Solutions FOR GET EQUIPPED JEE ADVANCED AND COMPREHENSION

Q.1 [C]

Sol. moles of H 3 PO4 0.2 50 = 10 m moles

moles of Na 3 PO 4 0.2 50 = 10 m moles

H 2 PO 4 HPO 42
H 3 PO 4 Na 3 PO 4
10 10 0 0
0 0 10 10

Buffer of NaH 2 PO 4 & Na 2 HPO 4

HPO 24
pH Pka 2 log 8 log1 8
H 2 PO 4

Q.2 [A]

Sol. In one litre initial pH=7

Final pH = 4; H 10 4

H by drop 10 4 10 7 10 4

Moles of H in 1L 10 4

So total moles after 2 drops = 2 10 4 in 1L

pH = 4 log 2 = 3.7

Q.3 [D]

At pH = 7.4 the best buffer is of H 2 PO 4 & HPO 42

HPO 24
Using 7.4 8 log
H2 PO4
H 3 PO 4 NaOH
NaH 2 PO 4 H 2 O
5m mole x5
0 0 5m moles

NaH 2 PO 4 NaOH
Na 2 HPO 4 H 2 O
5 x
5 x x

x
Solving, 7.4 8 log
5 x

x 1

5 x 4

x=1

total 5 + 1 = 6 m moles 0.1 V ml

V = 60 ml

Q.4 [A]

Sol. If both MX and M2Y starts ppting simultaneously then

K 1010
M sp 10 9
X 0.1

2
then K sp M 2 Y M Y 2

2

10 9 0.01 10 20

In Pure water for M 2 Y

4s3 1020
1
10 20 3
s
4

Q.5 [B]
Sol. Isoelectronic point implies net charge on the species must be zero so considering it as triprotic
Pka 2 Pka 3
acid 2 nd ionisation of H+ must be complete so it will be amphiprotic & pH
2

8.96 10.53

2

= 9.74

Comprehensions

Q.13 [A]

Sol. The stronger acid will be more deprotonated than weaker acid at same pH

So it will be less protonated

A & B curves are protonated

Q.14 [C, D]

Sol. for same acid lines must intersect at 0.5 as ordinato, So A & C are pairs & B & D

Q.15 [B]

Sol. pKa stronger pH 5 Ka stronger 105

pKa wea ker pH 7 Ka wea ker 107

105
100
10 7

Q.16 [C]

K sp 107
Sol. First Br starts precipitating in the form of AgBr(s) when Ag 105 M
Br 102

after which Ag Br K sp remains constant so a hyperbolic curve.

solution solution

Q.17 [D]

Sol. When AgCl (s) starts precipitating

K sp 10 5
Ag
2
10 3
solution Cl 10
 107
Ag Br 10 2 3 102 104
ppt ppt 10

Ag 103 102 10 4 0.0109

total

Solutions FOR EXPERTISE ATTAINER SUBJECTIVE

Q.1

Sol. OH 2.5 103 2 5 103 M

POH = 3 log 5 = 2.3

(a) For POH to be doubled

2
OH OH
final initial

25 106 106 so OH negligible conserving moles of OH from Ba OH2

water

25 106 V 5 10 3 1

5 103 103
V 200L
25 10 6 5

Water added = 200 1 = 199L

(b) POH to be tripled

3
OH OH
final initial

125 10 9 1.25 10 7 10 6

So OH in significant
water

1014
OH H H 7
8 108 M
water water net 1.25 10

Conserving moles of OH from Ba OH 2

12.5 10 8

8 108 V 5 103 1
4.5 108 V 5 103

5 10 3
V
4.5 108

106
L
9

(c) not possible as POH cannot be more than 7

Q.2

Sol. pH1 3 log 2 2.7

1
pH 2 pKa log C 2.7
2

On mixing the new concentration are

CH3COOH 0.1M HCl 103 M

CH 3COO H
CH 3COOH HCl
H Cl
103
0.1 103
0.11 0.1 3 0
10 0.1

0.1 cannot be neglected compared to 103

Ka
0.1 10 0.1 2 10
3
5
; 1 1
0.11

0.1 10
2 3
2 10 5

2 102 2 104 0

102 104 8 104 102 3 102

102
2 2

H 0.1 102 103 2 103

net

pH 3 2.7
 pH pH 2
So 1 2
pH 3

Q.3

HA H A
Sol.
C 1 C C

C 2 C
Ka H
1 1 1

pKa pH log
1

log pH pKa
1

10 pH pKa
1

10 pH pKa 1

1 10 pKa pH

pH pKa
1 10

Q.4

Sol.

(a) For pH to be doubled

2
H H
final initial

2
Cf f Ci i

2
Ci Ka 0.1 2 105

2 106

Cf 12 Ci i2
Also, 2 105
1 f 1 i
 Cf f f 2 105
1 f

2 106 f 2 105

t 10
10 ; f
1 f 11

11
Cf 2 106 2.2 106
10

Conserving WA Cf Vf Ci Vi

106
Vf
22

106
Vwater 1 L 45453L
22

(b) Not possible as pH cannot be > 7

Q.5

Zn OH 2(s) Zn 2 2OH
Sol.
a s1 s 2 s1 x

2
K sp Zn 2 OH

S1x 2 .(1)

2
Zn 2 4OH Zn OH 4

2
Zn OH 4
Kf 4
Zn 2 OH

2
Zn OH 2 s 2OH Zn OH 4
a s1 s 3 x s2
 s2
K sp K f .(2)
x2

1 2
2
K sp K f s1 s 2 s 2 s1 s 2
2

s 2 1.2 10 17 1016 1.44 10 18

s 1.2 10 9

Solubility of Zn OH 2(s) is s1 s 2 2s 2.4 10 9 M

K sp 1.2 1017
OH x 9
108 104
s1 1.2 10

POH = H

pH = 10

Q.6

Sol. Initially saturated solution of Ca OH 2 so Ca OH 2 dissolved is given by

Ca OH 2 s Ca 2 2OH
s 2s

K sp 4s3 4.42 105

4.42 105
S 3
4

= 0.022 M

1
Moles dissolved 0.022 0.011
2

When NaOH is mixed volume is doubled

Ca OH 2 Ca 2 2OH
s1 s
s1 2s1 0.2
 2
s1 2s1 0.2 4.42 10 5

2
s1 s1 0.1 1.105 105

Neglecting s1

1.105 10 5
s1 1.1103
0.01

moles of Ca 2 dissolved 1.1 103 1 moles

moles of Ca 2 deposited 11 103 1.1 10 3 9.9 103 moles

moles of Ca OH 2 9.9 103 74 gm 732.6 mg

Q.7

Sol. Fe 3 1ppm 1gm in106 gm

1
moles in 103 L 1.78 105 M
56
2
Fe 3 SCN Fe SCN

1.78 105 x 0
1.78 10 5
6 10 6 x 6 10 6
6 10
6

6 10 6 1 103

1.78 10 5
6 10 6 x 6 10
6
k dissociation 7.142

6 10 6 103


11.8 10 6 x 6 10 6 7.142
6 7.142
x 6 10 6 3.61 103 = 0.0036 M
11.8 103
Q.8

Sol.