UNIT # 07 (PART - II)

IONIC EQUILIBRIUM EXERCISE # 1


9. pH = 1 pH = 2 HCO 3
28. pH = pK a + log
[H + ] = 0.1 [H + ] = 0.01 H 2 CO 3
V = 50 V = 50  
7 = 7 – log + log HCO 3 HCO 3  4
N 1 V1  N 2 V2 50(0.1  0.01) H 2 CO 3 (H 2 CO 3 )
[H+] of mixture is[H+]= 
V1  V2 100
– 4
0.11 % HCO 3 =  100  80 %
+
[H ]   0.055 5
2
pH = 1.26 30. 2NaOH + H 3 PO 4  Na 3 PO 3
11. pH = 7 [H + ] = 10 –7 , [OH – ] = 10 –7 50mL,0.1M 60mL,0.15
new pH after addition of base 0 7.33
pH = 12 [H + ] = 10 –12 H 3 PO 4 

 H + H 2 PO 4–
–
[OH ] = 10 –2
[mass H + obtain from first ionization of H 3PO 4 ]
[OH + ] concentration increase 10 5 times. 1 1 1 1
pH = pK a  log C = pK a  log C
K a1 3  10 4 2 2 2 2
13. Relative strength = K  1.8  10 5   4 : 1 = 1.5 + 1.17 = 2.67
a2
32. Mg(NO 3 ) 2 + 2NaF   MgF 2 + 2NaNO 3
16. HCOOH + KOH
2.5 5
40mL,0.5 (M)  50 mL,0.2 M
 HCOOH + H 2 O 0 0 2.5
after reaction is forms Buffer solution
2.5
(MgF 2 ) =
10 10 35
[HCOOH] = [HCOOK] = MgF 2  Mg +2 + 2 F
90 90
Ionic product
pH = pK a + log
[salt]
pH = pK a 41. AgCNS   
 Ag + + CNS
[acid] (1– 1 ) (+ 2) 1
pH = 4 – log (1.8) pH = 3.75 AgCl 

 Ag + + Cl
19. Let weak acid is HA its sodium salt is NaA (1– 2 ) (+ 2)  2

Ka =
Kw
K H = CH 2  0.1 × (0.03) 2
 K sp AgCNS  ( 1 ) ( 1  2 ) .........(i)
KH
10 14  K sp AgCl  ( 2 ) ( 1  2 ) ........(ii)
Ka = K a =  1 × 10 –10
9  10 5 adde equation (i) and (ii)
22. CH 3COOH + NaOH    CH 3COONa + H 2 O
100 mL, 0.4 M 100 mL, 0.2M ( 1 +  2 ) 2 =  K sp  AgCNS   K sp  AgCl
40 20 ( 1 +  2 ) =  K sp AgCNS   K sp AgCl = 1.0  10 12  1.7  10 10
After reaction
(AgT) = ( 1 +  2) =1.3 × 10–5 divide eq. ii from i
20 20
[CH 3 COOH] = , [CH 3 COONa] = [Cl  ]  1.7  10 10
250 200 
 2 =  1.7 × 10 2
[CNS ] 1 1.0  10 12
[salt] 47. IP > K sp I.P. = (Ca +2 ) (F) 2
pH = pK a + log
[acid] I.P.  (10 –2) (10–3) 2  10–8 IP > K sp
pH = pK a [H + ] = K a = 1.8 × 10 –5
In  In 
24. CH 3 COONa + HCl  CH 3 COOH + NaCl 53. pH = p HIn + log 6 = 5 + log
HI A HIn
20
at equivalence the [CH 3 COOH] =  0.1 In 
200  10
HIn
1 1 54. At Half way [HIn] = In –
pH = pK a  log C
2 2
1 [salt] [salt]
1 pH = 5.5 + log 5.5 = pK a + log
pH = [5 log 2 – log10 ] [acid] [acid]
2
1 [salt] [salt]
pH = [6 – log 2]  pH = 3 – log 2 log =0.75   5.62
2 [acid] [acid]
IONIC EQUILIBRIUM EXERCISE # 2
4. HCl + NaCl pH = 4.2
1 ml, 0.1 99 ml C 6 H 5 COOH + NaOH  C 6H 5 COONa + H 2 O
+ 0.1 2 2
[H ] =   0.001 pH = 3 0 0 2
100
 – + 1 1
6. HF + H 2 O   F + H 3O pH = 7 + pKa + log C
2 2
Ka × K b= K w pK a + pK b = pK w
pK a =14 – 10.83 pK a = 3.17 1 2
–4 pH = 7 + 2.1 + log
K a = 6.75 × 10 2 200
Kw pH = 9.1 – 1 pH = 8.1
Kh
9. h = h = 25. CH 3 COOH + NaOH  CH 3 COONa + H 2 O
C Ka C
0.1 0.1
10 –14  8.0 At 1/3 neutralization
h = h = 2.48 % 2/ 3 1/3
1.3  10 –9  1
13. K sp = s
2
s = K sp = 6.4  10 –5 (salt)
pH = pKa + log
s = 8 × 10
–3
s = 8 mol/m
3 (acid)
+
15. AgNO 3 + NH 3  [Ag(NH 3 ) 2 ] 1/3
pH 1 = pKa + log ...(1)
1.6 x 2/3
5 × 10
–8
(x – 1.6) 0.8 at 2/3 neutralization
2/3
[Ag(NH 3 ) 2 ] pH 2 = pKa + log ...(2)
Ks = 1/3
(AgNO 3 )(NH 3 )
1
pH 1 – pH 2 = log – log 2
8 0.8 2 2
10 = (x – 1.6) = 0.16
(5  10 –8 )(x – 1.6)2 1
x = 2 M mole of NH3 = 4 = log = – 2 log 2
4
18. C 6 H 5 COOH + NaOH  C 6H 5 COONa + H 2 O – + 2–
27. HSO 4  H + SO 4
2 1 1
1 0 1 (1– )      
[salt] 1 2
pH = pK a + log pH = 4.2 + log 10
–2
=    0.09 pH=1.02
[acid] 1 1
IONIC EQUILIBRIUM EXERCISE # 3
COMPREHENSION BASED QUESTIONS 1
pH = [pK a1  log c] c = [H 3 PO 4 ] = 0.05 %
Comprehensi on # 1 2
1. Suppose volume of HCO 3– = V mL 0.05  10
millimoles of HCO 3– = 5V = mol L1 (M ) = 5.1 × 10 –3 M
98
millimoles of H 2 CO 3 = 20
–log c = 2.3, pK a1  2.12 pH = 2.21
[HCO 3 ]
pH = pK a + log [H  ]3 [PO 34  ]
[H 2 CO 3 ] 3.  K a1 K a 2 K a 3
V [H 3 PO 4 ]
7.40 = 6.11 + log , V = 78 mL 3log [H + ] + log[PO 43– ]
4
+
3. If CO2 escapes, [H ] decreases, hence pH increases. = log K a1 + log K a 2 + log K a 3 – log [H 3 PO 4 ]
( CO2 
, 
[H+] 
pH 
)
3pH–log[PO 43– ]=log[H 3 PO 4 ]= pK a1  pK a2  pK a3
Comprehensi on # 2
21 – log[PO 43– ] – 3 = 2.12 + 7.21 + 12.32
1. Phosphoric acid with three ionisable hydrogens ions
log[PO 43– ] = – 3.65
is a tribasic acid. H-atoms are attached to O-atoms,
[PO 43– ] = 2.24 × 10 –4 M
(
 H-
) 4. 
Zn 3 (PO 4 ) 2   2+
 3Zn + 2PO 4
3–

2. If first step is only taken (

 K sp = [Zn 2+ ] 3 [PO 4 3– ] 2
 ) 9.1 × 10 –33 = [Zn 2+ ] 3 (2.2 × 10 –4 ) 2
[Zn 2+ ] 3 = 1.88 × 10 –25 [Zn 2+ ] = 5.73 × 10 –9 M
 IONIC EQUILIBRIUM EXERCISE # 4[A]

Ka
1 . ( i ) H 2 O   +
 H + OH
–
14. For weak acid
–7 –7 +
10 10 [H ] = K 1 C 1  K 2 C 2 ...  K w
–5 –5 –14
[H  ][OH – ] 10 –7  10 –7 10 –14 = 1.8  10  0.02  6.4  10  .01  10
–16
Ka = = = =1.8×10
[H 2 O] 1000 / 8 55.5 = 100  10 –8
+ –3
[H  ][ACO – ]
–14
(ii) K a × K b = 10 [H ] = 10 Ka =
[ACOH]2
 –4
[ACO ] = 3.6 × 10
2 2 C1 1  –4
2. K a = C  = = =10 same [C 2 H 5 O 2 ] = 6.4 × 10
1 C2 1 / 100 +
2
15. HCN is a weak acid so H due to it can neglect
3. K a = C As comparision to HF
+
1 Ka 1 1.8  10 –5 [H ] = KC = 6.7  10 –4  0.1 = 67  10 –6

2 Ka 2 = 6.2  10 –10 –3
= 8.18 × 10
–3
1 1 pH = – log [8.18 × 10 ] = 3 – log [8.18]
4.(a) pH = pK a – log C p H = 2.087
2 2 + –2
4.50 × 2 = pK a –log (0.1) 16. H 2S  2H + S
–8 + –4
9 – 1 = pK a pK a = 8 K a = 10 [H ] = 2 × 10 , [H 2S] = 0.1 M
–7 –7
+
5.(c) [H ] = Ka C = 1.8  10 = 3 – log 1.8 = 2.87
–6 K = K 1× K 2 K = 10 × 10
–21
(e)
+ –8 –7 –7
[H ] = 10 + 10 = 10 [0.1 + 1] K = 10
pH = 7 –log 1.1 = 6.95 –21 [2  10 –4 ]2 [S –2 ] –21 –8 –2
(f)
– –10 –7 –7
[OH ] = 10 + 10 = 10 [1.001]  10 = 10 = 4 × 10 [S ]
[0.1]
POH = 7 –log 1.001 = 6.99
pH = 7.0004 1
+  10 –14 = [S –2 ] 2.5 × 10
–15
= [S ]
–2

(g) [H ] = Ka C = –5
1.8  10  10 –6 4
+ – –3
+
[H ] = –11 = 18  10 –12 = 4.24 × 10
–6 17.(i) H 3 PO 4   H + H 2PO 4 K 1 = 7.225 × 10
1.8  10
0.01 M C (1 – ) C1 C 1
pH = 6- log 4.24 = 5.37 (ii)
– –2
H 2 PO 4    HPO 4 + H
+
K 2 = 6.8 × 10
–8

6. pK w = 14 - log 2.56 = 13.59  13.6 C1 (1 – 2) C12 [C1]

pK w (iii)
–2
HPO 4   PO 4
–3 +
+ H K 3 = 6.8 × 10
–8
pH = =6.795
2 12C 1(1–  3) C (123) [C1]
+ –11.5
10. pH = 11.5 [H ] = 10
2
–
[OH ] = 10
–2.5
–3 C 12 0.01  1
Kb
7.225 × 10 = =
  + – (1  1 ) 1
NH O H4   NH + OH 4
–2.5 –2.5 RxN. (i)
10 10 2
(1 – ) × 0.7225 =  1
10 –5 –5 1 2
 1 + 0.7225  – 0.7225 = 0
= 1.8 × 10 C = =0.556 M
C 1.8  1 = 0.562
–2 + –3
11. C = 10 , [H ] = 10 
+
[H ] = 0.01 × 0.562
+
[H ] = 5.6 × 10
–3

10 –3  10 –3 10 –3 –4

[H 2PO 4 ]  5.6 × 10
–3
RxN. (ii)
Ka =  = 1.1 × 10
10 –2 – 10 –3 9
13. CHCl 2 COOH  H
+
+ CHCl2COO
– –8 [HPO 4–2 ][H  ]
6.8 × 10 = from [i] reaction.
0.01 [H 2 PO 4– ]
0.01 – x 0.01+ x x –2 –8
 [HPO 4 ] = 6.8 × 10 M RxN. (iii)
x(0.01  x) –2
= 2.55 × 10
0.01 – x –13 [PO 4–3 ][H  ]
2 –4
0.01 x + x = 2.55 × 10 – 2.55 × 10 x
–2 4.5 × 10 =
2
[HPO 4–2 ]
x + 0.355x – 0.000255 = 0
4.5  10 –13  6.8  10 –8 –3
–0.0355  0.04775 –2 –3 = [PO 4 ]
x = =1.1 × 10 5.6  10
2 –18 –3
–
CHCl 2 COO = 6.126 × 10
–2 5.464 × 10 = [PO 4 ]
 +
20. NH 4 Cl  NH 4 + Cl – 30. CH 3 COO



+ H 2O  CH 3 COOH + OH

+
NH 4 OH  NH 4 + OH – 10 –14
[NH ][OH ] – 0.08 Kb =
4 1.8  10 –5
Kb =
[NH 4 OH] x2 10 2 0.8
+   10 –10 x =  10 –10
[NH 4 ] = is due to salt because NH 4OH ionise in 0.08 1.8 1.8
2 –10 –5
less amount due to common ions effect x = 0.44 × 10 x = 0.66 × 10
0.1  [OH – ] 32.
+
C 5 H 6 N + H 2 O 
 C 5 H 5 NOH + H
+

1.8 × 10 –5 = 9 × 10 –6 = [OH – ]
0.05 1
 pH = [pK w – pK b – log C]
21. HC 2H 3 O 2 + NaOH    CH 3 COO + H 2 O 2
50ml, 0.2M 50ml, 0.1M
1
10m mol 5m mol 2.699 = [14 – pK b + 0.6]
2
O
 2.398 = 14.6 – pK b


CH3–C–OH + OH   
 CH 3 COO + H 2 O pK b = 14.6 – 5.398 = 9.802
–9.802
10 5 K b = 10
5 0 5 5 pK 1  pK 2
38. pH =
pH = pK a =5 – log 1.8 pH = 4.74 2
22. (NH 4 ) 2 SO 4 11  7 – 2 log 4.5
pH = = 9 – log 4.5 = 8.54
 x  2
 –
Molarity (NH 4 ) 2 SO 4 =   40. CH 3 COOH+OH CH 3 COO +H 2O (WASB)
 100 
 2x  1
pH = [pK w + pK a + log C]
Molarity of NH 4 + =   2
 100 
1 1
= [14 + 5 – log1.9 + log ]
 0.1  2 20
Molarity of NH 4 OH =   =10 –3 1
 100  = [19 – log1.9 – log 20]
2
 2x / 100  1
14 – 9.26 = 4.24 + log   pH= [19 – log 20 × 1.9] = 8.78
 0.1 / 100  2

pOH= 5.28 [OH ] = 10 –5.28
0 = log (20x)  1 = 20x  
[OH ] = 10 –6 × 10 0.72 [OH ] = 5.24 × 10 –6
x = 1/20 mole x = 0.05 mole

IONIC EQUILIBRIUM EXERCISE # 4[B]


 adding both ( 
)
1. Q + + H 2 O  QOH + H
+
k w /k 1
n1 n ' n '  k w (k 2 n 1 '  k 1 n 2 ')
 n '1 (x + y) 2 = k w  1  2  =
V  k1 k2  k1k 2
n'1 – x x x + y
kw
[H + ] = (x + y) = (k 2 n 1  k 1 n 2)
R +
+ H2O 

 ROH + H +
k1k 2 V
n2 pH = –log [H + ]
 n 2'
V
n'2 – y y y+x 1  k k  V 
pH = log  1 2  (k n  k n ) 
k w x(x  y ) x(x  y) 2  k w  2 1 1 2 
=  ..........(i)
k1 n 1'  x n 1'
kw
k w y(x  y) y(x  y) 2. 

Na 4 Y+H 2 O  Na 3 HY+NaOH  1.818  10 4
=  .........(ii) k4
k2 n 2'  y n 2' 0.1
Assuming (  ) x << n 1 ' & y << n 2 ' 0.1 – x x x
from equation (i) & (ii) ( (i)  (ii) ) x 2
=1.818× 10–4 5500.55x 2 + x – 0.1 = 0
k k 0.1  x
x (x + y) = w n 1 ' & y (x + y) = w n 2 ' x = 4.17 × 10 –3
k1 k2
 

Na 3 HY+H 2 O 
k
 Na H Y+NaOH w  1.445  10 8 5. 

Cu 3 (AsO 4 ) 2  +2 –3
 3Cu +2AsO 4 K sp =8×10
–36

2 2 k 3
3x 2x+2y
x
x – y y y + x


Pb 3(AsO 4 ) 2  +2 –3
 3Pb +2AsO 4 K sp =4.096×10
–36

since y << x x – y ~ x, x + y ~ x 3y 2y+2x

Let solubility of Cu 3(AsO 4) 2 & Pb 3(AsO 4) 2 is x & y
1.445 × 10 –8 =
y.x
y respectively. ( 
Cu 3 (AsO 4 ) 2  Pb 3 (AsO 4 ) 2 
x
 x  y 
)


kw
 4.7  10 12
108 x 3 (x + y) 2 = 8 × 10 –36 .....(i)
Na 2 H 2 Y+H 2 O  NaH 3 Y+NaOH
k2 108 y 3 (x + y) 2 = 4.096 × 10 –36 ....(ii)
y
y – z z z + x (i) x3 8
 3   x = 1.25 y
y – z ~ y, z + x ~ x (ii) y 4.096
z.x putting this in equation (ii) ((ii)
)
4.7 × 10 –12 = z = 1.628 × 10 –17
y 3 2
108 y (2.25 y) = 4.096 × 10 –36



kw y = 2.3 × 10 –8 x = 1.25 y = 2.875 × 10 –8
NaH3Y+H2O  H4Y+NaOH  9.8  10 13
k1 [Cu +2 ] = 3x = 8.825 × 10 – 8
z [Pb +2 ] = 3y = 7.1 × 10 – 8
z – t t t + x


6.(a) Al(OH) 3  +3
 Al + 3OH
–
K sp
z – t ~ z, t + x ~ x
t.x 

Al(OH) 4–  +3 –
9.8 × 10 –13 = t = 3.82 × 10 –27  Al + 4OH K
z
K sp
t 

Al(OH) 3 + OH –  –
 Al(OH) 4 K  38.46
fraction ( 
) = = 3.82 × 10 –2 6
0.1
 Al(OH  ) 4  10 3
3. s=[Zn(OH) 2 (aq)]+Zn(OH) + +Zn +2 +Zn(OH)–3+ Zn(OH) 4–2 38.46 =   =

 [OH ]  [OH  ]
k1k 2 k k k
s=k 1 + + 1 2 3 +k 1 k 4[OH – ] + k 1 k 4 k 5 [OH – ] 2
[OH  ] [OH  ]2 [OH – ] = 2.6 × 10 –5
10 13 10 17 pOH = 4.585
s=10 –6 + + +10 –3 [OH – ]+10 –2 [OH – ] 2 pH = 9.415
[OH ] [OH  ]2


(a) pH = 5, pOH = 9, [OH – ] = 10 –9 (b) K sp = [Al +3 ] [OH – ] 3

s = 10 –6 + 10 –4 + 10 + 10 –12 + 10 –20 = 10 M 5 × 10 –33 = [1 × 10 –3 ] [OH – ] 3
(b) pH = 9, pOH = 5, [OH – ] = 10 –5 [OH – ] = 1.7 × 10 –10
s=10 –6 +10 –8 +10 –7 +10 –8 +10 –12 = 1.12 × 10 – 6 M pOH = 9.767
(c) pH = 13, pOH = 1, [OH – ] = 10 –1 pH = 4.23
s = 10 –6 + 10 –12 + 10 –15 +10 –4 +10 –4 = 2 × 10 –4 M 7. HCl            0.09 M
4. Given :
CH 3 COOH   C 1 = 0.1 M, 1 , K a1  10 –5
1
Ag+ 

Cl  AgCl G°1 =–109.7kJ/mole –1 Cl 2 CHCOOH  C 2 = 0.09 M,  2 , K a 2  ?
2 2
+
pH = 1, [H ] = 0.1
Ag  Ag + + e – G°2 = 77.2 kJ/mole –1
0.1 = 0.09 + C 1  1 + C 2  2
1 C 1  1 + C 2  2 = 0.01 ........(i)
e– + Cl 2   Cl – G°3 =–131.2kJ/mole –1
2 CH 3 COOH   
 CH 3 COO – + H +
so for reaction ( 
) C1
C 1 – C 1 1 C 1 1 0.1


AgCl  +
 Ag +Cl
–
G°=–G°1 +G°2 + G°3 
Cl 2 HCCOOH  Cl 2 HCCOO – + H +
G° = 55.7 kJ/mole C2
G° = – RT ln K sp C 2 – C 2 2 C 2 2 0.1
55.7 × 10 –3 = –8.314 × 298 ln K sp
K sp = 1.723 × 10 – 1 0 (C 1 1 )(0.1) ~  × 0.1 = 10 –5
K a1  1
1.723 × 10 –10 = [Ag + ] [Cl – ] = s × 0.05 C 1 (1  1 )
s = 3.446 × 10 –9 M  1 = 10 –4
 putting this in equation (i)((i) 
) 12. k 1 = 7.5 × 10 –3 , k 2 = 6.2 × 10 –8 , k 3 = 10 –12
10 –4 × 0.1 + 0.09 2 = 0.01 (a) H 3 PO 4 + NaOH  NaH 2 PO 4 + H 2 O
6 3
 2 = 0.111
3 – 3
(C 2 2 )(0.1) (0.111)(0.1) pH = pk 1 = 2.12
K a2  = = 1.248 × 10 – 2
C 2 (1  2 ) 1  0.111 (b) H 3 PO 4 + NaOH  NaH 2 PO 4 + H 2 O
6 6
10  0.935  1000 – – 6
8. C = = 5.5 M
17  100 pk 1  pk 2
K a = C 2  5.5 × 10 –6 = 5.5  2 pH = = 4.66
2
 = 10 –3 (c) H 3 PO 4 + NaOH  NaH 2 PO 4 + H 2 O
[OH – ] = C = 5.5 × 10 –3 4.8 7.2
pOH = 2.26 , pH = 11.74 – 2.4 4.8
NaH 2 PO 4 + NaOH  Na 2 HPO 4 + H 2 O
k w2 H  1 1 
9. ln  T  T  4.8 2.4
k w1 R  1 2  2.4 – 2.4
5.474  10 14 H  1 1  pH = pk 2 = 7.2
ln =    (d) H 3 PO 4 + NaOH  NaH 2 PO 4 + H 2 O
1.08  10 14 8.314  298 323 
4 10
H = 51952.6 J = 51.95 kJ/mole – 6 4
10. In begining [H + ] = K a C NaH 2 PO 4 + NaOH  Na 2 HPO 4 + H 2 O
4 6
[H + ] =
1.8  10 5 = 0.004242
– 2 4
pH = 2.372
Na 2 HPO 4 + NaOH  Na 3 PO 4 + H 2 O
On doubling pH, new pH(pH 
, pH) 4 2
= 4.744 2 – 2
[H + ] = 1.8 × 10 –5 pH = pk 3 = 12
CH 3 COOH 


–
 CH 3 COO + H
+ 13. For H 2 CO 3  k 1 = 4.2 × 10 –7 , k 2 = 4.8 × 10 –11
H 3 PO 4 k 1 =7.5× 10 –3 , k 2 =6.2× 10 –8 , k 3 = 10 –12
C
(a) Na 2 CO 3 + HCl    NaHCO 3 + NaCl
C – C   C C
2 2
(C  ) 2 – – 2
K a = , C = [H + ] = 1.8 × 10 –5
C(1   )
pk 1  pk 2
(1.8  10 5 ) 2
–5
pH = = 8.347
1.8 × 10 = 2
C  C
(b) Na 3PO 4 + HCl    Na 2 HPO 4 + NaCl
C – C = 1.8 × 10 –5
0.8 1.6
C = 3.6 × 10 –5
– 0.8 0.8
1 Na 2 HPO 4 + HCl    NaH 2 PO 4 + NaCl
V = = 2.77 × 10 4 L
C 0.8 0.8
11 .(a) PV = nRT – – 0.8
1 × 0.959 = n × 0.0821 × 298
pk 1  pk 2
n = 0.03919 pH = = 4.66
2
volume of H 2 O = 1 mL (per volume of H 2 O)
(c) Na 3 PO 4 + NaH 2PO 4  2Na 2 HPO 4
(H2O   = 1 mL (H2O   
)) 5 5
n 0.03919 – – 10
C = = = 39.19 M
V 10 3 pk 2  pk 3
pk b = 3.39  k b = 4 × 10 –4 pH = = 9.6
2
[OH – ] = K b C  0.1252M (d) H 3 PO 4 + Na 3PO 4  Na 2 HPO 4 + NaH 2PO 4
4 4
pOH = 0.9023 pH = 13.097
– – 4 4
(b) M = 0.1252 for NaOH (NaOH   0.1252) pH = pk 2 = 7.2
14. BOH + HCl  BCl + H 2 O 16. Initial (   = pKb =4.744
) pOH
4 4 Let x mole of NaOH has been added so (
NaOH
– – 4
x 
)
At end point m moles of BOH = m moles of HCl
[NH 4+ ] = 0.1 + x, [NH 3 ] = 0.1 – x
(
BOH m moles)
pOH = 5.744
0.16 × V = 4 V = 25 mL
Total volume (  ) = 40 + 25 = 65 mL 5.744 = 4.744 + log
0.1  x
4 0.1  x
[BCl] = 0.1  x
65
1 = log
since BCl is SAWB 0.1  x
1 1 0.1  x 0.9
pH = 7 – pk b  log C = 10  x = = 0.0818 moles
2 2 0.1  x 11
1 1 4
5.23 = 7 – pk b  log 17. Na 3 PO 4 + H 2 O  Na 2 HPO 4 + NaOH
2 2 65
pk b = 4.75 Kw
Now on further adding NaOH 
NaOH  K =
K3
= 0.0222

 Na 2 HPO 4 + H 2 O  NaH 2 PO 4 + NaOH

BCl + NaOH  BOH + NaCl
4 1.8 Kw
K = = 1.58 × 10 –7
2.2 – 1.8 K2
2.2 NaH 2 PO 4 + H 2 O  H 3 PO 4 + NaOH
pOH = pkb + log = 4.837 pH = 9.1628
1.8
0.06 Kw
15 .(a) pH = pK a + log K = = 1.4 × 10 –12
0.05 K3
pH = 3.744 + log 1.2 = 3.823
since equilibrium constant of 2 nd & 3rd reaction is
(b) On diluting solution 10 times (
10  very less, [OH–] will mainly come from 1st reaction.
) (
2nd  3rd 
[HCOOH] = 0.005, [HCOONa] = 0.006

, [OH–] 
1st 
)

HCOOH  
 H
+
+ HCOO –
Na 3 PO 4 + H 2 O  Na 2 HPO 4 + NaOH
0.005 0.1
0.005 (1 – ) 0.005 0.005 + 0.006 0.1–x x x
(0.005   0.006) (0.005  )
K a = 1.8 × 10 –4 = x2
0.005(1   ) = 0.0222  45x 2 + x – 0.1 = 0
0.005  2  0.006  0.1  x
= 1.8 × 10 –4
1 x = 3.73 × 10 –2
 27.772 + 34.33 – 1 = 0  = 0.0285 [OH – ] = x = 3.73 × 10 – 2 M
+
[H ] = 0.005 = 1.425 × 10 –4
pH = 3.846 Na 2 HPO 4 + NaOH  NaH 2 PO 4 + NaOH
(c) On further diluting solution by 10 times ( x
x – y y y + x

10 
)
x – y ~ x, y + x ~ x, so
[HCOOH] = 0.0005, [HCOONa] = 0.0006
 + (y  x)
HCOOH   H + HCOO – 1.58 × 10 –7 = yy
(x  y)
0.0005
NaH 2 PO 4 + H 2 O  H 3 PO 4 + Na OH
0.0005(1–) 0.0005   0.0005+0.0006
y
(0.0005   0.0006)(0.0005  ) y – z z z + x
K a = 1.8 × 10 –4 =
0.0005(1   ) y – z ~ y, z + x ~ x
0.0005 2  0.0006 
= = 1.8 × 10 –4 z(x  z) z  x z  3.73  10 –2
1 1.4 × 10 –12 = = =
2.77 2 + 4.33 – 1 = 0   = 0.2047 (y  z) y 1.58  10 7
[H + ] = 0.0005 = 1.0235 × 10 –4 z = 5.93 × 10 –18
pH = 3.9899 [H 3 PO 4 ] = z = 5.93 × 10 – 18 M
18. pH = 8, [H + ] = 10 –8 , [OH – ] = 10 –6 22. 4 m mole of H+ ion will produce (H+  4m


HCO 3–  +
 H + CO 3
–2
K = 5 × 10 –13 mol 
)
4  10 3
0.0005 [H + ] = = 0.04
0.1
0.0005–y–z 10 –8 y 1
PO 4–3 + H +  HPO 4–2
k3
Kw


HCO 3– +H 2 O  –
 H 2 CO 3 +OH K= =2 × 10 –8 0.02 0.04 0.08
K1 – 0.02 0.1
0.0005 1
HPO 4–2 + H +  H 2 PO 4– k2
0.0005–y–z z 10 –6
0.1 0.02
since equilibrium constant for first reaction is very
0.08 – 0.02
less y << z (
so now they form a buffer solution of HPO 4–2 &
y << z) H PO – (   HPO –2  H PO –  
2 4 4 2 4

z(10 ) 6 
)
2 × 10 –8 =
0.0005  z 0.08
pH = pk 2 + log (k 2 = 6.3 × 10 –8 )
51 z = 0.0005,  z = 9.8 × 10 –6 0.02
pH = 7.2 + log 4 = 7.8
[H 2 CO 3 ] = 9.8 × 10 –6 M 23. At equivalence point ( 
) 
[HCO 3– ] = 0.0005 – 9.8 × 10 –6 = 4.9 × 10 – 4 M meq. of HA = meq. of NaOH = 3.612
NaA + HCl    HA + HCl
10 –8  y
5 × 10 –3 = 3.612 1.806
4.9  10 4
1.356 – 1.806
[CO 3 –2 ] = y = 2.45 × 10 –8 M
[S]
pH = pK a + log
19. Fe +3 + H 2 O  Fe(OH) +2 + H + k = 6.5 × 10 –3 [A ]
x 1.356
4.92 = pK a + log
1.806
0.95x 0.05x 0.05x
pK a = 5.044
–3 (0.05) 2 x No w NaOH + HA  NaA
6.5 × 10 = x = 2.47
0.95 2 2
[H + ] = 0.05x = 0.1235 pH = 0.908 – – 2
salt 2
20. pH = pK 2 + log [NaA] =  0.1
acid 20
y
6.7 = 7.2 + log 1 1 5.044 1
0.005 pH = 7 + pK a + log C = 7 +  log 0.1
2 2 2 2
y = 1.58 × 10 –3 mole
pH = 9
21. When indicator is half in ionic form pH(   2 4 . In begining let x m mole of BOH are present (
   pH) = pKa = 7.2 
BOH x m mole) 
pH = 7.2 + log 5 = 7.898 BOH + HCl   BCl + H 2 O
x
now with this pH (   pH 
) 3x x
7.898 = pK a + log 4 = pK a = 7.2959 4 4
1 1
1
again when 50% of new indicator is in ionic form pOH = pk b + log
3
(
50% 
) 14 – 9.24 = pk b – log 3
pH = pK a = 7.2959 pk b = 5.237
1
k b = 5.8 × 10 –6
 now BCl + NaOH    B O H
26. 

Zn(OH) 2(s)  +2 –
 Zn (aq) + 2OH (aq) K sp
x
6 
Zn(OH) 2(s) + 2OH –   –2
4  [Zn(OH) 4] (aq) K C
– – x dissolved Zn(OH) 2 is present in form of Zn +2 &
x [Zn(OH) 4 –2 ]
= 6,  x = 24 so solubility s = [Zn +2 ] + [Zn(OH) 4 ] –2
4
24 (
Zn(OH)2Zn+2  [Zn(OH)4–2] 
[BOH] =  0.48
50 
[OH – ] = k b  C = 1.668 × 10 –3   
s = [Zn+2] + [Zn(OH) 4] –2 )
pOH = 2.77
K sp
pH = 11.22 s = + K C [OH – ] 2
[OH  ]2
25. (a) pH at one fourth neutralization (  
For min. solubility ( 
)

pH)
x/4 ds 2K sp
(pH)1 = pka + log = pka + log  = 0  + 2K C [OH – ] = 0
3x / 4 d[OH ] [OH  ]3
1
1/4
3  K sp 
–
pH at three fourth neutralization (  [OH ] = 
 KC 



pH)
[OH – ] = 9.8 × 10 –5
3x / 4 pOH = 4.00869
(pH)2 = pka + log = pka + log
x/4 pH = 9.9913
3
27. 

AgCl (s)  Ag + + Cl – K sp
pH = (pH) 2 – (pH) 1 = 2 log 3 =
0.9542 

Ag + + 2NH 3  +
 Ag(NH 3 ) 2 K 1 × K 2
x/3
(b) 4.45 = pk a + log = pk a – log 2 

AgCl (s) +2NH 3  Ag(NH 3 ) 2++Cl – , K = K sp K 1 K 2
2x / 3
pk a = 4.751 0.2
(c) pH = 2 i.e. 0.2–2x x x

(pH) 1 = pk a + 1, (pH) 2 = pk a – 1 x2
K = = K sp K 1 K 2 = 0.002828
[S] (0.2  2x)
For pk a + 1   10
[A ]
x
x = 0.05318
= 10   x = 10a – 10x 0.2  2x
a x
x = 0.009613
10a
x = Solubility ( 
) = 9.6 × 10 –3 M
11
28. [Cl – ] = 0.02 M
10 th
i.e. stage
11 

Ag(CN) 2–  +
 Ag +2CN
–
K inst = 4 × 10 –19
[S] 1 0.05
For pk a – 1  
[A ] 10 0.05–x ~ 0.05 x 2x
2
x 1 x.(2x )
= 4 × 10 –19 =
ax 10 0.05
a 4x3
x = = 4 × 10 –19  x = 1.7 × 10 –7
11 0.05
1 th
[Ag] [Cl] = 1.7 × 10 –7 × 0.02 = 3.4 × 10 –9 > K sp
i.e. stage
11 so AgCl w i ll precipitate. (  AgCl 

)
29. After mixing with equal volume (
kw
A –2 + H 2 O 


–
 HA + OH
–

) k2

[Ag + ] = 0.01 M, HCN = 0.01 M

kw


HA – + H 2 O  H 2 A + OH –


HCN  H + CN + –
Ka k1

1 k w [HA  ][OH  ] k w [A 2 ]


Ag + + CN –  AgCN (s) =  [HA –
] =
K sp k2 [A 2 ] k 2 [OH  ]


k w [H 2 A ][OH ] k w [HA  ]
=  [H 2 A] =


HCN + Ag +  + k1 [HA ]
k 1 [OH  ]
 H + AgCN (s) ,

Ka k 2w [A 2 ]
K = = 2.25 × 10 6 [H 2 A] =
K sp k 1 k 2 [OH  ]2

0.01 0.01 From mass balance (

) 

x x 0.01
k w [A 2 ] k 2w [A 2 ]
since K value is very high almost all of reactant will s = x + +
k 2 [OH  ] k 1 k 2 [OH – ]2
convert into product

(
K 
[H  ]x [H  ]2 x
s = x + 

) k2 k 1k 2

0.01
= 2.25 × 10 6 X = 6.6 × 10 –5 s
x2 x =
[H ] [H  ]2

1 
[Ag + ] = 6.66 × 10 –5 M k2 k 1k 2

30. MA  M + 2 + A –2

s s s2
k sp = [M +2 ] [A –2 ] = s . x =
[H  ] [H  ]2
1 
Let solubility is s. (
s 
) k2 k 1k 2

But some amount of A –2 will undergo hydrolysis.

Let x is the amount of A –2 left in solution.
 [H  ] [H  ]2 
s = k sp  1   
(A–2 
x  k2 k1k 2 


A–2 
)
IONIC EQUILIBRIUM EXERCISE # 4[B]

1.  pH = 1 ; H + = 10 –1 = 0.1 M 6. H 2 CO 3 (aq) + H 2 O()  HCO3– (aq) + H 3O + (aq)

+ –2
pH = 2 ; H = 10 = 0.01 M 0.034–x x x
 M 1 = 0.1 V1 = 1
M 2 = 0.01 V 2 = ? [HCO 3 ][H 3 O  ] xx
K1 = =
From [H 2 CO 3 ] 0.034  x

M 1V 1 = M 2V 2
0.1 × 1 = 0.01 × V 2 x2
 4.2 × 10 –7   x = 1.195 × 10 –4
V 2 = 10 litre 0.034

 volume of water added = 10 – 1 = 9 litre. As H 2CO 3 is a weak acid so the concentration of

H 2 CO 3 will remain 0.034 as 0.034 >> x.
+ [H  ] 10 3
2. H = C ;  = or  = = 10 –2 x = [H + ] = [HCO 3– ] = 1.195 × 10 –4
C 0.1
Now, HCO 3– (aq) + H 2O()  CO 2–
3
(aq) + H 3O +(aq)
Ka = C  2 = 0.1 × 10 –2 × 10 –2 = 10 –5
x–y y y
3. 

Cr(OH) 3 (s)  3+ –
 Cr (aq.) + 3OH (aq.) –
As HCO is again a weak acid (weaker than H2CO3)
3
27S 4 = K sp with x >> y.

1/4 1/ 4
 K sp   1.6  10 30  [CO 23  ][H 3 O  ] y  (x  y )
S =   =   K2 = 
[HCO 3 ] (x  y )
 27   27 

4. pH = 5 means Note : [H 3 O + ] = H + from first step(x) and from

[H + ] = 10 –5 second step(y) = (x + y)
[As x >> y so x + y  x and x – y  x]


HA  +
 H + A
–1

t = 0 c 0 0 yx
So, K 2  = y
x
teq c(1 – ) c c
 K 2 = 4.8 × 10 –11 = y = [CO 32– ]
[H  ][A  ] (c  )2 [H  ]2
Ka =   So the concentration of [H + ]  [HCO 3– ]
[HA ] c(1   ) c  [H  ]
= concentrations obtained from the first step. As
+
But, [H ] << C the first step. As the dissociation will be very low
–5 2 –10
 K a = (10 ) = 10 in second step so there will beno change in these
5. 

AgBr  Ag + Br
+ – concentrations.
[H + ] = [HCO 3– ] = 1.195 × 10 –4 & [CO 32– ]
K sp = [Ag +] [Br – ]
= 4.8 × 10 –11
For precipitation to occur
7. AgBr  Ag + = Br –
Ionic product > Solubility product
K sp = [Ag + ] [Br]
–13
K sp 5  10 For precipitation to occur Ionic product > Solubility
[Br – ] =  = 10 –11
[Ag  ] 0.05
product
–11
i.e., precipitation just starts when 10 moles of
K sp 5  10 13
KBr is added to 1 AgNO 3 solution [Br –] =   10 11
[Ag  ] 0.05
 Number of moles of Br – needed from
KBr = 10 –11 i.e., precipitation just starts when 10–11 moles of
 Mass of KBr = 10 –11 × 120 = 1.2 × 10 –9 g KBr is added to 1 AgNO 3 solution
  Number of moles of Br– needed from KBr = 10–11 11. 

MX 2  M ++ + 2X –
–11 –9
 Mass of KBr = 10 × 120 = 1.2 × 10 g s 2s
+ 2–
8. Na 2 CO 3 2Na + CO 3 Where s is the solubility of MX 2
1× 10 –4 M 1× 10 –4 M 1× 10 –4 M then K sp = 4s 3 ; (2s) 2 = 4 × 10–12 = 4s 3 ; s = 1 × 10 4
2+ 2–
K SP (BaCO 3 ) = [Ba ] [CO 3 ]  [M ++ ] = s = 1 [M ++ ] = 10 × 10 –4

5.1× 10 –9 1
[Ba 2+ ] = = 5.1× 10 –5 M 12. pH = –log[H + ] = log
1  10 4 [H  ]
9. In corresponds to choice (c) which is correct answer.

 1
BA + H 2 O  BOH + HA 5.4 = log
[H  ]
Base Acid
On solving, [H + ] = 3.98 × 10 –6
Now pH is given by
13. MX 4  M 4+ + 4X –
1 1 1
pH = pK w + pKa – pK b S 4S
2 2 2
K SP = [s] [4s] = 256 s 5
4

Substituting given values, we get

1/5
K 
1  s =  sp 
pH = (14 + 4.80 – 4.78) = 7.01  256 
2

10. Let s = solubility 14. Mg(OH) 2  [Mg 2+ ] + 2[OH – ]



AgIO 3  Ag + + IO 3 – x 2x
s s K sp = [Mg] [OH] = [x] [2x] 2 = x.4x 2 = 4x 3 .
2

K sp = [Ag + ] [IO 3– ] = s × x = s 2 15. AB 2  A +2 + 2B –

Given K sp = 1 × 10 –8 [A] = 1.0 × 10 –5 , [B] = [2.0 × 10 –5 ],
K sp = [B] 2 [A] = [2 × 10 –5 ] 2 [1.0 × 10 –5 ] = 4 × 10 –15
 s = K sp  1  10 8

= 1.0 × 10 –4 mol/lit
= 1.0 × 10 –4 × 283 g/lit
( Molecular mass of Ag IO 3 = 283)

1.0  10 4  283  100

= gm/100ml
1000

= 2.83 × 10 –3 gm/100 ml