QUESTION BANK ON

ACIDITY, BASICITY
AND
TAUTOMERISM
 ACIDITY AND BASICITY

Q.1 Write correct order of acidic strength of following compounds:

O O
|| ||
(i) (a) NO 2  CH 2  C  O  H (b) F  CH  C  O  H
2

O O
|| ||
(c) Ph  CH 2  C  O  H (d) CH 3  CH 2  C  O  H

O O
|| ||
(ii) (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

O O Cl O
|| || | ||
(iii) (a) Cl  CH 2  C  O  H (b) Cl  CH  C  O  H (c) Cl  C  C  O  H
| |
Cl Cl

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

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

COOH COOH COOH
COOH COOH CH 2  COOH
(vi) (a) | (b) CH2 (c) |
COOH COOH CH 2  COOH

(vii) (a) H–F (b) H–Cl (c) H–Br (d) H–I

(viii) (a) CH4 (b) NH3 (c) H2O (d) H–F

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


(c) Br–CH2–CH2–O–H (d) NH3  CH2  CH2  O  H

Q.2 Write increasing order of basic strength of following:

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

(ii) (a) F  (b) Cl  (c) Br  (d) I 

(iii) (a) NH3 (b) MeNH2 (c) Me2NH (d) Me3N (in H2O)
(iv) (a) NH3 (b) MeNH2 (c) Me2NH (d) Me3N (Gas phase)

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

||
O
O
(vi) (a) (b)
NH NH

NH2 NH2

(vii) (a) (b)

N N N
(viii) (a) (b) (c)
O2N Me F

NH2 NH2
NH2 NH2

(ix) (a) (b) (c) (d)


NH3 Cl CH3 H

Q.3 Write correct order of acidic strength of following compounds:

O–H
O–H O–H O–H
O
N NO2 NO2 NO2
(i) (a) (b) O (c) (d)
NO2
NO2 NO2

O–H O–H O–H

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

NO2 Cl CH3

O–H O O–H O–H O–H

N
(iii) (a) O (b) O (c) (d)
N
O N
O O

O–H O–H O–H O–H

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

 O–H O–H O–H
Cl
(v) (a) (b) (c)
Cl
Cl
O O
C–O–H C–O–H
CH3
(vi) (a) (b)

COOH COOH
Cl Br
(vii) (a) (b)

O
O O
C–O–H
C–O–H C–O–H
OMe
(viii) (a) (b) (c)

OMe OMe

O
C–O–H O O
C–O–H C–O–H
(ix) (a) (b) (c) NO2

N NO2
O O

Q.4 Write increasing 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) N H 2 C  N H 2
|| || ||
O N

H N

H

NH2

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

H N

NH2 NH2 NH2 NH2

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

NO2 CN OMe NH2
 NH2
NH2 NH2
NO2
(v) (a) (b) (c)
NO2 NO2
NMe2 Me Me
NMe2 N
OMe
(vi) (a) (b) (c)
OMe OMe
NH2 NH2
Me Me

(vii) (a) (b) Me Me

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

NH2 NH2
NH2 H
C H
(ix) (a) (b) H (c)
H C H
H C
H H
H
NH2 NH2 H NH2
C H
(x) (a) (b) (c)
H

Q.5 Arrange the given phenols in their decreasing order of acidity:

(I) C6H5–OH (II) F OH (III) Cl OH (IV) O2N OH

Select the correct answer from the given code:
(A) IV > III > I > II (B) IV > II > III > I (C) IV > III > II > I (D) IV > I > III > II
Q.6 Which one of the following is the most acidic?

(A) (B) (C) (D) CH2=CH–CH3

Q.7 Which one of the following phenols will show highest acidity?

(A) (B) (C) (D)

Q.8 Which of the following is weakest acid?

(A) (B) (C) (D)

Q.9 Arrange pH of the given compounds in decreasing order:

(1) Phenol (2) Ethyl alcohol (3) Formic acid (4) Benzoic acid
(A) 1 > 2 > 3 > 4 (B) 2 > 1 > 4 > 3 (C)3 > 2 > 4 > 1 (D) 4 > 3 > 1 > 2
Q.10 Arrange acidity of given compounds in decreasing order:
(I) CH3–NH–CH2–CH2–OH (II) CH3–NH–CH2–CH2–CH2–OH

(III) (CH 3 )3 N  CH 2  CH 2  OH
(A) III > I > II (B) III > II > I (C) I > II > III (D) II > I > III
Q.11 Consider the following compound
O
||
CH 3CCOOH
I II III
Which of the above compounds reacts with NaHCO3 giving CO2
(A) I, II and III (B) I and III (C) II and III (D) I and II
Q.12 Say which pka belong to which functional group in case of following amino acids :

(i) cysteine : 1.8, 8.3 & 10.8

(ii) glutamic acid : : 2.19, 4.25, 9.67

Q.13 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
Q.14 Explain which is a stronger acid.
O O
|| ||
(a) CH3CH3 BrCH2NO2 (b) CH 3  C  CH 3 & CH 3  C  CH 2CN

OH OH

(c) or (d) or (e) or

O=C–CH3 O=C–CH3
Q.15 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
Q.16 Consider the following bases:
(I) o-nitroaniline (II) m-nitroaniline (III) p-nitroaniline
The decreasing order of basicity is:
(A) II > III > I (B) II > I > III (C) I > II >III (D) I > III > II
Q.17 Consider the basicity of the following aromatic amines:
(I) aniline (II) p-nitroaniline (III) p-methoxyaniline (IV) p-methylaniline
The correct order of decreasing basicity is:
(A) III > IV > I > II (B) III > IV > II > I (C) I > II > III > IV (D) IV > III > II > I
Q.18 Which one of the following is least basic in character?

(A) (B) (C) (D)

Q.19 In each of the following pair of compounds, which is more basic in aqueous solution? Give an explanation
for your choice:
(a) CH3NH2 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
Q.20 From the following pair, select the stronger base:
(a) p-methoxy aniline or p-cyanoaniline (b) pyridine or pyrrole
(c) CH3CN or CH3CH2NH2
Q.21 Choose the member of each of the following pairs of compunds that is likely to be the weaker base.
(a) H2O or H3O (b) H2S, HS–, S2– (c) Cl–, SH–
(d) F–, OH–, NH2–, CH 3 (e) HF, H2O, NH3 (f) OH–, SH–, SeH–
Q.22 Explain which compound is the weaker base.

(a) or (b) CH2 = CH – CH = CH – CH2– or CH2 = CH – CH2–

O O O O
|| || || ||
(c) O   C  C  OH or HO  C  C  OH (d) or

Q.23 Rank the following amines in increasing basic nature.

(a)

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

(b)

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

(c)

(i) (ii) (iii)

Q.24 Arrange the basic strength of the following compounds.
(a) OH– CH3COO– Cl–
(i) (ii) (iii)
(b) CH  C– CH2 = CH– CH3CH2–
(i) (ii) (iii)
(c) CH2 = CHCH2NH2 CH3CH2CH2NH2 CH  C – CH2NH2
(i) (ii) (iii)

(d)

(i) (ii) (iii)

(e)

(i) (ii) (iii)

Q.25 Arrange the following compounds in order of increasing basicity.
(a) CH3NH2, CH3 NH 3 , CH3NH— (b) CH3O—, CH3NH—, CH3 CH 2
(c) CH3CH = CH—, CH3CH2 CH 2 , CH3CC—
TAUTOMERISM
Q.26 Among the following the compounds having the highest enol content :
(A) CH3CHO (B) CH3COCH3
(C) CH 3  C  CH 2CHO (D) CH3–CO–CH2–CO2CH3
||
O
Q.27 Which compound show tautomerism:
O
OH N OH

(A) (B) (C) (D) None of these

N=O
Q.28 Tautomerism form of this compound is/are:
OH
HO OH

HO OH
OH

O O O
HO O HO OH O O
(A) (B) (C) (D) All of these
HO OH O O HO OH
O OH OH
Q.29 In each of the following pairs which is more stable :

(a) l (b) l

(c) l (d) l

(e) l

Q.30 In each of the following pairs which is more stable :

(a) (b)

(c) l (d) l

(e) l

Q.31 In each of the following pairs which will have higher enol content :

(a) and
 (b) and

(c) and

(d) and

Q.32 In each of the following pairs which will have less enol content :

(a) and (b) and

(c) and (d) and

(e) CH 2  CHO and CH 3  CHO

|
Cl

Q.33 In each of the following pairs which will have less enol content :

(a) and (b) and

Q.34 In each of the following sets of compounds write the decreasing order of % enol content.

(a)

(b)

(c)
 (d)

(e)

Q.35

Among these give ease of enolization.

Q.36 % enol content of acetylacetone in following solvents is found as :

Solvent % enol content
H

2 O 15
Liquid state 76
hexane 92
gas phase 92
Explain the observation.

Q.37

Explain the observation.

 ANSWER KEY
Q.1 (i) a > b > c > d (ii) a > b > c (iii) c > b > a (iv) a > b > c
(v) c > b > a (vi) a > b > c (vii) d>c>b>a (viii) d>c>b>a
(ix) d>b>a>c

Q.2 (i) a > b> c> d (ii) a > b > c > d (iii) c > b> d> a (iv) a < b< c< d
(v) a > b> c (vi) a < b (vii) a > b (viii) b > c> a
(ix) c > d> b > a

Q.3 (i) d > c > a > b (ii) a > b > c (iii) c > a > b > d (iv) d > b > c > a
(v) a > b > c (vi) b > a (vii) b > a (viii) c > b > a
(ix) c > a > b

Q.4 (i) a > b > c (ii) d > c > b > a (iii) b > c > a (iv) d > c > b > a
(v) b > a > c (vi) c > a > b (vii) b > a (viii) c > b > a
(ix) c > b > a (x) a > b > c

Q.5 C Q.6 B Q.7 C Q.8 B Q.9 B Q.10 A Q.11 A

Q.12 (i) cysteine : (ii) glutamic acid :

Q.13 (a) 3<2<1; (b) 1<2<3; (c) 3<2<1; (d) 2<1<3; (e) 2<3<1

Q.14 (a) 2; (b) 2; (c) 1; (d) 1; (e) 1 Q.15 (a) 2; (b) 2; (c) 2

Q.16 A Q.17 A Q.18 A Q.19 (a) i, (b) ii, (c) i, (d) ii, (e) i

Q.20 (a) i, (b) i, (c) ii Q.21 (a) 2; (b) 1; (c) 1; (d) 1; (e) 1; (f) 3

Q.22 (a) 2; (b) 1; (c) 2; (d) 2 Q.23 (a) 3<2<1<4; (b) 1<2<3<4; (c) 3<1<2

Q.24 (a) 1>2>3; (b) 1<2<3; (c) 3<1<2; (d) 2<1<3; (e) 1<2<3

Q.25 (a) 2<1<3; (b) 1<2<3; (c) 3<1<2 Q.26 C Q.27 A,C

Q.28 A,B Q.29 (a) 1; (b) 1; (c) 1; (d) 1; (e) 1

Q.30 (a) 2; (b) 2; (c) 1; (d) 2; (e) 1 Q.31 (a)1; (b) 2; (c)1; (d) 2

Q.32 (a) 2; (b) 1; (c) 2; (d) 1; (e) 2 Q.33 (a) 2; (b) 2

Q.34 (a) 3>1>2; (b) 4>2>1>3; (c) 4 > 1 > 3 > 2 ; (d) 3>1>4>2; (e) 3>4>2>1

Q.35 3>1>2