1

IITians PACE Edu. Pvt. Ltd.

Part - A
1. The reactivity order of photochemical monohalogenation of following alkanes is
(1) CH
4
(2) C
2
H
6
(3)
3
3 3
3
CH
|
CH C C H
|
CH
(4)
3 3
3 3
3 3
CH CH
| |
CH C C CH
| |
CH CH

(A) 1 >2 >3 >4 (B) 2 >1 >3 >4 (C) 4 >3 >2 >1 (D) 2 >3 >1 >4
2. Which of the following reaction has zero activation energy
(A) CH Cl
4
+
-

CH H Cl
3
-
+ (B)
Cl Cl

Cl Cl
- -
+
(C) CH CH
3 3
- -
+

CH CH
3 3
(D)CH Cl Cl
3
-
+

CH Cl +Cl
3

-
3. Photochemical fluorination is explosive while iodination is too slow to occur. The reason for this is
(A) Bond dissociation energy of I
2
is minimum
(B) Formation of CH
3
F is most exothermic
(C) Formation of H F is most exothermic while formation of H I is endothermic
(D) F
2
has lower bond dissociation energy than Cl
2
or Br
2
4. Which statement is incorrect about free radical halogenation of alkanes
(A) The number of product molecules formed by one photon is very high
(B) If O
2
is added, initially the rate of reaction decreases, then it increases
(C) Inhibitors combine with free radical and terminate the chain reaction
(D) presence of
O O
|| ||
H C OC CO H C
5 6 5 6

inhibits the free radical reaction.
5. Which statement is correct about photochemical bromination of Butane
CH
3
CH
2
CH
2
CH
3


u h , Br
2
(A) 1-Bromobutane and 2-Bromobutanes are formed in equal amounts.
(B) 2-Bromobutane is formed with faster rate than 2-chlorobutane in the other experiment of chlo-
rination.
(C) The major product is an equimolar mixture of two compounds
(D) Homolysis of C H bond has lower activation energy than homolysis of Br Br bond.
6. Which of the following is not the chain propagation step in the chlorination of an alkane
(A) R

+SO
2
Cl
2

RCl +

SO
2
Cl (B)

SO
2
Cl

SO
2
+Cl

(C) Cl

+R H

R

+H Cl (D) R' OOR +2RH

2R'OH +2R

7. An alkane can not be chlorinated by using the following reagent/s

(A) Cl
2
/hu (B) SO
2
Cl
2
(C) tBuOCl (D) HCl
8. Which of the following is/are endothermic reactions
(A) Combustion of CH
4
(B) Decomposition of H
2
O
(C) Dehydrogenation of ethane to ethene (D) Conversion of graphite to diamond
9. The alkane, for which Wurtz reaction is suitable method for preparation:
(1) n-Pentane (2) n-Butane (3) 2,2,4,4-tetramethylbutane (4) Propane
(A) 2 (B) 2, 3 (C) 1, 2, 3 (D) 1, 2, 3

Alkane
2
IITians PACE Edu. Pvt. Ltd.
10. The isomerisation of n-butane reaction in presence of AlCl
3
, HCl yields
(A) (B) (C) (D)
11. For the following reactions
HC CH
Catalyst
2
H

H
2
C =CH
2
AH
1
H
2
C =CH
2

Catalyst
2
H

CH
3
CH
3
AH
2
Which of the following facts is expected to be correct?
(A) |AH
1
| =|AH
2
| (B)|AH
1
| >|AH
2
| (C) |AH
1
|<|AH
2
| (D)|3AH
1
|= |2AH
2
|
12. The substance treated with (NaOH +CaO) and revolution of gas (A) results. The gas (A)
(A) can turn moistened red litmus paper blue
(B) can turn moistened mercurous nitrate paper black
(C) can act as Lewis base (D) All are correct
13. CH
4
can be prepared from
(A) Wurtz reaction (B) Corey-house process
(C) Kolbes Electrolysis (D) Decarboxilation of Carboxylic acid salt
14. To prepare alkane with n carbon, which of following combination is true?
(A) Wurtz reaction: alkylhalide with (n/2) carbon
(B) Decarboxylation: Na salt of carboxylic acid (n-1) carbon
(C) Kolbes Electrolysis: Na salt of carboxylic acid (n/2 +1) carbon
(D) Hydrolysis of Grignards reagent with n carbon.
Question No. 15 to 18 (4 questions)
More branched alkanes are more stable and have lower heat of combustion.
e.g. CH
3

I
2
CH
CH
2
CH
3
II
H
|
CH C CH
|
CH
3 3
3

stability : II >I AH
comb.
:

I >II
More branched alkane has more no. of primary C H bonds. (therefore it has more bond energy).
Homolouges : Higher homologes have higher heat of combustion.
15. Out of the following, which one has highest heat of combustion?
(A) CH
4
(B) C
2
H
6
(C) C
3
H
8
(D) C
4
H
10
16. Out of the following, which one has highest heat of combustion?
(A) C C C C C (B) C C C C
|
C
(C)
C
|
C C C
|
C

(D) Equal in all
17. Out of the following, which one has highest heat of combustion per -CH
2
- unit?
(A) (B) (C) (D)
18. Correct order of heat of combustion of the following hydrocarbons is :
(1) Pent-1-ene (2) n-Pentane (3) neopentane (4) isopentane
(A) 1>2>4>3 (B) 2>4>3>1 (C) 1>2>3>4 (D) 4>3>2>1
3
IITians PACE Edu. Pvt. Ltd.
Part - B
1. Allot IUPAC nomenclature to the following compounds :
(a) (b) (c)
2. Arrange the following in decreasing order of :
(i) Reactivity towards Cl
2
/ hu :
(A) CH
4
(B) CH
3
CH
3
(C) CH
3
CH
2
CH
3
(D)
3 3
3
CH CH CH
|
CH

(ii) Relative reactivity in photochemical halogenation :
(A) CH
3
CH
2
CH
2
CH
2
CH
3
(B)
3 2 3
3
CH CH CH CH
|
CH

(C)
3
3 3
3
CH
|
CH C CH
|
CH

(D) CH
3
CH
3
(iiii) The reactivity of following free radicals :
(A)
3
H C
-
(B)
2
H C
-
CH
3
(C) (CH
3
)
2
H C
-
(D) (CH
3
)
3
-
C
(iv) The stability of following free radicals :
(A) (B) (C) (D)
(v) Heat of combustion :
(A) (B) (C) CH
3
CH
2
CH
2
CH
3
(D)

3 3
3
CH CH CH
|
CH

(vi) Reactivity of X
2
:
(CH
3
)
3
CH
2
X
;
(A) Br
2
(B) Cl
2
(C) F
2
(D) I
2
3. Predict the proportions of isomeric products from chlorination at room temperature
(in presence of light) of :
(a) propane (b) isobutane (c) 2,3dimethylbutane
(d) n-pentane (e) isopentane (f) 2, 2, 3-trimethylbutane
(g) 2, 2, 4-trimethylpentane.
Relative rates of alkyl radical formation by a chlorine radical at room temperature:
tertiary : secondary : primary = (5.0) : (3.8) : 1
4
IITians PACE Edu. Pvt. Ltd.
4. Write major organic products for the following reactions :
(a) Sec-butylbromide
Li
H
I Cu
J
I
5 2
H C
K
(b)
4
LiAlH
(c)
is Electrolys
(d)
A

+ CaO NaOH
(e) +Na
ether
(f) + D
2

Pt
5. Complete the following reactions by writing monohalogenation products.
(i)

u h Br
2
/
(ii)

u h Br
2
/
(iii)

u h Br
2
/
(iv)
3
4 3
3
CH
|
CCl H C CH
|
CH
+
2 2
O R
(v) (CH
3
)
4
C +Cl
2

u h
(vi) + Br
2

u h
(vii) +Br
2

u h
5
IITians PACE Edu. Pvt. Ltd.
Isomer
) H C ( Z , Y , X
8 4
) 1 (
Ni / H
2

) (
/
2
h Br
2

u
W
7. For the given reaction :
3
3 2 3
3 3
CH
|
CH CH CH C CH
| |
CH CH



u h / Br
2
(a) Write the number of possible monobromo products. (all isomers)
(b) Arrange all the monobromo products in decreasing order of rate of their formation.
(c) Arrange in decreasing order of % yield of monobromo products.
(d) How many products are optically active ? (all isomers)
8. Identify the unknown compounds in the following sequence of reaction .
9. An alkane with the formula C
6
H
14
can be synthesized by treating (in separate reactions) five
different alkyl chlorides (C
6
H
13
Cl) with zinc and aqueous acid. Give the structure of the alkane and
the structures of the alkyl chlorides.
10. An alkane with the formula C
6
H
14
can be prepared by reduction (with Zn and HCl) of only two alkyl
chlorides (C
6
H
13
Cl) and by the hydrogenation of only two alkenes (C
6
H
12
). Write the structure of this
alkane, give its IUPAC name, and show the reactions.
11. Ignoring compound with double bonds, write structural formulas and give names for all of the
isomers withthe formula C
5
H
10
.
12. Write product with proper mechanism for the following reaction
CH
3
CH
2
CH
3

+
2 2 2 2
O R Cl SO
6
IITians PACE Edu. Pvt. Ltd.
An swers
Part - A
1. C 2. C 3. C 4. D
5. C 6. D 7. D 8. B, C, D
9. A 10. B 11. B 12. D
13. D 14. A, B, C, D 15. D 16. A
17. A 18. A
Part - B
1. (a) 2,5Dimethyl4,4dipropylheptane (b) 2,6Dimethyl4,4bis(2methylpropyl)heptane
(c) 2Bromo4chloro3ethyl3isopropylpentane
2. (i) D >C >B >A (ii) B >A >C >D (iii) A >B >C >D
(iv) D >A >C >B (v) C >D >A >B (vi) C >B >A >D
3. (a) CH
3
CH
2
CH
2
Cl (44%) ,
Cl
|
CH CH CH
3 3
(56%)
(b) Cl CH CH CH
|
CH
2 3
3
(64%) ,
Cl
|
CH C CH
|
CH
3 3
3

(36%)
(c)
Cl CH CH CH CH
| |
CH CH
2 3
3 3

(55%) ,
Cl
|
CH CH C CH
| |
CH CH
3 3
3 3

(45%)
(d) CH
3
CH
2
CH
2
CH
2
CH
2
Cl (21%) ,
Cl
|
CH CH CH CH CH
3 2 2 3
(53%)
Cl
|
CH CH CH CH CH
3 2 2 3
(26%) ,
(e)
3 2 2
3
CH CH CH CH Cl
|
CH
(28%) ,
Cl
|
CH CH C CH
|
CH
3 2 3
3
(23%)
Cl
|
CH CH CH CH
|
CH
3 3
3
(35%) , Cl CH CH C CH
|
CH
2 2 3
3
(14%)
(f)
3
3 2
3 3
CH
|
CH CH C CH Cl
| |
CH CH
(45%) ,
l C CH
| |
CH C C CH
| |
CH CH
3
3 3
3 3
(25%),
3
2 3
3 3
CH
|
Cl CH CH C CH
| |
CH CH
(30%)
7
IITians PACE Edu. Pvt. Ltd.
(g)
3
2 2 3
3 3
CH
|
Cl CH C CH CH CH
| |
CH CH
(33%) ,
3
3 3
3 3
CH
|
CH C CH CH CH
| | |
CH Cl CH
(28%)
3
3 2 3
3 3
CH Cl
| |
CH C CH C CH
| |
CH CH
(18%) ,
3
3 2 2
3 3
CH Cl
| |
CH C CH CH CH
| |
CH CH
(22%)
4. (a) H :
3 2 3
CH CH CH CH
|
Li
J :
CuLi
CH CH
|
H C
2
3
5 2
|
|
|
.
|

\
|

K :
3 2 3
5 2
CH CH CH CH
|
H C

(b) (c) (d)
H
|
CH C Ph
|
CH
3
3

(e)
3 2 2 3
3 3
CH CH CH CH CH CH
| |
CH CH
(f)
5. (i)
Br
|
CH C CH
|
CH
3 3
3

(ii) +
(iii) (iv)
3
3 3
3
CH
|
CHCl Cl C CH
|
CH
+
(v)
3
2 3
3
CH
|
Cl CH C CH
|
CH

(vi) (vii)
6. (X) CH
3
CH
2
CH =CH
2
, (Y)
(Z) , (W)
Br
|
CH CH CH CH
3 2 3

7. (a) 6 monobromo products (b) 3 >2 >1 (9) >1 (6)
(c) 3 >2 >1 (9) >1 (6) (d) 4 products are optically active
8
IITians PACE Edu. Pvt. Ltd.
8. (R) (S) (T)
(U) (V) (W) CH
2
=O
9. Alkane :
3 2 2 3
3
CH CH CH CH CH
|
CH

Alkyl chlorides :
(I)
3 2 2 3
2
CH CH CH CH CH
|
Cl CH
(II)
Cl
|
CH CH CH C CH
|
CH
3 2 2 3
3

(III)
Cl
|
CH CH CH CH CH
|
CH
3 2 3
3

(IV)
Cl
|
CH CH CH CH CH
|
CH
3 2 3
3

(V) Cl CH CH CH CH CH
|
CH
2 2 2 3
3

10. Alkane :
3 3
3 3
CH CH CH CH
| |
CH CH
2, 3-Dimethylbutane
Alkyl chloride : (I)
Cl
|
CH CH CH CH
| |
CH CH
3 2
3 3
(II)
Cl
|
CH CH C CH
| |
CH CH
3 3
3 3

Alkenes : (I)
3 2
3 3
CH CH C CH
| |
CH CH
=
(II)
3 3
3 3
CH C C CH
| |
CH CH
=
11. cyclopentane Methylcyclobutane
Ethylcyclopropane 1, 2-Dimethylcyclopropane 1, 1-
Dimethylcyclopropane
12.
3 3
CH CH CH
|
Cl