Chapter 12 : Hydrocarbons

ALKANES

INTRODUCTION

Alkanes are known as saturated hydrocarbon
which contain only single covalent bonds.

General formula of alkanes is CnH2n+2
where n = 1, 2, …….

Each carbon atom in alkanes is sp3 hybridised
and tetrahedral with four sigma bond formed by
the four sp3 hybrid orbitals. All bond angles are
close to 109.5o

Alkanes IUPAC names have the –ane suffix.

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Chapter 12 : Hydrocarbons

Table 12.1: The First Ten Unbranched Alkanes

Number
of Molecular
Name Carbon
Structure
Formula
Atoms

Methane 1 H-CH2-H CH4

Ethane 2 H-(CH2)2-H C2H6
Propane 3 H-(CH2)3-H C3H8
Butane 4 H-(CH2)4-H C4H10
Pentane 5 H-(CH2)5-H C5H12
Hexane 6 H-(CH2)6-H C6H14
Heptane 7 H-(CH2)7-H C7H16
Octane 8 H-(CH2)8-H C8H18
Nonane 9 H-(CH2)9-H C9H20
Decane 10 H-(CH2)10-H C10H22

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Chapter 12 : Hydrocarbons

IUPAC NOMENCLATURE

Branched-chain alkanes are named according to the

following rules:

1. Locate the longest continuous chain of carbon

atoms; this chain determines the parent name for
alkanes.

Examples:

CH3CH2CH2CH2CHCH3
|
CH3 Parent name: hexane

CH3CH2CH2CH2CHCH3
|
CH 2
|
CH3
Parent name:
heptane

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Chapter 12 : Hydrocarbons

2. Number the longest chain beginning with the end

of the chain nearer the substituent.

Examples:

7 6 4 3 2 1
CH3CH2CH2CH2CHCH3
|
CH3 substituent

7 6 5 4 3
CH3CH2CH2CH2CHCH3
substituent
|
2 CH2
|
1 CH3

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Chapter 12 : Hydrocarbons

3. Use the numbers obtained by application of rule 2

to designate the location of the substituent group.
 The parent name is placed last, and the
substituent group preceded by the number
designating its location on the chain, is
placed first.
 Numbers are separated from words by a
hyphen.

Examples:

6 5 4 3 2 1
CH3CH2CH2CH2CHCH3
|
CH3
2-methylhexane

7 6 5 4 3
CH3CH2CH2CH2CHCH3
|
2 CH2
|
1 CH3

3-methylheptane

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Chapter 12 : Hydrocarbons

Table 12.2: Some Common Substituent Groups

Substituent Name

-CH3 methyl
CH2CH3
CH2CH2CH3 ethyl
CH-CH3
| propyl
CH3

CH2CH2CH2CH3 isopropyl

CH2-CH-CH3
| butyl
CH3
CHCH2CH3
| isobutyl
CH3

CH3
| sec-butyl
C-CH3
|
CH3
tert-butyl
CH2CH2CH2CH2CH3

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Chapter 12 : Hydrocarbons

CH2CH2CHCH3 pentyl
|
CH3
CH3
|
CH2-C-CH3 isopentyl
|
CH3

 neopentyl


cyclopropyl

cyclobutyl
C6H5 or

CH2

Phenyl
F

Cl benzyl

Br
fluoro
I

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Chapter 12 : Hydrocarbons

chloro
NO2
bromo
NH2
iodo
OH
nitro

amino

hydroxyl

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Chapter 12 : Hydrocarbons

4. When two or more substituents are present, give

each substituent a number corresponding to
its location on the longest chain.
 the substituent groups should be listed
alphabetically.
 In alphabetizing, the prefixes i.e di, tri, tetra,
sec-, tert-, etc. are ignored except iso and
neo.

Example:
1 2 3 4 5 6
CH3CHCH2CHCH2CH3
| |
CH3 CH2
|
CH3

4-ethyl-2-methylhexane

5. When two substituents are present on the

same carbon atom, use that number twice.

Example:
CH3
|3 4 5 6
CH3CH2 C CH2CH2CH3
|
2 CH2
|
1 CH3

3-ethyl-3-methylhexane

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Chapter 12 : Hydrocarbons

6. When two or more substituents are identical,

indicate this by the use of prefixes di-,tri-,
tetra-, and so on. Commas are used to separate
numbers from each other.

Example:

CH3CH - CHCH3
| |
CH3 CH3
2,3-
dimethylbutane

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Chapter 12 : Hydrocarbons

7. When two chains of equal length compete for

selection as the parent chain, choose the chain
with the greater number of substituents.

7 6 5 4 3 2 1
CH3CH2-CH CH CH CHCH3
| | | |
CH3 CH2 CH3 CH3
|
CH2
|
CH3

2,3,5-trimethyl-4-propylheptane
(four substituents)

NOT
4 3 2 1
CH3CH2-CH CH CH CHCH3
| | | |
CH3 5 CH2 CH3 CH3
|
6CH2
|
7CH3

4-sec-butyl-2,3-dimethylheptane
(three substituents)

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Chapter 12 : Hydrocarbons

8. When branching first occurs at an equal distance

from either end of the longest chain, choose the
name that gives the lower number at the first
point of difference.

6 5 4 3 2 1
CH3CHCH2CH CHCH3
| | |
CH3 CH3 CH3

2,3,5-trimethylhexane NOT 2,4,5-

trimethylhexane

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Chapter 12 : Hydrocarbons

CYCLOALKANES

 Cycloalkanes – alkanes which carbon atoms

are
joined in rings.
 Cycloalkanes are known as saturated
hydrocarbon, because it has the maximum
number of bonded hydrogen ( only has single
bonds).
 General formula: CnH2n where n = 3, 4, 5, ……

NOMENCLATURE OF CYCLOALKANES

1. Cycloalkanes with only one ring are named by

attaching the prefix cyclo- to the names of the
alkanes possessing the same number of
carbon atoms.

Examples: Monocyclic compounds.

; C3H6 ; cyclopropane

; C4H8 ; cyclobutane

; C5H10 ; cyclopentane

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Chapter 12 : Hydrocarbons

2. If only one substituent is present, it is not

necessary to designate its position.

Examples:

CH3
Cl
Chlorocyclopropane
methylcyclohexane

3. When two substituents are present, number

carbon in the ring beginning with the substituent
according to the alphabetical order and number
in the direction that gives the next substituent the
lowest number possible.

Examples:
CH3

CH2CH3

1-ethyl-2-methylcyclohexane
(NOT 1-ethyl-6-methylcyclohexane)

Cl Cl

1,3-dichlorocyclopentane
(NOT 1,5-dichlorocyclopentane)

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Chapter 12 : Hydrocarbons

4. When three or more substituents are present,

begin at the carbon with substituent that leads to
the lowest set of locants.

Example:
CH2CH3

Cl CH3

4- chloro-2-ethyl-1-methylcyclohexane
(NOT 1-chloro-3-ethyl-4-methylcyclohexane)

H3C CH2CH3

CH3

1-ethyl-1,3-dimethylcyclopentane
(NOT 3-ethyl-1,3-dimethylcyclopentane)

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Chapter 12 : Hydrocarbons

5. When a single ring system is attached to a single

chain with a greater number of carbon atoms, or
when more than one ring system is attached
to a single chain, then it is appropriate to name
the compounds as cycloalkylalkane.

Examples:

CH2CH2CH2CH2CH3

1-cyclobutylpentane 1,3-
dicyclohexylpropane

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Chapter 12 : Hydrocarbons

PHYSICAL PROPERTIES OF ALKANES AND

CYCLOALKANES

1. Physical state

 At room temperature (25oC) and atmospheric

pressure (1 atm), the first four members of the
homologous series of unbranched alkanes are
gases; the C5 – C17 unbranched alkanes are
liquids; and the unbranched alkanes with 18 and
more carbon atoms are solid.

2. Boiling points

 The boiling points of the unbranched alkanes

show a regular increase with increasing
molecular weight. Branching of the
alkanes chain, however, lower the boiling
point.

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Chapter 12 : Hydrocarbons

Examples: C5H12

CH3CH2CH2CH2CH3 ; Boiling point = 36oC

(pentane)

CH3CHCH2CH3 ; Boiling point = 28oC

|
CH3
(2-methylbutane)

CH3
|
CH3CCH3 ; Boiling point = 10oC
|
CH3
(2,2-dimethylpropane)

 The explanation for this effect lies in the Van

der Waals forces. As molecular weight
increases, so does molecular size and
molecular surface area. With increasing
surface area, the Van der Waals forces
increase; therefore, more energy is required
to separate molecules from one another
and thus give a higher boiling point.

 Chain branching, makes a molecule more

compact, reducing its surface area and
reducing the strength of the Van der Waals

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Chapter 12 : Hydrocarbons

forces and this causes the lowering of the

boiling points.

3. Solubility

 Alkanes and cycloalkanes are almost totally

insoluble in water because they are non-polar
molecule and therefore unable to form
hydrogen bond.

 Liquid alkanes and cycloalkanes are soluble in

one another, and they generally dissolve in
non-polar solvents.

 Good solvents for alkanes are benzene,

carbon tetrachloride, chloroform, and other
hydrocarbons.

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Chapter 12 : Hydrocarbons

SYNTHESIS OF ALKANES

1. Hydrogenation of alkenes

 Alkenes and alkynes react with hydrogen in the

presence of metal catalysts such as nikel,
palladium and platinum to produce alkanes.

General reaction:

Pt or Pd or Ni
C C + H2 C C

H H

Examples:

i.
Ni
H3C CH CH2 + H2 H3C CH CH2

H H
ii.
CH3 CH3
Pt
H3C C CH2 + H2 H3C C CH2

H H

iii.
Pd
+ H2

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Chapter 12 : Hydrocarbons

2. Hydrolysis of Grignard reagents

 Grignard reagents are usually prepared by the

reaction of an alkyl halide and magnesium
metal in ether solvent.

RX + Mg ether
  RMgX
alkylmagnesium halide

Examples:

CH3CH2CH2Cl + Mg ether
  CH3CH2CH2MgCl

 Hydrolysis of Grignard reagent gives an alkane.

RMgX + H2O H
 RH + Mg(OH)X

Examples:
i. CH3CH2CH2MgCl + H2O H
 CH3CH2CH3 + Mg(OH)Cl

ii. CH3CHCH3 + H2O H

 CH3CH2CH3 + Mg(OH)Cl
|
MgCl

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Chapter 12 : Hydrocarbons

3. Wurtz reaction

 A process utilising an active reducing agent

(such as Na) to synthesise longer alkanes from:

a) identical alkyl halides

2RX + 2Na  RR + 2NaX

Example:

2CH3CH2Br + 2Na  CH3CH2CH2CH3 +

2NaBr

b) more than one types of alkyl halide; a mixture

of products will form.

RX + R’X + 6Na  RR + RR’ + R’R’ +

6NaX

Example :

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Chapter 12 : Hydrocarbons

4. Decarboxylation of alkanoate salt.

 Alkanes can be produced by heating the

alkanoate salt with soda lime.

RCOONa + NaOH  RH + Na2CO3

Only sodium etanoate can react easily, while the

others give a mixture of product.

Examples:

CH3COONa + NaOH  CH4 + Na2CO3

(90%)

CH3CH2COONa + NaOH  CH3CH3 + CH4 + H2 + other

unsaturated
compounds

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Chapter 12 : Hydrocarbons

CHEMICAL REACTION OF ALKANES

Non-reactivity of alkanes

 Alkanes are generally inert towards many

chemical reagents. Carbon and hydrogen have
nearly the same electronegativity, the carbon-
hydrogen bonds of alkanes are only slightly
polarised. As a consequence, they are generally
unaffected by most bases.
 The low reactivity of alkanes toward many
reagents accounts for the fact that alkanes were
originally called paraffins.
 (Latin : parum affinis= low affinity).

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Chapter 12 : Hydrocarbons

Halogenation: a free radical substitution

reaction.

 Alkenes react with halogen such as chlorine

and bromine to produce haloalkanes in the
presence of light or temperature greater
than 100 oC.

R–H + X2 hv
 R–X + HX

 With methane, the reaction produces a mixture

of halomethanes and a hydrogen halide.

Examples:

i. CH4 + Cl2 hv
 CH3Cl + CH2Cl2 + CHCl3 + CCl4 +
HCl

ii. CH3CH3 + Cl2 hv

 CH3CH2Cl + HCl

CH3 CH 3
| |
iii. CH3 CCH3 + Cl2 hv
 CH3 CCH2Cl + HCl
| |
CH3 CH3

(ii) & (iii): 1 product only because all the

hydrogen atoms are
identical

iv. CH3CH2CH3 + Cl2 hv

 CH3CH2CH2Cl + CH3CHCH3 +
HCl

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Chapter 12 : Hydrocarbons

|
Cl
( minor)
( major)

Reaction mechanism

CH4 + Cl2 hv
 CH3Cl + HCl

i) Chain initiation step

Cl–Cl hv
 2Cl•

ii) Chain propagation steps

CH4 + Cl•  •CH3 + HCl

•CH3 + Cl2  CH3Cl + Cl•

iii) Chain termination step.

•Cl + •Cl  Cl2

•Cl + •CH3  CH3Cl
•CH3 + •CH3  CH3CH3

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Chapter 12 : Hydrocarbons

 Chain propagation step can be repeated to

form
CH3Cl , CH2Cl2 ,CHCl3 and CCl4 .

CH3 + •Cl  •CH2Cl + HCl

•CH2Cl + Cl2  CH2Cl2 + •Cl

CH2Cl2 + •Cl  •CHCl2 + HCl

•CHCl2 + Cl2  CHCl3 + •Cl

CHCl3 + •Cl  •CCl3 + HCl

•CH3 + Cl2  CCl4 + •Cl

27