SOLVED EXAMPLES

Example 1 :What are the products formed during the monohalogenations of ethane in the presence of
diffused sunlight.
Solution : The monohalogenation of ethane proceds via free radical mechanism as follows :
CH3 CH3 + Cl2 hv CH CH Cl + HCl .
3 2 . .
During such a mechanisms the different free Radicals formed are CH3 CH2 and Cl
During the termination process these free radicals combine as follows
. .
CH3 CH2 + CH3 CH2 CH3 CH 2 CH2 CH3
. .
CH3 CH2 + Cl CH3 CH2Cl
. .
Cl + Cl Cl Cl
. .
CH3 CH2 CH2 = CH2 + H
. . CH3 CH3
CH3 CH2 H
. .
H + Cl HCl

Hence apart from CH3CH2 Cl the other products would be CH2 = CH2, CH3CH2CH2CH3,
CH3CH3 and HCl.

Example 2 : What happens when an alkane is reacted with tertiary butyl hypochlorite. (t-BuOCl). Explain
Solution : When an alkane is reacted with t-Bu OCl an alkyl chloride is obtained
R H + (CH3)3 COCl R Cl + (CH3)3 COH

Mechanism
CH3 CH3
. .
CH3 C O Cl CH3 C O + Cl
CH3 CH3

CH3 CH3
. .
CH3 C O + R H CH3 C O H + R
CH3 CH3

CH3 CH3
. .
R + CH3 C O Cl R Cl + CH3 C O
CH3 CH3

Example 3 : Which of the following species have not been identified. Explain the bonding.

CH3 and CH5

Solution : Both the species CH3 and CH5 have been detected.

Every one is aware of CH3 and CH3 but then bonding is as follows.
The electronic configuration of carbon is
1s2 2s2 2px 2py

ABHISHEK TUTORIALS
 64 The Hydrocarbons

1s 2s 2p
E.S.

But in CH3 one electron is less hence the electronic configuration is

ES. (Carbon)

H sp2

S - obitar
CH
sp2 HO

We have therefore 3 sp2s overlap with the sp2 HOs of carbon and s AO of H.

In CH5 it contains 3-identical bonds of sp2s overlap of carbon and hydrogen.
Each lobe of carbons remaining p-AO bonds with one H each above and below the plane of
the carbon and the three Hs.
H
P

S
C 2 H
sp S
S P

Example 4 :Among CH4 and CD4 which is more reactive towards chlorine and why ?
Solution : CH4 reacts approximately ten times faster than tetradeutro methane CD4.
This is because C D bonds are stronger than C H bonds.

Example 5 :Complete the following equations

Mg
(a) Cl CH2 CH2 CH2 Cl
Mg
(b) Cl CH2CH2CH2CH2Cl

3CH(Br)CH Zn
(c) CH2 CH(Br)CH
3

CH2
Solution : (a) CH2 CH2 This reactions is called (Freunrd reactions)

CH2 CH2
(b) This reactions again is called (Freunrd reactions)
CH2 CH2

CH3
CH
(c) CH2
CH
CH3

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The Hydrocarbons 65

Example 6 :An alkane (A) C5H12 on chlorinations at 300C gives a mixture of four different monochlorinated
(B), (C), (D) and (E). Two of these derivatives give the same stable alkene (F) on
dehydrahalogenation. On oxidation with hot alkaline KMnO4 followed by acidification (F),
gives two products (G) and (H). Give structure of (A) to (H) with proper reasoning.
Solution : 1. Alkane (A) C5 H12 on chlorination gives four monochloro product and hence it should be
isopentane.
CH3 CH CH2 CH3

CH3

n-Pentane would give 3-mono chloro Products and neopentane gives only one mono
chloro product
Cl Cl
CH3 CH CH2 CH3 Chlorination CH2 CH CH2 CH3 CH2 C CH2 CH3
(B) (C)
CH3 CH3 CH3

Cl
CH3 CH CH CH3 CH3 CH CH2 CH3
(D) (E)
CH3 CH3

(B) CH2 CH CH2 CH3 Dehydrohalogenation CH2 = C CH2 CH3

Cl CH3 CH3

Cl
CH3
(C) CH3 C CH2 CH3 Dehydrohalogenation C = CH CH3
CH3 CH3 Major

CH3
(D) CH3 CH CH CH3 C = CH CH3
CH3
CH3 Cl (F)

(E) CH3 CH CH2 CH2 Cl CH3 CH CH = CH2

CH3 CH3
CH3 KMnO4 CH3
CH3 C = CH CH3 CH3 C = O + CH3 COOH
(G) (H)

Example 7 :Optically active 2-Iodo butane on treatments with NaI in acetone gives a product which does
not show optical activity. Explain.
Solution : The C-I bond is broken and reformed to give racemic mixture of 2-Iodo butane. Presence of
I provides opportunities for making of the CI bonds.
CH3 CH3 CH3
Na I ICH
HCI H CI +
acetone
C2 H5 C2 H5 C2 H5

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 66 The Hydrocarbons

Example 8: A certain compound A has a molecular formula C6H13Br. When reacts with Mg metal in
anhydrous ether, a Gringnards reagent is formed which upon hydrolysis with acid produces the
compound n-hexane as a product. When the compound A reacts with sodium metal in a Wurtz
reaction, the product obtained is 4, 5-diethyl octane. What is A ? Draw its structure and give its
IUPAC name.
Mg H2O
Solution : 1. C6H13Br Dry ether
C6H13MgBr C6H14
H+
n-hexane
2. Wurtz reaction involves coupling of 2 moles of an alkyl halide to give an alkane. Since the
alkane is 4, 5-diethyloctane, i.e.
CH3 CH2 CH2 CH CH CH2 CH2 CH3
C2H5 C2H5

The alkyl halide must be CH3CH2CH2CHBr C2H5 i.e., 3-Bromohexane. Thus :

Dry ether
CH3 CH2 CH2 CH Br + 2Na + Br CH CH2 CH2 CH3
C2H5 C2H5

CH3 CH2 CH2 CH CH CH2 CH2 CH3

C2H5 C2H5

Example 9: a) Arrange the following compounds in order of their increasing boiling points ? n-pentane,
2-methyl pentane, n-hexane, 2,2-dimethyl pentane, ethane.
b) An unknown alkyl halide, C4H9Br, reacts with sodium to give a hydrocarbon C8H18. The
hydrocarbon is shown to be identical to that produced by the Kolbes electrolysis of the
sodium salt of the acid CH3 CH CH2 COOH
CH3

What are the structures of the hydrocarbon and the alkyl halide ?
c) Give the structural formulae and names for all dibromo derivatives of propane.
Solution : a) Ethane < Pentane < 2-Methyl pentane < n-Hexane < 2, 2-Dimethyl pentane
This is because the boiling point is directly propotinal to molecular forces of attraction
which in turn being vander waals is directly proportional to surface area.
Dry ether
b) RI + 2Na + IR R R + 2NaI (Wurtz reaction)
Electrolysis
2RCOONa + 2H2O R R + CO2 + 2NaOH + H2

The sodium salt of the acid, CH3 CH CH2 COOH should give alkane
CH3

2H3C CH CH2 COONa + 2H2O Electrolysis H3C CH CH2 CH2 CH CH3 + 2CO2 + 2NaOH + H2
CH3 CH3 CH3

This alkane with molecular formula C8H18 (2, 5-dimethylhexane) can be obtained by
Wurtz synthesis by coupling 2 moles of CH3 CH CH2 Br i.e. Isobutylbromide
CH3

2CH3 CH CH2 Br + 2Na Dry ether CH3 CH CH2 CH2 CH CH3 + 2NaBr
CH3 CH3 CH3
Thus the alkyl bromide C4H9Br is Isobutyl bromide (1-Bromo-2-methylpropane).

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The Hydrocarbons 67

c) The two Brs are placed first on the same carbon and then on different carbons.
Propane : CH3CH2CH3
Br Br
(i) Br CH CH2 CH3 (ii) CH3 C CH3
1,1-Dibromopropane
Propylidene dibromide
Br
2,2-Dibromopropane
Isopropylidene dibromide

Br
(iii) Br CH2 CH CH3 (iv) BrCH2CH2CH2 Br
1,2-Dibromopropane 1,3-Dibromopropane
Propylene dibromide Propane , - dibromide component

Example 10: A 1.37 g sample of n-butyl bromide was converted to the Grignards reagent. What volume of
butane, measured over water at 20C and at 750 mm pressure will be produced on addition of
water to the Gringnards reagent ? Aqueous tension at 20C is 17.4 mm.

Dry ether
Solution : C4 H9Br + Mg C4 H9 MgBr
n-Butyl bromide Butyl magnesium bromide
1 mole

C4 H9 Mg Br + HOH C4 H10 + Mg (OH)Br

H OH Butane
1 mole (22.4 L at NTP)

Given weight of n-butyl bromide = 1.37 g

Molecular weight of n-butyl bromide = 12 4 + 1 9 + 80 = 48 + 9 + 80 = 137
m 1.37
No. of moles of n-butyl bromide = = = 0.01 mole
M 137

1 mole of n-butyl bromide gives butane = 0.01 mole

Hence volume of 0.01 mole of butane at 750 mm pressure and temperature 293 K = PV = nRT
nRT
V=
P
732 .6
n = 0.01, R = 0.082, P = (750 17.4) = 732.6 mm = 760 atm., 293K

0.01 0.082 293 760

= 0.24934 litre = 249.24 ml.
732.6

Example 11: A certain hydrocarbon (A) was found to contain 85.7% carbon and 14.3% hydrogen.This
compound consumes 1 mole of hydrogen to give a saturated hydrocarbon (B) 1 g of hydrocarbon
(A) just decoloursed 38.05 g of a 5% solution by weight of Br2 in CCl4. Compound (A) on
oxidation with concentrated KMnO4 gave compound (C) (molecular formula C4H8O) and acetic
acid. Compound (C) could easily be prepared by the action of acidic aqueous H2SO4/HgSO4 on
2-butyne. Determine the formula of (A) and deduce the structure of A, B and C.

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 68 The Hydrocarbons

Solution : a)
Element %age At. Mass Relative No. Simple Atomic
of Atoms ratio
85.7 7.14
C 85.7 12 7.14 1
12 7.14
14.3 14.3
H 14.3 1 14.3 2
1 7.14

Empirical formula compound = CH2

b) Synthesis of compound (C) :
O
H2O
CH3 C C CH3 CH3 C CH2CH3
H2SO4 + HgSO4
Butane - 2 Butanone - 2 (C)

c) Structure of A. Since A, upon oxidation gives Butanone-2 (C) and CH3COOH, it is alkene
of the type
C2H5 C = CH CH3
CH3
3 - Methylpentene - 2
O
O OO KMnO4/H2SO4
Reaction : H3 C CH2 C == CH CH3 H3 C CH2 C CH3 + H3C COOH
Butanone - 2 Acetic acid
CH3
Thus (A) is CH3 CH2 C = CH CH3
CH3
3 - Methylpentene - 2 - ene (C6H12 with empirical formula CH 2)

d) The compound (A) consumes 1 mole of H2 to give a saturated hydrocarbon (B). Thus (B)
should be

H H Nil
H3 C CH2 C == CH CH3 + H2 H3 C CH2 CH CH CH3
CH3 CH3
3 - Methylpentene - 2 3 - Methylpentane
(A) (B)

e) (A) decolourises Br2

Br Br
H3C CH2 C = CH CH3 + Br2 H3 C CH2 C CH CH3
Orange
CH3 CH3
3 - Methylpentene - 2 2, 3 - Dibromo - 3 - methylpentane

84 g of alkene (A) consumes Br2 = 160 g

160 1
1g of alkene (A) consumes Br2 = = 1.90 g
84
Wt. of Solute
Wt. of bromine in 5% solution = 100
Wt. of Solution
1.9
or 5 = 100
Wt. of Solution
1.9 100
Wt. of Solution = = 38g
5
This is in agreement with given data.

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The Hydrocarbons 69

Example 12: It required 0.70 g of a hydrocarbon (A) to react completely with Br2 (2.0g). On treatment of
(A) with HBr, it yielded monobromo alkane (B). The same compound (B) was obtained when
(A) was treated with HBr in the presence and absence of peroxide. Write down the structural
formulae for (A) and (B) and explain the reactions involved.
Solution : Since hydrocarbon (A) consumes only one mole of bromine, therefore, it should be an alkene.
M.W. of Br2 = 2 80 = 160
2g of Br2 reacts with alkene = 0.70 g
0.70 160
160g of Br2 reacts with alkene = = 56g
2
Since molecular weight of alkene is 56,
therefore, possible alkene may be = CnH2n 12 n + 2n = 56
14n = 56, n = 4
CnH2n is C4H8
C4 H8 has three possible isomers as alkene
H3C CH2 CH = CH2 CH 3 CH = CH CH3
H3C
C = CH2
Butene - 1 Butene - 2 H3C
Isobutene (2-Methylpropene-1)
Since monobromoalkane obtained on adding HBr to (A) is same with peroxide or without
peroxide, it suggests that alkene should be symmetrical, i.e. butene-2
H3 C CH = CH CH3 + HBr H3 C CH CH2 CH3
Butene - 2
Br
2-Bromobutane
Br

Since Butene1 and Isobutene give different products, they are ruled out.
HBr
C2H5CHBrCH3
C2H5 CH =CH2 HBr. Peroxide
Butene - 1 C2H5CH2CH2Br
(A)
Since (B) is not the one single product, so this structure of (A) is ruled out
HBr
CH3CH2CHBrCH3
CH3 CH = CH CH3 HBr. Peroxide (B)
Butene - 2 CH3CH2 CHBrCH3
(A)
(B)
Since A here gives (B) which is one single product
Thus (A) is Butene-2, a symmetrical alkene which shows cis-trans isomerism.

Example 13: Give synthesis of alpha-tetralone using Friedel-Crafts synthesis.

O
O O
CH2 C
O AICl3 C CH2 CH2 C OH
Solution : + CH C
2
Benzene O
Succinic
anhydride

CH2
CH2
O
CH2CH2 CH2 C OH CH2 AICl3
- Tetralone
Zn/Hg
SOCl2
Cl C CS2
HCl
4-Phenyl butanoic acid
O O
4-Phenyl butanoylchloride

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 70 The Hydrocarbons

Example 14: Compound A, C6H12O, is reacted with conc. H2SO4 to form compound B, C6H10. When (B)
is treated with Cl2 at 400 C, compound (C), C6H9Cl, is obtained. Then (C) is treated with
alcoholic KOH to form (D), C6H8, which reacts with 1 mole of Br2 at low temperature to form
the compound (E), C6H8Br2. (E), upon ozonolysis followed by hydrolysis forms only
O O
H C CHBr CHBr CH2CH2 C H as a product. Form the above information, deduce the
structure of compound (A) to (E)
Solution : (A) The product of ozonolysis is
O O
H C CH CH CH2 CH2 C H
Br Br
Going backward
Br
2 1 Br
HC CH
2
2 1
Br HC CH2 1
4 5
or
(C6H8Br2)
Br HC CH2
(E)

(B) Since (E) is obtained from (D) C6H8 on absorbing one mole of Br2, therefore, (D) must be
Br
Br

(D) + Br2
Cyclohexadiene (E)
(C) Since (D) is obtained from (C) C6H9Cl on treatment with alc. KOH, it suggests that (C) is
Cl

(C) alc.KOH
(C6H9Cl) (D)
3-Chlorocyclohexene

(D) Since (C) is obtained from (B) C6H10 on treatment with Cl2 at 400C, therefore, (B) must
be, Cl
Cl2
400C
(B) HCl
Cyclohexane (C)
(E) Since (B) is obtained from (A) C6H12O on treatment with conc. H2SO4, therefore, (A)
must be.
OH
Conc.H2SO4
(C6H12O) H 2O
(B)
(A)
OH Cl Br
Br
Hence A = B= C= D= E=

Example 15: An organic compound (A) of molecular formula C5H8 when treated with Na in liquid ammonia
followed by reaction with n-propyl iodide yields (B), C8H14. (A) gives a ketone C5H10O when

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The Hydrocarbons 71

treated with dil. H2SO4 and HgSO4. (B) on oxidation with alkaline. KMnO4 gives two isomeric
acids (D) and (E), C4H8O2. Give structure of compounds (A) to (D) with proper reasoning.
Solution : The molecular formula C5H8 suggests that , it is an alkyne, as it satisfies CnH2n2, general
formula of alkyne, when n = 5.
As C5H8 reacts with Na/liq. NH3, therefore, it must be a terminal alkyne. So, possibly compound
is
CH3
H3C CH2 CH2 C CH or H3C CH C CH
Pentyne-1 3-Methylbutyne
(A) I (A) II

Since compound (A) on treatment with Na/liq NH3 followed by treatement with n-propyl
iodide gives a compound (B) C8H14.
Therefore, (B) must be either Octyne-4 or 2-Methylheptyne-3.
(i) Na/liq. NH3
H3C CH2 CH2 C CH H3C CH2 CH2 C C CH2 CH2 CH 3
(ii) CH3CH 2CH2I Octyne-4
(A) I
(B) III

CH3 CH3
(i) Na/liq. NH3
H3C CH C CH H3C CH C C CH2 CH2 CH3
(ii) CH3CH2CH2I
(A) II 2-Methylbutyne - 3
(A) IV

Since (B) on oxidation with alkaline KMnO4 gives two acids with molecular formula C4H8O2,
therefore, possible acids may be
COOH
H3C CH2 CH2 COOH H3C CH CH3
Butanoic acid
2-Methylpropanoic acid
(D or E)
(E or D)

The above two acids can only be obtained by oxidation of (B) - (IV).
CH3 CH3
Akl. KMnO4
H3 C CH C C CH2 CH2 CH3 H3C CH COOH + HOOC CH2 CH2 CH3
Isomeric acids
(D and E)

Where as
aK K MnO2
CH3CH2CH2CCCH2CH2CH3 CH3CH2CH2COOH+COOHCH2CH2CH3
Therefore, possible alkyne C5H8 is
CH3
H3C CH C CH
3-Methylbutyne-1
(B)
Since (B) on treatment with dil. H2SO4 and HgSO4 gives ketone (C), therefore, possible ketone
(C) is CH3 CH C CH3
CH3 O

Example 16:a) If a rocket were fueled with kerosene and liquid oxygen, what weight of oxygen would be
required for every litre of kerosene ? (Assume kerosene to have average composition of
n-C14H30)

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 72 The Hydrocarbons

b) How much heat would be evolved in the combustion of one litre of kerosene ? (Assume
157 kcal /mol for each -CH2-group and 186 kcal/mol for each-CH3 group).
c) If it were to be feasible to fuel a rocket with free hydrogen atoms, what weight of fuel
would be required to provide the same heat as a litre of kerosene and necessary oxygen.
(Assume H2 as the sole product). Density of n-C14H30 = 0.764 g/ml.
43
Solution : a) n-C14H30 + O 14 CO2 + 15 H2O
2 2
Density of Kerosene = 0.764 g/cc
Vol. of kerosene = 1000 cc
Mass of kerosene = 1000 0.764 = 764 g
Mol. wt. of kerosene = 14 12 + 30 1 = 168 + 30 = 198
Given wt. 764
No. of moles of kerosene = = = 3.85 moles
Mol. wt. 198
1 mol. of kerosene requires oxygen = 43/2 mol
43
3.85 mol. of kerosene requires oxygen = 3.85 = 82.95 mol. = 82.95 32 = 2654 g
2
b) Molecular formula of kerosene = H3C (CH2)12 CH3

12 ( CH2 ) = 12 157 = 1884 kcal

Also 2(CH3) = 2 186 = 372 kcal
Total heat of combustion = 1884 + 372 = 2256 k cal/mol
1 mol. of kerosene evolves heat = 2256 Kcal
3.85 mol. of kerosene evolves heat = 2211 3.85 = 8512.35 kcal
c) H + H H2, H = 104 kcal/mol.
104 kcal heat is evolved by H2 = 1 mol
8512.35
8512.35 kcal heat is evolved by H2 = = 81.84 mol
104
= 81.84 2 = 163.69 g

Example 17:Suggest oxidising agents for the following conversions :

CH3 CH3
a) CH3 COOH

Me COOH

b)
NO2 NO2

Solution : a) dil. HNO3

b) Na2Cr2O7/H2SO4

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