(Physical Chemistry) IONIC EQUILIBRIUM

EXERCISE # (O-I)
Dissociation of Water & pH of Water
1. Ionic product of water will increase, if:

(A) Pressure is decreased (B) H+ is added

(C) OH– is increased (D) Temperature is increased

2. At 60°C, pure water has [H3O+]=10–6.7mol/lit. what is the value of KW at 60°C:

(A) 10–6 (B) 10–12 (C) 10–67 (D) 10–13.4

3. The pH of solution is increased from 3 to 6. Its H+ ion conc. will be:

(A) Reduced to half (B) Doubled
(C) Reduced by 1000 times (D) Increased by 1000 times

4. A solution with pH 2.0 is more acidic than the one with pH 6.0 by a factor of:
(A) 3 (B) 4 (C) 3000 (D) 10000

pH of Strong Electrolyte

5. What is the quantity of NaOH present in 250 cc of the solution, so that it gives a pH= 13:

(A) 10–13 g (B) 10–1 g (C) 1.0 g (D) 4.0 g

6. An aqueous solution of HCl is 10–9 M HCl. The pH of the solution should be:
(A) 9 (B) Between 6 and 7
(C) 7 (D) Unpredictable

7. How many moles of HCl must be removed from 1 litre of aqueous HCl solution to change its pH
from 2 to 3:
(A) 1 (B) 0.02 (C) 0.009 (D) 0.01

M M
8. 10 ml of H2SO4 is mixed with 40 ml of H SO . The pH of the resulting solution is
200 200 2 4

(A) 1 (B) 2 (C) 2.3 (D) none of these

APNI KAKSHA 1
(Physical Chemistry) IONIC EQUILIBRIUM
𝐩𝐇 of Weak Electrolyte
9. For two monobasic acids A and B, pKa1= 1.2, pKa2 = 2.8 respectively in value, then which is

true:
(A) A & B both have equal acidic strength
(B) A is stronger than B
(C) B is stronger than A
(D) Depends on concentration

10. When ammonia is added to water it decreases the concentration of which of the following ion

(A) OH– (B) H3O+ (C) NH+4 (D) NH4+ & OH–

11. Which one of the following has highest pH:

(A) Distilled water (B) 1 M NH3

(C) 1 M NaOH (D) 1M HCl

12. Degree of dissociation of 0.1 N CH3COOH is: (Dissociation constant = 1×10–5)

(A) 10–5 (B) 10–4 (C) 10–3 (D) 10–2

13. The pH of a 0.02 M ammonia solution which is 5% ionised will be:

(A) 2 (B) 11 (C) 5 (D) 7

𝐩𝐇 of Mixture of More Than One Acid/Base

14. Consider an aqueous solution, 0.1 M each in HOCN, HCOOH, (COOH)2 and H3PO4. For HOCN,

[H + ][OCN − ]
we can write: Ka(HOCN) = . [H+] in this equation is:
[HOCN]

(A) H+ ions released by HOCN

(B) Sum of H+ ions released by all monoprotic acids

(C) Sum of H+ ions released only the first dissociation of all the acids.

(D) Overall H+ ion concentration in the solution.

APNI KAKSHA 2
(Physical Chemistry) IONIC EQUILIBRIUM
15. The pH of the solution produced when an aqueous solution of strong acid pH 5 is mixed with
equal volume of an aqueous solution of strong acid of pH 3 is:
(A) 3.3 (B) 3.5 (C) 4.5 (D) 4.0

16. What are [H+], [A–] and [B–] in a solution that contains 0.03 M HA and 0.1 M HB. Ka for HA and

HB are 3.0×10–4 and 1.0×10–10 respectively.

(A) [H+] = 3×10–3 M (B) [A¯] = 3×10–3 M

(C) [B¯] = 3.33×10–9 M (D) All of these

17. pH of a solution obtained by mixing equal volumes of 0.1 M Triethyl amine (Kb = 6.4×10–5) &

4
M NH4OH (Kb = 1.8×10–5) will be:
45
(A) 11.3 (B) 10.3 (C) 12.3 (D) 11.45

18. An aqueous solution contains 0.01 M RNH2 (Kb = 2 ×10–6) & 10–4 M NaOH. The concentration

of OH¯ is nearly:

(A) 2.414 ×10–4 (B) 10–4 M (C) 1.414×10–4 (D) 2×10–4

Polyprotic Acid Base

–7 –
19. Approximate pH of 0.10 M aqueous H2S solution having K1 and K2 for H2S at 25ºC 10 and 10
13
respectively is :
(A) 4 (B) 5 (C) 9 (D) 8

20. In a solution containing 0.1 M HCl & 0.1 M H3PO4 (having dissociation constants

K a1 , K a 2 & K a 3 ), assuming << 1 for H3PO4:

(A) pH = 1 (B)  H3PO 4 = 10 K a1

(C) [ HPO 2–
4 ] = 10 (D) All of these

APNI KAKSHA 3
(Physical Chemistry) IONIC EQUILIBRIUM
21. In a solution containing 0.1 M HCl & 0.1 M H3PO4 (having dissociation constants

K a1 , K a 2 & K a 3 ), assuming << 1 for H3PO4:

(A) [PO 3–
4 ] = 100 K a1 K a 2 K a 3 (B) [PO 3–
4 ] = 10 K a1 K a 2 K a 3

(C) [PO 3–
4 ] = 1000 K a1 K a 2 K a 3 (D) [PO 3–
4 ] = K a1 K a 2 K a 3

Conjugate Acid Base, Bronsted Theory

22. The conjugate acid of NH2– is

(A) NH3 (B) NH2OH (C) NH +4 (D) N2H4

23. Which of the following is not a Bronsted acid:

(A) CH3 NH+4 (B) CH3COO– (C) H2O (D) HSO4–

24. In the reaction, HNO3 + H2O H3O+ + NO3− , the conjugate base of HNO3 is:

(A) H2O (B) H3O+

(D) H3O+ and NO3−

–3
(C) NO

25. If equilibrium constant of

CH3COOH + H2O CH3COO– + H3O+

–5
Is 1.8×10 , equilibrium constant for

CH3COOH + OH– CH3COO– + H2O is

–9 9
(A) 1.8 ×10 (B) 1.8×10
–9 10
(C) 5.55×10 (D) 5.55×10

26. If pKb for fluoride ion at 25° C is 10.83, the ionisation constant of hydrofluoric acid in water at

this temperature is:

–5 –3 –4 –2
(A) 1.74×10 (B) 3.52×10 (C) 6.75×10 (D) 5.38×10

APNI KAKSHA 4
(Physical Chemistry) IONIC EQUILIBRIUM
27. A certain weak acid has Ka = 1 × 10–4. Calculate the equilibrium constant for its reaction with
strong base -
(A) 106 (B) 108 (C) 1010 (D) 10–10

Salt Hydrolysis

28. pH of an aqueous solution of NaCl at 85°C should be

(A) 7 (B) > 7 (C) < 7 (D) 0

29. 1 cc of 0.1 N HCl is added to 99 cc solution of NaCl. The pH of the resulting solution will be
(A) 7 (B) 3 (C) 4 (D) 1

30. The highest pH value is of:

(A) 0.1 M NaCl (B) 0.1 M NH4Cl

(C) 0.1 M CH3COONa (D) 0.1 M HCl

31. What is the percentage hydrolysis of NaCN in N/80 solution when the dissociation constant for
–9 –14
HCN is 1.3×10 and Kw = 1.0×10

(A) 2.48 (B) 5.26 (C) 8.2 (D) 9.6


32. Degree of Hydrolysis of solution of KCN is (Given Ka = 1.4×10–9)
100
–3 –2 –4 –5
(A) 2.7×10 (B) 2.7×10 (C) 2.7×10 (D) 2.7×10

Salt Hydrolysis of Multivalent Cation or Anion

33. A solution of FeCl3 in water acts as acidic due to:

(A) Acidic impurities (B) Ionisation

(C) Hydrolysis of Fe3+ (D) Dissociation

34. pH of K2S solution is:

(A) 7 (B) Less than 7 (C) More than 7 (D) 0

APNI KAKSHA 5
(Physical Chemistry) IONIC EQUILIBRIUM

35. For a c M K3A (potassium salt of a tribasic acid H3A) solution:

(Dissociation constants of acid are K a1 , K a 2 & K a3 ; h << 1)

1 1
(A) pH = (pKw + pK a 3 + log c) (B) pH = (pKw + pK a 2 + log c)
2 2
1 1
(C) pH = (pKw + pK a1 + log c) (D) pH = (pKw – pK a 3 – log c)
2 2
Amphiprotic Salt and Salt of WA + WB
36. The degree of hydrolysis of a salt of weak acid and weak base in it’s 0.1 M solution is found to
be 50%. If the molarity of the solution is 0.2 M, the percentage hydrolysis of the salt should be
(A) 100% (B) 50% (C) 25% (D) none of these

37. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous

solution of the corresponding salt, BA, will be:

(A) 8.58 (B) 4.79 (C) 7.01 (D) 9.22

38. Out of the following, amphiprotic species in aqueous medium are

II OH–
2–
I: HPO3 III H2PO4– IV HCO3–

(A) I, III, IV (B) I and III (C) III and IV (D) All

Buffer Solution and pH of Buffer Solution

39. The buffer solution play an important role in:

(A) Increasing the pH value (B) Decreasing the pH value
(C) Keeping the pH constant (D) Solution will be neutral

40. The pH of blood is maintained by CO2 and H2CO3 in the body and chemical constituents of

blood. This phenomenon is called:

(A) Colloidal (B) Buffer action
(C) Acidity (D) Salt balance

APNI KAKSHA 6
(Physical Chemistry) IONIC EQUILIBRIUM
41. 1 M NaCl and 1M HCl are present in an aqueous solution. The solution is
(A) not a buffer solution and with pH < 7 (B) not a buffer solution with pH > 7
(C) a buffer solution with pH < 7 (D) a buffer solution with pH > 7

42. pKb for NH4OH at certain temperature is 4.74. The pH of basic buffer containing equimolar

concentration of NH4OH and NH4Cl will be:

(A) 7.74 (B) 4.74 (C) 2.37 (D) 9.26

43. If equal volume of 0.05 M ammonium hydroxide solution and 0.001 M ammonium chloride solution

are mixed. What will be the OH– ion concentration of this solution Kb(NH4OH) = 1.8×10–5

(A) 3.0×10–3 (B) 9.0×10–4 (C) 9.0×10–3 (D) 3.0×10–4

44. Calculate the pH of a buffer prepared by mixing 300 cc of 0.3 M NH3 and 500 cc of 0.5 M NH4Cl.


  
Kb for NH3 = 1.8×10–5 ,  log 
25
 = 0.188 
  16.2  

(A) 8.1187 (B) 9.8117 (C) 8.812 (D) 7.812

45. 500 ml of 0.2 M acetic acid are added to 500 ml of 0.30 M sodium acetate solution. If the
–5
dissociation constant of acetic acid is 1.5×10 then pH of the resulting solution is:
(A) 5.0 (B) 9.0 (C) 3.0 (D) 4.0

46. 50 ml. of 2N acetic acid mixed with 10 ml. of 1N sodium acetate solution will have an

approximate pH of (Ka = 10–5):

(A) 4 (B) 5 (C) 6 (D) 7

–10 0
47. Ka, for HCN is 5×10 at 25 C. For maintaining a constant pH of 9, the volume of 5M KCN

solution required to be added to 10ml. of 2M HCN solution is-

(A) 4 ml (B) 7.95 ml (C) 2 ml (D) 9.3 ml

APNI KAKSHA 7
(Physical Chemistry) IONIC EQUILIBRIUM
48. What amount of sodium propanoate should be added to one litre of an aqueous solution

containing 0.02 mole of propanoic acid (Ka = 1.34×10–5 at 25°C) to obtain a buffer solution of

pH 4.75 (101/4 = 1.78)

(A) 4.52×10–2 mol (B) 3.52×10–2 mol

(C) 2.52×10–2 mol (D) 1.5×10–2 mol

49. To a 50 ml. of 0.05M formic acid how much volume of 0.10M sodium formate must be added to
get a buffer solution of pH = 4.0? (pKa of the acid is 3.7) (log2 = 0.3)

(A) 40 ml. (B) 4 ml. (C) 50 ml. (D) 100 ml.

50. In a buffer solution the ratio of concentration of NH4Cl and NH4OH is 1: 1 when it changes in 2:

1 what will be the value of pH of buffer:

(A) Increase (B) Decrease (C) No effect (D) None

51. Henderson equation pH – pKa = 5 will be applicable to an acidic buffer when:

5
(A) [Acid] = [Conjugate base] (B) [Acid]×10 = [Conjugate base]
5
(C) [Acid] = [Conjugate base]×10 (D) [acid] = 2 [conjugate base]

Change on pH of Buffer Solution & Buffer Capacity

52. How many gm of solid NaOH must be added to 100 ml of a buffer solution which is 0.1 M each

w.r.t. Acid HA and salt Na+ A– to make the pH of solution 5.5. Given pka (HA) = 5.

(Use antilog (0.5) = 3.16)

(B) 3.05×10–3 (C) 2.01×10–2

–1
(A) 2.08×10 (D) None
of these

53. 10 ml. of a solution contains 0.1 M NH4Cl + 0.01M NH4OH.

Which addition would not change the pH of solution:

(A) Adding 1 ml. water (B) Adding 5 ml. of 0.1 M NH4Cl

(C) Adding 5 ml. of 0.1 M NH4OH (D) Adding 10 ml. of 0.1 M NH4Cl

APNI KAKSHA 8
(Physical Chemistry) IONIC EQUILIBRIUM
54. When 0.02 moles of NaOH are added to a litre of buffer solution, its pH changes from 5.75 to
5.80. What is its buffer capacity:
(A) 0.4 (B) 0.05 (C) – 0.05 (D) 2.5

55. A buffer solution is prepared by mixing 'a' moles of CH3COONa and 'b' moles of CH3COOH such

that (a + b) = 1, into water to make 1L buffer solution. If the instantaneous (differential) buffer
capacity of this buffer solution is plotted against moles of salt CH3COONa (a), then the plot

obtained will be (to the scale) approximately

0.25
Buffer capacity

0.20

(A) 0.15 (B)

0.10
0.0 0.2 0.4 0.6 0.8 1.0
a

0.55
0.50
Buffer capacity

0.45

0.40
(C) (D)
0.35

0.30
0.0 0.2 0.4 0.6 0.8 1.0
a

Problems related with mixing ... Titration type

56. 8 gm NaOH and 4.9 gm H2SO4 are present in one litre of the solution. What is its pH

(A) 1 (B) 13 (C) 12 (D) 2

57. The pH of the solution containing10 ml of a 0.1M NaOH and 10 ml. of 0.05M H2SO4 would be

(assuming sulphate ion is not hydrolysed)

(A) Zero (B) 1 (C) < 7 (D) 7

APNI KAKSHA 9
(Physical Chemistry) IONIC EQUILIBRIUM
58. Which of the following solution will have pH close to 1.0?
(A) 100 ml of M/100 HCl + 100 ml of M/10 NaOH
(B) 55 ml of M/10 HCl + 45 ml of M/10 NaOH
(C) 10 ml of M/10 HCl + 90 ml of M/10 NaOH
(D) 75 ml of M/5 HCl + 25 ml of M/5 NaOH

59. Which can act as buffer:

(A) NH4OH + NaOH

(B) HCOOH + HCl

(C) 40 ml. of 0.1 M NaCN + 20 ml. of 0.1 M HCl
(D) All of them

60. Which of the following solutions does not act as buffer:

(A) H3PO4 + NaH2PO4 (B) NaHCO3 + H2CO3

(C) NH4Cl + HCl (D) CH3COOH + CH3COONa

61. If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH [Ka = 2×10–4], the pOH of the

resulting solution is
(A) 3.4 (B) 3.7 (C) 7 (D) 10.3

62. On addition of NaOH to CH3COOH solution, 60% of the acid is neutralised. If pKa of CH3COOH

is 4.7 then the pH of the resulting solution is:

(A) More than 4.7 but less than 5.0 (B) Less than 4.7 but more than 4.0
(C) More than 5.0 (D) Remains unchanged

63. Half of the formic acid solution is neutralised on addition of a KOH solution to it.

If Ka (HCOOH) = 2×10–4 then pH of the solution is: (log 2 = 0.3010)

(A) 3.6990 (B) 10.3010 (C) 3.85 (D) 4.3010

N N
64. acetic acid was titrated with NaOH. When 25%, 50% and 75% of titration is over then the
10 10

pH of the solution will be: [Ka = 10–5]

(A) 5 + log 1/3, 5, 5 + log 3 (B) 5 + log 3, 4, 5 + log 1/3
(C) 5 – log 1/3, 5, 5 – log 3 (D) 5 – log 1/3, 4, 5 + log 1/3
APNI KAKSHA 10
(Physical Chemistry) IONIC EQUILIBRIUM
M M
65. 10 mL of CH3COONa solution is titrated with HCl solution. The pH value at equivalence
5 5
point is: (pKa(CH3COOH) = 4.76)

(A) 0.7 (B) 1 (C) 1.88 (D) 2.88

66. H2A is a diprotic acid for which K a1 = 10–7 and K a 2 =10–11. The solution which will have a pH

closest to 9 is:
(A) 0.1 M H2A (B) 0.1 M Na2A

(C) 0.1 M NaHA (D) 0.1 M NaHA + 0.1 M Na2A

67. The total number of different kind of acidic buffers obtained during the titration of H3PO4 with

NaOH are:
(A) 3 (B) 1 (C) 2 (D) 0

68. 50 mL of 0.1 M NaOH is added to 60 mL of 0.15 M H3PO4 solution (K1, K2 and K3 for H3PO4

are 10–3, 10–8 and 10–13 respectively). The pH of the mixture would be about:
(A) 3.1 (B) 5.5 (C) 4.1 (D) 6.5

Indicators & Double Indicator

69 The rapid change of pH near the stoichiometric point of an acid–base titration is the basis of
indicator detection. pH of the solution is related to ratio of the concentrations of the acid (HIn)
and conjugate base (In–) forms of the indicator by the expression:
 HIn   HIn 
(A) log −
= PKIn – pH (B) log = pH – pKIn
 In  In − 
   

 In −   In − 
(C) log   = pH + pKIn (D) log   = pK – pH
 HIn   HIn  In

70 Calculate the pH range in which an acid indicator with Kacid (indicator) = 1.0×10–5 changes colour when
the concentration of the indicator is 1×10–3M.
(A) 5 ± 1 (B) 11 ± 1 (C) 3 ± 1 (D) 8 ± 1

71 pH–range of Methyl red indicator is:

(A) 4.2–6.3 (B) 8.5–10.3 (C) 8.3– 10 (D) 3.1 – 4.4

APNI KAKSHA 11
(Physical Chemistry) IONIC EQUILIBRIUM
72 Indicator which is used in the titration of CH3COOH & NaOH:
(A) Methyl orange (B) Methyl red (C) Phenolphthalein (D) Litmus

73 In the volumetric estimation of HCl, if we make use of phenolphthalein as an indicator, which base is
unsuitable for the titration:
(A) NaOH (B) RbOH (C) KOH (D) NH4OH

74 What is the suitable indicator for titration of NaOH and oxalic acid:
(A) Methyl orange (B) Methyl red (C) Phenolphthalein (D) None

75 Phenolphthalein does not act as an indicator for the titration between:

(A) KOH and H2SO4 (B) NaOH and CH3COOH
(C) Oxalic acid and KMnO4 (D) Ba(OH)2 and HCl

76 For weak acid and strong base titration, the indicator used is:
(A) Potassium di-chromate (B) Methyl orange
(C) Litmus (D) Phenolphthalein

77. 20 ml of 0.2M RNH2 (Kb = 10–5) is titrated against 0.2 M HCl. Which of the following graph is correct-

(A) (B)

(C) (D)

78 An acid-base indicator has a Ka = 1.0×10–5. The acid form of the indicator is red and the basic form is
blue. Calculate the pH change required to change the colour of the indicator from 80% red to 80%
blue.
(A) 1.20 (B) 0.80 (C) 0.20 (D) 1.40
79. 10gm NaHCO3(s) sample is heated in open to constant weight, the residue is titrated against 0.1M HCl
in presence of phenolphthalein as an indicator, 500 ml of acid was required to reach end point hence
% purity of sample is-
(A) 21% (B) 42 % (C) 63% (D) 84%

APNI KAKSHA 12
(Physical Chemistry) IONIC EQUILIBRIUM
80. A mixture of NaOH & Na2CO3 when titrated against 0.1N H2SO4 solution, it requires 30 ml to
decolorise the phenolphthalein. Now methyl orange is added to it and further 20 ml of same acid are
added it observe methyl orange end point then millimoles of NaOH & Na2CO3 in mixture respectively
-
(A) 2 & 2 (B) 2 & 4 (C) 1 & 2 (D) 2 & 1

Solubility and Ksp

81. The solubility of A2X3 is y mol dm–3. Its solubility product is

(A) 6 y2 (B) 64 y4 (C) 36 y5 (D) 108 y5

82. If Ksp for HgSO4 is 6.4 ×10–5 M2 then solubility of this substance in mole per m3 is

(A) 8 ×10–3 (B) 6.4 ×10–5 (C) 8×10–6 (D) 8

83. If the solubility of AgCl (formula mass=143) in water at 25°C is 1.43×10–4 gm./100 ml. of
solution then the value of Ksp will be:

(A) 1×10–5 (B) 2×10–5 (C) 1×10–10 (D) 2×10–10

84. One litre of saturated solution of CaCO3 is evaporated to dryness, 7.0 g of residue is left. The

solubility product for CaCO3 is:

(A) 4.9×10–3 (B) 4.9×10–5 (C) 4.9×10–9 (D) 4.9×10–7

85. Which of the following is most soluble in water?

(A) MnS (Ksp= 8×10–37) (B) ZnS (Ksp= 7×10–16)

(C) Bi2S3 (Ksp= 1×10–72) (D) Ag3(PO4) (Ksp= 1.8×10–18)

86. Ksp of Ag2CrO4 at a certain temperature is 8.64×10–13. How many times is its solubility in

water greater than in 0.6 M Na2CrO4 solution?

(A) 10 (B) 10 (C) 1000 (D) 129

APNI KAKSHA 13
(Physical Chemistry) IONIC EQUILIBRIUM
87. Solubility of AgBr will be minimum in:
(A) Pure water (B) 0.1 M CaBr2

(C) 0.1 M NaBr (D) 0.1 M AgNO3

88. SrCO3 (Ksp = 10–10) and ZnCO3 (Ksp =1.5×10–11) are dissolved together in a solution. The

ratio of [Sr2+]/[Zn2+] in the solution is:

10 3 20 3
(A) (B) (C) (D)
3 10 3 20
Precipitation

89. Solid Ba(NO3)2 is gradually dissolved in a 1.0×10–4 M Na2CO3 solution. At what concentration

of Ba2+ will a precipitate begin to form?

(Ksp for BaCO3 = 5.1×10–9)

(A) 4.1×10–5 M (B) 5.1×10–5 M (C) 8.1×10–8 M (D) 8.1×10–7 M

90. Solubility product of Mg(OH)2 is 1×10–11. At what pH, precipitation of Mg(OH)2 will begin

from 0.1 M Mg2+ solution:

(A) 9 (B) 5 (C) 3 (D) 7

91. What will happen if the pH of the solution of 0.001 M Mg(NO3)2 solution is adjusted to pH = 9

(Ksp of Mg(OH)2 = 8.9×10–12)

(A) ppt will take place (B) ppt will not take place
(C) Solution will be saturated (D) None of these

92. 50 litre of a solution containing 10–5 mole of Ag+ is mixed with 50 litre of a 2×10–7 M HBr

solution. [Ag+] in resultant solution is: [Given: Ksp (AgBr) = 5×10–13]

(A) 10–5 M (B) 10–6 M (C) 10–7 M (D) 10–8 M

93. The remaining molar concentration of Ag+ ion if 100 ml of 0.1 M AgNO3 solution is mixed with
400 ml of 0.2 M K2 Cr2O4 solution is,
[Given Ksp (Ag2CrO4 ) = 1.5 × 10–11 M3]
(A) 10–10 (B) 2.5 × 10–3 (C) 5 × 10–3 (D) 10–5
APNI KAKSHA 14
(Physical Chemistry) IONIC EQUILIBRIUM
94. The moles of Ag+ which must be added to decrease the concentration of Cl– from 4×10–5M to
10–5M in 100 ml solution, if Ksp for AgCl is 10–10M2 at 25ºC
(A) 4 × 10–5 mole (B) 2 × 10–5 mole (C) 3 × 10–6 mole (D) 4 × 10–6 mole

95. In a saturated solution of AgCl, NaCl is added gradually. The concentration of Ag+ is plotted
against the concentration of Cl–. The graph appears as:

[Ag+] [Ag+]
(A) (B)
[Cl–] [Cl–]

[Ag+] [Ag+]
(C) (D)
[Cl–] [Cl–]

Effect of Complex Formation and Hydrolysis on Solubility

96. What is the effect of pH on the solubility of M(CN)2 ?

(Neglect hydrolysis of M2+ ion)

(A) As pH decreases, solubility decreases.
(B) As pH decreases below 7 or increases above 7, solubility increases in both cases.
(C) As pH decreases, solubility increases.
(D) No dependence on pH of solution.
97. At 300oC, In which of the one litre solution, the solubility of Ag2CO3 (solubility product=8×10–12)
will be maximum:
(A) 0.05 M Na2CO3 (B) Pure water (C) 0.05 M AgNO3 (D) 0.05 M NH3
98. 1 mole of AgNO3 is added to 10 litre of 1 M NH3 . What is the concentration of Ag(NH3)+ in
solution ?
[Given : For Ag(NH3) +2 , K f1 = 2.0 × 103 ; K f2 = 104 ]

(A) 8 × 10–5 (B) 1.25 × 10–5

(C) 4 × 10–6 (D) 1.25 × 10–4
99. pH of a saturated solution of silver salt of monobasic acid HA is found to be 9.
Find the Ksp of sparingly soluble salt Ag A(s).
Given : Ka (HA) = 10–10
(A) 1.1 × 10–11 (B) 1.1 × 10–10 (C) 10–12 (D) None of these
APNI KAKSHA 15
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE # (S-I)
Dissociation of Water, pH of Water
1. Calculate the number of H+ present in one ml of solution whose pH is 13.

2. (i) Kw for H2O is 9×10–14 at 60°C. What is pH of water at 60°C. (log 3 = 0.47)
(ii) What is the nature of solution at 60°C having
(a) pH = 6.7 (b) pH = 6.35

3. Percentage ionisation of water as follows at certain temperature is 3.6×10–7 %. Calculate Kw

and pH of water at this temperature. 2H2O H3O+ + OH–

4. At –50°C, liquid NH3 has ionic product is 10–30 M2. How many amide (NH2–) ions are present

per mm3 in pure liquid NH3 ? (Take NA = 6×1023)

pH of Strong Electrolyte
5. Calculate pH of following solutions :
(a) 0.1 M HCl

(b) 10–3 mole of KOH dissolved in 100 L of water.

(c) Decimolar solution of Baryta (Ba(OH)2), diluted 100 times.
(d) 10–8 M HCl [ 401 = (20.02)] [log 1.051 = 0.03]

(e) 10–10 M NaOH

6. 0.1 mole HCl is dissolved in distilled water of volume V. Then, at lim , (pH)solution is equal to
V →

7. pH of a dilute solution of HCl is 6.95. Calculate molarity of HCl solution.

10−.95 = 11.22 10−8 
 −7.05 
10 = 8.90 10−8 

𝐩𝐇 of Weak Electrolyte
8. Calculate pH of following solutions :

(b) 0.1 M CH3COOH (Ka= 1.8 × 10–5) (log 1.8 = 0.13)

(c) 0.1 M NH4OH (Kb= 1.8 × 10–5)

(f) 10–7 M CH3COOH (Ka= 10–5)

(g) 10–8 M CH3COOH (Ka= 1.8 × 10–5) [ 401 = (20.02)] [log 1.051 = 0.03]
APNI KAKSHA 16
(Physical Chemistry) IONIC EQUILIBRIUM
9. Calculate:
(a) Ka for a monobasic acid whose 0.10 M solution has pH of 4.50.
(b) Kb for a monoacidic base whose 0.10 M solution has a pH of 10.50.
10−3.5 10−3.5
Kb = = 10–6
0.1 − 10−3.5

10. Calculate the ratio of degree of dissociation ( 2/ 1) when 1 M acetic acid solution is diluted

100 times. [Given Ka=10–5 M]

11. Calculate the ratio of degree of dissociation of acetic acid and hydrocyanic acid (HCN) in 1 M

their respective solution of acids.[Given Ka ( CH3COOH ) = 1.8×10–5 ; Ka(HCN) = 6.2×10–10]

 18 
 = 1.704 
 6.2 

12. The pH of aqueous solution of ammonia is 10. Find molarity of solution. Kb (NH4OH) = 10–5.

13. The solution of weak monoprotic acid which is 0.01 M has pH = 3. Calculate Ka of weak acid.

14. Boric acid is a weak monobasic acid. It ionizes in water as

B(OH)3 + H2O + H+: Ka = 5.9×10–10

(
Calculate pH of 0.3 M boric acid. [ log 1.77 = 0.13] )
𝐩𝐇 of Mixture of More Than One Acid/Base
15. Calculate pH if equal volume of HCl solution (PH = 4) + 0.0019 N HCl solution

16. Calculate pH of following solutions:

(a) 0.1 M H2SO4 (50 ml) + 0.4 M HCl 50 (ml) [log 0.3 = – 0.522]

(b) 0.1 M HA + 0.1 M HB [ Ka (HA) = 2×10–5 ; Ka (HB) = 4×10–5] [log = 0.39]

–
17. Upon passing 0.01 mole HCl gas through 100 mL of 0.05 M Formic acid solution (Ka = 1.8×10

), determine change in pH of solution and [HCOO–] in resulting solution.

4

18. Calculate [H+] and [CHCl2COO–] in a solution that is 0.01 M in HCl and 0.01 M in CHCl2COOH.

Take (Ka = 3×10 )

–2
( 30 = 5.5 )

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(Physical Chemistry) IONIC EQUILIBRIUM
19. Calculate [H+], [CH3COO–] and [ C7 H5O2–] in a solution that is 0.02 M in acetic acid and 0.01M

in benzoic acid. Ka(acetic) = 1.8×10–5 , Ka (benzoic) = 6.4×10–5.

Polyprotic Acid Base

20. What are the concentration of H+, H2C2O4, HC2O4− and C2O42− in a 0.1 M solution of oxalic acid ?

[K1 = 10–2 M and K2 = 10–5 M ]

21. Calculate [H+], [H2PO4–], [HPO42–] and [PO43–] in a 0.01M solution of H3PO4.

Take K1 = 10–3, K2 = 10–8 , K3 = 10–13.

22. What are the concentrations of H+, HSO−4 , SO24− and H2SO4 in a 0.20 M solution of sulphuric
acid?

Given:H2SO4 H+ + HSO−4 ; strong

HSO−4 H+ + SO24− ; K2 = 10–2 M

23. Calculate the pH of a 0.1M solution of H2NCH2CH2NH2 ; ethylenediamine (en). Determine the en

H22+. Concentration in the solution. K b1 and K b2 values of ethylenediamine are 8.5×10–5 and

7.1×10–8 respectively.
Conjugate Acid Base, Bronsted Theory
24. Which of the following ions or compounds in a solution tend to produce an acidic, a basic or a
neutral solution ?

(a) C2H5O– (d) F–

+2 2–
(b) Cu (c) SO3

(e) NH4+ (f) CH3COONa (g) KNO3 (h) NaOCl

5(i) Na2CO3 (j) ZnCl2

25. What is ionisation constant of HOCl, if Kb of OCl – = 4×10–10 ? Also find its pKa.

26. Ka1 , Ka2 and Ka3 values for H3PO4 are 10–3, 10–8 and 10–12 respectively. If Kw (H2O) = 10–

14, then:

(i) What is dissociation constant of HPO42– ?

(ii) What is Kb of HPO42– ?

(iii) What is Kb of H2PO4– ?

(iv) What is order of Kb of PO43– ( K b 3 ), HPO42–( K b 2 ) and H2PO4–( K b 1 ) ?

APNI KAKSHA 18
(Physical Chemistry) IONIC EQUILIBRIUM
Salt Hydrolysis

27. What is the OH– concentration of a 0.08 M solution of CH3COONa.

[Ka(CH3COOH)=1.8×10–5]

28. Calculate the pH of a 2.0 M solution of NH4Cl. [Kb (NH3) = 1.8×10–5]

29. 0.25 M solution of pyridinium chloride C5H6N+Cl– was found to have a pH of 2.699. What is Kb
for pyridine, C5H5N ? (log2 = 0.3010) antilog (0.796) = 6.25

30. Calculate the percent hydrolysis in a 0.06 M solution of KCN.

[Ka(HCN) = 6×10–10]

31. Calculate the pH of 1.0 ×10–3 M sodium phenolate, NaOC6H5. Ka for HOC6H5 is 1.05×10–10.
43 − 1
= 0.26 & log 26 = 1.43
21

Salt Hydrolysis of Multivalent Cation Or Anion

32. Calculate the OH– concentration and the H3PO4 concentration of a solution prepared by
dissolving 0.1 mol of Na3 PO4 in sufficient water to make 1L of solution.

K1 = 7.1×10–3 , K2 = 6.3×10–8 , K3=4.5×10–13.

33. Calculate the extent of hydrolysis of 0.005 M K2CrO4. [K2 = 3.1×10–7 for H2CrO4]
(It is essentially strong for first ionization).
1
= 0.26
5  3.1

34. A 0.010 M solution of PuO2(NO3)2 was found to have a pH of 4.0. What is the hydrolysis

constant, Kh, for PuO22+ and what is Kb for PuO2OH+ ?

35. The acid ionization (hydrolysis) constant of Zn2+ is 1.0×10–9

(a) Calculate the pH of a 0.001 M solution of ZnCl2

(b) What is the basic dissociation constant of Zn(OH)+?

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(Physical Chemistry) IONIC EQUILIBRIUM

Amphiprotic Salt and Salt of WA + WB

36. Calculate the extent of hydrolysis & the pH of 0.02 M CH3COONH4.

[Kb (NH3)= 1.8×10–5, Ka(CH3COOH)=1.8×10–5]

37. What is the pH of 0.1M NaHCO3?

K1 = 4.5 x 10–7, K2 = 4.5×10–11 for carbonic acids.

log(4.5) = 0.66

38. Calculate pH of 0.05M potassium hydrogen phthalate, KHC8H4O4.

H2C8H4O4 + H2O H3O+ + HC8H4O4– pK1 = 2.94

HC8H4O4– + H2O H3O+ + C8H4O2–4 pK2 = 5.44

pH of buffer solution and Change on pH of Buffer Solution

39. Determine [OH–] of a 0.050 M solution of ammonia to which sufficient NH4Cl has been added to

make the total  NH +4  equal to 0.100. Kb( NH3 ) = 1.8 10−5 

 

40. A buffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of
ammonia into 100 mL solution. If pKb of ammonia is 4.74, calculate value of x.

41. (a) Determine the pH of a 0.2 M solution of pyridine C5H5N . Kb = 1.5×10–9

(b) Predict the effect of addition of pyridinium ion C5H5NH+ on the position of the equilibrium.
Will the pH be raised or lowered ?
(c) Calculate the pH of 1.0 L of 0.10 M pyridine solution to which 0.3 mol of pyridinium chloride

C5H5NH+Cl, has been added, assuming no change in volume.

42. Calculate the pH of 0.5 L of a 0.2 M NH4CI – 0.2 M NH3 buffer before and after addition of (a)
0.05 mole of NaOH and (b) 0.05 mole of HCl. Assume that the volume remains constant. [Given:
pKb of NH3 = 4.74]

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(Physical Chemistry) IONIC EQUILIBRIUM

Problems Related with mixing... Titration type

43. Calculate the pH of the resulting solution formed by mixing the following solutions:
(a) 20 mL of 0.2 M Ba(OH)2 + 30 mL of 0.1 M HCl

(b) 2 mL of 0.1 M HCl + 10 mL of 0.01 M Sr(OH)2

(c) 10 mL of 0.1 M H2SO4 + 10 mL of 0.1 M KOH.

44. How many of the following statement(s) is/are correct for making a buffer solution ?
(i) It can be formed by mixing equal moles of HCl and CH3COONa

(ii) It can be formed by mixing equal moles of HNO3 and NH3

(iii) It can be formed by mixing equal moles of HCN and Aniline.

(iv) It can be formed by mixing unequal moles of NH4OH and HCl.

(v) It can be formed by mixing unequal moles of HCN and KOH.

45. Calculate the pH of a solution prepared by mixing 50.0 mL of 0.200 M HC2H3O2 and 50.0 mL of

0.100 M NaOH.[ Ka ( CH3COOH ) = 1.8×10–5]

46. 50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of NH +4 is
9.26, calculate pH.

47. Calculate the pH of a solution which results from the mixing of 50.0 ml of 0.3 M HCl with 50.0

ml of 0.4 M NH3. [Kb (NH3) = 1.8×10–5]

48. Calculate the pH of a solution made by mixing 50.0 ml of 0.2M NH4Cl & 75.0 ml of 0.1 M NaOH.

[Kb (NH3) = 1.8×10–5]

49. Calculate OH– concentration at the equivalent point when a solution of 0.2 M acetic acid is

titrated with a solution of 0.2 M NaOH. Ka for the acid = 10–5.

50. Calculate the hydronium ion concentration and pH at the equivalence point in the reaction of

22.0 mL of 0.10M acetic acid, CH3COOH, with 22.0 mL of 0.10 M NaOH. [Ka = 1.8×10–5]

(10+0.29 = 1.95)

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(Physical Chemistry) IONIC EQUILIBRIUM
51. Calculate the hydronium ion concentration and the pH at the equivalence point in a titration of

50.0 mL of 0.40 M NH3 with 0.40M HCl.[Kb = 1.8×10–5]

100.02 = 1.05
52. CH3COOH (50 ml, 0.1 M) is titrated against 0.1 M NaOH solution. Calculate the pH at the

addition of 0 ml, 10 ml 20 ml, 25 ml, 40 ml, 50 ml of NaOH. Ka of CH3COOH is 2×10–5.

[log 2 = 0.3010, log3 = 0.4771]
Indicators
53. For the acid indicator thymol blue, pH is 2.0 when half the indicator is in unionised form. Find

the % of indicator in unionised form in the solution with [H+] = 4×10–3 M.

54. An acid indicator has a Ka of 3×10–5. The acid form of the indicator is red & the basic form is
blue. By how much must the pH change in order to change the indicator form 75% red to 75 %
blue? [log 3 = 0.4771]

55. Bromophenol blue is an acid indicator with a Ka value of 6×10–5. What % of this indicator is in
its basic form at a pH of 5 ?

56. At what pH does an indicator change colour if the indicator is a weak acid with Kind = 4×10–4.
For which one(s) of the following neutralizations would the indicator be useful? Explain.
(a) NaOH + CH3COOH (b) HCl + NH3 (c) HCl + NaOH

57. What indicator should be used for the titration of

0.10 M KH2BO3 with 0.10 M HCl ?

Ka (H3BO3) = 7.2×10–10 .[log  20  = 0.44]

 7.2 

Double Indicator, Solubility and Ksp

58. 100 ml solution containing Na2CO3 & NaHCO3 is titrated with 0.1 M solution of triprotic strong
acid then following results were obtained
(i) 25 ml solution required 10 ml of acid using phenolphthalein as indicator
(ii) 20 ml solution required 20 ml of acid using methyl orange indicator
What will be the value of sum of millimoles of Na2CO3 & NaHCO3 in original solution.

APNI KAKSHA 22
(Physical Chemistry) IONIC EQUILIBRIUM
59. Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with

water. For A2X3, [Ksp = 1.08×10–23]

60. The solubility of PbSO4 water is 0.038 g/L. Calculate the solubility product constant of PbSO4.

= 1.25 (1.25)2 = 1.56

380
Molar mass PbSO4 = 304 g/mole,
304

61. A solution of saturated CaF2 is found to contain 4.1×10–4 M fluoride ion. Calculate the Ksp of
3
CaF2. Use 4  
4.1
34.
 2 

62. The solubility of ML2 (formula weight, 60 g/mol) in water is 2.4×10–5 g/100 mL solution.
Calculate the solubility product constant for ML2.

63. The values of Ksp for the slightly soluble salts MX and QX2 are each equal to 4.0×10–18. Which
salt is more soluble? Explain your answer fully.
SOLUBILITY IN PRESENCE OF COMMON ION
64. How many mol CuI (Ksp = 5×10–12) will dissolve in 1.0 L of 0.10 M NaI solution ?

65. Determine the solubility of AgCl in 0.1 M BaCl2. [Ksp for AgCl = 1×10–10]

66. Calculate the Simultaneous solubility of AgSCN and AgBr.

Ksp (AgSCN) = 1.1×10–12, Ksp(AgBr) = 5×10–13.  1.1 0.9,

5 
4
 1.26 1.26 

67. Calculate F– in a solution saturated with respect of both MgF2 and SrF2. Ksp(MgF2)= 9.5×10–9,

Ksp(SrF2) = 4×10–9.
Precipitation
68. A solution has a Mg2+ concentration of 0.0010 mol/L. Will Mg(OH)2 precipitate if the OH–

concentration of the solution is [Ksp= 1.2×10–11]

(a) 10–5 mol/L (b) 10–3 mol/L ?

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(Physical Chemistry) IONIC EQUILIBRIUM
69. 8×10–6 M AgNO3 solution is gradually added in 1 L of 10–4 M KCl solution. Up to what volume

AgNO3 solution being added (in L), precipitation of AgCl will not take place? (Ksp of AgCl =

2×10–10)
70. Solubility of Ag2CrO4 in water at 25ºC is 10–3M. If 0.1 moles of K2CrO4 are added to 1 litre
saturated solution of Ag2CrO4. Then find moles of Ag2CrO4 precipitated at 25ºC.
If your answer is x × 10y then fill ‘x’ in OMR. Where ‘x’ is single digit number.

71. What mass of Pb2+ ion is left in solution when 50.0 mL of 0.20M Pb(NO3)2 is added to 50.0 mL

of 1.5 M NaCl ? [Given Ksp for PbCl2 = 1.7 ×10–4]

[5.6×208 = 1.2×103] [Atomic mass of Pb = 208,

1.7
= 5.6]
( 0.55 )2

72. The solubility of CaCO3 is 7 mg/litre. Calculate the solubility of BaCO3 (in mol/L) from this

information and from the fact that when Na2CO3 is added slowly to a solution containing

equimolar concentration of Ca+2 and Ba+2, no precipitate of CaCO3 is formed until 90% of

Ba+2 has been precipitated as BaCO3 . (Assume no hydrolysis of CO32– ion).

Effect of Complex Formation And Hydrolysis on Solubility

73. A recent investigation of the complexation of SCN– with Fe3+ led of 130, 16, and 1.0 for K1, K2,
and K3, respectively. What is the overall formation constant of Fe(SCN)3 from its component
ions, and what is the dissociation constant of Fe(SCN)3 into its simplest ions on the basis of
these data ?

74. How much AgBr could dissolve in 1.0 L of 0.40 M NH3 ? Assume that Ag(NH3)2+ is the only
complex formed.

[Kf (Ag(NH3)2+ ) = 1 ×108 ; Ksp (AgBr) = 5 ×10–13]  50 7  S

75. At 25ºC, the solubility of Ag2CO3 (Ksp = 4.3×10–13) would be in what order in the following

solutions ?
(a) 0.01 M AgNO3 (b) 0.04 M K2CO3

(c) pure water (d) in a buffer (pH = 4)

APNI KAKSHA 24
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE # (O-II)
1. If K1 & K2 be first and second ionisation constant of H3PO4 and K1 >> K2 which is correct.

(A) [H+] = [H2PO4–] (B) [H+] = K1  H3PO4  (C) [HPO42–] = K2 (D) [H+] = 3  PO34− 

2. Choose the correct statement(s)

(A) Ka for an acid HA is 1×10–6. Kb for A– would be 10–8

(B) The value of Kw increases with increase in temperature

(C) Larger the value of pKa weaker is the acid.

(D) Salts of strong acids and weak bases undergo cationic hydrolysis.

3. Choose the correct statement(s)

(A) pH of 0.1M CH3COOH solution decreases with increase in temperature

(B) pOH of 0.1M NH4OH solution decreases with increase in temperature

(C) 10–4M HCl solution is more acidic than 0.1M HCN (KaHCN = 10–5) solution.

(D) On dilution degree of dissociation of weak electrolytes increases.

4. Choose the incorrect statement(s)

(A) When a solution of a weak monoprotic acid is titrated against a strong base, at half-
1
neutralization point, pH = pKa.
2
(B) The pH of a solution which is 0.1 M in sodium acetate and 0.01 M in acetic acid (pKa=4.74)

would be 5.74.
(C) In a mixture of weak acid and its salt, the ratio of concentration of salt to acid is increased
Ten times. The pH of the solution would Increase by one unit.
(D) A buffer has maximum buffer capacity when the ratio of salt to acid is 10.

5. Select the correct statement(s):

(A) If pOH of aq. solution at 70ºC is 7, then solution will be acidic

(B) If [H+] concentration is decreases 100 times, pH of solution increases by 2 units

(C) If solution of CH3COONa(aq.) is diluted then pH increases.

(D) Buffer capacity remains constant with dilution.

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(Physical Chemistry) IONIC EQUILIBRIUM
6. Which of the following is correct for 0.1 M BOH solution (Kb = 10–5)

(A) pH of solution is 11

(B) OH– concentration is 10–3 mol/L

(C) it's salt with HCl (i.e., BCl) form the acidic solution in water
(D) Phenolphthalein indicator can be used during the titration of BOH with HCl

7. When equal volumes of the following solutions are mixed, precipitation of

AgCl (Ksp = 1.8×10–10) will occur

(A) 10–4 M (Ag+) and 10–4 M (Cl¯ ) (B) 10–5 M (Ag+) and 10–5 M (Cl¯ )

(C) 10–6 M (Ag+) and 10–6 M (Cl¯ ) (D) 10–10 M (Ag+) and 10–10 M (Cl¯ )

8. Choose the correct statement(s)

(A)From an equimolar solution of Cl– and Br– ions, the addition of Ag+ will precipitates Br–ion

first (Ksp of AgCl & AgBr are 1×10–10 & 1×10–13 respectively).\

(B) If the salts M2X, QY2 and PZ3 have same solubilities (<<<1), their Ksp values are related as

M2X = QY2 > PZ3

(C) If the solubility of the salt Li3Na3(AlF6)2 is x, then its solubility product would be 2916 x8.

(D) Ksp of Fe(OH)3in aqueous solution is 3.8 × 10–38 at 298K. The concentration of Fe3+ will
increase when [H+] ion concentration decreases

9. Choose the correct statement(s)

(A) AgCl is less soluble in aqueous sodium chloride solution than in pure water.
(B) In the presence of a common ion (incapable of forming complex ion), the solubility of salt
decreases.

(C) The solubility of CH3COOAg in water considering hydrolysis of CH3COO– ions would be

Greater than that ignoring the hydrolysis.

(D)The solubility of AgCl in NH3 is greater than the solubility in pure water because of complex

ion, [Ag(NH3)2]+ formation.

APNI KAKSHA 26
(Physical Chemistry) IONIC EQUILIBRIUM
Paragraph for Question 10 to 12
1 litre of 1M CH3COOH (very weak acid) taken is a container initialy. Now this solution is
diluted upto volume V (litre) so that pH of the resulting solution becomes the twice of the
original value. (Ka (CH3COOH) = 10–6). Now equal volume of 0.5 × 10–6M NaOH solution is
added to this resulting solution. So that a buffer solution is obtained.
 [Anion]   [Cation] 
pH (acidic buffer) = pKa + log10   & pOH (Basic buffer) = p + log10 
Kb

 [Acid]   [Base] 
10. Find [H+] in original solution
(A) 1 M (B) 10–3M (C) 10–7 M (D) 10–11 M

11. Find value of V (litre)

(A) 5 × 105 litre (B) 1 litre
(C) 2 litre (D) 2 × 10–6 litre

12. Find pH of final solution (log3 = 0.477)

(A) 6 (B) 6.477 (C) 5.523 (D) 3

Paragraph for Q.13 to Q.15

100ml of 1M Na3PO4 is titrated with 1M HCl the following observation were made
Stage of titration pH
I half equivalence point 12
I equivalence point 10
II equivalence point 6

13. pH at III equivalence point should be -

(A) 4 (B) 4 – log2 (C) 3 – log5 (D) 2 – log5

14. pH at II half equivalence point will be -

(A) 4 (B) 8 (C) 11 (D) 12
15. What is the value of equilibrium constant for the reaction -

Na3PO4(aq.) + H2O (l) Na2HPO4 (aq.) + NaOH(aq.)

(A) 10–2 (B)10–4 (C) 10–6 (D) 10–8

APNI KAKSHA 27
(Physical Chemistry) IONIC EQUILIBRIUM
Paragraph for Question 16 to 17
A solution contains one mole each of HA & HB (both are weak acids) in one litre solution. Now
one mole of NaOH is added to this solution so that both the acids are partially neutralised. Heat
of neutralisation of HA & HB are –11.8 and –12.4 kcal per mole respectively and heat produced
during partial neutralisation of HA & HB is –12.25 kcal.

16. Mole ratio of neutralisation of HA & HB is -

(A) 1: 4 (B) 1: 2 (C) 1: 3 (D) 1: 5

17. pH of solution containing mixture of 1 mol of HA & 1 mole of HB in 1 litre solution is

Ka(HA) = 1×10–5 , Ka(HB) = 9×10–5

(A) 2 (B) 3 (C) 4 (D) 5

Paragraph for question nos. 18 to 20

To find the Ksp of AgBrO3 a student prepared one litre of a just saturated solution by adding
AgBrO3 at 27°C. He found that a copper wire left in the solution overnight became covered with
silver and Cu+2 (aq) ions were also formed in solution. The wire was cleaned, dried, and found
to weight 7.04 mg less than it did originally. (R = 8 J/mol/K; ln x = 2.3 log x)
Given : Cu(s) + 2Ag+ (aq) ƒ Cu+2 (aq) + 2Ag(s) G° = 110.4 kJ.

18. The number of moles of Cu which reacted was

(A) 1.1 × 10–4 (B) 1.1 (C) 0.11 (D) 1.1 × 10–3
19. The [Ag+ (aq)] in the original saturated solution have been
(A) 1.1 × 10–2 (B) 1.1 × 10–4 (C) 2.2 × 10–4 (D) 5.5 × 10–5
20. The Ksp for AgBrO3 as calculated from the above data is about
(A) 1.21 × 10–8 (B) 3.025 × 10–9 (C) 1.7 × 10–4 (D) 4.84 × 10–8
21. Match the effect of addition of 1 M NaOH to 100 mL 1 M CH3COOH (in Column I) with pH (in

Column II):
Column-I Column-II
(A) 25 mL of NaOH (P) pKa

(B) 50 mL of NaOH (Q) pKa + log 3

(C) 75 mL of NaOH (R) pKa – log 3

1
(D) 100 mL of NaOH (S) [pKw + pKa – log 2]
2

APNI KAKSHA 28
(Physical Chemistry) IONIC EQUILIBRIUM
22. Column-I Column-II
PH Solution

(A) 3 (P) When equal volumes of 0.2M NH4OH (Kb = 10–5) & 0.2M

HCl are mixed

(B) 5 (Q) When equal volumes of 0.2M CH3COONa & 0.2M

HCl are mixed (Ka(CH3COOH) = 10–5)

(C) 8 (R) 0.1M Na2HPO4

(for H3PO4 ; Ka1= 10–4 ; Ka2= 10–6 ; Ka3= 10–10)

(D) 9 (S) At 1st half equivalence point of H2CO3 when titrated against

0.1M NaOH , Ka1 = 10–5 , Ka2= 10–9

(T) Mg(OH)2 ; Ksp = 5×10–16

APNI KAKSHA 29
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE # (S-II)

1. Determine the [S2–] in a saturated (0.1M) H2S solution to which enough HCl has been added to

produce a [H+] of 2×10–4 . K1 = 10–7 , K2 = 10–14.

2. Nicotine, C10H14N2, has two basic nitrogen atoms and both can react with water to give a basic
solution a

Nic (aq) + H2O (l) NicH+ (aq) + OH– (aq)

NicH+ (aq) + H2O (l) NicH22+ (aq) + OH– (aq)

Kb1 is 7×10–7 and Kb2 is 10–10. Calculate the approximate pH of a 0.020 M solution.

(
 log 1.4 = 0.07 
  )
3. Calculate the pH of 0.1 M solution of (i) NaHCO3, (ii) Na2HPO4 and (iii) NaH2PO4. Given that:

CO2 + H2O H+ + HCO3− ; K1 = 4.2×10–7 M

HCO3− H+ + HCO3− ; K2 = 4.8×10–11 M

H3PO4 H+ + H2 PO4− ; K1 = 7.5×10–3 M

H2 PO4− H+ + H2 PO4− K2 = 6.2×10–8 M

HPO24− H+ + PO34− ; K3 = 1.0×10–12 M

4. Calculate the pH of the following solutions.

[K1 = 7.5×10–3 M ; K2 = 6.2×10–8 M ; K3 = 1.0×10–12 M]

(a) 50 ml of 0.12 M H3PO4 + 20 ml of 0.15 M NaOH;
(b) 50 ml of 0.12 M H3PO4 + 40 ml of 0.15 M NaOH;
(c) 40 ml of 0.12 M H3PO4 + 40 ml of 0.18 M NaOH;
(d) 40 ml of 0.10 M H3PO4 + 40 ml of 0.25 M NaOH.

5. A buffer solution was prepared by dissolving 0.02 mol propionic acid & 0.015 mol sodium

propionate in enough water to make 1.00 L of solution .(Ka for propionic acid is 1.34×10–5)
(a) What is the pH of the buffer?

(b) What would be the pH if 1.0×10–5 mol HCl were added to 10 ml of the buffer ?

(c) What would be the pH if 1.0×10–5 mol NaOH were added to 10 ml of the buffer.
(d) Also report the percent change in pH of original buffer in cases (b) and (c).

APNI KAKSHA 30
(Physical Chemistry) IONIC EQUILIBRIUM
6. A weak base (50.0mL) was titrated with 0.1 M HCl. The pH of the solution after the addition of
10.0 mL and 25.0 mL were found to be 9.84 and 9.24, respectively. Calculate Kb of the base and
pH at the equivalence point. [log2 = 0.3]

7. The indicator phenol red is half in the ionic form when pH is 7.2. If the ratio of the
undissociated form to the ionic form is 1: 5, find the pH of the solution. With the same pH for
solution, if indicator is altered such that the ratio of undissociated form to dissociated form
becomes 1: 4, find the pH when 50 % of the new indicator is in ionic form.

8. What [H 3 O + ] must be maintained in a saturated H 2 S solution (0.1 M) to precipitate

Pb 2+ , but not Zn2+ from a solution in which each ion is present at a concentration of 0.01 M ?

(K 1 K 2 of H 2 S = 1.1×10 –21 ; K sp of ZnS = 1.0×10 –21 ; 11 = 3.3)

9. What minimum pH must be maintained in a saturated H2S solution (0.1 M) to cause

precipitation of both Mn2+ & Fe2+ from a solution, in which each ion is present at a
concentration of 0.01 M?

(K 1 K 2 of H2S = 9.6×10–21 ; Ksp of MnS = 2.5×10–13 ; Ksp of FeS = 6.4×10–18)

10. 2M solution of Na 2 CO 3 is boiled in a closed container with exce ss of CaF 2 . Very

little amount of CaCO 3 and NaF are formed. If the solubility product (K sp ) of CaCO 3

is x and molar solubility of CaF 2 is y, find the molar concentration of F – in

resulting solution after equilibrium is attained.

11. Determine the concentration of NH3 solution whose 1 L can dissolve 0.1 mole CuCO3. Given:

Ksp of CuCO3 = 1.4×10–10 and Kf of [Cu(NH3)4]2+ = 2×1013.

Take 4 1000 = 4.4. Assume no other reaction to take place.

2.8

12. Calculate solubility of MnS in a buffer solution of given pH. Solubility constant of MnS is Ksp
and dissociation constants of H2S are K1 & K2 respectively.
APNI KAKSHA 31
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE # JEE-MAINS
1. The solubility in water of a sparingly soluble salt AB2 is 1.0×10–5 mol L–1. Its solubility

product will be [AIEEE-2003]

() 1×10– 15 () 1×10–10 (C) 4×10–15 (D) 4×10–10

2. The solubility of Mg(OH)2 is x mole/lit. then its solubility product is: [AIEEE-2002]

() x3 () 5x3 (C) 4x3 (D) 2x2

3. The molar solubility in mol L–1 of a sparingly soluble salt MX4 is 's'. The corresponding

solubility product is KSP. 's' is given in terms of KSP by relation: [AIEEE-2004]

1/4 1/4 1/5 1/5
() s = (KSP / 128) () s = (128KSP) (C) s = (256KSP) (D) s = (KSP/256)

4. The conjugate base of H2PO–4 is [AIEEE-2004]

() H3 PO4 () P2 O5 (C) PO3–

4 (D) HPO 2–
4

5. Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be: [AIEEE-2005]

(A) 3.88 × 106 (B) 3.98 × 108 (C) 3.98 × 10−6 (D) 3.68 × 10−6

6. The solubility product of a salt having general formula MX2, in water is: 4×10–12. The

concentration of M2+ ions in the aqueous solution of the salt is: [AIEEE-2005]
(A) 1.0 × 10−4 M (B) 2.0 × 10−6 M (C) 4.0 × 10−10 M (D) 1.6 × 10−4 M

7. What is the conjugate base of OH– ? [AIEEE-2005]

(A) 02− (B) O− (C) H2 O (D) O2

8. The first and second dissociation constants of an acid H2A are 1.0×10–5 and 5.0×10–10

respectively. the overall dissociation constant of the acid will be [AIEEE-2007]

(A) 0.2 × 105 (B) 5.0 × 10−5 (C) 5.0 × 1015 (D) 5.0 × 10−15

9. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffer solution of HA in which 50%

of the acid is ionised is [AIEEE-2007]

() 7.0 () 4.5 (C) 2.5 (D) 9.5

APNI KAKSHA 32
(Physical Chemistry) IONIC EQUILIBRIUM

10. In a saturated solution of the sparingly soluble strong electrolyte AglO3 (molecular mass = 283)

the equilibrium which sets in is: [AIEEE-2007]

AglO3 Ag(+aq ) + IO3−( aq )

If the solubility product constant Ksp of AgIO3 at a given temperature is 1.0×10–8, what is the

mass of AgIO3 contained in 100 ml of its saturated solution?

(A) 28.3 × 10−2 g (B) 2.83 × 10−3 g (C) 1.0 × 10−7 g (D) 1.0 × 10−4 g

11. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous

solution of the corresponding salt. BA, will be: [AIEEE-2008]

() 9.58 () 4.79 (C) 7.01 (D) 9.22

–4
12. Solid Ba(NO3)2 is gradually dissolved in a 1.0×10 M Na2CO3 solution. At what concentration
2+ –9
of Ba will a precipitate begin to form?(KSP for Ba CO3 = 5.1×10 ) [AIEEE-2009]

() 8.1×10–8 M () 8.1×10–7 M (C) 4.1×10–5 M (D) 5.1×10–5 M

13. Solubility product of silver bromide is 5.0×10–13. The quantity of potassium bromide (molar

mass taken as 120 g mol–1) to be added to 1 litre of 0.05 M solution of silver nitrate to start the
precipitation of AgBr is: [AIEEE–2010]

() 5.0×10–8 g () 1.2×10–10 g (C) 1.2×10–9 g (D) 6.2×10–5 g

14. In aqueous solution the ionization constants for carbonic acid are [AIEEE–2010]

K1 = 4.2×10–7 and K2 = 4.8×10–11

Select the correct statement for a saturated 0.034 M solution of the carbonic acid:

() The concentration of H+ is double that of CO32–

() The concentration of CO32– is 0.034 M

(C) The concentration of CO32– is greater than that of HCO3–

(D) The concentrations of H+ and HCO3– are approximately equal

APNI KAKSHA 33
(Physical Chemistry) IONIC EQUILIBRIUM
15. At 25° C, the solubility producct of Mg(OH)2 is 1.0×10–11. At which pH, will Mg2+ ions start

precipitating in the form of Mg(OH)2 from a solution of 0.001 M Mg2+ ions ? [AIEEE–2010]

() 8 () 9 (C) 10 (D) 11

16. Three reactions involving H2PO4– are given below: [AIEEE-2010]

(i) H3PO4 + H2O H3O+ + H2PO4– (ii) H2PO4– + H2O HPO42– + H3O+

(iii) H2PO4– + OH– H3PO4 + O2–

In which of the above does H2PO4– act as an acid?

() (ii) only () (i) and (ii) (C) (iii) only (D) (i) only

17. The Ksp for Cr(OH)3 is 1.6×10–30. The molar solubility of this compound in water is:

[AIEEE–2011]

() 2 1.6 10−30 () 4 1.6 10−30 (C) 4 1.6 10−30 / 27 (D) 1.6×10–30/27

18. An acid HA ionises as

HA H+ + A–

The pH of 1.0 M solution is 5. Its dissociation constant would be: [AIEEE–2011]

() 1×10–10 () 5 (C) 5×10–8 (D) 1×10–5

19. If Ksp of CaF2 at 25ºC is 1.7×10–10, the combination amongst the following which gives a

precipitate of CaF2 is: [JEE-MAIN(online)–2012]

() 1×10–2 M Ca2+ and 1×10–5 M F– () 1×10–4 M Ca2+ and 1×10–4 M F–

(C) 1×10–3 M Ca2+ and 1×10–5 M F– (D) 1×10–2 M Ca2+ and 1×10–3 M F–
20. The pH of a 0.1 molar solution of the acid HQ is 3. The value of the ionization constant, Ka of
this acid is: [AIEEE–2012]

() 1×10–7 () 3×10–7 (C) 1×10–3 (D) 1×10–5

21. Solid Ba(NO3)2 is gradually dissolved in a 1.0×10–4 M Na2CO3 solution. At which

concentration of Ba2+, precipitate of BaCO3 begins to form?

(Ksp for BaCO3 = 5.1×10–9) [JEE-MAIN(Online)–2013]

() 5.1×10–5 M () 8.1×10–7M (C) 4.1×10–5 M (D) 7.1×10–8M

APNI KAKSHA 34
(Physical Chemistry) IONIC EQUILIBRIUM
22. NaOH is a strong base. What will be pH of 5.0×10–2M NaOH solution? (log2 = 0.3)
[JEE-MAIN(Online)–2013]
() 13.70 () 13.00 (C) 14.00 (D) 12.70

23. Which one of the following arrangements represents the correct order of solubilities of
sparingly soluble salts Hg2Cl2, Cr2(SO4)3, BaSO4 and CrCl3 respectively ?

[JEE-MAIN(Online)–2013]
1 1 1 1 1 1
1
 K sp  3  K sp  8  K sp  4  K 3  K sp  4  K sp  3
() ( K sp )
1
()   , (
 , K sp ) 2 ,  2 ,  sp  ,   ,  
 4   108   27   4   27   108 
1 1 1 1 1 1
1 1
 K sp  3  K sp  4  K sp  3  K sp  3  K sp  4  K sp  3
(C) ( K sp ) ,
2
  ,   ,   (D)   ,   , ( K sp ) ,2
 
 108   27   4   108   27   4 

24. What would be the pH of a solution obtained by mixing 5 g of acetic acid and 7.5 g of sodium
acetate and making the volume equal to 500 mL? [JEE-MAIN(Online)–2013]

(Ka = 1.75×10–5, pKa = 4.76)

() 4.76 < pH < 5.0
() pH < 4.70
(C) pH of solution will be equal to pH of acetic acid
(D) pH = 4.70

25. How many litres of water must be added to 1 litre of an aqueous solution of HCl with a pH of 1
to create an aqueous solution with pH of 2 ? [JEE-MAIN(Online)–2013]
() 0.1 L () 0.9 L (C) 2.0 L (D) 9.0 L

26. In some solutions, the concentration of H3O+ remains constant even when small amounts of

strong acid or strong base are added to them. These solutions are known as:
[JEE-MAIN(Online)–2014]
() Colloidal solutions () True solutions (C) Ideal solutions (D) Buffer solutions

APNI KAKSHA 35
(Physical Chemistry) IONIC EQUILIBRIUM
27. Zirconium phosphate [Zr3(PO4)4] dissociates into three zirconium cations of charge +4 and

four phosphate anions of charge –3. If molar solubility of zirconium phosphate is denoted by S
and its solubility product by Ksp then which of the following relationship between S and Ksp is

correct? [JEE-MAIN(Online)–2014]

() S = {Ksp/144}1/7 () S = {Ksp/(6912)1/7}

(C) S = (Ksp/6912)1/7 (D) S = {Ksp/6912}7

28. pKa of a weak acid (HA) and pKb of a weak base (BOH) are 3.2 and 3.4, respectively. The pH of

their salt (AB) solution is [JEE-MAIN–2017]

() 7.2 () 6.9 (C) 7.0 (D) 1.0

29. An alkali is titrated against an acid with methyl orange as indicator, which of the following is a
correct combination? [JEE-MAIN–2018]
Base Acid End Point
() Strong Strong Pink to colourless
() Weak Strong Colourless to pink
(C) Strong Strong Pinkish red to yellow
(D) Weak Strong Yellow to Pinkish red

30. An aqueous solution contains an unknown concentration of Ba2+. When 50 mL of a 1 M

solution of Na2 SO4 is added, BaSO4 just begins to precipitate. The final volume is 500mL. The

solubility product of BaSO4 is 1×10–10. What is the original concentration of Ba2+?

[JEE-MAIN–2018]

() 1.0×10–10 M () 5×10 –9 M (C) 2 ×10–9 M (D) 1.1 ×10 –9 M

31. An aqueous solution contains 0.10 M H2S and 0.20 M HCl. If the equilibrium constants for the

formation of HS– from H2S is 1.0×10–7 and that S2– from HS– ions is 1.2×10–13 then the

concentration of S2– ions in aqueous solution is [JEE-MAIN–2018]

() 5×10–19 () 5×10–8 (C) 3×10–20 (D) 6×10–21

APNI KAKSHA 36
(Physical Chemistry) IONIC EQUILIBRIUM
32. Which of the following salts is the most basic in aqueous solution? [JEE-MAIN–2018]
() Pb(CH3COO)2 () Al(CN)3 (C) CH3COOK (D) FeCl3

33. The minimum volume of water required to dissolve 0.1 g lead (II) chloride to get a saturated

solution (Ksp of PbCl2 = 3.2×10–8; atomic mass of Pb = 207 u ) is: [JEE Main-2018 Online]

() 0.36 L () 0.18 L (C) 17.98 L (D)1.798 L

34. Following four solutions are prepared by mixing different volumes of NaOH and HCl of different
concentrations, pH of which one of them will be equal to 1? [JEE Main-2018 Online]
M M M M
() 75mL HCl + 25mL NaOH () 100mL HCl + 100mL NaOH
5 5 10 10
M M M M
(C) 55 HCl + 40mL NaOH (D) 60mL HCl + 40mL NaOH
10 10 10 10

35. 20 mL of 0.1 M H2SO4 solution is added to 30 mL of 0.2 M NH4OH solution. The pH of the

resultant mixture is: [pkb of NH4OH = 4.7]. [JEE Main-2019 (Jan)]

() 9.4 () 5.0 (C) 9.0 (D) 5.2

36. A mixture of 100m mol of Ca(OH)2 and 2g of sodium sulphate was dissolved in water and the

volume was made up to 100 mL. The mass of calcium sulphate formed and the concentration of

OH– in resulting solution, respectively, are: (Molar mass of Ca(OH)2, Na2SO4 and CaSO4 are 74,

143 and 136 g mol–1, respectively; Ksp of Ca(OH)2 is 5.5×10–6) × [JEE Main-2019 (Jan)]

() 13.6 g, 0.14 mol L–1 () 1.9 g, 0.14 mol L–1

(C) 1.9 g, 0.28 mol L–1 (D) 13.6 g, 0.28 mol L–1

37. If Ksp of Ag2CO3 is 8×10–12, the molar solubility of Ag2CO3 in 0.1M AgNO3 is:

[JEE Main-2019 (Jan)]

() 8×10–10 M () 8 ×10–13 M

(C) 8×10–12 M (D) 8×10–11 M

APNI KAKSHA 37
(Physical Chemistry) IONIC EQUILIBRIUM
38. If solubility product of Zr3 (PO4)4 is denoted by Ksp and its molar solubility is denoted by S,

then which of the following relation between A and Ksp is correct? [JEE Main-2019 (Apr)]
1 1 1 1
 K sp  7  K sp  6  K sp  9  K sp  7
() S =   () S =   (C) S =   (D) S =  
 6912   144   929   216 

39. In an acid-base titration, 0.1 M HCl solution was added to the NaOH solution of unknown
strength. Which of the following correctly shows the change of pH of the titration mixture in
this experiment? [JEE Main-2019 (Apr)]

(A) (B) (C) (D)

() D () A (C) C (D) B

40. Consider the following statements [JEE Main-2019 (Apr)]

(a) The pH of a mixture containing 400 mL of 0.1 M H2SO4 and 400 mL of 0.1 M NaOH will be

approximately 1.3.
(b) Ionic product of water is temperature dependent.

(c) A monobasic acid with Ka = 10–5 has a pH = 5. The degree of dissociation of this acid is

50%.
(d) The Le Chatelier’s principle is not applicable to common-ion effect.
The correct statements are:
() (a), (b) and (c) () (a) and (b) (C) (b) and (c) (D) (a), (b) and (d)

41. The pH of a 0.02 M NH4Cl solution will be [given Kb(NH4OH) = 10–5 and log 2 = 0.301]

[JEE Main-2019 (Apr)]

() 5.35 () 4.65 (C) 4.35 (D) 2.65
42. What is the molar solubility of Al(OH)3 in 0.2 M NaOH solution? Given that, solubility product

of Al(OH)3 = 2.4×10–24: [JEE Main-2019 (Apr)]

() 12×10–23 () 3×10–22 (C) 12×10–21 (D) 3×10–19

APNI KAKSHA 38
(Physical Chemistry) IONIC EQUILIBRIUM
43. The molar solubility of Cd(OH)2 is 1.84×10–5 M in water. The expected solubility of Cd(OH)2 in a

buffer solution of pH = 12 is: [JEE Main-2019 (Apr)]

() 6.23×10–11 M () 2.49×10–10 M (C) 1.84×10–9 M (D) 10–9 M

44. Arrange the following solutions in the decreasing order of pOH: [Jee Main, 2020]
(A) 0.01 M HCl (B) 0.01 M NaOH
(C) 0.01 M CH3COONa (D) 0.01 M NaCl
() (B) > (C) > (D) > (A) () (A) > (C) > (D) > (B)
(C) (B) > (D) > (C) > (A) (D) (A) > (D) > (C) > (B)

45. An acidic buffer is obtained on mixing : [Jee Main, 2020]

() 100 mL of 0.1 M HCl and 200 mL of 0.1 M NaCl
() 100 mL of 0.1 M HCl and 200 mL of 0.1 M CH3COONa
(C) 100 mL of 0.1 M CH3COOH and 100 mL of 0.1 M NaOH
(D) 100 mL of 0.1 M CH3COOH and 200 mL of 0.1 M NaOH

46. Given below are two statements. [JEE Main, August 2021]

Statement I: In the titration between strong acid and weak base methyl orange is suitable as
an indicator.
Statement II: For titration of acetic acid with NaOH phenolphthalein is not a suitable indicator.

In the light of the above statements, choose the most appropriate answer from the options
given below:
() Statement I is false but Statement II is true
() Statement I is true but Statement II is false
(C) Both Statement I and Statement II are true
(D) Both Statement I and Statement II are false

47. The solubility of Ca(OH)2 in water is: [JEE Main, Feb 2021]
[Given : The solubility product of Ca(OH)2 in water = 5.5 × 10–6]
() 1.77 × 10–6 () 1.11 × 10–6 (C) 1.11 × 10–2 (D) 1.77 × 10–2
48. When 35 mL of 0.15 M lead nitrate solution is mixed with 20 mL of 0.12 M chromic sulphate
solution, ________ × 10–5 moles of lead sulphate precipitate out. (Round off to the Nearest
Integer) [JEE Main, March 2021]

APNI KAKSHA 39
(Physical Chemistry) IONIC EQUILIBRIUM
49. The solubility of AgCN in a buffer solution of pH=3 is x. The value of x is: (Assume : No cyano
complex is formed; Ksp (AgCN) =2.2×10–16 and Ka(HCN) = 6.2×10–10]
[JEE Main, Feb 2021]
() 0.625 × 10–6 () 1.9 × 10–5
(C) 2.2 × 10–16 (D) 1.6 × 10–6

50. The number of moles of NH3, that must be added to 2 L of 0.80 M AgNO3 in order to reduce the
concentration of Ag+ ions to 5.0×10–8 M (Kformation for [Ag(NH3)2]+ =1.0× 108) is ________ .
(Nearest integer)
[Assume no volume change on adding NH3] [JEE Main, August 2021]

51. Ka for butyric acid (C3H7COOH) is 2 × 10–5. The pH of 0.2 M solution of butyric acid is _______ ×
10-1. (Nearest integer) [Given log 2 = 0.30] [JEE Main, July 2022]

52. 200 mL of 0.01 M HCl is mixed with 400 mL of 0.01M H2SO4. The pH of the mixture is __________.
[JEE Main, July 2022]
() 1.14 () 1.78 (C) 2.34 (D) 3.02
53. Class XII students were asked to prepare one litre of buffer solution of pH 8.26 by their
chemistry teacher. The amount of ammonium chloride to be dissolved by the student 1n 0.2 M
ammonia solution to make one litre of the buffer is [JEE Main, July 2022]
(Given pKb (NH3)=4.74; Molar mass of NH3=17g mol–1; Molar mass of NH4Cl= 53.5g mol–1)
() 53.5 g () 72.3 g (C) 107.0 g (D) 126.0 g

54. In base vs. Acid titration, at the end point methyl orange is present as [JEE Main, July 2022]
() quinonoid form () heterocyclic form(C) phenolic from (D) benzenoid form

55. The solubility of AgCl will be maximum in which of the following? [JEE Main, June 2022]
(A) 0.01 M KCl (B) 0.01 M HC1
(C) 0.01 M AgNO3 (D) De-ionised water

APNI KAKSHA 40
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE # JEE-ADVANCED
1. What will be the resultant pH when 200 ml of an aqueous solution of HCl (pH = 2.0) is mixed
with 300 ml of an aqueous solution of NaOH (pH = 12.0) ? [JEE 1998]

2. The solubility of Pb(OH)2 in water is 6.7×10–6M. Calculate the solubility of Pb(OH)2 in a buffer

solution of pH = 8. [JEE 1999]

3. A buffer solution can be prepared from a mixture of [JEE 1999]

(A) sodium acetate and acetic acid in water
(B) sodium acetate and hydrochloric acid in water
(C) ammonia and ammonium chloride in water
(D) ammonia and sodium hydroxide in water.

4. The pH of 0.1 M solution of the following salts increases in the order [JEE 1999]
(A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN

(C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl

5. The average concentration of SO2 in the atmosphere over a city on a certain day is 10 ppm,

when the average temperature is 298 K. Given that the solubility of SO2 in water at 298 K is

1.3653 moles litre–1 and the pKa of H2SO3 is 1.92, estimate the pH of rain on that day.

[JEE 2000]
6. An aqueous solution of 6.3 g oxalic acid dihydrate is made up to 250 mL. The volume of 0.1 N
NaOH required to completely neutralise 10 mL of this solution is [JEE 2001]
(A) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL

7. For sparingly soluble salt ApBq, the relationship of its solubility product (Ls) with its solubility
(S) is: [JEE 2001]

(A) Ls = Sp+q, pp. qq (B) Ls = Sp+q, pp. qp (C) Ls = Spq, pp. qq (D) Ls = Spq, (p.q)p+q

8. 500 ml of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25°C.
(a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the
solution.
(b) If 6 g of NaOH is added to the above solution, determine final pH. Assume there is no change

in volume on mixing. Ka of acetic acid is 1.75×10–5 M. [JEE 2002]

APNI KAKSHA 41
(Physical Chemistry) IONIC EQUILIBRIUM
9. Will the pH of water be same at 4°C and 25°C? Explain. [JEE 2003]

10. A solution which is 10–3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10–16M

sulphide ion. If Ksp, MnS, FeS, ZnS and HgS are 10–15, 10–23, 10–20 and 10–54 respectively,

which one will precipitate first? [JEE 2003]

(A) FeS (B) MnS (C) HgS (D) ZnS

11. HX is a weak acid (Ka = 10–5). It forms a salt NaX (0.1 M) on reacting with caustic soda. The

degree of hydrolysis of NaX is [JEE 2004]

(A) 0.01% (B) 0.0001% (C) 0.1% (D) 0.5%
12. 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point.

Given Ka(HA) = 5×10–6 and h << 1. [JEE 2004]

13. CH3NH2 (0.1 mole, Kb = 5×10–4) is added to 0.08 moles of HCl and the solution is diluted to

one litre, resulting hydrogen ion concentration is [JEE 2005]

(A) 1.6×10–11 (B) 8×10–11 (C) 5×10–5 (D) 2×10–2

14. The species present in solution when CO2 is dissolved in water: [JEE 2006]

(A) CO2, H2CO3, HCO32– (B) H2CO3, CO32–

(C) CO32– , HCO3– (D) CO2, H2CO3

15. Solubility product constants (KSP) of salts of types MX, MX2 and M3X at temperature 'T' are

4.0×10–8, 3.2 ×10–14 and 2.7 ×10–15, respectively. Solubilities (mol dm–3) of the salts at
temperature 'T' are in the order: [JEE 2008]
(A) MX > MX2 > M3X (B) M3X > MX2 > MX

(C) MX2 > M3X > MX (D) MX > M3X > MX2

M weak monoacidic base (Kb = 1×10–12 at 25°C) is titrated with M HCl in water
2 2
16. 2.5 mL of
5 15

at 25°C. The concentration of H+ at equivalence point is (Kw = 1×10–14 at 25°C)

[JEE 2008]

(A) 3.7×10–13 M (B) 3.2×10–7 M (C) 3.2×10–2 M (D) 2.7×10–2 M

APNI KAKSHA 42
(Physical Chemistry) IONIC EQUILIBRIUM
17. The dissociation constant of a substituted benzoic acid at 25°C is 1.0×10–4. The pH of a 0.01 M
solution of its sodium salt is [JEE 2009]

18. Aqueous solutions of HNO3, KOH, CH3COOH and CH3COONa of identical concentrations are

provided. The pair(s) of solutions which form a buffer upon mixing is(are) – [JEE -2010]
(A) HNO3 and CH3COOH (B) KOH and CH3COONa

(C) HNO3 and CH3COONa (D) CH3COOH and CH3COONa

19. In 1 L saturated solution of AgCl [Ksp(AgCl) = 1.6×10–10], 0.1 mol of CuCl

[Ksp(CuCl)=1.0×10–6] is added. The resultant concentration of Ag+ in the solution is 1.6×10–x.

The value of ‘x’ is. [JEE -2011]

20. The Ksp of Ag2CrO4 is 1.1×10–12 at 298 K. The solubility (in mol/L) of Ag2 CrO4 in a 0.1 M

AgNO3 solution is (Kw = 1×10–14 at 25°C) [JEE 2013]

(A) 1.1×10–11 (B) 1.1×10–10 (C) 1.1×10–12 (D) 1.1×10–9

21. The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100th of that
of a strong acid (HX, 1M), at 25ºC. The Ka of HA is [JEE 2013]

(A) 1×10–4 (B) 1×10–5 (C) 1×10–6 (D) 1×10–3

Paragraph For Questions 22 and 23

When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH in an insulated beaker at
constant pressure, a temperature increase of 5.7 ºC was measured for the beaker and its
contents. (Expt-1). Because the enthalpy of neutralisation of a strong acid with a strong base is

a constant (–57.0 kJmol–1), this experiment could be used to measure the calorimeter constant.

In a second experiment (Expt-2), 100 mL of 2.0 M acetic acid (Ka = 2.0×10–5) was mixed with

100 mL of 1.0M NaOH (under identical conditions to (Expt-1)) where a temperature rise of 5.6
ºC was measured.

(Consider heat capacity of all solutions as 4.2 Jg–1K–1 and density of all solutions as 1.0 g mL–
1)

APNI KAKSHA 43
(Physical Chemistry) IONIC EQUILIBRIUM
22. Enthalpy of dissociation (in kJ mol–1) of acetic acid obtained from the Expt-2 is

(Kw = 1×10–14 at 25°C) [JEE 2015]

(A) 1.0 (B) 10.0 (C) 24.5 (D) 51.4

23. The pH of the solution after Expt-2 [JEE 2015]

(A) 2.8 (B) 4.7 (C) 5.0 (D) 7.0

24. The solubility of a salt of weak acid (AB) at pH 3 is Y ×10–3 mol L–1. The value of Y is ____.

(Given that the value of solubility product of AB (Ksp) = 2×10–10 and the value of ionization
–8
constant of HB (Ka) = 1× 10 [JEE 2018]

25. Dilution processes of different aqueous solutions, with water, are given in LIST-I. The effects of

dilution of the solutions on [H+] are given in LIST-II.

(Note: Degree of dissociation (a) of weak acid and weak base is << 1; degree of hydrolysis of

salt <<1; [H+] represents the concentration of H+ ions) [JEE Advance 2018]
LIST-I LIST-II

(P) (10 mL of 0.1 M NaOH + 20 mL of (1) the value of [H+] does not change
0.1 M acetic acid) diluted to 60 mL on dilution

(Q). (20 mL of 0.1 M NaOH + 20 mL of (2) the value of [H+] changes to half
0.1 M acetic acid) diluted to 80 mL of its initial value on dilution

(R) (20 mL of 0.1 M HCl + 20 mL of (3) the value of [H+] changes to two
0.1 M ammonia solution) diluted to 80 mL times of its initial value on dilution
1
(S) 10 mL saturated solution of Ni(OH)2 in (4) the value of [H+] changes to
2
equilibrium with excess solid Ni(OH)2 is times of its initial value on dilution

diluted to 20 mL (solid Ni(OH)2 is still

present after dilution). (5) the value of [H+] changes to 2

times of its initial value on
dilution
Match each process given in LIST-I with one or more effect(s) in LIST-II. The correct option is
(A) P → 4; Q → 2; R → 3; S → 1 (B) P → 4; Q → 3; R → 2; S → 3
(C) P → 1; Q → 4; R → 5; S → 3 (D) P → 1; Q → 5; R → 4; S → 1

APNI KAKSHA 44
(Physical Chemistry) IONIC EQUILIBRIUM
26. A solution of 0.1M weak base (B) is titrated with 0.1M of a strong acid (HA). The variation of pH
of the solution with the volume of HA added is shown in the figure below. What is the pK b of
the base? The neutralization reaction is given by [JEE Advance 2020]
B + HA &rarr; BH + + A− .

27. An acidified solution of 0.05MZn2+ is saturated with 0.1MH2 S. What is the minimum
molar concentration (M) of H + required to prevent the precipitation of ZnS ?
Use K sp (ZnS) = 1.25 × 10−22 and overall dissociation constant of H2 S,
K NET = K1 K 2 = 1 × 10−21 . [JEE Advance 2020]
28. A solution is prepared by mixing 0.01 mol each of H2 CO3 , NaHCO3 , Na2 CO3 , and NaOH in
100 mL of water. pH of the resulting solution is
[GivenpK a1 and pK a2
of H2 CO3 are 6.37 and 10.32 , respectively; log⁡ 2 = 0.30 ] [JEE Advance 2022]
29. Concentration of H2 SO4 and Na2 SO4 in a solution is 1M and 1.8 × 10−2 M, respectively. Molar
solubility of PbSO4 in the same solution is X × 10−Y M (expressed in scientific notation). The
value of Y is
[Given: Solubility product of PbSO4 (𝐾𝑠𝑝 ) = 1.6 × 10−8 . For H2 SO4 , 𝐾𝑎1 is very large and 𝐾𝑎2 =
1.2 × 10−2 ]

30. On decreasing the pH from 7 to 2 , the solubility of a sparingly soluble salt (MX) of a weak acid
(HX) increased from 10−4 mol L−1 to 10−3 mol L−1. The pK a of HX is
[JEE Advance 2023]
(A)3 (B)4 (C)5 (D) 2

APNI KAKSHA 45
(Physical Chemistry) IONIC EQUILIBRIUM
ANSWER KEY
EXERCISE # O-I
1. (D) 2. (D) 3. (C) 4. (D) 5. (C) 6. (B) 7. (C)
8. (B) 9. (B) 10. (B) 11. (C) 12. (D) 13. (B) 14. (D)
15. (A) 16. (D) 17. (A) 18. (D) 19. (A) 20. (D) 21. (A)
22. (A) 23. (B) 24. (C) 25. (B) 26. (C) 27. (C) 28. (C)
29. (B) 30. (C) 31. (A) 32. (B) 33. (C) 34. (C) 35. (A)
36. (B) 37. (C) 38. (C) 39. (C) 40. (B) 41. (A) 42. (D)
43. (B) 44. (C) 45. (A) 46. (A) 47. (D) 48. (D) 49. (C)
50. (B) 51. (B) 52. (A) 53. (A) 54. (A) 55. (B) 56. (B)
57. (D) 58. (D) 59. (C) 60. (C) 61. (D) 62. (A) 63. (A)
64. (A) 65. (A) 66. (C) 67. (A) 68. (A) 69. (A) 70. (A)
71. (A) 72. (C) 73. (D) 74. (C) 75. (C) 76. (D) 77. (D)
78. (A) 79. (D) 80. (C) 81. (D) 82. (D) 83. (C) 84. (A)
85. (D) 86. (A) 87. (B) 88. (C) 89. (B) 90. (A) 91. (B)
92. (C) 93. (D) 94. (D) 95. (C) 96. (C) 97. (D) 98. (B)
99. (A)

EXERCISE # S-I

1. 6.022 × 107 2. (i) 6.53 ; (ii) (a) Basic , (b) Acidic 3. K w = 4 × 10−14 , pH = 6.7
4. 600 ions /mm3 5. (a) + 1, (b) 9 (c) 11.30 (d) 6.97, (e)7,
6. 7 7. 2.32×10–8 M 8. (b) 2.87, (c) 11.13 (f) 6.78, (g) 6.97

9. (a) K a = 10−8 , (b) Kb = 10−6 10. 10 11. 170.14

12. 1.1×10–3 M 13. 1.11 × 10−4 14. 4.87

15. 3 16. 2.61 17. 9×10–5 M
18. [H + ] = 1.75 × 10−2 M, [CHCl2 COO− ] = 0.75 × 10−2 M
19. [H + ] = 10−3 M, [CH3 COO− ] = 3.6 × 10−4 M, [C7 H5 O− −4
2 ] = 6.4 × 10 M

20. 0.027M, 0.073M, 0.027M, 10−5 M

21. [H + ] = [H2 PO− −3 2− −8 3−
4 ] = 2.7 × 10 , [HPO4 ] = 10 , [PO4 ] = 3.7 × 10
−19

22. [H+] = 0.209M

[SO42–] = 0.009 M
[HSO4–] = 0.191 M

APNI KAKSHA 46
(Physical Chemistry) IONIC EQUILIBRIUM
23. pH = 11.46, [enH22+ ] = 7.1 × 10−8 M
24. (a) Basic (b) acidic (c) basic (d) basic (e) acidic (f) basic
(g) neutral (h) basic (i) basic (j) acidic
25. 2.5 × 10−5 ; 4.6
26. (i) 10−12, (ii) 10−6, (iii) 10−11 , (iv) K b1 < K b2 < K b3
27. [OH − ] = 6.664 × 10−6
28. pH = 4.477
29. K b = 6.25 × 10−10
30. 1.66 %
31. pH = 10.43
32. [OH − ] = 3.73 × 10−2 M, [H3 PO4 ] = 6 × 10−18 M
33. 4.19
34. 10−6 ; 10−8
35. (a) 6, (b) 1 × 10−5
36. 0.56%, pH = 7
37. 8.34
38. 4.19
39. [OH − ] = 9.0 × 10−6
40. 0.05 mol
41. (a) pH = 9.239 (b) lowered (c) pH = 4.699
42. pH = 9.26; (a) pH = 9.74;
43. (a) 13 ; (b) 7 ; (c) 1.3.
44. 3
45. 4.74
46. 9.56
47. 8.7782
48. 9.7324
49. 10−5 ⁡M
50. 8.71, [H3 O+ ] = 1.95 × 10−9 M
51. 4.98,1.05 × 10−5 M
52. (i) 2.85, (ii) 4.0969, (iii) 4.5229, (iv) 4.699, (v) 5.301, (vi) 8.699
53. [HI𝑛 ] = 28.57%
54. ΔpH = 0.954
55. 85.71%

APNI KAKSHA 47
(Physical Chemistry) IONIC EQUILIBRIUM
56. (b), (c)
57. one with pKIn = 5.22 , methyl orange
58. (018)
59. 1.0 × 10−5 mol/lit
60. 1.56 × 10−8
61. 3.4 × 10−11
62. 2.6 × 10−16
63. QX2 is more soluble
64. [Cu+ ] = 5 × 10−11 M
65. 5 × 10−10 M
66. 4 × 10−7 mol/LAgBr, 9 × 10−7 mol/LAgSCN
67. [F − ] = 3 × 10−3 M
68. (a) no precipitation will occur, (b) a precipitate will form
69. 1
70. (9 × 10–4) ; OMR ANS (9)
71. 12 mg
72. 4.9×10–10
73. 69K d = 1/K f = 4.8 × 10−4 Q. 700.444M
74. 2.82 × 10–3 mole
75. (d) > (c) > (b) > (a)

EXERCISE # O - II
1. (ABC) 2. (ABCD) 3. (A,B,D) 4. (A,D) 5. (A,B) 6. (A,B,C)
7. (A) 8. (ABC) 9. (ABCD) 10. (B) 11. (A) 12. (C)
13. (C) 14. (B) 15. (A) 16. (C) 17. (A) 18. (A)
19. (C) 20. (D) 21. (A)→R; (B)→P; (C)→Q; (D)→S
22. (A)-Q, (B)-P,S, (C)-R, (D)-T

APNI KAKSHA 48
(Physical Chemistry) IONIC EQUILIBRIUM
EXERCISE: S-II
1. [S 2− ] = 2.5 × 10−15
2. 10.07
3. 8.35, 9.60, 4.66
4. (a) 2.12 (b) 4.66 (c) 7.2 (d) 12
5. (a) 4.7525 (b) 4.697, (c) 4.798
(d) 1.134 % on acid addition 0.96 % on base addition.
6. K b = 1.8 × 10−5 , 5.27
7. pH = 7.3; pH = 7.898, pH = 7.29
8. 3.3 × 10−2
9. (5.21)

8y 3
10. [F–] =
x
11. 0.444 M
[H+ ] [H+ ]2
12. s = √K sp (1 + +K )
K2 1 K2

EXERCISE # JEE-MAINS
1. (C) 2. (C) 3 (D) 4. (D) 5. (C) 6. (A) 7. (A)
8. (D) 9. (D) 10. (B) 11. (C) 12. (D) 13. (C) 14. (D)
15. (C) 16. (A) 17. (C) 18. (A) 19. (D) 20. (D) 21. (A)
22 (D) 23. (A) 24. (A) 25. (D) 26. (D) 27. (C) 28. (B)
29. (D) 30. (D) 31. (C) 32. (C) 33. (B) 34. (A) 35. (C)
36. (C) 37. (A) 38. (A) 39. (B) 40. (A) 41. (A) 42. (B)
43. (B) 44. (D) 45. (B) 46. (B) 47. (C) 48. (525) 49. (B)
50. (4) 51. (27) 52. (2) 53. (C) 54. (A) 55. (D)
EXERCISE # JEE-ADVANCED
1. pH = 11.3010 2. s = 1.203 × 10–3M 3. (A, B, C)
4. (B) 5. pH = 4.86 6. (A) 7. (A)
8. (a) 0.0175% , (b) 4.757 9. No it will be > 7 10. (C) 11. (A)
12. pH = 9 13. (B) 14. (A) 15. (D)
16. (D) 17. (8) 18. (CD) 19. (7)
20. (A) 21. (A) 22. (A) 23. (B)
24. (4.47) 25. (D) 26. 3.3
27. [𝐇 + ] ≥ 𝟎. 𝟐 28. ∴ 𝐩𝐇 = 𝟏𝟎. 𝟎𝟐29. 𝐘 = 𝟔 30. (B)

APNI KAKSHA 49
(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 50
(Physical Chemistry) IONIC EQUILIBRIUM
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 51
(Physical Chemistry) IONIC EQUILIBRIUM
[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 52
(Physical Chemistry) IONIC EQUILIBRIUM
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 53
(Physical Chemistry) IONIC EQUILIBRIUM
% 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

[NH 3 ] 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 54
(Physical Chemistry) IONIC EQUILIBRIUM
[CH3COO – ]
45. pH = pKa + log
[CH3COOH]
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 55
(Physical Chemistry) IONIC EQUILIBRIUM
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 56
(Physical Chemistry) IONIC EQUILIBRIUM
(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 57
(Physical Chemistry) IONIC EQUILIBRIUM
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 58
(Physical Chemistry) IONIC EQUILIBRIUM
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 59
(Physical Chemistry) IONIC EQUILIBRIUM
 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 + s 2

ZnCO3 → Zn 2+ + CO32−
s2 s 2 + 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 60
(Physical Chemistry) IONIC EQUILIBRIUM
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 61
(Physical Chemistry) IONIC EQUILIBRIUM
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)
K v / Ka

S–x x x

Kw x2 10 −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 62
(Physical Chemistry) IONIC EQUILIBRIUM
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  =  NH +4  = 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 63
(Physical Chemistry) IONIC EQUILIBRIUM
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 64
(Physical Chemistry) IONIC EQUILIBRIUM
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 65
(Physical Chemistry) IONIC EQUILIBRIUM
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 C2  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 66
(Physical Chemistry) IONIC EQUILIBRIUM
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 67
(Physical Chemistry) IONIC EQUILIBRIUM
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 H5O2−  10−3
6.4×10–5 =
0.01 − 10−3
C7 H 5O 2−  = 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 42−

x–y x+y y
(x + y)(x − y)
10–2 =
0.1 − x

APNI KAKSHA 68
(Physical Chemistry) IONIC EQUILIBRIUM
(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 42− ] = 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+ + PO34−

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 69
(Physical Chemistry) IONIC EQUILIBRIUM
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

[ PO34− ] = 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 70
(Physical Chemistry) IONIC EQUILIBRIUM
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–, SO32 − )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+ + PO34−

(i) Dissociation constant of HPO24− = Ka3 = 10−12

(ii) Ka H 2 PO −4 ×Kb HPO −42 = Kw

−2 10 −14
Kb HPO = = 10–6
10 −8
4

(iii) KaH3PO4 ×Kb H 2 PO −4 = Kw

10 −14
Kb H 2 PO −4 = = 10–11
10 −3
Kw 10 −14
(iv) Kb PO34− = = −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 71
(Physical Chemistry) IONIC EQUILIBRIUM
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 ⎯⎯
→ C6 H5OH+ OH−

10–3–x x x

APNI KAKSHA 72
(Physical Chemistry) IONIC EQUILIBRIUM
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. PuO22+ + H2O ⎯→ PuO2OH+ + H+

APNI KAKSHA 73
(Physical Chemistry) IONIC EQUILIBRIUM
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 74
(Physical Chemistry) IONIC EQUILIBRIUM
[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 H5 NH + ]
(c) pOH = pKb + log
[C5 H5 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 75
(Physical Chemistry) IONIC EQUILIBRIUM
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 76
(Physical Chemistry) IONIC EQUILIBRIUM
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 77
(Physical Chemistry) IONIC EQUILIBRIUM
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 78
(Physical Chemistry) IONIC EQUILIBRIUM
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 79
(Physical Chemistry) IONIC EQUILIBRIUM
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 80
(Physical Chemistry) IONIC EQUILIBRIUM
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 = −6
= 4×10–7 M
1.6 10
APNI KAKSHA 81
(Physical Chemistry) IONIC EQUILIBRIUM

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 82
(Physical Chemistry) IONIC EQUILIBRIUM

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+ + CO 32 −

7×10–5
BaCO3 ⎯→ Ba2+ + CO 32 −

7×10–5
10−5  [CO32− ] 5 10−10
=
7 10−5  0.1 [CO32− ] K sp (BaC O3 )

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 + + 2NH 3 ⎯⎯
→ Ag(NH 3 ) 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 83
(Physical Chemistry) IONIC EQUILIBRIUM
75. (a) [Ag+] = 10–2 (b) [CO32− ] = 4×10–2 (d) CO 32 − + 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 84
(Physical Chemistry) IONIC EQUILIBRIUM
[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 85
(Physical Chemistry) IONIC EQUILIBRIUM

Qip < ksp (ppt does not take place)

10 –10 10 –10 1
(D) Qip =  = × 10–20
2 2 4

Qip < ksp (ppt does not take place)

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.
CH3COO– + H2O ⎯→ CH3COOH + OH–
(D) TRUE

10. In original solution

[H+] = Ka  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 86
(Physical Chemistry) IONIC EQUILIBRIUM
[CH3COO− ][H + ] x.x
Ka = =
[CH3COOH] (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
K a1 Ka2
p
pH at II equivalence point = =6
2
p =4
Ka1

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 87
(Physical Chemistry) IONIC EQUILIBRIUM
= 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 a 2 C 2 = 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 88
(Physical Chemistry) IONIC EQUILIBRIUM
(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
[HCO3– ]
(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 89
(Physical Chemistry) IONIC EQUILIBRIUM
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)+ H 2O 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 90
(Physical Chemistry) IONIC EQUILIBRIUM
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 ⎯⎯

→ NaH2PO4 + H2O

6 3 0 (initial mmoles)
3 0 3 (equilibrium mmoles)

pH = pka1 = 3 – log 7.5= 2.12

(b) H3PO4 + NaOH ⎯⎯

→ NaH2PO4 + H2O

6 6 0 (initial mmoles)
0 0 6 (equilibrium mmoles)

pka 2 + pka1 7.2 + 2.12

pH = = = 4.66
2 2
(c) H3PO4 + NaOH ⎯⎯
→ NaH2PO4 + H2O

4.8 7.2 0 (initial mmoles)

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

4.8 2.4 0 (initial mmoles)

2.4 0 2.4 (equilibrium mmoles)

pH = pka2 = 7.2

APNI KAKSHA 91
(Physical Chemistry) IONIC EQUILIBRIUM
(d) H3PO4 + NaOH ⎯⎯
→ NaH2PO4 + H2O

4 10 0 (initial mmoles)
0 6 4 (equilibrium mmoles)
NaH2 PO4 + NaOH ⎯⎯
→ Na 2HPO4 + H2O

4 6 0 (initial mmoles)
0 2 4 (equilibrium mmoles)
NaHPO4 + NaOH ⎯⎯
→ Na 3PO4 + H2O

4 2 0 (initial mmoles)
2 0 2 (equilibrium mmoles)

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 92
(Physical Chemistry) IONIC EQUILIBRIUM
% 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 93
(Physical Chemistry) IONIC EQUILIBRIUM
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 94
(Physical Chemistry) IONIC EQUILIBRIUM
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 + + 
 k 2 k1k 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 95
(Physical Chemistry) IONIC EQUILIBRIUM
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

13. For pptn to start

Ksp = Qip

APNI KAKSHA 96
(Physical Chemistry) IONIC EQUILIBRIUM
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 97
(Physical Chemistry) IONIC EQUILIBRIUM

20. HQ ⎯→ H+ + Q– pH = 3
0.1 – x x x [H+] = 10–3
10−3 10−3
Ka = = 10–5
0.1

21. For pptn to start

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 98
(Physical Chemistry) IONIC EQUILIBRIUM
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 99
(Physical Chemistry) IONIC EQUILIBRIUM
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 4OH] 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 100

(Physical Chemistry) IONIC EQUILIBRIUM

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 101

(Physical Chemistry) IONIC EQUILIBRIUM
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) + H2 O(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 102

(Physical Chemistry) IONIC EQUILIBRIUM
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 103

(Physical Chemistry) IONIC EQUILIBRIUM
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 104

(Physical Chemistry) IONIC EQUILIBRIUM
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
106
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 105

(Physical Chemistry) IONIC EQUILIBRIUM
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 106

(Physical Chemistry) IONIC EQUILIBRIUM

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
[CH 3 NH 2 ]
[OH–] = Kb×
[CH 3 NH 3+ ]

0.02 5
= 5×10–4 × = ×10–4
0.08 4
Kw 
[H+] = −
= ×10–10 = 8×10–11 M
[OH ] 5

APNI KAKSHA 107

(Physical Chemistry) IONIC EQUILIBRIUM
14. CO2 + H2O ⎯→ HCO3− + H+

HCO3− ⎯→ CO 32 − + 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 108

(Physical Chemistry) IONIC EQUILIBRIUM
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 109

(Physical Chemistry) IONIC EQUILIBRIUM

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 -
CH3COO– + H2O ⎯→ CH3COOH + OH–

K w  Ka
CH+ =
C
1
[H+] 
C

APNI KAKSHA 110

(Physical Chemistry) IONIC EQUILIBRIUM
(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 111

(Physical Chemistry) IONIC EQUILIBRIUM
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 112

(Physical Chemistry) IONIC EQUILIBRIUM
∴ 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 113

(Physical Chemistry) IONIC EQUILIBRIUM
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 114