IONIC EQUILIBRIUM.

Q.30 If Ksp for HgSO4 is 6.4 ×10–5, then solubility of this substance in mole per m3 is
(A) 8 ×10–3 (B) 6.4 ×10–5 (C) 8 × 10–6 (D*) None of these
[Sol. HgSO4 (s) Hg2+ (aq.) + SO 4 2 (aq.)

solubility, s = 6.4 10 5 = 8 × 10–3 mol/L = 8 mol/m3 ]

Q.31 A vessel of 250 litre was filled with 0.01 mole of Sb2S3 and 0.01 mole of H2 to attain the equilibrium at
440°C as Sb2S3 (s) + 3H2 (g) 2Sb (s) + 3H2S (g)
After equilibrium the H2S formed was analysed by dissolving it in water and treating with excess of Pb2+
to give 1.19 g of PbS are precipitate. What is value of Kc of the reaction at 440°C?
(A*) 1 (B) 2 (C) 8 (D) 4
[Sol. Sb2S3 (s) + 3H2 (g)  2Sb (s) + 3H2S (g)
0.01 0.005
1.19
H2S + Pb2+  PbS + 2H+ PbS = 1.19 gm  = 0.005 mole
238

 0.005   0.005   0.005 

3
 [H2] =   ;  [H2S] =   Kc =   = 1 Ans. ]
 250   250   0.005 
Q.32 0.1 mole of AgNO3 is added to 1 litre of 3.0 M NH3. What is the concentration of Ag(NH3)+ in
solution. K f  2.1 103 ; K f  8.1 103
1 2

(A*) 4.4 × 10–6 (B) 7 × 10–10 (C) 4.4 × 10–3 (D) 7 × 10–8
[Sol. Ag+ + 2NH3 Ag( NH 3 ) 2
x 2.8 0.1
Ag( NH 3 ) 2 Ag(NH3)+ + NH3
0.1–x x 2.8 + x
~ 0.1 ~ 2.8
1 1 (2.8) x
K f = 8.1103 = 0.1 x = 4.4 × 10–6 Ans.]
2

Q.33 When NO2 is bubbled into water, it disproportionates completely into HNO2 and HNO3.
2NO2 + H2O (l)  NHO2 (aq.) + HNO3 (aq.)
The concentration of NO 2 in a solution prepared by dissolving 0.05 mole of NO 2 gas in 1 litre H2O is
{Ka (HNO2) = 5 × 10–4} is
(A*) ~ 5 × 10–4 (B) ~ 4.8 × 10–5 (C) ~ 4.8 × 10–3 (D) ~ 2.55 × 10–2
Q.34 Arrange the following electrolytes in the increasing order of coagulation power for the coagulation of
As2S3 solution. (I) Na3PO4 (II) MgCl2 (III) AlCl3
(A*) I < II < III (B) III = II < I (C) I < III < II (D) III < I < II
[Sol. As2S3 is negativley charged sol., so coagulation power Al3+ > Mg2+ > Na+ ]
Q.35 Consider the following statements
I Ksp of Fe(OH)3 in aqueous solution is 3.8 × 10–38 at 298K. The concentration of Fe3+ will
increase when [H+] ion concentration decreases
II In a mixture of NH4Cl and NH4OH in water, a further amount of NH4Cl is added. The pH
of the mixture will decreases.
III An aqueous solution of each of the following salts(NH4I, Cr(NO3)3·9H2O, KCN) will be
basic, basic, acidic respectively.
Choose the correct alternative.
(A) only I is correct (B*) only II is correct
(C) II and III are correct (D) All are incorrect
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 IONIC EQUILIBRIUM.

Q.36 The concentration of bivalent lead ions in a sample of polluted water that also contains nitrate ions is
determined by adding solid sodium sulphate (M = 142) to exactly 500 mL water. Calculate the molarity
of lead ions if 0.450 gm of sodium sulphate was needed for complete precipitation of lead ions as
sulphate.(A) 4.36 × 10–3 M (B) 3.64 × 10–3 M (C*) 6.33 × 10–3 M (D) 6.68 × 10–3 M
[Sol. Pb2+ + SO 24 (from Na2SO4)  PbSO4
0.45
Moles of Na2SO4 req. = Moles of Pb2+ ions = = 0.003169
142
0.003169
[Pb2+] = = 6.338 × 10–3 M ]
0.50
Q.37 Which of the following expression for % ionisation of a monobasic weak acid in aqueous solution at
appreciable concentration is not correct?

Ka  K 
(A) 100 (B) 
a
 
 100
C  K a  [H ] 

 [H]  100
(C*)   
 100 (D)
 K a  [H ]  1  10
( pK a  pH )

[Sol. HA H+ + A–
C(1–) C C
C 2 2
Ka = neglecting  w.r.t. 1 as conc. is appriciable
C(1   )

Ka Ka
=  % dissociation = 100
C C

[A  ] Ka 1
also  = = =
[ A ]  [ HA ]
 K a  [H ]

1
[H  ]
Ka

1
also – [H+] = 10 pH Ka = 10  pK a  = =[ ]
1
1  10
10  pH
( pK a  pH )
1  pK a
10
 100 
Exact expression for % dissociation =   ]
 1  10 
pK a  pH

Q.38 Which have maximum pH in aqueous solution

(A*) NaOCl (B) NaClO4 (C) NaClO3 (D) NaClO2
Q.39 A 1 litre solution containing NH4Cl and NH4OH has hydroxide ion concentration of 10–6 mol/lit. Which
of the following hydroxides could be precipitated when the solution is added to 1 litre solution of 0.1 M
metal ions
I Ag(OH) (KSP = 5 × 10–3) II Ca(OH)2 (KSP = 8 × 10–6)
III Mg(OH)2 (KSP = 3 × 10 )–11 IV Fe(OH)2 (KSP = 8 × 10–16)
(A) I, II, IV (B*) IV (C) III and IV (D) II, III, IV
[Sol. when 1 litre each are mixed
[OH–] = 10–6 M (Buffer solution)
M = 0.05 M
n+

for M2+ = Q = [0.5][10–6]2 = 5 × 10–14

Q > KSP only for Fe2+
only Fe(OH)2 is ppt. ]

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 IONIC EQUILIBRIUM.

Q.40 If K1 & K2 be first and second ionisation constant of H3PO4 and K1 >> K2 which is incorrect.
(A) [H+] = [ H 2 PO 4 ] (B) [H+] = K1[H 3PO 4 ] (C) K2 = [HPO 4  ] (D*) [H+] = 3[PO34 ]
Q.41 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)
Q.42 From separate solutions of four sodium salts NaW, NaX, NaY and NaZ had pH 7.0, 9.0, 10.0 and 11.0
respectively. When each solution was 0.1 M, the strongest acid is:
(A*) HW (B) HX (C) HY (D) HZ
Q.43 A buffer solution was prepared by dissolving 0.02 mole acetic acid & 0.01 mole sodium acetate in
enough water to make 1.0 L of solution ( K a ( CH = 2 ×10–5). If 5 × 10–4 mole NaOH were
3COOH )

added to 100 ml of the buffer. The resultant pH of the solution would be [given log 5 = 0.70]
(A) 5 (B*) 4.7 (C) 5.3 (D) None
Question No. 44 & 45 (2 questions)
Amino acid glycine ( NH 2  CH 2  COOH ) exist as a zwitterion in aq. solution. The Ka and Kb value of
glycine are 1.6 × 10–10 (pKa = 9.8) and 2.5 × 10–12 (pKb = 11.6) respectively. The Ka and Kb values

are for zwitterion of Amino acid with following structure [ NH 3  CH 2  COO — ]
Q.44 What is the Kb for –NH2 group in glycine
(A) 4 × 10–3 (B) 1.6 × 10–10 (C*) 6.25 × 10–5 (D) 2.5 × 10–12
Kw 1014
[Sol. Kb(NH2) = = = 6.25 × 10–5 ]
K a ( NH 3 )1.6 1010
Q.45 An aqueous solution of glycine has pH
(A) slightly less than 7.9 (B) slightly less than 6.1
(C*) slightly greater than 6.1 (D) equal to 7.9

[Sol. When [NH2–CH3–COO–] = [ NH  CH  COOH]
3 2

pK1  pK 2 (14  pK b  pK a ) 2 .4  9 .8
pH = = = = 6.1
2 2 2
In aq. solution of Glycine ionisation is represented as

NH 3  CH 2  COO  + H2O NH
3  CH 2  COOH
+ OH–

 NH 2  CH 2  COO  + H3O+
NH 3  CH 2  COO  + H2O
Exact expression will yield

[ NH3  CH 2  COOH] + [H+] = [ NH 2  CH 2  COO  ] + [OH–]
since, [H+] > [OH–]

 [ NH 2  CH 2  COO  ] is slightly greater than [ NH3  CH 2  COOH]
 pH must be slightly greater than 6.1 ]

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 IONIC EQUILIBRIUM.

Q.46 Liquid NH3 ionises to a slight extent. At a certain temp. it's self ionization constant K SIC ( NH ) = 10–30.
3

The number of NH4+ ions are present per 100 cm3 of pure liquid are
(A) 10–15 (B) 6.022 × 108 (C*) 6.022 × 107 (D) none
[Sol. 2NH3 NH4+ + NH2– [NH4+] = K SIC
KSIC = [NH4+][NH2–] [NH4+] = 10–15 M
 Number of NH4+ ions in 1000 cm3 = 10–15 × 6.022 × 1023
100
 Number of NH4+ ions in 100 cm3 = 10–15 × 6.022 × 1023 ×
= 6.022 × 107 ]
1000
Q.47 How many moles NH3 must be added to 2.0 litre of 0.80 M AgNO3 in order to reduce the Ag+
concentration to 5 × 10–8 M. Kf of [Ag(NH3)2+] = 108
(A) 0.4 (B) 2 (C) 3.52 (D*) 4
[Sol. Ag2+ + 2NH3 Ag(NH3)2+
0.8-x z–2x x ; kf = 108; so x  0.8
5 × 10 –8 z–0.8×2 0.8
) ]
kf = = = 108
[ Ag ( NH 3 0 .8
[ Ag 
][ NH 3 ]2 5  10 8
( z  1 .6 ) 2

(z – 1.6)2 = 0.16; z – 1.6 = 0.4 ; z=2

Initial concentration n
V
= 2 ( V = 2 litre) ;  n = 4 litre ]
Q.48 100 cm3 of a solution of an acid (Molar mass = 82) containing 39 gm of the acid per litre were completely
neutralized by 95.0 cm3 of aq. NaOH containing 20 gm of NaOH per 500 cm3. The basicity of the acid is
(A) 1 (B*) 2 (C) 3 (D) data insufficient
[Sol. meqn + acid = meqn of base Acid: 3.9 gm acid present in 100 cm3
Base: 20 gm NaOH present in 500 cm3 N1V1 = N2V2

 20 
3 .9
× 1000 = 95 ×   100  ; n=2 ]
 82 
   40500 
 n 

Q.49 Consider the equilibrium HgO(s) + 4I– (aq) + H2O (l) HgI42– (aq) + 2OH– (aq), which changes will
increase the equilibrium concentration of HgI42–
(i) Adding 0.2 M HCl (ii) Increasing [I–] (iii) Increasing no. of moles of HgO(s)
(A) (i) only (B) (ii) only (C*) (i) & (ii) (D) (ii) & (iii)
Q.50 Calcium lactate is a salt of weak organic acid and strong base represented as Ca(LaC)2. A saturated
solution of Ca(LaC)2 contains 0.6 mole in 2 litre solution. pOH of solution is 5.60. If 90% dissociation
of the salt takes place then what is pKa of lactic acid
(A*) 2.8 – log(0.54) (B) 2.8 + log(0.54) (C) 2.8 + log (0.27) (D) none
[Sol. Ca(LaC)2 — Ca2+ + 2LaC–
Initial 0.6/2 M = 0.3 M
After dissociation 0.3 × 0.10 0.3 × 0.9 2 ×0.3 × 0.9 = 0.27 × 2 M
= 0.54 M

pH = 1/2[ pK w + pK a + log(LaC–)] ; 14 – 5.6 = 1/2[14 + pK a + log(0.54)]

16.8 – 14 = log(0.54) + pK a ; pK a = 2.8 – log(0.54) Ans. ]

[H 3A ]
Q.51 10 ml of 0.1 M tribasic acid H3A is titrated with 0.1 M NaOH solution. What is the ratio of [ A 3 ]
at 2nd
equivalence point. Given K1 = 7.5 × 10–4, K2 = 10–8, K3 = 10–12
(A) ~10–4 (B) ~ 10+4 (C*) ~ 10–7 (D) ~ 10+6
[Sol. At second equivalence point the only species present at appreciable conc. = HA2–
pk  pk 8  12
So, pH = = = 10 [H+] = 10–10 and = = 1.33 × 10–7 Ans. ]
2 3 [H 3A ] [ H  ]3
2 2 k 1k 2 k 3
3
[A ]

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 IONIC EQUILIBRIUM.

Q.52 The solubility of metal sulphides in saturated solution of H2S {[H2S]= 0.1 M}can be represented by
[M 2 ][H 2S]
MS + 2H+ M2+ + H2S ; Keq =
[H  ]2
The value of Keq is given for few metal sulphide. If conc. of each metal ion in solution is 0.01 M, which
metal sulphides are selectively ppt at total [H+]= 1M in saturated H2S solution.

Metal sulphides MnS ZnS CoS PbS

[M 2 ][H 2S]
Keq = 3 × 1010 3 × 10–2 3 3 × 10–7
[H  ]2
(A) MnS, ZnS, CoS (B) PbS, ZnS, CoS (C) PbS, ZnS (D*) PbS
[ 0 . 01 ][ 0 . 1]
[Sol. All metals are soluble for which Q < K Q= = 0.001
[1] 2
Q < K for MnS, ZnS and CoS: hence they do not precipitate ]
Q.53 At 400 K, which of the following solution can have pH = 7
(A) NaCl (B) NH4Cl (C) ZnCl2 (D*) NaCN
[Sol. at 400 K pH for neutral H2O < 7  pH = 7 = solution is basic ]
Q.54 Calculate the percentage of hydrolysis and pH of 0.003 M aqueous solution NaOCN.
(Ka of HOCN = 3.33 × 10–4 M) (A) 7.533 (B) 8.477 (C*) 7.477 (D) 6.533
 3 . 33  10 1
[Sol. [H+] = = = =
K ·K a 10  14 4  14
w 10
 10 7
c 0 . 003 9 3

pH = –log( 3  10 ) = 7 + log 3 = 7.4771 ]

1 7

Q.55 Calculate the pH of a solution containing 0.2 M HCO3– and 0.1 M CO32–
[K1(H2CO3) = 4 × 10–7 ; K2 (HCO3–) = 4 × 10–11]
(A) 10.4 (B*) 10.1 (C) 6.1 (D) 10.7
[ CO 2  ]
[Sol. pH = pK a 2 + log [ HCO  ]  (11 – log 4) + log  2   10.1 ]
3  1 
3

Q.56 1.0 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the solution at 1
atm is ( K b( H 2O)  0.52 K kg mol )
1

(A) 274.76 K (B) 377 K (C) 376.4 K (D*) 374.76 K

[Sol. Tb = i.Kb.m = (1+4)Kbm A2B3 (aq) 2A3+(aq) + 3B2–(aq)
= (1 + 4 × 0.6) × 0.52 × 1 n=5
= 1.76; Tb = 373 + 1.76 so, i = 1 + (5 – 1) ×  ]
Q.57 What minimum volume of a buffer solution which is 0.1 M each in both lactic acid
(Ka =1.4 × 10–4) and sodium lactate must be diluted to exactly 100 ml so that the resulting buffer
solution will change its pH by not more than 0.3 pH unit upon the addition of 10 ml of 0.01 M HCl?
(Given : log2 = 0.3) (A) 1 ml (B*) 3 ml (C) 20 ml (D) none
[Sol. Let m moles of acid & salts are a & s respectively; Initial concentration is same so, s = a
Let initial volume is V ml
 s  0 .1 
pH = pKa +  s 
log    (pH)1 = pKa ...(1) (pH)2 = pKa + log   ...(2)
 a   a  0 .1 

 a  0 .1   a  0 .1  a  0 .1
pH = (pH)1 – (pH)2  log   0.5 = log  2=
 a  0 .1   a  0 .1  a  0 .1
2a – 0.2 = a + 0.1
a = 0.3
a/V = 0.1  0.3/V = 0.1  V = 3 ml ]

Page No.183
 IONIC EQUILIBRIUM.

Q.58 What is the pKa of a weak acid whose 0.1 M solution has pH = 4.
(A) 6 (B*) 7 (C) 8 (D) 9
1 1
[Sol. pH = pKa – log C pKa = 2pH + log C  8–1 = 7 ]
2 2
Q.59 What is the degree of dissociation of weak acid HA (C = 0.1 M) in presence of strong acid
HB (C = 0.1M ). Given : Ka (weak acid) = 10–6
(A*) 10–5 (B) 10–6 (C) 10–4 (D) 10–3

[Sol. HA H+ + A–
c–x 0.1 + x x
HB  H+ + B–
(0.1) 0.1
( 0 .1  x ) ( x ) K a .c
Ka = {Let x c << c (approx)}  sub. 0.1 + x = 0.1 ;x = = Ka { c = 0.1}
cx 0.1

x
= = 10–5 ]
c
Q.60 What is the pH of a 0.4 M NaCN (aq) solution? Since pKb of CN– = 4.70
(A)  9.15 (B*)  11.45 (C)  11.85 (D) None
[Sol. pKa for HCN = 14 – 4.70 = 9.30
Due to small degree of anionic hydrolysis
1 1 1
pH = [pKw + pKa + log C] = [14 + 9.30 + log 0.4] = [23.30 – 0.4] = 11.45 ]
2 2 2

Page No.184