IIT ASHRAM

GOC

Q.1 Write stability order of following intermediates:

CH 3
  |
(i) (a) CH 3  CH 2 (b) CH 3  CH  CH 3 (c) CH 3  C 
|
CH 3

(ii) (a) + (b) + (c) +


 
(iii) (a) (b) (c)


(iv) (a) (b)  (c)


  

(v) (a) (b) (c) (d)

  
(vi) (a) CF3  CH 2 (b) CCl3  CH 2 (c) CBr3  CH 2

Q.2 Write stability order of following intermediates:

CH 3
  |
(i) (a) CH 3  CH 2 (b) CH 3  CH  CH 3 (c) CH 3  C 
|
CH 3


 
(ii) (a) (b) (c)


(iii) (a) (b)  (c)

  
(iv) (a) HC  C (b) CH 2  CH (c) CH 3  CH 2
 Q.3 Rank the following sets of intermediates in increasing order of their stability.

 
CH2 CH2

(i) (a) (b)

F Cl

CH2
 CH2 CH2

CH2

(ii) (a) (b) (c) (d)

Cl N C N
O O
 
(iii) (a) CH 2  CH (b) CH 2  CH 3
||
O
Q.4 Write stability order of following intermediates:

CH 3
  |
(i) CH 3  CH 2 (b) CH 3  CH  CH 3 (c) CH 3  C 
|
CH 3

(ii) (a) (b) (c)

(iii) (a) (b) (c)

(iv) (a) (b) (c) (d)

(v) (a) (b) (c)

 Q.5 In each of the following pairs of ions which ion is more stable:
 
(a) (I) C6H5– CH 2 and (II) CH2=CH– CH 2
 
(b) (I) CH3– CH 2 and (II) CH2 = CH

(c) (I) and (II)

(d) (I) CH 3  CH  CH 3 and (II) CH 3  N  CH 3

| |
CH 3  C  CH 3 CH 3  C  CH 3
 

 
(e) CH2—CH=NH CH2=CH–NH

O O O¯ O
(f) CH3—C–CH–C—CH3 CH3—C=CH–C—CH3

NH2 NH2
(g) +
CH3—CH2—C—NH2 CH3—CH2—C = NH2
+

Q.6 Rank the following sets of intermediates in increasing order of their stability.

(i) (a) (b) (c)

(ii) (a) (b)

 
CH2 CH2 
CH2
H
(iii) (a) (b) H (c) C H
C H H
H
H C H
H
 Me Ph
| |

iv) (a) Me  C  (b) Ph — C
| |
Me Ph

(v) (a) (b) (c) (d)

(e)

Q.7 Rank the following sets of intermediates in increasing order of their stability.


(i) (a) C (b) CH (c) CH2

 
(ii) (a) CH 2  CH (b) CH 2  CH  CH 2 (c) CH2 (d) CH3

CH2
CH2 CH2

(iii) (a) (b) (c)

Cl Cl

CH2 CH2
(iv) (a) (b) (c)

(v) (a) (b) (c)

   
(vi) (a) (b) (c)

8.Which of the following pairs has higher resonance energy :

(a) & (b) CH2 = CH – O – CH = CH2 & CH2 = CH – NH – CH = CH2

 
(c) CH 2  CH  N H & HN  CH  N H (d) CH2 = CH – F & CH2 = CH – Br


(e) & CH2 = CH – C H 2

9. Which of the following pairs has higher resonance energy :


(a) CH3COOH & CH3COONa (b) CH2 = CH – O & CH2 = CH – OH

(c) & (d) &

(e) & CH2 = CH – CH = CH – CH = CH2

10 .Identify less stable canonical structure in each of the following pairs :

 
(a) C H 2  O  CH 3 
 CH 2  O  CH 3 (b)

(c) (d)

(e)
 
 
CH2 CH2
11 Identify more stable canonical structure in each of the following pairs :
 
O 
O CH2 CH2
(a) C C (b) 

..   C C 
H OH H OH Me2N OMe Me2N OMe
 (c) (d)

 
(e) C H 2  CH  CH  O 
 CH 2  CH  CH  O (f)

12.In which of the following pairs, indicated bond is of greater strength :

(a) and CH 2  CH 2 (b) CH3  C  CH and HC  CH

  

(c) and CH 3  CH 2  Cl

(d) CH 2  CH  CH  CH 2 and CH 2  CH 2  CH 2  CH 3
 

(e) CH 2  CH  CH  CH 2 and CH 2  CH  NO 2
 

(f) and

13.Write correct order of acidic strength of following compounds:

CH3
(i) (a) CH3–CH2–O–H (b) CH 3  CH  O  H (c) CH3–C–O–H
|
CH 3 CH3

(ii) (a) F–CH2–CH2–O–H (b) NO2–CH2–CH2–O–H


(c) Br–CH2–CH2–O–H (d) NH3  CH2  CH2  O  H
(iii) (a) CH3COOH (b) CH3CH2OH (c) C6H5OH (d) C6H5SO3H

(iv) (a) (b) (c)

COOH COOH COOH
COOH COOH CH 2  COOH
(v) (a) | (b) CH2 (c) |
COOH COOH CH 2  COOH
 O O Cl O
|| || | ||
(vi) (a) Cl  CH 2  C  O  H (b) Cl  CH  C  O  H (c) Cl  C  C  O  H
| |
Cl Cl

O O
|| ||
(vii) (a) CH 3  CH 2  CH  C  O  H (b) CH 3  CH  CH 2  C  O  H
| |
F F
O
||
(c) CH 2  CH 2  CH 2  C  O  H
|
F
14. Write correct order of acidic strength of following compounds:

O–H O–H O–H

(i) (a) (b) (c)

NO2 Cl CH3

O–H O–H O–H

Cl
(ii) (a) (b) (c)
Cl
Cl

O–H O–H O–H O–H

(iii) (a) (b) (c) (d)

15.Record the following sets of compounds according to increasing pKa ( = – log Ka)

(a) , , cyclohexane carboxylic acid.

(b) 1-butyne, 1-butene, butane

(c) Propanoic acid, 3-bromopropanoic acid, 2-nitropropanoic acid
(d) Phenol,o-nitrophenol, o-cresol
(e) Hexylamine, aniline, methylamine
16.Explain which is a stronger acid.
O O
|| ||
(a) CH3CH3 & BrCH2NO2 (b) CH 3  C  CH 3 & CH 3  C  CH 2CN
(c) CH3 – CHO & CH3 – NO2
17.Which of the following would you predict to be the stronger acid ?

(a) or

(b) CH3 – CH2 – CH2 – OH or CH3 – CH = CH – OH

(c) CH3 – CH = CH – CH2 – OH or CH3 – CH = CH – OH
18.Write decreasing order of basic strength of following:
(i) (a) F  (b) Cl  (c) Br  (d) I 

(ii) (a) CH 3 (b) NH 2 (c) OH  (d) F 

(iii) (a) R–NH2 (b) Ph–NH2 (c) R  C  NH 2

||
O

(iv) (a) NH3 (b) MeNH2 (c) Me2NH (d) Me3N (Gas phase)

(v) (a) NH3 (b) MeNH2 (c) Me2NH (d) Me3N (in H2O)

O
(vi) (a) (b) (c)
NH NH N

Me
NH2 NH2

(vii) (a) (b) (c)

NH

N N N
(viii) (a) (b) (c)
O2N Me F
19.Write decreasing order of basic strength of following:
  
(i) (a) CH3–CH2– N H 2 (b) CH3–CH= NH (c) CH3–C N

        
(ii) (a) CH 3  C  NH 2 (b) CH3–CH2– NH 2 (c) CH 3  C  N H 2 (d) NH 2 C  N H 2
|| || ||
O N H N

H


NH2

(iii) (a) N (b) (c)

H N

O
NH2 NH–CH2–CH3
NH–C–CH3
(iv) (a) (b) (c)

NH2 NH2
Me Me

(v) (a) (b) Me Me

N N
O O O O

20.Write decreasing order of basic strength of following:

NH2 NH2 NH2 NH2

(i) (a) (b) (c) (d)

NO2 CN OMe NH2

NH2 NH2
NH2 H
C H
(ii) (a) (b) H (c)
H C H
H C
H H
H
 NH2
NH2 NH2
NO2
(iii) (a) (b) (c)
NO2 NO2

NH2 NH2 H NH2

C H
(iv) (a) (b) (c)
H

NMe2 Me Me
NMe2 N
OMe
(v) (a) (b) (c)
OMe OMe

21.Select the strongest base in following compound :

O S
(i) (a) (b) (c)
N
N N
H
H H

NH2

(ii) (a) (b) (c) (d)

NH N
N
H
H H Me
+
N¯Li N N N
(iii) (a) (b) (c) (d)

22. Arrange the following compound in decreasing order of their basicity.

(i) (a) H2C = CHNa (b) CH3CH2Na (c) CH3CH 2ONa (d) HC  CNa

(ii) (a) HO¯ (b) NH 3 (c) H2O

23. In each of the following pair of compounds, which is more basic in aqueous solution? Give an explanation
for your choice:
(a) CH 3NH2 or CF3NH2 (b) CH3CONH2 or H2N NH2
(c) n-PrNH2 or CH3CN (d) C6H5N(CH3)2 or 2,6-dimethyl-N-N-dimethylaniline
(e) m-nitroaniline or p-nitroaniline

24. From the following pair, select the stronger base:

(a) p-methoxy aniline or p-cyanoaniline (b) pyridine or pyrrole
(c) CH3CN or CH3CH2NH2

25. Choose the member of each of the following pairs of compunds that is likely to be the weaker base.
(a) H 2S, HS–, S2– (b) Cl–, SH–
(c) F–, OH–, NH2–, CH 3 (d) OH–, SH–, SeH–
26 . Rank the following amines in increasing basic nature.

(a)

(i) (ii) (iii) (iv)

(b)

(i) (ii) (iii) (iv)

27 Arrange the basic strength of the following compounds.

(a) OH– CH3COO– Cl–
(i) (ii) (iii)
(b) CH  C– CH2 = CH– CH3 CH2 –
(i) (ii) (iii)
(c) CH2 = CHCH2NH2 CH3CH2 CH2NH2 CH  C – CH2NH2
(i) (ii) (iii)
28. Arrange the basic strength of the following compounds.

(a)

(i) (ii) (iii)

(b)

(i) (ii) (iii)

 NH2 NH2 NH2
(c)
H3C O2N
(i) (ii) (iii)

29. Arrange the following compounds in order of increasing basicity.

(a) CH3NH2, CH3 NH 3 , CH3NH— (b) CH3O—, CH3NH—, CH3 CH 2
(c) CH 3CH = CH—, CH3CH2 CH 2 , CH3CC—

30. Rank the amines in each set in order of increasing basicity.

H
NH2 NH2 N
(a)

H
H N H H H
N N N N N N
(b) (c)

31.Compare heat of hydrogenation (Decreasing order)

(i) &

(ii) &

(iii) &

CH3
(iv) CH2 = CH – CH & CH3 –CH = C
CH3
32.Compare heat of hydrogenation (Decreasing order)
33. Among the following pairs identify the one which gives higher heat of hydrogenation :

(a) and (b) and

(c) CH3 – CH = CH – CH3 and CH3 – CH2 – CH = CH2

(d) and
ANSWER KEY
1.i [Ans. c > b > a] ii [Ans. b > c > a] iii [Ans. c > b > a] iv [Ans. b > c > a] v [Ans. d>c > b>a]
vi [Ans.a < b < c ]
2. i [Ans. a > b > c] ii [Ans. a > b > c] iii [Ans. a > c > b] iv [Ans. a > b > c]
3. i [Ans. a < b] ii [Ans. b > c > a > d] iii [Ans. a > b]
4. i [Ans. c > b > a] ii [Ans. c > b > a] iii [Ans. b > c > a] iv [Ans. a > b > c > d]
v [Ans. a > c > b]
5. [Ans. (a) I, (b) I, (c) II, (d) II, (e) II, (f) II, (g) II ]
6. i [Ans. a > b > c] ii [Ans.a > b] iii [Ans. c > a > b] iv [Ans. b > a]
v [Ans.d > e > b > a > c ]
7. i [Ans.a > b > c ] ii [Ans.d > b > c > a] iii [Ans.b > a > c ] iv [Ans.a > c > b ]
v [Ans.b > c > a ] vi [Ans.b > c > a ]
8.[Ans. (a) I, (b) II, (c) II, (d) I, (e) I]
9.[Ans. (a) II, (b) I, (c) I, (d) I, (e) I]
10. [Ans. (a) I, (b) II, (c) II, (d) II, (e) I]
11.[Ans. (a) I, (b) I, (c) I, (d) I, (e) II, (f) II]
12.[Ans. (a) II, (b) II, (c) I, (d) I, (e) II, (f) II]
13. i [Ans. a > b > c] ii [Ans. d>b>a>c] iii [Ans. d > a > c> b] [Ans. c > b > a] v [Ans. a > b > c]
vi [Ans. c > b > a] vii [Ans. a > b > c ]
14. i [Ans. a > b > c] ii [Ans. a > b > c] iii [Ans. d > b > c > a]
15. [Ans. (a) 3<2<1; (b) 1<2<3; (c) 3<2<1; (d) 2<1<3; (e) 2<3<1]
16. [Ans. (a) 2; (b) 2; (c) 2] 17. [Ans. (a) 2; (b) 2; (c) 2]
18. i [Ans. a > b > c > d] ii [Ans. a > b> c> d] iii [Ans. a > b> c] iv [Ans. d > c> b> a]
v [Ans. c > b> d> a] vi [Ans. c > b > a] vii [Ans. c > a > b] viii [Ans. b > c> a]
19. i [Ans. a > b > c] ii [Ans. d > c > b > a] iii [Ans. b > c > a] iv [Ans. c > b > a]
v [Ans. b > a]
20. i [Ans. d > c > b > a] ii [Ans. c > b > a] iii [Ans. b > a > c] iv [Ans. a > b > c]
v [Ans. c > a > b]
21. i [Ans.C ] ii [Ans. b] iii [Ans. a]
22. i [Ans. b > a > d > c] ii [Ans. a > b > c ]
23. [Ans. (a) i, (b) ii, (c) i, (d) ii, (e) i]
24. [Ans. (a) i, (b) i, (c) ii] 25. [Ans. (a) 1; (b) 1; (c) 1; (d) 3] 26. [Ans. (a) 3<2<1<4; (b) 1<2<3<4]

27. [Ans. (a) 1>2>3; (b) 1<2<3; (c) 3<1<2; ] 28. [Ans. (a) 2<1<3; (b) 1<2<3; (c) 2 > 1 > 3]
29. [Ans.(a) 2<1<3; (b) 1<2<3; (c) 3<1<2 ] 30. [Ans. (a) 2 > 1> 3, (b) 1 > 2> 3, (c) 1 > 3 > 2, ]
31. [ A ns. (i) 2 > 1 (ii) 2 <1 (iii) 1 < 2 (iv) 1 > 2] 32. [Ans. E > C > D > B > A]
33. [Ans. (a) I, (b) I, (c) II, (d) I]