenoalkane, the reaction with phenylamine happens in
the same series of complicated steps as with any other amine.
• but this would instantly be followed by a reversible reaction in which some unreacted
phenylamine would take a hydrogen ion from the salt to give some free secondary amine: N-
ethylphenylamine.
110 | P a g e
Chapter 15: Amides
• Amides are derived from carboxylic acids. A carboxylic acid contains the -COOH group, and
in an amide the -OH part of that group is replaced by an -NH2 group.
• Amides have a functional group
15.1 NOMENCLATURE OF AMIDES

• Notice that in each case, the name is derived from the acid by replacing the "oic acid" ending
by "amide".
Structural Formulae Nomenclature

HCONH2 methanamide
CH3CONH2 ethanamide
CH3CH2CONH2 propanamide
CH3CH2CONHCH3 methylpropanamide
CH3CONHC6H5 Phenylethanamide
• If the chain was branched, the carbon in the -CONH2 group counts as the number 1 carbon
atom. For example:

• Generally, amides have high melting and boiling points because they can form hydrogen
bonds. The hydrogen atoms in the -NH2 group are sufficiently positive to form a hydrogen
bond with a lone pair on the oxygen atom of another molecule.
• The boiling point increases as the homologous series of hydrocarbons increases. This is
because there are more electrons, hence more temporary dipoles (Van Der Waals forces)
can be set up.
111 | P a g e
15.2.2 Solubility of amides
• The small amides are soluble in water because they have the ability to hydrogen bond with
the water molecules.
15.2.3 Acid Base Nature of Amides

• Unlike amines, amides are neutral in water and can only be protonated by strong acid.
• Although they contain a nitrogen atom, the lone pair of electrons on nitrogen atom is not
available for donation due to the presence of an electron withdrawing carbonyl group
which pulls electrons by resonance effect.
112 | P a g e
15.3 Preparation of Amides
15.3.1 Making amides from acyl chlorides
• To make ethanamide from ethanoyl chloride, you normally add the ethanoyl chloride to a
concentrated solution of ammonia in water.
• There is a very violent reaction producing lots of white smoke - a mixture of solid
ammonium chloride and ethanamide.
• Then the hydrogen chloride produced reacts with excess ammonia to give ammonium
chloride.
• Combine all this together to give one overall equation:
15.4 CHEMICAL REACTIONS OF AMIDES

• Amides are the least reactive of the common acid derivatives and undergo relatively few
nucleophilic acyl substitution reactions because of the high degree of positive charge on the
carbon atom in protonated amides.
15.4.1 HYDROLYSIS OF AMIDES

• Technically, hydrolysis is a reaction with water.
15.4.1.1 Hydrolysis under acidic conditions

Reagent: Dilute acid e.g. (dilute HCl(aq)),
Taking ethanamide as a typical amide:
• If ethanamide is heated under reflux with a dilute acid (such as dilute hydrochloric acid),
ethanoic acid is formed together with ammonium ions.
• So, if you were using hydrochloric acid, the final solution would contain ammonium chloride
and ethanoic acid.
113 | P a g e
15.4.1.2 Reaction Mechanism of acidic hydrolysis
15.4.1.3 Hydrolysis under alkaline conditions

Reagent: Aqueous alkaline solution e.g. (NaOH(aq)),
Type of Reaction: Hydrolysis/Nucleophilic Substitution
Taking ethanamide as a typical amide:
• If ethanamide is heated with sodium hydroxide solution, ammonia gas is given off and you
are left with a solution containing sodium ethanoate.
• The sodium ethanoate can be converted to ethanoic acid by adding dilute acid.
15.4.5 REDUCTION OF AMIDES

• Amides can be reduced to amines by LiAlH4 in dry ether under reflux condition.
114 | P a g e
Chapter 16: Azo Compounds
• These can also be referred to as Azo Dyes
• Azo dyes are formed from primary aromatic compounds in a two-stage process.
16.1 Stage 1: REACTIONS OF DIAZONIUM SALTS

• Aryl amines form fairly stable diazonium salts at very low temperatures. Under these
conditions Nitrogen is not evolved but a solution of diazonium salt is formed.
• The positive ion, containing the -N2+ group, is known as a diazonium ion. The "azo" bit of
the name refers to nitrogen.
16.2 STAGE 2: COUPLING REACTIONS OF DIAZONIUM IONS

16.2.1 The reaction with phenol
• Phenol is dissolved in sodium hydroxide solution to give a solution of sodium phenoxide.
• There is a reaction between the diazonium ion and the phenoxide ion and a yellow-orange
solution or precipitate is formed.
• The product is one of the simplest of what are known as azo compounds, in which two
benzene rings are linked by a nitrogen bridge.
115 | P a g e
16.2.2 The reaction with naphthalen-2-ol
• Naphthalen-2-ol is also known as 2-naphthol or beta-naphthol. It contains an -OH group
attached to a naphthalene molecule rather than to a simple benzene ring. Naphthalene has
two benzene rings fused together.
• The reaction is done under exactly the same conditions as with phenol. The naphthalen-2-ol
is dissolved in sodium hydroxide solution to produce an ion just like the phenol one. This
solution is cooled and mixed with the benzenediazonium chloride solution.
Observations
• An intense orange-red precipitate is formed - another azo compound.
16.2.3 The reaction with phenylamine (aniline)

• Some liquid phenylamine is added to a cold solution of benzene diazonium chloride, and the
mixture is shaken vigorously.
• These strongly coloured azo compounds are frequently used as dyes known as azo dyes.
The one made from phenylamine (aniline) is known as "aniline yellow"
Observations
• A yellow solid is produced.
116 | P a g e
16.3 THE USE OF AN AZO DYE AS AN INDICATOR - METHYL ORANGE
• Azo compounds contain a highly delocalised system of electrons which takes in both
benzene rings and the two nitrogen atoms bridging the rings.
• If white light falls on one of these molecules, some wavelengths are absorbed by these
delocalised electrons. The colour you see is the result of the non-absorbed wavelengths. The
groups which contribute to the delocalisation (and so to the absorption of light) are known
as a chromophore.
• Methyl orange is an azo dye which exists in two forms depending on the pH:
16.4 SUBSTITUTION REACTIONS OF DIAZONIUM IONS

• In this set of reactions of the diazonium ion, the -N2+ group is replaced by something else.
The nitrogen is released as nitrogen gas.
117 | P a g e
CHAPTER 17: Amino Acids
• They are compounds containing an amino group, -NH2, and a carboxylic acid group, -COOH.
17.1 IDENTIFICATION OF THE FUNCTIONAL GROUP:

17.1.1 Alpha Amino acids
• The biologically naturally occurring important amino acids have the amino group attached
to the carbon atom next door to the -COOH group.
• They are known as 2-amino acids.
• They are also known (slightly confusingly) as alpha-amino acids.
17.1.2 Beta Amino Acids

• A beta amino acid is an artificial amino acid where the amino group of -NH2 is attached to
the secondary carbon rather than the alpha carbon.
17.2 NOMENCLATURE OF AMINO ACIDS
118 | P a g e
17.3.1 Zwitterions
• The general structure of an amino acid has both a basic amine group and an acidic
carboxylic acid group.
• There is an internal transfer of a hydrogen ion from the -COOH group to the -NH2 group to
leave an ion with both a negative charge and a positive charge. Zwitterion formation
involves self-neutralization, in which the acidic –COOH group protonates the basic –NH₂
group
• A zwitterion is a species that possesses positive and negative charge of equal magnitude.
• This is called a zwitterion
• This is the form that amino acids exist in even in the solid state. Instead of the weaker
hydrogen bonds and other intermolecular forces ,amino acids have much stronger ionic
attractions between one ion and its neighbours.
• The net charge on a zwitterion is therefore zero. Zwitterion formation depends on the pH of
the medium in which the amino acids are found. At a pH of 7, glycine and alanine exist as
zwitterions.

• The amino acids are white crystalline solids at room temperature with surprisingly high
melting and boiling points due to the strong ionic attractions which requires more energy to
break.
119 | P a g e
17.3.3 Solubility
• Amino acids are generally soluble in water and insoluble in non-polar organic solvents such
as hydrocarbons.
• This again reflects the presence of the zwitterions. In water, the ionic attractions between
the ions in the solid amino acid are replaced by strong attractions between polar water
molecules and the zwitterions. This is much the same as any other ionic substance
dissolving in water.
• The extent of the solubility in water varies depending on the size and nature of the "R"
group.
• The lack of solubility in non-polar organic solvents such as hydrocarbons is because of the
lack of attraction between the solvent molecules and the zwitterions.
• Without strong attractions between solvent and amino acid, there won't be enough energy
released to pull the ionic lattice apart.
17.4 THE ACID-BASE BEHAVIOUR OF AMINO ACIDS

17.4.1 They are amphoteric
• This means that they exhibit both acidic and basic behaviour.
• The carboxyl group gives an amino acid the properties of an acid.
• The amino group gives an amino acid the properties of a base.
• An amino acid can therefore react with both bases and acids, forming salts.
17.4.1 Adding an alkali to an amino acid solution

• If the pH of a solution of an amino acid is increased by adding hydroxide ions, the hydrogen
ion is removed from the -NH3+ group.
17.4.2 Adding an acid to an amino acid solution

• If you decrease the pH by adding an acid to a solution of an amino acid, the -COO- part of the
zwitterion picks up a hydrogen ion.
120 | P a g e
• This time, during electrophoresis, the amino acid would move towards the cathode (the
negative electrode).
17.5 Electrophoresis
• This is the method used to identify, purify and separate charged particles in biochemical
analysis.
• The separation is based on the different molecular sizes of the charged particles and the
different charges of the charged particles.
• During the process of electrophoresis, charged particles are placed on an electric field
created on an on absorbent paper or on a gel electrophoretic plate.
• Depending on the PH of the buffer on the electrophoretic plate, the amino acids will be
charged.
• pH greatly influences the total charge of molecules.
• When electricity is applied to the medium containing amino acids, depending on their net
charge and molecular size, they migrate differentially, thus different amino acids can be
separated.
• Positively charged amino acids will be attracted to the cathode and negatively charged
amino acids will be attracted to the anode when the switch is closed
• The speed of the movement of amino acids depend on the molecular size and the charge of
the amino acids as a result separation is achieved.
• A series of lines or bands is observed on the paper or gel once a chemical is applied.
• Sometimes ultraviolet light is used to show the bands up. The series of bands is called an
electropherogram.
17.5.1 Paper Electrophoresis
17.6 Chemical Reactions of Amino Acids

17.6.1 Amino acids are nucleophilic
• The –NH₂ group behaves as a nucleophilic centre, capable of attacking and forming a dative
bond to a relatively positively charged carbon atom.
• Combination of amino acids to form proteins involve nucleophilic substitution, in which the
–NH₂ group on one amino acid attacks the Cδ+ atom of the –COOH group of another amino
acid.
121 | P a g e
17.6.1 Peptide Formation
• Amino acid molecules can also react with each other; the acidic -COOH group in one
molecule reacts with the basic -NH2 group in another molecule.
• When two amino acids react together, the resulting molecule is called a dipeptide.
• Note the amide link between the two amino acids. An amide link between two amino acid
molecules is also called a peptide link.
• The reaction is a condensation reaction as a small molecule, in this case water, is eliminated
when the reactant molecules join together.
• If three amino acids are joined together, tripeptide is formed. If more than three but less
than 20 amino acids are joined together, a polypeptide is formed.
17.7 ASSIGNMENT
1. Choose a tripeptide amino acid of your choice and hydrolyse it with dilute HCl under reflux
condition.
122 | P a g e
CHAPTER 18: Polymerisation
• Polymerization is a chemical reaction in which the product molecules are able to grow
indefinitely in size as long as reactants are supplied. Polymerization can occur if the
monomers involved in the reaction have the proper functionalities.
18.1 Terms used in Polymerisation

18.1.1 Polymer
• Polymer means “many parts” and designates a larger molecule/macromolecule made up of
smaller repeating units. Thus, the structure of polystyrene can be written as
18.1.2 Monomer
• A monomer is a molecule that combines with other molecules of the same or different type
to form a polymer. Acrylonitrile, CH2=CHCN, is the monomer for polyacrylonitrile:
18.1.3 Repeating Unit

• The repeating unit of a linear polymer (which is defined below) is a portion of the
macromolecule such that the complete polymer (except for the ends) might be produced by
linking a sufficiently large number of these units through bonds between specified atoms.
18.1.4 Homopolymer
• A homopolymer is a macromolecule derived from a single monomer.
18.1.5 Copolymer
• Copolymer contains structural units of two or more different precursor/monomers.
18.2 Properties of Polymerisation

• The molecules are saturated, as all of the bonds holding the carbon chain together are
single. This makes them generally unreactive and chemically inert.
• Addition polymers are generally non-polar
123 | P a g e
18.2.1 Advantages of Addition Polymerisation
• They are safe and durable
• They are very strong because they are very long chains because Van Der Waals forces are
relatively strong
18.2.2 Disadvantages of addition polymerisation

• They are non-biodegradable when left in the environment, making them a pollution hazard.
• They are also difficult to dispose of need to be burned under special conditions to avoid the
formation of extremely toxic by-products such as dioxins.
18.3 TYPES OF POLYMERISATION

There are two major types of polymerisation
i. Addition Polymerisation
ii. Condensation Polymerisation
18.3.1 ADDITION POLYMERISATION

• This is the joining together of monomer units with double bonds to form a larger molecule
called a polymer.
18.3.1.1 Polyethene
Examples of Addition Polymerisation
Polymer: Poly(ethene) (polythene or polyethylene)
Monomer: Ethene
The conditions required for this to happen are as follow:
Temperature - about 60°C
Pressure - a few atmospheres
Catalyst - Ziegler-Natta catalysts or other metal compounds
Uses of Polyethene
• Poly(ethene) is commonly used to make carrier bags e.g. plastic bag and plastic bottles.
18.3.1.2 Polyvinylchloride
Polymer: Poly(chloroethene) (polyvinyl chloride or PVC)
Monomer: Chloroethane
124 | P a g e
Uses of Polyvinyl chloride
• Building construction (water pipes) which resist corrosion.
• Used for household goods, gumboots and raincoats which are durable and cheap.
• Used for packaging.
18.3.1.3 Polypropene
Polymer: Poly(propene)
Monomer: Propene
18.4 TACKLING QUESTIONS ON ADDITION POLYMERS

In your exam, you might be asked to:
i. deduce the repeat unit of a polymer obtained from a given unsaturated monomer
ii. identify the monomer(s) present in a given section of a polymer
125 | P a g e
18.5 CONDENSATION POLYMERISATION
• This is the joining of monomer units to large molecules called a polymer in a reaction
caused by the release of a small molecule of either water and acid.
• A large protein molecule, formed by condensation polymerisation, can contain thousands of

amino acid monomers.
• As each amino acid monomer joins the chain a peptide link forms, and an H2O molecule is
also produced.
• Condensation polymerisation is characterised by monomers that contain two different
functional groups capable of reacting with each other.
This occurs in two ways:

i. the two different functional groups are found within the same molecule, as in amino acids;
each amino acid monomer molecule has an NH2 functional group and a COOH functional
group
ii. the two different functional groups are found in two different molecules; for example, nylon
6,6 is made from two different monomers – one monomer has two NH2 functional groups
and the other monomer has two COOH functional groups.
• Condensation polymerisation also leads to the formation of small molecules such as H2O or
HCl.
18.6 Properties of Condensation Polymers

• They contain either amide or ester linkages
• The linkages are reactive towards acids and bases which cause the polymer to break down.
126 | P a g e
18.6.1 Advantages of Condensation Polymerisation
• Condensation polymers are biodegradable and do not pose the same pollution hazard as
addition polymers.
• Condensation polymers are generally strong because intermolecular hydrogen bonds are
formed between different chains.
• In proteins ,intramolecular hydrogen bond is possible and so the molecules forms a helix.
18.6.2 Disadvantages of Condensation Polymers

• The linkages are reactive towards acids and bases which cause the polymer to break down
18.7 EXAMPLES OF POLYAMIDES

18.7.1 Nylon 6
• Nylon 6 is an example of a condensation homopolymer.
• The monomers which link up during the polymerization process are identical.
• The monomer for nylon 6 is 6-aminohexanoic acid, which in turn is obtained by heating
caprolactam, a cyclic amide, in the presence of water. This causes hydrolysis of the amide
bond, so that the chain opens up, as shown below.
• The monomer has an amine group on one end and a carboxyl group on the other.
• The monomers are therefore able to react by linking ‘head to tail’, so that the amino group
on one molecule reacts with the carboxylic acid group on another molecule, as shown
below.
127 | P a g e
18.7.2 Nylon-6,6
• Nylon -6,6 is made from two monomers each of which contain 6 carbon atoms - hence its
name. One of the monomers is a 6-carbon acid with a -COOH group at each end - hexane
dioic acid.
• The other monomer is a 6-carbon chain with an amino group, -NH2, at each end. This is 1,6-
diaminohexane (also known as hexane-1,6-diamine).
• When these two compounds polymerise, the amine and acid groups combine, each time
with the loss of a molecule of water. This is known as condensation polymerisation.
18.7.3 Nylon-6,10
• Nylon -6,10 is made from two monomers each of which contain 6 carbon atoms on diamine
group and 10 carbon atoms on carboxylic group- hence its name.
• One of the monomers is a 10-carbon acid with a -COOH group at each end - decane dioic
acid.
HOOC-(CH2)8-COOH
• The other monomer is a 6-carbon chain with an amino group, -NH2, at each end. This is 1,6-
diaminohexane (also known as hexane-1,6-diamine).
18.6.3.1 Repeating Unit of Nylon 6,10
128 | P a g e
18.7.4 Kevlar
• Kevlar is a polyamide, containing benzene rings. It is very strong, 5 times stronger than steel
but also flexible.
• It is also resistant to fire and abrasion because of its properties and structure.
• It is a long, linear polymer that can line up next to each other in a regular pattern. This
results in extensive hydrogen bonding between the polymer chains of Kevlar.
18.7.4.1 Monomers of Kevlar
18.7.4.2 Repeating unit of Kevlar
129 | P a g e
18.7.5 Uses of Polyamides
• Apart from obvious uses in textiles for clothing and carpets, a lot of nylon is used to make
tyre cords - the inner structure of a vehicle tyre underneath the rubber.
• The exceptional properties of Kevlar have led to its use in making bullet-proof vests, ropes,
fire-protective clothing (as used by Formula 1 racing drivers) and modern ‘leathers’ worn
by motorcycle riders. It is also used to reinforce other materials, such as the rubber in tyres.
18.8 POLYESTER
• A polyester is a chain of repeating units where the individual units are held together by
ester linkages.
• The usual name of this common polyester is polyethylene terephthalate (Terylene)

• A polyester is made by a reaction involving an acid with two -COOH and an alcohol with two
-OH groups.
18.8.1 Monomers of Terylene
• When the two monomers react in a condensation/addition elimination reaction a small

molecule is lost (water).
130 | P a g e
18.7.2 Hydrolysis of Polyester
Reagent: Dilute acid (dilute HCl(aq)) or NaOH(aq), Polyester
• Polyesters are attacked more readily by alkaline but much more slowly by acids.
• During hydrolysis the ester linkage is broken.
18.8.3 Uses of Polyester

• They are used as fibres to make clothes
• They are also used to make bottles e.g. PET
18.9 Disposal of Polymers

• Non-biodegradable polymers are disposed of in three main ways
a) Landfill
b) Incineration
c) Recycling
FOR ONLINE LESSONS CALL/APP SIR LAYAN ON 0774372589
131 | P a g e

Anic Chemistry

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Anic Chemistry

Uploaded by

Copyright:

Available Formats

ADVANCED LEVEL

ORGANIC CHEMISTRY 2020

CHAPTER 2: Alkanes ....................................................................................................... 20

CHAPTER 3: Alkene Chemistry.................................................................................... 29

CHAPTER 4: ARENE CHEMISTRY ................................................................................ 38

Chapter 5: Organohalides ............................................................................................ 50

CHAPTER 6: HALOGENOARENES ................................................................................ 61

CHAPTER 7: Hydroxyl Compounds ............................................................................ 63

CHAPTER 8: Phenol ......................................................................................................... 72

Chapter 9: Carbonyl Chemistry .................................................................................. 77

CHAPTER 10: Carboxylic acids ................................................................................... 86

CHAPTER 11: CHEMISTRY OF ESTER ........................................................................ 93

CHAPTER 12: ACYL HALIDES ....................................................................................... 96

CHAPTER 13: AMINES .................................................................................................. 100

CHAPTER 14: Aromatic Amines................................................................................ 107

Chapter 15: Amides ...................................................................................................... 111

Chapter 16: Azo Compounds ..................................................................................... 115

CHAPTER 17: Amino Acids ......................................................................................... 118

CHAPTER 18: Polymerisation ................................................................................... 123

1.1 HOMOLOGOUS SERIES

1.2 FUNCTIONAL GROUP

1.2.1 Common Functional Groups in Organic Chemistry

1.3.1 Empirical formula

1.3.2 Molecular formula

1.3.3 Structural formula

1.3.4 Displayed formulas

• Remember to show the correct orientation of atoms of benzene and hydroxyl

1.4.1 Difference between Structural and Stereoisomerism

1.4.2.1 Chain Isomerism

1.4.2.2 Positional isomerism

1.4.2.3 Functional Isomerism

• To identify geometrical(cis-trans) isomers, it is essential to draw the groups around the

Draw the isomers of the following compounds

For a compound to be optically active:

Represents a bond sticking out in front of the plane of the paper

Other Compounds which exhibit optical Isomerism

1.5.1 Homolytic and heterolytic bond fission

1.5.3.1 Functional groups with Electron Deficient Carbon

[ Note: A benzene ring is an electron-rich region]

2.2 BRANCHED-CHAIN ALKANES

2. Name the substituent groups – the branches

2 → di ,3 → tri ,4 → tetra ,5 → penta and 6 → hexa

As a result, alkanes a few chemical reactions and these are

2.4.1 Free Radical Substitution

Reagent: Chlorine gas, Cl2 or bromine gas, Br2

Step 2: Propagation step

Step 3: Termination step

• When alkanes react with halides, a mixture of monohalogenoalkanes compounds is formed

2.4.2.1 The Inductive Effect of Alky Groups

The 2-methylprop-2-yl radical:

2.4.3.1 Complete Combustion

2.4.3.1 Incomplete Combustion

• Other hydrocarbons are not good fuels

2.4.4 CATALYTIC CRACKING

3.1 NOMENCLATURE AND ISOMERISM OF ALKENES

Trans Pent-2-ene Cis Pent-2-ene

3.2.1 Reduction of Alkenes

3.2.2.1 Mechanism of The Reaction is as Follow:

3.2.3 Addition of halogen, X2 In Inert Solvent (Halogenation)

3.2.3.1 Reaction Mechanism

3.2.4.1 Reaction Mechanism

3.2.5.1 Reaction Mechanism