Sheet - 01 (Solution) _ Ionic Equlibrium (Exercise) NJ_247

(Physical Chemistry) IONIC EQUILIBRIUM
SOLUTIONS
EXERCISE # O-I
1. H2O → H+ + OH+ H = +ve
kw if T Keq = Kw
2. Kw = [H+] × [OH–]
for pure water [H+] = [OH–]
Kw = 10–6.7 × 10–6.7 = 10–13.4
3. pHi = 3 Þ [H+]i = 10–3 M
pHƒ =6 Þ [H+]ƒ =10–6 M
[H+]i Vi = [H+]ƒ Vƒ
10–3 × Vi = 10–6 × Vƒ
Vƒ = 1000 Vi
Ci = 1000 Cƒ
4. pHi = 2  [H+]i = 10–2 M
pHƒ = 6 [H+]ƒ = 10–6 M
[H + ]i 10−2
=
[H + ]ƒ 10−6
[H+]i = 104 [H+]ƒ
5. pH = 13, so pOH = 1  [OH–] = 0.1
Moles of OH −
0.1 =
0.25
Moles of OH– = 0.025
Mass of NaOH = 0.025 × 40 = 1 g
6. pH of acid < 7
So pH sol should Þ 6 – 7
7. [H+]i = 10–2 [H+]ƒ = 10–3
initial moles = 10–2 final moles of H+ = 10–3
Moles of H+ should be removed = 10–2 – 10–3 = 0.009
1 1
10   2 + 40  2
200 200 1
8. [H+]ƒ = =  pH = 2
50 100
9. Higher the Ka , stronger the acid
10. NH3 is base, so [OH–] , [H+] ¯
12. CH3COOH CH3COO– + H+

APNI KAKSHA 1
0.1 (1 – ) 0.1  0.1 
0.1  0.1
10–5 =
0.1(1 − )
0.1 2 2
10–5 =  = 10–4 a = 10–2
1−  1− 
13. NH4OH → NH4+ + OH–

c(1 – ) c c
5
[OH–] = c = 0.02 × = 10–3
100
pOH = 3  pH = 11
10–3 + 10 –5 101
15. [H+]ƒ = = 10–5
2 2
101
pH = 5 – log = 3.3
2
16. [H+] = Ka1C1 + Ka 2C2 = 310−4  0.03 + 110−10  0.1 = 3 × 10–3 M
3 10−4  0.03
[A–] = −3
= 3 × 10–3 M
3 10
110−10
[B–] = −3
= 3.33 × 10–9 M
3 10
0.1 4 1 8
17. [OH–] = Ka1C1 + Ka 2C2 = 6.4  10−5  + 1.8  10−5   =  10−6 = 2 × 10–3 M
2 45 2 2
pOH = 3 – log2
pH = 11 + log2 = 11.3
18. → RNH3+ + OH –
RNH2 + H2O ⎯⎯
0.01-x x x
x − (x + 10–4 )
2 × 10–6 =
0.01– x
x2 + 10–4 x – 2 × 10–8 = 0
x = 10–4
APNI KAKSHA 2
[OH–] = 2 × 10–4
20. 0.1 M HCl + 0.1 M H3PO4 (a << 1)
H3PO4 H+ + H2PO–
0.1(1 – ) 0.1 + 0.1 0.1
» 0.1
[H+] = 0.1  pH = 1
0.1 0.1
Ka1 =  a= 10 K1
0.1
H2PO4– H+ + HPO42–
0.1 0.1 2
0.1 [HPO24− ]
Ka2 =
0.1
[HPO42–] = K2 = 10 Ka1 Ka2
21. [HPO42–] = 10 Ka1 Ka2
HPO42– → H+ + PO43–
10 Ka1 Ka2–x x+ 0.1 x
» 0.1
0.1  x 0.1  x
Ka3 = =
10Ka1Ka 2 − x 10Ka1Ka 2
[PO43–] = x = 100 Ka1 Ka2 Ka3
22. NH2– + H+ → NH3

Base C.A.
24. Bronsted acid → which can given H+
24. NHO3 + H2O H3O+ + NO3–

Acid Base C.A C.B.
25. CH3COOH + OH– CH3COO– + H2O
APNI KAKSHA 3
1 Ka 1.8  10−5
Keq = = = = 1.8 × 109
Kh Kw 10−14
26. Ka HF × Kb F– = Kw
pKa = 14 – 10.83= 3.17
Ka = 10–3.17 = 6.75 × 10–4
28. At 85ºC neutral pH < 7
0.01
29. [H+] = = 10–3 M  pH = 3
100
30. (A) 0.1 M NaCl  pH = 7

(B) 0.1 M NH4Cl  pH < 7
(C) 0.1 M CH3COONa  pH > 7
(D) 0.1 M HCl  pH = 1
Kw 10−14 1/ 80 10 −6
31 h= C = =
Ka 1.3 10−9 8  1.3
CN– + H2O → HCN + OH–

1/80(1 – h) h/80 h/80
10−14 h2 8
= Þ h2 =  10 −4
1.3 10−9 80(1 − h) 1.3
h = 2.48 × 10–2
% h = 2.48
32. CN − + H2O → HCN + OH −
0.01(1 − h) 0.01h 0.01h
10−14 0.01h 2
=
1.4 10−9 1− h
10
h2 =  10−4
1.4
h = 2.67 × 10–2
APNI KAKSHA 4
% h = 2.67%
K b3  K b2  K b1
33. Fe3+ + H2O → Fe(OH)2+ + H+
34. S2– + H2O → HS– + OH–
35. A3– + H2O → HA2– + OH–

Kw
Kh1 =
Ka 3
1
pH = (pKw + pKa3 + logC)
2
h
36. = Kh (for salt of WA + WB)
1− h
h does not depend on conc.
1 1
37. pH = (pKw + pKa – pKb) = × (14 + 4.8 – 4.78) = 7.01
2 2
38. Amphiprotic species ® which can given as well as take H+ ion.
41. For 1 M NaCl & 1 M HCl solution

 pH < 7
42. pOH = pKb = 4.74

pH = 9.26
[NH3 ] 0.05
43. [OH–] = Kb × = 1.8 × 10–5 × = 9.0 × 10–4
[NH +4 ] 0.001
500  0.5
44. pOH = 5 – log 1.85 + log
300  0.3
25
= 5 + log = 5.188
16.2
pH = 14 – 5.188 = 8.812
APNI KAKSHA 5
[CH 3COO – ]
45. pH = pKa + log
[CH 3COOH]
3
= 4.82 + log =5
2
10  1
46. pH = 5 + log =5–1=4
50  2
5  VmL
47. pH = 10 – log5 + log =9
10  2
5VmL
log = log0.5
20
VmL = 2 mL
x
48. 4.74 = 5 – log1.34 + log
0.02
x = 1.5 × 10–2 mol
0.1 VmL
49. 4 = 3.7 + log
50  0.05
0.01 VmL
2=  VmL = 50 mL
50  0.05
50. If [NH4OH] ¯, [OH–]¯, pH ¯
[C.B]
51. pH = pKa + log
[Acid]
[C.B]
Ph – pKa = log = 5 = log 105
[Acid]
[C.B.] = 105 × [Acid]
52. HA + NaOH → NaA + H2O

10 mmol x mmol 10 mmol –
10–x 0 10+x –
[A – ]
pH = pKa + log
[HA]
APNI KAKSHA 6
10 + x
5.5 = 5 + log
10 – x
10 + x
3.16 =  x = 5.2
10 – x
Mass of NaOH added = 5.2 × 40 × 10–3g= 2.08 × 10–1g
53. On moderate dilution pH of buffer solution does not change.
0.02
54. Buffer capacity = = 0.4
0.05
8 1
56. Moles of OH– = =
40 5
4.9 1
Moles of H+ = 2 =
98 10
0.1
[OH–] = = 0.1
1
pOH = 1  pH = 13
57. H2SO4 + 2NaOH → Na2SO4 + H2O

0.5 mmol 1 mmol
0 0 1 mmol
Solution will be neutral so pH = 7
58. M Moles of H+ = 15
M Moles of OH– = 5
10 1
[H+]ƒ = = Þ pHƒ = 1
100 10
64. NaCN + HCl ¾→ HCN + NaCl

mmi 4 2 0 0
mmƒ 2 0 2 2
60. (A) H3PO4 + NaH2PO4 (W.A + its salt)

(B) H2CO4 + NaHCO3 (W.A + its salt)
APNI KAKSHA 7
(C) NH4Cl + HCl (W.A + its salt)
(A) CH3COOH + CH3COONa (W.A + its salt)
61. HCOOH + KOH → HCOOK + H2O

mm : 16 8 0 0
mmƒ 8 0 8 -
8
pH = 3.7 + log = 3.7
8
pOH = 10.3
0.6
62. pH = 4.74 + log = 4.916
0.4
63. pH = pKa = 3.7
25
64. pH = 5 + log (25% neutralization)
75
1
= 5 + log
3
pH = 5 (50% neutralization)
75
pH = 5 + log (75% neutralization)
25
= 5 – log3
65. CH3COONa + HCl → CH3COOH + NaCl

mmi 2 2 0 0
mmƒ 0 0 2 -
2
[CH3COOH] = = 0.1
20
− +
CH 3COOH ⎯⎯
→ CH3COO + H
0.1− x x x
x2
1.8 × 10–5 =
0.1 − x
−3
[H+] = x = 1.8 10
pH = 2.88
APNI KAKSHA 8
66. For 0.1 M NaHA
7 + 11
pH = =9
2
for 0.1 M H2A pH < 7
for 0.1 M Na2A pH > 7
for 0.1 M NaHA + 0.1 M Na2A  pH = pKa2 = 11
67. N3PO4 + NaH2PO4

NaH2PO4 + Na2HPO4
Na2HPO4 + Na3PO4
68. H3PO4 + NaOH → NaH2PO4 + H2O

mmi 9 5 0 0
mmƒ 4 0 5 -
5
pH = 3 + log = 3.1
4
69.
[In − ]
pH = pKIn + log
[H I n]
70. pH = pKIn ± 1
71. pH range of methyl red

 4.2 – 6.3
72. pH at equivalence point is (5.5 – 11)
73. For HCl Vs NH4OH  pH range (3 – 8.5)
74. For NaOH Vs H2C2O4 titration

pH range is (11 – 5.5)
75. Oxalic acid Vs KMnO4 titration is a redox titration.
76. For WA Vs SB titration

pH range is 5.5 – 11. So suitable indicator is Hph.
APNI KAKSHA 9
20
78. pHi = pKa + log
80
80
pHƒ = pKa + log
20
pH = 2 log4 = 1.2

79. 2NaHCO3(s) ⎯⎯ → Na2CO3(s) + CO2 + H2O a mol a/2 mol
Na2CO3 + HCl ⎯⎯⎯ → NaHCO3 + NaCl
HPh
a
= 0.1 × 0.5
2
a = 0.1 mol
w = 0.1 × 84 = 8.4 gm
8.4
% purity = × 100 = 84%
10
81. Ksp = (28)2 × (3s)3 = 108 s5
82. Ksp = s2 = 64 × 10–6

s = 8 × 10–3 M
= 8 × 10–3 mol/L
= 8 mol/m3
14.3 10−4
83. s= = 10–5 M
143
Ksp = s2 = 10–10 M2
7
84. s= = 7 × 10–2 M
100
Ksp = s2 = 4.9 × 10–3
85. (A) Ksp = s2
s= 80 × 10–19 M
(B) Ksp = s2
s= 7 × 10–8 M
(C) Ksp = 108 s5 = 1 × 10–72
1
 1000  5
s=   × 10–15 M
 108 
(D) Ksp = 27 s4
APNI KAKSHA 10
 180 
s=   × 10 M
–5
 27 
86. 4s3 = 8.64 × 10–13
s3 = 216 × 10–15
s = 6 × 10–5 M (in water)
2−
Ag2CrO4 ¾→ 2Ag + + CrO 4
2s s + 0.6
 0.6
(2s)2 × 0.6 = 8.64 × 10–13

4s2 = 14.4 × 10–13
s2 = 3.6 × 10–13
s = 6 × 10–7 M
87. 0.1 M CaBr2  [Br–] = 0.2 M

0.1 M NaBr  [Br–] = 0.1 M
0.1 M AgNO3  [Ag+] = 0.1 M
In case of 0.1 M CaBr2, morality of common ion is maximum so. There maximum common ion
effect.
88. SrCO3 → Sr 2+ + CO32−

s1 s1 +s2
ZnCO3 → Zn 2 + + CO32−
s2 s2 +s1
(s1 + s 2 )s1 10−10 100

= =
(s1 + s 2 )s 2 1.5 10 −11
15
s1 20
=
s2 3
89. [Ba2+] [CO32–] = Ksp
5.1 × 10–9 = [Ba2+] × 10–4
[Ba2+] = 5.1 × 10–5 M
90. Ksp = [Mg2+] [OH–]2

1 × 10–11 = 0.1 × [OH–]2
[OH–] = 10–5 M
pOH = 5 Þ pH = 9
APNI KAKSHA 11
91. QIP = 10–3 × 10–10 = 10–13
QIP < Ksp (no ppt)
92. Ag+ + Br– → AgBr

Ci 10–7 M 10–7 M 0
Qip=10–7 × 10–7 =10–14 ,Qip < Keq,
So there will be no precipitation
93. Ag2CrO4 2Ag+ + CrO 24 −
10mmol 80mmol
5 0 75
x 75
500 500
2
 x   75  –12
then     = 15 × 10
 500   500 
x
= 10–5
500
x = 5 × 10–3
5 10−3
+
[Ag ] = = 10–5
500
94. AgCl(s) Ag+ (aq.) + Cl– (aq.)

y x–y 4 × 10–5 – y
4 × 10–5 – y = 10–5
y = 3 × 10–5
(x – y) (4 × 10–5 – y) = 10–10
(x – y) (10–5) = 10–10
x – y = 10–5
x – 3 × 10–5 = 10–5
x = 4 × 10–5
95. Ksp = [Ag+] [Cl–]
[Ag+]
[Cl–]
APNI KAKSHA 12
96. CN– + H2O → HCN + OH–
Solubility if [OH–] ¯, [H+] , pH¯
97. Solubility of Ag2CO3 will be max. in NH3 due to complex formation.
98. Ag+ + 2NH3 Ag(NH3) +2
x 0.8 0.1
Ag (NH3) +2 Ag (NH3)+ + NH3
0.1 – x x 0.8 + x
0.1 0.8
1 1 (0.8)x
= 4 =  x = 1.25 × 10–5
K f2 10 0.1
Ksp
99. Ag A (s) Ag+ (aq) + A–(aq)
S S–x
A–(aq) + H2O AH (aq) + OH–(aq)
Kv / Ka
S–x x x
−10
Kw x2 10 10−10
10–4 = =   (S – x) = = 10–6
Ka S − x S− x 10−4
 S = x + 10–6 {but x = 10–5}  S = (1.1 × 10–5)
Ksp = [Ag+ (aq)] [A–(aq)]  1.1 × 10–5 × 10–6
Ksp = 1.1 × 10–11
APNI KAKSHA 13
EXERCISE:S-1
1. pH = 13
[H+] = 10–13 M
= 10–13 mol/L
= 10–13×6×1023 ions/L
Q 1 L contains 6×1010 ions
10–3 L will contain = 6×1010×10–3
= 6×107 ions
2. (i) Kw = [H+][OH–] = 9×10–14

In pure water
[H+] = [OH–2] = 3×10–7
pH = 7 – log3 = 6.52
(ii) At 60°C neutral pH = 6.52
If pH < 6.52 then solution will be acidic and pH > 6.52. Then solution will be basic.
3. 2H2O → H3O+ + OH–

C(1–) C C
1000
[H+] = ×3.6×10–9 = 2×10–7 M
18
Kw = [H+][OH–]= 2×10–7×2×10–7 = 4×10–14
4. 2NH3 → NH +4 + NH −2
 NH+4   NH−2  = 10–30
 NH−2  =  NH4+  = 10–15 M
 NH −2  = 10–15×6×1023 ions/L
1 L contains 6×105 NH −2 ions
10–6 L (1 mm3) will contain= 6×108×10–6 = 600 NH −2 ions
5. (a) [H+] = 10–1  pH = 1

10–3
(b) [OH–] = = 10–5M
100
APNI KAKSHA 14
pOH = 5  pH = 9
1 
(c) [OH–] =  = 2×10–3
10 10
pOH = 3–log2
pH = 11 + log2 = 11.3
(d) H2O → H+ + OH–

X +10–8 x
Kw = (x + 10–8)x = 10–14
x = 9.5×10–8
[H+] = 10.51×10–8 M
pH = 8–log10.51 = 8 – 1.03 = 6.97
(e)
H2O → H+ + OH–
x 10–10 + x
Kw = (x + 10–10)x = 10–14
x » 10–7
pH = 7
6. If V→¥, then solution will almost neutral. So pH = 7
7. HCl → H+ + Cl–
x+y x
H2O → H+ + OH–
x+y y
x + y = 10–6.95
(x + y)×y = 10–14
y = 10–7.05
APNI KAKSHA 15
x + y = 11.22×10–8
y = 8.9×10–8
x = 2.32×10–8 M
8. (b) CH3COOH → CH3COO– + H+

0.1–x x x
x2
1.8×10–5 =
0.1 − x
x2 = 1.8×10–6
[H+] = x = 1.36×10–3
pH = 3 – log1.3 = 2.87
(c) NH4OH → NH +4 + OH–
0.1–x x x
x2
1.8×10–5 =
0.1 − x
[OH–] = x = 1.34×10–3
pOH = 2.87  pH = 11.13
(f) 10–7 M CH3COOH

CH3COOH → CH3COO– + H+
Acid will completely dissociate, so a » 1

Taking contribution of water
[H+] = 1.62 x10–7  pH = 6.78
K a 1.8 10−5
(g) = = 1.8×100
C 10−8
Acid will completely dissociate, so a » 1
CH3COOH → CH3COO– + H+
10–8 10–8 + x
H2O → H+ + OH–
10–8 + x x
Kw = (10–8 + x)x = 10–14
APNI KAKSHA 16
x = 9.51×10–8
[H+] = 10.51×10–8  pH = 6.97
9. (a) HA → H+ + A–
10–4.5 10–4.5
10–4.5 10–4.5 10−9
Ka = = = 10–8
0.1 − 10−4.5 0.1
(b) BOH ⎯→ B+ + OH–

10–3.5 10–3.5
10−3.5 10−3.5
Kb = = 10–6
0.1 − 10−3.5
C112 C 2  22
10. =
1 − 1 1 −  2
 22 
12 = 10−2  22  = 100  2 = 10
1 2
1
1 12
11. 1.8×10–5 = = 1 12
1 − 1
1 12
6.2×10–10 = = 1  22
1 − 2
12 1.5 10 −5

= = 2.9×10–4
 22 6.2  10 −10
1
= 1.70×102
2
12. NH4OH ⎯→ NH +4 + OH–
10–4 10–4
10 –8
10–5 =
C − 10 –4
C – 10–4 = 10–3
C = 1.1×10–3 M
APNI KAKSHA 17
13. HA ⎯→ H+ + A-
10–3 10–3
10–6 10–6 1
Ka = = =  10 −3
10 − 10
–2 –3
9 10 –3
9
x2
14. 5.9×10–10 =
0.3 − x
x2 = 5.9×0.3×10–10
x = 1.77 10−5
pH = 5 – log 1.77 = 4.87
10–4 19
15. [H+] = +  10 −4 = 10×10–4 = 10–3
2 2
 pH = 3
10 + 20 30
16. (a) [H+] = =
100 100
pH = 1 – log3 = 0.52
(b) [H+] = 2 10−5  0.1 + 4 10−5  0.1 = 6 10−3
pH = 3 – 0.39 = 2.61
17. HCOOH ⎯→ H+ + HCOO–

0.05–x x x
x2
1.8×10–4 =
0.05 − x
x2 = 1.8×10–4×0.05
x2 = 9×10–6
pH i = 2.52
HCOOH ⎯→ H+ + HCOO–
0.05–x 0.1+x x
(0.1 + x) x
1.8×10–4 =
0.05 − x
x2 + 0.1x – 9×10–6 = 0
APNI KAKSHA 18
x = 0.9×10–4
[H+] = 0.1
pHf = 1
pH = 1 – 2.52 = –1.52
0.1 [HCOO− ]
1.8×10–4 =
0.05
[HCOO–] = 0.9×10–4 = 9×10–5 M
18. CHCl2COOH ⎯→ CHCl2COO– + H+

0.01–x x x+0.01
x(x + 0.01)
3×10–2 =
0.01 − x
x2 + 4×10–2x–3×10–4 = 0
x = 0.64×10–2
[H+] = 1.64×10–2 M
[CHCl2COO–] = x = 0.64×10–2 M
19. [H+] = 1.8 10−5  0.02 + 6.4 10−5  0.01 = 10–3 M
[CH3COO− ] 10−3
1.8×10–5 =
0.02 − 10−3
[CH3COO–] = 1.8×10–2×19×10–3 = 3.42×10–4 M
 C7 H 5O 2−  10 −3
6.4×10–5 =
0.01 − 10−3
C7 H5O2−  = 6.4×10–2×9×10–3 = 5.76×10–4 M
20. H2C2O4 ⎯→ H+ + HC 2 O 4−
0.1 –x x+y x–y

HC 2 O 4− ⎯→ H+ + C 2 O 24 −
x–y x+y y
(x + y)(x − y)
10–2 =
0.1 − x
APNI KAKSHA 19
(x + y)y
10–5 =
x−y
xy
10–5 =
x
Ka1 >> Ka2 ,so x >> y
x2
10–2 =
0.1 − x
x2 + 10–2x – 10–3 = 0 Þ x = 2.7×10–2
[H+] = [ HC 2 O 4− ] = 2.7×10–2 M
[ C 2 O 24 − ] = 10–5 M
[H2C2O4] =7.3×10–2 M
21. H3PO4 ⎯→ H+ + H 2 PO−4
10–2–x x+y+z x–y

H 2 PO−4 ⎯→ H+ + HPO 24−
x–y x+y+z y–z

HPO 24− ⎯→ H+ + PO 34−
y–z x+y+z z
Ka1 >> Ka2>> Ka3, so x >> y >> z

(x + y +z)(x − y)
10–3 =
10−2 − x
x2
10–3 =
10−2 − x
x2 + 10–3x – 10–5 = 0 Þ x = 2.7×10–3
(x + y+ z)(y− z)
10–8 =
x−y
xy
10–8 = Þ y = 10–8
x
(x + y+ z)  z
10–13 =
y−z
APNI KAKSHA 20
x  z 2.7 10−3  2
10–13 = =
y 10−8
1
z= ×10–18 = 3.7×10–19
2.7
[H+] = [ H 2 PO−4 ] = 2.7×10–3 M
[ HPO −4 ] = 10–8 M
[ PO 34− ] = 3.7×10–19
H3PO4 = 7.3×10–3 M
22. → H+ + HSO4−
H2SO4 ⎯⎯
0.2 0.2 0.2

H2SO4− ⎯⎯
→ H+ + SO42−
0.2–x 0.2+ x 0.2

(0.2 + x)
10 −2 =
0.2 − x
x2 + 21 × 10–2x – 2 × 10–3 = 0
x = 0.9127 × 10–2
[H+] = 0.209127 M
[SO42–] = 0.009127 M
[HSO4–] = 0.190873 M
23. → enH + + OH −
en + H 2 O ⎯⎯ kb1 = 8.5 × 10–5
0.1–x x–y x+y

x x
enH + + H 2 O ⎯⎯
→ enH 22+ + OH − kb2 = 7.1 × 10–8
x–y y x+y
x x
kb1 >> kb2 so x >> y
x2
8.5 × 10–5 =  x2 = 8.5 × 10–6  x = 2.91 × 10–3
0.1 − x
[OH–] = 2.91 × 10–3 M  pH = 11.46
APNI KAKSHA 21
xy
7.1 × 10–8 =  y = 7.1 × 10–8
x
[enH22+] = 7.1 × 10–8 M
24. All cations (Cu2+, NH4+)are acid and all anions (C2H5O– ,F–, SO 32 − )are base
Solution of salt of SA + SB ⎯→ Neutral (KNO3)

Solution of salt of SA + WB ⎯→ Acidic (ZnCl2)
Solution of salt of WA + SB ⎯→ Basic (NaOCl,CH3COONa, Na2CO3)
10−14
25. Ka(HOCl) = = 3.5×10–5
4 10−10
26. H3PO4 ⎯→ H+ + H 2 PO−4
H 2 PO−4 ⎯→ H+ + HPO 24−
HPO −42 ⎯→ H+ + PO 34−
(i) Dissociation constant of HPO24− = Ka3 = 10−12
(ii) Ka H 2 PO−4 ×Kb HPO −42 = Kw
−2 10−14
Kb HPO 4 = −8 = 10–6
10
(iii) KaH3PO4 ×Kb H 2 PO−4 = Kw
10−14
Kb H 2 PO−4 = = 10–11
10−3
Kw 10−14
(iv) Kb PO 34− = = −12 = 10–2
K a3 10
27. CH3COO– + H2O ⎯→ CH3COOH + OH–

0.08–x x x
10−14 x2
=
1.8 10−5 0.08 − x
10−9 x2
=
1.8 0.08
0.08
x2 = ×10–9 = 0.44×10–10
1.8
x = [OH–] = 0.66×10–5 M
APNI KAKSHA 22
28. NH +4 +H2O ⎯→ NH4OH + H+
2–x x x
10−14 x2
=
1.8 10−5 2 − x
2 10−9
x2 =
1.8
10
x = [H+] = ×10–5  pH = 4.48
3
29. C6H5NA + H2O ⎯→ C5H5N + H3O+
0.25–x x x
10−14 4  10−6
=
Kb 0.25 − 2 10−3
10−14 4 10−6
=
Kb 0.25
0.25 10−14 1
Kb = −6
= ×10–8 = 6.25×10–10
4 10 16
30. CN − + H2O ⎯→ HCN + OH −
0.06(1 − h) 0.06h 0.06h
10−14 .06h 2
=
6 10−10 1− h
1 0.06h 2
×10–14 =
6 1− h

0.06h2 = ×10–4
6

h2 = ×10–2
36
1
h= = 0.0166= 1.66 %
60
31. C6 H5O− + H2O ⎯⎯
→ C6H5OH+ OH−
10–3–x x x
APNI KAKSHA 23
10−14 x2
=
1.05 10−10 10−3 − x
x2
10−4 =
10−3 − x
x2 + 10–4x – 10–7 = 0
41 − 1
[OH–] = x = 10−4 = 2.7 × 10–4
2
pH = 10 + log2.7 = 10.3
32. PO34− + H2O ⎯⎯

→ HPO42− + OH−
0.1− x x x
10−14 x2
=
4.5 10−13 0.1 − x
x2 1
=
0.1 − x 45
45x2 + x – 0.1 = 0
[OH–] = x = 4.911 × 10–1
[H2PO4–] = 6.2 × 10–8 M
H2PO4– + H2O ⎯→ H3PO4 + OH–
33. CrO24− + H2O ⎯→ HCrO−4 + OH−
0.005–x x x
k w 0−14 x2
kh1 = =
k a 2 3.110−7 0.005 − x
10−7 x2 5  10−10
=  x2=
3.1 5 10−3 3.1
x = h =1.26×10–5
.26 10−5
h= = 2.52×10–3
5 10−3
34. PuO 22+ + H2O ⎯→ PuO2OH+ + H+
APNI KAKSHA 24
0.01–x x x
= 10–4 = 10–4
0−8 0−8
Kb = = = 10–6
0.01 − 10−4 0.01
Ka (Pu O 22+ ) ×Kb(PuO2OH+ )= Kw
Ka Pu O 22+ = 10–6
10−14
Kb PuO2OH+ = = 10–8
10−6
2+ + +
35. (a) Zn + H2O ⎯→ Zn(OH) + H
0.001–x x x
x2
10–9 =
10−3 − x
x2 = 10–12
x = [H+] =10–6 M  pH = 6
(b) Ka Zn+ ×Kb Zn(OH)+ = Kw

10–9 × Kb Zn(OH)+ = 10–14
Kw Zn(OH)+ = 10–5
1
36. pH = (pKw + pKa – pKb)
2
pH = 7
pK 2 + pK1 10.34 + 6.34

37. pH = = = 8.34
2 2
pK 2 + pK1 5.44 + 2.94

38. pH = = = 4.19
2 2
[NH +4 ][OH − ]
39. Kb =
[NH 4 OH]
0.1 [OH− ]
1.8×10–5 =
5 10−2
APNI KAKSHA 25
[OH–] = 1.8×5×10–6 = 9×10–6 M
40. Moles of (NH4)2SO4 = x
Moles of NH3 = 1
 NH +4 ]
pOH = pKb + log
[NH 3 ]
2x
4.74 = 4.74 + log
0.1
0.1
2x = 0.1 Þ x = = 0.05
2
41. (a) C5H5N + H2O ⎯→ C5H5N+ + OH–

0.2–x x x
x2
1.5×10–9 =
0.2 − x
x2 = 3×10–10
[OH–] = x = 3 ×10–5 M
1 1
pOH = 5 – log3  pH = 9 + log3 = 9.15
2 2
(b) Equilibrium will shift to backward reaction so [OH–]¯, pOH , pH¯
[C5 H 5 NH + ]
(c) pOH = pKb + log
[C5 H 5 N]
0.3
= 9 – log1.5 + log = 9 – log1.5 + log3= 9.3
0.1
pH = 4.7
42. (a) NH4OH + NaOH ⎯→ NH4OH– + NaCl

0.1 0.05 0.1 – (initial moles)
0.05 0 0.15 – (moles at equilibrium)
pOHi = 4.74  pHi = 9.26
0.05
pOHf = 4.74 + log = 4.74 – log3
0.15
pHf = 9.26 + log3 = 9.74
(b) NH4OH + HCl ⎯→ NH4Cl + H2O
0.1 0.05 0.1 (initial moles)
0.05 0 0.05 (moles at equilibrium)
APNI KAKSHA 26
pOHi = 4.74  pHi = 9.26
0.05
pOHf = 4.74 + log = 4.74 + log3
0.15
pHf = 9.26 – log3 = 8.78
43. (a) millimoles of OH– = 8
millimoles of H+ = 3
5
[OH–] = = 0.1
50
pOH = 1  pH = 13
(b) millimoles of H+ = 0.2
millimoles OH– = 0.2
Hence solution will be neutral, so pH = 7
(d) millimoles of H+ = 1×2

millimoles of OH– = 1
1
[H+] =
20
pH = log20 = 1.3
44. In case of (iii) buffer can be prepared

In case of (iv) and (v) buffer can be prepared if moles of weak acid or weak base is more
45. CH3COOH + NaOH ⎯→ CH3COO×1a + H2O

10m mol 5m mol – –
5m mol 0 5m mol –
pH = pKa = 4.74
46. NH4Cl + NaOH ⎯→ NH4OH + NaCl

7.5m mol 5m mol – –
2.5m mol 0 5m mol –
2.5
pOH = 4.74 + log = 4.74 – log2
5
pH = 9.26 + log2 = 9.56
APNI KAKSHA 27
47. NH3 + HCl ⎯→ NH4Cl
20m mol 15m mol –
5m mol 0 15m mol
15
pOH = 4.74 + log = 4.74 + log3
5
pH = 9.26 – log3 = 8.78
48. NH4Cl + NaOH ⎯→ NH4OH + NaCl

10m mol 7.5m mol – –
2.5m mol 0 5m mol –
2.5 1
pOH = 4.74 + log = 4.74 + log
5 2
49. CH3COO− + H2O ⎯→ CH3COOH+ OH−
0.1–x x x
10−14 x2
=
10−5 0.1 − x
x2
10–9 =
0.1
x2 = 10–10
x = [OH–] = 10–5
pOH = 5  pH = 9
50. CH3COO− + H2O ⎯→ CH3COOH+ OH−
0.05–x x x
10−14 x2
=
1.8 10−5 0.05 − x
x2 = 0.05×10–14 = 1.8×10–5
[OH–] = x = 0.52×10–5
[H+] = 1.92×10–9 M  pH = 8.71
51. NH +4 + H2O ⎯→ NH4OH+ H+
0.2–x x x
APNI KAKSHA 28
10−14 x2
=
1.8 10−5 0.2 − x
1
x2 = ×10–9
9
[H+] = x = 1.05×10–5  pH = 4.98
52. (i) CH 3COOH ⎯→ CH3COO− + H+
0.1–x x x
x2
2×10–5 =
0.1 − x
x2 = 2×10–6
[H+] = x = 2 ×10–3
pH = 3 – 0.15 = 2.85
(ii) CH3COOH + NaOH ⎯→ CH3COONa + H2O
5mmol 1mmol –
4mmol 0 1mmol
1
pH = 4.7 + log = 4.7 – 0.6 = 4.1
4
(iii) CH3COOH + NaOH ⎯→ CH3COONa + H2O
5mmol 2mmol –
3mmol 0 2mmol

pH = 4.7 + log = 4.52
3
(iv) CH3COOH + NaOH ⎯→ CH3COONa + H2O
5mmol 2.5mmol –
2.5mmol 0 2.5mmol
pH = pKa = 4.7
(v) CH3COOH + NaOH ⎯→ CH3COONa + H2O

5mmol 4mmol –
1mmol 0 4mmol
pH = 4.7 + log4 = 5.3
(vi) CH3COOH + NaOH ⎯→ CH3COONa + H2O

APNI KAKSHA 29
5mmol 5mmol –
0 0 5mmol
CH3COO– + H2O ⎯→ CH3COOH + OH–
0.05–x x x
10−14 x2
=
2 10−15 0.05 − x
1 1
x2 = ×10–9×0.05= ×10–10
2 4
1
[OH–] = x = ×10–5
2
pOH = 5 + log2
pH = 9 – log2 = 8.7
53. pKIn = 2
KIn = 10–2
[H + ][In − ] 4 10−3[In − ]
KIn =  10 =
–2
[HIn] [HIn]
[In − ] 0
= = 2.5
[HIn] 4
1
% of [HIn] = ×100 = 28.57 %
3.5
25 1
54. pHi = pKa + log = pKa = log
75 3
5
pHf = pKa + log = pKa + log3
25
pH = 2log3 = 0.96
[H + ]  [Basic]
55. KIn =
[Acidic]
10−5  [Basic]
6×10–5 =
[Acidic]
6
% of [Basic] =  100 = 85.71 %
7
APNI KAKSHA 30
56. pH = pKIn ± 1
pH range of indicator = 2.4 – 4.4
57. At equivalence point H3BO3 will present in solution.

H 3 BO 3 + H2O ⎯→ B(OH)−4 + H+
0.05 − x x x
x2
7.2×10–10 =
0.05 − x
7.2
x2 = ×10–10
20
7.2
[H+] = x = ×10–5 M
20
1 7.2
pH = 5 – log = 5.44
2 20
pH range of titration = 4.44 – 6.44
So suitable indicator methyl red (4.2 – 6.3)
58. (018)
59. A3X3(s) ⎯→ 2A3+(aq) + 3X2–(aq)

2s 3s
Ksp = (2s)2 ×(3s)3 = 108s5 =1.08×10–23
s = 10–5 M
0.038
60. s= = 1.25×10–3 M
3.04
Ksp = s2 = (1.25)2×10–8 = 1.56×10–8 M
61. CaF2 ⎯→ Ca2+ + 2F–

10−4
4.1× 4.1×10–4
2
4.110−4
Ksp =  (4.110−4 )2 = 3.44×10–11
2
APNI KAKSHA 31
2.4 10−5
62. s= 10 = 4×10–6 M
60
Ksp = 4s3 = 4×(4×10–6)3
= 2.56×10–16
63. For MX
s2 = Ksp = 4×10–18
s = 2×10–9 M
For QX2
4s2 = Ksp = 4×10–18
s = 10–6 M
Solubility of QX2 is more
64. CuI ⎯→ Cu+ + I–

s s+0.1 » 0.1
s×0.1 = 5×10–12
[Cu+] = s = 5×10–11 M
65. AgCl ⎯→ Ag+ + Cl–

s s+0.2
s×0.2 = 1×10–10
s = 5×10–10 M
66. AgSCN ⎯→ Ag+ + SCN–
s1+s2 s1
AgBr ⎯→ Ag+ + Br –
s1+s2 s2
(s1 + s2)s1 = 1.1×10–12
(s1 + s2)s2 = 5×10–13
(s1 + s2)2 = 1.6×10–12
s1 + s2 = 1.6 10−6
1.110−12
s1 = = 9×10–7 M
1.6 10−6
5 10−13
s2 = = 4×10–7 M
1.6 10−6
APNI KAKSHA 32
67. SrF2 ⎯→ Sr2+ + 2F–

s1 2(s1+s2)
MgF2 ⎯→ Mg2+ + 2F–
s2 2(s1+s2)
s1 × 2(s1 + s2) = 4×10–9
s2 × 2(s1 + s2) = 9.5×10–9
3(s1 + s2)2 = 13.5×10–9
13.5
(s1 + s2)2 =  10 −10 = 45×10–10
3
s1 + s2 = 45 10−5
[F–] = 2(s1 + s2) = 2× 45 10−5 M = 1.34×10–4 M
68. For pptn Ksp= QIP

(a) QIP = 10–3 ×(10–5)2 = 10–13
So QIP < Ksp No pptn
(b) QIP = 10–3×10–6 = 10–9
QIP > Ksp pptn will occur
8 10−6  v 10−4
69.  = 2×10–10
v +1 v +1
(v–1)2 = 0 Þ v = 1 L
70. Ksp = 4s3 = 4 × (10–3)3 = 4 × 10–9

4 × 10–9 = [Ag+]2 [Cr O 24 − ]
= [Ag+]2 [10–1]
[Ag+] = 2 × 10–4 M
[Ag+] moles precipitated = 2 × 10–3 – 2 × 10–4 = 18 × 10–4
moles of Ag2CrO4 precipitated = 9 × 10–4
1
71. Pb2+ + 2Cl− ⎯⎯
→ PbCl2 (s) k=
ksp
0.1x 0.75 M 0
x 0.55 M 0.1M
APNI KAKSHA 33
1 1
−4
=
1.7 10 x  (0.55) 2
1.7
x= 2
10−4 = 5.6 × 10–4
(0.55)
[Pb2+] = 5.6 × 10–4
Moles of Pb2+ = 5.6 × 10–5
Mass of Pb2+ = 5.6 × 208 × 10–5= 1.2 × 10+3 × 10–2 mg= 12 mg
72. CaCO3 ⎯→ Ca2+ + CO32 −
7×10–5
BaCO3 ⎯→ Ba2+ + CO32 −
7×10–5
10−5  [CO32− ] 5 10−10
=
7 10−5  0.1 [CO32− ] Ksp (BaCO3 )
Ksp(BaCO3) = 4.9×10–10
73. Fe3+ + 3SCN– ⎯→ Fe(SCN)3

Kf = K1×K2×K2 = 130×16×1 = 2080

Kd = = 4.8×10–4
Kf
74. → Ag + + Br −
AgBr ⎯⎯ x × s = 5 × 10–13
x s
Ag + + 2NH3 ⎯⎯
→ Ag(NH3 )2+ keq = 1 × 108
s 0.4 0
x 0.4 − 2s s
s
= 1108
x(0.4 − 2s)
2
 s 
 = 10 × 5 × 10
8 –13

 0.4 − 2s 
s
= 50 10 −3
0.4 − 2s
s= 50 × 10–3 × 0.4= 2.82 × 10–3 M
APNI KAKSHA 34
75. (a) [Ag+] = 10–2 (b) [CO32− ] = 4×10–2 (d) CO32 − + H+ ⎯→ HCO3−
As [H+] increases, solubility of Ag2CO3 increases.

d>c>a>b
EXERCISE # O-II
1. H3PO4 ⎯→ H+ + H2PO4–
H3PO4– ⎯→ H+ + H2PO42–
HPO42– ⎯→ H+ + PO43–
if K1 >> K2
[H+] = [H2PO4–] [HPO42–] = K2
[H+] = K1 (H3PO4 ) [H+] >> [PO43–]
Kw 10−14
2. (A) TRUE Kb A– = = −6 = 10–8
KaHA 10
(B) TRUE If T , Kw 
1
(C) TRUE Acidic strength  Ka 
pKa
(D) TRUE Salt of SA + WB ( NH4Cl) undergoes cationic hydrolysis.
3. (A) If T increases, then [H+] increases, pH¯

(B) If T increases , then [OH–] increases ,pOH¯
(C) For 10–4 M HCl, pH = 4
0.01x 2
10–5 =  x2 = 10–4  x = 10–2  pH = 2
1− x
(D) HA ⎯→ H+ + A–
C(1–) c c
C 2 1
Ka =  
1−  C
4. (A) FALSE At half equivalence point pH = pKa

0.1
(B) TRUE pH = 4.74 + log = 5.74
0.01
APNI KAKSHA 35
[C.B.]
(C) TRUE pH = pKa + log
[Acid]
S
(D) FALSE Buffer capacity is max when =1
a
5. (A) As, T increases , Kw increases and [H+] [OH–] also increase, so neutral pH < 7
If pOH =7, then pH < 7 solution will be acidic.
(B) pH = –log [H+]
(C) For CH3COONa(aq)
kw
[OH–] = C Þ [OH–]  C
Ka
On dilution [OH–]¯, pOH, pH¯

s.a
(D) Buffer capacity = 2.303
s+a
6. 0.1 M BOH (Kb = 10–5), it is weak base.

For salt BCl
B+ + H2O ⎯⎯
→ BOH+ H+
0.1–x x x
x2
10–9 =  x2 = 10–10  x = 10–5  pH = 5
0.1x
7. For ppt Qip ³ Ksp

Ksp of AgCl = 1.8 × 10–10
10 –4 10 –4 1
(A) Qip =  = × 10–8
2 2 4
Qip > ksp (ppt will take place)

10 –5 10 –5 1
(B) Qip =  = × 10–10
2 2 4
Qip < ksp (ppt does not take place)

10 –6 10 –6 1
(C) Qip =  = × 10–12
2 2 4
APNI KAKSHA 36

10–10 10–10 1
(D) Qip =  = × 10–20
2 2 4
8. (A) TRUE Ksp AgCl > Ksp AgBr

So AgBr will ppt first
(B) TRUE For M2x Ksp = 4s3

For Qy2 Ksp = 4s3
For Pz3 Ksp = 27s3
(C) FALSE Li3Na3 (AlF6)2 ⎯→ 3Li+ + 3Na+ + 2AlF63–

3s 3s 2s
Ksp = 2916 ×s8
9. (A) TRUE due to common – ion effect of Cl–.

(B) TRUE
(C) TRUE Due hydrolysis of CH3COOH solubility increases.
(D) TRUE
10. In original solution
[H+] = K a  C = 10−6 1 = 10–3M
11. Let resulting solution (After dilution) have concentration Co
CH3COOH CH3COO– + H+
Co 0 0
Co–X X X
pH = 2 × 3 = 6 [H+ ] = x = 10–6
APNI KAKSHA 37
[CH 3COO − ][H + ] x.x
Ka = =
[CH 3COOH] (Co − x)
(10−6 )2
10–6 =
Co − 10−6
Co = 2 × 10–6 M
Now, for CH3COOH
1 M × 1 litre = 2 × 10–6 M × V
V = 5 × 105 litre.
12. CH3COOH + NaOH CH3COONa + H2O

2 × 10–6 ,V 0.5 × 10–6, V
1.5 10−6  V 0.5 10−6  V

0
2V 2V
 anion 
pH = pKa + log10  
 acid 
= 6 – log10 3 = 5.523
13. pH at I half equivalence point = p = 12

K a3
+p
Ka2 K a3
p
pH at I equivalence point = = 10
2
p =8
Ka 2
+p
Ka1 Ka 2
p
pH at II equivalence point = =6
2
p =4
K a1
At III equivalence point

Na3OP4 + 3HCl ⎯⎯→ 3NaCl + H3PO4
100 300 – –
× × 100 100
100 1
C= = M
400 4
(H + ) 2
Ka1 = 10–4 =  (H+) = ka1C
C
10−2
=
2
APNI KAKSHA 38
= 5 × 10–3
pH = 3 – log 5
14. at II half equivalence point

Na2HPO4 + HCl ⎯⎯→ NaCl + NaH2PO4
100 50 – –
50 × 50 50
50
pH = p + log = p a2 = 8
Ka2 K
50
15. Equilibrium constant = Kw / k a 3
16. Let moles of HA is x and moles of HB is (1-x) which reacts with NaOH
x  11.8 + (1 − x)  12.4 = 12.25
17. [H+] = k a1 C1 + k a2 C2 = 110–5 + 9 10–5 = 10 × 10–3 = 10–2
pH = 2
7.04
18. Number of moles Cu oxidised = × 10–3
64
= 1.1 × 10–4
19. Cu + 2Ag+ Cu+2 + 2Ag
Since equilibrium constant is very large
[Ag+] = 2.2 × 10–4
20. Ksp = [Ag+]2 [BrO3]
= 4.84 × 10–8
21. (A) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 2.5 mmol 0 0
7.5 mmol 0 2.5 mmol
2.5
pH = pKa + log = pKa – log 3
7.5
(B) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 5 mmol
5 mmol 0 5 mmol
at half equivalence point pH = pKa
APNI KAKSHA 39
(C) CH3COOH + NaOH ⎯→ CH3COONa + H2O
10 mmol 7.5mmol – –
2.5 mmol 0 7.5 mmol
pH = pKa + log 3
(D) It volume of final solution is doubled then conc. will be half.
1 1 1
pH = (pKw + pKa + log )= (pKw + pKa – 2)
2 2 2
22. (P) NaOH + HCl ⎯→ NH4Cl + H2O

0.2 V 0.2V 0 –
0 0 0.2V –
[NH4Cl] = 0.1 M
1 1
pH = (pKw – pKb – log C) = (14 – 5 –log 0.1) = 5
2 2
(Q) CH3COONa + HCl ⎯→ CH3COOH + NaCl

0.2 V 0.2V 0 –
0 0 0.2V –
[CH3COOH] = 0.1 M
CH3COOH ⎯→ CH3COO– + H+
0.1 – x x x
x2
10–5 =
0.1 – x
x = 10–3  pH = 2
(R) 0.1 M Na2HPO4
pK a3 + pk a 2 10 + 6
pH = = =5
2 2
[HCO 3– ]
(S) pH = pKa1 + log
[H 2 CO 3 ]
at half equivalence point

[HCO3–] = [H2CO3]  pH = 5
(T) Mg(OH)2 ⎯→ Mg2+ + 2OH–

s 2s
APNI KAKSHA 40
4s3 = 5 × 10–16
1 1
s3 = × 10–15 Þ s = × 10–5
8 2
[OH–] = 10–5
 pOH = 5
 pH = 10
Exercise: S-II
1. H 2S → H + + HS−
0.1–x x +2×10–4 x–y

 2×10–4  x
HS− ⎯⎯
→ H + + S2 −
x–y 2×10–4 y
x
2 10−4  x 2 10−4  x
10−7 = =
0.1 − x 0.1
x = [HS–] = 5 × 10–5 M
2 10−4  y
10–14 =
5 10−5
y = [S2–] = 2.5 × 10–15 M
2. NiC(aq)+ H2O NiCH + + OH − kb1 = 7 × 10–7
0.02–x x–y x+y

x x
NiCH+ + H 2O NiCH 22+ + OH − kb2 = 10–10
x–y y x+y
x x
kb1 >> kb2 , x >> y
x2
x2 = 1.4 × 10–8  x = OH  = 1.4 × 10–4
–
7×10–7 = 
0.02 − x
[OH–] = 7 × 10–6  pH = 10.073
APNI KAKSHA 41
3. For NaHCO3
pka 2 + pka1 6.38 + 10.32
pH = =
2 2
For Na2HPO4
pka 3 + pka 2 12 + 7.2
pH = = = 9.6
2 2
For NaH2PO4
pka 2 + pka1 7.2 + 2.12
pH = = = 4.66
2 2
4. (a) H3PO4 + NaOH ⎯⎯

→ NaH2 PO4 + H2O
6 3 0 (initial mmoles)
3 0 3 (equilibrium mmoles)
pH = pka1 = 3 – log 7.5= 2.12
(b) H3PO4 + NaOH ⎯⎯

→ NaH2 PO4 + H2O
pka 2 + pka1 7.2 + 2.12

pH = = = 4.66
2 2
(c) H3PO4 + NaOH ⎯⎯
→ NaH2 PO4 + H2O
4.8 7.2 0 (initial mmoles)

0 2.4 4.8 (equilibrium mmoles)
NaHPO4 + NaOH ⎯⎯
→ Na 2HPO4 + H2O
4.8 2.4 0 (initial mmoles)

2.4 0 2.4 (equilibrium mmoles)
pH = pka2 = 7.2
APNI KAKSHA 42
(d) H3PO4 + NaOH ⎯⎯
→ NaH2 PO4 + H2O
NaH2 PO4 + NaOH ⎯⎯
→ Na 2 HPO4 + H2O
NaHPO4 + NaOH ⎯⎯
→ Na 3PO4 + H2O
pH = pka3 = 12
0.015
5. (a) pH = 5 – log 1.34 + log = 5 – log 1.34 + log 0.75= 4.75
0.02
(b) C3H5O2Na + HCl ⎯→ C3H5O2H + NaCl

1.5 × 10–4 0.1 × 10–4 2 × 10–4 (initial moles)
1.4 × 10–4 0 2.1 × 10–4 (equilibrium moles)
1.4 10−4
pH = 4.87 + log = 4.693
2.110−4
(c) C3H5O2H + NaOH ⎯→ C3H5O2Na + H2O

2 × 10–4 0.1 × 10–4 1.5 × 10–4 (initial moles)
1.9 × 10–4 0 1.6 × 10–4 (equilibrium moles)
1.6 10−4
pH = 4.87 + log = 4.795
1.9 10−4
(d) % change in case of b
4.75 − 4.693
pH =  100 = 1.2%
4.75
APNI KAKSHA 43
% change in case of c
4.75  4.75
pH =  100 = 0.94%
4.75
6. BOH+ HCl ⎯⎯
→ BCl+ H2O
50C 1 0 0 (initial moles)
50C–1 0 1 – (equilibrium moles)
1
14 – 9.84 = pkb + log (i)
50C − 1
BOH+ HCl ⎯⎯
→ BCl+ H2O
50C 2.5 0 0 (initial moles)

50C–2.5 0 2.5 – (equilibrium moles)
2.5
14 – 9.24 = pkb + log (ii)
50C − 2.5
(i) – (ii)
2.5(50C − 1)
0.6 = log = log4  C = 0.1
50C − 2.5
pkb = 4.75, ka = 1.8 × 10–5

at equivalence point
1 1
pH = (pkw – pkb – logC) = (14 – 4.76 – log0.05) = 5.27
2 2
7. pH = pkIn = 7.2
5
pH = 7.2 + log = 7.2 + 0.7 = 7.9
1
for new indicator
7.9 = pkIn + log21  pkIn = 7.3
pH = pkIn = 7.3 (when 50% is ionized)
APNI KAKSHA 44
9. When MnS start to ppt, FeS has already ppted for pptn of MnS
0.01 × [S2–] = 2.5 × 10–13
[S2–] = 2.5 × 10–11 = 25 × 10–12
[H + ]2  25 10−12
9.6 × 10–21 =
0.1
9.6 9.6
[H+]2 =  10 −10 Þ [H+] = 10−5
25 25
pH = 5.21
[Ca 2+ ][CO32– ] x
10. 2+ – 2
= 3
[Ca ][F ] 4y
2 x 8y 3
– 2
= 3  [F–] =
[F ] 4y x
CuCO3(s) + 4 NH3 → Cu(NH3 )4  (aq) + CO32 − (aq)

2+
11.
0.1 x 0 0
0 x–0.4 0.1 0.1
Cu( NH ) CO
3
2+ 2−
3

= ksp  kf =2.8× 103
 NH  3 4
0.1  0.1
= 2.8  103  x = 0.444 M
( x − 0.4)4
12. → Mn 2+ + S2−
MnS ⎯⎯
s s
S2– + H2O ⎯→ HS– + OH–
kw [HS− ][OH − ]
=
k2 [S2− ]
kw [S2− ] [H + ]
[HS–] = × = [S ] ×
2–
k 2 [OH − ] k2
HS– + H2O ⎯→ H2S + OH–

kw [H 2S][OH − ]
=
k1 [HS− ]
APNI KAKSHA 45
kw [HS− ] [H + ]
[H2S] =  = [HS–]
k1 [OH − ] k1
[H + ]2 2–
[H2S] = [S ]
k 1k 2
s = [S2–]f +[HS–]f + [H2S]f
 [H + ] [H + ]2 
s = [S2–]ƒ 1 + + 
 k2 k1k 2 
s s
ksp = +
[H ] [H + ]2
1+ +
k2 k1k 2
 [H + ] [H + ]2 
s= ksp 1 + + 
 k2 k 1k 2 
EXERCISE # JEE-MAINS
1. Ksp = 4s3= 4 × (1.0 × 0–5)3= 4 × 10–15
2. Ksp = 4s3
= 4x3
3. MX4 ⎯→ M4+ + 4X–
s 4s
Ksp = s × (4s)4
= 256 s5
1/5
 Ksp 
s=  
 256 
4. H2PO4– ⎯→ H+ + HPO42–
Acid C.B.
5. pH = 5.4
[H+] = 10–5.4 = 100.6 × 10–6= 4 × 10–6
6. MX2 ⎯→ M2+ + 2x–

s 2s
APNI KAKSHA 46
Ksp = 4s3 = 4 × 10–12
s = 10–3 M
[M2+] = 10–3 M
7. OH– ⎯→ H+ + O2–
Acid C.B.
8. H2A ⎯→ H+ + HA– Ka1
HA– ⎯→ H+ + A2– Ka2
––––––––––––––––
H2A ⎯→ 2H+ + A2– Koverall = Ka1 × Ka2
[A − ]
9. pH = pKa + log
[HA]
pH = pKa= 4.5(if acid is half ionize)
pOH = 9.5
10. Ksp = s2 = 1.0 × 10–8

s = 0–4 M
= 10–6 × 283 g/L
= 283 × 10–5 g/100 mL
= 2.83 × 10–3 g/100 mL
1 1
11. pH = (pKw + pKa – pKb) = (14 + 4.8 – 4.78)
2 2
1
= × 14.02 = 7.01
2
12. For pptn to start

Ksp = Qip
[Ba2+] × 10–4 = 5.1 × 10–9
[Ba2+] = 5.1 × 10–5 M

Ksp = Qip
APNI KAKSHA 47
0.05 × [Br] = 5 × 10–13
[Br–] = 10–11 M
moles of Br– = 1 × 10–11
mass of KBr = 1 × 10–11 × 120 = 1.2 × 10–9 g
14. K1 >> K2
H2CO3 ⎯→ H+ + HCO3–
c–x x x–y
» x
HCO3– ⎯→ H+ + CO32–
x–y x+y y
» x » x
[H+] » [HCO3–] = 1.2 × 0–6 M
[CO32–] = Ka2 = 4.8 × 10–11 M
15. Ksp = Qip

10–3 × [OH–]2 = 1.1 × 10–11
[OH–]min = 10–4
pOH = 4  pH = 10
16. In reaction (ii) H2PO42– given H+ ion.

17. Ksp = 27s3
27s3 = 1.6 × 10–30
1/3
 1.6  10−30 
s=  
 27 
18. HA H+ + A– pH = 5
1–x x x [H+] = 10–5
10−5 10−5
Ka = = 10–10
1
19. If Ksp < Qip

Ksp = 1.7 × 10–10
For option (4)
Qip = 1 × 10–2 × (1 × 10–3)2 = 10–8
APNI KAKSHA 48
20. HQ ⎯→ H+ + Q– pH = 3
0.1 – x x x [H+] = 10–3
10−3 10−3
Ka = = 10–5
0.1

Ksp = Qip
5.1 × 10–9 = [Ba2+] × [CO32–]
[Ba2+] × 10–4 = 5.1 × 10–9
[Ba2+] = 5.1 × 10–5 M
22. [OH–] = 5 × 10–2

pOH = 2 – log5
Þ pH = 12 + log5 = 12.7
23. Hg2Cl2 ⎯→ Hg22+ + 2Cl–

s 2s
1/3
 Ksp 
Ksp = 4s3 Þ s=  
 4 
Cr2(SO4)3 ⎯→ 2Cr3+ + 3SO42–
2s 3s
1/5
 Ksp 
Ksp = 108s5 Þ s=  
 108 
For BaSO4 Ksp = s2 Þ s = (Ksp)1/2
1/4
 Ksp 
For CrCl3 Ksp = 27s4 Þ s=  
 27 
5
24. Moles of CH3COOH = = 0.083
60
7.5
Moles of CH3COONa = = 0.091
62
0.091
pH = 4.76 + log
0.083
APNI KAKSHA 49
pH > 4.76
Range of pH Þ pKa ± 1
25. pHi = 1 [H+]i = 0.1

pHƒ = 2[H+]ƒ = 0.01
MiVi = MƒVƒ
0.1 × 1 = 0.01 × Vƒ  Vƒ = 10 L
water should be added = 9L
26. Refer notes.
27. Zr3(PO4)4 ⎯→ 3Zr+4 + 4PO43–

3s 4s
Ksp = (3s)3 × (4s)4 = 6912 s7
1/7
 Kps 
s=  
 6912 
1
28. pH = (pKw + pKa – pKb)
2
1
= (14 + 3.2 – 3.4)
2
1
= ×13.8 = 6.9
2
29. pH range of methy orange = 3.1 – 4.4

in titration of W.A. Vs SA at end point pH should be less than 7.
30. pptn to start
Ksp = Qip
[Ba2+]ƒ [SO42–]ƒ = Ksp BaSO4
50  1 Mi  450
 = 1×10–10
500 500
Mi = 1.1 × 10–9 M
31. H2S H+ + HS– Ka1 = 1.0 × 10–7
APNI KAKSHA 50
HS– H+ + S2– Ka2 = 1.2 × 10–13
–––––––––––––––––––
H2S 2H+ + S2– Ka = 1.2 × 10–20
[H + ]2  [S2− ]
1.2 × 10–20 =
[H 2S]
(0.2)2  [S2− ]
1.2 × 10–20 =
0.1
[S2–] = 3 × 10–20 M
32. CH3COOK is salt of WA + S.B.
So pH > 7
33. Ksp PbCl2 = 3.2 × 10–8 = 4s3

s = 2 × 10–3 M = 0.414 g/L
0.1
Vol. of water require to dissolve 1g of PbCl2= = 0.241 L
0.414
34. (i) M Mol of H+ = 15

M Mol of OH– = 5
10
[H+]ƒ = = 0.1  pH = 1
100
35. 2NH4OH + H2SO4 ⎯→ (NH4)2SO4 + H2O

6 2 0 –
2 0 2 –
[NH +4 ] 4
pOH = pKb + log = 4.7 + log = 4.7 + log2
[NH 4 OH] 2
pH = 9.3 – log2 = 9
36. Ca(OH)2 + Na2SO4 ⎯→ CaSO4 + 2NaOH

0.1 m mole 0.014 m mole 0 0
0.086 m mole 0 0.014 m mol 0.014 m mole
Mass of CaSO4 = 0.014 × 136 = 1.90 g
0.014
[OH–] = = 0.28 M
0.2
APNI KAKSHA 51
37. Ag2CO3 2Ag+ + CO32–

s1 2s1 + 0.1 s1
» 0.1
8 × 10–12 = (0.1)2 × s1
s1 = 8 × 10–10 M
38. Zr3(PO4)4 ⎯→ 3Zr4+ + 4PO43–

s 3s 4s
Ksp = 6912 s7
1/7
 Ksp 
s=  
 6912 
39. Initial pH > 7 ,at equivalence point pH = 7

400  0.1 2 − 400  0.1
40. (a) [H+] = = 0.05 M
800
pH = 1.3
(b) Kw = [H+] [OH–]
T, Kw
(c) HA ⎯→ H+ + A–
c(1 – a) ca ca
c 2 2 1
Ka = Þ 10–5 = 10–5 × Þ =
1−  1−  2
(d) Le-Chatelier principle is applicable to common ion effect.
1 1
41. pH = (pKw – pKb – logc) = (14 – 5 – log2 × 10–2) = 5.35
2 2
42. Al(OH)3 ⎯→ Al3+ + 3OH–
APNI KAKSHA 52
s 3s + 0.2
» 0.2
(0.2)3 × s = 2.4 × 10–24  s = 3 × 10–22 M
43. Ksp = 4s3 = 4 × (1.84 × 10–5)3
Cd(OH)2 Cd2+ + 2OH–

s 28 + 0.01
» 0.01
s × (0.01)2 = 4 × (1.84 × 10–5)3
s = 2.49 × 10–10 M
44. pH of 0.01 M HCl = 2

pH of 0.01 M NaOH = 12
pH of 0.01 M CH3COONa > 7
pH of 0.01 M NaCl = 7
order of pOH : A > D > C > B
45. Acidic buffer solution contains weak acid and its salt with strong base.
Option (A) : Solution is containing strong acid and its salt with strong base.
0.1100mm 0.1200mm
Option (B) : HCl(aq) + CH3COONa (aq) ⎯⎯
→ CH3COOH(aq) + NaCl(aq)
0 10mm 10mm
Resulting solution contains weak acid and its salt with strong base.
0.1100mm 0.1100mm
Option (C) : CH3COOH(aq) + NaOH(aq) ⎯⎯
→ CH3COONa (aq) + H 2O(l )
0 0 10mm
Resulting solution contains only salt of weak acid and strong base.
46. Titration curve for strong acid and weak base initially a buffer of weak base and conjugate acid
is:
APNI KAKSHA 53
Formed, thus pH falls slowly and after equivalence point, so the pH falls sharply so methyl
arrange,
having pH range of 3.2 to 4.4 will weak as indicator. So statement-I is correct.
Titration curve for weak acid and strong base (NaOH) Initially weak acid will form a buffer so
pH
increases slowly but after equivalence point. It rises sharply covering range of phenolphthalein
so it will
be suitable indicator so statement-II is false.
50. Let moles added = a

+ +
Ag(aq) + 2NH3(aq) Ag(NH3 )2(aq.)
a
t=0 0.8  
2
a 
t= 5×10–8  − 1.6  0.8
2 
0.8
2
= 108
a 
(5 10−8 )  − 1.6 
2 
a
 − 1.6 = 0.4  a = 4
2
51. Ka of Butyric acid  2×10–5 pKa = 4.7

pH of 0.2 M solution
1 1
pH = pK a − log C
2 2
1 1
= (4.7) log(0.2)
2 2
= 2.35 + 0.35 = 2.7
pH= 27 × 10–1
APNI KAKSHA 54
52. HCl + H2SO4
(0.01 200) + (0.01  2  400)
 H +  =
600
2 + 8 10 1
= = =
600 600 60
1
pH = − log  
 60 
= 1.78
53. pOH = 14 – 8.26

[NH +4 ]
= pKb + log
[NH 3 ]
[NH +4 ]
= 5.74 = 4.74 + log  [NH +4 ] = 2
0.2
Hence, NH4Cl = 2 × 53.5 = 107 g
54.
(QUINONOID FORM)
55. In deionized water no common ion effect will take place so maximum solubility
APNI KAKSHA 55
EXERCISE # JEE-ADVANCED
1. HCl + NaOH ⎯→ NaCl + H2O

2m mol 3mmol 10 -
0 1mmol 2m mol -
1
[OH–] = = 2×10–3
500
pH = 11 + log2 = 11.3
2. pH = 8  pOH = 6
[OH–] = 10–6 M
Pb(OH)2 ⎯→ Pb2+ + 2OH–
Ksp = 4s2 = 4×(6.7)3×10–18 = 1.2×10–15
Pb(OH)2 ⎯→ Pb2+ + OH–
s 2s+10–6
s(2s + 10–6) = 1.2×10–15
s×10–2 = 1.2×10–15
s = 1.2×10–3 M
4. HCl  pH < 7 NaCl  pH = 7

NaCN  pH > 7 NH4Cl  pH < 7
NaCN < NaCl > NH4Cl > HCl
10
5. Amount of SO2 in atmosphere = = 10×10–6
10 6
Molar conc. of SO2 in water = Amount of SO2 × Solubility of SO2
= 10×10–6×1.3653
= 1.3653×10–5 M
H2SO3 ⎯→ H+ + HSO 3−
1.3653×10–5 – x x x
x2
Ka = = 10–1.92
1.3653 10−5 − x
x = 1.364×10–5 pH = 4.865
APNI KAKSHA 56
6. Equation of H2C2O4.2H2O = Equation of NaOH
10 63
  2 = 0.1×V(L)
250 126
1
V(L) =
25
V(mL) = 40
7. ApBq(s) ⎯→ pAq+(aq) + qBp–(aq)

s ps qs
Ksp = (ps)p(qs)q
= ppqq(s)p+q
8. [CH3COOH]f = 0.1 M
[HCl]f = 0.1 M
(a) CH3COOH ⎯→ CH3COO– + H+
0.1–x x x+0.1
x(x + 0.1)
1.75×10–5 =
0.1 − x
x = 1.75×10–5
0.1× = 1.75×10–5
a = 1.75×10–4
[H+] = 0.1  pH = 1
6
(b) Moles of NaOH = = 0.15 mol
40
CH3COOH + NaOH ⎯→ CH3COONa + H2O
ni 0.1 0.05 0 -
nf 0.05 0 0.05 -
0.1 moles NaOH will be consumed by 0.1 mol of HCl
pH = pKa = 4.75
9. T increases , Kw increases , H+, pH ¯
10. Which has minimum value of Ksp i.e. HgS
APNI KAKSHA 57
11. X– + H2O ⎯→ 4X + OH–

0.1(1–h) 0.1 h 0.1 h
Kw 10−14
Kh = = = 10–9
K a (HX) 10−5
Ch 2 0.1h 2
Kh = = = 10–9
1− h 1− h
0.1 h2 = 10–9
h2 = 10–8
h = 10–4
% h = 0.01 %
12. At end point HA will completes reacts with NaOH

HA + NaOH ⎯→ NaOH + H2O
[A–] = 0.05 M
1
pH = (pKw + pKa + logC)
2
1
= (14 + 6 – log5 + log0.05)
2
1
= (20 – log5 – log20)
2
 pH = 9
13. CH3NH2 + HCl ⎯→ CH 3 NH 3+ Cl −
0.1 mol 0.08 mol 0

0.02 mol 0 0.05 mol
[CH3 NH 2 ]
[OH–] = Kb×
[CH3 NH3+ ]
0.02 5
= 5×10–4 × = ×10–4
0.08 4
Kw 
[H+] = −
= ×10–10 = 8×10–11 M
[OH ] 5
APNI KAKSHA 58
14. CO2 + H2O ⎯→ HCO3− + H+
HCO3− ⎯→ CO32− + H+
15. For MX
Ksp = s2 = 4×10–8
s = 2×10–4 M
For MX2
Ksp = 4s2 = 32×10–14
s2 = 8×10–15
s = 2×10–5 M
For M3X
Ksp = 27s4 = 2.7×10–15
s = 10–14 M
MX > M3X > MX2
16. BOH + HCl ⎯→ BCl + H2O
It equivalence point
Moles of BOH = moles of HCl
2 2
2.5× = ×V(mL)
5 15
V(mL) = 7.5 mL
Vf = 10 mL
1
[BCl] = = 0.1 M
10
+
B+ + H2O ⎯→ BOH + H
0.1(1− h) 0.1− h 0.1− h
K w 10−14
Kh = = = 10–2
K b 10−12
0.1 − h 2
10–2 =
1− h
h = 0.27
Þ [H+] = 0.1×h = 0.027 M
1
17. pH = (pKw + pKa + logC)
2
APNI KAKSHA 59
1 1
= (14 + 4 + log0.01) = ×16 = 8
2 2
18. (A) HNO3 + CH3COOH (S.A. + W.A.)

It can’t be a buffer
(B) KOH + CH3COONa (S.B. + Salt)
It can’t be a buffer
(C) CH3COONa + HNO3 ⎯→ CH3COOH + NaNO3
It can form buffer if volume of CH3COONa and HNO3 is different.
(D) CH3COOH + CH3COONa
It is a buffer
19. For CuCl

Ksp = s2 = 10–6
s = 10–3
AgCl(s) ⎯→ As+(aq) + Cl– (aq)
s s+10–3
s(s + 10–3) = 1.6×10–10
s×10–3 = 1.6×10–10
s = 1.6×10–7
20. For Ag2CrO4 Ksp = 1.1×10–12

Ag2CrO4 ⎯→ 2Ag+ (aq) + CrO 24 −
2s+0.1 s
» 0.1
(0.1)2 ×s = 1.1×10–12
8 = 1.1×10–10 M
21. r  [H+]1
Ka  C 1
=
1 100
K a  C = 10–2
Ka = 10–4
APNI KAKSHA 60
22. From exp.-1

5.7×1000 = C×5.7
From exp-2
q = C×5.6
q = 5.65 kJ
5.6
H = − = –56 kJ. / mol
0.1
Hion = –56 + 57= 1 kJ/ mol
23. CH3COOH + NaOH ⎯→ CH3COONa + H2O

0.2 mol 0.1 mol 0 0
0.1 mol 0 0.1 mol 0
pH – pKa = 4.7
 H+ 
24. s= K sp  + 1
 Ka 
 10−3 
= 20  10−10  −8 + 1
 10 
= 2 10−5 = 4.47×10–3 M
25. (P) CH3COOH + NaOH ⎯→ CH3COONa + H2O

2m mol 1m mol 0 -
1m mol 0 1m mol -
If forms a buffer and pH does not change with dilution.
(Q) CH3COOH + NaOH ⎯→ CH3COONa + H2O
2m mol 2m mol 0 -
0 0 2m mol -
Kw  Ka
CH+ =
C
1
[H+] 
C
APNI KAKSHA 61
(R) NH3 + HCl ⎯→ NH4Cl
2m mol 2m mol 0
0 0 2m mol
NH +4 + H2O ⎯→ NH4OH + H+
Kw
[H+] = C Þ [H+]  C
Kb
(S) Ni(OH)2(s) ⎯→ Ni2+(aq) + 2OH–(aq)

On dilution [OH–] remains same in saturated solution of Ni(OH)2
26. B + HA ⟶ BH ⊕ + A−
0.1M 0.1M
0mL pH = 13
3 mL → 50% Neutralization pH = 11
6 mL → equivalence point pH = 3 to 9
Equivalence point
B + HA ⟶ BH + + A−
0.1 × 6 0.1 × 6
= 0.6 m mol = 0.6 m mol
0 0 0.6 m mol
Total volume = 12ml
0.6
Concentration of Salt =
12
k 10−14 ×0.6
pH = 6 = √ kw × c = √ {pH = 0.6, [H + ] = 10−6 }.
b kb ×12
K w 0.1 × 6
⇒ [H + ] = 10−6 = √ ×
Kb 12
10−14 × 10−1 1
10−12 = ×
Kb 2
k b = 5 × 10−4
pk b = −log k b = −log (5 × 10−4 ) = −log 5 + 4log 10
pk b = 4 − 0.7
pk b = 3.3
27. [Zn+2 ][S 2− ] ≤ K sp (ZnS)
5 10−22
[S 2− ] ≤ ×
4 0.05
APNI KAKSHA 62
H2 S ⇔ 2H + + s 2−
Knet ×[H2 S]
[S 2− ] = [H+ ]2
Knet ×[H2 S] 5 10−22

[H+ ]2
≤ 4 × 10−2 ×5
10−21 ×10−1 ×4
[H + ]2 ≥
10−20
[H + ] ≥ 2 × 10−1 = 0.2
Alternate:
[Zn+2 ][S 2− ] ≤ K sp
5 10−22 1
[S 2− ]
≤ × = × 10−20
4 0.05 4
+ 2−
H2 S ⇔ 2H + S
K1 K2 ×[H2 S] 10−21 ×0.1
[H + ]2 = =
[S2− ] [ S2− ]
10−22 1
[S 2− ] = ≤ 4 × 10−20
[H+ ]2
[H + ] ≥ 0.2
28. First acid base reaction between H2 CO3 and NaOH takes place.
In the final solution, we have 0.01 mole Na2 CO3 and 0.02 moles of NaHCO3 .
Here, we have a buffer of NaHCO3 and Na2 CO3 .
[ Salt ]
∴ pH = pK a2 + log
∣ Acid ]
0.01
( 0.1 )
= 10.32 + log
0.02
( 0.1 )
1
= 10.32 + log
2
= 10.32 − log 2
= 10.32 − 0.3
= 10.02
∴ pH = 10.02
+
29. H2 SO4 ⟶ HM 4 (K a1 is very large )
+ HSO2−
1M
1M4
HSO4 ⇌ H + SO2−
− +
4 K a2 = 1.2 × 10−2
[SO24 2 ] coming from Na2 SO4 = 1.8 × 10−2
[SO24 ][H + ] 1.8 × 102 × 1

= > K a2
[HSO4 ] 1
APNI KAKSHA 63
∴ Rather than dissociation of HSO4 − into H + andS O4 2− ions, association between already
present H + and SO4 2− will take place.
∴ [SO2−
4 ] = 1.8 × 10
−2
−x
[H + ] = 1 − x ≈ 1
} ( assuming x << 1)
[HSO− 4] = 1 + x ≈ 1
(1.8 × 102 − x)1

= 1.2 × 10−2
1
⇒ x = 0.6 × 10−2
[SO2− −2
4 ] = 1.2 × 10 M
PbSO4 (s) ⇌ Pb2+ (aq) + SO2−

4 (aq)
If solubility of PbSO4 = sM
∴ [Pb2+ ] = s
[SO24 ] = s + 1.2 × 10−2 ≈ 1.2 × 10−2
(assuming s ≪ 1.2 × 10−2 )
∴ s × 1.2 × 10−2 = 1.6 × 10−8
1.6
s= × 10−6 = 1.33 × 10−6
1.2
On comparing with X × 10−Y
Y=6
30. 𝑀𝑋 ⇌ 𝑀⊕ + 𝑋 ⊖
X ⊖ + H ⊕ ⇌ HX
H⊕
S = √K sp (+ K )
a
10−7
10−4 = √K sp (1 + )
Ka
10−2
10−3 = √K sp (1 + )
Ka
Squaring Equation [(1)/(2)] gives

10−7
(1 + )
𝐾𝑎
10−2 =
10−2
(1 + )
𝐾𝑎
APNI KAKSHA 64
10−4 10−7
10−2 + =1+
𝐾𝑎 𝐾𝑎
10−4 − 10−7
= 0.99
𝐾𝑎
10−4
= 0.99
𝐾𝑎
10−4 1
𝐾𝑎 = = × 10−2
0.99 99
K 𝑎 = 2 + log 99 = 4
APNI KAKSHA 65

Sheet - 01 (Solution) _ Ionic Equlibrium (Exercise) NJ_247

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Sheet - 01 (Solution) _ Ionic Equlibrium (Exercise) NJ_247

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(Physical Chemistry) IONIC EQUILIBRIUM

12. CH3COOH CH3COO– + H+

13. NH4OH → NH4+ + OH–

16. [H+] = Ka1C1 + Ka 2C2 = 310−4  0.03 + 110−10  0.1 = 3 × 10–3 M

21. [HPO42–] = 10 Ka1 Ka2

22. NH2– + H+ → NH3

24. Bronsted acid → which can given H+

24. NHO3 + H2O H3O+ + NO3–

25. CH3COOH + OH– CH3COO– + H2O

28. At 85ºC neutral pH < 7

30. (A) 0.1 M NaCl  pH = 7

CN– + H2O → HCN + OH–

0.01(1 − h) 0.01h 0.01h

33. Fe3+ + H2O → Fe(OH)2+ + H+

34. S2– + H2O → HS– + OH–

35. A3– + H2O → HA2– + OH–

38. Amphiprotic species ® which can given as well as take H+ ion.

41. For 1 M NaCl & 1 M HCl solution

42. pOH = pKb = 4.74

50. If [NH4OH] ¯, [OH–]¯, pH ¯

52. HA + NaOH → NaA + H2O

53. On moderate dilution pH of buffer solution does not change.

57. H2SO4 + 2NaOH → Na2SO4 + H2O

64. NaCN + HCl ¾→ HCN + NaCl

60. (A) H3PO4 + NaH2PO4 (W.A + its salt)

61. HCOOH + KOH → HCOOK + H2O

65. CH3COONa + HCl → CH3COOH + NaCl

67. N3PO4 + NaH2PO4

68. H3PO4 + NaOH → NaH2PO4 + H2O

71. pH range of methyl red

72. pH at equivalence point is (5.5 – 11)

73. For HCl Vs NH4OH  pH range (3 – 8.5)

74. For NaOH Vs H2C2O4 titration

75. Oxalic acid Vs KMnO4 titration is a redox titration.

76. For WA Vs SB titration

82. Ksp = s2 = 64 × 10–6

85. (A) Ksp = s2

(2s)2 × 0.6 = 8.64 × 10–13

87. 0.1 M CaBr2  [Br–] = 0.2 M

88. SrCO3 → Sr 2+ + CO32−

(s1 + s 2 )s1 10−10 100

90. Ksp = [Mg2+] [OH–]2

92. Ag+ + Br– → AgBr

94. AgCl(s) Ag+ (aq.) + Cl– (aq.)

95. Ksp = [Ag+] [Cl–]

97. Solubility of Ag2CO3 will be max. in NH3 due to complex formation.

98. Ag+ + 2NH3 Ag(NH3) +2

2. (i) Kw = [H+][OH–] = 9×10–14

3. 2H2O → H3O+ + OH–

 NH+4   NH−2  = 10–30

 NH−2  =  NH4+  = 10–15 M

1 L contains 6×105 NH −2 ions

10–6 L (1 mm3) will contain= 6×108×10–6 = 600 NH −2 ions

5. (a) [H+] = 10–1  pH = 1

(d) H2O → H+ + OH–

6. If V→¥, then solution will almost neutral. So pH = 7

8. (b) CH3COOH → CH3COO– + H+

(c) NH4OH → NH +4 + OH–

(f) 10–7 M CH3COOH

Acid will completely dissociate, so a » 1

(b) BOH ⎯→ B+ + OH–

12 1.5 10 −5

12. NH4OH ⎯→ NH +4 + OH–

pH = 5 – log 1.77 = 4.87