Ionic Equilibrium 7.

31

HINTS AND EXPLANATIONS

EXERCISE I (JEE MAIN)

Basics
d 1.02 × 103 g/L
1. Dissociation of water into ions will increase 6. (a) [ D2 O] = = = 51 M
M 20 g/mol
2. Dissociation of water into ions will increase and
5.1× 10 −15
hence PH will decrease. Water will remain neutral. (b) K d = K w /[D2 O] = = 10 −15
51
3. H2 O 
 H+ + OH− (c) [ D+ ] = [ OD − ] = K w
1000
CM = M 0 0 Kw 5.1 × 10 −15 10 −8
18 ∴α= = =
C 51 51
Equilibrium C(1 – α)M CαM CαM
1000
K w = [H+ ][ OH − ] = Cα ⋅ Cα = α 2 ⋅ C 2 (d) Molality = = 50 m
20
2
⎛ 1000 ⎞
= (1.8 × 10 −9 )2 × ⎜
⎝ 18 ⎟⎠ 7. ln
K 2 ΔH ⎛ 1
=
1⎞
− ⎟
K1 ⎜
R ⎝ T1 T2 ⎠
= 1.0 × 10–14
K2 13.7 × 103 ⎛ 1 1 ⎞
[H+ ][ OH− ] or, ln = ⎜⎝ − ⎟
4. Kd = 10 −14 2 298 323 ⎠
[H2 O]
⇒ K2 = 5.9 × 10–14
α 2 ⋅C 1000
= ≈ α 2 ⋅ C = (1.8 × 10 −9 )2 ×
1− α 18 Kw 10 −14
−16
8. [ OH− ] = = = 5 × 10 −11 M
= 1.8 × 10 [H3 O + ] 2 × 10 −4

5. [H+ ] = K w ⇒ P H = − log( 2.5 × 10 −14 )1/ 2 = 6.8 9. NaCl solution is neutral and at 60°C, PH < 7
1 × 10 −12
10. No. of H3O+ ions × 6.02 × 1023 = 6.02 × 108
1000

HINTS AND EXPLANATIONS

Strong Acids and Bases
11. PH = – log (4 × 10–4) = 3.4 Now, [H+][OH–] = Kw ⇒ (x + 10–7) ⋅ x = 10–14

12. POH = –log(0.005) = 2.3 ⇒ x = 6.18 × 10–8

∴ [H+] = (x + 10–7) M = 1.618 × 10–7 M
∴ PH = 14 – 2.3 = 11.7
⇒ PH = 6.79
500 × 10 −2
13. M= × 36.5 = 0.1825 gm
1000 15. PH is close to 7.0 and hence, contribution of water
is considered. let water dissociates only upto ‘x’ M
14. As the acid is very dilute, the contribution of water
is presence of CM-NaOH.
should be taken. Let H2O dissociates only upto
xM in presence of HCl. H2O  H+ + OH–
Equilibrium xM (x + C) M
H2O  H+ + OH–
Equilibrium (x + 10–7) M xM 10 −14
Now, x = 10–7.3 and x + C = = 10 −6.7
x
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 7.32 Chapter 7

∴ C = 10–6.7 – 10–7.3 = 2 × 10–7 – 5 × 10–8

25 × 0.1 25 × 0.1
= 1.5 × 10–7 M 19. neq of H+ = ×1+ × 2 = 7.5 × 10 −3
1000 1000
∴ Mass of NaOH = (20 × 103) × 1.5 × 10–7 × 40
50 × 0.1
= 0.12 gm neq of OH– = = 5 × 10 −3
1000
V × 0.1 + V × 0.1 × V × 0.1 ∴ neq of H+ left = 2.5 × 10–3
16. [H+]final =
3V + 2.5 × 10 −3
= 0.1 N = 0.1 M ⇒ [H ] = × 1000 = 0.025 M
100
∴ PH = – log (0.1) = 1.0 ∴ PH = – log (0.025) = 1.6 ⇒ POH = 14 – 1.6 = 12.4

17. As all have 0.1 M concentration, [KOH]final = 0.1 M 20. On neglecting the contribution of water, [H+]
= 10–6 M
∴ POH = – log(0.1) = 1.0 and PH = 13
When contribution of water is considered,
100 × 0.5 H2O  H+ + OH–
18. nOH− taken = = 0.05
1000 Equilibrium (x + 10–6) M xM
250 × 0.2 Now, (x + 10–6)⋅x = 10–14 ⇒ x = 9.9 × 10–9
nH+ taken = = 0.05
1000
∴ [H+]2 = (x + 10–6) M = 1.0099 × 10–6 M
H –6
Hence, resulting solution is neutral P = –log(10 )
[H+ ]2 − [H+ ]
= 6.0 Now, % error in[H+] = [H+ ] × 100%
[ H + ]2
= 0.98%

Weak Acids and Bases

21. Smaller PKa, stronger acid, greater [H+] 25. HA  H+ + A–

low PH ⇒ High [H+]
– +
22. CH3COOH  CH3COO + H ⇒ Equilibrium in backward direction
1M 0 0.1 M High PH ⇒ low [H+]
Equilibrium 1–x x 0.1 + x ⇒ Equilibrium in forward direction
 1M  0.1M 2 × 0.36 / 180
26. Conc. of aspirin = = 0.016 M
[CH3COO − ][H+ ] x × 0.1 0.250
Now, K a = ⇒ 2 × 10–5 =
[CH3COOH] 1 Now, [H+ ] = K a ⋅ C = 4 × 10 −9 × 0.016
HINTS AND EXPLANATIONS

⇒ x = 2 × 10–4 M = 8 × 10 −6 M
∴ PH = 5.1
+
[H ]HCOOH ( K a ⋅ C )HCOOH
23. +
= K K
[H ]CH3COOH ( K a ⋅ C )CH3COOH 27. α= = = K ⋅V
C 1/ V
1.77 × 10 −4
= = 3.18 28. H
PCH OH
= PNH H
= 3.2 ⇒ PNH = 14 − 3.2 = 10.8
1.75 × 10 −5 3COOH 3 3

29. ( K a ⋅ C )HA = [H+ ]HCl

24. [H+ ]CH3COOH = [H+ ]CH2 ( CN )COOH
or, K a × 0.2 = 4 × 10 −4 ⇒ Ka = 8 × 10–7
n n V 1
or, 0.000018 × = 0.0036 × ⇒ 1 = 10 −14
V1 V2 V2 200 ∴ Kb of A− = −7
= 1.25 × 10 −8
8 × 10

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 Ionic Equilibrium 7.33

30. P K b = 10.3 = − log K b ⇒ Kb = 5 × 10–11 (x + y) ⋅ x (x + y) ⋅ x

⇒ 2 × 10 −12 = ≈
( 0.02 − x ) 0.02
Kw 10 −14
∴ K a ( HF) = = = 2 × 10 −4 or, 4 × 10 −14 = ( x + y ) ⋅ x (1)
Kb (F − ) 5 × 10 −11
and Kw = [H+][OH–] ⇒ 10–14 = (x + y) ⋅ y (2)
11.6
31. [C5H11COOH] = = 0.1 M From (1) + (2), ( x + y ) = 5 × 10 −14 M = [H+ ]
116
∴ PH = – log(5 × 10–14)1/2 = 6.65
Now, [H+ ] = K a ⋅ C ⇒ 10 −3 = K a × 0.1

⇒ Ka = 10–5 Ka Ka
34. α 2 = 2 × α1 ⇒ × V2 = 2 × × V1
n n
Ka 0.00024 ⇒ V2 = 4 × V1 = 4 × 300 = 1200 ml
32. α= = = 0.346 or 34.6%
C 0.002 ∴ Vwater added = 1200 – 300 = 900 ml
Hence, α can not be neglected. 35. HCN  H+ + CN–
α 2 ⋅C α 2 × 0.002 Equilibrium (0.2 – x)M (x + y)M xM
Ka = ⇒ 0.00024 = ⇒ a = 0.29
1 − ga 1− α (x + y) ⋅ x y ⋅ x
9.6 × 10 −10 = ≈
+
Now, [H ] = Ca = 0.002 × 0.29 = 5.8 × 10 –4 ( 0.2 − x ) 0.2

33. [H+ ] = K a ⋅ C = 2 × 10 −12 × 0.02 = 2 × 10 −7 M HCOOH  H+ + HCOO–

Equilibrium (0.1 – y)M (x + y)M yM
As [H+] is very small, contribution of H+ from
water must be considered. (x + y) ⋅ y y ⋅ y
2.56 × 10 −5 = ≈
HA  H +
+ A– ( 0.1 − y ) 0.1
Equilibrium (0.02 – x)M (x + y) M xM ∴ y = 1.6 × 10–3 and x = 1.2 × 10–7
H2O  H+ + OH– Option (d) may be answered without solving
because solution is acidic.
Equilibrium (x + y) M yM
[H+ ][ A − ]
Now, K a =
[HA]

Polyprotic Acids and Bases

HINTS AND EXPLANATIONS

36. Y(OH)2  Y(OH)+ + OH– 38. H2CO3  H+ + HCO3−
4 × 10–3 M 0 0 0.1
× 1000 M 0 0
Final 0 4 × 10–3 M 4 × 10–3 M 100
Equilibrium (1 – x) M (x + y) M (x – y) M
Y(OH)+  Y2+ + OH–
HCO3− HCO


 − 
+
3HH ++32 −+ CO32 −
++CO
H
4 × 10–3 –2 × 10–3 2 × 10–3 M 4 × 10–3 +2 × 10–3
Equilibrium (x – y) M (x + y) M yM
= 2 × 10–3 M = 6 × 10–3 M
[H+ ][HCO3− ]
∴ POH = –log (6 × 10–3) = 2.22 ⇒ PH = 11.78 Now, K a1 =
[H2 CO3 ]
37. All are correct answers, but if only one is to select, (x + y) ⋅ (x − y) x ⋅ x
then (a), because it have more species. ⇒ 4 × 10 −6 = ≈
(1 − x ) 1

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 7.34 Chapter 7

∴ x = 2 × 10–3 Kw 10 −14
[ OH − ] = = = 5 × 10 −12 M
[H ][C O32 − ]
+ +
[H ] 2 × 10 −3
and K a2 =
[HCO3− ]
39. For. PH, 2nd dissociation may be neglected.
−11 (x + y) ⋅ y x ⋅ y
⇒ 5 × 10 = ≈ [H+ ] = K a1 ⋅ C = 9 × 10 −5 × 0.1 = 3 × 10 −3 M
(x − y) x
∴ y = 5 × 10–11 ∴ PH = –log(3 × 10–3) = 2.52
∴ [H+] = (x + y) ≈ x = 2 × 10–3 M 40. For POH, 2nd protonation may be neglected
[HCO3− ] = (x – y) ≈ x = 2 × 10–3 M [O H − ] = K b1 ⋅ C = 3.6 × 10 −6 × 0.1 = 6 × 10 −4 M
[CO3− ] = y = 5 × 10–11 M ∴ POH = –log(6 × 10–4) = 3.22 ⇒ PH = 10.78

Buffer Solutions
[CH3 NH+3 ]0
Ka H P OH = P K b + log
41. P = 5 ⇒ P range = 4 to 6 [CH3 NH2 ]0
42. For maximum buffer capacity, PH = PKa 0.08
= − log(5 × 10 −4 ) + log
0.02
+ [ NH3 ] 0
43. P H = P K a ( NH4 ) + log 5 × 10 −4 10 −14
[ NH+4 ] 0 ∴ [ OH − ] = ⇒ [H+ ] = = 8 × 10 −11 M
4 [ OH − ]
0.02
= 9.26 + log = 9.26 47. On adding acid, PH should decrease slightly. As none
0.01 × 2
of the option is slightly less than 4.0, answer is 4.0
44. Sodium acetate is basic in nature.
K 6 ⋅ [ Pyridine] 1.5 × 10 −9 × 0.2
45. –
CH3COOH + OH  CH3COO + H2O – 48. [ OH− ] = =
[ Pyridinium ion] ⎛ 0.15 ⎞
⎜ × 10000 ⎟
a mole x mole 0 ⎝ 500 ⎠
Final (a – x)mole 0 x mole = 1 × 10 −9 M
x ∴ POH = – log (10–9) = 9.0 ⇒ PH = 5.0
P H = P K a + log
a−x
[CN − ]0
1
For th neutralization, 49. P H = P K a + log
4 [HCN ]0
HINTS AND EXPLANATIONS

80 × 0.4 / 100
a/4 1 = − log( 2.5 × 10 −10 ) + log
P1H = P K a + log = P K a + log 20 × 0.8 / 100
a−a/4 3
= 9.9
3
For th neutralization,
4 50. B + H+  BH+
(Imidazole)
3a / 4
P2H = P K a + log = P K a + log 3 V × 0.02 (120 − V ) × 0.02
a − 3a / 4 M M 0
120 120
∴ ΔP H = P2H − P1H = 2 log 3 ( 2V − 120 ) × 0.02 (120 − V ) × 0.02
Final M 0 M
120 120
46. CH3NH2 + H+  CH3 NH3+
[BH+ ]0 120 − V
0.1 mole 0.08 mole 0 P OH = P K b + log ⇒ 7 = 7 + log
[ B ]0 2V − 120
Final 0.02 mole 0 0.08 mole ⇒ V = 80

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 Ionic Equilibrium 7.35

Hydrolysis of Salts

51. Stronger the acid, smaller is PH. CH3COONH4 = Neutral, NaOH = strong base,
HCl = strong acid
52. Potassium propionate is the salt of strong base
and weak acid and hence. Kh Kw 10 −14
60. h= = = = 10 −4 or 0.01%
1
P H = 7 + ( P K a + log C )
C K a ⋅C 10 −5 × 0.1
2
1 1
1 61. P H = 7 + ( P K a − P K b ) = 7 + (3.8 − 4.8) = 6.5
or, 8 = 7 + ( P ka + log 0.001) 2 2
2
⇒ P K a = 5 ⇒ Ka = 10–5 62. P K b of CN − = 4.70 ⇒ P K a of HCN = 9.30

H 1 K
53. The order of acidic strength is HCl > H2CO3 Now, P = 7 + ( P a + log C )
> HCN 2
1
54. NaCl does not hydrolysis but CH3COONH4 = 7 + (9.30 + log 0.5 ) = 11.5
2
undergoes cationic as well as anionic hydrolyisis.
63. Equal volumes of both will consume and hence,
– H Ka [HA − ]0
55. Point A: Buffer H2A + HA ; P = P + log 0.01
[ H 2 A ]0 [CH3COONa] = = 0.005
2
Point B: 1st equivalent point HA– ; 1 K
H
1 K Now, P = 7 + ( P a + log C )
P H = (P a1 + P K a 2 ) 2
2 1
K a2 [ A 2 − ]0 = 7 + ( 4.7 + log 0.005 ) = 8.2
Point C: Buffer HA– + A2– ; P H = P + log 2
[HA − ]0
nd 2– 64. Zn2+ + H2O  Zn(OH)+ + H+ ;
Point D: 2 equivalent point, A ;
Equilibrium (0.001 – x)M xM xM
1 K
P H = 7 + (P a1 + log C ) Ka = 2 × 10–10
2 x⋅x x2
+ + Now, 2 × 10 −10 = ≈
56. B + H2O  BOH + H ; ΔH = positive ( 0.001 − x ) 0.001
57. Point B : Buffer HA + A– ⇒ x = 2 × 10 −13
58. NaCl = Neutral, NH4Cl = Acidic, NaCN = Basic, ∴ PH = – log x = – log (2 × 10–13)½ = 6.35
HCl = Acid
65. Ammonium chloride is acidic in nature.
59. CH3COONa = Basic, CH3COOH = Weak acid,

HINTS AND EXPLANATIONS

Indicators
[In − ]
66. P K1n = − log K1n = − log(5 × 10 −6 ) = 5.3 67. P H = P K ln + log
[HIn]
[1n − ] C
Now, P H = P K1n + log ⇒ 2 = P kln + log ⇒ P K ln = 2
[HIn ] C
⎛ 1⎞ [In − ]
Only for acidic form, PH ≤ ⎜ 5.3 + log ⎟ = 4.0 Now, P H = P K ln + log
⎝ 20 ⎠ [HIn]

Only for basic form, PH ≥ (5.3 + log 40 ) = 6.9 ⇒ − log( 4 × 10 −3 ) = 2 + log

100 − x
x
∴ x = 71.4

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 7.36 Chapter 7

68. Yellow colour with methyl red means PH > 6.2 70. X– + H+  HX
Yellow colour with phenol red means PH < 6.4 10 × 0.1 10 × 0.1
M M 0
H 20 20
69. For complete colour change, P should change
Final 0 0 0.05 M
⎛ 1⎞
from , PH ≤ ⎜ P kln + log ⎟ to PH ≥ P kln + log 10
⎝ 10 ⎠
( ) (10 ml HCl solution is needed for equivalent point)

and hence, minimum PH change should be of 2.0 At equivalent point [H+ ] = K a × C

units. = 10 −6 × 0.05
∴ PH = – log (5 × 10–8)1/2 = 3.65

Solubility

71. XaYb  aXb+ + bYa– 76. (a) AgCl(s)  Ag+ + Cl– ; K1 = 10–10
a mole b mole (b) AgCl(s) + Br–  AgBr (s) + Cl– ; K2 = 200
a− b (c) 2 AgBr(s) + S2–  Ag2S(s) + 2Br– ;
∴ Moles of Y = × moles of X b +
a K3 = 1.6 × 1024
From 2(a) – 2(b) – 2(c); Ag2S(s)  2Ag+ + S2– ;
2+ 3– x
72. A3B2(s)  3A + 2B (Solubility = mol/l) (10 −10 )2
M K= = 1.5625 × 10 −49
( 200 )2 × 1.6 × 1024
3x 3x
M M 77. Adding both reactions, Ksp = 1.3 × 10–34 × 38.5
⎛ 3x ⎞ ⎛ 2 x ⎞
3
108x5
2
≈ 5 × 10–33
Ksp = [ A2 + ]3 [ B 3 − ]2 = ⎜ ⎟ ⋅ ⎜ ⎟ =
⎝ M⎠ ⎝ M ⎠ M5 78. Kformation = K1 ⋅ K2 ⋅ K3 = 125 × 20 × 1 = 2500
[B3 − ] 2x / M M4 1
∴ = = ∴ Kdissociation = = 4 × 10 −4
K sp 108x5 / M5 54 x 4 K formation

79. BaF2(s)  Ba2+ + 2F–

50
73. [ OH − ] = 0.1 × = 0.05 M (S + C) M 2S M
100
where S = solubility of BaF2 in CM-Be(NO3)2
2+
K sp 10 −14 −12 solution
∴ [Zn ] = = = 4 × 10 M
[ OH − ]2 ( 0.05 )2 [F − ]
HINTS AND EXPLANATIONS

Hence, Solubility, S =
2
74. Ag+ form complex with NH3
80. CaF2(s)  Ca2+ + 2F–
3+ –
75. Fe(OH)3(s)  Fe (aq) + 3OH (aq); S1M 2S1M
3+ –3
Ksp = [Fe ][OH ] Now, K sp = S1 ⋅ ( 2S1 )2
Now, for given reaction, ⎛ K sp ⎞
1/ 3
⎛ 3.2 × 10 −11 ⎞
1/ 3
−4
+ 3+ ⇒ S1 = ⎜ ⎟ = ⎜
⎜ ⎟⎟ = 2 × 10 M
Fe(OH)3(s) + 3H3O  Fe + 6H2O 4 4
⎝ ⎠ ⎝ ⎠
[Fe3+ ] [ OH − ]3 K sp Now, in KF solution,
K eq = × =
[H3 O ] + 3
[ OH ] − 3
K w3 K sp 3.2 × 10 −11
S2 = − 2 = = 2 × 10 −6 M
[F ] ( 4 × 10 −3 )2
4 × 10 −38
= = 4 × 10 4
(10 −14 )3 S2 2 × 10 −6 1
Now, = =
S1 2 × 10 −4 100

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 Ionic Equilibrium 7.37

81. A2X3(s)  2A3+ + 3X2– 88. Mg(OH)2 (s)  Mg2+ + 2OH–

2yM 3yM SM 2SM
3+ 2 2– 3 2 3 5 1/ 3
Ksp = [A ] [X ] = (2y) ⋅ (3y) = 108y ⎛ 9 × 10 −12 ⎞
Now, K sp = 4S 3 ⇒ S = ⎜ ⎟ M
2+ P–
⎝ 4 ⎠
82. ApBq(s)  pA + qB
1/ 3
p⋅s M q⋅s M ⎛ 9 × 10 −12 ⎞
Now, [ OH − ] = 2S = 2 × ⎜ ⎟
Solubility product, Ls = (p ⋅ s)p ⋅ (q ⋅ s)q ⎝ 4 ⎠
= pp ⋅ qq ⋅ s(p + q) = (18 × 10 −12 )1/ 3M

83. K f = K f1 ⋅ K f2 = 1.6 × 103 × 6.8 × 103 = 1.08 × 107 ∴ POH = –log(18 × 10–12)1/3 = 3.58 ⇒ PH = 10.42

89. Zn(OH)2(s) + 4NH3  Zn(NH3 )2+

4 + 2OH
–
−8
84. For MX : Solubility = K sp = 4 × 10
1M 0 0
−4
= 2 × 10 M Equilibrium (1 – 4S)M SM 2SM
1/ 3
⎛ 3.2 × 10 −14 ⎞ 1/ 3
⎛ K sp ⎞ [ Zn[NH3 ]24 + [ OH − ]2 [ Zn2 + ]
For MX2 : Solubility = ⎜ =⎜ ⎟ K eq = ×
⎝ 4 ⎟⎠ ⎝ 4 ⎠ [NH3 ] 4
[ Zn2 + ]
= 2 × 10 −5 M = Ksp ⋅ Kstab = 1.6 × 10–17 × 1.6 × 1010 = 2.56 × 10–7
1/ 4 1/ 3
⎛ K sp ⎞ ⎛ 2.7 × 10 −15 ⎞ −7 S × ( 2S )2 4S 3
For M3X : Solubility = ⎜ ⎟ = ⎜⎜ ⎟⎟ Now, 2.56 × 10 = ≈
⎝ 27 ⎠ ⎝ 27 ⎠ (1 − 4S )4 1

= 1× 10 −4 M ⇒ S = 4 × 10–3M
∴ Order of solubility = MX2 < M3X < MX 90. AgCl(s) + Cl–  AgCl2−
0.001435 aM 0
85. S= = 10 −5 M
143.5 ⎛ 0.01⎞
Final ⎜⎝ a − ⎟M 10–4 M
∴ Solubility product, Ksp = S = 10 2 –10 100 ⎠

0.0744 / 372 [AgCl2− ] [ Ag + ][Cl − ]

86. Solubility, S = = 2 × 10 −3 M Now, K eq = × = K sp ⋅ K f
100 / 1000 [Cl − ] [ Ag + ][Cl − ]
Li3Na3(AlF6)2 (s)  3Li+ + 3Na+ + 2 AlF63 − = 2 × 10 −10 × 2.5 × 105 = 5 × 10 −5

HINTS AND EXPLANATIONS

3S 3S 2S 10 −4
∴ 5 × 10 −5 = ⇒ a ≈ 2M
Ksp = [Li+]3 [Na+]3 [ AlF63− ]2 = (3S)3 ⋅ (3S)3 ⋅ (2S)2 ( a − 10 −4 )
Hence, the minimum mass of NaCl added =
= 7.46496 × 10–19 (100 × 2) × 58.5 = 11700 gm
87. For CaF2 : Ksp = 4S3
91. Ag 2 CO3 (s) + C 2 O24 − 


2−
 Ag 2 C 2 O 4 (s) + CO3
1/ 3
⎛ 1.08 × 10 −10 ⎞ 1/ 3
⎛ K sp ⎞
⇒ S=⎜ =⎜ 0.15
⎟
⎝ 4 ⎟⎠ ⎝ 4 ⎠ Initial
500
× 1000 0

= 3 × 10–4 M = 0.3 M
⎛ 500 × 3 × 10 −4 ⎞ 0.035
∴ Mass of CaF2 needed = ⎜
1000 ⎟ × 78 Final 0.3 – x x= × 1000
⎝ ⎠ 500
= 1.17 × 10–2 gm = 0.23 M = 0.07 M

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 7.38 Chapter 7

95. For saturated solution of Pb(OH)2 in water,

[CO32 − ] [ Ag + ]2 K sp ( Ag 2 CO3 )
Now, K eq = × = Ksp = 4. S3
[C 2 O24 − ] [ Ag + ]2 K sp ( Ag 2 C 2 O 4 )
= 4 × (6 × 10–6)3 = 8.64 × 10–16
0.07 K sp ( Ag 2 CO3 ) Now, for the given buffer, [OH–] = 10–6 M
or, =
0.23 2.3 × 10 −11 K sp 8.64 × 10 −16
∴ Solubility, S = [ Pb2 + ] = =
⇒ Ksp (Ag2CO3) = 7 × 10–12 [ OH − ]2 (10 −6 )2
= 8.64 × 10–4 M
92. Ag +
+ 2CN  –
Ag(CN)2− ;
1 18
96. Ag(NH3 )2+ 


+
 Ag + 2 NH3 ; Keq = 6.8 × 10
–8
K= = 2.5 × 10
4 × 10 −19 0.2 M 0 0
0.03 M 0.1 M 0 Eqn 0.2 – x xM 2xM
100% 0 (0.1 – 0.06)M 0.03 M = 0.2 M
= 0.04 M x × ( 2 x )2
Now, 6.8 × 10 −8 =
Eqn. xM (0.04 + 2x)M (0.03 – x)M 0.2
≈ 0.04 M ≈ 0.03 M ⇒ x = 1.5 × 10 M = [Ag+]
–3

0.03 Cu 2 +  2+
Now, 2.5 × 1018 = 97. + 4 NH3  Cu(NH3 )4 ;
2
x × ( 0.04 ) Keq = 1.25 × 1012
⇒ [Ag+] = x = 7.5 × 10–18 M 0.0125 M 0.25 M 0
100% 0 0.25 – 0.05 0.0125 M
93. 2 AgCl(s) + CO32 − 

 Ag 2 CO3 (s ) + 2Cl
− = 0.20 M
Equ. xM 0.2 + 4 x 0.0125 – x
2.0 M 0 ≈ 0.2 M ≈ 0.0125 M
0.00355
Equ. (2 – x)M 2x = 0.0125
35.5 Now, 1.25 × 1012 = 4
⇒ x = 6.25 × 10–12
x × ( 0.2 )
≈ 2M ∴ x = 5 × 10–5
2 98. AgSCN(s)  Ag+ + SCN–
[Cl − ]2 [Ag + ]2 K sp (AgCl)
Now, K eq = × = (x + y)M xM
[CO32 − ] [Ag + ]2 K sp ( Ag 2 CO3 )
AgBr (s)  Ag+ + Br–
−5 2 2
(5 × 10 ) K sp ( AgCl) (x + y)M yM
HINTS AND EXPLANATIONS

or, = −12
2 8 × 10
Now, (x + y) ⋅ x = 1 × 10–12 (1) x = 9.09 × 10–7
⇒ Ksp(AgCl) = 1 × 10–10
(x + y) ⋅ y = 2.1 × 10–13 (2) y = 1.909 × 10–7
 + −
94. AgCl(s) + 2 NH3 (aq )  Ag(NH3 )2 (aq ) + Cl (aq ) 99. AgCN (s)  Ag+ + CN– ; Ksp = 1.2 × 10–16
1.0 M 0 0 1 1
Eqn. (1 – 2x)M xM xM CN– + H+  HCN ; keq = =
K a 4.8 × 10 −10
[ Ag(NH3 )2+ ][Cl − ] [ Ag + ] K sp Adding both reactions,
Now, K eq = × =
[ NH3 ]2 [ Ag + ] K c AgCN (s) + H+  Ag+ + HCN ;
K sp 1
1.8 × 10 −10 1 Keq = =
= = Ka 4 × 106
7.2 × 10 −8 400 10 –3
SM SM
x⋅x 1 1 1 S ⋅S
Now, 2
= ⇒ x= = 0.045M Now, = ⇒ 1.58 × 10–5 M
(1 − 2 x ) 400 22 4 × 106 10 −3

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M07 Advanced Problems in Physical Chemistry xxxx_Part B.indd 38 7/16/2019 11:50:41 AM
 Ionic Equilibrium 7.39

100. PbCl2(s)  Pb2+ + 2Cl– Now, Ksp = [Pb2+][Cl–] = constant

S1M 2S1M or, S1 × (2S1)2 = (0.8S2) × (1.6S2)2 ⇒ S1 = 0.512S2
When it is 80% ionized, then ⇒ S2 > S1
PbCl2(s)  Pb2+ + 2Cl–
0.8 S2 M 1.6 S2

Precipitation
K sp
101. [OH–]min to start ppt. of Mg(OH)2 = 104. Ag+ + 2NH3  Ag(NH3)+;
[Mg 2+ ] 2
Kstab = 1.6 × 107
4 × 10 −11 0.1 M 1M 0
=
x 100% 0 (1 – 0.2) M 0.1 M
8 × 10 −6 = 0.8 M
For Cd(OH)2, [OH–]min = Equ. xM 0.8 + 2x 0.1 – x
x
≈ 0.8 M ≈ 0.1 M
1/ 3
⎛ 8.5 × 10 −23 ⎞
– 0.1
For Al(OH)3, [OH ]min = ⎜ ⎟ Now, 1.6 × 107 = ⇒ x = 9.76 × 10–9 M
⎝ x ⎠ x × ( 0.8) 2

⎛ 1.8 × 10 −14 ⎞ Now, on adding NaCl, Q = [Ag+][Cl–]

For Zn(OH)2, [OH–]min = ⎜ ⎟ = 9.76 × 10–9 × 0.01
⎝ x ⎠
= 9.76 × 10–11 < Ksp
Considering significant concentration of metal Hence, no precipitation of AgCl.
ion (x is not extremely small), [OH–] needed is
minimum for Al3+ and hence, it will precipitate 105. Ag+ + Cl–  AgCl(s);
first.
1 1
Keq = =
102. [Ag+]min for the start of precipitation of K sp 2 × 10 −10
K sp ( AgBr) 5 × 10 −13 500 × 2.5 × 10 −5 2000 × 5 × 10 −2
AgBr = = = 5 × 10 −12 M
[Br − ] 0.1 2500 2500
= 5 × 10–6 M = 4 × 10–2 M
1.8 × 10 −10
For Cl– : [Ag+]min = = 1.8 × 10 −9 M 100% 0 (4 × 10–2 – 5 × 10–6)
0.1
≈ 4 × 10–2 M

HINTS AND EXPLANATIONS

8.1 × 10 −12 Equ. xM (4 × 10–2 + x) ≈ 4 × 10–2 M
For CO32 − : [ Ag + ]min = = 9 × 10 −6 M
0.1 1 1
Now, = ⇒ x = 5 × 10–9
⎛ 1 × 10 −22 ⎞ 1/ 3 2 × 10 −10 x × 4 × 10 −10
For AsO34− : [ Ag + ]min = ⎜ ⎟ = 1 × 10 −7 M
⎝ 0.1 ⎠ Hence, Ag+ ppt = (5 × 10–6 – 5 × 10–9) ≈ 5 × 10–6 M
As [Ag+] needed is minimum for AgBr, it will ∴ Mass of AgCl ppt
precipitate first. ⎛ 2500 × 5 × 10 −6 ⎞ −2
= ⎜⎜ ⎟⎟ × 143.5 = 1.79 × 10 gm
+
103. Ag2CrO4(s)  2Ag + CrO2−
4 ⎝ 1000 ⎠
To prevent ppt (backward reaction), 106. PbI2 (s)  Pb2+ + 2I–
Q ≤ Ksp To prevent ppt, Q ≤ Ksp
or, [Ag+]2 × 3 × 10–4 ≤ 1.2 × 10–11 or, 0.005 × [I–]2 ≤ 7.2 × 10–9
∴ [Ag+]max = 2 × 10–4 M ∴ [I–]max = 1.2 × 10–3 M

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 7.40 Chapter 7

Hence, maximum mass of NaI 111. Cd2+ + H2S  CdS(s) + 2H+

⎛ −3 ⎞ 10 × 0.08
= ⎜ 500 × 1.2 × 10 ⎟ × 150 = 0.09 gm 0.1 × 10–3 mole
⎝ 1000 ⎠ 1000
= 0.8 × 10–3 mole
107. AgBr (s)  Ag+ + Br– Final 0 0.8 × 10–3 + 0.2 × 10–3
For precipitation, Q > Ksp = 10–3 mole
or, 0.0004 × [Br–] > 4 × 10–13 10 −3
∴ [H+]final = × 1000 = 0.01 M ⇒ PH = 2.0
100
∴ [Br–] > 10–9 M
Hence, minimum mass of NaBr needed 112. [I–]min for ppt of AgI
⎛ −9 ⎞ K sp 8.5 × 10 −17
= ⎜ 200 × 10 ⎟ × 103 = 2.06 × 10 −8 gm = = = 8.5 × 10 −16 M
⎝ 1000 ⎠ [ Ag + ] 0.1
[I–]min for ppt of Hg2I2
108. CaSO4 (s)  Ca2+ + SO2−
4
K sp 2.5 × 10 −26
To start ppt, Q > Ksp = = = 5 × 10 −13 M
[Hg 22 + ] 0.1
or, 0.005 × [ SO2− ] > 2.4 × 10 –5
4
Hence, AgI will precipitate first. The [I–] to start
∴ [ SO2− –3
4 ] > 4.8 × 10 M precipitation of other metal ion = 5 × 10–13 M
Now, [Ag+]left when Hg2I2 start precipitating
4.8 × 10 −3
∴ [Al2(SO4)3]min = = 1.6 × 10 −3 M K sp 8.5 × 10 −17
3 = − = = 1.7 × 10 −4 M
[I ] 5 × 10 −13
109. Pb2+ + SO2−
4  PbSO4 (s) ; Hence, % of Ag+ precipitate
1 1 0.1 − 1.7 × 10 −4
Keq = = = × 100 = 99.83%
K sp 1.6 × 10 −7 0.1
8.32 × 10 −3 / 200 10 −4 ⎛ −3 ⎞ 2
113. Ksp of CaCO3 = ⎜ 7 × 10 ⎟ = 4.9 × 10 −9
100 / 1000 100 / 1000 ⎝ 100 ⎠
= 4 × 10–4 = 10–3 Let initial [Ca2+] = [Ba2+] = xM. From question
100% 0 (10–3 – 4 × 10–4) 10
final [Ba2+] = x × = 0.1xM . But [CO32− ] is
= 6 × 10–4 M 100
Equ. xM (6 × 10–4 + x)M same for both. Hence,
K sp (BaCO3 ) [Ba 2 + ][CO32 − ]
As [Pb2+][SO2− –4
4 ] = Ksp ⇒ x ⋅ (6 × 10 + x) = 1.6 × 10
–7
=
K sp (CaCO3 ) [Ca 2 + ][CO32 − ]
HINTS AND EXPLANATIONS

–4
⇒ x = 2 × 10 M
∴ Mass of lead unprecipitated K sp (BaCO3 ) 0.1x
⇒ −9
= ∴ Ksp(BaCO3) = 4.9 × 10–10
⎛ −4 ⎞ 4.9 × 10 x
= ⎜ 100 × 2 × 10 ⎟ × 208
⎝ 1000 ⎠ 114. [ NH4 OH] 0.05
–3 [ OH − ] = K b ⋅ = 2 × 10 −5 × = 4 × 10 −6 M
= 4.16 × 10 gm [ NH4+ ] 0.25
110. M + H2S  MS(s) + 2H+
2+
K sp 8 × 10 −12
∴ [Mg 2 + ] = = = 0.5 M
For ppt. of MS(s), Q < keq [ OH − ]2 ( 4 × 10 −6 )2
[H+ ] K a1 ⋅ K a2 115. For ppt, Q > Keq
or, 2+
<
[M ][H2S] K sp For the metal sulphides,
[ H + ]2 10 −7 × 1.5 × 10 −13 [M2 + ][H2S] 0.01 × 0.1
or, < Q= + 2
= = 10 −3 >
0.04 × 0.1 6 × 10 −21 [H ] (1.0 )2 Keq for PbS only
∴ [H+]max = 0.1 M ⇒ Pmin
H
= 1.0 Hence, only Pbs will precipitate.

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 Ionic Equilibrium 7.41

EXERCISE II (JEE ADVANCED)

Section A (Only one Correct)

1. [ NH2− ] = 10 −30 = 10 −15 M 9. [H+ ]HCOOH = [H+ ]CH3COOH

∴ Number of NH2− ions per ml or, 2.4 × 10 −4 × 0.6 = 1.8 × 10 −5 × C ⇒ C = 8 M

10 −15 × 1 100 × 8
= × (6 × 1023 ) = 6 × 105 ∴ Moles of CH3COOH added = = 0.8
1000 1000
2. On increasing temperature, the dissociation of
10. Ka(HA) = Kb(A–) = Kw = 10 −7
water will increase. It will result increase in [H+]
and as well as in [OH–] and hence, decreases in PH Now, [H+ ] = 10 −7 × 0.1 = 10 −4 M ⇒ P H = 4.0
and as well as POH.
3. For maximum dissociation, [H+] = [OH–]. K f = 3.4 × 1010 M−1S−1
11. NH+4 +OH − NH3 +H2 O
200 × 10 −2 Kb = ?
4. [H+] = 10–2 M ⇒ nH+ = = 2 × 10 −3
1000 Given : NH+4 


+ −10
 NH3 + H ; K1 = 5.6 × 10 M
300 × 10 −2
[OH–] = 10 –2 M ⇒ nOH− = = 3 × 10 −3 
and H2 O 
+ − −14
 H + OH ; K 2 = 1.0 × 10 M
2
1000
K1
∴ Moles of excess OH– remained = 1 × 10–3 ∴ NH+4 + OH − 

 NH3 + H2 O; K eq =
K2
1 × 10 −3
[OH–] = × 1000 = 2 × 10 −3 M
500 3.4 × 1010 5.6 × 10 −10
Now, =
∴ POH = – log (2 × 10–3) = 2.7 ⇒ PH = 11.3 Kb 10 −14
⇒ K b = 6.07 × 105 S−1
– 80 × 0.1 − 20 × 0.2
5. [OD ]excess = = 0.04 M
100 −
12. 
CH3COOH  CH3COO + H+
OD 0.1− x x 0.1+ x + y ≈ 0.1+ y
∴ P = – log (0.04) = 1.4
Now, PKw of D2O = PD + POD = 13.6 + 1.4 = 15 
Cl2 CHCOOH 
−
 Cl2 CHCOO + H+
0.1− y 0.1+ x + y ≈ 0.1+ y
∴ Kw = 1 × 10–15 y

HINTS AND EXPLANATIONS

400 × 0.2 − 100 × 0.4 y × ( 0.1 + y )
6. [OT-]excess = = 0.08 M 0.15 = ⇒ y = 0.05
500 ( 0.1 − y )
∴POT = – log(0.08) = 1.1 ∴ [H+] = 0.1 + x + y ≈ 0.1 + y = 0.15 M
Now, PT = PKw – POT = 2 × 7.60 – 1.1 = 14.1 ∴ PH = – log(0.15) = 0.82
Kw 10 −14 0.4 4.25 / 17
7. Kb = = = 5 × 10 −5 13. [ OH − ] = × = 0.004 M
Ka 2 × 10 −10 100 250 / 1000

8. 
NH3 + H2 O 
+
 NH4 + OH
− POH = – log(0.004) = 2.4
∴ PH = 14 – 2.4 = 11.6
ΔH° = (–52.21) + (54.70) = 2.49 kJ
ΔS° = 1.6 + (–76.3) = – 74.7 J/K 14. [ OH − ] = K b × C = 1.6 × 10 −6 × 0.0025
Now, ΔH° = – RT. ln Keq = 4 × 10 −9 M
or, 2490 – 300 × (–74.7) = –8.3 × 300 × ln Keq
P OH = − log 4 × 10 −9 = 4.2 ⇒ P H = 9.8
∴ Keq = e–10

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 7.42 Chapter 7

22. PH = – log (2 × 10–6) = 5.70

4 × 10 −4
15. [HSaC ]O = = 2 × 10 −3 M
200 / 1000 6.67 × 10 −3
23. [OH–] = 6.67 × 10–3 + + 0 ≈ 10 −2 M
and PH = 3.0 ⇒ [H+] = 10–3 M 2
∴ POH = – log (10–2) = 2.0 ⇒ PH = 12.0
[S aC − ] × 10 −3
Now, 2 × 10 −12 = + − −5
2 × 10 −3 24. 
en + H2 O  enH + OH ;K b1 = 8.1 × 10
( 0.09 − x )M ( x − y )M ( x + y )M
⇒ [SaC − ] = 4 × 10 −12 M
enH+ + H2 O 


2+ −
 enH2 + OH ;K b2 = 7.0 × 10
−8
20 × 0.5 ( x − y )M yM ( x + y )M
16. [HA ]O = = 0.2 M
50 ( x − y )( x + y ) x⋅x
30 × 0.2 Now, 8.1 × 10 −5 = K≈
[HB]O = = 0.12 M ( 0.09 − x ) 0.09
50
+ −
⇒ x = 2.7 × 10 −3
HA 
H + A
0.2 − x x+ y y ⋅ (x + y) y ⋅ x
x
and 7.0 × 10 −8 = ≈ ⇒ y = 7.0 × 10 −8
 − + (x − y) x
HB H + B
0.12 − y x+ y y
∴ [en H+] = (x – y) ≈ xM = 2.7 × 10–3 M
(x + y) ⋅ x (x + y) ⋅ x [enH2+ −8
2 ]= y = 7.0 × 10 M
Now, 2 × 10 −4 = ≈
0.2 − x 0.2 ∴ [OH–] = (x + y) = x = 2.7 × 10–3 M
–5
∴ (x + y) ⋅ x = 4 × 10 (1) and POH = – log (2.7 × 10–3) = 2.56 ⇒ PH = 11.44
(x + y) ⋅ y (x + y) ⋅ y
and, 5 × 10 −5 = ≈ [ H + ]2 [ 5 2 − ]
( 0.12 − y ) 0.12 25. K a1 ⋅ K a2 =
[ H 2 S]
∴ (x + y) ⋅ y = 6 × 10–6 (2)
( 0.1)2 × [52 − ]
+
From (1) and (2), [H ] = x + y = 6.78 × 10 M –3 or, (1.4 × 10 −7 ) × (1.0 × 10 −14 ) =
0.2
17. 10 −5 = K a × 0.01 ⇒ K a = 10 −8 ⇒ [52 − ] = 2.8 × 10 −20 M

Now, [ OH − ] = 10 −8 × 0.1 = 10 −4.5 ⇒ P OH = 4.5 26. [H+ ] = 0.2 × 2 × 10 −5 = 2 × 10 −3 M

∴ PH = 9.5 Now, ( 2 × 10 −5 ) × (5 × 10 −9 ) × ( 4 × 10 −12 )

 + − ( 2 × 10 −3 )3 × [ A3+ ]
18. RNH2 +H2 O  RNH3 + OH =
0.01− x x x +10 −4 [H3 A ]
x( x + 10 −4 ) [ A3− ]
2 × 10 −6 = ⇒ x = 10 −4 ∴ = 5 × 10 −17
HINTS AND EXPLANATIONS

0.01 − x [H3 A ]
∴ [OH–] = 2 × 10–4 M
27. [H+ ] = 0.1 × 10 −5 = 10 −3 M
19. As on adding HCl, [H+] is not changing and will
remain unchanged. [H+ ][ A3 − ] [ A3− ] 10 −13
Now, K a3 = ⇒ = = 10 −10
− + [HA 2 − ] [HA 2 − ] 10 −3
20. 
Co2 +H2 O 
 HCo3 + H
↓
←
Shiftleft ∴ PX = 10
Decrease

As [H+] decreases, PH increases. 28. OH − + ACOH 



−
 ACO + H2 O
2 m mol 3 m mol 0
Final 0 1 m mol 2 m mol
0.16 / 32
21. [ W2 H4 ]O = = 0.01 M
500 / 1000 2
pH = 4.74 + log = 5.04 (Acidic)
−6
1
4 × 10
∴∝= = 0.02 or 2% Addition of 1 ml ACOH will decrease PH by 0.3
0.01
unit.

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 Ionic Equilibrium 7.43

29. Millimoles of ACOH = 6 × 0.1 = 0.6

0.28 35 × 0.1
Millimoles of ACO– = 12.× 0.1 = 1.2 36. nHA = nOH− ⇒ = ⇒ M= 80
M 1000
1.2
∴ pH = 4.75 + log = 5.05
0.6 37. Fe3+ + H2 O 


2+
 Fe(OH ) + H
+
0.9 xM 0.1x M ?
30. 1st solution will finally have 1 mole of CH3COOH.
0.1x × [H+ ]
1 9 × 10 −3 = ⇒ [H+ ] = 0.081 ⇒ P H = 1.08
∴ P1H = P Ka 0.9x
2
and for 2nd solution, P2H = P Ka 38. In final solution: [HA] = [A–]
Kw
39. [ NH3 ] = × C = 8.33 × 10 −4 M
31. P2H = P1H + 0.6 Ka ⋅ K b
y/M x /M
pKa + log = P Ka + log + log 3.98 2 2
C C 40. For equivalence point, 2.5 × = VHcl ×
5 15
y ∴ VHCl = 7.5 ml
∴ = 3.98
x
10 −12
BOH + H+ 

 B
+
+H2 O; K aq = = 102
C 10 −14
32. 4.0 = 5.0 + log 1 ⇒ C1 = 0.05 M 2.5 ×
2
7.5 ×
2
0.5 5M 15 M 0
C 10 10
6.0 = 5.0 + log 2 ⇒ C 2 = 5.0 M 0 0 0.1M
0.5 Eqn. xM XM (0.1− x )M
V × 0.05 + V × 5.0
Now, final P H = 5.0 + log = 5.7 0.1 − x
V × 0.5 + V × 0.5 100 = ⇒ x = 2.7 × 10 −2 M = (H+ )
x⋅x
αβ 41. At 2nd equation point:
33. For maximum β, = 0 ⇒ P H = P Ka
α [H+ ] 1 K a2 K 8 + 12
PH = ( P +P a3 ) = = 10
+ H+  + 2 12
34. BOH  B + H2 O
40 × C V × 0.1 0 [H+ ][ A3 − ]
M 40 + V
M Now, K a1 ⋅ K a2 ⋅ K a3 =
40 + V 0.1V [H3 A ]
40 C-0.1V 0 40 + V
Final (10 −10 )3 × [ A3 − ]
40 + V
or 7.5 × 10 −4 × 10 −8 × 10 −12 =
H+ must be a limiting reagent because both PH are [H3 A ]
above >.0.
[H3 A ] 10 −6
∴ = = 1.33 × 10 −7

HINTS AND EXPLANATIONS

0.1V
OH K
Now, P =P b +log [ A3− ] 7.5
40C − 0.1V
0.1× 5 1
14 − 10 =P K b +log (1) 42. CO32 − + H+ 


−
 HCO3 ; K =
40C − 0.1× 5 0.35 M 0.35 M 0 4 × 10 −11
100% run 0 0 0.35 M
0.1× 20
14 − 9 =P K b +log (2)
40C − 0.1× 20 For HCO3− solution,
∴ Kb = 2 × 10–5
[H+ ] = K a1 , K a2 = 1.4 × 10 −8 M
35. For maximum buffer capacity:
[ ACOH] 2 2M [H+ ][C O32 − ]
= ⇒ [ NaOH]= = 1M Now, K a2 =
[ NaOH] 1 2 [HCO3− ]

500 × 1 4 × 10 −11 × 0.35

∴ Mass of NaOH added = × 40 = 20 gm ∴ [CO32 − ] = = 10 −3 M
1000 1.4 × 10 −8

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M07 Advanced Problems in Physical Chemistry xxxx_Part B.indd 43 7/16/2019 11:51:04 AM
 7.44 Chapter 7

0.125 K a ⋅ [HA ]
43. [ LaC − ]0 = × 2 = 0.5 M [H+ ] =
0.5 [A− ]
1 ⎛ 75 25 ⎞
Now, P OH = 7 − ( P Ka + log C ) ∴ [H+ ]required = [ H + ]2 − [ H + ]1 = K a ⎜ − ⎟
2 ⎝ 25 75 ⎠
1 = 8 × 10–5 M
5.6 = 7 − ( P Ka + log 0.5 )
2
[ ACo− ]O
∴ P Ka = 3.1 ⇒ K a = 8 × 10 −4 48. 5.5 = 4.75 + log
[ ACOH]O
44. As HA is stronger acid, it will react [ ACo− ]O 5.62
first. For first equivalent point, ∴ =
VNaOH × 0.2 = 50 × 0.05 ⇒ VNaOH = 12.5 ml [ ACOH]O 1

At first equivalent point, 224 30 × 1

49. nCO2 = = 0.01 and nH+ used = = 0.03
50 × 0.05 22400 1000
[A− ] = = 0.04 M
62.5 CO2 +OH − ⎯⎯
→ HCO3−
0.01 mole (L.R. ) 0.01 mole or less
50 × 0.08
[HB]= = 0.064 M
62.5 Hence, moles of H+ used should be 0.01 or less
and titration of HCO3− and H+ should not be
Now, A − + HB 


−
 B + HA ; detected by phenolphthalein. Hence, OH– must be
0.04 − x 0.064 − x x x
 0.04  0.064 in excess.
K a (HB) 10 −8.2 CO2 + 2OH − → CO32 − + H2 O
⎯⎯
K eq = = = 10 −4.4 = 4 × 10 −5 0.01 mole 0.02 mole 0.01 mole
K a (HA) 10 −3.8
x⋅x Thus, 0.01 mole of CO32− will require only 0.01
4 × 10 −5 = ⇒ x = 3.2 × 10 −4 mole of H+ in the presence of phenolphthalein.
0.04 × 0.064
As the mole of H+ used is 0.03, 0.02 mole OH–
[H+ ][ A − ] must be present in excess.
Now, K a (HA ) =
[HA ] Hence, total moles of OH– used = 0.02 + 0.02 =
[H+ ] × 0.04 0.04,
⇒ 1.6 × 10 −4 = 0.04
3.2 × 10 −4 ∴ [ NaOH]used = = 0.04 M
1
∴ [H+ ] = 1.28 × 10 −6 ⇒ P H = 5.9
304
50. PbSO 4 = 2 × 10 −9 ×  1.36 × 10 −3 g/100ml
45. CrO24 − 
+H2 O 
−
 HCrO4 +OH ; −
10
HINTS AND EXPLANATIONS

0.005 − x x x
97
Kw ZaS = 10 −22 × = 9.7 × 10 −11 g/100ml
Kh = = 2 × 10 −8 10
K a2
188
x⋅x x2 AgBr = 4 × 10 −13 × = 1.19 × 10 −5 g/100ml
2 × 10 −8 = ≈ ⇒ x = 10 −5 10
0.005 − x 0.005
10 −5 123
∴ h= = 0.002 CuCo3 = 10 −8 × = 1.23 × 10 −3 g/100ml
0.005 10

46. P
K a1
= 2.40 and P
K a2
= 9.60 51. Hg 2+ + 4Cl − 


2−
 HgCl 4
0.1 M 0.9 M 0
100% ram 0 0.5M 0.1M
1 0.5M
Eqn. 1.6×10 −17 M 0.1M
∴ Required pH = ( 2.40 + 9.60 ) = 6.00
2
0.1
+ −
∴ K form = −17 4
= 1017
47. 
HA H + A 1.6 × 10 × ( 0.5 )
Red Blue

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M07 Advanced Problems in Physical Chemistry xxxx_Part B.indd 44 7/16/2019 11:51:09 AM
 Ionic Equilibrium 7.45

52. AgBr(s) + 2S2 O32 − 



3−
 Ag(S2 O3 )2 + Br
−
61. [CO32 − ] = 2.0 M
0.1 aM 0 0
Eqn/final 0 a − 0.2 0.1 0.1 K sp (CaCO3 ) [CO32 − ]
Now, =
0.1 × 0.1 K sp (CaF2 ) [ F − ]2
K eq = 4 × 10 −13 × 1.6 × 1012 = 2
⇒ a = 0.325
( a − 0.2 )
x 2 8 y3
⇒ 3
= −
⇒ (F− ) =
53. 
Tl2S(S) 
+
 2Tl + S
2− 4y [F ] x
2SM x
Kw 62. BaF2 (s ) + C 2 O24 − (aq) ⇒ BaC 2 O 4 (s ) + 2 F − (aq)
S2 − + H 2 O 


− −
 HS + OH ; K h = ( 0.1− x )M 2 xM
xM SM SM K a2
[F − ] K sp (BrF2 ) 10 −6
10 −14 2 × 10 −6 × 2 × 10 −6 K eq = = = = 10 4
= ⇒ x = 4 × 10 −12 [C 2 O24 − ] K sp (BrC 2 O 4 ) 10 −10
10 −14 x
–
∴ x ≈ 0.1 ⇒ [F ] = 0.2 M
∴ K sp = ( 2 × 2 × 10 −6 )2 × 4 × 10 −12 = 6.4 × 10 −23
10 −6
∴ [Ba 2 + ] = = 2.5 × 10 −5 M
56. M3+ + SCN−3− 

 M(SCN )
2+
( 0.2 )2
2 ×10 −3 M 1.51×10 M 0
Eqn. 2 ×10 −3 − x 1.51×10 −3 − x xM
S = [ Zn(OH)2 (aq)] + [ Zn(OH)+ ] + [ Zn2 + ]
=1.0 ×10 −5 M =1.5 ×10 −3 M
63.
= 5 ×10 −4 M
+ [ Zn(OH)3− ] + [ Zn(OH)24 − ]
1.5 × 10 −3
∴ Kf = = 3 × 105
5 × 10 −4 × 1× 10 −5 K 2 ⋅ K1 K3 ⋅ K 2 K1
= K1 + −
+
 2+ 2− [ OH ] [ OH − ]2
57. SrCO3 (s)  Sr + CO3
2 ×10 −4 M 2 ×10 −4 − x + K 4 K1 [ OH − ] + K5 K 4 K1 [OH − ]2
CO32 − 
+ H2 O 
−
 HCO3 + OH−6
−
10 −7 × 10 −6 10 −4 × 10 −7 × 10 −6
( 2 ×10 −4
− x )M xM 4 ×10 M = 10 −6 + +
0.1 ( 0.1)2
10 −14 x × 4 × 10 −6 0.01
Now, −11
= −4
⇒x= + 103 × 10 −6 × 0.1 + 10 × 103 × 10 −6 × ( 0.1)2
5 × 10 ( 2 × 10 − x) 51
4 =10–6 +10–12 + 10–15 + 10–4 + 10–4 ≈ 2 × 10–4 M
∴ K sp = ( 2 × 10 −4 ) × ( 2 × 10 −4 − x ) = × 10 −8
51
2+ 2−
64. For molecular solubility of CaCl2,
58. 
MnS(S)  Mn + S
SM ( S − x )M ΔHsolution = 209.2 + (–33.5) = 175.7 KJ > 30 KJ
2−  − −
S + H2 O  HS + OH For ionic solubility of CaCl2,
( S − x )M xM xM
ΔHsolution = 209.2 + 1004.2 + 1715.4 – 1598.3 –

HINTS AND EXPLANATIONS

10 −14 x⋅x 719.6 – 711.2 = – 100.3 KJ
−14
=and 2.5 × 10 −10 = S ⋅ (S − x )
10 (S − x ) For molecular solubility of HgCl2,
∴ S = 6.3 × 10–4 M ΔHsolution = 83.7 – 66.9 = 16.8 KJ < 30 KJ
 − −
59. AgCl(s) + Br (aq)  AgBr(s)+ Cl (aq ) For ionic solubility of HgCl2,
0.1− 0.075 xM 0.075 0.075 M
ΔHsolution = 83.7 + 460.2 + 2815.8 – 1845.1 – 719.6
[Cl − ] K sp (AgCl) 0.075 2 × 10 −10 – 711.2
K eq = = ⇒ =
[Br − ] K sp (AgBr) [Br − ] 4 × 10 −133 = 83.3 KJ > 30 KJ
∴ [Br − ] = 1.5 × 10 −4 M Hence, CaCl2 is ionic and HgCl2 is molecular
solubility.
60. [ Ag(CN )2− ] = 0.01M
6 × 0.001 × 5
[ Ag + ][CN − ]2 [ Ag + ] × ( 2.5 × 10 −7 )2 65. [C 2 O24 − ] = = 6 × 10 −5 M
K diss = ⇒ 1 × 10 −20 = 250 × 2
[ Ag + (CN )2− ] 0.01
∴ K sp = (6 × 10 −5 )2 = 3.6 × 10 −9
+ −9
∴ [ Ag ] = 1.6 × 10 M

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 7.46 Chapter 7

66. Sr 2 + + NO3− 

 Sr(NO3 )
+ 10 −3
50 = ⇒ [ OH − ] = 2 × 10 −5 M ⇒ P H = 9.30
0.001M
Eqn. 0.001− x
0.05 M
0.05 − x
0
x
[OH − ]
75  0.05M
= 0.001×
100
As the calculated [OH–] is minimum OH–, PH is
∴ x = 0.00025 minimum.
 3+ − −33
2.5 × 10 −4 20 Al(OH)3 (s)  
 Al + 3OH ; K = 8 × 10
Now, K f = = 10−3 M
−4
7.5 × 10 × 0.05 3
8 × 10 −33 = 10 −3 × [ OH − ]3 ⇒ [ OH − ] = 2 × 10 −10 M
 + −
67. ACOAg(s) + H + Cl  ACOH + AgCl(s) ⇒ P H = 4.30
0.1 Mole 0.1 M 0.1 M
As the calculated [OH–] is maximum OH–, PH is
[ ACOH] [ ACO − ] [ Ag + ] maximum.
K eq = × ×
[H+ ][Cl − ] [ ACO − ] [ Ag + ]
72. From the question,
K sp [ ACOAg]
= [Cu(CN)34− = 0.1 M and [CN–] = 0.2 M
K sp (AgCl) × K a
K Instab ⋅ [Cu(CN)34− ] 6.4 × 10 −15 × 0.1
10 −8 7 ∴ [Cu + ] = =
= = 10 ⇒ Almost complete reaction [CN − ]4 ( 0.2 )4
10 −10 × 10 −5
= 4 × 10 −13 M
+ 0.1 −4
∴ [ ACOH]  0.1M, [H ] = =10 M
107 K sp (Cu 2S) 2.56 × 10 −27
Now, [S2 − ] = =
+ 2
Ka × [ ACOH] [Cu ] ( 4 × 10 −13 )2
−
and [ ACO ] = = 0.01 M
[H+ ] = 1.6 × 10 −2 M
K a × [ H 2 S] 1.6 × 10 −21 × 0.1
68. 
A x B y (s) 
y+
 xA + yB
x− ∴ [H+ ] = 2−
= −2
= 10 −10 M
[S ] 1.6 × 10
1
H
⎛ K sp ⎞ x+ y and P = 10.0
K sp = x x ⋅ y y ⋅ s x + y ⇒ s = ⎜⎜ x y ⎟⎟
⎝x ⋅y ⎠ 4 × 10 −3 × 136
73. S = 1.6 × 10 −5 = 4 × 10 −3 M = × 106
As Ksp << 1, greater the value of (x + y), greater is s. 103
69. Theory based = 4 × 136 ppm
For increase in concentration 4 times, volume should
K sp
70. s = [ Zn2 + ] + [ Zn(OH)4− = + K f [ OH − ]2 1 th
[ OH − ]2 be . Hence, 75% water should be evaporated.
4
HINTS AND EXPLANATIONS

dS
For maximum or minimum S, =0 74. During precipitation, the concentration of both
d[ OH− ] Ba2+ and SO2− 4 ions will decrease.
−2K sp
or, + 2 K f [ OH − ] = 0 75. K sp ( AgCl) = 10 −4 × 10 −6 = 10 −10
[ OH − ]3
1 K sp (Ag 2 CrO 4 ) = (10 −4 )2 × 8 × 10 −4 = 8 × 10 −12
⎛ K sp ⎞ 4
⇒ [ OH − ] = ⎜ −4
⎟ = 10 M After precipitation of AgCl, find the concentration
⎝ Kf ⎠
of Cl–. [Cl − ]final = 1.0 × 10 −6 − 8 × 10 −7 × 2 × 10 −7 M
∴ PH = 10 and Smin = 2.4 × 10–9 M
71. Al(OH)3 (s) + OH− 
 − [CrO24 − ]final K sp ( Ag CrO 4 )
 Al(OH)4 ; Now, =
[Cl − ]2final 2
K sp ( Ag Cl)
?
From question 10−3 M
[CrO24 − ]final 8 × 10 −12
= ⇒ [CrO24 − ]final = 3.2 × 10 −5 M
8 × 10 −33 ( 2 × 10 −7 )2 (10 −10 )2
K= = 50
1.6 × 10 −34
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 Ionic Equilibrium 7.47

Hence, moles of Ag2CrO4 precipitated

2 × 10 −5 × 0.25
= 8 × 10 −4
− 3.2 × 10 −5
= 7.68 × 10 −4 = = 3.33 × 10 −5 > 4 × 10 −6 M
0.15
76. To prevent precipitation of AgCl, the concentration Hence, no precipitation. To start precipitation
K sp ( AgCl) [H+] should decrease and hence, CH3COONa
of Ag+ needed in solution = should be added.
(Cl − )
2 × 10 −5 × 0.25
1.8 × 10 −10 Now, 4 × 10 −6 =
=
<< 1.8 M [CH3COONa]O
0.16
Hence, almost all Ag+ ion must form complete ∴ [CH3COONa]O = 1.25 M
with CN– ions.
79. Mg(OH)2 (S) + 2 NH4+ 


2+
 Mg + 2 NH4 OH
Ag + + 2 CN − 


−
 Ag(CN)2 ; K f = 6.4 × 10
17

To re-dissolve Mg(OH)2, Q ≤ Keq

1.8 ×10 −10 CM
M 1.8 M
0.16 [Mg 2 + ][ NH4 OH]2 K sp
or, ≤
[H2 CO3 ] [NH+4 ]2 K b2
77. [CO32 − ] = K a (overall ) ⋅
[ H + ]2 2
To prevent precipitation of MCO3, ⎛ 0.15 × 0.1 ⎞ ⎛ 0.35 × 0.1 ⎞
⎜ ⎟⎜ ⎟ 1.2 × 10 −11
0.5 ⎠ ⎝ 0.5 ⎠
or, [M2 + ][CO32 − ] ≤ K sp or, ⎝ ≤
⎛ n ⎞
2
( 2.0 × 10 −5 )2
K a ⋅ [H2 CO3 ] ⎜ ⎟
or, [M2 + ] ⋅ ≤ K sp ⎝ 0.5 ⎠
[H+ ]2 ∴ n ≥ 0.035
2+
[M ] ⋅ K a [H2 CO3 ] Hence, minimum mass of (NH4)2SO4 needed
∴ [H+ ] ≥
K sp 0.035
= × 132 = 2.31 gm
2
0.1 × 5 × 10 −17 × 0.05
For MgCO3 : [H+ ] ≥
9 × 10 −8 Ag + Cl − 
80. +  AgCl(S)
−6
= 2.5 × 10 M 500 × 0.01 250 × 0.02
∴ PH ≤ 5.6 1000 1000

+ 0.1 × 5 × 10 −17 × 0.05 = 5 ×10 −3 M = 5 ×10 −3 M

For SrCO3 : [H ] ≥
9 × 10 −10 Eq 5 ×10 −3 − ( x + y ) M ( 5 ×10 −3 − x ) M

5 × 10 −5
= M Ag + + Br − 
 AgBr(S)

HINTS AND EXPLANATIONS

3
∴ PH ≤ 4.78 = 5 ×10 −3 M = 5 ×10 −3 M

For precipitation of SrCO3 without any 5 ×10 −3 − ( x + y ) M ( 5 ×10 −3 − y ) M

precipitation of MgCO3, the PH range should be
As both reactions will tend towards completion,
4.78 to 5.6
(x + y) = 5 × 10–3
78. Mn2+ (aq) + H2S(aq)  MnS(s) + 2H+(aq)
Now, [Ag + ](5 × 10 −3 − x ) = 10 −10 (1)
To just start precipitation of MnS, Q < Keq
+ −10
⇒ [ Ag ] ⋅ y = 10
[ H + ]2 K a (H2S)
or, <
[Mn2 + ][H2S] K sp (MnS) and [Ag + ](5 × 10 −3 − y ) = 5 × 10 −13 (2)
+ 2 −21 y 1
[H ] 1.0 × 10
or, < ⇒ [H+ ] < 4 × 10 −6 M From (1) ÷ (2), −3
= 200 ⇒ y =
0.04 × 0.1 2.5 × 10 −13 5 × 10 −y 201
K ⋅ [CH3COOH]O
Now, in the given buffer, [H+ ] = a ∴ [Br − ] = 5 × 10 −3 − y ≈ 2.5 × 10 −5 M
[CH3COO − ]O

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 7.48 Chapter 7

Section B (One or More than one Correct)

+ −
1. (a) Complete neutralization ⇒ PH = 7.0 9. 
NH4 OH(aq)  NH4 + OH
+ 55 × 0.1 − 45 × 0.1 Addition of solid NH4OH will increase
(b) [H ]final = = 0.01 M
100 NH4OH(aq) concentration and hence, [OH–] will
⇒ P H = 2.0 increase.
(c) OH– is in excess.  + −
10. (c) H2 O + H2 O  H3 O + OH ; ΔH ° = + ve
1 1
75 × − 25 ×
5 5 = 0.1 M ⇒ P H = 1.0 (d) HA + OH − 


−
 A + H2 O
(d) [H+ ]final =
100 a a 0
2
a a
2. For basic solution: [H+ ] < [ OH − ] and [H+ ] < Kw Final
2 2

P kw P kw a/2
∴ PH > POH or P H > or P OH < P H = P Ka + log = P Ka
2 2 a/2

 + − 11. [H+ ] >> [CO32 − ]

3. HA H +A
C(1−α )M Cα M Cα M
12. Theory based
2
Cα ⋅Cα α ⋅C Ka 
Ka = = ≈ α 2 ⋅C ⇒ α = 13. NH4 Cl + NaOH  NH4 OH+ NaCl
C (1 − α ) 1 − α C
a b 0
+ +
[H ] ⋅ C α [H ] ⋅ α Ka For buffer: (a −b ) ≈0 ⇒ a >b
Now, K a = = ⇒α = b
C (1 − α ) 1− α K a + [H+ ]

CH3COONa + HCl  CH3COOH+ NaCl
1 1
= = b
[H+ ] a 0
Ka
− PH )
1+ 1 + 10( P
For buffer: (a −b ) ≈0 b ⇒ a >b
Ka

4. Dilution results in increased degree of dissociation 14. KCN is a salt of weak acid (HCN) and strong base
but decrease in concentrations of all active (KOH).
components. 15. BOH + H+ 


+
 B + H2 O
5. Relation is valid only for conjugate pairs. a mole b mole 0
H +
6. P may decrease only on increasing [H ]. 1 a
th run a − 0 a
5 5 5
 − +
7. CH3COOH  CH3COO + H Equivalent point  0
0
HINTS AND EXPLANATIONS

a mole
( 0.1− x ) M xM ( 0.1+ x ) M
[B − ]
 0.1 M  0.1 M Now, for 1/5th reaction, P OH = P K b + log
[BOH]
x × 0.1
Now, 1.8 × 10 −5 = ⇒ x = 1.8 × 10 −5 a/5
0.1 or, (14 − 9 ) = P K b + log
4a / 5
x
and α = = 1.8 × 10 −4 ∴ P K b = 5.6 ⇒ K b = 2.5 × 10 −6
0.1
Kw 1
Now, [HT ]from water = [ OH − ] = +
= 10 −13 M At equivalent point: P H => − ( P K b + log C)
[H ]acid 2
1
+ − or, 4.5 => − (5.6 + log C) ⇒ C = 0.25 M
8. 
RNH2 ( g)+ H2 O(l)  RNH3 (aq )+ OH (aq ) 2
1 bar xM xM Now, nHCl used = nB+ formed
x⋅x V × 0.5 (100 + V ) × 0.25
10 −6 = ⇒ x = 10 −3 ⇒ P OH = 3.0 ⇒ P H = 11.0 or, = ⇒ VHCl = 100 ml
1 1000 1000

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 Ionic Equilibrium 7.49

Finally, nBOH takes = nHcl used for equivalent point 1 K a1 K 1

PH = (P + P a2 ) = ( 2.22 + 9.78) = 6.0
w 100 × 0.5 2 2
or, = ⇒ w = 2.25 gm
45 1000 ⊕
2.25 [NH3 CH2 COO − ][H+ ]
∴ Percentage purity of base = × 100 = 90% Now, K a =
1 ⊕
2.5 [NH3 CH2 COOH]
0.01× 10 −6
16. CO32 − + H2 O 


− −
 HCO3 + OH ; ⇒ 10 −2.22 = ⊕
( 0.5 − x ) M ( x − y )M ( x + y )M
[NH3 CH2 COOH]
Kw ⊕
K h1 = = 2 × 10 −4 ∴ [NH3 CH2 COOH] = 10 −5.78 = 1.7 × 10 −6 M
K a2
% of glycine in cationic form
HCO3− + H2 O 


−
 H2 CO3 + OH ; 1.7 × 10 −6
( x − y )M yM ( x + y )M = × 100 = 0.017%
0.01
Kw
K h2 = = 2.5 × 10 −9 18. At equivalent point, the solution should be acidic.
K a1

(x − y) ⋅ (x + y) x ⋅ x 19. Sodium acetate solution is basic.

Now, 2 × 10 −4 = ≈ ⇒ x = 10 −2
( 0.5 − x ) 0.5
20. For precipitation of Fe(OH)2,
y ⋅ (x + y) y ⋅ x
and 2.5 × 10 −9 = ≈ ⇒ y = 2.5 × 10 −9 8 × 10 −16
(x − y) x [ OH − ]min = = 2 × 10 −7
0.02
x
Now, h = = 0.02 OH
⇒ Pmax H
= 6.7 ⇒ Pmin = 7.3
0.5
P OH = − log( x + y ) ≈ − log(10 −2 ) = 2.0 ⇒ P H = 12.0 For precipitation of Fe(OH)3,
1/ 3
and [H2CO3] = y = 2.5 × 10–9 M ⎛ 4 × 10 −28 ⎞
[ OH − ]min = ⎜ ⎟ = 2 × 10 −9
+
= 2.22
K
P a1
+ ⎝ 0.05 ⎠
17. N H3CH2 COOH ⎯⎯⎯⎯⎯ → N H3CH2 COO −
OH H
⇒ Pmax = 8.7 ⇒ Pmin = 5.3
P Ka2 =9.78 −
⎯⎯⎯⎯⎯
→ NH3CH2 COO

HINTS AND EXPLANATIONS

Section C (Comprehensions)
Comprehension I

[ Dimer] x (D imer ) x x 9
1. K = 1.5 × 102 = = ∴ = ⇒ =
[Monomer] 2
( 0.1 − 2 x ) 2 [Monomer] 0.1 − 2 x 0.1 2500
5
⇒x= 3. [H+ ] ≈ 0.1 × 2 × 10 −5 = 2 × 10 −3 M
120
[ Dimer ] x 5 (Dimerization is negative as Q. 2)
∴ = =
[Monomer] 0.1 − 2 x 2 ∴ PH = 2.85

( Dimer ) x
2. K = 3.6 × 10 −2 = =
[Monomer ] 2
( 0.1 − 2 x )
−4
⇒ x = 3.6 × 10

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 7.50 Chapter 7

Comprehension II
0.7 × 10 −3
4. [CH3COOH]O = = 7 × 10 −8 M ∴ P H = − log(7 × 10 −8 + x ) = 6.85
10 × 103
The solution is so dilute that we may assume
−
almost complete dissociation of acid. 5. 
CH3COOH  CH3COO + H+
∴ [H+ ]acid ≈ 7 × 10 −8 M Eqn. yM 7 ×10 −8M 7 ×10 −8 + x
=14 ×10 −8 M

Now, H2 O  H+ + OH − 7 × 10 −8 × 14 × 10 −8
( 7 ×10 −8 + x ) M xM
Now, 2.0 × 10 −5 =
y
10 −14 = (7 × 10 −8 + x ) ⋅ x ⇒ x = 7 × 10 −8
∴ y = 4.9 × 10–10 M

Comprehension III
(8 × 10 −3 )2 [H+ ] × (1.0 × 0.8)
7. Ka = = 3.2 × 10 −4 6. K a = 3.2 × 10 −4 =
0.2 0.2
∴ [H+] = 8 × 10–5 = ⇒ PH = 4.1

Comprehension IV

[ NH3 ]O + [ NH3 ]O 0.5

8. pH = pKa ( NH+4 ) + log pH = pKa (NH4 ) + log = 9.3 + log = 9.3
[ NH+4 ] [ NH+4 ]O 0.5
0.8 10. H+ added in excess. Final [H+] = 1.0 – 0.8 = 0.2 M
= 9.3 + log = 9.9
0.2
∴ PH = – log(0.2) = 0.7
+  +
9. NH4 OH+ H  NH4 + H2 O
0.8 M 0.3 M 0.2 M

Final 0.5 M
≈0 0.5 M

Comprehension V
10 −14
11. No hydrolysis ⇒ pH = 7.0 ∴ [H+ ] = = 1.58 × 10 −8 M
6.32 × 10 −7
12. Concentration of
HINTS AND EXPLANATIONS

11.85 / 474
KAl(SO 4 )2 .12H2 O = 14.
100 / 1000 Al3+ + SO24 − + H2 O 


2+ −
 Al(OH ) + HSO 4
= 0.25 M 0
0.25 M 0.5 M 0
2+ +
Al3+ + H2 O 

 Al(OH ) + H Eqn. ( 0.25 − x ) M (0.5 – x)M x x

( 0.25 − x ) M xM xM
1.4 × 10 −5 x⋅x x2
x⋅x x 2 = 
1.4 × 10 −5 =  1.25 × 10 −2 ( 0.25 − x )( 0.5 − x ) 0.25 × 0.5
( 0.25 − x ) 0.25
⇒ x = 1.87 × 10 −3 M = [H+ ] ∴ x = 1.18 × 10–2

1.18 × 10 −2 × [H+ ]
13. SO24 − + H2 O 


−
 HSO 4 + OH
− Now, 1.4 × 10 −5 =
0.25
( 0.5 − x ) M x x
∴ [H+] = 2.97 × 10–4 M
10 −19 x⋅x x2
=  ⇒ x = 6.32 × 10 −7 M
1.25 × 10 −2 ( 0.5 − x ) 0.5
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 Ionic Equilibrium 7.51

Comprehension VI

x⋅x x2
15. PuO22 + + H2 O 


+
 PuO2 (OH ) + H+ ∴ Kh =  = 2.56 × 10 −6
0.01 − x 0.1
0.01− x x x =1.6 ×10 −4
≈ 0.01 Kw
16. Ka = ⇒ K b = 3.9 × 10 −9
Kb

Comprehension VII
1 K a2 K 1
17. pH = (P + P a3 ) = (8 + 13) = 10.5 HPO24 − + H+ 

−
 H2 O 4
2 2
10 millimole 5 millimole 0
18. For 2nd equivalent point, Final 5 ≈0 5
nNaoH = 2 × nH3PO4
5
∴ P H = 8 + log = 8.0
V × 0.5 100 × 0.1 5
= 2× ⇒ V = 40 ml
1000 1000 K sp 4.0 × 10 −30
After adding HCl, 19. S= − 2
= −6 2
= 4.0 × 10 −18 M
[ OH ] (10 )

Comprehension VIII

[HCO3− ]O 8 [HCO3− ]O [H CO ] 1
20. P H = P Ka + log = 6.4 + log = 7.3 21. 7.4 = 6.4 + log ⇒ 2 −3 O =
[H2 CO3 ]O 1 [H2 CO3 ]O [HCO3 ]O 10
22. More CO2 should dissolve in solution.

Comprehension IX
1 K 1
23. pH = 7 + ( P a2 + log C)=7+ (10.6 + log 1) = 12.3 26. CO32 − + H+ 


−
 HCO3
2 2
50 ×1 75 ×1 0
M M
125
24. CO32 − + H + 

−
 HCO3
125
Final 0 25 50
M M
50 ×1 25 ×1 0 125 125
M M
75 75

HINTS AND EXPLANATIONS

25 25 HCO3− + H+ 

 H2 CO3
Final M ≈0 75
M
75 25
50 M 0
M 125
[CO32 − ]O
125
K a2 1/ 3
pH = P + log = 10.6 + log = 10.6 25 25
[HCO3− ]O Final M =0 M
1/ 3 125 125

[HCO3− ]O
∴ pH = P Ka + log
25. CO32 − + H+ 


−
 HCO3 [H2 CO3 ]O
50 ×1 50 ×1 0 25 / 125
M
100
M 100 = 5.4 + log = 5.4
25 / 125
Final ≈0 50
≈0 100
M
50 × 10 1
1 Ka1 K 1 27. [H2 CO3 ] = = M
∴ pH = (P + P a2 ) = (5.4 + 10.6 ) = 8.0 150 3
2 2
1 Ka1 1 1
∴ pH = (P + log C ) = (5.4 + log ) = 2.94
2 2 3

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 7.52 Chapter 7

Comprehension X
+ K = 2.5 ×10 −12
28. ⎯⎯⎯⎯⎯⎯
N H3 − CH3 − COOH ← ⎯⎯⎯⎯⎯
b2
→ Required K b = K b1 = 6.25 × 10 × 10 −5
−3 ⎯
K a1 = 4 ×10

+ K =1.6 ×10 −10 1 Ka1 K 1

⎯⎯⎯⎯⎯⎯
N H3 − CH3 − COO − ← ⎯⎯⎯⎯⎯
a2
→ 29. ∴ pH = (P + P a2 ) = ( 2.4 + 9.8) = 6.1
−5 ⎯ 2 2
K b1 = 6.25 ×10

N H2 − CH2 − COO −

Comprehension XI
6.35 × 10 −3
30. Moles of Cu reacted = = 10 −4 ∴ [ Ag + ] = 2 × Mole of Cu reacted = 2 × 10–4 M
63.5

ΔG ° −120 × 103 32. K sp = [ Ag + ][BRO3− ] = ( 2 × 10 −4 )2 = 4 × 10 −8 M2

31. ln K eq = = = 50 ⇒ K eq >>> 1
−RT −8.0 × 300

Comprehension XII
K sp [ AgCN ] 1.0 × 10 −16 K sp
33. S= −
= = 5.0 × 10 −15 M 35. s = [Ag + ] + [Ag(Cu )2− ]; + K f ⋅ K sp ⋅ [Cu − ]
[CN ] 0.02 [Cu − ]
5M

ds
34. AgCN(s) + CN − 


−
 Ag(CN )2 For minimum solubility: =0
d[Cu − ]
( 0.02 −S )M SM
K sp
K eq = K sp × K f = 15 or, − + K f ⋅ K sp = 0
[Cu − ]2
s 0.3
15 = ⇒s= = 1.875 × 10 −2 M 1
0.02 − s 16 ⇒ [Cu − ] = = 2.58 × 10 −9 M
Kf

Section D (Assertion–Reason)
HINTS AND EXPLANATIONS

1. For acidic solution, pH < 7.0 at 25° C. 7. K a (CH3COOH) = K b ( NH4 OH ) and hence,

2. If there were no common ion effect, PH should lie CH3COONH4 solution is also neutral. But, it
in between 7.0 and 7.3 undergoes hydrolysis.
3. [H+ ]HCl = 10 −4 M < [H+ ]HCOOH = 3.16 × 10 −2 M 8. Theory based
4. Dilution results decrease in concentration of BOH 9. Reaction occurs but at equivalent point, pH will
(aq), B+ (aq) as well as OH– (aq). be less than 7.
5. The pH of buffer remains constant on slight 10. As dilution does not change the concentration of
dilution but for acidic solution, the dilution results ions in saturated solution, the mole of ions will
in the decrease in [H+] and hence, increase in pH. increase.
6. pH of buffer containing HA and A– may be less
than, greater than or equal to 7.0.

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 Ionic Equilibrium 7.53

Section E (Column Match)

1. True electrolytes produce ions in pure liquid form (T) A− 

+ H2 O 
−
 HA + OH ;
as well as in solution. Potential electrolytes are
( 6 ×10 −5 − x ) M xM xM
molecular in pure liquid state but it produces ions
in solution. Kw
= 2 × 10 −6
Ka
K sp
2. (P) [OH–] to just start precipitation =
[Mg 2+ ] x⋅x
2 × 10 −6 = ⇒ x = 1 × 10 −5
(6 × 10 −5 − x )
2 × 10 −6
= −3
= 10 −1.5 ∴ POH = 5 ⇒ pH = 9
2 × 10
OH H 3. Theory based
∴ p = 1.5 ⇒ P = 12.5
1/ 3 1/ 3 K a1 [H2 A − ]O
⎛ K sp ⎞ ⎛ 10 −28 ⎞ 4. (A) pH = P + log = 4.0
(Q) [ OH − ]max =⎜ ⎟ =⎜ ⎟ [H3 A]O
⎝ [ Al3+ ] ⎠ ⎝ 0.1 ⎠
[HA 2 − ]O
= 10 −9 M (B) pH = P
K a2
+ log = 8.0
[ H 2 A − ]O
∴ pOH
min =9⇒ pH
max = 5.0
K a3 [A3 − ]O
(C) pH = P + log = 12.0
 − + [HA 2 − ]O
(R) CH3COOH  CH3COO + H
10 ? 1 Ka1 K 1
⎛ 10 ⎞
⎜⎝ 0.1− 0.1× ⎟⎠ M 0.1× M (D) pH = (P + P a2 ) = ( 4 + 8) = 6.0
11 11 2 2
0.1 1
= M = M 1 K a2 1
11 K
11 (E) pH = (P + P a3 ) = (8 + 12 ) = 10.0
2 2
1
× [H+ ]
Now, K a = 10 −5 = 11 ⇒ [H+ ] = 10 −6 M Kw 10 −14
0.1 5. (A) K a (H2 O) = K b (H2 O)= =
[H2 O] ⎛ 1000 ⎞
11 ⎜⎝ ⎟
18 ⎠
∴ pH = 6.0 = 1.8 × 10 −16
(S) [H+ ] = K a ⋅ C = 10 −7 × 0.001 = 10 −5 M (C) On increasing temperature, Kw increases and
hence, PKw decreases.
⇒ pH = 5.0

HINTS AND EXPLANATIONS

Section F (Subjective)
Single-digit Integer Type From given data: x = K = 10 −3 M
∴ Percentage of HCOOH molecules converted
1. [ D+ ] = K W = 10 −16 = 10 −8 M into HCOO–
⇒ P D = − log[ D+ ] = 8 x 10 −3
= × 100 = × 100 = 4 × 10 −3
C 25
1.15 × 103
2. [HCOOH]O = = 25 M = C
46 10 / 17
3. [ NH3 ]O = × 103 = 5 M
+ − 100 / 0.85

HCOOH+ HCOOH  HCOOH2 + HCOO
C−x C−x x x

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 7.54 Chapter 7

Kw 7. Buffer capacity,
[ OH − ] = K b ⋅ C = ⋅C
K a (NH4+ ) [H+ ] added 0.05 / 0.2
β=− =− =5
ΔP H
( −0.05 )
10 −14
= × 5 = 10 −2 M
5 × 10 −10 8. HA + OH − 

 A− + H2 O
−14
Kw 10 a millimole 36.12 × 0.1 0
∴ [H3 O + ] = = = 10 −12 M millimole
[ OH − ] 10 −2 3.612 millimole
Equ.point 0 0

A− + H+ 
 HA
4. [H+ ] = K a ⋅ C = 4 × 10 −10 × 0.0025 = 10 −6 M
3.612 mmole 18.06 × 0.1 mmole 0
H −6
∴ P = − log10 =6 Final 1.806 mmole 0 1.806 mmole

1.28 [ A − ]O 1.806
5. [H2SO3 ]O = = 0.02 M ∴ pH = P Ka + log = 5 + log =5
64 [HA]O 1.806


H2SO3 
+ −
 H + HSO3 9.
H2 A + + OH − 
 HA + H2 O
( 0.02 − x ) M xM
xM 30 × 0.06 mmole 20 × 0.09 mmole
x⋅x Final  0 0 1.8 mmole
Now, K a = 10 −2 =
( 0.02 − x ) 1 Ka1 K 1
⇒ x = 0.01 M ⇒ pH = − log x = 2 ∴ pH = (P + P a2 ) = ( 2.28 + 9.72 ) = 6
2 2

10. For appearance of only ln+ colour,

K a1 [HC 4 H4 O6− ]O
6. pH = P + log
[H2 C 4 H4 O6 ]O [ln + ] 4.6 − 3.4
log = = 0.6 = log 4
18.8 / 18.8 [ln OH] 2
= 3.3 + log =3
30 / 150 [ln + ]
∴ =4
[ln OH]

Four-digit Integer Type

+ − [H+ ][CH3COO − ]
1. 
C 6 H5 NH2 + H2 O  C 6 H5 NH3 + OH 2. Ka =
HINTS AND EXPLANATIONS

[CH3COOH ]
0.2 M 0 CM
4 × 10 −4 × [CH3COO − ]
Eqn. ( 0.2 − x ) M xM (C + x ) M ⇒ 1.8 × 10 −5 =
 CM 0.2
 0.2 M =10 −8 M
∴ [CH3COO − ] = 9 × 10 −3 M
[C 6 H5 NH3+ ][OH − ]
Now, K b = ∴ Mass of CH3COONa added
C 6 H5 NH2
10 −8 × C 9 × 10 −3 × 500
⇒ 4 × 10 −10 = × 82 = 0.369 gm = 369 mg
0.2 1000

∴ C = 8 × 10–3 M  + −
3. H2SO3  H + HSO 4
Now, mass of NaOH added CM 0 0
−3 CM
8 × 10 Final 0 CM
= × 500 × 40 = 0.16 gm = 160 mg
1000

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 Ionic Equilibrium 7.55

HSO 4− 


+ 2−
 H + SO 4
0.254
Fianl ( C − x )M ( C + x )M xM
= = 0.001
=0.01 M 254

0.01 × x 6 ∴ x = 0.049
Now, 1.2 × 10 −2 = ⇒x= C x
C−x 11 Now, K c =
( 0.05 − x )( 0.1 − x )
0.01 × 11
and C + x = 0.01 ⇒ C = M 0.049
17 = = 960
0.001 × 0.051
[ NaHCo3 ]O
4. P H = P Ka + log 9. Concentration of Ca(OH)2 in its saturated
[H2 Co3 ]O solution
V ×5 1/ 3 1/ 3
or, 7.4 = 6.1 + log ⇒ V = 80 ml ⎛ K sp ⎞ ⎛ 3.2 × 10 −5 ⎞
10 × 2 =⎜ =⎜ ⎟ = 0.02 M
⎝ 4 ⎟⎠ ⎝ 4 ⎠
1.8 / 120
5. [HSO 4− ]O = = 0.15 M Ca 2 + +
100 / 1000 Now, 2OH− 

 Ca(OH)2 (s )
0.02M 0.04 M
HSO 4− 


+ 2−
 H + SO 4 On adding NaOH
( 0.15 − x )M xM xM 0.01 M (0.02 + 0.8) M
x⋅x = 0.82 M
4 × 10 −2 = Equ (0.01 – x)M = 0 (0.82 – 2x)
0.15 − x
M = 0.8M
⇒ x = 6 × 10 −2 M = 60 millimole/L
3.2 × 10 −5
OH2 +
∴ [Ca 2 + ]left = = 5 × 10 −5 << 0.01
6. Al(H2 O )36+ + H2 O 

 Al(H2 O )5 + H3 O +
( 0.8)2
( C − x )M xM xM ∴ Ca(OH)2 precipitated = 0.01 mole = 0.01 × 74
=10 −3 M = 0.74 gm = 740 mg
−5
Now, 10 = C ≈ 0.1M

∴ Mass of Al(OH)3 added = 400 × 0.1 × 133.5 0.0055 / 550

10. S= = 10 −4 M
= 5.34 gm = 5340 mg 100 / 1000

Ka 60 ∴ Ksp of Ca(pam)2 = 4S3 = 4 × 10–12 M

7. 9.18 = P + log (1)
40 Ca 2 + + 2 pam − 

Now,  Ca(pam)2 (s )
x
9.00 = P Ka + log (2) 40 / 40
×102 0.1 M

HINTS AND EXPLANATIONS

100 − x 106

∴ x = 50 =10 −3 M

Final =0 0.1M
8. I2 + I− 


−
 I3
12.7 0.1 M 0
∴ Ca(pam)2 participated = 10–3 × 10 = 0.01 mole
254 = 0.01 × 550 = 5.50 gm = 550 mg
= 0.05M
0.1− x x
Eqn. (0.05 − x )M

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