Physical Properties of alkanes

(a) Physical State:

All are colourless & possess no characteristic odour.Lower alkanes (C1 to C4) are gases, middle one
(C3 to C17) are liquids and higher are solids.The boiling point of alkanes increases with increase in
molecular weight due to increase in van der waals forces with increase in molecular weight i.e.,B.pt.
order : pentane < hexane < heptanes.
Also the branching in alkanes gives a decrease in surface area (as the shape approaches to
spherical) which results in decrease in van der Waals forces. That is why b.pt. of isomeric alkanes
who the order : pentane > isopentane > neopentane
The melting points of alkanes do not show a regular trend. Alkanes with even number of carbon
atoms have higher m.pt. than their adjacent of odd number of carbon atoms.
M.pt. order :

propane
(-187.7oC)

<

ethane

(-172.0oC)

<

methane
(-182.5oC)

The abnormal trend in m.pt. is probably due to the fact that alkanes with odd carbon atoms have their
end carbon atom on the same side of the molecule and in even carbon atom alkane, the end carbon
atom on opposite side. Thus alkanes with even carbon atoms are packed closely in crystal lattice to
permit greater intermolecular attractions.

(b) Density : The density of alkanes increases with increase in molecular weight and becomes
constant at 0.76 g/ml. Thus all alkanes are lighter than water.
(c) Solubility :
Alkanes being non polar and thus insoluble in water but soluble in non polar solvents e.g., C 6H6, CCI4,
ether etc. The solubility of alkanes decreases with increase in molecular weight.Liquid alkanes are
themselves good, non polar solvents.

Chemical properties of Alkanes:

Alkanes are quite inert substances with highly stable nature. Their inactiveness has been explained
as:
1.

In alkanes all the C-C & C-H bonds being stonger sigma bonds and are not influenced by
acids, alkalies, oxidants under ordinary conditions.

2.

The C-C (completely non polar) & C-H (weak polar) bonds in alkanes- are practically non
polar because of small electronegativity difference in C (2.6) and H (2.1). Thus polar species i.e.,
electrophiles or nucleophiles are unable to attack these bonds under ordinary conditions.

?
Inspite of less reactive nature, alkanes show some characteristic reactions.
Oxidation Reactions of Alkane:
Oxidation of alkanes gives different products under different conditions.
1. Complete oxidation or combustion : Alkanes burn readily with non luminous flame in presence
of air or oxygen to give CO 2 & water along with evolution of heat. Therefore alkanes are used as
fuels.
CnH2n+2 + [(3n+1)/2]O2 nCO2 + (n+1)H2O;
CH3 + 2O2 CO2 + 2H2O;

H = -ve

H = -ve

2. Incomplete oxidation : Incomplete oxidation of alkanes in limited supply of air gives carbon black
and carbon monoxide.
2CH4 + 3O2 2CO + 4H2O
CH4 + O2

+ 2H2O

carbon black

3. Catalytic oxidation :
Lower alkanes are easily converted to alcohols and aldehydes under controlled catalytic oxidation.

Higher alkanes on oxidation in presence of manganese acetate give fatty acids.

CH3(CH2)nCH3 + 3O2

CH3(CH2)nCOOH

4. Chemical oxidation : Tertiary alkanes are oxidized to tertiary alcohols by KMnO4

Substitution reactions of alkanes :

Substitution in alkanes shows free radical mechanism. For mechanism see free radical
substitution.Following substitution reactions in alkanes are noticed.

1. Halogenation of Alkanes :
Chlorination may be brought about by photo irradiation, heat or catalysts, and the extent of
chlorination depends largely on the amount of chlorine used. A mixture of all possible isomeric
monochlorides is obtained, but the isomers are formed in unequal amounts, due to difference in
reactivity of primary, secondary and tertiary hydrogen atoms.
The order of ease of substitution is
Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen
Chlorination of isobutane at 300 oC gives a mixture of two isomeric monochlorides

The tertiary hydrogen is replaced about 4.5 times as fast as primary hydrogen. Bromination is similar
to chlorination, but not so vigorous. Iodination is reversible, but it may be carried out in the presence
of an oxidising agent such as HIO3, HNO3 etc., which destroys the hydrogen iodide as it is formed and
so drives the reaction to the right, e.g.
CH4 + I2
5HI + HIO3

CH3I + HI
3I2 + H2O

Iodides are more conveniently prepared by treating the chloro or bromo derivative with sodium iodide
in methanol or acetone solution. e.g
RCl + NaI

RI + NaCl

This reaction is possible because sodium iodide is soluble in methanol or acetone, whereas sodium
chloride and sodium bromide are not. This reaction is known as Conant Finkelstein reaction.
Direct fluorination is usually explosive; special conditions are necessary for the preparation of the
fluorine derivatives of the alkanes.
RH + X2

RX + HX

(Reactivity of X2: F2 > Cl2 > Br2; I2 does not react)

The mechanism of methane chlorination is:

Initiation Step
Cl : Cl

2Cl

DH = + 243 KJ mol-1

The required enthalpy comes from ultraviolet (uv) light or heat.

Propagation Step
i). H3C : H + Cl H3C + H : Cl

H = - 4KJ mol-1 (rate determining)

ii). H3C + Cl : Cl H3C : Cl + Cl

H = - 96 KJ mol-1

The sum of the two propagation steps in the overall reaction,

CH4 + Cl2 CH3Cl + HCl

H= - 100 KJ mol-1

In propagation steps, the same free radical intermediates, here Cl and H3C, being formed and
consumed. Chains terminate on those rare occasions when two free-radical intermediates form a
covalent bond.
Cl + Cl

Cl2 ; H3C + Cl CH3 : Cl

H3C + CH3 H3C : CH3

Inhibitors stop chain propagation by reacting with free radical intermediates, e.g.

In more complex alkanes, the abstraction of each different kind of H atom gives a different isomeric
product. Three factors determine the relatives yields of isomeric product.
Probability Factor: This factor is based on the number of each kind
of H atom in the molecule. For example, in CH3CH2CH2CH3 there are six
equivalent

1o Hs

and

four

equivalent

abstracting a 1oH are thus 6 to 4, or 3 to 2.

2o Hs.

The

ratio

of

Reactivity of H :

The order of reactivity of H is 3o > 2o > 1o.

Reactivity of X :

The more reactive Cl is less selective and more

influenced by the probability factor. The less reactive Br is more

selective

and

assummarized by

less

influenced

by

the

the Reactivity-Selectivity

probability
Principle.

factor,
If

the

attacking species is more reactive, it will be less selective, and

the yields will be closer to those expected from the probability
factor.

In the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to the
formation of isobutyl chlorides, whereas abstraction of a single tertiary hydrogen leads to the
formation of tert-butyl chloride. The probability favour formation of isobutyl chloride by the ratio of 9:1.
But the experimental results show the ratio roughly to be 2:1 or 9:4.5. Evidently, about 4.5 times as
many collisions with the tertiary hydrogen are successful as collisions with the primary hydrogens.
The Eact is less for abstraction of a tertiary hydrogen than for abstraction of a primary hydrogen.
The rate of abstraction of hydrogen atoms is always found to follow the sequence 3 o > 2o > 1o. At
room temperature, for example, the relative rate per hydrogen atom are 5.0:3.8:1.0. Using these
values we can predict quite well the ratio of isomeric chlorination products from a given alkane. For
example:

Inspite of these differences in reactivity, chlorination rarely yields a great excess of any single isomer.
The same sequence of reactivity, 3 o > 2o > 1o, is found in bromination, but with enormously larger
reactivity ratios. At 127oC, for example, the relative rates per hydrogen atom are 1600:82:1. Here,
differences in reactivity are so marked as vastly to outweigh probability factors. Hence bromination
gives selective product.
In bromination of isobutane at 127oC,

Hence, tert-butyl bromide happens to be the exclusive product (over 99%).

2. Nitration :
Replacement of H atom of alkane by -NO 2 group is known as nitration.Nitration of alkane is made by
heating vapours of alkanes and HNO 3 at about 400oC to give nitroalkanes. This is also known as
vapour phase nitration.
CH4(g) + HNO3(g)

CH3NO2 + H2O

During nitration, C-C bonds of alkanes are also decomposed due to strong oxidant nature of HNO 3 to
produce all possible nitroalkanes.

The nitration of alkane also shows the order:T.H. > S.H. > P.H. > methane
The nitration of alkanes follows free-radical mechanism

HONO2

HO + NO2

C3H7-H + HO C3H7 + H2O

C3H7 + NO2 C3H7NO2
3. Sulphonation :
Replacement of H atom of alkane by -SO 3H is known as sulphonation. Lower normal alkanes are
not suphonated, but higher normal alkanes show sulphonation (hexane onwards) when heated with
oleum (i.e., conc. H2SO4) at 400oC.
C6H14 + H2SO4 C6H13SO3H + H2O
Lower members are sulphonated in vapour phase sulphonation.The reactivity order for sulphonation
is T.H. > S.H. > P.H. Thus isobutene is easily sulphonated as it contains tertiary hydrogen atom.

Sulphonation of alkanes also follows free radical mechanism.

HOSO3H

HO + SO3H

C3H13-H + OH C6H13 + H2O

C3H13 + SO2H C6H13SO3H
4. Isomerization :
The process of conversion of one isomer into other is known isomerization.Straight chain alkanes on
heating with AICI3 + HCI at about 200oC and 35 atm pressure are converted into branched chain
alkanes.

5. Aromatization :
The process of conversion of aliphatic compound into aromatic compound is known as
aromatization. Alkanes having six to 10 carbon atoms are converted into benzene and its
homologues at high pressure and temperature in presence of catalyst.

C6H14

+ 4H2

6. Dehydrogenation : Alkanes are dehydrogenated on heating in presence of catalyst to produce

corresponding alkenes.

C3H8

C3H6 + H2

7. Pyrolysis :
The decomposition of a compound on heating in absence of air is known as pyrolysis. The
phenomenon of pyrolysis of alkane is also known as cracking. Alkane vapours on passing through
red hot metal tube in absence of air decomposes to simpler hydrocarbons. The product formed
during cracking depends upon
(a) nature of alkane
(b) temperature and pressure
(c) presence or absence of catalyst
The ease of cracking in alkanes increases with increase in molecular weight and branching in
alkane.Fission of C-C bonds produces alkane and alkenes whereas fission of C-H bonds produces
alkene and hydrogen.

Presence of Cr2O3, V2O2, MoO3 catalyses C-H bond fission and presence of SiO 2, AI2O3, ZnO
catalyses C-C bond fission.The no. of products obtained during cracking increases with increase in
molecular weight of alkane undergoing cracking.

Cracking has an important role in petroleum industry. Higher alkanes are converted into lower one
(petrol C6 to C11) by cracking.