Ionic Equilibrium

1. When dissolved in aqueous solution, Al3+ forms a complex of coordination number six with
water that can undergo dissociation according to the following equation :
 [Al(OH2)5 (OH)]2+(aq) + H3O+(aq) Ka = 1.0 × 10–5
Al(OH2)63+(aq) + H2O(l) 
If the initial concentration of Al(OH2)63+ is 0.10 mol L–1, what is the approximate pH of the
solution ? [Ionic Equilibrium (M)]
(A) 1.00 (B) 3.00 (C) 4.00 (D) 5.00
Ans. (B)
x2
Sol. Ka = 10–5 =
0.1 – x
 x << 0.1

 x = 10–3 = [H+]
 pH = 3

2. H2CO3 is diprotic acid for which K1 = 1.0 × 10–7 and K2 = 1.0 × 10–11. Which solution will
produce a pH closest to 9 ? [Ionic Equilibrium (M)]
(1) 0.1 M H2CO3 (2) 0.1 M Na2CO3
(3) 0.1 M NaHCO3 (4) 0.1 M NaHCO3 and 0.1 M Na2CO3
Ans. (3)

Sol. (A) [H+] = c Ka 1 = 0.1  1.0 10 7 = 10–4 M

1
(B) pH = [pK w  pKa2  logc] = 12
2
1
(C) pH = [pKa1  pKa2 ] = 9
2
[CO23 ]
(D) pH = pK a 2  log = 11
[HCO3 ]

3. If NH4Cl and KNH2 in liquid NH3 as solvent react with each other then select the correct
statement(s) among the following. [Ionic Equilibrium-M]
(A) NH4Cl acts as an acid and KNH2 acts as a base
(B) NH4Cl acts as a base and KNH2 acts as a acid
(C) The reaction of NH4+ and NH2– is neutralisation reaction
(D) The reaction of K+ and Cl– is neutralisation reaction
Ans. (A, C)

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 Answer Q.4, Q.5 and Q.6 by appropriately matching the information given in the three
columns of the following table [Ionic Equilibrium (T)]

Column-1 (Solution) Column-2 (pH) Column-3

100 ml, 0.2 M CH3COOH
pH does not change on
(I) +100 ml, 0.2 M NaOH (i) 8.5 (P)
moderate dilution
(Ka = 10–5)
100 ml, 0.1 M H2CO3
(II) +100 ml, 0.1 M NaOH (ii) 9 (Q) pH increase on dilution
(Ka1 = 10–7, Ka2 = 10–10)
100 ml, 0.2 M NH4OH
(III) +100 ml, 0.2 M HCl (iii) 8 (R) pH decrease on dilution
(Kb = 10–5)
100 ml, 0.1 M H3PO4
+150 ml, 0.1 M NaOH
(IV) (iv) 5 (S) Solution is acidic at 25ºC
(Ka1 = 10–3, Ka2 = 10–8,
Ka3 = 10–11)

4. Which of the following option is the only CORRECT combination ?

(A) (III) (iii) (P) (B) (IV) (i) (S) (C) (II) (iv) (P) (D) (I) (ii) (R)
Ans. (D)

5. Which of the following option is the only INCORRECT combination ?

(A) (III) (iv) (Q) (B) (II) (i) (R) (C) (III) (iv) (S) (D) (II) (i) (P)
Ans. (B)

6. Which of the following option is the only CORRECT combination ?

(A) (II) (iii) (P) (B) (I) (ii) (Q) (C) (IV) (iii) (P) (D) (IV) (iii) (R)
Ans. (C)
Sol.: I-(ii), R
II-(i), P
III-(iv), Q,S
IV-(iii), P

7. To prepare a buffer of pH 8.26 amount of (NH 4)2 SO4 to be added to 500 mL of 0.01 M
NH4OH solution is : [pKa (NH4+) = 9.26] [Ionic Equilibrium(M)]
(A) 0.05 mole (B) 0.025 mole (C) 0.10 mole (D) 0.005 mole
Ans. (B)
Sol. For the buffer solution of NH3 & NH4+
[NH3 ] (500  0.01)
pH = pKa + log 
8.26 = 9.26 + log 
[NH 4 ] m.moles of NH 4 
  m. moles of NH4+ = 50  moles of (NH4)2 SO4 required = 0.025.

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8. A saturated solution is made by dissolving AgCl(s) into 10 –5 M KCl(strong electrolyte).
Calculate osmotic pressure of this solution at 300 K in milibar. (Ksp of AgCl = 12 × 10–10).
[Use R  0.08Lbar mol–1K –1 ] [Ionic Equilibrium (M)]
Ans. (1.92)

Sol.  Ag+ (aq) + Cl– (aq)

AgCl(s) 

× (x + 10–5)
[Ag+] [Cl–] = Ksp
x(x + 10–5) = 12 × 10–10
x = 3 × 10 5 M
[Ag+] = 3 × 10–5 M, [Cl–] = 4 × 10–5 M, [K+] = 10–5 M
Osmotic pressure = CRT = (8 × 10–5) ×0.08 × 300 = 1.92 mbar.

9. For the reaction [Ionic Equilibrium(M)]

 Ag(S2O3)23– (aq) + Br– (aq.) ; KC = 25
AgBr(s) + 2S2O32– (aq.) 
What is the solubility of AgBr in 0.1 M Na2S2O3 aqueous solution?
(A) 0.5 M (B) 0.45 M (C) 0.045 M (D) 0.1 M
Ans. (C)
Sol. AgBr(s) + 2S2O32– (aq) Ag(S2O3)2–(aq) + Br –(aq)
s 0.1-2s s s
s2
25 =
(0.1 – 2s) 2
s
=5
(0.1– 2s)
11s = 0.5
1
s= = 0.045 M
22
10. A solution contains 0.01 M Zn2+ and 0.01 M Cu2+ ions. It is saturated by passing H2S gas in the
solution. The S2– ion concentration is 9.2 × 10–22 M. The solubility products of ZnS and CuS
are 3.0 × 10–22 and 8.0 × 10–36 respectively. Which of the following is true ?
[Ionic Equilibrium(M)]
(1) ZnS will precipitate
(2) CuS will precipitate
(3) Both ZnS and CuS will precipitate
(4) Both Zn2+ and Cu2+ will remain in the solution.
Ans. (2)
KIP. of Cus > KSP of Cus
& KIP of Zns < KSP of Zns
 Cus will precipitate
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11. Given Ka values of 5.76 × 10–10 and 4.8 × 10–10 for NH4+ and HCN respectively. What is the
equilibrium constant for the following reaction :- [IONIC EQUILIBRIUM-(M)]
NH4CN(aq)  NH3(aq) + HCN (aq)
(1) 0.83 (2) 1.2 (3) 8.0 × 10–11 (4) 2.76 × 10–10
Ans. (2)

Sol. K eq =
 NH3 × HCN  =
Ka(NH +4 ) 5.76  1010
= =1.2
 NH 4 +  ×  CN –  Ka(HCN) 4.8  1010

12. The indicator changes colour at around pH-9. This indicator is suitable for accurate
determination of the end point in the titration of [Ionic Equilibrium-E]
(A) CH3COOH with NaOH (B) HCl with NH4OH
(C) HCl with NaOH (D) HCl with KOH
Ans. (A,C,D)

13. An aqueous solution contains 0.01 M RNH2 (Kb = 2 × 10–6) & 10–4 M NaOH.
The concentration of OH– is nearly : [IONIC EQUILIBRIUM (M)]
–4 –4 –4
(A) 1.414 × 10 M (B) 10 M (C) 2 × 10 M (D) 5 × 10–4 M
Ans. (C)
Sol. RNH2 + H2 O   R NH 3 + OH–
0.01(1 –) 0.01 0.01 + 10–4
0.01 (0.01  10 –4 )
= 2 × 10–6
0.01(1– )
   0.01
 [OH–] = 0.01(0.01) + 10–4 = 2 × 10–4 M.

14. A solution containing certain amount of H2X, the pH of which is 3. If K a1 & K a 2 of H2X are
10–5 and 10–7 respectively. Calculate the concentration of X– – is the solution (If your answer is
a×10–b then fill a + b) [Ionic Equilibrium-M]
Ans. (8.00)
C
Sol.  H   Hx 
H 2 X (aq) 
x x
C x

x2
K a1 = 10–5 =
Cx
 x = [H+] = 10–3 M & x << C
 C = 0.1 M
0.1
  2H   X  
H 2 X (aq)  3 y
10
0.1 x

–12 (103 ) 2  y
K = K1 × K a 2 = 10 =
(0.1)
y = 10–7
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15. pH of a saturated solution of silver salt of monobasic acid HA is found to be 9.
Find the Ksp of sparingly soluble salt AgA(s). [Given : Ka(HA) = 10–10 ][Ionic Equilibrium-T]
(1) 1.1 × 10–11 (2) 1.1 × 10–10 (3) 10–12 (4) Data insufficient
Ans. (1)
Sol. A– + H2O  HA + OH– (Hydrolysis)
t=0 c 0 0
t = eq c(1 – h) ch ch
KW ch 2
Kh = = = 10–4. But [OH–] = ch = 10–5 M. (pH = 9)
Ka 1  h
105 h 10
So,  104 . Therefore, h = .
1  h 11
So, c = 1.1 × 10–5 M.
Ksp = [Ag+] [A–] = c × c(1 – h) = 1.1 × 10–5 × 10–6 = 1.1 × 10–11.

16. An aqueous solution contains 0.01 M RNH2 (Kb = 2 × 10–6) & 10–4 M NaOH.
The concentration of OH– is nearly p, then the value 100 × p is : [Ionic Equilibrium-M]
Ans. (0.02)
Sol. RNH2 + H2 O   R NH 3 + OH–
0.01(1 –) 0.01 0.01 + 10–4
0.01 (0.01  10–4 )
= 2 × 10–6
0.01(1– )
   0.01
 [OH–] = 0.01(0.01) + 10–4
= 2 × 10–4 M.

17. Solubility of AgCl in 0.2 M NaCl is 'x' and that in 0.1 M AgNO 3 is 'y' then which of the
following is correct [Ionic Equilibrium
(E)]
(1) x = y (2) y = 2x (3) x = y2 (4) x = 2y
Ans. (2)

18. If NH4Cl and KNH2 in liquid NH3 as solvent react with each other then select the correct
statement(s) among the following. [Ionic Equilibrium (M)]
(A) NH4Cl acts as an acid and KNH2 acts as a base
(B) NH4Cl acts as a base and KNH2 acts as a acid
(C) The reaction of NH4+ and NH2– is neutralisation reaction
(D) The reaction of K+ and Cl– is neutralisation reaction
Ans. (AC)

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19. What is the change in pH that results from the addition of 20 ml of 0.1M NaOH solution to a
buffer solution made by mixing 200 ml of 0.07M benzoic acid (Ka = 6.4 × 10–5) with 100 ml of
0.07 M sodium benzoate solution ? [Ionic Equilibrium (M)]
(A) 0.31 (B) 0.20 (C) 0.18 (D) 0.10
Ans. (C)
[salt]
Sol. pH before addition of NaOH = PKa + log = 3.9
[acid]
[salt]
pH after addition of NaOH = PKa + log = 4.08
[acid]
pH = 0.18
 Correct option is (3)

 HPO 2– 
20. The pH of blood is 7.4. What is the ratio of  4
– 
in the blood. pKa (H2PO4–) = 7.1
 H 2 PO 4 
[Ionic Equilibrium (E)]
(1) 2 : 1 (2) 1 : 2 (3) 3 : 1 (4) 1 : 3
Ans. (1)
Sol. H2PO4– HPO42– + H
 HPO 2–4

pH = pKa + log  – 
 H 2 PO 4 
 HPO 2– 
log  4
– 
= 7.4 –7.1 = 0.3
 H 2 PO 4 

–5
21. To 100 ml of an aqueous solution of 0.1 M CH3COOH (Ka = 2 × 10 ), 0.01 mol of HCl(g) is
passed. Select correct options regarding the resulting solution. [IONIC EQ._M]
–4
(A) Degree of dissociation of acetic acid in resulting solution is 10
(B) pH of resulting solution is nearly 1
–15
(C) Degree of dissociation of water in resulting solution is 1.8 × 10
– –7
(D) Concentration of OH ions contributed by water is resulting solution is 10 M.
Ans. (B,C)
Sol. MolesofCH3COOH = 0.1 × 0.1 = 0.01 mol.
MolesofHCl = 0.01 mol
+ 0.01
[H ]f = = 0.1M
0.1
pH = 1
– +
CH3COOH CH3COO + H
0.1 – x x (x + 0.1)
–5 x × 0.1
2 × 10 =
0.1
–5
x = 2 × 10
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 2×10 –5 –4
 CH3COOH = = 2 × 10
0.1
+ – –14 –
H2O H + OH , 10 = 0.1 × [OH ]
– –13
[OH ] = 10 M
10 –3
–16 –15
(H2O) = 1000 = 18 × 10 = 1.8 × 10
18

22. The pKa values of H3PO4 are 2.12, 7.21 and 12.67 Calculate the pH of resulting solution
formed by mixing 0.1M, 100 mL H3PO4 aqueous solution with 0.1M 200 mL Na3PO4 aqueous
solution. [IONIC-M]
Ans. (9.94)

Sol. H3PO4+ Na3PO4 NaH2PO4 + Na2HPO4

10 20 0 0
0 10 10 10
NaH2PO4 + Na3PO4 2Na2HPO4
10 10 0
0 0 10
pKa 2 + pKa 3 7.21+12.67
pH = = = 9.94
2 2

23. Choose the correct statement among the following : [IONIC EQUILIBRIUM (M)]
(1) With increases in temperature pOH of water decreases.
(2) Solubility of AgCl increases with dilution of solution.
(3) Solubility of AgCl decreases with increases in temperature.
(4) pH of pyridine solution increases with decrease in temperature.
Ans. (1)

24. What is the pH at 25°C, if a solution which is twice as alkaline (i.e. which contains twice as
many hydroxide ions) as pure water ? [IONIC EQUILIBRIUM
(E)]
(1) 7.3 (2) 6.7 (3) 14 (4) 1
Ans. (1)
Sol. At 25°C for water
[OH–] = 10–7M
for given solution
[OH–] = 2 × 10–7M
Kw 1014 1
 [H ] = +

 7
 × 10–7M
[OH ] 2 10 2
 pH = 7 + log2 = 7.3

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25. The concentration of H+ ions in solution containing cM HCN (Ka = 10–3) and 0.1M HCl is
0.105M calculate the value of c. [IONIC EQUILIBRIUM
(M)]
Ans. (0.53)
C
Sol. Hx  H   H 
C x x x

 +
[H ] = 0.1 + x = 0.105 ....(1)
  x = 0.005
 H    x  
  Ka = = 10–3
Cx
0.105  0.005
  = 10–3
C  0.005
 C = 0.53

26. The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3
concentrations. What volume of 5M NaHCO3 solution, should be mixed with 10ml sample of
blood which 2M in H2CO3 in order to maintain a pH of 7.4. K1 for H2CO3 is 4 × 10–7. [Use :
log2 = 0.3]
[IONIC EQUILIBRIUM (E)]
(A) 10ml (B) 20ml (C) 40ml (D) 80ml
Ans. (C)
Sol. Let Vml of NaHCO3 is needed
milimoles of NaHCO3 = 5 × V
 milimoles of H2CO3 = 2 × 10 = 20
m.m.of NaHCO3
pH = pK a1 + log
m.m.of H 2 CO3

7.4 = –log (4 × 10–7) + log

 5V 
 20 
 V = 40ml

27. Which of the following option is correct for a solution saturated with AgCl and AgBr. If their
solubilities are x and y mol per unit litre in separate solutions. [Ionic Equilibrium (M)]
+
(1) [Ag ] = x + y (2) [Ag ] = [Br ] + [Cl–]
+ –

(3) [Br–] = y (4) [Cl–] > x

Ans. (2)
Sol. [Ag+] < x + y , [Br–] < y , [Cl–] < x (due to common ion effect)
AgCl  Ag+ + Cl–
x+y x
AgBr  Ag + Br– +

x+y y
so [Ag ] = [Cl ] + [Br–]
+ –

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28. A 0.010 M solution of a weak acid, HA, is 0.40 % ionized. What is its ionization constant ?
[Ionic Equilibrium (E)]
–10 –7 –5
(1) 1.6 × 10 (2) 1.6 × 10 (3) 4.0 × 10 (4) 4.0 × 10–3
Ans. (2)
C 2 0.01 (0.004) 2
Sol. Ka =  = 1.6 × 10–7
1  1  0.004
29. According to the solubility curve shown, how many grams of solute can be recrystallized when
20 mL of a saturated solution at 60°C are cooled to 0°C ? [Ionic Equilibrium (M)]
Solubility (g solute/100 mL soln)
60

40
soln)

20

10 30 50 70
Temperature (°C)
Ans. (8.00)
Sol. Solubility at 60°C = 60 gm/100 ml
Solubility at 0°C = 20 gm/100 ml
On cooling 100 mL sol. 40 gm salt will recrystallized per 100 mL solution.
 Per 20 mL sol is will be 8 gm.

30. In which of the following solution, the solubility of AgCN will be greater than that in pure
water? Given : Ksp(AgCN) = 4×10–16, Ka(HCN) = 5×10–10 [IONIC
EQUILIBRIUM-M]
(A) 0.01 M Ag NO3 solution (B) A buffer solution of pH = 12
(C) 0.2 M NH3 solution (D) A buffer solution of pH = 5
Ans. (C, D)
Sol. In AgNO3 solution, the solubility of AgCN will decrease as compared to pure water because of
common ion effect of Ag+ ion.
In NH3 solution and buffer of pH = 5, the solubility of AgCN will increase due to complex
formation in case of NH3 solution and hydrolysis of CN– ions in case of buffer of pH = 5.

31. The solubility of AgCN in a buffer solution of pH = 3.0 is (K sp of AgCN = 1.2×10–16, Ka of

HCN = 4.8×10–10). [Ionic
Equilibrium-T]
(1) 1.58×10–5 M (2) 2.0×10–5 M (3) 1.58×10–4M (4) 2.5×10–9 M
Ans. (1)
Sol.  Ag+ + CN– ; Ksp = 1.2×10–16
AgCN(s) 
s s–x
s ( s–x) = 1.2×10–16 (i)

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 – 
 – KW 1014
CN + H2O HCN + OH ; Keq = 
K a 4.8  1010
s–x x 10–11

x  1011 1014
 (ii)
sx 4.8  1010
from equation (i) and (ii) x  s  2.5  1010  s 2  2.5  10 10

32. pH of which of the following solution is affected by moderate dilution ?

[IONIC EQUILIBRIUM-M]
(1) 0.01 M NaHC2O4
(2) Mixture of a 0.01 M CH3COONa and 0.01 M CH3COOH
(3) 0.01 M CH3COONa
(4) 0.01 M CH3COONH4
Ans. (3)
pK a1  pK a 2
Sol. (1) NaHC2O4 is a salt of strong base with amphiprotic anion, Its pH =
2
Salt 
(2) Mixture is a buffer solution its pH  pKa  log
 Acid 
So pH does not change with dilution
1 1
(3) CH3COONa is WASB salt pH  7  pKa  log c
2 2
So pH changes with dilution
1 1
(4) CH3COONH4 is salt of WAWB. Its pH = 7  pKa  log c
2 2
So no effect of diluton of pH.

33. Calculate [S2–] in a solution originally having 0.1 M – HCl and 0.2 M – H2S. For H2S,
Ka1 = 1.4 × 10–7 and Ka2 = 1.0 × 10–14. [Ionic Equilibrium-E]
–20 –22
(1) 0.1 M (2) 2.8 × 10 M (3) 2.8 × 10 M (4) 1.4 × 10–20 M
Ans. (2)
[H  ]2 [52 ]
Sol. K a1  K a 2 
[H 2S]
(0.1) 2  [52 ]
or, (1.4 × 10–7) × (1.0 × 10–14) =
0.2
 [S2–] = 2.8 × 10–20 M

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34. Solubility of AgCl in 0.2 M NaCl is 'x' and that in 0.1 M AgNO 3 is 'y' then which of the
following is correct [Ionic Equilibrium
(E)]
(1) x = y (2) y = 2x (3) x = y2 (4) x = 2y
Ans. (2)

35. A buffer solution made with NH3 and NH4Cl has a pH of 10.0. Which procedure(s) could be
used to lower the pH? [Ionic Equilibrium (M)]
1. adding HCl
2. adding NH3
3. adding NH4Cl
(1) 1 only (2) 2 only (3) 1 and 3 only (4) 2 and 3 only
Ans. (3)

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