JEE (MAIN + ADVANCED) : LEADER COURSE

SUBJECT : PHYSICAL CHEMISTRY

Topic : Ionic Equilibrium Exercise : S-I

1. IE0001
Ans. (6.022 ×107)
Sol. [H+] = 10–pH = 10–13 mol/L

10 -13 10 -13
No. of H+ = ´ NA = ´ 6.023 ´ 10 23
1000 1000
= 6.023 × 107
2. (i) IE0002
(ii) IE0003
Ans. ((i) 6.53 ; (ii) (a) Basic , (b) Acidic

Sol. (i) [H+] = k w = 3 × 10–7

pH at 60°C = 7 – log3 = 6.53

(ii) Neutral pH at 60°C = 6.53 (from (i) part)
(a) pH (6.7) > Neutral pH Þ Basic
(6.53)
(b) pH (6.35) < Neutral pH Þ Acidic
(6.53)
3. IE0004
Ans. (6.8)

Sol. [H+] = Kw = 1.6 × 10–7 = 16. × 10–8

pH = 8 – 4 log 2 = 6.8
4. (a) IE0005
(b) IE0006
(c) IE0007
(d) IE0008
(e) IE0009
(f) IE0010
(g) IE0011
(h) IE0012
(i) IE0013
(j) IE0014
Ans. ((a) 1, (b) 2.87, (c) 11.13 (d) 6.97, (e) 7, (f) 6 , (g) 6.97, (h) 11.30 (i) 9 , (j) 3)
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

Sol. (a) [H+] = 10–10 M Þ pH = 1

Ka
(b) < 10 -3 Þ [H + ] = K a .C = 1.8 ´ 10 -5 ´ 0.1
C

pH = 3 – log 1.8 = 2.87

Kb
(c) < 10 -3 Þ [OH - ] = K b ·C = 1.8 ´ 10 -5 ´ 0.1
C

= 1.8 ´ 10 -3

pOH = 3 – log 1.8 = 2.87

pH = 14 –pOH = 14 – 2.87 = 11.83

-
(d) HCl (aq.) ® H + (aq.) + Cl (aq.)
10 0-8 (10 -8 + x) 10 -8

H2 O ƒ H + (aq.) + OH - (aq.)
(x +10 -8 ) x

Kw = [H+] [OH–]
10–10 = (x + 10–8)x
x2 + 10–8x – 10–14 = 0

-10 -8 ± 10 -16 + 4 ´ 10 -14

x=
2
[H ] = x + 10 = 1.051 × 10–7
+ –8

pH = 7 – log 1.051 Þ 6.97

(e) [OH–] = 10–10 + 10–7 ; 10–7
pOH ; 7 Þ pH = 14 – 7 ; 7

Ka
(f) > 10 Þ Behave like strong acid
C

[H+] = 10–6 Þ pH = 6

K a 1.8 ´ 10 -5
(g) = > 10 Þ behave like strong acid so 10–8 M CH3COOH is like 10–8 M HCl
C 10 -8

(as part (d))

 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

CH 3COOH(aq.) ® OH3COO - + H +
10 -8 10 -8 + x

H 2 O(l) ƒ H + + OH -
(x +10 -8 ) x

Kw = 10–14 = (x + 10–8)x
Solving quadratic x can be calculated
[H+] = 10–8 + x = 1.051 × 10–7
pH = 7 – log 1.051 × 10 = 6.97
M initial
(h) [OH–] = 2 × Mfinal M final =
100
= 2 × 10–3M 1 / 10
= = 10 -3
pOH = 3 – log 2 = 2.7 Þ pH = 14 – 2.7 = 11.30 100

10 -3
(i) [OH–] = = 10 -5 M Þ pOH = 5
100
Þ pH = 14 – 5 = 9
(j) M1 = 10–4 M : M2 = 19 × 10–4 M
Let V litre of both the two are mixed

M1V1 + M 2 V2
[H + ]final = = 10–3 M
V1 + V2

pH = 3
5. IE0015
Ans. (a) Ka = 10–8, (b) Kb = 10–6

x2
Sol. (a) Ka = ; x = [H+] = 10–4.5
C

[10 –4.5 ]2
= = 10 –8
0.1

6. IE0016
Ans. (10)

Ka a C1 C1
Sol. a= Þ 2 = = = 10
C a1 C2
( C1
100 )
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

7. IE0017
Ans. (173.2 : 1)

Ka a Ka1 1.8 ´ 10 -5
Sol. a= Þ 2 = =
C a1 Ka2 6 ´ 10 -10

1.732 ´ 100
= 173.2 :1
1
8. IE0018
Ans. (0.009)
Sol. H+ removed = moles of H+ initially – finally
= M1V1 – M2V2
= 10–2 × 1 – 10–3 × 10
= 9 × 10–3
9. IE0019
Ans. (1.1 × 10–3 M)

x2
Sol. Kb = | x = [0H–] = 10–4
C-x

(10 -4 )2
10–5 = Þ C = 1.1 ´ 10 -3 M
C - 10 –4

10. IE0020
Ans. (1.11 × 10–4)

x2 (10 -3 )2
Sol. Ka = = = 1.11 ´ 10 -4
-
C - x (10 - 10 )
2 -3

11. IE0021
Ans. (4.7)

Ka
Sol. < 10-3 Þ [H+ ] = K a .C = 8 ´10-10 ´ 0.5
C
= 2 × 10–5 M
pH = 5 – log 2 = 4.7
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

12. IE0022
Ans. (3.3)

Sol. When equal volume are mixed

10 -5 ´ v + 10 –3 ´ v
+
[H ]final = = 50.5 ´ 10 -5 M
v +v

pH = 5 – log (50.5) = 3.3

13. IE0023

Ans. ((a) 0.522 , (b) 2.522)

0.1 ´ 50 ´ 2 + 0.4 ´ 50 ´ 1
Sol. (a) [H+]final = = 0.3
(50 + 50)

pH = 1 – log 3 = 0.522

(b) [H+]final = K a1 C1 + K a 2 C 2 (Mixing of weak acids)

= 3 × 10–3 M

pH = 3 – log 3 = 2.522

14. IE0024

Ans. (1)

Sol. HCl ® H + + Cl -
0.01M 0.01M

Ha(aq.) ƒ H + (aq.) + Al - (aq.)

0.1 - -

(0.1–x) (x+0.1) x

; 0.1 ; 0.1

Ka
as < 10 -3 Þ x can be neglected
C

[H+] = 0.1 M Þ pH = 1
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

15. IE0025
Ans. (0.027 M , 0.073 M , 0.027 M , 10–5 M)

Sol. H2C2O4(aq.) ƒ H+(aq.) + HC2O42– (aq.) : K a

1

0.1 - -
0.1 – x (x + y) ; x (x – y) ; x
HC2O4– (aq.) ƒ H+ (aq.) + C2O42– (aq.) : K a
2

(x-y) ; x (y + x) ; x y

(as K a1 >> K a2 Þ x >> y )

x2
10 -2 = K a1 = Þ x 2 + 10 -2 x - 10 -3 = 0
0.1 - x
Þ x = 2.7 × 10–2 M (Solving quadratic)

x.y
K a 2 = 10 -5 = =y
x
[H+] = x = 0.027 M = [HC2O4–]
[C2O42–] = y = 10–5 M ; [H2C2O4] = 0.1 – x = 0.073 M
16. IE0026
Ans. (11.3)
Sol. Diacidic weak base gives OH– mainly due to I step

x2 x2
K b1 = Þ 2 ´ 10 -5 =
C 0.2

x = [OH - ] = 2 ´ 10 -5 ´ 0.5 = 2 ´ 10 -3 M
pOH = 3 – log 2 Þ pH = 14 – pOH = 11 + log 2 = 11.3
17. IE0027
–5
Ans. (10 M)
Sol. Salt of S.B. & W.A.

Kw 10 -14 x2
Kh = = =
K a 1.8 ´ 10 -5 C

10 -14
x = [OH - ] = ´ 0.18 = 10 -5 M
1.8 ´ 10 -5
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SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

18. IE0028
Ans. (pH = 4.5)

1 1
Sol. pH = 7 – – pK b - log C (Salt of S, A & W.B.)
2 2

= 7 - 1 ´ (5 - log 2) - 1 log 2 = 4.5

2 2
19. IE0029
Ans. (Kb = 6.25 × 10–10)
Sol. Salt of S.A. & W.B.

10 -14 x 2 x = [H + ] = 10 –pH
Kh = =
Kb C = 2 × 10 -3
C = 0.25
Kb = 6.25 × 10–10
20. IE0030
Ans. (0.56%, pH = 7)

1 1
Sol. pH = 7 + pK a - pK b (Salt of W.A. & W.B.)
2 2
= 7 (as Ka = Kb)

10 -14
%h = ´ 100 = 0.56%
Ka ´ K b

21. IE0031
Ans. (1.667%)

Kh 10 –14
Sol. %h = ´ 100 = ´ 100 = 1.667%
C Ka ´ C

Salt of W.A. & S.B.

22. IE0032
Ans. (8.3)
Sol. Amphiprotic anion

pK a1 + pK a 2 7 - log 5 + 11 - log5
pH = = = 8.3
2 2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

23. IE0033
Ans. ((a) 6, (b) 1 × 10–5)
x2
Sol. (a) Kh = Þ x = [H + ] = K h ·C
C

= 10 -9 ´ 0.001 = 10 -6 M
Þ pH = 6

10 -14 10 -14 10 -14

(b) Kh = Þ K b2 = = = 10 -5
K b2 Kh -9
10
24. IE0034
Ans. (9.0)
æ 0.1 ö
pH = pKa + log æç ö÷ = 9 + log ç
S
Sol. ÷=9
èaø è 0.1 ø
25. IE0035
Ans. (9.56)
æ 0.1 ö
pOH = pKb + log æç ö÷ = 5 – log 1.8 + log ç
S
Sol. ÷
èbø è 0.2 ø
pH = 14 – pOH = 9.56
26. IE0036
Ans. (5.04)

æSö æ 0.4 ö
Sol. pH = pKa + log ç ÷ = 5 – log 1.8 + log ç ÷
èaø 500
ç 0.4 ´ ÷
è 1000 ø
= 5.04
27. IE0037
Ans. (0.05 mol)
Sol. (NH4)2 SO4 ¾® 2NH4+ + SO42–
x mol - -
0 2x x
æSö
pOH = pKb + log ç ÷
èbø

æ 2x ö
(14 – 9.26) = 4.74 + log ç ÷
è 0.1 ø
0.1
x= = 0.05
2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

28. IE0038
Ans. ([OH–] = 9.0 ×10–6M)

[NH +4 ][OH - ] [0.1][OH - ]

Sol. 1.8 ´ 10 -5 = =
[NH 4 OH] 0.05

[OH–] = 9 × 10–6 M
29. IE0039
Ans. (10.1)

[CO32- ] æ 0.1 ö
Sol. pH = pK a (HCO3- ) + log = 11 - log 4 + log ç ÷
[HCO3- ] è 0.2 ø

= 10.1
30. IE0040
Ans. (4.74)
Sol. CH3COOH + NaOH ¾® CH3COONa + H2O
50 × 0.2 = 10 5 (50 × 0.1) -
5 0 5
For acidic buffer formed

æSö æ5ö
pH = pKa + log ç ÷ = 4.74 + log ç ÷ = 4.74
èaø è5ø

31. IE0041
Ans. (9.56)
Sol. NH4Cl + NaOH ¾® NH4OH + NaCl
75 × 0.1 50 × 0.1 = 5 - -

2.5 x 5 5

Basic buffer

æSö æ 2.5 ö
pOH = pKb + log ç ÷ = (14 – 9.26) + log ç ÷
èbø è 5 ø

= 14 – 9.26 – log 2
pH = 14 – pOH = 9.26 + log 2 = 9.56
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

32. IE0042
Ans. (8.7782)
Sol. NH3 + HCl ¾® NH4Cl
20 15 -
5 x 15

Basic buffer
æSö æ 15 ö
pOH = pKb + log ç ÷ = 4.74 + log ç ÷ = 4.74 + log 3
èbø è 5ø
pH = 14 – pOH = 8.7782
33. IE0043
Ans. (3.33)
Sol. Let b millimoles of NaOH are added
CH3COOH + NaOH ® CH3COONa + H2O
Initially 10 b 10
After reaction 10 – b × 10 + b

æ 10 ö
pH1 = pKa + log ç ÷ = pK a
è 10 ø

æ 10 + b ö
pH2 = pKa + log ç ÷
è 10 - b ø

æ 10 + b ö 10
pH2 – pH1 = log ç ÷ = 0.3 = log 2 Þ b = = 3.33 (on solving)
è 10 - b ø 3
34. IE0044
Ans. (10–5 M)
Sol. CH3COOH + NaOH ¾® CH3COONa + H2O

0.2 0.2
= 0.1M = 0.1M - -
2 2
x x 0.1 M
(at equivalence point equal volumes are added so concentration becomes half)
For salt of S.B. & W.A.

10 -14 x2
Kh = =
Ka 0.1

10 -14
x = [OH–] = ´ C = 10–5 M
Ka
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SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

35. IE0045
Ans. (8.7 , [H3 O +] =2× 10–9M)
0.1
Sol. At equivalence point CH3COONa forms, C = M
2

10 -14 x2
Kh = = x = [OH–]
Ka C

10 -14 0.1 10 -5
[OH–] = x = ´ =
2 ´ 10 -5 2 2

10 -14 10 -14
+
[H ] = = = 2 ´ 10 -9
- -5
[OH ] [10 / 2]

pH = 9 – log 2 = 8.7
36. IE0046
Ans. (5, 10–5 M)
0.4
Sol. At equivalence point NH4Cl forms, C = = 0.2M
2

10 -14 x 2
Kh = = = x = [H + ] = 10 –5 M
Kb C

pH = 5
37. IE0047
Ans. ((i) 2.85, (ii) 4.0969, (iii) 4.5229, (iv) 4.699, (v) 5.301, (vi) 8.699)
Sol. (a) at 0 ml NaOH

For CH3 COOH, (H + ) = K a .C = 2 ´ 10 -3

1
pH = 3 - log 2 = 2.85
2
(b) at 20 ml NaOH
CH3COOH+NaOH ® CH3COONa + H 2O
5 20 × 0.1 = 2 -
3 x 2

Basic buffer

æSö æ2ö
pH = pKa + log ç ÷ = (5 - log 2) + log ç ÷
èaø è 3ø
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SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

(c) At 25 ml NaOH
CH3COOH+NaOH ® CH3COONa + H 2O
5 25 × 0.1 = 2.5 -
æSö æ 2.5 ö
pH = pKa + log ç ÷ = (5 - log 2) + log ç ÷
èaø è 2.5 ø
= 4.699
(d) At 40 ml NaOH
CH3COOH+NaOH ® CH3COONa + H 2O
5 4 -
1 x 4
æSö æ4ö
pH = pKa + log ç ÷ = 5 – log 2 + log ç ÷
èaø è1ø
= 5.0310
0.1
(e) At 50 ml NaOH :- CH3COONa, C = M
2
1 1
pH = 7 + pK a + log C = 8.699
2 2
38. IE0048
Ans. ([HIn] = 80%)
[I ]
n-
Sol. pH = pK I n + log
[HI n ]

When éë I n – ùû = [HIn] = 50% Þ pH = pKI n = 3

[H + ][I ] (100 - x)
But KIn = n- = 4 × 10–3 ×
10–3 [HI n ] x

Þ x = % of HIn = 80 %
39. IE0049
Ans. (85.71%)

[H + ][I ] æ x ö
n- = 10 -5 ´ ç
Sol. Ka = 6 × 10 = –5
÷
[HI n ] è 100 - x ø

Þ x = % of basic form (In–) = 85.71 %

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SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

40. IE0050
Ans. ((b), (c))
Sol. Theorically indicator changes the colour when
pH = pKIn = 4 – log 4 = 3.4
i.e. pH range = 2.4 to 4.4
So suitable for titrations involving strong acids only like option (b) & (c).

41. IE0051
Ans. (DpH = 0.954)

æI – ö
Sol. pH = pK I n + log ç n ÷
ç HI ÷
è nø

HIn (Red) In– (blue)

æ 25 ö 75% 25%
pH1 = pK I n + log ç ÷ Case-1
è 75 ø Case-2 25% 75%

æ 75 ö
pH2 = pK I n + log ç ÷
è 25 ø

DpH = pH2 – pH1 = 2 log 3 = 0.954

42. IE0052
Ans. (QX2 is more soluble)

Sol. MX :- Ksp = S2 Þ S1 = K sp = 2 ´ 10 -9 M

1/3
æ K sp ö
QX2 :- Ksp = 4S Þ S2 = ç
3
÷ = 10 -6 M
è 4 ø

S2 > S1

43. IE0053
Ans. (4 × 10–8)

0.0608
Sol. S= = 2 ´ 10 -4 M
304

Ksp = S2 = (2 × 10–4)2 = 4 × 10–8

 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-I

44. IE0054
Ans. (5 × 10–11)
Sol. CuI(s) ƒ Cu+ (aq.) + I– (aq.) ; Ksp
x mol/L x (x + 0.1) (from NaCl)
; 0.1
+ –
Ksp = [Cu ] [I ] = x × 0.1

K sp
x= = 5 ´ 10 -11 M
0.1
45. IE0055
Ans. (3.2 × 10–11)
Sol. CaF2(s) ƒ Ca+2(aq.) + 2F– (aq.) ; Ksp
x 2x = 4 × 10–4
Ksp = x(2x)2 = 2 × 10–4 × (4 × 10–4)2 = 3.2 × 10–11
46. IE0056
Ans. (2.56 ×10–16)

2.4 ´ 10 -5 ´ 1000
Sol. Ksp = 4 s3 S=
60 ´ 100
= 4 (4 × 10 –6)3
= 2.56 × 10–16 = 4 × 10–6 mol/L
47. IE0057
Ans. (1.0 × 10–5 mol/lit)
Sol. Ksp = (2)2 (3)3 S5 = 108 S5

1/5 1/5
æ K sp ö æ 1.08 ´ 10 -23 ö
S= ç ÷ =ç ÷ = 10 -5 M
è 108 ø è 108 ø

48. IE0058
Ans. (5 × 10–10 M)
Sol. AgCl(s) ƒ Ag+(aq.) + Cl– (aq.)n ; Ksp
'x' mol/L x (x + 2 × 0.1) from BaCl2
; 0.2
Ksp = x × 0.2

Ksp
x= = 5 ´ 10 –10
0.2
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49. IE0059
–7
Ans. (5 × 10 )

Sol. Ca3(PO4)2(s) ƒ 3 Ca+2(aq.) + 2 PO34- (aq.) ; K sp

'x' (3x + 0.1) (from CaCl2) 2x

; 0.1
Ksp = [Ca+2]3 [PO43–]2 = (0.1)3 (2x)2

1/2
æ -15 ö
x = ç 10 = 5 ´ 10 -7 M
ç (0.1)3 ´ 4 ÷÷
è ø

50. IE0060
Ans. (4 × 10–7 mol/L AgBr, 1.6 × 10–6 mol/L AgSCN)
Sol. AgCN(s) ƒ Ag+(aq.) + SCN– (aq.) ; K sp
1

x (x + y) x

AgBr(s) ƒ Ag+ (aq.) + Br–(aq.) ; K sp

2

(x + y) y

K sp = (x + y) x ...(1), K sp = (x + y)y ...(2)

1 2

(1) + (2) Þ (x + y) = K sp1 + K sp2 = 2 ´ 10 -6

Þ x = 1.6 × 10–4 M ; y = 4 × 10–7 M

51. IE0061
Ans. (8 × 10–3 M)

2
æ x ö x
Sol. Ksp × Kf = ç ÷ Þ = K sp ´ K f
è C - 2x ø C - 2x

here C = 0.2 M & x is solubility

x
= 4 × 10–4
0.2 - 2x

Þ x = 8 × 10–3 M
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52. IE0062
Ans. (4 × 10–2M)

Ksp x2
Sol. = ; x = solubility
Ka [H + ]

K sp 8 ´ 10 -10
x= ´ (H + ) = ´ 10 -3 = 4 ´ 10 -2 M
-10
Ka 5 ´ 10

53. IE0063
Ans. ((a) no precipitation will occur, (b) a precipitate will form)
Sol. (a) Qsp = [M+2] [OH–]2 = 10–3 × (10–5)2 = 10–13
Qsp < Ksp Þ No ppt.
(b) Qsp = (10–3) (10–3)2 = 10–9
Qsp > Ksp Þ ppt.
54. IE0064
Ans. (No.)
Sol. After mixing of solutions:

C1V1 200 2
[Ag+] = = 2 ´ 10–4 ´ = ´ 10-4 M
V1 + V2 600 3

C2 V2 400
[Cl–] = = 1.2 ´ 10–6 ´ = 8 ´ 10-7 M
V1 + V2 600

16
Qsp = [Ag+][Cl–] = ´ 10 –11 < K sp Þ No.ppt.
3

55. IE0065
Ans. (0.284 gm)
Sol. Ksp = 8 × 10–8 = [Ba+2] [SO42–]
Q [Ba+2] = 2 × 10–5
[SO42–] = 4 × 10–3 mol/L

4 ´ 10 -3
Mass of Na2SO4 in 500 ml = ´ 142
2
= 0.284 gm
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SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-II

1. IE0066
Ans. (0.209 M, 0.191 M, 9.13 × 10–3 M, 0)
Sol. H2SO4(aq.) ¾® H+(aq.) + HSO4– (aq.)

0.2 - -
0 (0.2 + x) (0.2 – x)
HSO4 (aq.) ƒ H+(aq.) + SO42– (aq.) ; K2
–

0.2 0.2 -
(0.2 – x) (0.2 + x) x

(0.2 + x)x
K2 = 10–2 =
(0.2 - x)

0.2 × 10–2 – 10–2 x = 0.2 x + x2

x2 + 0.21 x – 2 × 10–3 = 0
x = 9.13 × 10–3 M
Þ [SO42–] = x = 9.13 × 10–3M
[H2SO4] = 0
[H+] = 0.2 + x = 0.209 M
[HSO4–] = 0.2 – x = 0.191 M
2. IE0067
Ans. (10.6)

Sol. as K b1 >> K10 2 Þ OH - is given by I step only

NiC(aq.) + H2O ƒ NiCH+(aq.) + OH– (aq.) ; K b

1

0.2 - -
(0.2 – x) = 0.2 x x
é K b1 ù
êQ < 10 -3 Þ (0.2 - x) ; 0.2 ú
ë 0.2 û
x2
K b1 =
0.2

[OH–] = x = K b1 ´ 0.2 = 16 ´ 10 –8

= 4 × 10–4 M
pOH = 4 – log 4
pH = 14 – pOH = 10 + log 4 = 10.6
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Topic : Ionic Equilibrium Exercise : S-II

3. IE0068
Ans. (2 × 10–4M)
Sol. NaOH(aq.) ¾® Na+ (aq.) + OH–(aq.)
0 10–4 10 –4
RNH2(aq.) + H2O ƒ RNH3+ (aq.) + OH–(aq.) ; Kb
10–2 - 10 –4
(from NaOH)
(10–2 – x) = 10–2 x (10–4 + x)

é Kb -3 -2 -2 ù
êQ -2 < 10 Þ (10 – x) ; 10 ú
ë 10 û

x(10 -4 + x)
Kb = 2 × 10–6 =
10 -2
2 × 10–8 = 10–4x + x2
x2 + 10–4 x – 2 × 10–8 = 0
x = 10–4 M
[OH–] = 10–4 + x = 2 × 10–4 M
4. IE0069
Ans. (pH = 10.52)
Sol. Salt of strong base & weak acid
C6H5O–(aq.) + H2O ƒ C6 H5OH (aq.) + OH–(aq.)
(C–x) ; C = 10–3 M

1014 10 -14 10 -4
Kh = = =
Ka 0.6 ´ 10 -10 0.6

10 -4 x2
=
0.6 10 -3

10 -4 ´ 10 -3 10 -3
[OH - ] = x = =
0.6 6

1
pOH = 3 + log 6
2

1
pH = 14 – pOH = 11 – log 6 = 10.52
2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-II

5. IE0070
Ans. (8.35, 9.60, 4.66)
Sol. All salts having amphiprotic anion so we can use direct formula for solution of amphiprotic anions

pK a1 + pK a 2
(i) NaHCO3 Þ pH =
2

7 - log 4.2 + 11 - log 4.8

=
2

= 8.35

pK a 2 + pK a 3
(ii) Na2HPO4 Þ pH =
2

8 - log 6.2 + 12
=
2

= 9.6

pK a1 + pK a 2
(iii) NaH2PO4 Þ pH =
2

3 - log 7.5 + 8 – log 6.2

=
2

= 4.66

6. IE0071
Ans. (9.6)

[NH 4 Cl]
Sol. pOH = pKb + log [NH ]
3

æ NH 4 Cl ö
(14–9) = 5 – log 2 + log ç ÷
è 0.25 ø

[NH 4 Cl]
Þ = 2 Þ [NH4Cl] = 0.5 M
0.25
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-II

When kOH is added to buffer

kOH + NH4Cl ® NH4OH + kCl
(or NH3 )
initialy (500×0.1) (200 × 0.5) (200 × 0.25) -
= 50 = 100 = 50 -
Finally x 50 100 50
|_____________|
Buffer sol.
æ5ö
New pOH = pKb + log ç ÷
èbø

æ 50 ö
= 5 – log 2 + log ç ÷
è 100 ø
= 5 – 2 log 2
New pH = 14 – pOH = 9 + 2 log 2
= 9.6
7. IE0072
Ans. (10–5M)
Sol. As S.A. & S.B. react so,
HCl + NaOH ¾® NaCl + H2O
Milli-moles 2 1 -
1 0 1
1 1
After reaction, [HCl] = = M
10 + 10 + 10 30
0.1 ´ 10 1
Finally [HA] = = M
10 + 10 + 10 30
HA(aq.) ƒ H+(aq.) + A–(aq.) : Ka
1 1
-
30 30
(from HCl)
æ 1 ö 1 æ 1 ö 1
ç - x÷ ; ç + x÷ ; x
è 30 ø 30 è 30 ø 30
Ka
[x is negligible as < 10 -3 ]
C

1
.[A - ]
–5
Ka = 10 = 30
1
30
[A–] = 10–5 M
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-II

8. IE0073
–3
Ans. (10 M)
Sol. HCN + KOH ¾® KCN + H2 O
150 × 0.5 V2 × 1.5
= 75 = 75 -
x x 75 millimoles

75 75
Concn. (C) = =
150 + V2 200

= 3.75 × 10–1 M
Salt formed (KCN) undergoes hydrolysis
CN– (aq.) + H2O ƒ HCN (aq.) + OH–(aq.) ; Kh
(C–x) ; C x x

10 -14 x2 x2
Kh = = =
Ka C-x C

10 -14
x = [HCN] = ´ 3.75 ´ 10 -1
-9
3.75 ´ 10
= 10–3 M
9. IE0074
–3
Ans. (2.8 × 10 mole)
Sol. Let solubility of AgBr is 'x' mol/L
AgBr(s) ƒ Ag+ (aq.) + Br–(aq.) ; Ksp
x x
Ag (aq.) + 2NH3(aq.) ƒ Ag(NH3)2+(aq.) ; Kf
+

x 0.4 -
- (0.4 – 2x) x
____________________________________
AgBr(s) + 2NH3(aq.) ƒ Ag(NH3)2+ (aq.) + Br– (aq.)
(0.4 – 2x) x x

x2
Ksp × Kf =
(0.4 - 2x)2

x
K sp ´ K f =
0.4 - 2x
x = 2.8 × 10–3 M
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : S-II

10. IE0075
Ans. (1.6 × 10–3)
Sol. Let solubility of PbI2 be 's' mol/L. As salt is only 90% ionized so,
PbI2 (s) ƒ Pb+2(aq.) + 2I–(aq.) ; Ksp
's' 0.9 S 1.8S
+2 – 2
K sp = [Pb ] [I ]
1.4 × 10–8 = (0.9 S) (1.8 S)2

1/3
æ 1.4 ´ 10 -8 ö
S = çç ÷
2÷
è 0.9 ´ (1.8) ø

= 1.6 × 10–3 M
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

1. IE0076
Ans. (A)
Sol. To write conjugate acid add H+.
2. IE0077
Ans. (B)
Sol. Bronsted acid is proton donor.
CH3COO– is a Bronsted base. It can accept a proton.
3. IE0079
Ans. (C)
Sol. H3PO3 is a dibasic acid, so HPO32– is not an amphiprotic species.
Amphiprotic species give both H+ and OH– in water.
H2PO4– ƒ + HPO42–
H2PO4– + H2O ¾® H3PO4 + OH–
Þ H2PO4– is amphiprotic. Similarly HCO3– is also amphiprotic.
4. IE0080
Ans. (B)
Sol. On adding NH3, conc. of OH– increases Þ [H3O+] decrease.
5. IE0082
Ans. (D)
Sol. Ionic product (Kw) depends only upon temperature and it increases with increase in tempt.
6. IE0083
Ans. (D)
Sol. In pure water, [H3O+] = [OH–] = 10–6.7
Always
Kw = [H3O ] × [OH–] = 10–6.7 × 10–6.7 = 10–13.4
+

7. IE0084
Ans. (C)
Sol. 2NH3 ƒ NH2– + NH4+
x x
Kself ionization const. = [NH2 –] [NH4+]
10–30 = x2 Þ x = 10–15 mole/L
\ [NH4+] = 10–15 mole/L
= 10–15 × 6.022 × 1023 ions/1000 ml
= 6.022 × 108 ions/1000 ml.

6.022 ´ 108 ´ 100

= ions / 100ml
1000
= 6.022 × 107 ions/100 ml.
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

8. IE0085
Ans. (C)
Sol. pH1 = 3 Þ [H+]1 = 10–3
pH2 = 6 Þ [H+]2 = 10 –6.

[H + ]1 10 -3
\ = = 1000
[H + ]2 10 -6

\ [H+] ion is reduced by 1000 times.

9. IE0086
Ans. (C)

1
Sol. [H2SO4] = mole / m 3
200

1
= mole / 1000L Q 1 m3 = 1000 L
200

1
= mole / L
200 ´ 1000

= 0.5 × 10–5 mole/L = 5 × 10–6 mole/L

\ [H+] = 2 × 5 × 10–6 = 10–5 mole/L = PH = 5
\ POH = 14 – 5 = 9

10. IE0088
Ans. (B)

5
Sol. [NH3] = C = 0.02 M, a = = 0.05.
100

[OH–] = Ca = 0.02 × 0.05 = 0.0010 = 10–3 M.

\ POH = 3 Þ PH = 11

11. IE0089
Ans. (B)
Sol. C = 1M, a = 0.01
[H+] = Ca = 1 × 0.01 = 10–2 M
Þ PH = 2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

12. IE0091
Ans. (C)

10 -14
Sol. V = 250 ml, PH = 13 Þ [H+] = 10–13 Þ [OH–] = -13 = 10–1 M.
10
\ [NaOH] = [OH–] = 10–1 M

n ´ 1000
or, = 0.1 (where n = moles of NaOH)
250

1
or, n= mole
40

1
\ mass of NaOH = n × 40 = × 40 g = 1g
40
13. IE0092
Ans. (B)
Sol. When [Strong acid] £ 10–9 Þ pH » 7.
Exact PH will be very slightly less than 7 but very close to 7
14. IE0095
Ans. (B)

8
Sol. NaOH = 8 g = mole = 0.2 mole Þ OH– = 0.2 mole
40

4.9 1
H2SO4 = 4.9 g = mole = mole = 0.05 mole \ H+ = 2 × 0.05 = 0.1 mole
98 20
Q moles of OH– > mole of H+

0.2 - 0.1
\ [OH–] = = 0.1 mole/L Þ pOH = 1
1
Þ pH = 13
15. IE0096
Ans. (B)

1 1
´ 10 ´ 2 + ´ 40 ´ 2
0.1 + 0.1 0.5
Sol. [H + ] = 200 200 = = = 10 -2 M
(10 + 40) 50 50

\ pH = 2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

16. IE0097
Ans. (D)

1 1
Sol. (A) [H+] = ´ 100 = 1 m mole [OH–] = ´ 100 = 10m mole
100 10
Q [OH–] > [H+] Þ pH > 7

1 1
(B) [H+] = ´ 55 ´ 5.5m mole, [OH–] = 45 × ´ 4.5m mole
10 10

5.5 - 4.5 1
[H+] = = = 10 -2 Þ pH = 2
[55 - 45] 100

1 1
(C) [H+] = ´ 10 = 1m mole, [OH–] = ´ 90 = 9m mole
10 10

Q [OH–] > [H+] Þ pH > 7

1 1
(D) [H+] = 75 ´ = 15m mole, [OH–] = 25 ´ = 5m mole
5 5

(15 - 5) 10
[H+] = = = 0.1 = 10 -1 M
(75 + 25) 100

\ pH = 1

17. IE0098
Ans. (D)
Sol. pH1 = 2 Þ [H+]1 = 10–2 M
pH2 = 6 Þ [H+]2 = 10–6 M

[H + ]1 10 -2
= = 10 4
[H + ]2 10 -6

18. IE0099
Ans. (C)

Sol. KOverall = K a1 ´ K a 2

= 1 × 10–5 × 5 × 10–10 = 5 × 10–15

 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

19. IE0100
Ans. (C)
Sol. pKb –
F
= 10.4
Q pKa HF + pKb F– = 14 (Q HF and F– are conjugate acid-base pair)
\ pKa HF = 14 – 10.4 = 3.6

10 -3 10 -3 10 -3
or, Ka HF = 10 –3.6
= 10 –3–0.6
= = =
10 0.6 10 2´0.3 102´log 2

10 -3 10 -3
= = = 2.5 ´ 10 -4
10 log 4 4

20. IE0101
Ans. (C)
Sol. As T ­ Kw ­ Þ pH of pure water will be less than 7 at temperature greater than 25°C
Also pH of NaCl solution = pH of pure water Þ < 7
21. IE0102
Ans. (B)
Sol. For HCl, Normality = Molarity

0.1 ´ 1 0.1
[H+] = = = 10–3 M Þ PH = 3
(1 + 99) 100
22. IE0103
Ans. (B)
Sol. For a salt of weak acid and weak base,

h
= K h = Independent of concentration
(1 - h)
\ 'h' will remain unchanged. \ h = 0.5
% hydrolysis = h × 100 = 50%
23. IE0104
Ans. (A)
Sol. For NaCN solution, Normality = molarity.
1
C= M
80

Kh Kw 10 -14
h= = = = 4 ´ 10 -4 = 0.02
Ka ´ C 1
2 ´ 10 -9 ´
C
80

% hydrolysis = h × 100 = 0.02 × 100 = 2%

 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

24. IE0106
Ans. (B)
Sol. Ka = 1.8 × 10–5

1 K a 1.8 ´ 10 -5
Required equilibrium const. = = =
K h Kw 10 -14

= 1.8 × 109
25. IE0107
Ans. (C)

1
Sol. pH = 7 + (pK a - pK b )
2

1
= 7 + (4.8 - 4.78)
2

= 7.01
26. IE0108
Ans. (C)
Sol. (A) 0.1 M NaCl Þ pH = 7
(B) 0.1 M NH4Cl Þ pH < 4 (WB. + SA)
(C) 0.1 M CH3COONa Þ Q Salt of strong base + weak acid.
(D) 0.1 M CH3COONH4 Þ pH » 7 (Q Ka CH3COOH » Kb NH4OH)
27. IE0110
Ans. (B)
Sol. For KCN, Normality = Molarity.

1014 10 -5 10 -4
[KCN] = [CN–] = C = = =
1.6 ´ 10 -19 1.6 16

Kh 10 -4 10 -2 0.1
h= = = = = 0.025
C 1 16 4
16 ´
100

= 2.5 × 10–2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

28. IE0112
Ans. (D)
Sol. KOH + HCOOH ® HCOOK + H2O
0.2 H, 40 ml 0.1 M. 160 ml
8 m mole 16 m mole 0
0 8 m mole 8 m mole
Mixture of weak acid HCOOH and salt HCOOK
Þ Acidic buffer solution.

[HCOOK] 8
pH = pKa + log = 3.7 + log = 3.7
[HCOOH] 8

pOH = 14 – 3.7 = 10.3

29. IE0114
Ans. (C)

[A - ]
Sol. pH = pKa + log
[HA]

0.5
or, pH = 4.5 + 10 g
0.5
= 4.5
\ pOH = 14 – 4.5 = 9.5
30. IE0115
Ans. (C)
Sol. Let volume of sodium formate required = V ml.

[HCOO - ]
pH = pKa + log
[HCOOH]

(0.1 ´ v)
or, 4 = 3.7 + log
(0.05 ´ 50)

(0.1 ´ v)
or, 0.3 = log
(0.05 ´ 50)

0.1v
or, 0.3 = log
2.5

0.1v 0.1v 5
or, log2 = log Þ = 2Þv= = 50 ml
2.5 2.5 0.1
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

31. IE0116
Ans. (C)
Sol. NaCN + HCl ¾® NaCl + HCN
0.01M, 40 ml 0.1 M, 20 ml
4 m mole 2 m mole 0 0
4–2 = 2 m mole 0 2 m mole 2 m mole
(Salt of weak acid) (Weak acid)
Þ Acidic buffer solution.
32. IE0117
Ans. (B)

0.05
Sol. (NH4OH) = = 0.025M = 2.5 × 10–2 M
2

0.001
[NH4Cl] = = 0.0005 M = 5 × 10–4 M.
2
1.8 × 10–5
NH4OH (aq.) ƒ NH4+(aq.) + OH–(aq.)
2.5 × 10–2 – x 5 × 10–4 + x x

( 5 ´ 10 -4 + x ) x
1.8 × 10–5 =
(2.5 ´ 10 -2 - x)

4.5 × 10–7 – 1.8 × 10–S x = x2 + 5 × 10–4 x

x2 + 5 × 10–4 x + 1.8 × 10–5x – 4.5 × 10–7 = 0
or, x2 + 5.18 × 10–74 x – 4.5 × 10–7 = 0

–5.18 × 10 –4 + (5.18 ´ 10 -4 )2 + 18 ´ 10 -7
x=
2

Q x>0

–5.18 × 10 –4 +14.38 ´ 10 -4
or, x =
2

or, x = 4.6 × 10–4 M

\ [OH–] = x = 4.6 × 10–4 M
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

33. IE0118
Ans. (C)
Sol. NH3 = 0.6 × 600 = 360 m mole Kb = 1.8 × 10–5
NH4Cl = 0.5 × 400 = 200 m mole \ pKb = 5 – log 1.8 = 5 – 0.26 = 4.74

[NH +4 ]
pOH = pKb + log
[NH3 ]

200
or, pOH = 4.74 + log
360

or, pOH = 4.74 – log 1.8 = 4.74 – 0.26 = 4.48

\ pH = 14 – 4.48 = 9.52

34. IE0119
Ans. (D)

[NH +4 ]
Sol. pOH = pKb + log
[NH 4 OH]

1
= 4.74 + log
1

= 4.74
PH = 14 – 4.74 = 9.26

35. IE0120
Ans. (A)
Sol. CH3COOH(aq.) + NaOH (aq.) ƒ CH3COONa(aq.) + H2O(l)
0.4 0.6 Q 60% acid is neutralized

[CH3COO - ]
PH = pKa + log
[CH3COOH]

0.6 3
= 4.7 + log = 4.7 + log = 4.7 + 0.18 = 4.88
0.4 2
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

36. IE0122
Ans. (D)
Sol. Let moles of sodium propanoate required = x in 1 L Solution
C2H5COOH ƒ C2H5COO– + H+
0.02 x 2 × 10–5 PH = 4.7

[C 2 H 5COO - ] ´ [H + ]
Ka = [H+] = 2 × 10–5
[C2 H 5COOH]

x ´ 2 ´ 10 -5
or, 3 × 10–5 =
0.02
or, x = 3 × 0.01 = 3 × 10–2 mole
37. IE0123
Ans. (B)

1
Sol. POH1 = pKb + log = pKb
1

2
POH2 = pKb + log = Pb + log2
1
Þ POH2 > POH1 Þ POH increases
Þ PH decreases
38. IE0125
Ans. (A)
Sol. Following three reactions will occurs :
H3PO4 + NaOH ® NaH2PO4 + H2O
NaH2PO4 + NaOH ® Na2HPO4 + H2O
Na2HPO4 + NaOH ® Na3PO4 + H2O
Therefore buffer solution will be :
(i) H3PO4 + NaH2PO4
(i) NaH2PO4 + Na2HPO4
(i) Na2HPO4 + Na3PO4
No. of buffer solutions = 3
 JEE (MAIN + ADVANCED) : LEADER COURSE
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Topic : Ionic Equilibrium Exercise : O-I

39. IE0126
Ans. (C)
Sol. (NH4Cl + HCl) is a mixture of strong acid and its salt
Þ not a buffer solution.
Others are mixture of weak acid and its own salt with a strong base.
40. IE0127
Ans. (A)
Sol. pKa = 4 – log 2 = 3.699
HCOOH + KOH ® HCOOK + H2O
1

1 1 1
1- = Þ Acidic buffer solution
2 2 2

[HCOO - ] 1/2
PH = pKa + log = 3.699 + log = 3.699
[HCOOH] 1/2

41. IE0128
Ans. (A)

db x 0.02 0.02
Sol. BC = = = = = 0.4
d(PH) D(PH) 5.8 - 5.75 0.05

42. IE0129
Ans. (A)
Sol. CH3COOH (aq.) + NaOH(aq.) ¾® CH3COONa(aq.) + H2O(l)
0.2 M, 100 ml 0.2 M, 100 ml
= 20 m mole = 20 m mole
0 0 20 m mole (salt of WA + SB)

20 20
\ C = [CH3COO–] = = = 0.1 M
(100 + 100) 200

Kh 1 1 1
< 10 -2 , pH = 7 + (pK a + log C) = 7 + (5 + log 0.1) = 7 + (5 – 1)
C 2 2 2
Þ pH = 9
 JEE (MAIN + ADVANCED) : LEADER COURSE
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Topic : Ionic Equilibrium Exercise : O-I

43. IE0130
Ans. (B)
Sol. HNO3(aq.) + NaOH(aq.) ¾® NaNO3 (aq.) + H2O(l)
0.2 M, 100 ml 1 M, 20 ml
= 20 m mole = 20 m mole
0 0 20 m mole
(salt of strong base and strong
acid Þ neutral solution.)
\ PH = 6
Q At 90°C, neutral solution has PH = 6
44. IE0131
Ans. (D)
Sol. NaOH + HCl ® Neutral solution Þ no effect on either

1 1
M, 20 ml M, 10 ml red or blue litmus
20 10

= 1 m mole = 1 m mole Q neutral.

Colour in acidic region Colour in basic region
Litmus Red Blue
Phenol phthalein Colourless Pink
Methyl orange Pink (red) yellow
45. IE0132
Ans. (A)

[ln - ]
Sol. PH = pK l n + log
[Hl n ]

[ln - ]
\ log = pH - pK l n
[Hl n ]

[H ln - ]
or, log = pK l n - pH
[l - ]
n
 JEE (MAIN + ADVANCED) : LEADER COURSE
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Topic : Ionic Equilibrium Exercise : O-I

46. IE0133
Ans. (A)

Sol. pH range of indicator = pK l - 1 to pK l + 1

n n

=5–1 to 5 + 1
= 4 to 6
i.e. 5 ± 1
47. IE0134
Ans. (B)

Sol. pOH range of the indicator = pK l n - 1 to pK l n + 1

= 11 – 1 to 11 + 1
= 10 to 12
\ pH range = 2 to 4
=3±1
48. IE0135
Ans. (C)
Sol. At equivalence point pH > 7 (Q WA + SB)
pH range of phenolphthalein = 8.2 to 10
49. IE0137
Ans. (A)
50. IE0139
Ans. (C)
Sol. phenolphthalein is used in the titration of
(i) Strong acid + Strong base
(ii) Weak acid + Strong base
It can't be used in a Redox titration.
51. IE0141
Ans. (D)

Sol. A2 X3 (s) ƒ 2A3+ (aq.) + 3X -2 (aq.)

2y 3y
Ksp = [A ] [x ] = (2 y)2 × (3y)3
3+ 2 2– 3

= 4 × 27 × y5 = 108 y5
 JEE (MAIN + ADVANCED) : LEADER COURSE
SUBJECT : PHYSICAL CHEMISTRY
Topic : Ionic Equilibrium Exercise : O-I

52. IE0142
Ans. (D)

Sol. Ksp = [Hg2+] [SO42–] HgSO4(s) ƒ Hg2+(aq.) + SO42–(aq.)

s s

6.4 × 10–5 = s × s = s2

or, s = 64 ´ 10 -6 = 8 ´ 10 -3 mole / L

= 8 ´ 10 -3 mole / 10 -3 meter3

= 8 mole/meter3

53. IE0143

Ans. (C)

Sol. s = 1.43 × 10–4 g/100 ml, Molar molar mass of AgCl = 143 g/mol

1.43 ´ 10 -4 1000
or, s = ´ mole / L
143 100

s = 10–5 mole/L

AgCl (solid) ƒ Ag+(aq.) + Cl–(aq.)

s s

= Ksp = [Ag+] [Cl–] = s × s = s2 = (10–5)2 = 10-10

54. IE0144

Ans. (A)

Sol. M CaCO = 100g

3

7
s= mole / L CaCO3(s) ƒ Ca2+(aq.) + CO32– (aq.)
100

s s

2
Ksp = s2 = æç 7 ö÷ = 49 × 10–4
è 100 ø
= 4.9 × 10–3
 JEE (MAIN + ADVANCED) : LEADER COURSE
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Topic : Ionic Equilibrium Exercise : O-I

55. IE0145
Ans. (C)
x
Sol. A3B2(s) ƒ 3A2+(aq.) + 2B3– (aq.) Molar solutiblity 's' =
M
3s 2s
3 3– 2
Ksp = (3s) × [B ]

1 [B3- ]2
or, =
27s3 K sp

1 [B3- ]
or, =
27s3 ´ [B3- ] K sp

[B3- ] 1 1 1 1 M4
or, = = = ´ =
K sp 27s3 ´ 28 54s4 54 æ x ö4 54 ´ x 4
ç ÷
56. èMø IE0146
Ans. (B)
Sol. Ag2CrO4(s) ƒ 2Ag+(aq.) + CrO42–(aq.)
2s (0.1 + s)
» 0.1
Ksp = (2s)2 × 0.1
or, 4 × 10–13 = 4s2 × 0.1

10 -13
or 2
s = = 10 -12
0.1
or, s = 10–6 mole/L
57. IE0147
Ans. (B)
Sol. Let solubility in pure water = s1 and in KF solution is s2
K
ˆˆˆˆ
In pure water, CaF2(solid) ‡ˆˆˆ
sp
† 2+ -
ˆ Ca (aq.) + 2F (aq.)
s1 2s1
2
Ksp = s1 × (2s1) or 3.2 × 10 –11
= 4 × s1 Þ 8 × 10–12 = s13
3

Þ s1 = 2 × 10–4 mole/L

In 4 × 10–3 M KF solution
CaF2(s) ƒ Ca2+(aq.) + 2F–(aq.)
s2 (4 × 10–3 + 2s2) » 4 × 10–3
Ksp = s2 × (4 × 10–3)2

s1 2 ´ 10 -4
or, 3.2 × 10 –11
= s2 × 16 × 10 Þ s2 = 2 × 10 mole/L \
–6 –6 = = 100
s2 2 ´ 10 -6
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58. IE0148
Ans. (D)

Sol. 0.05 M Na2CO3 Þ Common ion CO23 - , so solubility decreases.

0.05 M AgNO3 Þ Common in Ag+, so solubility decreases.

In NH3(aq.) solution, Ag+ form complex [Ag(NH3 )2]+. So solubility will be maximum in NH3(aq.)
59. IE0149
Ans. (B)

K sp 10 -14
Sol. pH = 9 Þ [H+] = 10–9 Þ [OH–] = = = 10 -5 mole / L
+ -9
[H ] 10

[Mg2+] = 0.001 M = 10–3 M

Mg(OH)2 (solid) ƒ Mg2(aq.) + 2OH–(aq.)
ionic product = [Mg3+] [OH–]2 = 10–3 × (10–5)2 = 10–13 < KspMg(OH)2
Þ no ppt.
60. IE0150
Ans. (B)
Sol. Let x mole Na3PO4 can be added in 10 L – BaCl2 solution without any precipitation.

x
\ [Na3PO4] = [PO43–] = M, [Ba2+] = 10–5 M, M Na 3PO 4 = 164
10

Ba3(PO4)2 (solid) ƒ 3Ba2+(aq.) + 2PO34- (aq.)

Ksp = [Ba2+]3 [PO43–]2

2
æ xö
or, 4×10–23 = (10–5)3 × ç ÷
è 10 ø

4 ´ 10 -23
or, x2 = = 4 ´ 10 -6
-17
10

\ x = 2 × 10–3 mole
= 2 × 10–3 × 164 = 0.328 gram
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1. IE0151
Ans. (A)
Sol. pH = 5 Þ (H+) = 10–5M ; VL
pH = 3 Þ (H+) = 10–3M ; VL

10 -5 V + 10 -3 V
finally [H+] =
V+V

10 -5 + 10 -3 10 -3
= ; M
2 2
pH = 3 + log 2 = 3.3
2. IE0152
Ans. (C)
Sol. pH = 2 Þ (H+) = 10–2M ; M1
pH = 3 Þ (H+) = 10–3M ; M2

Moles of HCl removed = n H + (initial) - n H + (final)

(moles) (moles)

= 10–2 × 1 – 10–3 × 1
= 9 × 10–3 = 0.009
3. IE0153
Ans. (D)

Sol. (A) Ksp = S2 Þ S = 8 ´ 10 -37

(B) Ksp = S2 Þ S = 7 ´ 10 -16

1/5
æ K sp ö
(C) Ksp =108 S Þ S = ç
5
÷
è 108 ø

1/4
æ K sp ö
(D) Ksp = 27 S Þ ç
5
÷ Þ Maximum
è 27 ø

4. IE0154
Ans. (B)
Sol. [Common ion] ­ Þ Solubility ¯
Max. concentration of common ion, (Br–) = 0.2 M in 0.1 M CaBr2
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5. IE0155
Ans. (C)
Sol. Na2CO3 + HCl ¾® NaHCO3 + NaCl

a
a – –
4

3a æaö
x ç ÷
4 è4ø

n
Buffer sol

æ aö
æSö ç3 ÷
pH = pKa + log ç ÷ = 11 + log ç 4 ÷
èaø çç a ÷÷
è 4 ø

pH = 11 + log 3
6. IE0156
Ans. (A)

Sol. [HIn] [ In – ] pH
80 20 æ 20 ö
pK I n + log ç ÷
è 80 ø
20 80 æ 80 ö
pK I n + log ç ÷
è 20 ø

DpH = 2log 4 = 4 log 2 = 4 × 0.3 = 1.2

7. IE0157
Ans. (A)
Sol. [OH–] = 10–7 + 10–7 = 2 × 10–7 Þ pOH = 7 – log 2
pH = 7 + log 2
= 7.3
But due to common ion effect for H2O Þ [OH–] < 2 × 10–7; Hence pH < 7.3
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8. IE0222
Ans. (B)

Sol. Phenolphthalein can be used as indicator when strong base is involved. (like here NaOH) at equivalence
point salt of W.A. & S.B. will be formed, So solution will be basic. But is not the correct explanation
because it can be used when pH change of indicator lies in pH range of titration.

9. IE0159

Ans. (A,B,C)

Sol. (A) [OH–] = K b .C = 10 -5 ´ 0.1 = 10–3 M

&

(B) pOH = 3 ; pH = 14 – 3 = 11

(C) Salt of S.A. & W.B. is acidic solution.

(D) for phenolphthalein indicator can be used when strong base is present.

10. IE0160

Ans. (A,B,C,D)

Kw 10 -14
Sol. (A) Keq. = Kh = = = 5 × 10–9
K a 2 ´ 10 -6

(B) HA + NaOH ƒ NaCl + H2O ;

1 K 2 ´10 -6
Keq. = = a = = 2 × 108
K h Kw 10 -14

(C) [H+] = K a .C = 2 ´ 10 -6 ´ 0.1 = 20 ´ 10 -4

1
pH = 4 – log 20 = 3.35
2

(D) A - + H 2 O ƒ HA + OH - (Basic)
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11. IE0161
Ans. (D)

Sol. H3PO4 ƒ H+ + H2PO4– ; K a1

C–x (x + y + z) ; x (x – y) ; x

H2 PO 4- ƒ H+ + HPO 24- ; K a 2

(x – y) ; x (x + y + z) ; x (y –z) ; y

HPO 24- ƒ H+ + PO34- ; K a 3

(y – z) ; y (x + y + z) ; x z

(as K a >> K a >> K a Þ x >> y >> z)

1 2 3

(A) [H+] = [H2PO4–] = x

x2
(B) K a1 = Þ x = [H + ] = K1[H3 PO4 ]
[H3 PO4 ]

x.y
(C) K2 = = y = [HPO24- ]
x
(D) [PO43–] = Z
12. IE0162
Ans. (A)
Sol. (A) No effect of dilution on pH of buffer

æSö
(B), (C) & (D) :- pOH = pKb + log ç ÷
èbø

(S) = [NH4Cl] ­ Þ pOH ­ Þ pH ¯

(b) = [NH4OH] ­ Þ pOH ¯ Þ pH ­
13. IE0163
Ans. (A)
Sol. When equal volumes are mixed concentration of each ion will be half of initial
for precipitation of AgCl,
Qsp = [Ag+] [Cl–] > Ksp = 1.8 × 10–10

16 -4 10 -4
(A) Qsp = ´ = 2.5 ´ 10 -9 > K sp [Qsp = Ionic product]
2 2
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14. IE0164
Ans. (B)

8 ´ 1000
Sol. C= = 1M
80 ´ 100

Ka
as < 10 -3 Þ [H+] = K a .C = 10 -2 M
C
Þ pH = 2
15. IE0165
Ans. (B)
Sol. HX + NaOH ¾® NaX + H2O
0.1 moles 0.1 = M2V2 -
x x 0.1 moles at equivalence point

0.1 1
(Salt of W.A. & S.B.) C = 100 = = 0.2 M
5
+ 0.4
1000

1 1
pH = 7 + pK a + log C = 8.65
2 2
16. IE0166
Ans. (B)
Sol. Mixing of S.A. (HCl) & W.A. (HX)

10 -3
[HCl] = = 10 -2 M
æ 100 ö
ç ÷
è 1000 ø

H × (aq.) ƒ H+(aq.) + X–(aq.) ; Ka = 10–4

1M 10 –2 –
(1 – x) ; 1 –2
(10 + x) x

(10 -2 + x)x
Ka = 10–4 =
1
10–4 = 10–2 x + x2
x2 + 10–2x – 10–4 = 0
x = 0.62 × 10–2
[H+] = 10–2 + x = 1.62 × 10–2 M
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17. IE0167
Ans. A-(R) ; B-(P) ; C-(Q) ; D-(S)
Sol. (A) CH3COOH + NaOH ¾® CH3COONa + H2O

100 25 –

75 x 25

æSö æ 25 ö
pH = pKa + log ç ÷ = pKa + log ç ÷
èaø è 75 ø

= pKa – log 3

(B) CH3COOH + NaOH ® CH3COONa + H2O

100 50 –

50 x 50

æ 50 ö
pH = pKa + log ç ÷ = pKa
è 50 ø

(C) CH3COOH + NaOH ® CH3COONa + H2O

100 75 –

25 x 75

æ 75 ö
pH = pKa + log ç ÷ = pK a + log3
è 25 ø

(D) CH3COOH + NaOH ® CH3COONa + H2O

100 100 –

x x 100

100 1
C= = M
200 2

1 1
pH = 7 + pK a + log C
2 2

1
= [pK w + pK a - log2]
2
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18. IE0168
Ans. (D)
Sol. (A) CH3COOH + NaOH ® CH3COONa + H2O

0.2 0.1
= 0.1M M –
2 2

0.1 0.1
M x M
2 2

æSö
pH = pKa + log ç ÷ = pKa = 5
èaø

(B) CH3COOH ƒ CH3COO– + H+ ; Ka

0.1 0.1
M M from HCl
2 2

æ 0.1 ö æ 0.1 ö 0.1

ç - x÷ x ç - x÷ ; M
è 2 ø è 2 ø 2

Ka
(x is negligible as £10 -3 )
C

0.1
[H+] = M Þ pH = 1 + log 2 = 1.3
2
(C) CH3COOH + NH4OH ¾® CH3COONH4 + N2O

0.1 0.1 0.1

M M M
2 2 2
x x

1 1
pH = 7 + pK a - pK b = 7
2 2
(Salt hydrolysis)
(D) NH4Cl + NaOH ¾® NH4OH + NaCl
20 10 – –
10 x 10
pOH = pKb = 5 Þ pH = 9
as [NH4OH] = [NH4Cl] Þ Buffer capacity is maximum
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19. IE0169
Ans. (B)
Sol. First strong acid will react with NaOH
HCl + NaOH ¾® NaCl + H2O
moles 0.1 0.15 -
x 0.05 0.1
CH3COOH + NaOH ¾® CH3COONa + H2O
0.1 0.05 -
0.05 x 0.05

æSö
pH = pKa + log ç ÷ = pKa = 5
èaø

20. IE0170
Ans. (C)
Sol. HCl + NaOH ¾® NaCl + H2O
moles 0.1 0.1 -
x x 0.1

0.2
only CH3COOH remain in solution with C = = 0.1 M
2

[H+] = K a .C = 10 -3 M

pH = 3
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1. IE0182
Ans. (2)

1 1
Sol. pH = 7 + pK a - pK b = 6.9
2 2

2. IE0183
Ans. (3)

Sol. pH = pKa + log æç S ö÷

èaø

6 = 5 + log æç S ö÷ Þ log æç S ö÷ = 1
èaø èaø

æ S ö = 10
ç ÷
èaø

3. IE0184
Ans. (3)
Sol. NH3 + HCl ® NH4Cl
10 5 -
5 x 5

Buffer soln

æSö
pOH = pKb + log æç S ö÷ = 4.75 + log ç ÷ = 4.7
èaø èSø

pH = 14 – 4.75 = 9.25
4. IE0185
Ans. (1)
Sol. CH3COOK is most basic because it is salt of strong base with weak acid.
5. IE0186
Ans. (2)
Sol. Methyl orange is yellow in basic medium while pinkish red in acidic medium.
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6. IE0187
Ans. (1)
Sol. H2S(aq.) ƒ 2H+(aq.) + S2–(aq.) ; Keq = K1 × K2

[H + ]2 [S2- ]
K1 × K2 =
[H 2 S]

(0.2)2 (S2- )
1 × 10–7 × 1.2 × 10–13 =
0.1
[S2–] = 3 × 10–20M
7. IE0188
Ans. (2)
Sol. Let initial concentration of Ba+2 is C1 & volume = 500 – 50 = 450 ml
when precipitate just begins to form
Ksp = 1 × 10–10 = [Ba+2] [SO42–)
é C1 ´ 450 ù é 1 ´ 50 ù
1 × 10–10 = ê
ë 500 ûú ëê 500 ûú
C1 = 1.1 × 10–9 M
8. IE0189
Ans. (1)

1 1
´ 75 – ´ 25
Sol. (i) [H+] = 5 5 = 10 -1 Þ pH = 1
100
(ii) [H+] = [OH–] Þ pH = 7

1 1
´ 55 – ´ 45
(iii) [H+] = 10 10 = 10 -2 Þ pH = 2
100
9. IE0190
Ans. (2)
1/3 1/3
æK ö æ 3.2 ´ 10 -8 ö
Sol. Ksp = 4s Þ
3
S = ç sp ÷ =ç ÷
è 4 ø è 4 ø
S = 2 × 10–3 mol/L

æ 0.1 ö
ç ÷
2 × 10–3 =
Molesof PbCl 2 = è 278 ø
V(L) V

V = 0.18 L
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10. IE0240
Ans. (2)
Sol. Ag2CO3(s) ƒ 2Ag+(aq.) + CO32–(aq.); Ksp
'x' (2x + 0.1) x
; 0.1
Ksp = 8 × 10–12 = (0.1)2 (x)
x = 8 × 10–10 M
11. IE0241
Ans. (1)
Sol. Number of gm-equivalent of HCl º Na2CO3
M × 25 × 1 = 30 × 0.1 × 2

6
M=
25
gm equi. of HCl º NaOH

6
´ V = 30 ´ 0.2
25
V = 25 ml
12. IE0244
Ans. (3)
Sol. H2SO4 + 2NH4OH ® (NH4)2SO4 + 2H2O
20 × 0.1 = 2 30×0.2 = 6 –
(L.R.)
x 2 2

NH4+ = 2 × (NH4)2SO4
Buffer soln

æSö æ 2´2 ö
pOH = pKb + log ç ÷ = 4.7 + log ç ÷=5
èbø è 2 ø

pH = 14 – pOH = 14 –5 = 9
13. IE0245
Ans. (4)
Sol. Ksp = (3)3 (4)4 S7 = 6912 S7
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14. IE0246

Ans. (1)

Sol. When HCl is added to NaOH, first pH decrease slowly but near the equivalence point sudden change
(decrease) is observed.

15. IE0248

Ans. (4)

Sol. Ksp = 4s3 = 4 × (1.84 × 10–5)3

Cd (OH)2(s) ƒ Cd+2 (aq.) + 20 H– (aq.) ; Ksp

'x' 'x' (2x + 10–2)

= 10–2 (buffer)

Ksp = 4 × (1.84 × 10–3)3 = x (10–2)2

x = 2.49 × 10–10 M

16. IE0249

Ans. (10.60)

9.8
Sol. H2SO4 in 10 L = 98 ´ 10 = 10 -2 moles
100

4
NaOH in 40 L = 40 ´ 40 = 4 × 10–2 moles
100

In resultant solution after reaction

4 ´ 10 -2 - 10 -2 ´ 2 9 ´ 10 -2
[OH–] = = = 4 ´ 10 -4
50 50

pOH = 4 – log 4 Þ pH = 14 – pOH

= 10 + log 4 = 10.6
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17. IE0250
Ans. (5.22 to 5.24)
Sol. millimoles of HCl = 0.1 × 250 = 25 (in 500 ml)

3
millimoles of CH3COOH = ´ 1000 = 50 (in 500 ml)
60

In 20 ml of solution

25
HCl = ´ 20 = 1 millimoles
500

50
CH3COOH = ´ 20 = 2 millimoles
500

1
NaOH added = 5 × = 2.5 millimoles
2

HCl & NaOH react first, after this reaction

CH3COOH + NaOH(left) ¾® CH3COONa + H2O
2 1.5 –
0.5 x 1.5

æSö
Buffer solution Þ pH = pKa + log ç ÷ = 4.75 + log æç 1.5 ö÷ = 5.227
èaø è 0.5 ø

18. IE0252
Ans. (2)
Sol. H2O ƒ H+ + OH–; DH = +ve (endothermic)
T ­ Þ (H+) ­ Þ pH ¯

19. IE0253
Ans. (2)
Sol. Qsp = (Pb+2) [Cl–]2

2
æ 300 öæ 100 ö -3
= ç 0.134 ´ ÷ç 0.4 ´ ÷ = 10
è 400 øè 400 ø

Qsp > Ksp = (1.6 × 10–5)

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20. IE0273
Ans. (4)
Sol. Ag+ concentration needed to precipitate Cl –

Ksp (AgCl) 1.7 ´ 10 -10

+
[Ag ]1 = = = 1.7 ´ 10 -9 M
[Cl- ] 0.1

Ag+ concentration needed to precipitate CrO42–

K sp (Ag 2 CrO4 ) 1.9 ´ 10 -12

[Ag + ]2 = =
(CrO24- ) 10 -3

= 19 × 10–5 M
[Ag+]1 < [Ag+]2 Þ AgCl will ppt. first.
21. IE0274
Ans. (3)
Sol. Ksp = 4 S3

1/3 1/3
æK ö æ 5.5 ´ 10 -6 ö
S = ç sp ÷ =ç ÷
è 4 ø è 4 ø
= 1.11 × 10–2 M
22. IE0275
Ans. (2)

Ksp x2
Sol. =
Ka [H + ]

K sp 2.2 ´ 10 -16
x= ´ [H + ] = ´ 10 -3
-10
Ka 6.2 ´ 10
= 1.9 × 10–5
23. IE0276
Ans. (1)
Sol. [OH–] = 2 × M = 2 × 5 × 10–3 = 10–2 M

10 -14 10 -14
[H3O+] = [H+] = –
= -2
= 10 -12
[OH ] 10
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24. IE0277
Ans. (1)
Sol. H2SO3(aq.) ƒ H+ + HSO3– ; K a1
C–x x x

x2 x2
K a1 = Þ 1.7 ´ 10 -2 =
C-x 0.588 - x
x2 + 1.7 × 10–2 x – 10–2 = 0
x = [H+] = 9.185 × 10–2
pH = 2 – log(9.185) = 1.037 ; 1
25. IE0278
Ans. (50)

1/3
æ K ap ö
Sol. A2X ; Ksp = 4s Þ S = ç 3
÷
è 4 ø

1/3
æ 4 ´ 10 -12 ö
S(A 2x) =ç ÷ = 10 -4 M
è 4 ø

MX ; Ksp = s2 × s = K sp

4 ´ 10 -12 = 2 × 10 M
–6
S(MX) =

SA2 X 10 -4
= = 50
SMX 2 ´ 10 -6
26. IE0280
Ans. (141)
Sol. Pb(NO3)2(aq.) ¾® Pb+2(aq.) + 2NO3–(aq.)
0 0.1M 0.2 M
PbI2(s) ƒ Pb (aq.) + 2I (aq.)
+2 –

(x) (x + 0.1) 2x
; 0.1
Ksp = [Pb+2] [I–]2
8 × 10–9 = 0.1 × (2x)2

x= 2 ´ 10 -8 = 1.41 ´ 10 -4
= 141 × 10–6 M
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27. IE0282
Ans. (6021)
Sol. HCl + NaOH ® NaCl + H2O
Millimoles 50 30 -
20 x 30

20
[H+]finally = = 2.5 × 10–1
(50 + 30)

pH = 1 – log (2.5) = 0.6021

= 6021 × 10–4
28. IE0283
Ans. (108)
Sol. Ksp = 33 · 22 · s5 = 108 s5

æ xö
çS = ÷
è Mø

5
æ x ö
K sp = 108 ç ÷
èMø

Þ a = 108
29.
Ans. (A)
Sol. Titration curve of NH4OH vs HCl (WB + SA).
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30.
Ans. (B)

éSalt ùû
Sol. pH = pK a + log ë
ëéAcid ûù

éCH3CH2COO- ùû
4 = 5 - log1.3 + log ë
ëéCH3CH2COOHûù

éCH3CH2COO- ùû 1.3
log ë = log1.3 - 1 = log
ëéCH3CH2COOHûù 10

éëCH3CH2COO- ùû
= 0.13
ëéCH3CH2COOHûù
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1. IE0262
Ans. (C)
Sol. Qsp = [M+2] [S2–] = 10–3 × 10–16 = 10–19
for ppt. Qsp > Ksp
for HgS Þ Qsp >>> Ksp(least value)
or

K sp K sp
[S2–] required for precipitate = =
[M +2 ] 10 –3

[S2–] for ppt. µ Ksp

for HgS is least, so it will require least (S2–) for ppt. It will ppt. first.
2. IE0264
Ans. (Ph = 9)
Sol. pH = 9
HA + NaOH ® NaA + H2O

0.1 0.1
Initially: M M
2 2

0.1 0.1
At end-point: -x -x x
2 2
Note: At end point equal volume of reagents is added so concentration becomes 1/2 of initial

10 -14 x2 x2
kh = = ;
- x æç
Ka 0.1 0.1 ö
÷
2 è 2 ø
10 -14 0.1
–
x = [OH ] = ´ = 10 -5 M
5 ´ 10 -6 2

pOH = 5 Þ pH = 14 – 5 = 9
3. IE0265
Ans. (A)

Kh 10 -14
Sol. h= = = 10 -4
-
c 10 ´ 0.1
5

% h = 10–4 × 100 = 0.01%

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4. IE0266
Ans. (B)
Sol. CH3NH2 + HCl ¾® CH3NH3+Cl–
0.1 0.08 –
0.02 x 0.08 (Buffer is formed)

[CH3 NH3+ ][OH - ] 5 ´ 10 -4 ´ 0.02

Kb = Þ [OH - ] =
[CH3 NH 2 ] 0.08

Þ [H+] = 10–14/[OH–] = 8 × 10–11

5. IE0267
Ans. (D)
Sol. Ag+ + 2NH3 ƒ Ag(NH3)2+ ; Kf = formation const.
Kf = K1 × K2 = 1.088 × 107
6. IE0268
Ans. (A)
Sol. CO2 + H2O ƒ H2CO3
H2CO3 ƒ H+ + HCO3–
HCO3– ƒ H+ + CO32–
CO2, H2CO3, HCO3–, H+, & CO32– are present in solution.
7. IE0269
Ans. (D)
Sol. BOH + HCl ¾® BCl + H2O

2 2
millimoles ´ 2.5 = 1 1 = ´ V2 - - (at equivalence pt. equal moles will be used)
5 15
x x 1 (Salt of S.A. & W.B)

1 1
C= = = 0.1M
(2.5 + 7.5) 10

10 -14 x2 K
Kh = = (here x is not negligilble as h > 10 -3 )
10 -12 0.1 - x C

on solving the quadratic equation

x = [H+] = 2.7 × 10–2 M
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8. IE0270

Ans. (D)

Sol. MX :- Ksp = S12 Þ S1 = K sp = 2 × 10–4 M

1/3
æK ö
MX2 :- Ksp = 4S2 Þ S2 = ç sp ÷
3
= 2 × 10–5 M
è 4 ø

1/4
æ K sp ö
M3X :- Ksp = 27S3 Þ S3 = ç
4
÷ = 10–4 M
è 27 ø

Þ S1 > S3 > S2

9. IE0271

Ans. (8)

Sol. C6 H 4- R COONa Þ Salt of S.B. & W.A.

10 -14 x2 10 -14 x2
Kh = = Þ =
Ka C 10 -4 0.01

x = [OH–] = 10–6 M

pOH = 6 ; pH = 8

10. IE0272

Ans. (C,D)

Sol. (C) HNO3 + CH3COONa ¾® CH3COOH + NaNO3

identical concentrations may have different volumes so different moles.

(D) Example of acidic buffer

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11. IE0196
Ans. (7)

Sol. AgCl(s) ƒ Ag+(aq.) + Cl–(aq.) ; K sp

1

'x' x (x + y)

CuCl(s) ƒ Cu+(aq.) + Cl–(aq.) ; K sp

2

'y' y (x + y)

K sp = x(x + y) ...(1)
1

K sp = y(x + y) ...(2)
2

(1) + (2) Þ (x + y) = K sp1 + Ksp2 = 1.6 ´ 10 -10 + 10 -6

= 10 -6 = 10 -3 M

from eqn. (1)

K sp1 1.6 ´ 10 -10

Þ [Ag ] = x =
+
=
(x + y) 10 -3

= 1.6 × 10–7 M
12. IE0197
Ans. (A)
Sol. r = K[H+] [ester]
Þ r a [H+]

rW.A.(HA) [H + ]HA 1
= +
= (given)
rS.A.(HX) [H ]HX 100

[H + ]HA 1
= Þ [H + ]HA = x = 10 -2
1 100

x2 (10 -2 )2
Ka = = = 10 -4
C - x 1 - 10 -2
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13. IE0198
Ans. (B)

Sol. Ag 2 CrO4 (s) ƒ 2Ag + (aq.) + CrO 42- (aq.);K sp

'x' (2x + 0.1) x

; 0.1 (from AgNO3 )
Ksp = [Ag+]2[CrO42– ]
1.1 × 10–12 = (0.1)2 (x)
x = 1.1 × 10–10 M

14. IE0199
Ans. (A)
Sol. |DH| × gm equivalent neutralised = (CCalorimeter + Csoln.) DT
Expt.-1

1 ´ 100
57 × = [Ccalorimeter + 200 ´ 1 ´ 4.2] ´ 5.7 ...(1)
1000

Expt.-2

1 ´ 100
|DH| × = [Ccalorimeter + 200 ´ 1 ´ 4.2] ´ 5.6 ...(2)
1000

(2) | DH | 5.6
eqn. Þ = Þ| DH |= 56 kJ/mol
(1) 57 5.7

DHdissociation = 57 – |DH| = 57 – 56 = 1 kJ/mol

15. IE0200
Ans. (B)
Sol. CH3COOH + NaOH ¾® CH3COONa + H2O
millimoles 200 100 -
100 x 100 (buffer solution is formed)

pH = pKa + log æç S ö÷ = 5 - log 2 + log æç 100 ö÷ = 4.7

èaø è 100 ø
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16. IE0201
Ans. (4.47)
Sol. AB(s) ƒ A+(aq.) + B–(aq.) ; Ksp = 2 × 10–10
'x' x x

1
H+(aq.) + B–(aq.) ƒ HB(aq.) ; = 108 (large value)
Ka

C x –
C–x - x
_____________________________________

K sp
AB(s) + H+(aq.) ƒ A+(aq.) + HB(aq.) ;
Ka

(C–x) = 10–3 x x

K sp x2
=
Ka 10 -3

K sp 2 ´ 10 -10
x= ´ 10 -3 = ´ 10 -3
Ka -8
10

= 4.47 × 10–3 M
17. IE0284
Ans. (8.92 or 8.93)
Sol. Fe+2(aq.) + S2–(aq.) ƒ FeS(s) ; Kc = 1.6 × 1017

0.06 0.2
at t = 0 = 0.03M = 0.1 M -
2 2
at eqbm. x 0.1 – 0.03 -
= 0.07

1
KC =
[Fe ][S2 - ]
+2

1 1
[Fe +2] = =
2-
K c ´ [S ] 1.6 ´ 10 ´ 0.07
17

= 8.928 × 10–17 M
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18. IE0285
Ans. (0.11)
Sol. Vol. of NaOH used = 9.0 ml
gm equivalent of NaOH º H2C2O4
M × 9 × 1 = 0.1 × 5 × 2

1
M= = 0.11
9
19. IE0286
Ans. (0.20)
Sol. Ksp = [Zn+2] [S2–]
1.25 × 10–22 = 0.05 × [S2–]

1
[S2–] = ´ 10 -20
4
H2S(aq.) ƒ 2H+ (aq.) + S2–(aq.); K1 × K2

[H + ]2 [S2- ]
K1 × K2 =
[H 2 S]

é1 ù
[H + ]2 ê ´ 10 -20 ú
ë4 û
10–21 =
(0.1)

[H+] = 0.2 M
20.
Ans. (10.02)
Sol. H2CO3 + NaOH ¾¾
® NaHCO3 + H2O
Milli moles 10 10 -
At end 0 0 10 + 10 = 20
Final mixture has 20 milli moles NaHCO3 and 10 milli moles Na2CO3
Salt
pH = pKa 2 + log
Acid

æ 10 ö
pH = pKa 2 + log ç ÷ [Buffer : Na2CO3 + NaHCO3]
è 20 ø
= 10.32 – log 2 = 10.02
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21.
Ans. (6)

Sol. H2SO4 ˆˆ†

‡ˆˆ HSO4- + H +

1M – –
1M 1M
Na2SO4 ¾¾
® 2Na+ + SO24-
1.8 × 10–2 M – –
3.6×10–2 M 1.8 × 10–2 M

HSO4- ˆˆ†
‡ˆˆ H+ + SO42– ; Ka2 = 1.2 × 10–2 M

1M 1M 1.8 × 10–2 M
Since QC > KC it will move in backward direction.
1+x 1–x 1.8 × 10–2 – x

(1 - x ) (1.8 ´ 10-2 - x )
Ka2 = 1.2 × 10-2 =
(1 + x )
Since x is very small (1 + x) ; 1 and (1 – x) ; 1

(
x = 1.8 ´ 10-2 - 1.2 ´ 10-2 M )
(
éëSO24- ùû = 1.8 ´ 10-2 - 0.6 ´ 10-2 M )
= 1.2 × 10–2 M
PbSO4 ¾¾
® Pb2+ + SO24-
s – 1.2×10–2 M
– s (s + 1.2 × 10–2)
Ksp = s (s + 1.2 × 10–2) = 1.6 × 10–8
(PbSO4)
Here, (s + 1.2 × 10–2) ; 1.2 × 10–2 (since 's' is very small)
s(1.2 × 10–2) = 1.6 × 10–8
1.6
==> s = ´ 10-6 M = X ´ 10- Y M
1.2
==> Y = 6