1.

Alkane
General methods of preparation :
(1) By catalytic reduction of alkenes and alkynes :
H , 25 C
R – C  C – R  2  
 R – CH2 – CH2 – R
Ni, Pt or Pd
2 H , 25C
R – CH = CH – R    
 R – CH2 – CH2 – R
Ni, Pt or Pd
Hydrogenation  Addition of H2 to unsaturated bond.
Hydrogenation is of two kinds
(a) Heterogeneous (b) Homogeneous
(a) Heterogeneous : It is two phase hydrogenation the catalyst is finely devided metal like Ni, Pt or Pd and
a solution of alkene.
(b) Homogeneous : It is one phase hydrogenation both catalyst and alkenes are in solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, quantitative and during the hydrogenation, total heat evolved to hydrogenate
one mole of unsaturated compound is called heat of hydrogenation. Heat of hydrogenation is the measurment
of stability of isomeric alkenes.
1
stability of alkene  Heat of hydrogenat ion
Note : Hydrogenation of alkene or alkyne in presence of metal catalyst is syn addition

Pd Pd
(a) + H2 
 (b) + H2 

CH3 COOH CH3 COOH

(Meso) (Racemic mixture)

(2) From alkyl halide :
(i) By wurtz reaction :
dry ether
2R – X + 2Na    R – R + 2NaX
Na
R – X + R – X    R – R, R – R, R – R
ether ( dry )

Mechanism  Two mechanisms are suggested

(a) Ionic mechanism
2Na  2Na  +

R  X + 2e¯ 
(1 , 2)

S 2 R–R
N

 NaX
(b) Free radical mechanism

Na 

R–X +  R  +
R  + R   R – R
JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 343
Note : The alkyl halide should be 1° or 2°, with 3° R – X SN2 and free radical coupling is not possible due to
steric hinderence so in that case elimination or disproportionation is possible.

In the ionic mechanism alkyl sodium gives strong base as well as nucleophile which gives SN2

with R – X, ether should be dry otherwise if moisture is present than forms R – H instead of R – R with H2O.
Na
(a) CH3 – CH2 – Br  CH3 – CH2 – CH2 – CH3
Na
(b) CH3 – Cl + CH3 – CH2 – Cl  CH3 – CH3 + CH3 – CH2 – CH3 + CH3 – CH2 – CH2 – CH3
(ii) By reduction of alkyl halides :
(A) with metal-acid

RX R – H + HX
1
Reducing agent
Zn / HCl , Zn – Cu / H2O or Zn – Cu + CH3COOH
Zn – Cu / C2H5OH, Na – Hg / HCl, Al – Hg / H2O etc.
(B) With metal hydrides
(a) TPH (Ph3SnH) Triphenyltin hydride : It reduces 1°, 2° & 3° R – X
3Ph SnH
R–X    R – H

1º / 2º / 3º

4 NaBH
(b) NaBH4 : R  X    R – H
2 & 3

4 LiAlH 4 LiAlH
(c) LiAlH4 : R  X    R–H ; R  X    Alkene
1 & 2 3

(3) From organometallic compound :

(i) By Grignard Reagent.
Mg
RX   RMgX
ether
1, 2 3

all active
RMgX + H containg  R – H
compound

H2O
R–H + Mg (OH) X
ROH
R–H + Mg (OR) X
RMgX NH3
R–H + Mg (NH2) X
R – C  CH
R–H + Mg (C  CR) X
RSH
R–H + Mg (SR) X
R – COOH
R–H + Mg (OCOR) X

(ii) By Corey House alkane synthesis ;

R  X
2Li CuX R 2CuLi (1  2)
RX 
      R – R
Lithium dialkyl
(1, 2, 3)
cuprate (Gilman ' s reagent )

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 344

Mechanism

R2CuLi is the source of R

R – R

R2CuLi does not reacts with – NO2, – CN, etc.

(iii) By Franklands reagent :

Ether
R – X + Zn + R – X  
 R – R + Zn X2

(4)From carboxylic acids:

(i) By soda lime :
Fatty acids are good source of hydrocarbon, continuous heating of sodium salt of carboxylic acid (R –
COONa) with soda lime (NaOH – CaO) gives hydrocarbon, this process is known as decarboxylation (e.g.
replacement of – COOH group by – H) decarboxylation also takes place on heating only, when compound is
gem dicarboxylic acid or there is keto group or double bond on  carbon.
NaOH CaO
R  C  OH     R – H + Na CO
 2 3
||
O
(ii) By Kolbe’s electrolysis :
Electrolysis
2RCOOK + 2HOH   
 R – R + 2CO2 + H2 + 2KOH

Mechanism
R CO2K R CO2– + K+
At Anode: - R CO2–  R CO 2 + e– (oxidation)
(I)
R CO 2  R  + CO2
(II)
 
R + R  R – R

If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n–1) carbon atoms.
Electrolysis
e.g. 2CH3 – COOK + 2H2O   
 CH3CH3 + 2CO2 + H2 + 2KOH.

(5) By Reduction :
(i) By Clemmensen’s reduction (Zn – Hg / conc. HCl):
Zn  Hg / conc . HCl
R – CHO      RCH3 + H2O
O
||
Zn  Hg / conc . HCl
R  C  R      RCH2R + H2O
Zn  Hg / conc . HCl
e.g. CH3 – CHO     
 CH3CH3 + H2O

O
||
Zn  Hg / conc . HCl
CH3  C  C 2H5 + 4[H]      CH3CH2C2H5 + H2O

Clemmensen reduction is not used for compounds which have acid sensitive group.

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 345

(ii) By Wolff-kishner reduction (NH2NH2 / KOH) :
2 2 NH NH / KOH
RCHO     RCH3


NH2NH2 / KOH
RCO – R    
 RCH2R


Wolff-kishner reduction is not used for compounds which have base sensitive groups.

Zn  Hg / conc . HCl
eg.     


Clemmemsen’s reduction can be can be used to reduce the given compounds.

(iii) By Red P & HI :
Red P & HI is a strong reducing agent
Re d P  H I Re d P  H I
(a) R – COOH     R – CH3 ; (b) R  C  Cl      R – CH
3
||
O
Re d  H I
(c) R  C  OEt  P  R – CH ; (d)
Re d P  H I
R – X     R – H
3
||
O
Re d  H I
(e) R – OH  P  R – H

Physical Properties of Alkanes :

Physical state :
The first four members (C1 to C4) are gases ; the next thirteen members, (C5 to C17) are liquids while the
higher members are waxy solids.
Boiling points :
The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms.

Among the isomeric alkanes, the branched chain isomers have relatively low boiling points as compared to
their corresponding straight chain isomers. Greater the branching of the chain, lower is the boiling point. This
is due to the fact that branching of the chain makes the molecule more compact and brings it close to a
sphere, so the magnitude of vander wall forces decreases.
Melting Point :
It is evident that the increase in melting point is
relatively more in moving from an alkane having odd
number of carbon atoms to the higher alkane with
even no. of ‘C’ while it is relatively less in moving
from an alkane with even number of carbon atoms
to the higher alkane.

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 346

Solubility :
In keeping with the popular rule “like dissolves like” hydrocarbons are insoluble in polar solvent like water
because they are predominantly non-polar in nature.
Density :
The densities of alkanes increase with increasing molecular weight but become constant at about
0.8 g cm–3. This means that all alkanes are lighter than water.
Chemical Reactions of Alkanes :
Characteristic reaction of alkanes are free radical substitution reaction, these reactions are generally
chain reactions which are completed in three steps.
(i) chain initiation (ii) chain propagation. (iii) chain termination
Halogenation :
UV Light or temp
R – H + X2          R – X + HX
250  400C
Mechanism :
(i) Chain initiation  it is an endothermic step.
UV or temp. •
X2        2 X
250   400 C
(ii) Chain propagation 
• •
X + R – H  R + HX
• •
R + X – X  R – X + X
(iii) Chain termination  it is always exothermic
• •
X + X  X2
• •
R + R  R – R
• •
R + X  R – X

Steps of halogenation, Value of H for each step. (Kcal/mole)

F Cl Br I
•
(i) X2  2 X + 38 + 58 +46 +36
• •
(ii) X + CH4  C H3 + HX – 32 +1 + 16 + 33

• •
(iii) C H3 + X2  CH3X + X – 70 – 26 – 24 – 20
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3°H > 2°H > 1° H
With F2 alkanes react so vigorously that even in the dark and at room temperature, reactant is diluted with an
Inert gas. Iodination is reversible reaction, since HI formed as a by product and It is a strong reducing agent
and reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidising
agent like HIO3, HNO3 or HgO.
R – H + I2 R – I + HI

5HI + HIO3  3H2O + 3I2

2HI + HgO  I2 + H2O + Hg

2HI + 2HNO3  I2 + 2H2O + NO2
Formation of alkyl free radical is rate determining step.

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 347

Order of stability of Free radical 
• • • •    •
Ph 3 C > Ph2 C H > Ph  C H2 > CH2  CH  C H2 > (CH3)3 C > (CH3)2 CH > CH3 CH 2 > C H3
Cl2 Cl Cl Cl
eg. CH4   CH3Cl 2
  CH2Cl2 2
  2
CHCl 3   CCl4
h  h h h 
 
HCl HCl HCl HCl

When equimolar amount of methane and Cl2 is taken, a mixture of four possible products are formed, but
when we take excess of CH4 then yield of CH3Cl will be high.
Each photon of light cleaves one chlorine molecule to form two chlorine radicals, each chlorine atom starts
a chain and on an average each chain contains 5000 repeatitions of the chain propagating cycle so about
10,000 molecules of CH3Cl are formed by one photon of light.
In a chain reaction following reagents are involved -
(i) Initiators  they initiate the chain reaction, Initiators are peroxide (R2O2), Perester's etc.
•
h
R – O – O – R 
 R O
or 

•
h
R C O O C R  R  C  O
|| || or  ||
O
O O
(ii) Inhibitors  A substance that slows down or stops the reaction is known as inhibitors
For example O2 is a good inhibitor
• • •
R + O2  R  O  O + R  R – O – O – R
all reactive alkyl free radicals are consumed so reaction stops for a period of time.
Relative reactivity of halogen towards methane 
Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (enthalpy change)

Halogenation of higher alkane :

2 Cl
(a) CH3 – CH2 – CH3    CH3  CH  CH3 + CH3  CH2  CH2  Cl
light , 25 C
|
Cl 45%
55%

2 Cl
(b) CH3 – CH2 – CH2 – CH3  CH3  CH2  CH  CH3 + CH3  CH2  CH2  CH2  Cl
light , 25C |
Cl 28%
72%

CH3
Cl2 |
(c) CH3  CH  CH3  CH3  CH  CH2  Cl + CH3  C  CH3
light , 25C
| | |
CH3 CH3 Cl
64% 36%

Br 2
(d) CH3 – CH2 – CH3     CH3  CH2  CH2  Br + CH3  CH  CH3
heat, 127C
|
3% Br
97%

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 348

 CH3
|
2 Br
(e) CH  CH  CH     CH3  CH  CH2Br + CH3  C  Br
3 3 heat, 127C
| | |
CH3 CH3 CH3
trace over 99%

Relative amounts of the various isomers differ remarkably depending upon the halogen used. From the above
reaction, it is observed that chlorination gives mixture in which no isomer greatly dominates while, in bromination
gives a mixture in which one isomer dominates greatly (97% – 99%),
Factors affecting the relative yields :
Factors determining the relative yields of the isomeric products.

(i) Probability factor : This factor is based on the number of each kind of H atom in the molecule.
(ii) Reactivity of hydrogen : The order of reactivity is 3° > 2° > 1° the relative rate per hydrogen atom is
found to be

(iii) Reactivity v/s selectivity principle 

The more reactive is halogen less selective it will be, so the more reactive chlorine free radical is less
•
selective and more influenced by the probability factor and the less reactive B r is more selective and less
influenced by the probability factors.
Based on relative reactivity of different types of H, percentage of each in the product mixture can be calculated.

e.g.

6 15.2
% yield A = × 100 = 28.3 % ; % yield B = × 100 = 71.%
21.2 21.2

Sulphonation :
Lower alkanes are not easily sulphonated but hexane & higher members are sulphonated on heating with
oleum (conc. H2SO4 + SO3) at 400°C
400C
C6H14 + H2SO4   C6H13SO3H + H2O

Isomerisation :
Anhyd . AlCl / HCl
3
CH3CH2CH2CH3     
 CH3  CH  CH3
300C
|
CH3
Isobu tan e

CH3
|
AlCl3 / HCl
CH3 – (CH2)3 – CH3 300
   CH3  C  CH3
C
|
CH3
Neopentane

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 349

Alkylation :
Isoalkanes add to isoalkenes in presence of conc. H2SO4 or HF to give higher branched alkane

CH3 CH3
| |
CH3  C  H + H C  C  CH conc. H SO4
2 3   2  CH3  C  CH2  CH  CH3
| | | |
CH3 CH CH3 CH3
3
Isobu tane Isooc tan e
Isobutene
Aromatisation :
Alkanes containing 6 or more number of C atoms are oxidised (dehydrogenate & cyclised) in presence of
oxidising agent at higher temparature and form benzene or its derivatives.

Cr O  Al O
CH3 – (CH2)4 – CH3 23 
2 3
 + 4H2
600C
High P

Cr O  Al O
CH3 – (CH2)5 – CH3 23 
2 3

600C
High P

Cr O  Al O
CH3(CH2)6CH3 23 
2 3
 +
600C
High P

CH3
| Cr O  Al O
CH3  (CH 2 ) 4  CH  CH3 23 
2 3

600C
High P

CH3
| Cr O  Al O
CH3  (CH 2 )3  CH  CH2  CH3 23 
2 3

600C
High P

Pyrolysis / Cracking :
CH3 – CH2 – CH3 CH3CH3 + CH3CH = CH2 + CH2 = CH2+ CH4 + H2

Higher alkanes are heated in absence of air so these compounds break down into smaller alkanes which are
better fuel. Mixture of products contains all lower alkanes, alkenes & hydrogens.

Combustion :
 3n  1  combustion
CnH2n+2 +   O     nCO2 + (n + 1) H2O (Hcombustion = -ve)
 2  2 
exothermic reaction
 y combustion y
CxHy +  x   O2     xCO2 + HO
 4  2 2
combustion
C5H12 + 8O2     5CO2 + 6H2O


JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 350

Heat of combustion :
Amount of heat liberated when 1 mole of hydrocarbon is completely burnt into CO2 & H2O.
 H of combustion is a measurement of stability of alkane :
Combustion is used as a measurment of stability.
More branched alkanes are more stable and have lower heat of combustion.

CH3
|
e.g. CH3 – CH2 – CH2 – CH3 CH3  C  CH3
|
I H
II

Hcomb. : I > II
Stability : II > I
Points to remember for H of combustion :
Homologes : Higher homologes have higher heat of combustion.
CH4 < C2H6 < C3H8
Isomers : Branched isomer has lower heat of combustion.More branched alkane has more no. of primary
C – H bonds. (therefore it has more bond energy).

> >

Cyclo-alkanes : More strained ring has higher heat of combustion per – CH2 – unit.

> > > (Hcomb. per ‘CH2’ unit)

Octane Number :
It is a scale of fuel efficiency when the fuel burns during combustion, more branched alkanes have lower
knocking (cracking sound). so are better fuels. On commercial scale iso-octane has been alotted a rating
i.e. octane no. of Isooctane is 100 & n-heptane is - ‘0’

If the octane no. of a fuel is 80, it means that the efficiency of the fuel is equivalent to the efficiency of mixture
of 80% isoctane and 20% n-heptane.

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 351

 Miscellaneous Solved Problems

1.

Sol. In all cases product is

2. Arrange the following alkenes in decreasing order of their stability

R2C = CR2, CH2 = CH2, R2C = CH2, R – CH = CH – R (cis, trans), R2C = CHR, RCH = CH2

Sol. R2C=CR2 > R2C = CHR >R2C = CH2 > R  CH  CH  R > RCH  CHR > R – CH = CH2 > CH2 = CH2
trans cis

3. What is the order of stability of following alkene

CH3
|
CH3  CH  CH  CH2 , CH2  C  CH2  CH3 , CH3  C  CH  CH3
| |
CH3 II CH3
I III
Ans. III > II > I
Sol. Stability of alkene  Hyperconjugative Structure.

Na
4. C2H5Cl   products
Ether
Write all possible product

Sol. CH3 – CH2 – Cl  CH3  CH2  CH2  CH3

major

CH3 – CH2 – Cl CH3  C H2
coupling
   CH3 – CH2 – CH2 – CH3

disproportion
    CH3 – CH3 + CH2 = CH2

5. Wurtz reaction will not be observed in

(A) (B) (C) CH3  CH  Br (D) none of these

|
CH3
Ans. B

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 352

Sol. Na + H2 gas


Li CuI Y
6. CH3 – Br  A  B  C
if C is CH3 – CH2 – (CH2)5 – CH3, than what is Y.
Ans. CH3 – (CH2)6 – Br
Li CuI
CH3 – (CH2 )5 – CH2 – X
Sol. CH3 – Br  CH3Li  (CH3)2CuLi     CH3 – CH2 – (CH2)5 – CH3

 NaOH
7.  A   B
CaO / 

What are A and B

Sol. A is , B is

8. Explain why the chain initiating step in thermal chlorination of CH4 is

• • •
 
Cl2  C l and not CH4  C H3 + H
Sol. Because Eact of Cl2 is less than Eact of CH4

9. Chlorination of CH4 involves following steps :

•
(i) Cl2  2 Cl
• •
(ii) CH4 + C l  C H3 + HCl
• •
(iii) C H3 + C l  CH3Cl

Which of the following is rate determining ?

(A) Step (i) (B) Step (ii) (C) Step (iii) (D) Step (ii) and (iii) both
Ans. B
Sol. Formation of alkyl free radical is Rds step.

JEE(Main + Advanced) Hydrocarbons (Alkane, Alkene & Alkyne) # 353