CHM 102

General Chemistry II

Dr. Paul Matthew

Osamudiamen 1

Chemical and Food Science

Department
 Course outline
Inorganic Chemistry
• Extraction of metals
• Introduction to transition metal chemistry
• Nuclear chemistry
Organic Chemistry
• Hybridization
• Shapes of simple molecules

2
 Course outline
• Tetravalency of carbon
• Structures of carbon compounds
• Functional groups
• Classes of carbon compounds
• Reaction mechanism and kinetic of organic compounds
• Chemistry of alkanes, alkenes, alkynes, ozonolysis, benzenes,
alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids and
derivatives, amines

3
 Course outline
• Structures of simple sugars, starch and cellulose
• Peptide and proteins
• Synthetic polymers from various classes of
compounds

4
 Overview of Topics for Consideration
• Hybridization and shapes of molecules
• Tetravalency of carbon
• Structures, Molecular composition and variety of
carbon compounds
• Functional groups and Classes of carbon compounds
• Reaction mechanism and kinetics of organic compounds

5
 Introduction
What is Organic Chemistry?
Organic chemistry is the study of the
structure, properties, composition,
reactions, and preparation of carbon-
containing compounds
These compounds include hydrocarbons
And other compounds with other
elements, including hydrogen, nitrogen,
oxygen, halogens, phosphorus, silicon, and
sulfur. 6
 Tetravalency of carbon
• A carbon atom has four electrons in its
outermost valence shell.
• It needs four more electrons to complete
its octet.
• A carbon atom completes its octet only by
sharing its valence electrons with other
atoms. .
7
 Tetravalency of carbon
• As a result, carbon atom forms four covalent
bonds by sharing valence electrons with other
atoms.
• This is known as tetravalency of carbon (tetra
means four).

8
 Organic Formula
A chemical formula is a format used to
express the structure of compounds.
The formula tells which elements and how
many of each element are present in a
compound.
Formulas are written using the elemental
symbol of each atom and a subscript to denote
the number of elements. 9
 Types of organic formula
General formula
Empirical formula
Molecular formula
Structural formula
a. Displayed structural formula
b. Condensed structural formula
c. Skeletal formula 10
 General formula

A general formula is a type of

empirical formula that represents the
composition of any member of an entire
class of compounds.
It is applicable to a series of compounds
E.g. alkanes are represented by CnH2n+2,
alkenes CnH2n and alkynes CnH2n-2 11
 Assignment
• Write the general formula for the following classes of compounds
1. Cycloalkanes
2. Cycloalkenes
3. Aromatic compounds or arenes
4. Alcohols
5. Aldehydes
6. Ketones
7. Carboxylic acids
8. Esters
9. Acid chlorides
10. Haloalkanes 11. Ethers 12. Amines 12
 Empirical and Molecular formula
The empirical formula represents the
simplest whole-integer ratio of the different
types of atoms in a compound. The
empirical formula for butanoic acid is
represented below

13
 Assignment
1. The elemental composition of a compound was found to
contain 62.07% carbon and 10.34% hydrogen. What is the
empirical formula of the compound?

14
 Empirical and Molecular formula
 The molecular formula shows the exact number of each type
of the different types of atoms present in a compound.
 The molecular formula for a compound can be the same as or
a multiple of the compound’s empirical formula.

Butanoic acid

15
 Assignment
1. The elemental composition of a compound was found to
contain 62.07% carbon and 10.34% hydrogen. What is the
empirical formula of the compound?
2. If the molar mass of the compound above is 58 g/mol,
what is the molecular formula of the compound.

16
 Structural Formula
 A structural formula is used not only to indicate the number of
atoms in a compound, but also their arrangement in space.
A structural formula provides information about the relative
positioning of atoms and the bonding between atoms.
Compounds that have the same molecular formula but have
different structural formula are known as isomers, and they can
have quite different physical properties.

17
 Condensed Structural Formula
Condensed Structural formula: The formula are displayed
without showing the bonds. Except in cyclic compounds where
the carbon-carbon bonds are shown. E.g. Butanoic acid

18
 Displayed Structural Formula
This shows all the atoms and all the bonds
present in an organic compound.
The bonds are represented as lines. Eg.
Butanoic acid

19
 Skeletal Formula
In this structure, most hydrogens are omitted.
The line ends or vertices represents carbons
Functional groups other than carbon and
hydrogen are still shown. E.g butanoic acid

20
 Assignement 4
• Draw the displayed structural formula of the following
compounds
1. 2-methylpropane
2. 1,2,3-trichlorobutan-2-ol
3. Cyclohexanol
4. 2,2-dimethyl hex-3-enoic acid
5. Aniline
6. 4-hydroxy benzoic acid
7. N-methylpropylamine 21
 Isomerism
• Constitutional or structural isomerism
• Chain isomers
• Position isomers
• Functional isomers
• Stereoisomerism
• Geometrical or Cis/Trans isomers
• Optical isomers 22
 Structural or Constitutional Isomers
• Structural isomers are isomers that have the same molecular
formula but different structures
• Chain isomers are compounds that have the same molecular formula
but differ in the branching of carbon atoms. E.g. C5H12

H3C CH2 CH2 CH2 CH3 CH3

pentane
H3C C CH3
H CH3

CH3
H3C C C CH3
2,2-dimethyl
H H propane
2-methyl butane

23
 Positional isomers
• Position isomers are compounds that differ in the position of the
functional group or substituent atoms.

24
 Functional isomers
• Functional isomers are compounds that have the same molecular
formula but differ in the functional groups. E.g

C3H6O
O O

H3C C CH3 H3C CH2 C H

Propanone Propanal
25
 Stereoisomers

• Stereoisomers are compounds that have the same molecular

formula but differ in the their relative positioning or orientation of
atoms in space.

26
 Optical isomers
• Optical isomers are also called enantiomers
• They exist as a pair of non-superimposable
mirror images of each other
• They don’t have a plane of symmetry
• They have at a chiral carbon – a carbon that
has four different substituents

27
Optical isomers

28
Optical isomers

29
 Geometric isomers (Cis/Trans Isomers)
• They occur when there is a restriction of rotation about a
double bond (e.g. a carbon-carbon double bond) or
• A restricted carbon due to a rigid ring structure.
• There are two different substituent groups attached to each
carbon in a carbon-carbon double bond

30
Geometric isomers

31
 Addition reaction
• This is a reaction that involves the combination of two
molecules to form a single product without the elimination of
any molecule.
• The reaction usually involves the formation of a saturated or a
more saturated compound from an unsaturated compound.
• The reagents involved in organic reactions usually determine
the type of reaction e.g. Electrophilic addition reaction,
Nucleophilic addition reaction or free radical addition
reaction.

48
Addition reaction

49
Electrophilic addition reaction

50
 Nucleophilic addition reaction
• Nucleophiles attack the electron deficient carbon, which
leads to the formation of an alkoxide, that is protonated to
give the final product.

51
 Free-radical addition reaction
• This take place in the presence of free radicals. The reaction
gives products that don’t obey the Markovnikov rule

52
 Substitution reaction
• Substitution reaction is a reaction involving the
replacement of an atom or group of atom with
another atom or group of atom.
• There are three types of substitution reaction
Electrophilic substitution reaction
Nucleophilic substitution reaction
Free radical substitution reaction

53
 Electrophilic substitution reaction
• This takes in benzene compounds. Although unsaturated
compounds usually undergo addition reactions, benzene
undergo substitution reaction so as to retain its resonance
stabilized aromatic ring.

54
 Nucleophilic substitution reactions
• Nucleophilic substitution is a type of reaction in which a
nucleophile selectively bond with or attacks the positive or
partially positive atom (or electrophile) to replace a leaving
group.

55
Free-radical Substitution reaction

This usually takes place in alkanes.

56
 Elimination reactions
• A reaction in which atoms or group of atoms are removed
from adjacent carbon atoms of a molecule to form an
unsaturated compound.
• NOTE: The product of a elimination reaction always yield an
unsaturated compound
• This is the opposite of addition reaction
• This is a typical reaction of alcohols and haloalkanes

57
 Elimination reaction
• These are examples of elimination reactions

58
 Oxidation reaction
• Oxidation is a process by which a carbon atoms gains bonds to
more electronegative elements, most commonly oxygen
• Reduction is a process a carbon atom gains bonds to less
electronegative elements, most commonly hydrogen

59
 Condensation reaction
• This is a reaction is which two molecules combine, usually in
the presence of a catalyst, with the elimination of small
molecules such as H2O, HCl etc to form a single compound.

60
 Rearrangement reaction
• A reaction in which atoms or groups of atoms in a molecule
change position or migrates from one carbon to another.
• It involves the reorganisation of bonds in a atom
• It leads to the formation of carbocation intermediates

61
Assignments

62
 Functional groups and
Classes of carbon compounds
A functional group is an atom or group of atoms that
determines the chemical properties of an organic compound.
Examples are given below.

63
Functional Groups and classes of organic compounds

64
Functional Groups and classes of organic
compounds

65
Functional Groups and classes of organic
compounds

66
Functional Groups and classes of Organic
compounds

CH3

Arenes - Methylbenzene

R-SH Thiols -thiols CH3CH2 SH Ethanethiol

R-C N Nitriles -nitriles CH3CH2C N Propanenitrile

O O
Acid chlorides
R C Cl or Acyl chlorides -oyl chloride CH3 C Cl Ethanoyl chloride
67
 Alkyl groups
If a hydrogen atom is removed from an alkane, the partial structure
that remains is called an alkyl group.
Alkyl groups are named by replacing the -ane ending of the parent alkane
with an -yl ending.

69
Naming Organic Compounds - Alkanes
• A chemical name has four parts
1. Prefix: This describes the type and position of the
substituents
2. Parent: This defines the number of carbon atoms
3. Locant: This defines the position of the primary functional
group
4. Suffix: this describes the primary functional group

70
71
72
73
74
Assignments- Name these compounds
Cl
O

1
4

Br
O

2 O

5 OH

Cl
Br
3
75
Alkanes
Module two

76
Preparation of
Alkanes
Module two

77
 Method of preparing alkanes
Methods for
preparation of
alkanes

From From
From alkyl
Unsaturated carboxylic
hydrocarbon halides
acids

78
 Preparation of alkanes –
From unsaturation alkanes
1. From unsaturated hydrocarbons-
Unsaturated hydrocarbons such as Alkenes and alkynes
undergo catalytic hydrogeneration in the presence of
catalyst (e.g. Raney Ni, Pt or Pd) to produce all alkanes
except methane)

79
 Preparation of alkanes –
From alkyl halide
2. i. From Alkyl halide:
Alkyl halide (except flourides) on reduction with zinc and
dilute hydrochloric acid gives alkanes

80
 Reactions of alkanes - From alkyl halide
ii. Wurtz reaction: Alkyl halides on treatment with sodium
metal in dry ether (solution free from water) gives higher
alkanes containing an even number of carbon atoms

81
 Preparation of alkanes -
From Carboxylic acid
3. Decarboxylation reaction – Sodium salts of carboxylic
acids on heating with soda lime ( a mixture of sodium
hydroxide and calcium oxide) gives alkanes containing
one carbon atom less than the carboxylic acids. (The
process of eliminating carbon dioxide from carboxylic
acid is known as decarboxylation)

82
Properties of Alkanes

83
 Properties of alkanes
Properties of
Alkanes

Physical Chemical
properties properties

84
 Properties of alkanes – Physical Properties
Alkanes are non-polar molecules which are
held by weak van der waal forces
The weak intermolecular forces depend only
upon the size and the structure of the
molecules
Due to the weak van der waal forces, C1 - C4
are gases, C5 – C17 are liquid and C18 and
above are solid at room temperature (298 K)
85
Properties of alkanes – Physical Properties
With increase in number of carbon atoms, the
molecular size increases and the magnitude of Van der
waal forces also increases
The boiling point increases with the number of
carbon atoms
They are insoluble in water, because they are non
polar, but they dissolve in non-polar solvents such as
ether, benzene, chloroform etc.
Alkanes are lighter than water, but their density
increase with the number of the carbon atoms
86
 Properties – Chemical properties
Chemical
properties

Substitution
Aromatisation Pyrolysis
reaction

Combustion Isomerisation
Controlled oxidation 87
 Substitution reaction
Substitution reaction: This is the reaction
whereby an atom or group of atoms in a
molecule is replaced by some other atom
or group of atoms.
Alkanes undergo substitution reaction
whereby hydrogen atoms are replaced by
different atoms or groups of atom such as
halogens (Cl, Br or I) Nitro group (-NO2)
or sulphonic acid group (-SO3H)
88
 Substitution reaction: Halogenation
• This involves the replacement of one or more atoms of
hydrogen in alkanes by halogen atoms
• The rate of reaction of alkanes with halogen is F2>Cl2>Br2>I2
• The rate of replacement of hydrogen of alkanes is 3o>2o>1o

89
 Mechanism of reaction:
Free radical substitution
• i. Initiation: The reaction is initiated by the homolysis of chlorine
molecule in the presence of light or heat.

• Propagation: Chlorine free radicals attacks the methane molecule

and takes the reaction forward by breaking the C-H bond to
generate methyl free radical with the formaton of H-Cl

90
 Mechanism of reaction:
Free radical substitution
• Termination: The reaction stops after some time due to
consumption of reactants and/or due to following side
reaction. The following chain terminating steps are possible

91
 Combustion
• Alkanes are oxidized to carbon dioxide and water on heating in the
presence of air with the evolution of large amount of heat.

• The general equation for combustion of any alkane is

Due to the large amount of heat during combustion, alkanes are used as
fuels.
92
 Controlled Oxidation
i. Alkanes on heating with a regulated supply of oxygen or air
at high pressure and in the presence of suitable catalyst give
a variety of oxidation products.

ii. When methane is mixed with oxygen and passed through

heated molybdenum oxide (Mo2O3), under pressure it is
oxidized to methanal.

93
 Isomerisation
• Straight chain alkanes isomerise to branched chain alkanes
when heated with anhydrous aluminium chloride (AlCl3) and
hydrogen chloride at 575 K under a pressure of about 30 – 35
atm

94
 Aromatisation
• The alkanes containing six or more carbon atoms when
heated at about 773 K under high pressure of 10 – 20 atm in
the presence of catalyst on alumina gel get converted to
aromatic compounds. This process is called aromatization.

95
 Pyrolysis
• When higher alkanes are heated to high temperature in the
presence of alumina or silica catalysts, the alkanes break down
to lower alkanes and alkenes.

• This reaction is called fragmentation or cracking or pyrolysis.

Pyrolysis of hexane gives the following products
C 6H12 + H
2
773 K
C6 H 14 C4H 8 + C
H
2
6

C
H
3
6+C
H
3
8 96
 Assignment
1 B a la n c e th e fo llo w in g re a c tio n

C 18H 38 + ___O 2 ----C O 2 + _ _ H 2O

2 W hat alkane on conbustion w ill give the follow ing products

____________ C 10 H 2 0 + C 4 H 1 0

3. Why does alkane not undergo addition reaction

4. Why does alkane undergo substitution reaction
5. Why does alkane under free radical substitution reaction 97
 Alkenes
Module Four

98
 Alkenes
• They are also called olefines
• They contain at least one carbon-carbon double bond (C=C)
• They have the general formula CnH2n (n=2,3…)
• They are classified as unsaturated hydrocarbons
• They are sp2 hydridized
• Examples include

99
Naming Alkenes

100
Naming Alkenes

101
 Naming Alkenes
Rule 3: Number the carbon chain of the
parent compound starting with the end
nearer to the double bond. Use the smaller
of the two numbers on the double-bonded
carbon to indicate the position of the
double bond. Place this number in front of
the alkene name
102
Naming Alkenes

103
Naming Alkenes

104
 Naming Alkenes
• Rule 4: Branched chains and other groups are treated as in
naming alkanes. Name the substituent group, and designate its
position on the parent chain with a number.

105
Naming Alkenes

106
 Physical properties of Alkenes
• Boiling points and densities: Most physical
properties of alkenes are similar to those of alkanes
e.g: boiling points of 1-butene, cis-2-butene, trans-2-
butene and n-butane are close to 0oC
• Boiling points of alkenes increase smoothly with
molecular weight
• Increased branching leads to greater volatility and
lower boiling points
107
• Polarity: Alkenes are relatively non-polar
• They are insoluble in water but soluble in non-polar solvents
such as hexane, gasoline, halogenated solvents and ethers
• They are slightly more polar than alkanes because electrons in
the pi bonds is more polarizable than sigma bonds

108
 Preparation of alkenes
• Alkenes can be prepared in the following ways:
1. Dehydration of alcohols

2. Dehydrohalogenation of haloalkanes (KOH can also be used)

109
 Reactions of Alkenes
• Alkenes are more reactive than alkanes because
• The carbon-carbon double bond consist of a σ bond and a π
bond. Its is easy to break the π bond while the σ bond
remains intact
• The π electrons in the double bond act as a source of
electrons. Therefore, alkenes are reactive towards eletrophiles
which are attracted to the negative charge of the π electrons
• Π bond will be broken, each carbon atom becomes an active
site which can form a new covalent bond with another atom.
• One π bond is converted to 2 σ bonds 110
 Reactions of alkenes
A. Addition reactions
1. Catalytic hydrogenation ( Addition of H2)
2. Addition of halogens (X2)
3. Addition of Halohydrins (HOX)
4. Addition of hydrogen halides
5. Free Radical addition of Hydrogen bromide
6. Addition with conc. H2SO4
7. Hydration (addition of water)
8. Combustion of alkenes
111
B. Oxidation reactions
1. Epoxidation
2. Hydroxylation
3. Ozonolysis
4. Reaction with Hot, Acidified KMnO4
C. Polymerization reaction
D. Test for alkenes
E. Determination of the position of the double bond in
alkenes
F. Uses of alkenes
112
 Addition reactions
1. Catalytic hydrogenation ( Addition of H2)
Hydrogenation of hydrogen to a double bond and a triple bond to
yield a saturated product.
Alkenes will combine with hydrogen in the present to catalyst to
form alkanes

113
Give the products of the following
reactions

114
 2a. Addition reactions
(Inert solvent)
2. Addition of halogens (Halogenation)
• In inert solvent: alkenes react with halogens at room
temperature and in the dark in inert solvent such as CH2Cl2 or
CCl4 to produce dihaloalkanes
• The reaction occurs with bromine and chlorine. Iodine will
not react because it is less reactive than chlorine and bromine.
• Flourine is very reactive, the reaction will produce an
explosion.

115
2. Addition of halogens

116
 2b. Addition of halogens
(aqueous medium)
• Addition of halogens (In water/aqueous medium)
• Chlorine dissolves in water to form HCl and chloric I acid (HOCl)
(aq)
• Bromine also dissolves in water to form HBr (aq)and bromo(I) acid
(HOBr) aq
• Reactions with alkenes and halogens in water (eg. Chlorine water and
bromine water) produce halohydrins (an alcohol with a halogen on the
adjacent carbon atom)

117
2b. Addition of halogens

118
119
3a. Addition of Hydrogen halides
• Alkenes react with hydrogen halides (in gaseous or in aqueous
solutions) to form addition products.
• The hydrogen and halogen atoms add across the double bond
to form haloalkanes (alkyl halides)

120
3a. Addition of Hydrogen halides

121
 Markonikov’s rule
• The addition of HX to an unsymmetrical alkene, the
hydrogen atom (or the positive atom) attaches itself
to the carbon atom (of the double bond) with the
larger number of hydrogen atoms

122
Application of Markonikov’s rule

123
 3b. Free radical addition of HBr
• Alkene reacts with HBr (not HCl or HI or HF) in the
presence of peroxides (H2O2)
• This reaction does not obeys Markovnikov’s rule
• The reaction occurs through a free radical adddition rather
than a polar electrophilic addition.

124
 5a. Hydration (Addition of water)
• Alkene undergoes hydration reaction in the presence
of Conc. sulfuric acid (0-15oC) or H3PO4 (300oC, 60
atm)
• It involves the addition of H and OH atoms from
the water molecules to the C=C atoms
• It obeys markonikov’s rule

125
5a. Hydration - Acid catalysed reaction

126
5a. Hydration – Acid catalysed reaction

127
 5b: Hydration:
Oxymercuration/Demecuration
• This lead to a Markonikov addition of H2O across the
double bond, with the OH adds to the carbon of the
double bond that has the lesser no of hydrogen

128
Practice questions

129
Practice questions

130
 5c: Hydration:
Hydroboration-Oxidation
• This lead to an anti-markonikov addition of
H2O across a double bond of an alkene.

131
Practice questions

132
 6. Oxidation of Alkenes
• There are three reactions involved in oxidation of
alkenes
1. Epoxidation: This is the reaction leading to the
formation of epoxides
2. Hydroxylation or Dihydroxylation: This is the reaction
leading to the addition of two hydroxyl groups to the
two carbon-carbon double bonds
3. Ozonolysis: This involves the use of ozone (O3) to
break the carbon-carbon double bond in such a way
that the double bonds leads to the formation of
carbonyl compounds. 133
 6.1 Epoxidation
• Epoxides also called oxiranes are three-membered cyclic ether

134
Epoxidation

135
 6.2: Hydroxlation of alkenes
• Hydroxylation is the addition of OH group to each carbon of
the carbon-carbon double bonds leading to the formation of
glycol or diols.
• Reagents used in hydroxylation of alkenes are:
• Osmium tetroxide (OsO4)
• Potassium permanganate (KMnO4)

136
6.2: Hydroxlation of alkenes

137
 6.3. Ozonolysis of Alkenes
• Alkkene react with ozone to form form ozonide, followed by
hydrolysis of ozonide to produce aldehyde and /or ketone
• This reaction is used to determine the position of the carbon-
carbon double bond.

138
6.3: Ozonolysis of alkenes

139
6.4: Oxidation by KMnO4/H+ under heat
• Acidified KMnO4 is a strong oxidizing agent, in the presence
of heat, alkenes undergoes bond cleavage just like ozonolysis
to form a ketone and a carboxylic acid.

140
 7. Combustion of alkenes
• Alkene undergo combustion reaction in the presence of
oxygen.

141
 8. Polymerization
• Polymer is a large molecule composed of many smaller
repeating units (the monomers) bonded together.
• Alkenes serve as monomers for some of the most common
polymers such as polyethylene (polyethene, polypropylene,
polystyrene, poly(vinyl chloride) etc

142
Uses of Alkenes

143
 Test for Alkenes
• KMnO4 is a strong oxidizing agent. Alkenes undergo oxidations
reactions with KMnO4 and it is used to test for unsaturation
1. Mild oxidations using cold, dilute, alkaline KMnO4 (Baeyer’s
test)
• The purple colour of alkaline KMnO4 solution disappears and
• a cloudy brown colour appears caused by precipitation of MnO2
• This is used to test for carbon-carbon double or triple bond
• A diol is formed containing two hydroxyl grorups on adjacent
carbon atoms.
144
Test for alkenes

145
 Test for alkenes
2. Use of Bromine solution
A solution of bromine in inert solvent (CH2Cl2 or CCl4) and
dilute bromine water are yellow in colour
The solution is decolorised when alkenes are added

146
Test for alkenes(Unsaturation)

147
 Determination of the position of the
double bond
• 1. Ozonolysis of alkenes
Ozonolysis is used to identify the position of alkenes.
For example, ozonolysis of an alkene produces methanal and
propanone, identify the alkene

148
Reaction with hot, acidified KMnO4

149
 Example
• An alkene with the molecular formaula C6H12 is oxidised with
hot KMnO4 solution. The carboxylic acids, butanoic acid and
ethanoic acid are produced. Identify the structural formula of
the alkene

150
Assignment

151
Practice questions

152
Assignments

153
Alkynes
Module Five

154
 Alkynes- Introduction
• Alkynes are hydrocarbons that contain Carbon-carbon triple
bonds
• They have the general formula of CnH2n-2
• The simplest member is C2H2 also known as acetylene

155
 Alkynes -Introduction
• Electronic Structure of alkynes
• In Alkynes, the carbon-carbon triple bond result
from the formation of sigma bond from the
nuclear overlap of the carbon-carbon hybridised sp
orbitals and two pi bonds from lateral overlap of
the unhybridised p orbitals
• The triple bond is shorted and stronger than single
bond and double bond
• Breaking a pi bond in alkyne requires more energy
(318 KJ) than in alkene (268 KJ)
156
 Nomenclature of alkynes
1. When naming alkynes, the suffix “–yne” is used indicating
an alkyne
2. The longest continuous carbon chain –including the triple
bond- is named in such a way so that the smallest number
possible include the triple bond.

Begin numbering from the carbon

nearer to the triple bond 157
Preparation of Alkynes

158
 Reactions of Alkynes
1. Addition reactions: Addition of HX and X2
• Addition reactions of alkynes are similar to those of alkenes
• Intermediate alkene reacts further with excess reagent
• The reaction is regiospecific according to Markovnikov rule

159
 Reactions of Alkynes
2. Addition reactions: Addition of H2
Addition of H2 over a metal catalyst such as palladium on
carbon, Pd/C converts alkynes to alkanes (complete reduction
reaction)
The addition first converts the alkynes to alkenes and further
addition gives alkanes
C
H H
CH H
CH
3
3 3
H
2 H
1234567 2
C
H
CCH
C
HCHC
HC
H H
C
2CC
H
CH
CHC
HC
H H
C
3CC
H
CH
C
2H
2C
H
2C
H
3
2223 2223

3
-met
hyl-
hept
-1-
yne
3-methylhept-1-yne 3-
m e
thyl
-he
pt-
1-ene
3-methylhept-1-ene 3
H-
m
et
h
yl
-
he
p
t
an
e
3-methylheptane
160
 Haloalkanes
(Alkyl halide)
Module six

161
 Definition
• Alkyl halides are the derivatives of alkanes in which hydrogen
atom is replaced by an halogen atom such as F, Cl, Br or I
• Alkyl halides are represented by the formula R-X, Where R
denotes an alkyl group and X denotes an halogen like Chloro,
Bromo, Fluro or Iodo group.
• They have the general formula CnH2n+1X.
• They are named as derivates or alkanes such as haloalkanes, eg.
chloromethane, chloroethane, chloro propane

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 Nomenclature of Haloalkanes
• Haloalkanes are named in similar ways to alkanes
1. Find the longest possible carbon chain that contain halogen
in the chain
2. Find the branched alkyl groups, and attached halogens
3. If there are more than 1 branched substance, arrange them
according to alphabetical order
4. Give the numbering of branched alkyl or halogen
accordingly

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Nomenclature of haloalkanes

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 Classification of Haloalkanes
• Haloalkanes are divided into Primary, Secondary and Tertiary
depending on the number of alkyl group attached to the
carbon bearing the halogen atom.

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 Preparation of Haloalkanes
• From alcohols
• From alkanes
• From alkenes

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 Haloalkanes from alcohols
• Haloalkanes can be prepared from alcohols using
several reagents as shown below:

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 Preparing Haloalkanes from alkanes
• They can be prepared from alkanes as follows

The reaction follows free radical substitution reaction

mechanism
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 Substitution reaction: Halogenation
• This involves the replacement of one or more atoms of
hydrogen in alkanes by halogen atoms
• The rate of reaction of alkanes with halogen is F2>Cl2>Br2>I2
• The rate of replacement of hydrogen of alkanes is 3o>2o>1o

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 Preparing Haloalkanes from alkenes
• Addition of hydrogen halides to an alkene gives the
corresponding haloalkane. This reaction takes place with
hydrogen chloride, hydrogen bromide or hydrogen iodide.

• Propene reacts with hydrogen iodide according to

markovnikovs rule to give 2-iodo propane as shown below

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 Physical properties of haloalkanes
• They are colourless in pure state but develop colour when
exposed in air
• The lower members are gases but higher members are liquid
and solids
• Most have pleasant smell
• The boiling points of derivatives of chlorides, bromides and
iodides are comparatively higher than the hydrocarbons of the
similar molecular mass
• Bromo, iodo and polychloro derivates of hydrocarbons are
heavier than water
• The haloalkanes are only very slightly solube in water. But they
tend to dissolve in organic solvents.
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 Reactions of haloalkanes
1. Hydrolysis of haloalkane
2. Formation of nitrile
3. Formation of amine
4. Formation of alkene
5. Formation of organometallic compound
(Grignard reagent)
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173
Reaction Mechanism: SN1

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Reaction mechanism : SN2

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Test for haloalkanes

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Macromolecules or
Polymers
Module ten

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 Macromolecules or Polymers
• Macromolecules simply means large molecules.
• There are two classes of macromolecules we will be
considering
1. Biomolecules or Biopolymers: These are molecules that are
synthesized by nature. Examples include Carbohydrates,
proteins, nucleic acids etc
2. Synthetic polymers: These are macromolecules that are
synthesized by scientist in the laboratories

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 Synthetic polymers
• A polymer is a large molecule made by linking together repeating
units of small molecules called monomers.
• The process of linking them together is called polymerization.

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 Types of Synthetic Polymers
• Synthetic Polymers can be further divided into TWO
1. Chain growth Polymers or Addition Polymers made by chain
reactions – the addition of monomers to the end of a growing
chain.

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 Types of Synthetic Polymers
• Step-growth polymers or Condensation polymers made by
linking monomers as a result of losing small molecules like
water, HCl etc

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 Chain Growth Polymers
– Addition Polymers
• The monomers used most commonly in
chain-growth polymerization are ethylene
(ethene) and substituted ethylenes
• Polymers formed from ethylene or
substituted ethylenes are called vinyl
polymers .
• Some of the many vinyl polymers
synthesized by chain-growth
polymerization are shown below 185
186
Assignment

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 Types of Addition polymers
• There are two types of addition polymers
1. Homopolymers: These are addition polymers that are
made from only one type of monomers sub-units e.g
Polyethylene
2. Copolymers: These are addition polymers that are made
from two or more monomers subunits.

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Copolymers

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 Assignment
• Draw the structure of the monomers used to synthesize the following
polymers

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 Step-growth Polymers

Step-growth polymers are formed by the inter-

molecular reaction of bifunctional molecules with
a functional group at each end.
When the functional groups react, in most cases a
small molecule such as H2O, alcohol or HCl is lost.
A step-growth polymer can be formed by the reaction of a
single bifunctional compound with two different functional
groups, A and B. Functional group A of one molecule reacts
with functional group B of another molecule to form the
monomer (A—X—B that undergoes polymerization.

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 Step-growth Polymers
 A step-growth polymer can also be formed by the reaction of
two different bifunctional compounds.
One contains two A functional groups and the other contains
two B functional groups.
Functional group A reacts with functional group B to form the
monomer (A—X—B) that undergoes polymerization.

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 Classes of Step-growth polymers
Polyamides= These are polymers that have amide linkages
O H

C N
Amide linkage

Polyesters = These are polymers that have the esters linkages

O

C O
E ster lin k ag e
Polyurethanes =these are polymers
O
with the urethane linkages.
H

O C N
U re th a n e lin k a g e 193
 Polyamides
Nylon 6 – a polymer of 6-aminohexanoic acid

Nylon 6,6 – a polymer of 1,6-haxanediamine and adipoyl

chloride. They are called nylon 6,6 because each of the starting
material has 6 carbon atoms

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 Polyamides
Kelvar – An aromatic polyamide made of 1,4-benzene
dicarboxylic acid and 1,4 diaminobenzene. It is a super fibre. It is
used for light weight bullet resistant vest and automobile parts. It
is five times stronger than steel.

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 Polyesters
Dacron- A polyester made from dimethyl terepthalate and 1,2-
ethanediol. The product is polyethylene terepthalate or PET. It is
used for making transparent soft drink bottles

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 Polyesters

• Kodel – a polyester made from dimethyl terepthalate and 1,4-

di(hydroxymethyl)cyclohexane it is used for making fibres.

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 Polyurethane
• A urethane —also called a carbamate—is a compound that
has an OR group and an NHR group bonded to the same
carbonyl carbon. Urethanes can be prepared by treating an
isocyanate with an alcohol, in the presence of a catalyst such
as a tertiary amine.

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 Polyurethane
Polyurethanes —polymers that contain urethane groups—
are prepared by the polymerization of toluene-2,6-
diisocyanate and ethylene glycol. If the reaction is carried out
in the presence of a blowing agent, the product is a
polyurethane foam. Blowing agents are gases such as nitrogen
or carbon dioxide.
Polyurethane foams are used for furniture stuffing, bedding,
carpet backings, and insulation.
Notice that polyurethanes prepared from diisocyanates and
diols are the only step-growth polymers in which a small
molecule is not lost during polymerization. 199
 Polyurethane
• Preparation of Polyurethane

200
 Recycling polymers
• Plastics can be recycled. When plastics are recycled, the various types
must be separated from one another.
• To aid in the separation, the manufacturers place a recycling symbol
on their products to indicate the type of plastic it is.
• The symbols consist of three arrows around on of seven numbers: an
abbreviation below the symbol indicated the type of polymers
• Polymers are assigned a number from 1– 6 that indicates the ease with
which that kind of polymer can be recycled—the lower the number,
the easier it can be recycled.
• Unfortunately, only polymers with the two lowest numbers PET (1)—
the polymer used to make soft drink bottles—and HDPE (2) — the
denser polymer used for juice and milk bottles — are recycled to any
significant extent. 201
Recycling polymers

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 Biodegradable polymers
• Biodegradable polymers are polymers that can be degraded
by microorganisms such as bacteria, fungi, or algae.
• Polylactide (PLA), a biodegradable polymer of lactic acid (2-
hydroxy propanoic acid), has found wide use.
• When lactic acid is polymerized, a molecule of water is lost
that can hydrolyze the new ester bond

203
 Biodegradable polymers
• Polyhydroxyalkanoates (PHAs) are also biodegradable
polymers. Just like Polylactides (PLAs)
• These are condensation polymers of 3-hydroxycarboxylic
acids. Thus, like PLA, they are polyesters.
• The most common PHA is PHB, a polymer of 3-
hydroxybutyric acid; it can be used for many of the things
that polypropylene is now used for. Unlike polypropylene that
floats, PHB sinks.
• PHBV is another PHA that is a copolymer of 3-
hydroxybutyric acid and 3-hydroxyvaleric acid.
• PHAs are degraded by bacteria to CO2 and H2O
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Biodegradable polymers

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Assignment

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Assignment

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