Answer Key Acdity & Basisity

Page # 1 Solution Slot - 1 (Chemistry)
ACIDITY & BASICITY

EXERCISE - 1 HINT & SOLUTON
Q.1
(i) (a) H F (b) H Cl (c) H Br (d) H I
Cl
F Br - I
In group we see the size factor more the size, more stable the anion, more the acidity.
d > c > b > a (acidic strength)
CH4 NH3 H2O HF

H+ H+ H+ H +
(ii) (a) (b) (c) (d)
CH3 NH2 OH F
In period we see the E.N. factor more the electron negativity, more stable the anion, more the
acidity.

E.N. order F > OH > NH2 > CH3
Acidity order = d > c > b > a
CH3
(iii) (a) CH3 CH2 O H (b) CH3 CH O H (c) CH3 C O H
CH3 CH3
+I CH3 CH2 O
CH3
More stable CH3 CH O

CH3 C O
CH3 CH3
2(+I) effect
Three + I group less stable
(acidic strength)a > b > c
(iv) (a) F CH2 CH2 O H F CH2 CH2 O

(b) NO2 CH2 CH2 O H NO2 CH2 CH2 O
(c) Br CH2 CH2 O H Br CH2 CH2 O

(d) N H3 CH2 CH2 O H N H3 CH2 CH2 O

I order = N H3 > NO2 > F > Br
acidic strength = d > b > a > c
Q.2(i) (a) CH3 COOH H+ CH3 = C O
||
O
H+
(b) CH3 CH2 OH +I CH3 CH2 O
(c) C6H5OH H+ C6H5 O

(Phenoxide ion)
394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

IVRS No : 0744-2439051, 52, 53, www. motioniitjee.com , hr@motioniitjee.com
Solution Slot - 1 (Chemistry) Page # 2
O
O O
S
(d) C6H5SO3
[I order C R > Ph]
O
(More the resonating structures, more the stability)

d>a>c>b
COOH COOH COOH

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

CO
C O C O
O
3 O 2 O sp
sp sp (more-I)
Stability = C > b > a

acidity = c > b > a
CH2 COOH
CH2 COOH
COOH
COOH H+
CH2
COOH COOH
H+ H+
COO
CH2 C O
(iii) (a) (b) (c)
COO
CH2 O
COO CH2 C O

COO
O
O O
Q.3 (a) Cl CH2 C O H H+ Cl CH2 C O - (one -I group)
O O
(b) Cl CH2 C O H H+
Cl CH2 C O (two -I grop)
Cl Cl
Cl O
Cl O
(c) Cl C C O H H+
Cl C C O (Three I groups)
Cl
Cl
(most stable)
Ans. c > b > a

O O
(ii) (a) CH3 CH2 CH C O H H+ CH3 CH2 CH C O
F F
(b) CH3 CH CH2 C O H H+ CH3 CH CH2 C O
F O F O
O
(c) CH2 CH2 CH2 C O H H+ CH2 CH2 CH2 C O
F F O
In this type of case are see "DNP" rule.
Distance Power
Number
Acidic strength = a > b > c
O O
(iii) (a) H+ NO2 CH2 C O
NO2 CH2 C O H O
O O
(b) F CH2 C O H H+ O
F CH2 C O
O O
(c) H+
Ph CH 2 C O H Ph CH2 C O
O O
(d) CH3 CH2 C OH H+ CH3 CH2 C O
Acidic Strength : a > b > c > d
:
:OH
:
Q.4(i) (a) (b) :OH (c) :OH
NO2 Cl CH3
(strongel acid)

O O O
NO2 Cl CH3
I I +I
(most stable
conjugate base)
Acidic strength = a > b > c

:
:OH
:
:
:O H :O
(ii) (a) Cl (b) (c)

Cl
Cl
Inductive effect by distance decreases.
Acidity order a > b > c
:
:O H
:
:
:OH :O H :O H
(iii) (a) (b) (c) (d)
H+ H+ H+ H+

O

O O O
CH3
CH3
stability of Conjugate base : d > b > c > a

acidity order : d > b > c > a
:
:O H
:
:OH :O H
P
:
N :O H
Q.5(i) (a) O (b) O (I) (c) (d)

N N
(M) Hydrogen Bonding O O
O
(M)
Acidity order = c > a > b > d

:
:
:
:O H :O H :O H :OH
O
N NO2 O2N NO2
O
(ii) (a) (b) (c) (d)
NO2 HBonding NO2 NO2
M (M) I I
Acidity order = d > c > a > b

O
COH O
COH
H+ CH3
O
Q.6(i) (a) (b)
CO
H+
O

CO
CH3
Due to ortho effect

COOH goes out of plane
b>a So max. acidity
COOH COOH
Cl Br
(ii) (a) (b) Br is more bulky then Cl ortho effect
O
.. O O
CO
.. H ..
CO
.. H COH
..
O
.. Me
..
:O
.. Me O
.. Me
O O O
(iii) (a) (b) CO
(c) CO

CO
O Me
O Me
+I Ortho effect max. acidity
O Me
(+M)
Acidity order c > b > a
O O O
COH COH C OH
NO2
(iv) (a) (b) (c)
NO2
I Ortho effect
N
O O
M
I
Acidity order = c > a > b

OH OH OH OH
Q.7(i) (a) (b) (c) (d)
CH3 NO2 Cl NH2

M
I
Strongest acid (b)
OH
OH OH OH
(ii) (b) (c) (d)

NO2
F CH3
I is more
So maximum acidity.
OH OH OH OH
O Me
(iii)(a) (b) (c) (d)
+M O Me
O Me
I
M
acidity with drawing tendency of group.
so (b) max. acidity.
Q.8 (I) C6H5 OH (II) F OH (III) Cl OH (iv) O2N OH

+M > I I > M M
IV > III > II > I
Q.9 (A) (b) (c) (d) CH2 CH CH3
The conjugate base of compound (b) is most stable due to aromaticity (i.e. )

CH3 CH3
OH H3C OH H3C OH OH
Q.10 (A) (B) (C) (D)
CH 3 H3C NO2 H 3C
O2N
NO2 I CH3 M NO2
I I
Maximum acidity (C). Ans. (C)

COOH COOH
COOH COOH
OH
Q.11 (A) (B) (C) (D) (ortho effect)
OH
OH +I
+M
(most acidic)
Compound (B) is less acidic due to (+M) effect of OH group because it is present on pera position.
OH OH HO OH
OH
Q.12 (I) (II) (III)
O O O
O O O

O
O O

O O

O O
O

O O O
4 eq. Aromatic R.S. Non aromatic
1
acidity Pk acidity (ka) order = I > II > III
a
Pka order = III > II > I
Q.13 (1) Phenol (2) Ethyl alcohol (3) Formic acid (4) Benzoic acid
OH CH 2 OH COOH
H C OH
O
1 1
pH
acidity stability of conjugate Base
COOH O CH2 O

Stability of conjugate base = H C OH > > >
O
Q.14 (I) CH3 NH CH2 CH2 OH CH3 NH CH2 CH2 O

(II) CH3 NH CH2 CH2 CH2 OH CH3 NH CH2 CH2 CH2 O

(III) (CH3)3 N CH2 CH2 OH N( C H3)3 CH2 CH2 O
Strong I effect
Acidity order = III > I > II
Q.15 Compound which are stronger acid than H2CO3 gives CO2 with NaHCO3.
Compound (A), (B), (C), (D) all are stronger acid than H2CO3.

16. (i) Cysteine :
COOH
HS
NH2
1
Acidity Pk
a
Acidity order = COO > S > NH

pka order = NH2 > S > COOH
10.8 8.3 1.8
(ii) glutomic acid : HOOC COOH

2
1
NH2
acidity : COOH > NH2
..
acidity of COOH (2) > COOH (1) due to I effect to NH2
order of acidity : COOH (2) > COOH (1) > NH2
order of Pka : NH2 > COOH (1) > COOH (2)
OH OH COOH
17. (a) , ,
COO O O
acidity stablity of CB = < <
COOH OH OH
acidity = > >
Pka order = 3 < 2 < 1
(b) 1 - butyne, 1-butene, butane

4 3 2 1
CH3 CH2 C CH
sp sp 2 sp 2
acidity order = 1 > 2 > 3
Pka order = 1 < 2 < 3

(c) Prophanoic acid, 3-Bromo propanoic acid 2-nitro propanoic acid

3 3 1 2 1
C C C OH C ? C ? C ? OH
C C C OH ||
Br O NO2 O
O
I (I)
acidity 3>2>1
pka order 3 < 2 < 1
(d) Phenol, O-nitrophenol, O-cresol
OH OH OH
NO2 CH3
M +I
I +H

PKa order = 2 < 1 < 3

(e) (1) CH3 CH2 CH2 CH2 CH2 NH2 CH CH CH CH CH CH NH
3 2 2 2 2 2

NH2 NH
+
H
(2)
+
(3) H NH
acidity stability of conjugate Base

stability order = 2 > 3 > 1
Pka = 2 < 3 < 1
O
||
18. (a) CH3 CH2 Br & CH3 NO2 (b) CH C CH (C) CH3 CHO
3 3
+I
(1) CH3 CH Br & CH3 C CH2 CN CH3 NO2
||
O
O
||
(2) CH2 NO2 (1) CH2 C CH3 (1) CH2CH
I ||
O
(2) is stronger acid (2) CH3CCHCN (2) CH NO
2 2
|| I
O
(2) > (1) (2) > (1) (2) > (1)

OH
OH
19. as (2) acidity M effect

O = C CH3
So (2) is weaker acid
OH
OH
(b) as (2)
O = C CH3
CH3
M +H
So (2) is weaker acid

SH OH S O
(c) or

S O
Stability of C.B. = .>
Acidity stability of C.B.

OH
So is weaker acid

O O
COOH or
|| O
+ ||
N C OH
O
20.
COO
O2N COO
M
acidity M effect
so (2) is more acidic
(b) CH3 CH2 CH2 OH or CH3 CH = CH OH

CH3 CH2 CH2 O CH3 CH = CH O
Showing Resonance so
more acidic
So (2) is stronger acid
(c) CH3 CH = CH CH2 OH or CH3 CH = CH OH

(d) CH3 CH = CH CH2 O (2) CH3 CH = CH O
Show Resonance
so more acidic
so (2) is stronger acid

EXERCISE - 2 HINT & SOLUTON

1
Q.1 (i) Basicity Stability of anion
Stability order F < Cl < Br < I (size)

Basicity order F > Cl > Br > I
(ii) Stability order CH3 < NH2 < OH < F (E.N.)
Basicity order CH3 > NH2 > OH > F
.. .. ..
(iii) R NH2 Pn NH2 R C NH2
.p. localised .p. delocalised
(more basic) (weak base) O
.p. more delocalised
(least base)
basicity order a > b > c
(iv) In gas phase basicity (+I) effect.
Basicity order
NH3 < Me NH3 < Me NH Me < Me N Me
+I +I +I +I +I
Me
+I
(v) In H2O, 3-amine is less basic than 1-amine due to less solvation.
Basicity order : 2amine > 1amine > 3amine > NH3
O
Q.2 (i) .. ..
NH NH N
Me
.p. localised
.. .p. delocalised
NH2 ..
NH2
NH
..
(ii)
.p. localised
(2 amine)
1amine
Basicity c > a > b

.. .. ..
N N N
(iii)
O2N Me F
Strong-I +I-effect Weak I effect
1
Basicity
(I) effect
(+I) effect
Basicity b > c > a

.. ..
NH2 NH2
+
(iv) (a) NH3 (b) Cl
Strong-I-effect
+
of Weak I effect of
NH3, least basic Cl, less basic
.. ..
NH2 NH2
(c) CH3 (d) No effect of any group.

+I effect of CH3, Weaker than C, but stronger
most basic than a & b compound.
.. .. ..
Q.3(i) (a) CH3 CH2 NH2 (b) CH3 CH = NH (c) CH3 C N
sp3 sp2 sp
Least electronegative. most electronegative
most basic least basic.
order a > b > c
.. ..
(ii) (a) CH3 C NH2 (b) CH3CH2NH2
O Lone pair localised

least basic, l.p. of
nitrogen is delocalised.
.. .. ..
(c) CH3 C NH2 (d) NH2 C NH 2
NH
.. NH
More basic due to Most basic, due to more
delocalisation of only delocalisation of l.p.
one l.p.
Basicity order d > c > b > a
(iii) (a) (b) (c)

NH
.. N
..
NH
.. 2
* Compound 'a' is least basic, because l.p. of Nitrogen will more take participate in resonance
due to aromaticity.
* Compound 'b' is most basic, because its l.p. is localised.
* Compound 'c' is more basic than 'b' because its l.p. is delocalised.

O
..
NH C CH3
(iv) l.p. of nitrogen is in conjugation with benzene as well as C CH3 , least basic.
O
..
NH2
l.p. of nitrogen is in conjugation only with benzene. it is more basic than compound 'a'.
..
NH CH2CH3
due to extra +I effect of CH2CH3 group, compound 'c' is most basic than a & b..
order c > b > a
NH2 NH2
CH3 CH3
(v)
Me Me
No2 NO2
Compound a is least basic than b, due to ortho effect of two CH3 group.
NH 2 NH2 NH2 NH2
Q.4(i)
NO2 CN OMe NH2

M M +M +M
Order of M NO2 > CN
Order of +M NH2 > OMe
1
Basicity +M
M
Basicity order d > c > b > a
NH2 Ortho effect NH2 NH2

CH3
(ii)
CH3
+I
CH3 +H
Compound C is most basic due to +H effect of CH3 group. But compound a is least basic due to
ortho effect of CH3 group.
Basicity order c > b > a

NH2 NH2
NH2 Ortho effect
NO2
(iii) (a) (b) (c)
NO2
+I
NO2
M
Order b > a > c
NH2 NH2 NH2 Me

CH3 C Me
(iv)
Me
Ortho effect, Greater ortho effect,
less basic least basic.
Order a > b > c
Me Me
N Me Me
N Me Me
N
SIR
OMe
(v)
OMe
+M OMe I
Order c > a > b
Q.5(i) (a) (b) ..

.. N
N2
sp H
2
sp & delocalisation of l.p.
S
(c) (d)
N N
2 3
H sp H sp
In compound 'd', hybridisation of N is sp3. i.e. less electronegative and I effect of S is less.
(ii)[b] In compound b, N atom is sp3 hybridised, and l.p. of nitrogen is localised.

(iii) Compound a is most basic because charge density on double bonded nitrogen is very high due to
resonance.
(iv) In compound a, the e charge density is very high due to ve charge.

1
Q.6(i) Basicity
E.N. of anion
Order of E.N.
CH3CH2 < CH2 = CH < HC C < CH3CH2O
.. ..
(ii) (a) NH2 (b) CH2 NH2
l.p. is in conjugation
l.p. localised, most basic
only with benzene ring.
..
(c) NH2 (d) C NH2
O
NO2
Ortho effect l.p. is in conjugation with
C group. Which is most
O
with drawing.
Order : b > a > c > d
O CH3 CH3
Nb
Q.7 H2N C H2C CH2 NH C CH3
c
NH2
a
N
CH3 d CH3
a is most basic due to high charge density.

b is more basic than d and c due to ortho effect.
c is least basic because l.p. of nitrogen is conjugated with C group..
O
Order : a > b > d > c
NH2 NH2 NH2

NO2
Q.8
NO2
I II
least basic due I NO2
M
to ortho effect III
NH2 NH2 NH2 NH2
Q.9 (I) (II) (III) (IV)
NO2 OCH3 CH3

M +M +H
Order : III > IV > I > II

Q.10
..
N
H
This lone pair very much delocalised because of getting Aromaticity so do not donate lone pair so
it is least basic.
Q.11 (a) CH3NH2 or CF3NH2

F
.. ..
CH3 NH2 F C NH2
+I F I
have more tendensity

to donate the pair of e.
NH
(b) CH3CONH2 or
H2N NH2
In aquous solution 2 are more basic because of solvation energy.
2>1
(c) n-Pr NH2 or CH3CN
.. ..
CH3 CH2 CH2 NH2 CH3 C N
3
sp 'N' sp Nitrogen
1>2 more E.N weak basic
(d) C6H5N (CH3)2 or 2,6-di methyl-N, N-dimethyl aniline.
H3C Goes out of plane

.. CH3
H3C CH3 N So more basic
N H3C CH3
Ortho effect
So 2 > 1
(e) m-Nitro aniline or p-nitro aniline
.. ..
NH2 NH2
NO2
I NO2
M
So more basic 1>2

Q.12
(a) p-methoxy aniline or p-cyano aniline
NH2
NH2
OCH3
+M CN
So more basic 1 > 2 M
(b) Puridine or Pyrrole
..
N
.. N Delocalised lone pair
Localised lone pair H so least basic.
..
(c) CH3C N or CH3CH2 N H2

sp nitrogen so less basic sp3 Nitrogen 2>1
..
Q.13 (a) H 2O or H3O+
(2) +ve charged spcie is weak base.
(b) H2S, SH, S2
(1) Neutral so weak base More ve charge more donating tendency.
(c) Cl, SH
(1) S Cl E.N. size small
More sable
less basic
(d) F OH NH2 CH3
CH3 NH2
OH F
Size
(1) F So more stable less basic

.. .. ..
(e) HF.. , H2O , NH3
..
'F' more electronegative so do not donate the pair of e so less basic.

(f)
OH SH SeH
Big size
ve charge stable, So weak base.
1
Basicity
Stability

.. ..
NH2 NH2
Q.14 (a) or
NO2
M so more tendency to
donate the pair of e of NH2
in the ring. So weak base

(b) CH2 = CH CH = CH CH 2 or CH2 = CH CH2
long resonance
Sove charge delocalised
So weak base
O O O O
(c) O C C OH or HO C C OH
Anions are more Basic than Neutral.
So (2) is a weak base.
.. ..
OH OH
CH3 CF3
+I I
or
Strong Base Weak Base
.. .. .. ..
NH2 NH 2 NH2 NH2
CH3 NO2
Q.15(a) (i) (ii) (iii) M (iv)
Ortho effect Localised l.p. of N
3<2<1<4
NH2 NH2 ..
NH2 CH2 NH2
CH3
(b) (i) (ii) (iii) (iv)
CH3
Ortho effect +I CH3
+H
1<2<3<4


Q.16(a) (i) OH (ii) CH3COO
(iii) Cl

>
Stability Cl
CH3COO > OH

Basicity order : OH > CH 3COO > Cl
1 2 3
(b) (i) CH C(ii) CH2 = CH (iii) CH3CH2
Stability = (i) > (ii) > (iii)
Basicity = (i) < (ii) < (iii)
2
sp ..
(c) (i) CH2 = CH CH2 NH2
3
sp ..
(ii) CH3 CH 2 CH2 NH 2
..
(iii) CH C CH2 NH 2
sp
Basic strength : 3 < 1 < 2
..
NH C6H5
NH2 NH2
Q.17(a) (i) (ii) (iii)

More resonance
More delocalised
so least basic
(ii) < (i) < (iii)
NH2 NH2 NH2

Cl
(b) (i) (ii) (iii)
Cl
Ortho effect More I Cl
Less I
1 <2<3
NH2 NH2 NH2

(c) (ii) (iii)
H3C O2N
2>1>3 +I +M
Q.18 (a) CH3NH2 (Neutral), CH3+NH3 (+ve charged), CH3NH (ve charged)
2<1<3
(b) CH3O, CH3NH, CH3CH2
More E.N. more stable 1 < 2 < 3

(c) CH3CH = CH , CH3CH2CH 2 , CH3 C C
2 3
sp sp sp
Stability = 3 > 1 > 2
Basicity order = 3 < 1 < 2

.. H
NH2 NH2 N
Q.19 (a)
More resonance
least basic
2>1>3
H
N
..
NH N:
(b)
Localised l.p. l.p. Delocalised
1>2>3
..
HN N NH NH
(c)
Participate in
resonance so
least basic
6
5
5
7
N 5
4 6
4
N1
8
Q.20 N N N :N H N 4 2
9
1 3 1 3 N
2 3
2 H
Pyrimidine Purine
Imidazole
Localised lone pair
Protonation takes Three basic 'N'
of N, 6e,aromatic
place on N1 N1, N3, N7
+
1 N NH
3
2

6e
aromatic
So (A), (C) & (D) are aromatic.


Answer Key Acdity &amp; Basisity

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Answer Key Acdity &amp; Basisity

Загружено:

Авторское право:

Доступные форматы

Page # 1 Solution Slot - 1 (Chemistry)

ACIDITY & BASICITY

CH4 NH3 H2O HF

(iii) (a) CH3 CH2 O H (b) CH3 CH O H (c) CH3 C O H

(iv) (a) F CH2 CH2 O H F CH2 CH2 O

(c) C6H5OH H+ C6H5 O

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

(More the resonating structures, more the stability)

COOH COOH COOH

Stability = C > b > a

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

(b) CH3 CH CH2 C O H H+ CH3 CH CH2 C O

In this type of case are see "DNP" rule.

Q.4(i) (a) (b) :OH (c) :OH

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

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

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

stability of Conjugate base : d > b > c > a

Q.5(i) (a) O (b) O (I) (c) (d)

Acidity order = c > a > b > d

Acidity order = d > c > a > b

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

Due to ortho effect

Acidity order = c > a > b

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

Q.7(i) (a) (b) (c) (d)

CH3 NO2 Cl NH2

Strongest acid (b)

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

Q.8 (I) C6H5 OH (II) F OH (III) Cl OH (iv) O2N OH

Q.9 (A) (b) (c) (d) CH2 CH CH3

Maximum acidity (C). Ans. (C)

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

Pka order = III > II > I

Q.14 (I) CH3 NH CH2 CH2 OH CH3 NH CH2 CH2 O

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

Acidity order = COO > S > NH

(ii) glutomic acid : HOOC COOH

acidity stablity of CB = < <

acidity = > >

Pka order = 3 < 2 < 1

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

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

(c) Prophanoic acid, 3-Bromo propanoic acid 2-nitro propanoic acid

acidity order = 2 > 1 > 3

acidity stability of conjugate Base

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

19. as (2) acidity M effect

So (2) is weaker acid

So (2) is weaker acid

Stability of C.B. = .>

Acidity stability of C.B.

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

EXERCISE - 2 HINT & SOLUTON

Stability order F < Cl < Br < I (size)

Basicity order CH3 > NH2 > OH > F

Basicity c > a > b

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

(c) CH3 (d) No effect of any group.

O Lone pair localised

Basicity order d > c > b > a

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

394,50 - Rajeev Gandhi Nagar Kota, Ph. No. : 93141-87482, 0744-2209671

Answer Key Acdity & Basisity

Answer Key Acdity & Basisity