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FACULTY OF SCIENCE, ENGINEERING AND TECHNOLOGY

DEPARTMENT OF BASIC SCIENCES

CHEM 130: ORGANIC CHEMISTRY I

STREAMS: BACHELOR OF EDUCATION (SCIENCE)

LECTURER: SILAS NJIRU MWIRA

Silas.njiru@tharaka.ac.ke

0723 081 306

COPYRIGHT © THARAKA UNIVERSITY

2025

ALL RIGHTS RESERVED

i
 Course outline

1.0 Introduction to organic chemistry:

1.1 Electronic configuration of carbon;

1.2 Hybridization, sp3, sp2 and sp.
1.3 Elemental analysis (qualitative).
1.4 Hydrocarbons

2.0 Alkanes:

2.1. Sources
2.2 Nomenclature
2.3 Structural isomerism
2.4 Physical properties
2.5 Chemical reactions
2.6 Mechanism for free radical substitution
2.7 Cycloalkanes: nomenclature, geometric isomerism
2.8 Preparation of alkanes

3.0 Alkenes

3.1 Sources
3.2 Nomenclature
3.3 Structural isomers, geometric isomerism (Cis – Trans, E-Z,)
3.4 Physical properties
3.5 Chemical reactions
3.6 Preparation of alkenes
3.7 Qualitative analysis of alkenes

4.0 Alkynes

4.1 Sources
4.2 Nomenclature
4.3 Physical properties
4.4 Chemical reactions
4.5 Preparation of alkynes
4.6 Qualitative analysis of alkynes

5.0 Functional groups

5.1 Alcohols, carboxylic acids, ketones,aldehydes,alkylhalides, and aliphatic amines,

phenols, ethers.
5.2 Their nomenclature and qualitative analysis).

ii
References books:

Organic Chemistry by Wade L. G.

Organic Chemistry by Wellinger and Stermitz
Organic Chemistry by Morrison and Boyd
Fundamentals of Organic Chemistry by John Mc Murry
Organic Chemistry by Solomon.
Organic Chemistry by F. Carey.

iii
 TABLE OF CONTENTS

1.0 INTRODUCTION TO ORGANIC CHEMISTRY .................................................................................... 1

1.1 Electronic configuration of carbon ........................................................................................................ 1

1.2 Hybridization, sp3, sp2 and sp .............................................................................................................. 2

1.3 Elemental analysis (qualitative) .......................................................................................................... 14

1.4 Hydrocarbons ..................................................................................................................................... 15

2.0 ALKANES ............................................................................................................................................ 16

2.1 Sources of alkanes .............................................................................................................................. 18

2.2 Nomenclature of alkanes .................................................................................................................... 18

2.3 Structural isomerism in alkanes .......................................................................................................... 24

2.4 Physical properties ............................................................................................................................. 24

2.5 Preparation of alkanes ........................................................................................................................ 34

2.6 Mechanism for free radical substitution .............................................................................................. 29

2.7 Cycloalkanes ...................................................................................................................................... 31

2.8 Chemical reactions of alkanes ............................................................................................................ 27

3.0 ALKENES ............................................................................................................................................. 39

3.1 Sources of alkenes .............................................................................................................................. 39

3.2 Nomenclature of alkenes .................................................................................................................... 39

3.3 Structural isomerism in alkenes (Cis ,Trans, E, Z) .............................................................................. 41

3.4 Physical properties of alkenes ............................................................................................................. 44

3.5 Preparation of alkenes ........................................................................................................................ 44

3.6 Chemical reactions of alkenes ............................................................................................................ 46

3.7 Qualitative test for alkenes ................................................................................................................. 53

4.0 ALKYNES ............................................................................................................................................ 55

4.1 Sources of alkynes.............................................................................................................................. 55

4.2 Nomenclature of alkynes .................................................................................................................... 55

4.3 Isomerism in alkynes .......................................................................................................................... 58

iv
 4.4 Physical properties of alkynes ............................................................................................................ 58

4.5 Preparation of alkynes ........................................................................................................................ 64

4.6 Chemical reactions of alkynes ............................................................................................................ 59

4.7 Qualitative test for alkynes ................................................................................................................. 65

5.0 FUNCTIONAL GROUPS ...................................................................................................................... 67

5.1 ALCOHOLS (ALKANOLS) .............................................................................................................. 68

5.2 CARBOXYLIC ACIDS ..................................................................................................................... 70

5.3 KETONES ......................................................................................................................................... 71

5.4 ALDEHYDES ................................................................................................................................... 72

v
1.0 INTRODUCTION TO ORGANIC CHEMISTRY

Organic Chemistry, branch of chemistry in which carbon compounds and their reactions are studied.

The compounds of carbon constitute the central chemicals of all living thing on this planet.

A wide variety of classes of substances—such as drugs, vitamins, plastics, natural and synthetic fibers,
as well as carbohydrates, proteins, and fats—consist of organic molecules.

Organic chemists determine the structures of organic molecules, study their various reactions, and
develop procedures for the synthesis of organic compounds.

Organic chemistry has had a profound effect on modern life: It has improved natural materials and it
has synthesized natural and artificial materials that have, in turn, improved health, increased comfort,
and added to the convenience of nearly every product manufactured today.

Naturally occurring Synthetic

carbohydrates, proteins, fats and oils, vitamins plastics, many medicines and drugs,

detergents, insecticides, many dyes

Of all elements, carbon alone is able to form an immense diversity of compounds ranging from simple
methane molecule to complex molecules such as carbohydrates, fats, proteins, vitamins e.t.c

Most organic molecules contain mainly C and H in their structures and in some cases O, S and N.

All living things contain organic compounds. Furthermore, many of the modern products and materials
upon which we depend are organic.

The knowledge of organic chemistry enables chemist to develop and manufacture drugs, agricultural
chemicals, anesthetics and other chemicals whose effects on life processes are important to humans.

Carbon atoms bond strongly to one another covalently forming long chains/skeletons and rings,
aunique phenomenon referred to as catenation.

1.1 Electronic configuration of carbon

Carbon has 6 electrons, 2 in the first shell and 4 in the second/outer shell.

The four valence electrons of Carbon are shared to form four covalent bonds and so it exercises a
valency of four.

6C (2 : 4) or (1s22s22p2) or (1s2 2s2 2px1 2py12pz0)

1
The first energy level has the 1s orbital. The ‘s’ orbital accommodates a maximum of two electrons.

The 4 electrons in the the second energy level are organized into the 2s and 2p orbitals. The one 2s has
2 electrons while the three 2p orbitals all accommodate 6 electrons in total in this case.

The ‘s’ orbital is spherical in shape. The ‘p’ orbitals are dumbell shaped and are oriented in x, y and z
planes. All the three ‘p’ orbitals i.e. pxpy pz are all degenerate meaning they are of same energy (see
figure 1)

y y y
Increasing
energy x x x
2p z z z
2px 2py 2pz

y
1s
x
2s z
2s

Figure 1: Energy profile and shapes of s and p orbitals

The 2s orbitals are lower in energy than the 2p orbitals.

The the 2px 2pyand 2pz are superimposed at 900 to one another.

Carbon atoms have no lone pairs or empty orbitals in their outer shells, so that they are unable to form
dative bonds. This properties is responsible for the kinetic stability of its compounds.

1.2 Hybridization, sp3, sp2 and sp

It is the four valence electrons that take part in bonding. Cabon can form single, double or triple bonds
depending on how orbitals of the valence shell (2s2 2px1 2py12pz0) mix or combine.

The mixing or combining of atomic orbitals to form a new set of atomic orbitals that are available for
bonding is called Hybridization.

In orbital hybridization, thenewly constructed atomic orbitals are neither‘s’ or ‘p’ but are now referred
to as hybrid orbitals.
2
Bond angles in organic compounds are usually close to 1090, 1200 or 1800.

These bond angles are explained by the valence shell electron pair repulsion theory. An angle of 109.5 0
is the largest possible separation for the 4 electron pairs, 120 0 for 3 electron pairs and 1800 for two
electron pairs. These shapes cannot result from bonding between simple ‘s’ and ‘p’ orbitals.

Hybridization explains the actual bond angles and type bonding (single, double or triple) in all organic
compounds.

Carbon is also unique in its ability to hybridize. Its four bonding electrons can undergo hybridization to form:

- Tetrahedral (sp3) hybrid orbitals as in alkanes

- Trigonal (sp2) hybrid orbitals as in alkenes
- Linear (sp) hybrid orbitals as in alkynes

1.2.1 sp3 hybridization (sp3 hybrid orbitals)

In sp3 hybridization, the (2s) and (2px , 2py & 2pz) are all hybridized resulting into four equivalent
orbitals arranged tetrahedrally i.e. pointing towards the four corners of the regular tetrahedron.

(a) ground state (b) excited state (c) hybridized state

2p 2p
sp3

2s 2s

atomic orbitals of carbon one electron from the 2s the s and p orbitals are combined to
at ground state is promoted to a 2p orbital form 4 equivalent sp3 hybrid orbitals

Figure 2: Illustration of sp3 hybridazation

The resulting 4 orbitals are called sp3 hybrid orbitals because they composed of one (2s) and three (2p)
orbitals (see figure 2). The four electrons in the sp3 orbitals are the ones that form covalent bonds with
other atoms.

Each of the four sp3 hybrid orbitals has 25% ‘s’ character and 75% ‘p’ character.

The energy of the four sp3 hybrid orbitals are a little less than that of the 2p orbitals but somewhat
greater than that of the 2s orbital.

3
The shape of sp3 hybrid orbitals resembles that of p orbitals except that the dumbell is lop-sided and
the electron is more likely to be found in the space that extends out a greater distance in one direction
from the nucleus (see figure 3).

2s 2px sp3
Figure 3: shape of an sp3 hybrid orbital

Each sp3 hybrid orbital has one node two lobes of unequal sizes which make the electron density
greater on one side of the nucleus. The larger lobe in each case overlaps with the orbitals of another
atom such as hydrogen during bond formation.

Hybrid orbitals form sigma() bonds when they overlap with other orbitals of the same or different
types (see figure 4).

overlap
+

1s sp3 s-sp3 sigma bond e.g. C-H

overlap
+

sp3 sp3 sp3 - sp3 sigma bond e.g. C-C

H
s - sp3
sigma 1s
H
bond sp3
109.50
H C H 109.50

H C
sp3
H 1s sp3
sp 3 1s
H
0
109.5 1s 109.50
H
H H
C
H
H
Figure 4: sigma bond formation
4
The four s-sp3 in methane (CH4) are localized molecular orbitals that define its tetrahedral structure.

sp3 hybridization is extended to compounds that contain C-C single bonds such as saturated alkanes
e.g. ethane, propane, butane e.t.c.

The C-C single bonds allow free rotation in space that is analogous to ‘wheel and axle’ in motion, the
axle resembling the bond in this case.

1.2.2 sp2 hybridization (sp2 hybrid orbitals)

In sp2 hybridization, one of the electrons in the 2s orbital is promoted to a 2p orbital. The 2s and two of
2p orbital are then hybridized resulting into three equivalent sp 2 hybrid orbitalsthat are degenerate (see
figure 5).

5
 (a) ground state (b) excited state (c) hybridized state

2p 2p 2pz
sp2

2s 2s
one s and two of the 2p orbitals are combined to
atomic orbitals of carbon one electron from the 2s
form 3 equivalent sp2 hybrid orbitals leaving one
at ground state is promoted to a 2p orbital
of the 2p orbitals undisturbed

Figure 5: illustration of sp2 hybridization

The remaining orbital (one of 2p) is undisturbed.

The three sp2 orbitals all lie on the same plane and are directed to the corners of a equilateral triangle, a
trigonal plannar arrangement. The bond angle is 120 0.

The remaining 2p orbital is perpendicular to the plane formed by the three sp 2 hybrid orbitals.

Each of the three sp2 hybrid orbitals has 33.3 % ‘s’ character and 66.6% ‘p’ character.

Each of the three sp2 hybrid orbitals contain a single electron such that the electronic configuration is
(1s)2 (2sp2)1 (2sp2) 1 (2sp2) 1 (2p) 1.

Carbon uses sp2 hybrid orbitals to form sigma bonds with other carbon atoms such as the case of ethane
(CH2CH2) molecule.

The undisturbed 2p orbitals of the two carbon atoms of ethene overlap in a side by side manner
resulting into the formation of pi (π) molecular bond (see figure 6).

6
 sp2

1200 1200
+ +
C
2
sp
sp2
1s 2px 2py
1200

Trigonal planar

N/B The 2pz remained undisturbed in the example given.

1/2 bond
2pz 2pz

sp2 sp2 sp2 sp2

sp2 sp2  bond

C + C C C
sp2 - sp2 sp2
sp2 sp2 sp2

1/2 bond

ethene

H bond H

s-sp2 s-sp2
bond C C bond

H bond H

Figure 6: Geometry of sp2 hybridization

7
The trigonal arrangement occur in compounds that contain a double bond which is regarded as being
made up of a strong sigma () bond between two sp2 hybrid orbitals and a weaker pi (π) bond.

As opposed to the sp3 hybrid orbitals, there is restricted rotation about the double bond.

The C=C (double) bond is shorter than the C-C (single) bond because the electron pairs draw the nuclei
more closer together than a single electron pair does.

Electrons in the π bond are less tightly held and are more polarized and so chemical reactions involving
alkenes involve initial attack at the π electrons of the double bond.

8
Structure and shape of the benzene C6H6 molecule:

Benzene C6H6 is a cyclic compound with six carbon atoms joined in a ring. Each carbon atom is sp 2
hybridised, and the ring is planar. Each carbon atom has one hydrogen atom bonded to it and an
unhybridised 2p orbital perpendicular to the plane of the  bonds of the ring. Each of these six 2p
orbitals can contribute one electron for  bonding. This type of p-orbital system leads to complete
delocalisation of all six  electrons giving rise to a highly stable structure of the benzene molecule.

It is known that all carbon-carbon bond length in benzene is the same, 0.140 nm. All six bonds are
longer than C=C double bonds, but shorter than C-C single bonds. From the bond lengths plus a body
of other evidence, chemists have concluded that benzene is a symmetrically molecule with six ring 
bonds (C-C bonds) and six  bonds of C-H bonds. Instead of alternating double and single bonds, the
six  electrons are completely delocalised in a cloud of electronic charge above and below the ring.

1.2.3 sp hybridization (sp hybrid orbitals)

A combination of the 2s with only one 2px orbital makes results into formation oftwo sp hybrid
orbitals. These orbitals extend in opposite directions from the carbon atoms (see figure 7).

9
 (a) ground state (b) excited state (c) hybridized state

2p 2p 2py 2pz
sp2

2s 2s
one s and one of the 2p orbitals are combined to
atomic orbitals of carbon one electron from the 2s form 2 equivalent sp hybrid orbitals leaving two
at ground state is promoted to a 2p orbital of the 2p orbitals undisturbed

Figure 7: illustration of sp hybridization

The angle between the hybrid orbitals is 180 oso as to minimize the repulsion between the electrons
placed in these two sp2 orbitals.

The remaining two valence electrons occupy the other two 2p orbitals (2p y and 2pz) that are mutually
perpendicular to the two sp hybrid orbitals.

sp hybridization results into a linear bonding arrangement.

Each sp hybrid bond has 50% ‘s’ character and 50% ‘p’ character. The two sp orbitals share a common
axis but their lobes are oriented in opposite directions.

The C – C triple bond in alkynes is viewed as multiple bonds of the +π + π type. The triple bond is
composed of one sigma bond formed by the overlap of sp hybrid orbitals from each carbon plus two π
bonds that arise from the 2py& 2pz overlaps.

10
 1800

+ sp sp
C

1s 2px

N/B The 2py & 2pz remained undisturbed in the example given.

y y

z z

x C C x

 bond (sp - sp)

 bond from 2pz overlap
 bond (sp - s)

H C C H
 bond from 2py overlap

ethyne/acetylene
Figure 8: Geometry of sp hybrid orbital

Shorter bonds tend to be stronger bonds. As the ‘s’ character increases, the electron pairs are more
strongly leading to contraction of the inter nuclear distance held hence requiring more energy to
cleave/break.

11
In summary:

Hybridization Geometry Approximate Number Number Number Number

Bond angles of Hybrid of of sigma of
orbitals remaining bonds pi bonds
orbitals
sp3 Tetrahedral 109.50 4 0 1 0
sp2 Trigonal 1200 3 1 1 1
Planar
sp Linear 1800 2 2 1 2

12
As the hybridization of carbon becomes more ‘s’ like and less ‘p’ like, the bond length decreases and
the bond energy increases.

Bond C-C C=C CC

Bond enthalpy kJmol-1 346 610 835

In the molecule given below, the arrows indicate selected atoms and bonds. Write the correct type of
hybridization in the case of selected atoms and the type of bonding (sigma, pi or both) for the selected
bonds.

H H H O

H C C C C C H

C H H

Determine the geometry of the following molecules and hence specify the hybridization state of all the
central carbon atoms.
- CH3CH=CH2
- (CH3)3CH
- CH3CN

The following two compounds have the same molecular formula C 5H8 but different structures :

H CH3
CH3 CH3 C CH CH C
C C C H H
H H

Give the hybridisation states of all carbon atoms for both compounds.

13
1.3 Elemental analysis (qualitative)

Common elements found in organic compounds include C, H, N, O, P, S, Br and certain metals.

The molecular formula gives the exact number of atoms of each element in one molecule of the
compound.

The molecular formula of a given compound is determine by two step process:

- Determination of the empirical formula, which is the simplest whole number ratio of atoms
of different elements present in the compound.
- Determination of molecular weight of the compound using mass spectrometer instrument.

Problem.

A compound was found to contain 42.9% C, 2.4% H, 16.7% N and 38.1% O by weight. Find its
molecular formula given that its molecular weight is 168 g/mol.

Solution:

C H N O

Mass in 100g 42.9 2.4 19.7 38.1

Moles (42.9/12) (2.4/1) (16.7/14) (38.1/16)

Moles 3.58 2.4 1.19 2.38

Ratio of atoms (3.58/1.19) (2.4/1.19) (1.19/1.19) (2.38/1.19)

Ratio of atoms 3 2 1 2
The empirical formula is C3H2NO2

N/B The calculation may not give the actual integers at this stage. It may give ratios such as 1.5: 1 or
1.33:1 or 1.67:1. These rendered in the lowest integral equivalents i.e. 3:2, 4:3, 5:3 respectively.

The molecular formula is integral multiple of the empirical formula. Given that the molecular weight is
168. The molecular weight can be computed as follows:

(C3H2NO2)n = 168

84 n = 168

n=2

The molecular formula is C6H4N2O4

14
1.4 Hydrocarbons

Hydrocarbons are compounds containing carbon and hydrogen only.

Hydrocarbons are divided into two main classes: Aliphatic and Aromatic, based on their structures.

Aliphatic hydrocarbons are further sub-divided into families/groups: Alkane, Alkenes, Alkynes and
their cyclic analogues (see figure 9).

Hydrocarbons

Aliphatic Aromatic

Alkanes Alkenes Alkynes Cyclic aliphatic

Figure 9: Classification of hydrocarbons

The molecules of both saturated and unsaturated aliphatic compounds are open-chain (acyclic) or
simple rings (cyclic) structures.

The term aromatic refers to a major class of unsaturated cyclic organic compounds which includes
benzene and its derivatives. Benzene is an unsaturated, but highly stable, cyclic molecule containing
six carbon atoms.

Aromatic hydrocarbons are hydrocarbons which have benzene ring in their structures. They are
sometimes called arenes.

Bond C-C C=C CC

Bond enthalpy 346 610 835

kJmol-1

15
 2.0 ALKANES

Alkanes are saturated hydrocarbons with general formula CnH2n+2.

Cyclic alkanes have the general formula CnH2n.

Where n is an integer.

All the carbon atoms in alkanes are sp3 hybridized.

A series of compounds in which each member differ from the next member by a constant amount is
called a homologousseries.

16
Homologous series of some straight chain alkanes include:

number name formula structure Line bond (or skeletal) structure

of
carbons
1 Methane CH4 CH4
2 Ethane C2H6 CH3CH3
3 Propane C3H8 CH3CH2CH3 H2
C
H3C CH3
4 Butane C4H10 CH3(CH2)2CH3 H2
C CH3
H3C C
H2
5 Pentane C5H12 CH3(CH2)3CH3
6 Hexane C6H14 CH3(CH2)4CH3
7 Heptane C7H16 CH3(CH2)5CH3
8 Octane C8H18 CH3(CH2)6CH3
9 Nonane C9H20 CH3(CH2)7CH3
10 Decane C10H22 CH3(CH2)8CH3
11 undecane C11H24 CH3(CH2)9CH3
12 dodecane C12H26 CH3(CH2)10CH3
13 tridecane C13H28 CH3(CH2)11CH3

17
N/B Straight chain alkanes are named according to the number of carbon atoms they have.

2.1 Sources of alkanes

1. Petroleum:

- is the primary source of alkanes.

- its is a complex mixture of organic compounds most of which are alkanes and aromatic

hydrocarbons.

- there are also small amounts of oxygen, nitrogen and sulfur containing compounds.

2. Fossil:

- Anaerobic oxidation of plant materials is a chief source of methane, the first member of the
alkane family.Natural gas is mainly composed of methane.

2.2 Nomenclature of alkanes

There are two systems of naming:

i) Semisystematic (old system)

ii) International Union of Pure and Applied Chemistry - IUPAC -(Current system)

Example:

CH3
neopentane (old system)
H3C C CH3
2,2-dimethylpropane (IUPAC system)
CH3

18
RULE 1:

(a) Find the longest continuous chain of carbon atoms and use the name of this chain as the base or
parent of this compound.

Example:

Side chain or substituent

CH3 H H H
equivalent to
2 4 6
H3C C C C C CH3
1 3 5
H H H H
2-Methylhexane

CH3
6 4
5 3

2
1
3-Methylheptane

- The longest continuous chain has 6 carbons and not 3 or 4 carbons. And it is considered the
parent/base of the compound. Sometimes not obvious, you may need to turn corners.
- The group attached to the main chain is considered as branch and is called a substituent.
And so methyl group is considered.
- If a hydrogen is removed from an alkane, the partial structure normally represented as “R-“
that remains is called an alkyl group. They are named by replacing the suffix “-ane” with ‘-
yl’.
o For example: CH4 – methane becomes CH3 – methyl. R = -CH3
C2H6 –ethane becomes C2H5– ethyl. R = -C2H5

- When the ‘R’ group is attached to a halogen, it is referred to as an akyl halide.

- Br-CH3 = Bromomethane, Cl -CH3 = Chloromethane are examples of alkyl halides.

19
(b) If two chains of equal length are present, choose the one with the larger number on branching
points.

CH3 CH3

2 4 6 4 6
1 3 5 H3C 3 5

2
1

Hexane with two substituents Hexane with one substituent

(correct) (Incorrect)

3-Ethyl,2-methylhexane

20
RULE 2:

Number the carbon atoms in the parent/main chain beginning at the end nearer to the first branching
point. The first substituent encountered along the main chain receives the lowest possible number.

CH3 CH3

2 4 6 8 7 5 3 1
1 3 5 8 6 4 2
7

CH3 CH3

(correct) (Incorrect)
2,3-dimethylhexane 6,7- are higher numbers compared to 2,3-

RULE 3:

Identify the number of substituents and locate each by the number assigned on the main chain
according to its point of attachment.

- Use hyphens to separate various prefixes and commas to separate numbers.

- If there are two substituents on the same carbon, assign them both the same number.

7 5 3 1
6 4 2

3-ethyl-4,4,7-trimethylnonane

RULE 4:

The parent alkane is the last part of the name and is preceded by names of the substituent groups and
their numerical locations. Write the name as a single word.

- If two or more substituents are present, name them in alphabetical order.

- Use prefixes di-, tri-, tetra- if identical substituents are present on the main chain.
- The prefixes are ignored in determining the alphabetical order.

21
 Br NO2

4-bromo-3-ethyl,4,4,7-trimethylnonane 4-fluoro-2-methyl-3-nitroheptane

NH2

F
4-ethyl-5-fluoroo-3-methylnonane
3-Amino-2,4,5-trimethyloctane

Me

3 1
6 4 2

Et Me

6-ethyl-3,4-dimethyloctane 3-ethyl-2,4-methylheptane

3,3-Dimethyl-5-(2-methylpropyl)-4-propylnonane 3-Ethyl-5-(1-ethyl-2-methylpropylnonane

3-Ethyl-2,5,6-trimethyl octane
5-(1,1-dimethylpropyl)-5-(2-methylpropyl) nonane

22
One further word in naming alkyl groups; certain prefixes can be used e.g. sec – (secondary), tert –
(tertiary). There are four possibilities:

10 20

H H

R C H R C H

H R

30 40

R
H

R C R R C R

R
R

10 Primary 20 Secondary 30 Tertiaryand 40 Quartenary

sec-butyl group
tert-butyl group
Isopentyl

isopropyl group (1-methylethyl)

isobutyl group

23
Problems:

Identify the carbon atoms that are primary, secondary and tertiary in the structures drawn under rule 3
above.

Draw alkane that meets the following descriptions.

1) An alkane with two tertiary carbon atoms

2) An alkane with one secondary carbon atom.
3) An alkane with three primary carbon atoms.

2.3 Structural isomerism in alkanes

- Isomers are different compounds with similar molecular formula.

- Structural isomers (constitutional isomers) are compounds that have the same molecular
formula but differ in the way atoms are arranged.

Example;

Butane (C4H10) has two isomers.

CH3
H2
C CH3 CH
H3 C C H 3C
H2 CH3

n-Butane 2-Methylpropane

Problem:

Draw all the possible isomers of pentane and hexane.

2.4 Physical properties

The normal alkanes from C1 to C4 are gasses at room temperature e.g. methane.

C5 to C17 are liquids e.g. kerosene.

C18 onwards are solids e.g. wax.

- All organic compounds including hydrocarbons are less dense than water.

24
Solubility

- Alkanes are generally non polar and dissolve only in non-polar solvents such as benzene,
ether and chloroform.

- Alkane are insoluble in water and other highly polar solvents. The non-polar nature of
alkanes is due to the fact that atoms on alkane molecules are held together by covalent
bonds.

Melting point

- Alkanes with even number of carbon atoms generally pack better into solid structure and
therefore higher temperatures are required to melt them compared to those with odd number
of carbon atoms. This is because alkanes with even number of carbon atoms pack so as to
permit greater intermolecular attraction between the atoms.

- Highly symmetrical compounds often melt at abnormally high temperatures because

molecule are also known to pack well in their crystal lattice.

- The highly branched alkanes melt at higher temperatures than the straight chain alkanes
with the same number of carbon atoms. This is because branching gives it a more compact
structure.

Problem:

Of the two isomers of butane, which one would be expected to melt at a higher temperature.

Boiling point

- Larger molecules have large surface areas resulting into increased intermolecular Van-der-
waals forces of attraction. This is true in the case of straight chain alkane where the boiling
points increase with increasing number of carbon. Decane (C10H22) has higher boiling point
than pentane (C5H12)

- In general, highly branched alkanes have lower boiling points than normal (straight chain)
alkanes.
With branching, the shape of a molecule tends to approach that of a sphere. As this happens,
the surface area is decreased resulting into weaker intermolecular forces that would require
lower temperatures to overcome.

25
Consider isomers the three of pentane C5H12.

n-Pentane 2,2-Dimethylpropane 2-Methylbutane

Bpt.(0C) 36 10 28
Mpt. (0C) -130 -20 -160

- n-Pentane and 2-Methylbutane are larger isomers. They have larger surface areas and
increased van-der-waals forces than 2,2-Dimethylpropane.

- 2,2-Dimethylpropane which is highly symmetrical has abnormally high melting point.

26
2.5 Chemical reactions of alkanes

The bonds in alkanes are single covalent and non-polar and hence they rarely react.

1. Combustion

Alkanes burn in air to give carbondioxide and water.

CH4 + 2 O2 CO2 + 2H2O + Energy

2CH4 + 3O2 2CO + 4 H2O + Energy

(incomplete combustion)

2. Nitration

CH3CH2CH2NO2
HNO3
CH3CH2CH3
4000C CH3CH(NO2)CH3

3. Oxidizing agent

- Alkane can be oxidized by potassium permanganate (KMnO4).

- Only when the alkane is tertiary.

27
 CH3 CH3

KMnO4
H 3C CH H3 C C OH

O CH3
CH3

tertiary alcohal Tertiary alcohol

4. Halogenation
- Under proper conditions, alkanes react with halogens, X2 i.e. (Cl2, Br2,I2 & F2) to
form alkyl halides.
H H
light
H C H + Cl-Cl H C Cl + HCl
4000C
H H

monohalogenated product

- If excess halogen is present, the reaction can proceed to polyhalogenated products.

28
 5. Pyrolysis (cracking)

400-600oC
Alkane Smaller alkanes + H2
- The decomposition of a larger compound by means of heat alone is known as pyrolysis. The
pyrolysis of alkanes particularly when petroleum is concerned is known as cracking.
- Cracking is mostly done in the industrial production of fuels.

H2, Heat
C12H26 C5H12 + C7H16 (catalytic hydrocracking)
Catalyst
shorter alkanes

C12H26 Heat C5H10 + C7H16 (catalytic cracking)

Catalyst
shorter alkanes
and alkenes

2.6 Mechanism for free radical substitution

A reaction mechanism is a step by step by step description of the bond breaking and bond forming
process that occurs when reagents react to form products.

Halogenations of alkanes occur via free radical (atom with one or more unpaired electron that is
represented by a dot) chain reaction. It is a three step process.

1. The initiation step:

light
Cl Cl Heat
Cl + Cl

2. Propagation step
H H
H C H Cl H C + HCl
H H

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

29
30
 3. Termination step

Cl Cl Cl Cl

H H H H
H C C H H C C H
H H H H

H H
H C Cl H C Cl
H H

2.7 Cycloalkanes
- Are alkanes in which the carbon atoms form a ring and the general molecular formula is
CnH2n.

- Examples:

cyclopropane cyclobutane cyclopentane cyclohexane

Geometric isomerism

- Are compounds with the same molecular formula but differ in orientation in space.

- examples:

31
 H3 C CH3
H
CH3

H H
CH3
H

Trans-1,3-dimethylcyclobutane Cis-1,3-dimethylcyclobutane
(methyl groups pointing in opposite sides of the plane) (methyl groups all pointing on the same side of the plane)

H3 C

H3 C
CH3

Trans-1,2-dimethylcyclobutane
Cis-1,2-dimethylcyclobutane
H3C

- In addition to the monocyclic compounds, there are more complicated compounds with
bridges linked across the rings. They are referred to as polycyclic.

Nomenclature of cycloalkanes:

- Cycloalkanes are named by adding the prefix ‘cyclo’ to the name on the corresponding open
chain alkane with same number of carbon atoms in the ring

- The ring is numbered in the direction that gives the lowest possible numbers to the
substituent groups at the first point of difference between the two directions. The
alphabetical order of listing the groups still applies.

- Examples:

CH2CH3

3 4 2
1 3 1
2 2
4
1 3

1-Isopropyldecane 1,1,2-Dimethylhexane 1,2,4-Trimethylhexane

4-Ethyl-1,2-dimethyloctane

- When the ring contains fewer carbon atoms than the alkyl group attached, the compound is
named as an alkane otherwise, it is named as a cycloalkane.

32
 2-Cyclopropylheptane 1-ethyl-2-methylcyclopentane

- According to the IUPAC system of cycloalkanes consisting of two rings only and having
two or more atoms in common take the prefix ‘bicyclo’ followed by the name of the
corresponding alkane.

- The number of carbon atoms in each of these bridges connecting the two carbon atoms is
indicated in brackets in descending order.

- Numbering begins with one of the bridgeheads and proceeds by the longest possible path to
the other bridgehead.

- Numbering then proceeds from this atom by the longer unnumbered path back to the first
bridgehead and is completed by the shortest path.

Examples:

One carbon bridge

Bridge head

Two caron bridge

Two caron bridge

Bridge head

33
 1 2
Cl
1 3
I 8

2 9

7 4

6 5
2-Iodobicyclo[2.2.2]octane
Bicyclo[3.3.0]octane 3-Chlorobicyclo[4.2.0]nonane

3 1 1 3
2
6
Br
4
5 7

3-Methylbicyclo[4.2.2]decane 7-Bromo-5-ethyl-2,3-dimethylbicyclo[2.2.1]heptane

Cl
F
Br 1
2
6
7
3
5

4
C(CH3)3

6-Bromo-3-tertbutyl-2-methylbicyclo[2.2.1]heptane
Cl

2-Chloro-4-fluorobicyclo[3.2.0]heptane 2-Chloro-1-ethyl-5-methylbicyclo[2.2.1]heptane

2.8 Preparation of alkanes

1. Hydrogenation of alkenes
Pt or Pd or Ni
In general; CnH2n + H2 CnH2n+2
(alkene) (alkane)

Ni
CH2=CH2 + H2 CH3CH3
Ethene Ethane

Pt
+ H2

1-Butene Butane

34
2. Reduction of alkyl halides by metal and acid

Zn/H+ R-H + ZnX2

(a) RX
Alkyl halide Alkane

e.g.
H2 H2
C CH3 + C CH3
Zn/H
(i) H3C CH H3C C
H2
Br

Zn/H+
(ii)
Cl

(b) Primary (10 ) and secondary (20) alkyl halides are readily reduced by
LiAlH4 (Lithium Aluminium Hydride)
LiAlH4 R-H + LiAlX4
RX
10 alkyl halide alkane

e.g.
H3 C CH3 H3 C CH3
(i) LiAlH4
CH C
H2
Br

Cl LiAlH4
(ii)

35
3. Use of Grignard reagent

Alkyl halides in ether (solvent) reacts with magnesium to form an alkyl magnesium halide
(Grignard reagent) which on treatment with water or dilute acids are decomposed to an alkane.

ether H+ or H2O
RX + Mg R-Mg-X R-H
alkyl halide grignard reagent Alkane

e.g.
H2
H2 H3C CH3
H3 C CH3 Mg C
(i) C
C
C CH
CH ether H2
H2
Mg-Br
Br

H+ or H2O

H2
H3C C CH3
C C
H2 H2

H2
Br Mg C Mg-Br
(ii)
ether H3C C
H2 Propylmagnesiumbromide

H+ or H2O

H2
C
H3 C CH3

36
4. Coupling of alkyl halides with organometallic

Li CuX
RX R-Li R2CuLi
10,20 or 30 alkyl lithium Lithiumdialkyl
alkyl halide

R'X
(must be 1o)

R'-R
(alkane)
e.g.
H2 H2 CuI
Li
(i) C C (CH3CH2)2CuLi
H3C Cl H3 C Li

CH3Cl

CH3CH2CH3

N/B. The above procedure is useful of lengthening the carbon chain.

5. Wurtz reaction

2 Na
R'X + R-X dry ether R'-R + X2

e.g.
2 Na
(i) CH3CH2Br + CH3CH2CH2Br dry ether
CH3CH2-CH2CH2CH3

37
6. Decarbonylation

- By heating the sodium salt of a carboxylic acid in soda lime.

C NaOH
R-H + Na2CO3
R ONa CaO
alkane
e.g.
NaOH
(i) CH3CH2COONa CH3CH3
CaO

38
 3.0 ALKENES

- Are unsaturated hydrocarbons with general formula CnH2n.

- A study of the reactions of alkenes is really the study of c=c double bond that consists of one
sigma and one pi bond.
- Due to the presence of the pi bond, that causes unsaturation, alkenes are more reactive than
alkanes.
- There is no free rotation about the c=c double bond. The double bond is rigid.
- older name of this family of compounds that is still often used is ‘olefins’

3.1 Sources of alkenes

- Catalytic cracking of petroleum

- Dehydration of ethanol that is produced by fermentation of carbohydrates.

3.2 Nomenclature of alkenes

- Names are derived by replacing the ending –ane of the corresponding alkane with –ene e.g
CH2=CH2 Ethene CH3CH=CH2 Propene

- The longest carbon chain with the double bond is considered to be the parent alkene.
- The chain is numbered in the direction that gives the double bonded carbon atoms the lowest
possible numbers.
- The rules for naming alkanes are pretty much the same as those for alkanes exceptthat the
double bond is given preference in numbering the chain. This because the double bond is
regarded as the functional group in the molecule.
- In substituted alkenes the numbers and names of substituents are mentioned first, followed by
the position of the double bond and lastly by the name of the parent alkene.

- Examples

39
 2
1 3
CH3CH=CHCH2CH3

2-Pentene or Pent-2-ene

5
4 8
7
4 2
3
3 1
6
2
5
6-Methyl-3-octene or 6-Methyloct-3-ene
1

3-Ethyl-2-methyl-1-pentene or 3-Ethyl-2-methylpent-1-ene

CH3
2
CH3
1 2 3 4 5 1
CH3C CHCHCH3
CH3
CH3 CH3
5,5-Dimethyl-1- hexene or 5,5-Dimethylhex-1-ene
4-Methylpent-2-ene or 4-Methyl-2-pentene
- :
- When two or more double bonds are present, the terminal –ane of the corresponding alkane
is replaced by –adiene, atriene e.t.c to obtain the name of the compound e.g

CH2=CHCH=CH2 1, 3-Butadiene

- The longest chain containing both double bonds is taken to be the parent chain.

H2C CHCHCH2CH2CH3
3-Propyl-1,4-pentadiene
HC CH2
- If more than one substituent is present, the substituents are named in alphabetical order e.g.
Cl C2H5
CH3CH2C CCHCH2CH3 3-Chloro-5-ethyl-4-methyl-3-heptene
CH3
- Cyclic alkenes are named by prefixing the word ‘cyclo-‘ or ‘bicyclo’ (whichever is applicable)
to the name of the corresponding open chain alkene. The carbon atoms of the double bond
are considered to be atposition 1. e.g.

40
 CH3
H3C

Cyclopentene 1,2-Dimethylcyclopentene 5-Methyl-1,3-cyclohexadiene

3.3 Structural isomerism in alkenes(Cis ,Trans, E, Z)

- Rigidity and lack of rotation of theC=C double bonds in alkenes give rise to ‘Cis’ and ‘Trans’
geometric isomerism depending on how the groups attached to the double bond are oriented in
space.

- The different spatial arrangement of the groups around the double bond give rise to difference in
chemical properties.

- Geometric isomerism cannot exist if either of the doubly bonded carbon atoms carry identical
groups. e.g.
4 3
H3C-H2C H
2 1
Identical groups Geometric isomerism not possible
C C
H H

1-Butene

4 4 1
H3 C H H3C CH3
3 2 3 2
C C 1
C C
H CH3 H H

Trans-2-butene Cis-2-butene Geometric isomerism

occur with different groups
3 attached to either carbon.
Cl H Cl CH3
1 2 1 2
C C C C
3
H CH3 H H

Trans-1-chloro-1-propene Cis-1-chloro-1-propene

- However, the ‘Cis – Trans’ nomenclature system can only be applied to a small number of alkenes.

- For instance the ‘Cis – Trans’ system cannot distinguish between the two isomers of 2-Bromo-1-
chloro-1-flouroethene.

41
 1 Cl Br
1
Br has a higher prority
1 2
Cl>F Br>H than H.
C C
2 F H 2

(Z) - 2-Bromo-1-chloro-1-fluoroethene

1
Cl H
2

1 2
Cl>F C C Br>H

2 F Br 1

(E) - 2-Bromo-1-chloro-1-fluoroethene

- In the modern ‘E-Z’ system of the Cahn Ingold Prelog convention, priorities are assigned to each of
the two groups attached to each of the two carbons based on their atomic numbers.

- We simply consider the two groups attached to the same carbon atom of the double bond and decide
which has a higher priority.

- The higher the atomic number, the higher the priority.

- When higher priority groups at each carbon atom are on the same side, the isomer is designated letter
(Z) (zusamen meaning together).

- It two groups of higher priority are on opposite sides of the double bond, it is designated letter (E)
(entegen meaning opposite).

- Examples:

42
 Br H3C H Cl
H H
C C C C C C
H3CH2C CH2CH2CH3 H CH3 Br CH2CH3
Trans-2-butene
(E)-3-Bromo-3-heptene or (Z)-1-Bromo-1-chloro-1-butene
(E)-2-Butene
Cl CH3 I Br
C C C C
F CH2CH3 Cl CH3
(E)-1-Chloro-1-fluoro-2-methylbut-1-ene (Z)-2-Bromo-1-chloro-1-iodoprop-1-ene

Cl
F
H3C CH2CH3
C C
H CH(CH3)2
(E)-3-Chlorohex-2-ene (Z)- 2-Fluoro-2-heptene

(E)-3-Ethyl-4-methyl-2-pentene

(2E,5Z)-3-Ethylhept-2,5-diene
(E)-6-secbutyl-3-methyl-7-cyclopropyl-2-decene

- Trans-alkenes are usually higher melting than their cis isomers because of higher symmetry, but their
boiling points differ very little.

- The cis-isomer has lower m.p., lower density and higher solubility than that of the trans-isomer. These
properties can be explained by the existence of intramolecular hydrogen bonding in the cis-isomer,
which reduces the chance of intermolecular hydrogen bonding, and thus weaken interactions between
molecules of the cis-isomer.

43
3.4 Physical properties of alkenes

- The first three members of alkenes are gases at room temperature (C 2-C4), C5-C15 are liquids
at room temperature and >C15 are solids at room temperature.
- They burn with a luminous flame.
- They’re insoluble in water, but more soluble than alkanes in some polar solvents like
alcohols.
- They’re less volatile than alkanes and their boiling points and melting points increase with
increase in molecular mass.
- They are less dense than water.
- Boiling points increase with increasing number of carbons.

3.5 Preparation of alkenes

1. Dehydrohalogenation of alkyl halides

alcohol
C C + KOH C C

X H

alkylhalide alkene

e.g.
alcohol
(i) CH3CH2CH2Br + KOH CH3CH=CH + KBr + H2O

Cl alcohol
+ KOH
(ii)

alcohol CH3CH=CHCH3 + CH3CH2CH=CH2

(iii) CH3CH2CHCH3 + KOH
major product minor product
Br 80% 20%

N/B. The most highly substituted is formed preferentially according to Zaitzeff's rule

44
2. Dehydration of alcohols

- Alcohals are converted to alkenes elimination of a water molecule (dehydration).

- This occurs in the presence of an acid and some heat.

C C heat
+ H2SO4 C C + H2O

H OH

alcohal alkene

e.g.
heat
(i) CH3CH2CH2OH + H2SO4 CH3CH=CH2

OH heat
+ H2SO4
(ii)
CH3

H3 C
heat
(iii) CH3-C-OH + H2SO4 C CH2

H3C
CH3

3. Dehalogenation of vicinal dihalides

- The method is purely 1,2-elimination of the vicinal halides.

CH3COOH
C C + Zn C C + ZnX2

X X

alcohal alkene

e.g.
CH3COOH
(i) CH3CHCHCH3 + Zn CH3CH=CHCH3

Cl Cl

CH3COOH
(ii) Cl + Zn
Cl

45
 4. Reduction of alkynes

R R
Lindlar catayst
C C Cis 'anti'
H2/Pd
H H

R-C C-R

R H
Na/NH3 (liquid) Trans 'syn'
C C
H R

e.g.
H3 C CH3
Lindlar catayst
C C Cis
H2/Pd
H H

CH3-C C-CH3

H3 C H
Na/NH3 Trans
C C
liquid
H CH3
- The hydrogenation here is partial.
- The ‘cis’ alkene product is almost 98%.

3.6 Chemical reactions of alkenes

- Most reactions occur at the double bond because it is the functional group.
- The double bond is an electron rich centre. These electrons attack nuclei of other atoms that are
relatively electron deficient.
- The pi electrons of alkenes are therefore nucleophilic and react readily with electrophiles.

46
1. Addition of hydrogen (Reduction)

R R
R R
H2, Pd, Ni
C C H C C H

H H
H H

e.g.

H2, Pd, Ni
(i) CH3CH2CH2CH=CH2 CH3CH2CH2CH2CH3

H2, Pd, Ni
(ii)

(iii) 3 H2
Catalyst
Heat

2. Halohydrin formation

R R
R R
H2 O
C C + X2 H C C H

H H
OH X
Halohydrin
e.g.
OH
H2O
(i) CH3CH2CH2CH=CH2 + Br2 CH3CH2CH2CHCH2

Br

47
3. Addition of sulphuric acid

C C + H2SO4 C C

H OSO3H

e.g.
H H
Conc. H2SO4
H3C C CH3 H 2O H3C C CH3
(i) CH3CH=CH2
OSO3H Heat OH

Isoproylhydrogensulphate Propan-2-ol

CH3 CH3 CH3

(ii) Conc. H2SO4 H 2O
H3C C CH2 H3C C CH3 H3C C CH3
Heat
OSO3H OH

tert-butylalcohol

N/B: Hydrogen adds the carbon atom with the larger number of hydrogen atoms

4. Addition of hydrogen halide (Markovnikovs rule)

- Addition of hydrogen halide to alkenes is governed by Markovnikovs rule.

- The rules states that when an acidic molecule adds to an asymmetric alkene, the major product is the
one in which the hydrogen atom attaches itself to the carbon atom already carrying the larger number
of hydrogen atoms.

- The reverse rule is referred to as ‘Antimarkovnikov’ when hydrogen peroxide (or any other
peroxide) is used.

- Alkenes form addition products with halogen acids in the following order of reactivity:

HI > HBr > HCl > HF . HI being the most reactive while HF being the least reactive.

48
 CH3 CH3 CH3
H3C
C C + HBr H C C H

H H H Br

Symmetric alkene

H CH2CH3

HCl H C C H
Markovnikov's
product

H Cl
H CH2CH3

C C
H H
H CH2CH3
Asymetric alkene HCl Antimarkovnikov's
H C C H
product
H 2 O2
Cl H

CH3 CH2CH3

HCl H C C CH3
Markovnikov's
product

H Cl
H3C CH2CH3

C C
H CH3
CH3 CH2CH3
Asymetric alkene HCl Antimarkovnikov's
H C C CH3
product
H2 O 2
Cl H

N/B: The halide adds to the more highly substituted carbon according to markovnikov's rule unless a peroxide is used.

HBr Markovnikov's
product
Br

Antimarkovnikov's
HBr product
ROOR
Br

49
5. Hydration of alkenes

- Addition of H2O across the double bond in the presence of dilute acid to form an alcohol.

dil. H2SO4
C C + H2O C C

OH

e.g.
H H

H+
(i) CH3CH=CH2 + H2O H3C C C H

OH H
Propan-2-ol

H+
(ii) + H 2O

OH
3-Methyl-3-hexanol
N/B: Hydrogen attaches to the carbon with higher number of hydrogen atoms

6. Ozonolysis

- This reaction is used to determine the location of the double bond in alkenes because it
involves cleavage of the double bond to give carbonyl compounds.
- Ozone is considered a mild oxidant.
O
R R R
R
C C + O3 C C
R R
R R O O
Ozone
Ozonide
Intermediate

Zn H2O

R R
O + O C
R R
Carbonyl compounds

50
 H3 C CH2CH3 H3C CH2CH3
Zn / H2O
(i) C C + O3 C O + O C
H H H
H

2-Pentene Ethanal Propanal

O
O3
(ii) + O
Zn / H2O
Propanal
4-Methyl-3-hexene Butan-2-one

(iii) O3
Zn / H2O
O

7. Oxidation of alkenes

a. Moderately strong oxidizing agents

e.g. HIO4 or (CH3COO-) 4Pb

O
HIO4
(CH3)2C=CH2 CH3CCH3 + HCHO

b. Strong oxidizing agents

They include acidified K2Cr2O7 or acidified KMnO4.
O
K2Cr2O7
(CH3)2C=CH2 CH3CCH3 + HCOOH
+
H or hot

51
8. Hydroboration of alkenes

- Alkenes undergo hydroboration with diborane (BH 3)2 to yield a trialkylborane (R3B), which upon
oxidation gives an alcohol.

H H R-CH2CH2 CH2CH2R
B
+ B
3 R-CH=CH2 2
H
Borane R-CH2CH2

NaOH / H2O2

3 R-CH2CH2-OH

- The hydroboration – oxidation process gives products that correspond to anti-markovnikovs addition of
water across the double bond.

e.g.

CH3 CH3
(i) (BH3)2 NaOH / H2O2
H3C C CH2 H3C C CH2

H OH

(ii) OH
(BH3)2 NaOH / H2O2 Anti-markovnikovs
product

(BH3)2 NaOH / H2O2

(iii)
OH

9. Polymerization
- A process that involves the joining together of many small molecules to form very large
molecules.
- The small molecules that form polymers are called monomers.
- When ethene it heated under high pressure with oxygen, a compound of high molecular
weight (approx. 20,000) is obtained which is essentially an alkane.

52
 e.g.

H H
O2, Heat
(i) n CH2=CH2 C C
Pressure

H H n
Ethylene
Polyethylene

H H H H

(ii) O2, Heat

n C C C C
Pressure

H Cl H Cl n

Vinylchloride Polyvinylchloride

- A compound made of many ethene (or ethylene) units is called polyethene (or
polyethylene).
- Polymerization of substituted ethylenes is also possible. e.g. polyvinylchloride that used to
make plastic pipes.

3.7 Qualitative test for alkenes

- Qualitative tests involve the detection of the presence of alkenes or basically test for unsaturation.
- Important general laboratory observations in testing mostly include:
o Colour changes or disappearances
o Effervesence or bubbles of a gas produced
o Peculiar smell
o Formation of precipitate
o Flame produced during burning i.e. luminous or non-luminous, sooty or not
o Water droplets on the surface of test tube during heating.

(a) Bromine test:

- Addition of Br2 in CCl4is used for the detection of the C=C double bond.
R R
R R
CCl4
C C + X2 H C C H

H H
X X

e.g.
(i) CH3CH2CH2CH=CH2 + Br2/CCl4 CH3CH2CH2CHBrCH2Br
Red Colourless

Br
CCl4
+ Br2
(ii)
Br
53
- Alkenes decolorize Bromine water (Orange) or Bromine in CCl4 (Red).

(b) Baeyer’s test:

- Cold dilute KMnO4 solution (Baeyer’s reagent) is also decolorized by alkenes.

cold
C C + KMnO4 C C
OH-
OH OH
Purple colourless diol

54
 4.0 ALKYNES

- Another class of unsaturated hydrocarbons with a general formula C nH2n-2 n=2,3,4…..

- They contain carbon carbon tripple bonds as their functional group.
- The triple bond is made of one sigma bond and two pi bonds.

4.1 Sources of alkynes

- The simplest member of this group is acetylene (or ethyne) C2H2 and is of chief industrial
importance. It is obtained by:
(a) Reaction of water and Calcium carbide.
(b) High temperature oxidation of methane.

4.2 Nomenclature of alkynes

- Alkynes are named in the same way as alkanes. The terminal –ane in the corresponding alkane is
replaced by –yne. The location of the triple bond is indicated by a number in such a way that the
carbon preceding the triple bond is given the lowest possible number.
- The hydrogen atom attached to the carbon of the triple bond is called acetylenic hydrogen which
is weakly acidic and can be removed by a strong base.
Acetylenic hydrogen

R C C H Ethyne

- The locations of the substituent groups attached to the branched alkynes are also indicated by
numbers.

55
 e.g.

HC CH Ethyne
CH3C CH Propyne terminal tripple bond

CH3CHC CH 3-Methyl-1-butyne

CH3

H3 C C C CH2CH2 5-Chloro-2-pentyne

Cl
CH3

6-Methylhept-2-yne or 6-Methyl-2-heptyne
Internal
tripple bond

3-Octyne

CH3
CH3
CH3
2,2,5-Trimethyl-3-hexyne
C

CH3

- When the molecule contains more than one triple bond the suffix –ane of the corresponding alkane
is replaced by a –di yne (2 triple bonds), -atriyne (3 triple bonds) etc.

HC CC CH 1,3-Butadiyne

HC CCH2CH2C CH 1,5-Hexadiyne

- When both a double bond and a triple bond are present in the same molecule, then the hydrocarbon
is called an alkenyne. The multiple bonds are given numbers as low as possible.
-
CH3CH CHC CH 3-Penten-1-yne

HC CCH2CH CH2 1-Penten-4-yne

56
- Double bond takes preference over the triple bond when there is a choice in numbering that is
given the lowest number possible.

H H H H H

H3 C C C C C C C C

H H H H

Oct-1-ene-6-yne

- Ketones also takes preference over the triple bond when there is a choice in numbering that is given
the lowest number possible.

H H O

HC C C C C CH3

H H

Hex-5-yne-2-one

- When a triple bond and an alcoholic group (-OH) are present, the –OH comes last and the
numbering is done from the end bearing the –OH group e.g.

HC CCH2CH2OH 3-Butyn-1-ol

H3 C
C

C CH3

C C

H H

Z-2-Hex-4-yne

57
Isomerism in alkynes

The first two alkynes do not show any isomerism.

(a) Position isomerism
Due to the various structures obtained by varying the position of the triple bond e.g.

CH3CH2C CH 1-Butyne

CH3C CCH3 2-Butyne

(b) Structural isomerism

Caused by differences in the type of carbon chain e.g.
CH3CH2CH2C CH 1-Pentyne

CH3CHC CH 3-Methyl-1-butyne

CH3
(c) Functional isomerism
Alkynes can be visualized as isomers of dienes (or alkenes) e.g.
CH3CH2C CH H2C CHCH CH2
1-Butyne 1,3-Butadiene
N/B Unlike alkenes, alkynes do not show geometric isomerism.

4.3 Physical properties of alkynes

- They are less generally volatile than either alkanes or alkenes.

- C2-C4 are gases, C5-C13 are liquids and >C13 are solids.
- They are colorless and odorless compounds, except ethyne which has a garlic odor.
- The boiling points, melting points, densities and heat of combustion increase with increase in
molecular mass.
- They’re sparingly soluble in water but readily soluble in organic solvents.

58
4.5 Chemical reactions of alkynes

- Alkynes undergo reactions typical to those of alkenes. The triple bond is the functional group.

1. Hydrogenation (Addition reaction)

It occurs in 2 stages.
H H H H

Pt/H2 Pt/H2
H C C H C C H C C H

H H H H

- Reduction of an alkyne at the double bond stage can unless the triple bond is a terminal one,
yield either Cis - alkene or Trans - alkene. Whichever of the two predominates depend kind of
the reducing agent.

H C2H5
Na, NH3(Liq)
C C Trans
H3 C H

H3 C C C C 2 H5

H3 C C2 H5

H2 / Pd C C Cis
Lindlar catalyst H H

59
2. Reaction with haloacids (HCl, HBr)
Br H
(i)
HBr H3 C C C H HBr H3 C C C H
H3C C C H

Br H Br H

Markovnikovs product

H Br
(ii)
HBr H3 C C C H HBr H3 C C C H
H3 C C C H
Peroxide Peroxide
H Br H Br

Anti-markovnikovs product

3. Reaction with halogens (Br2, Cl2)

X X

X2 X2
R C C H C C C C H

X X X X

e.g.
Br Br

Br2 Br2 H3C C C H

H3 C C C H H3 C C C H
CCl4 CCl4
Br Br Br Br

4. Hydration (addition of H2O)

- Like alkenes, alkynes can also be hydrated in the presence of an acid (and HgSO 4 for simple) and
water.

60
- The process leads to keto-enol tautomerism. Compounds whose structures differ markedly in
arrangement of atoms but which exist in easy and rapid equilibrium are called tautomers.

- The keto tautomer is mostly favored.

Tautomers H

H2SO4 R C C H
R C C H + H2O R C C H
HgSO4
OH H O OH

enol keto

e.g.

H2SO4
(i) H3 C C C H + H2O H3C C CH3
HgSO4
O

H2SO4
(ii) H C C H + H2O H3C C H
HgSO4
O

61
5. Reaction with Alkylmagnesium halide or alkyllithium

- Only works with terminal alkynes

e.g.

(i) H3C C C H + C2H5-MgBr C2H6 + H3C C C MgBr

(ii) H3C C C H + C4H9-Li C4H10 + H3C C C Li

6. Ozonolysis

e.g.

1. O3
(i) H3C C C H H3C C O + O C H
2. Zn / H3O H H

1. O3
(ii) H3C C C C2H5 H3C C O + O C C2H5
2. Zn / H3O H H

7. Reaction of metal acetylides and alkynyl/Grignard reagent with carbonyl (Aldehyde and
Ketones)

R C C Na + C O R C C C O Na

Metal acetylide

H+

R C C C OH

62
 R C C MgX + C O R C C C O MgX

alkynyl grignard
reagent
H+

R C C C OH

e.g.
CH3
H3C

(i) H C C Li + C O H C C C O Li
H3C
CH3

H+
CH3

H C C C OH

CH3

2-Methylbut-3-yne-2-ol

CH3
H3C
(ii) +
H
H3 C C C MgBr + C O H3 C C C C OH

H
H

Pent-3-yne-2-ol

63
4.6 Preparation of alkynes
1. Calcium carbide
- Used for laboratory as well as industrial preparation of ethyne.

CaC2 + 2H2O C2H2 + Ca(OH)2

2. Dehydrohalogenation of alkyl dihalides

- This involves double dehydrohalogenation of dihaloalkanes. The dihalide may be a vicinal or
geminal.

KOH NaNH2
C C C C C C
alcoholic
Alkyne
X X X

e.g.
H H H

KOH NaNH2
(i) H3C C C H H3 C C C H H3C C C H
alcoholic
Br Br Br Alkyne

Vicinal dihalide

(ii) Br H H

H3 C C C CH2CH3 KOH NaNH2

H3C C C CH2CH3 H3 C C C CH2CH3
alcoholic
Br H Br Alkyne

Geminal dihalide

3. Reaction of sodium acetyledes with primary alkyl halides

64
 - Used in the conversion of smaller alkynes to a larger ones.
- Sodamide (NaNH2) in liquid ammonia is a strong base capable of abstracting the acetylenic
hydrogen from the terminal alkyne.
- The smaller alkyne must be terminal and the alkyl halide must be primary.

NaNH2 R-X
C C H C C Na C C R
0
terminal alkyne must be 1

e.g.
NaNH2
(i) H3C C C H H3 C C C Na + NH3

CH3(CH2)4CH2-I

H3 C C C CH2(CH2)4CH3 + NaI

2-Nonyne

4.7 Qualitative test for alkynes

(a) Bromine test

- They also decolorize Br2 in CCl4.
e.g.
Br Br

Br2 Br2 H3 C C C H
H3 C C C H H3C C C H
CCl4 CCl4
Br Br Br Br

(b) Baeyer’s test

- Cold dilute KMnO4 solution (Baeyer’s reagent) is also decolorized by alkenes.
- Alkynes are oxidized to carboxylic acid.

OO KMnO4
KMnO4 CH3COOH + HCOOH
CH3C CH CH3CCH
OH- OH-

(c) Ammoniacal silver nitrate or Ammoniacal copper nitrate

- Terminal alkynesgive a white precipitate when treated with ammoniacal silver nitrate.
65
- This distinguishes between terminal and non-terminal alkynes.
- Terminal alkynesgive a brick red precipitate when treated with ammoniacal copper nitrate.

e.g.

AgNO3 / NH3
(i) CH3CH2C CH CH3CH2C C Ag
Etthanol
White colored ppt.

CuNO3 / NH3
(ii) CH3CH2C CH CH3CH2C C Cu
Etthanol
Brick red ppt.
AgNO3 / NH3
(iii) CH3CH2C CCH3 No reaction
or CuNO3 / NH3
internal alkyne

66
 5.0 FUNCTIONAL GROUPS

- A functional group is an atom, a group of atoms, or a bonding arrangement, which is responsible for
thecharacteristic reactivity and physical properties of an organic compound or class of compounds.

- The structure of a typical carbon compound can be considered as two parts : a saturated carbon-hydrogen
‘skeleton’, which is comparatively unreactive, and a reactive part consisting of one or more functional
groups. Two examples are shown below :

Functional groups

H H H H H H

H C C C O-H N C C C C H

H H H H H H

- In the event that there are more than one functional group in a molecule, the following order of
preference is given in the choice of the principal functional group which is to be given the lowest
number.

(i) Carboxylic acids

(ii) Aldehydes
(iii) Ketones
(iv) Alcohols
(v) Double bond
(vi) Tripple bond
(vii) Atoms and alkyl groups.
(viii) Alkanes

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 5.1 ALCOHOLS (ALKANOLS)

- These are organic compounds of the general formula R-OH, where the hydroxyl group (-OH) is
attached to an alkyl group(R) or cycloalkyl group.

- The OH group is the functional group of the alcohol and determines their reactivity and
characteristics. They from a homologous series of the general formula CnH2n+1OH, where n is the
number of carbon atoms. E.g CH3CH2OH.

Nomenclature (IUPAC rules)

1) Name the longest carbon chain to which the hydroxyl group is attached. The chain name is
obtained by dropping the final e from alkane name and adding the suffix –ol.

2) Number the chain starting at the end nearest the hydroxyl group and use the appropriate number
to indicate the position of the –OH group. NB; in numbering the longest carbon chain, the
hydroxyl group has priority over double and triple bond as well as over alkyl, cycloalkyl and
halogens substituents.

3) Name and locate any other substituent present.

4) In the alcohol where the –OH group is attached to a carbon atom in a ring, the hydroxyl group is
assumed to be on carbon 1.

Examples
CH3 CH3
(a) CH3CH2CCH2CH2CH3 3-Methyl-3-hexanol (f)
1,2-Dimethylcyclopentanol
OH OH
CH3
(b) CH3CH2CHCH2CH3 2-Ethyl-1-butanol
OH
CH2OH
OH
(g) 3,4-Dimethylcyclohexanol
CH3
(c) CH3CHCHCH2CHCH3 2,5-Dimethyl-3-hexanol CH3
CH3 CH3

(h) Cyclohexanol
(d) CH3CH2CHCH3 3-Methyl-1-pentanol
CH2CH2OH OH

(e) CH2=CHCH2OH 2-Propen-1-ol

68
Physical properties of alcohols

1) Boiling points of alcohols are higher than those of the hydrocarbons of approximately the same
molecular weight. This is due to hydrogen bonding between alcohol molecules.

R O H

H O R

hydrogen bond

2) Alkanols are soluble in water. Their solubility however decreases gradually as the hydrocarbon
part of the molecule increase.

Classification of alcohols

They are classified as primary (10), secondary (20) or tertiary(30) depending on the number of carbon
bearing groups attached to carbon bearing hydroxyl (-OH).

Primary alcohol is an alcohol in which the hydroxyl bearing carbon is attached to only one other carbon,
a secondary alcohol is an alcohol in which the hydroxyl bearing carbon is attached to two other carbon
atoms while a tertiary alcohol is an alcohol in which the hydroxyl bearing carbon atom is attached to
three other carbon atoms.

Examples

CH3
CH3CH2OH CH3CHOH CH3COH
CH3 CH3
0
1 alcohol 20 alcohol 30 alcohol

Qualitative test for alcohols

Lucas test:

- 10, 20 and 30alcohols are distinguished based on their reactivity towards hydrogen halides (Lucas
test). Lucas reagent, a mixture of conc.HCl/ZnCl2. The reaction proceeds and the alcohol is
converted to alkyl halide.

ZnCl2
C OH HCl C Cl

Clear solution Cloudy suspension due to

formation of 3o or 2o alkyl
halide

69
- Formation of alkyl chloride is indicated by cloudiness that appear when the chloride separates
from the solution; hence the time required for cloudiness to appear is a measure of reactivity of
the alcohol.

30 alcohol – forms cloudiness immediately

20 alcohol - forms within 5 minutes
10 alcohol – do not form appreciably at room temperature.

5.2 CARBOXYLIC ACIDS

- They have the general formula R-COOH.

- They are named by replacing the –ane of the corresponding alkane with –oic acid.
- The functional group (-COOH) is always terminal.
- The carbonyl carbon (C=O) is assigned position 1 in numbering the longest chain.

Examples:

H O

H C C O-H
Ethanoic acid
H

H H O

H C C C O-H Propanoic acid

H H

O
C
OH 2,5-Dimethylhexanoic acid

Qualitative test for carboxylic acids

Sodium hydrogen carbonate

- Carboxylic acids react with sodium hydrogen carbonate to give a precipitate.

O O
NaHCO3
H3C C O-H H3C C O-Na + H2O + CO2

Ethanoic acid Sodiumethanoate (ppt)

70
5.3 KETONES

- They have the general formula RCOR.

- They are named by replacing –e in the corresponding alkane with –one.
- The carbonyl carbon (C=O) takes priority in numbering the longest chain.

Examples

H H O
O

CH3(CH2)3CH2 C CH2CH2CH3 H C C C CH3

H H
4-Nonanone 2-Butanone

O
O

H3C C CH3

2-Propanone
6-Methylhept-5-ene-3-one or
Acetone

Qualitative test for ketones

Iodoform/Haloform test.

- Used to distinguish methyl ketones

- Aqueous solutions of iodine and potassium iodide are added to basic solutions of 2-pentanone
and 3-pentanone. The iodoform reaction is a classical test for methyl ketones.
-
- A light yellow precipitate of iodoform forms immediately with the methyl ketone 2-pentanone.

O O
NaOH
CH3(CH2)3CH2 C CH3 + I2 CH3(CH2)3CH2 C O- Na+ + CH3I

71
5.4 ALDEHYDES

- They have the general formula R-CHO.

- They are named by replacing –e in the corresponding alkane with –al.
- The carbonyl carbon (C=O) is always terminal.
Examples:

H3C C H Ethanal

H H O

H C C C H Propanal

H H

OH O
C 2,-Methyl-5-hydroxyhexanal
H

Qualitative test for aldehydes

Fehling’s test:
- This test is very specific for aldehydes; only aldehydes will give a positive result. Any alcohol
or ketone will give a negative result.

- It is basedupon the ability of the aldehyde group to reduce the Cu+2 ion of Cu(OH)2 (which
is blue) to the Cu+1 ion of Cu2O (which is dark red) in the presence of a base.

O O
NaOH
H3C C H 2 Cu(H2O) H3 C C O-Na + Cu2O + H2O

Blue Dark red

72
 Silver mirror test/ Tollens’ reagent.
- Most Aldehydes reduce Ammoniacal Silver Nitrate solution to give a precipitate of Silver metal
(pronounced coating on test tube wall).

O O

R C H Ag(NH3)2+ OH- R C OH + 2 Ag + NH4OH

Tollens' reagent Silver (precipitated)

73