ORGANIC CHEMISTRY

TARGET IIT JEE 2010

XIII (VXYZ)

QUESTION BANK ON
ACIDITY, BASICITY
AND
TAUTOMERISM

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 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

(x) (a) CH3COOH (b) CH3CH2OH (c) C6H5OH (d) C6H5SO3H

Q. Bank on Acidity, Basicity & Tautomerism [2]

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) (c)
NH NH N

Me

NH2 NH2

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

NH

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

NH2 NH2
NH2 NH2

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


NH3 Cl CH 3 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
Q. Bank on Acidity, Basicity & Tautomerism [3]
 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. Bank on Acidity, Basicity & Tautomerism [4]

Q.4 Select the strongest acid in each of the following sets :
OH OH OH OH

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

CH3 NO2 Cl NH2

OH OH OH OH

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

NO2 F CH3

OH OH OH OH
OMe
(iii) (a) (b) (c) (d)
OMe
OMe

OH OH OH OH
NO2
NO2
(iv) (a) (b) (c) (d)
NO2 NO2 NO2
NO2 NO2
NO2

Q.5 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) NH 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

Q. Bank on Acidity, Basicity & Tautomerism [5]

 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.6 Select the strongest base in following compound :

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

H H H

Q. Bank on Acidity, Basicity & Tautomerism [6]

 NH2

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

NH N
N
H
N
(iii) (a) (b) (c) (d)
N N N N

H H CH3 H

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

Q.7 Arrange the following compound in decreasing order of their basicity.

(i) (a) H2C = CHNa (b) CH3CH2Na (c) CH3CH2ONa (d) HC  CNa

(ii) (a) NH2 (b) CH2 – NH2 (c) NH2 (d) C – NH2
NO2 O

(iii) (a) HO¯ (b) NH3 (c) H2O (d) HSO4¯

Q.8 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.9 Which one of the following is the most acidic?

(A) (B) (C) (D) CH2=CH–CH3

Q.10 Which one of the following phenols will show highest acidity?

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

Q. Bank on Acidity, Basicity & Tautomerism [7]

Q.11 Which of the following is weakest acid?

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

Q.12 Basicity order in following compound is :

CH3 CH3
O
Nb
H2N– C – CH2 CH2 – NH – C – CH3
c
NH
a
N
CH3 d CH3

(A) b > d > a > c (B) a > b > d > c (C) a > b > c > d (D) a > c > b > d

Q.13 The correct pKa order of the follwoing acids is :

HO OH O HO OH

O O O O O O
(I) (II) (III)
(A) I > II > III (B) III > II > I (C) III > I > II (D) I > III > II

Q.14 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.15 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.16 Consider the following compound

O
||
CH3CCOOH
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. Bank on Acidity, Basicity & Tautomerism [8]

Q.17 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.18 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.19 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

O=C–CH3 O=C–CH3

(e) or

Q.20 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.21 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.22 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. Bank on Acidity, Basicity & Tautomerism [9]

Q.23 Which one of the following is least basic in character?

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

Q.24 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.25 From the following pair, select the stronger base:
(a) p-methoxy aniline or p-cyanoaniline (b) pyridine or pyrrole
(c) CH 3CN or CH3CH2NH2

Q.26 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.27 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.28 Rank the following amines in increasing basic nature.

(a)

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

(b)

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

(c)

(i) (ii) (iii)

Q. Bank on Acidity, Basicity & Tautomerism [10]

Q.29 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)

(d)

(i) (ii) (iii)

(e)

(i) (ii) (iii)

Q.30 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.31 What statement is correct for Keto-enol tautomerism ?

(A) Tautomersim is catalysed by acid and base.
(B) Tautomers are present in dynamic equilibrium state.
(C) Generally keto form is more stable than enol form.
(D) All

Q.32 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.33 Which compound show tautomerism:

O
OH N OH

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

N=O

Q. Bank on Acidity, Basicity & Tautomerism [11]

Q.34 Tautomerism form of this compound is/are:
OH
HO OH

HO OH
OH
O O
HO O HO OH
(A) (B)
HO OH O O
O OH
O
O O
(C) (D) All of these
HO OH
OH

Q.35 Tautomer of following compound is :

O O

C – CH2 – C

(A) C – CH = C (B) C – CH2 – C

O OH OH O

(C) CH – CH = CH (D) C – CH2 – C

OH OH O OH

Q.36 Tautomer in following is/are triad system :

O

(A) CH3COCH3 (B) CH3CH2NO2 (C) (D) HCN

Q.37 In each of the following pairs which is more stable :

(a) l (b) l

(c) l (d) l

(e) l

Q. Bank on Acidity, Basicity & Tautomerism [12]

Q.38 In each of the following pairs which is more stable :

(a) (b)

(c) l (d) l

(e) l

Q.39 In each of the following pairs which will have higher enol content :

(a) and

(b) and

(c) and

(d) and

Q.40 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. Bank on Acidity, Basicity & Tautomerism [13]

Q.41 In each of the following pairs which will have less enol content :

(a) and (b) and

Q.42 In each of the following sets of compounds write the decreasing order of % enol content.

(a)

(b)

(c)

(d)

(e)

Q.43

Among these give ease of enolization.

Q. Bank on Acidity, Basicity & Tautomerism [14]

Q.44 % enol content of acetylacetone in following solvents is found as :
Solvent % enol content
H2 O 15
Liquid state 76
hexane 92
gas phase 92
Explain the observation.

Q.45

Explain the observation.

Q. Bank on Acidity, Basicity & Tautomerism [15]

 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, (x) d > a > c> b

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 < c
(vii) c > 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) b , (ii) a, (iii) b , (iv) b

Q.5 (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.6 (i) d, (ii) b, (iii) c, (iv) a

Q.7 (i) b > a > d > c, (ii) b > a > c > d, (iii) a > b > c > d

Q.8 C Q.9 B Q.10 C Q.11 B Q.12 B Q.13 B Q.14 B

Q.15 A Q.16 A

Q.17 (i) cysteine : (ii) glutamic acid :

Q.18 (a) 3<2<1; (b) 1<2<3; (c) 3<2<1; (d) 2<1<3; (e) 2<3<1

Q.19 (a) 2; (b) 2; (c) 1; (d) 1; (e) 1 Q.20 (a) 2; (b) 2; (c) 2

Q.21 A Q.22 A Q.23 A Q.24 (a) i, (b) ii, (c) i, (d) ii, (e) i

Q.25 (a) i, (b) i, (c) ii Q.26 (a) 2; (b) 1; (c) 1; (d) 1; (e) 1; (f) 3

Q.27 (a) 2; (b) 1; (c) 2; (d) 2 Q.28 (a) 3<2<1<4; (b) 1<2<3<4; (c) 3<1<2

Q.29 (a) 1>2>3; (b) 1<2<3; (c) 3<1<2; (d) 2<1<3; (e) 1<2<3

Q.30 (a) 2<1<3; (b) 1<2<3; (c) 3<1<2

Q.31 D Q.32 C Q.33 A,C Q.34 A,B Q.35 A Q.36 A,B,C

Q.37 (a) 1; (b) 1; (c) 1; (d) 1; (e) 1 Q.38 (a) 2; (b) 2; (c) 1; (d) 2; (e) 1

Q.39 (a)1; (b) 2; (c)1; (d) 2 Q.40 (a) 2; (b) 1; (c) 2; (d) 1; (e) 2

Q.41 (a) 2; (b) 2 Q.42 (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.43 3>1>2
Q. Bank on Acidity, Basicity & Tautomerism [16]