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Physical properties of

alkanes & cycloalkanes

Physical Boiling
state Point

Solubility
Physical state
 At room temperature (25oC) and atmospheric
pressure (1 atm), for unbranched alkanes,
C1 – C4 : gases
C5 – C17 : liquids
C18 - more : solids
Boiling points
The boiling points of the straight alkanes
show a regular increase with increasing
molecular weight.
Branching of the alkanes chain, lower the
boiling point.
Mr ↑ boiling point ↑
C-H is non polar bond
 Intermolecular forces exist – London

dispersion
The London dispersion forces increase :

As molecular weight increases,
 Molecular size increases

 Molecular surface area increase


Therefore, more energy is required to
separate molecules from one another
 Result - a higher boiling point.

Mr ↑ boiling point ↑
Chain branching :
 makes a molecule more compact


Surface area reduces

The strength of the London dispersion
forces reduce
 Lower boiling points.
Isomeric Alkanes

Have different boiling point due to branching


Pentane 2-methylbutane 2,2-
dimethylpropane

CH3CH2CH2CH2CH3 CH3CHCH2CH CH3


CH3 CH3CCH3
CH3

37 C
o 28.5oC 9oC
For example, butane and 2-methylpropane both
have a molecular formula C4H10 , but the atoms
are arranged differently
CH3CH2CH2CH3 butane
CH3CH2CH2CH3

CH3CHCH3
CH3CHCH3 2-methylpropane
CH3
CH3
In butane the C atoms are arranged in a
single chain, but 2-methylpropane is a
shorter chain with a branch
Name Molecular structure
Boiling point

Butane has a higher boiling point because the dispersion


forces are greater.
The molecules are longer (and so set up bigger temporary
dipoles) and can lie closer together than the shorter, fatter
2-methylpropane molecules.
Cycloalkanes
The boiling points of cycloalkanes are 10oC
to 15oC higher than the corresponding straight
chain alkanes.
Cycloalkane Boiling point alkane Boiling
point
Cyclobutane 13oC Butane -0.5oC

Cyclopentane 49oC Pentane 36..3oC


Solubility

Alkanes – less dense than water

Alkanes and cycloalkanes are almost


totally insoluble in water

 They are non-polar molecule


 Unable to form hydrogen bond with H2O
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.
Nature sources of alkanes;
Natural gas
oil

Natural gas contains primarily methane


and ethane, with some propane and
butane

Oil is a mixture of liquid alkanes and


other hydrocarbons
CHEMICAL REACTION OF
ALKANES
Non-reactivity of alkanes

Alkanes are generally inert towards many


chemical reagents (bases, acids, dehydrating
agents and aqueous oxidizing agents)

C and H has nearly the same electronegativity,


the C-H bonds of alkanes are only slightly
polarised (non polar)
Reaction of alkanes

 Combustion
 Halogenation
Combustion of alkanes

 Alkanes burnt in air ( oxygen ) to give carbon


dioxide gas, water and heat.

y y
CxHy+ x + O2 → x CO2 + H2O
4 2
+ Heat
Examples:
Combustion of alkane in excess oxygen

C4H8+ 3O2 → 4CO2 + 4H2O


+ Heat
Examples:
Combustion of alkane in limited oxygen

C4H8+ 4O2 → 4CO + 4H2O


+ Heat
 Alkanes are unreactive towards polar or
ionic reagents but can react with non-
polar reagents such as oxygen and
bromine.
The low reactivity of alkanes toward
many reagents explain why alkanes
were originally called paraffins.
(Latin : parum affinis= low affinity).
Halogenation: a free radical
substitution reaction
 Alkanes react with halogen (chlorine & bromine) to
produce haloalkanes in the presence of light or
temperature >> 100 oC.

R–H + X2 hv R–X + HX
→
 With methane, the reaction produces a mixture of
halomethane and a hydrogen halide.
Examples:

i. CH4 + Cl2 hv CH3Cl + CH2Cl2


→
+ CHCl3 + CCl4
+ HCl

ii. hv
CH3CH3 + Cl2 → CH3CH2Cl + HCl
CH3 CH3
| |
hv
iii. CH3 CCH3 + Cl2 → CH3 CCH2Cl + HCl
| |
CH3 CH3

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


hydrogen atoms are identical
hv CH3CH2CH2Br
iv. CH3CH2CH3 + Br2 →
( minor)
+ CH3CHCH3
|
Br
( major)
+ HBr
Reaction mechanism
CH4 + Cl2
hv
→ CH3Cl + HCl

i. Chain initiation step


hv
Cl – Cl → 2Cl•
ii. Chain propagation steps

H
H-C H + •Cl → •CH3 + HCl
H

3 HC• + Cl Cl_ → CH3Cl + Cl•


iii. Chain termination step.

•Cl + •Cl → Cl2

•Cl + •CH3 → CH3Cl

•CH3 + •CH3 → CH3CH3


Example
The bromination of 2-methylbutane yields a
mixture of isomers.
CH2Br CH3 CH3

CH3 C CH2 CH3 CH3 C CHBr CH3 CH3 C CH2 CH3

H H Br

Increasing % yield
Exercise
 Chlorination reaction of certain
alkanes can be used for laboratory
preparations, for example in the
preparation of chlorocyclopentane
from cyclopentane. Give the
mechanism for the reaction.