THE HYDROCARBONS

Introduction
Certain organic compounds contain only two elements, hydrogen and carbon. They are called hydrocarbons.
On the basis of structure, hydrocarbons are divided into two main classes aliphatic and aromatic. Aliphatic
hydrocarbons are further classified into alkanes, alkenes, alkynes and also their cyclic analogues.
Hydrocarbons

Aliphatic Aromatic

Alkanes Alkenes Alkynes

Alkanes
Alkanes (Paraffin): The compounds of carbon and hydrogen with the general formula CnH2n+2 are called
alkanes. These are also known as saturated hydrocarbons or Paraffins.

Structure and Reactivity: The simplest member of this family is methane (CH4) where the C-atom is sp3
hybridized, which are overlapping with the s-orbitals of H-atoms at the corner of regular teltrahedron.This
structure is verified by electron diffraction method.
H
109.5
A C
1.10
H H
H
The next higher member in the family is ethane (C2 H6)

H H H

C
1.53 A

A C
1.10
H H
H
109.5

Here again each C-atom is sp3-hybridized with a dihedral angle of approximately 109.5

If one consider a molecule of methane or ethane or any other alkane, we find that all these molecules are non
polar and hence the interactive forces operative are Van der waals forces.

Hence within the family one would have stronger intermolecular forces if the surface area of molecule is
large.

-1 -
The Hydrocarbons 2

Name Formula M.pt C B.pt C

Methane CH4 183 162
Ethane CH3CH3 172 88.5
Propane CH3CH2CH3 187 42
Butane CH3CH2CH2CH3 138 0
Pentane CH3CH2CH2CH2CH3 130 36
Hexane CH3CH2CH2CH2CH2CH3 95 69
Heptane CH3CH2CH2CH2CH2CH2CH3 90 98

However if branching of alkyl chain takes place, its surface area decreases and the molecular forces of
attraction decrease.
e.g. n-Butane B.Pt = 0C CH3CH2CH2CH3 Large Surface area
Isobutane B.Pt = 12C CH3 CH CH3 Smaller surface area
CH3
This shows as branching takes place the molecular force of attraction decreases so boiling point decreases.
Except for very small alkanes, the boiling point rises by 20 to 30C for each carbon atom that is added to the
chain. Being saturated hydrocarbons they are least reactive and most of the reactions correspond to the
C-H bond cleavage which are very strong bonds.

Physical Properties
1. The first four members are colourless gases. The next 13 members (C5 to C17) are colourless liquids
and the higher ones are colourless solids.
2. The boiling points of the straight chain alkanes increases regularly with increase in molecular mass. On
the average boiling point increases by 20-30K, for the addition of each carbon atom (i.e. CH2) group.
Among the isomeric alkanes the boiling point of straight chain isomer is greater than branched chain
isomers
H H H H H
e.g. n-pentane H C C C C C H B.pt. 309 K
H H H H H

CH3
isopentane CH CH2 CH3 B.pt. 301 K
CH3

CH3
Neopentane CH3 C CH3 B.pt. 282.5 K.
CH3

Boiling point order is n-pentane > isopentane > neo-pentane.

However melting point order is Neopentane > Isopentane > n-pentane.
This is because as branching takes place the molecule assumes a spherical form that leads to a much
more closed packing.
3. The melting points of the alkanes do not show a regular trend. In general alkanes with even number of
carbon atoms have a higher melting point as compared to the next alkane with odd number of C-atoms.
This is called alteration effect or oscillation effect.

ABHISHEK TUTORIALS
 3 The Hydrocarbons

4. Alkanes are non-polar and hence are soluble in non-polar solvents but insoluble in solvents such as
water.

Preparations
A. REDUCTION METHODS
1. Hydrogenation of Alkenes and Alkynes :
When unsaturated hydrocarbons are catalytically hydrogenated we get alkane.
H2 + Pt, Pd or Ni
CnH2n CnH2n+2
200 300C

2H2
CnH2n2 CnH2n+2
Ni, Pt or Pd
200 300C

2 H /Ni
e.g. CH2 = CH2 300C CH3 CH3

Ni
CH CH + 2H2 CH3 CH3.
200 300C
In the above reactions, Raney nickel is often used as an effective catalyst. It is obtained by boiling
Ni-Al along with NaOH, when Aluminium dissolves leaving nickel in finely divided state, it is then
filtered and dried. When palladium or platinum is used the reactions can be carried even at room
temperature.
2. Reduction of Alkyl Halides
Zn Cu
(a) R X C H OH R H.
2 5
Mechanism
Zn Zn2+ + 2e
. . . .
R X R + X , R + e R , X + e X

R + H OC2H5 R H + C2H5O
Zn/HCl
(b) R X R H.

Zn/CH3COOH
(c) R X RH

Zn/NaOH
(d) R X RH
[Mechanisms for the reaction (b), (c) and (d) are the same as that of (a)]
LiAlH4
(e) R X
RH

[p and s- alkyl halides give alkanes but t- gives alkenes]

Mechanism

LiAlH4 Li+ + Al3+ + 4H

4R X + 4H 4R H + 4X

Li+ + X Li X

Al3+ + 3X AlX3

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The Hydrocarbons 4

(f) RX NaBH4 RH
[Here s- and t- are converted to alkanes but not p-]
Ph3SnH
(g) R X
RH

[All types of alkyl halides undergo this reaction.]

HI/Red P
RX R H.
3. Reduction of Alcohols
Red P
(a) R OH + HI 150C RH

Red P
CH3CH2 OH + HI CH3 CH3 + I2 + H2O

150C
(b) R OH + LiAlH4 R H + side products

CH3 CH2 CH CH3 LiAlH4

CH3CH2CH2CH3

OH
4. Reduction of Carbonyl Compounds (Aldehydes and Ketones)
(a) Using HI / Red P
Red P CH2 + H2O + I2
C = O + 4HI

CH3 C H + 4HI Red P

CH3 CH3 + H2O + I2

O

CH3 C CH3 + 4HI Red P

CH3 CH2 CH3 + I2 + H2O

O
(b) Clemmensens Reduction: The reduction of carbonyl compounds to alkanes by using Zn-
Hg/HCl is called Clemmensens reduction.

R C = O + 4[H]
Zn - Hg/HCl
R CH3 + H2O

H

CH3 C = O + 4[H] Zn - Hg/HCl CH3 CH3 + H2O.

H
Note: Clemmensens reduction should not be used if the molecule contains NH2 group or any basic
group apart from the carbonyl group.
O O
COOH COOH NH2
Zn - Hg/HCl Do not use ZnHg/HCl.

(c) Wolff Kishner Reduction: It is the reduction of carbonyl compounds to alkanes using hydrazine
in the presence of KOH/glycol. This method is not used if the molecule contains a COOH or
a acidic group apart from the carbonyl functional group.
KOH/glycol
R C = O + NH2 NH2 R C = N NH2 + H2O R CH3
473 K
H H

ABHISHEK TUTORIALS
 5 The Hydrocarbons

NH2 NH2
CH3 C CH3 +
KOH/glycol CH3CH2CH3.
O 473 K

O
NH2 NH2 NH2
NH2
+
glycol/KOH

O SO3 H
SO3 H Do not use wolff Kishner Reduction

5. Reduction of Carboxylic Acids

HI/Red P
RCOOH 150C R CH3

HI/Red P
CH3COOH 150C CH3 CH3.

B. DECARBOXYLATION METHODS
1. Soda Lime Decarboxylation
RCOOH + NaOH RCOONa + H2O
CaO
RCOONa + NaOH 630 K R H + Na2CO3

CaO
CH3COONa + NaOH 630 K CH4 + Na2CO3

2. Kolbes Electrolytic Decarboxylation

The electrolysis of aqueous salt solutions of carboxylic acids give alkane at anode
Electrolysis
2RCOONa + 2H2O R R + 2NaOH + 2CO2 + H2.
Electrolysis
2CH3COONa (aq) CH3 CH3 + 2NaOH + 2CO2 + H2.
Mechanism
R C ONa RCOO + Na+
O
H2O H + OH
Reaction at cathode
Na+ + e Na (Not possible)
1
H+ + e H (Possible)
2 2
(Because the discharge potential of H+ is less than the discharge potential of Na+)
Reaction at anode
4OH 2H2O + O2 + 4e (Not possible)

2R C O
R R + 2CO2 + 2e (Possible)
O

(Because discharge potential of RCOO < OH )

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The Hydrocarbons 6

Detailed reaction at anode Side Reaction

.. . . .
. .: R C O RCOR
RCO . .: + e R + RCOO
O O O

. . OH
R C O R + CO2 RCOR RCOONa + ROH
O O

. .
R +R R R Here ROH is side product: Also proper conjugation effects of
.
R leads to the formation of alkene as side products

. .
(a) CH3CH2 + CH3CH2COO CH3CH2COOCH2CH3

NaOH
CH3CH2COO CH2CH3 CH3CH2COONa + C2H5OH (side product)
.
(b) CH3CH2 CH2 = CH2 + H
. .
CH3CH2 + H CH3 CH3
Hence side products are CH2 = CH2 + CH3CH3 also

Limitation :
1. Methane cannot be perpared by this method
2. Only symmetrical alkanes can be prepared by this method

C. THROUGH FORMATION OF ORGANOMETALLIC COMPOUNDS

1. Wurtz reaction
When alkyl halides are reacted with Na in the presence ether we get alkane.
Dry
2R X + 2Na ether R R + 2NaX.
Other metals in a finely divided state may also be used in place of Na e.g. Cu or Ag.
Dry
2CH3Cl + Na ether
CH3CH3 + NaCl

Limitations
1. Methane cannot be prepared.
2. This reactions is not suitable for preparing unsymmetrical alkanes e.g. propane or pentane etc.
1. Mechanism
Ionic
. .
RX R +X
Na Na+ + e
.
R + e R
.
X + e X

R + Na RNa (organometallic compound)

X + Na NaX
RNa + R X R R + NaX + side products

Note : Side Products are due to elemination reaction on RX by RNa giving a mixture of alkene and
alkane.

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 7 The Hydrocarbons

Free radical Mechanism

. .
RX R +X
Na Na + e
.
X + e X
. .
R +R RR + other side products
The side products are formed are due to hyperconjugation effect.
2. From Grignards Reagent
When grignards reagent is made to react with any compound containing H-atom attached to
highly electronegative atom like O, N or F will give alkane corresponding the alkyl part of Grignards
Reagent.
RMg X + H OH R H + MgX (OH)
R Mg X + H OR R H + MgX (OR)
R Mg X + H NH2 R H + MgX (NH2)
R Mg X + H NHR R H + MgX (NHR)
R Mg X + H O C R R H + MgX O C R
O O
3. Frankland Reaction
RX + Zn R ZnX
The alkyl zinc halide or dialkyl zinc may be isolated and made to react with different alkyl halide
or same alkyl halide.
RZnX + RX R R + ZnX2
(unsymmetrical alkane)
e.g. CH3ZnCl + CH3CH2Cl CH3CH2CH3 + ZnCl2
RZnX + R X R R + ZnX2
(symmetrical alkane)
e.g. CH3ZnCl + CH3Cl CH3CH3 + ZnCl2
Hence Frankland reaction is useful for preparing both hydrocarbons containing odd number of C atoms as
well as even number carbon atom. i.e. for preparing symmetrical as well as unsymmetrical alkanes.
4. Corey House Synthesis
This reaction is very much useful in the preparations of unsymmetrical alkane.
ether
R2CuLi + R X R R + R Cu + LiX.
(unsymmetrical)
ether
R2CuLi + R X R R + RCu + LiX
(symmetrical)
2Li
CH3CH2 Br Dry ether
CH3CH2Li + LiBr.
2CH3CH2Li + CuI (CH3CH2)2CuLi + LiI
CH3 Cl
(CH3CH2)2CuLi CH3CH2 CH3 + CH3CH2Cu + LiCl.
CH3CH2 Cl
(CH3CH2)2CuLi CH3CH2 CH2CH3 + CH3CH2Cu + LiCl.
D. SOME SPECIAL REACTIONS
1. From Carbides :
Al4C3 + 12H2O 4Al(OH)3 + 3CH4.
(steam)
Be2C + 4H2O 2Be(OH)2 + CH4.

ABHISHEK TUTORIALS
The Hydrocarbons 8

2. From carbon monoxide :

Ni + C
CO + 3H2 250C CH4 + H2O
3. From CS2 and H2S :
CS2 + 2H2S + Cu CH4 + 4Cu2S
Red hot light
4. Berthlots reaction :
1200C
C + 2H2 electric spark CH4.
(electrodes)

Chemical Properties
The alkanes are sometimes referred to as paraffins. The reactivity depends upon the choice of reagents. If
alkanes are inert towards hydrochloric acid and sulfuric acid, they react with acids like HFSbF5 and FSO3 H
SbF5 (Magic acid) to form the corresponding fluoro compounds.
Much of the chemistry of alkanes involves free-radical chain reactions. Which takes place under vigorous
conditions and usually yield mixtures of products.
The reactions of alkanes can be classified under the following headings.
(A) Substitution reactions
(B) Combustion reactions
(C) Special reactions.

A. SUBSTITUTION REACTIONS
1. Halogenation
250 - 400C
C H + X2 C X + HX.
or light

CH4 + X2 U.V. CH3 X + HX.

(excess)

CH4 + X2 U.V. CH3 X CH2X2 CHX3 CX4

(excess)
Complete Sunlight
CH4 + 2X2 C + 4 HX.
diffused
CH3 CH3 + Cl CH3CH2 Cl + HCl.
(excess)
2 sunlight
diffused
CH3 CH3 + Cl2 CH3CH2Cl + mixture of products
(excess) sunlight
diffused
i.e. CH3 CH3 + Cl2 CH3 CH2 Cl + CH3CHCl2 + CH2 CH2 + CH3CCl3 +
(excess) sunlight
Cl Cl
CH2 CHCl2 + CH2 CCl3 + CHCl2 CCl3 + CCl3 CCl3.
Cl Cl
Mono halogenation of propane and Butane
CH3CH2CH2 Cl 45%
hv
CH3CH2CH3 + Cl2
CH3 CH CH3 55%
Cl

hv CH3CH2CH2 Cl 28%
CH3CH2CH2CH3 + Cl2 hv
CH3CH2 CH CH3 72%
Cl

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 9 The Hydrocarbons

hv CH3 CH CH3 (major) (96.5%)

CH3CH2CH3 + Br2 hv Br
CH3 CH2 CH2 Br (minor) (3.5%)

Hence these reactions show that the reaction depends upon the abstracting power of the halogen atoms as
well as the number of H-atoms present in the organic molecule.

The abstracting power of the halogen atoms refers to the selectivity factor which includes the HX bond
energy as well as bond dissociation energy of the CH bond.

Mechanism of Halogenation of CH4 (monohalogenation)

diffused
CH4 + X2 sunlight CH3X + HX
.
Initiation Step - I X2 2X .....(i)
. hv .
Propogation Step - II X + CH3 H CH3 + HX .....(ii)
. .
CH3 + X X CH3X + X .....(iii)
. .
X + CH3 H CH3 + HX .....(iv)
.
In this whole reaction the reactive species is CH3 . The formation depends upon the abstracting power of
halogen which in turn depends upon the bond strength of HX formed. Which is HF > HCl > HBr > HI and
also bond dissociation energy of X2 which is Cl2 > Br2 > F2 > I2.

Reactivity of halogen is
Reaction reversible and highly endothermic, so moves more
F2 > Cl2 > Br2 > I2 in backward direction

(reacts explosively)
. .
Termination Step-III The free Radicals present in the reactions are CH3 and X . The different
ways in which they can combine for terminating the reaction is
. .
CH3 + X CH3 X
. .
CH3 + CH3 CH3 CH3
. .
X +X X2
Reactivity of different H-atom
The general order of reactivity of different H-atoms is tertiary -H > secondary-H > primary-H because the
stabilities of the corresponding free radicals are tertiary free radical > secondary free radical > primary free
radical
The basic reactivity of H-atom is tertiary > secondary > primary but their reactivity ratio with chlorine or
bromine differs.
p:s :t
The reactivity order with chlorine 1 : 3.8 : 5
The reactivity order with Bromine 1 : 82 : 1600
The reaction of alkane with I2 can be performed by addition of oxidising agents like HNO3 or HIO3.
CH4 + I2 CH3 I + HI
This reaction is highly reversible with reactions proceding more in backward direction. But on adding HNO3
or HIO3 the HI gets oxidised to I2 thereby preventing the reduction of CH3-I to CH4.

ABHISHEK TUTORIALS
The Hydrocarbons 10

Ex. Calculate the % of yield of A and B in the following reactions.

CH3CH2CH3 + Cl2 hv CH3CH2CH2 Cl + CH3 CH CH3 A = p-Alkyl chloride
Cl B = s-Alkyl chloridse
(A) (B)
Here the different types of H-atoms are p- and s- types :
a) Reactivity p : s H-atoms to chlorine (selectivity) 1 : 3.8
b) Number of such atom available 6:2
Yield ratio 6 : 7.6 (obtained by multi playing selectivity
factor with availability factor).
6
Percentage of 1- chloropropane = 100 % = 44.1% approximately
13.6
7.6
Percentage of 2- chloropropane = 100 % = 55.88% approximately
13.6

Ex. Calculate the percentage yield of 1-bromopropane (primary) and 2-Bromo propane (secondary)
in the following reaction.
hv
CH3CH2CH3 + Br2 CH3CH2CH2 Br + CH3 CH CH3
Br
p:s
a) Reactivity of H-atom with Bromine (Selectivity) 1 : 82
b) Number of such H-atom 6:2
c) Yield ratio 6 : 164
6
Percentage of 1-bromo propane = 100 = 3.5%
170
164
Percentage of 2- bromo propane = 100 = 96.5%
170

Laboratory Chlorination
The laboratory chlorinations are usually done using SO2Cl2 (sulphuryl chloride) in the presence of alkyl
peroxides as initiator.
R H + SO2Cl2 ROOR R Cl + SO2 + HCl.
.
Initiation Step - I ROOR 2R O
. .
Step - II R O + R H R OH + [R
. .
Propogation Step - III [R + SO2Cl2 RCl + S O2Cl
. .
Step - IV SO 2Cl SO2 + Cl
. .
Step - V Cl + R H [R + HCl.

Then there is repeatition of step III, IV and V.

Termination :
. . . .
The different free radicals are R , S O2Cl and Cl , R O which can combine in many ways.

Evidence in support of free radical mechanism

(i) Effect of U.V. light :
The reaction does not take place at room temperature. This is because energy is needed to
cleave chlorine molecule homolytically into chlorine free radical.

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 11 The Hydrocarbons

(ii) Effect of number of photon :

For each photon or quantumn of light used, several thousand molecules of alkylhalide are formed.
(iii) Effect of Tetraethyl Lead :
It has been observed that if 0.02% of tetra ethyl lead is added to reaction mixture, chlorination of
methane takes place at 140C. This is because at 140C tetra ethyl lead decomposes to give free
radicals which cleave Cl2 molecule into Cl free radical.
Pb(C2H5)4 140C .
4C2H5 + Pb
. .
C2H5 + Cl2 C2H5Cl + Cl
(iv) Effect of Adding Inhibitors :
Inhibitors are substances which slow down the rate of reaction even when present in small amounts.
It has been observed that when a small amount of oxygen is added in the reaction mixture, halogenation
of alkanes slows down due to the formation of less reactive peroxy alkyl free radical.
. .
R + O = O ROO
Peroxyalkyl free radical
2. Nitration :The reaction in which H atom of an alkane is substituted by nitro group (NO2) is called
nitration.
High
R H + HO NO2 R NO2 + H2O
Temp. Nitroalkane
Alkane
Normally hexane and higher alkanes can be Nitrated very easily but will give many side products
H3C (CH2)4 CH3 + HNO3 H2O + H3C (CH2)4 CH2 NO2
Hexane Nitrohexane

Recently, developed technique of vapour phase nitration, has made nitration of lower alkanes
possible. But the vapour phase nitration also causes cleavage of CC bond and results in the
formation of more than one nitro compounds,
V.P.
H3C CH3 + HNO3 H3C CH2 NO2 + H3C NO2
500C
Ethane Nitroethane Nitromethane

V.P.
H3C CH2 CH3 + HNO3 H3C CH2 CH2 NO2 + H3C CH CH3
Propane 500C 1-Nitropropane
NO2
2-Nitropropane

+ H3C CH2 NO2 + H3C NO2

Nitroethane Nitromethane
3. Sulphonation : The reaction in which H atoms of alkanes are replaced by sulphonic group (SO3H)
is called sulphonation.

H3C (CH2)4 CH2 H + HO SO2OH 400C H3C (CH2 )4 CH2 SO3H + H2O
Hexane
SO3 Hexanesulphonic acid
(conc.)
The mixture of H2SO4 + SO3 =H2S2O7 is called as oleum or Fuming sulphuric acid.
4. Oxidation of alkanes :
(a) Combustion (complete oxidation).
Like other organic compounds alkanes on complete combustion from CO2 and H2O.
CH4 + 2O2 CO2 + 2H2O
Methane

7
C2H6 + 2 O2 2CO2 + 3H2O
Ethane

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The Hydrocarbons 12

(b) Controlled Oxidation

(i) When alkane is oxidised at 250C under 100 atm. in the presence of Cu, an alcohol is
formed.
1 Cu/250C CH3OH
CH4 + 2 O2
Methane 100 atm. Methane

(ii) Methane on oxidation in the presence of molybdenum oxide forms formaldehyde (HCHO)
CH4 + O2 Mo2O3 HCHO + H2O
Methane 270C, 100 atm Formaldehyde

(iii) Alkanes on oxidation in the presence of manganese acetate forms an acid.

3 (CH3COO)2Mn
R CH3 + O2 High pressure RCOOH + H2O
2 Acid

3 (CH3COO)2Mn CH3 COOH + H2O

CH3 CH3 + O High pressure
2 2 Acetic acid

(c) Chemical oxidation :

Alkanes are usually not affected by oxidising agents like KMnO4 or K2Cr2O7, but, alkanes
having 3 H atoms are easily oxidised by these oxidising agents to alcohols.
H3 C H3 C
KMnO4
H3 C C H + [O] H3 C C OH
H3 C H3 C
Isobutane tert. butyl alcohol

Special Reactions
(i) Isomerisation :
The process of conversion of one isomer into an other is called isomerisation.
CH3
AlCl3 + HCl
H3C CH2 CH2 CH3 H3C CH CH3
Butane 200C, 35 atm. Isobutane

(ii) Aromatisation :
The conversion of aliphatic compounds into aromatic compounds is known as aromatisation.
CH3
H2 C CH3 Cr2O3/Al2O3
+ 4H2
H2 C CH3 600C/15 atm.
CH2 Benzene (C
6 H6 )
Hexane (C6H14 )

(iii) Reaction with nitrogen :

electric 2HCN + 3H
2CH4 + N2 spark Hydrogen cyanide 2

(iv) Action of steam :

CH4 + H2O Ni/Al2O3
(steam) 800C
CO + 3H2

(v) Insertion of methylene.

Methylene can beinserted into any CH bonds of alkanes yielding higher alkanes.
Sunlight
CH3CH2CH2CH3 + CH2N2 CH3CH2CH2 CH2CH3 + CH3 CH CH2 CH3
Diazomethane N2 n-pentane
CH3
Isopentane

ABHISHEK TUTORIALS