(Physical Chemistry) REDOX EQUIVALENT

SOLUTIONS
EXERCISE # (O-I)
3. Oxidation state of Cr in both compounds is + 6 .

4. 2(+2) + 2x + 7( −2) = 0  x = +5

5.

6. (A) H 2S2O7 , Na 2S4O6 , Na 2S4O3 ,S8

(B) SO2+ , SO2− 2− −4
4 , SO3 , HSO4

(C) H 2SO5 ,H 2SO3 ,SCl2 ,H 2S

(D) H 2SO4 ,SO2 ,H 2S,H 2S2O8

4
7. 3x + 2(−2) = 0 ⇒ x = + 3

8.

9. CO is a neutral oxide.

10. 2x + 4(−2) + 2  0 + 2  0 = −2

 x = +3
11. H2O2 ⎯→ H2O + O2
Oxidation as well as reduction of O atom takes place.

12. All are disproportion reaction

13. A, B & C are disproportionation reaction

−
14. Oxidising agent = IO 3

Oxidised = Cr(OH)3
(nf)I = 6
APNI KAKSHA 1
(Physical Chemistry) REDOX EQUIVALENT
15. In option B
Cl2 is reduced to Cl–

16. On balancing
6HI + 2HNO3 ⎯→ 2NO + 3I2 + 4H2O

17. 2VO + 3Fe2O3 ⎯→ 6FeO + V2O5

x, y = 2, 3

18. Balancing 
AS2O3 + 6 NaOH ⎯→ Na3ASO3 + Na3AsS3 + 3H2O
x=1
y=6

19. On balancing
−
3CN– + 7 NO 3 + 10H+ ⎯→ 10 NO + 3CO2 + 5H2O

staichionetric coefficient of X − 5
20. −
=
staichionetric coefficient of XO3 1

21. On balancing
2 KMnO4 + 5 H2O2 + 3 H2SO4 ⎯→ 2 MnSO4 + 5 O2 + 8 H2O + K2SO4
Total = 26

22. Only (i) reaction is balanced.

M
23. NaHC2O4 is behaving as acid and hence, E= .
1
Molar mass
24. Equivalent wt. of Acid =
No.of replaceble H + ions

M
25. K 2CrO4 is behaving as salt and hence, E= .
2

APNI KAKSHA 2
(Physical Chemistry) REDOX EQUIVALENT
26. nf = 2
HNO2 ⎯→ N2O / HNO3

+5
−1
27. NO3− ⎯→ NH 2 OH

nf = 6

28. N = M × nf
0.6
M= = 0.2
3

29.
(O.A)
Fe0.9O Fe2O3

% Fe2+ % Fe+3
7 2
=
9 9
Fe+2 ⎯⎯⎯
K Cr O
→ Fe+3
⎯2 2 7

7
× 0.9
9
7
nf = 1 × × 0.9 = 0.7
9
M 10M
Equivalent mass = =
0.7 7
M
30.
5
2− 2− −
31. Ba(SCN)2 ⎯→ Ba2+ + SO 4 + CO3 + NO3

S−C  N
0 +2 −3

nf = 12 + 4 + 16
= 32
Redox titration (KMnO4 and K2Cr2O7 titration)

32. In option D ,
4
gm eq  KMnO4 = moles of KMnO4 × nf = ×5=4
5

gm eq  H2C2O4 = moles of H2C2O4 × nf = 2 × 2 = 4

APNI KAKSHA 3
(Physical Chemistry) REDOX EQUIVALENT
Also CO2 produced  4 moles
 4 × 22.7 lit.
33. 0.132 = 6 × moles
Moles = 0.022

34. 1 × 4 = 0.02 × 5 × V (ml)

35. KBrO3 + Na2S2O3  Br– + Na2S4O6

0.167 2
N1V1 = N2V2   6 = 45 × N × 10–3  N = N
167 15
36. Equivalents = Mol x nf

6 1020
= × 1 = 10–3
6 1023
37. gm eq. KMnO4 = gm eq  H2O2
n × 5 = 2 × (4)
n = 8/5

38. gm eq. KHC2O4  2H2C2O4 = gm eq. of H2O2

2.8
Moles × 6 = 3 × ×2×2
22.4
Moles = 0.25
m moles = 250

39. nf when acid = 1 + 4 = 5 = x

nf in redox = 2 + 4 + 6 + (4 × 6) + [3 × (1 + 2)]
= 45

40. MnO24− ⎯→ MnO −4 + MnO2

2− −
Gram eq. of MnO4 = gm eq. of MnO 4

 1 2  −
1×   = 1 × moles of MnO 4
 1+ 2 
− 2
Moles of MnO 4 =
3

APNI KAKSHA 4
(Physical Chemistry) REDOX EQUIVALENT
− 2
Mass of Mn in MnO 4 = × 55
3
2
 55
% mass of Mn = 3 × 100
1 55
= 66.66 %

0.678
41. V1 × 0.1 × 6 = × nf …….. (1)
38
0.678
V2 × 0.3 × 5 = × nf …….. (2)
38
(1) / (2)
V1 × 0.1 × 6 = V2 × 0.3 × 5
V1 15 5
= =
V2 6 2
2
V2 = V1
5
42. nf of FeS2 = 11
nf of CuS = 6
20 10 10
× N = 1 × 11 × +2×6×
1000 1000 1000
N = 11.5

43. XeF4 + KI ⎯→ I2 + Xe + KF
I2 + Na2S2O3 ⎯→ Na2S4O6 + I–
20
x × 10–3 × 4 = × 0.1
1000
x = 0.5

44. E ( AsO34− ) = E(I2)I

1
× 2 = E(I2)I
208

 2  1
n(I2)1 =  /2 =
 208  208

E(I2)II = E(Na2S2O3)

APNI KAKSHA 5
(Physical Chemistry) REDOX EQUIVALENT
1
× 2 = 0.2 × V (lit)
208
V (ml) = 48.1 ml

45. (1) V2O5 ⎯→ V2+

(2) V2+ + I2 ⎯→ VO2+ + I–
Let. Eq. (V2+)1 = Eq. (V2O5) = a
a
Moles of V2+ =
3
a
Eq. (V2+)2 = ×2= n I2 × 2
3
a
n I2 =
3
10
Eq. (V2O5) = ×6=a
182
10  6
n I2 =  0.11 moles
182  3

46. (I) KIO3 + KI ⎯→ I2

2− 2−
(II) I2 + S2O3 ⎯→ I– + S4O6
2−
Gm eq. of S2O3 = gm eq. of I2(II)
10
× 0.1 × 1 = mole I2(II) × 2
1000
10 − 3
Moles I2(II) = = moles I2(I)
2
Gm eq. of KIO3 = gm eq. of I2(I)
10 − 3  10  2 
Moles KIO3 × 5 =  
2  12 
1
 M. moles of KIO3 =
6

47. 2mole = 8eq 8eq

K3H(C2O4)2 + KMnO4 ⎯→ CO2
n=4 n=5
1mole=2eq 2eq

APNI KAKSHA 6
(Physical Chemistry) REDOX EQUIVALENT
H2C2O4 + KMnO4 ⎯→ CO2 + Mn2+
n=2 n =5
Total eq. of KMnO4 used = 10 eq = Normality × volume
10 eq = M × 5 × V1
10
V1 = lit.
5M

= lit.
M
2mole = 2eq 2eq = 1mole
K3H(C2O4)2 + Ba(OH)2 ⎯→ Ba(K3(C2O4)2)2 + H2O
n=1 n=2
1mole=2eq 2eq=1mole
H2C2O4 + Ba(OH)2 ⎯→ BaC2O4 + H2O
n=2 n =2
Total moles of Ba(OH)2 used = 2 mole = M × V2

V2 = lit.
M

V1
=1
V2

48. Let V1 & V2 are volumes of KMnO4 in 1st part & 2nd part
Reaction (1) KMnO4 + C 2 O 42 − ⎯⎯⎯
Acidic
→ CO2 + Mn2+

 0.5 × V1 × 5 = 1.5 × 125 × 2  V1 = 150 mL

Reaction (1) KMnO4 + I– ⎯⎯⎯
Basic
→ I2 + MnO2

 0.5 × V2 × 3 = 0.5 × 270 × 1  V2 = 90 mL

So initial volume = 150

49. Since AlCl3 & NaCl are formed

100 × 0.1 × 4 = 0.25 × V (ml)
V = 160 ml

+4 0 +2 −1
50. CHCl2 COOH ⎯→ 2CO 2 + H2O + Cl2 (C2 H 2 Cl2 O 2 )

nf = 6

APNI KAKSHA 7
(Physical Chemistry) REDOX EQUIVALENT
Moles × 6 = 600
Mole = 100 M moles
100 M moles 1
For NH3, moles NH3 =
1
= 100 M moles
= 0.1 moles

Acid – Base titration

51. Eq. (HNO3) = Eq. (NaOH)

M1 n1 V1 = M2 n2 V2
18.9 3.2
× 1 × V1 = × 1 × V2
63 40

V1 4
=
V2 15

52. x=1
y=1
z=1

25 1.06
53. N = 2
1000 106
N = 0.8
54. 23.6 mL of 0.1 NH2 SO4 solution will be required for complete reaction with a solution containing
0.125 g of pure Na2 CO3
For complete reaction no. of equivalents must be equal.
No. of moles of Na2 CO3 = mass / molar mass = 0.125/106 = 0.001179 mol
No. of equivalents of Na2 CO3 = no. of moles x valence factor = 0.001179 × 2 = 0.002358
This is no. of equivalents H2 SO4 must be present for complete reaction.
For H2 SO4 no. of equivalents = Normality × volume (in litres)

Meq of H2 SO4 = Meq of Na2 CO3

𝑉 0.125
0.1 × = ×2
1000 106
𝑉 = 23.6 mL

Therefore volume in L of H2 SO4 = 0.002358/0.1 = 0.02358 Litre = 0.02358 × 1000mil = 23.58ml

APNI KAKSHA 8
(Physical Chemistry) REDOX EQUIVALENT
55. Weight of metal = xgm and weight of oxide = y gm
∴ Oxygen consumed = (y − x)gm
Since (𝑦 − 𝑥) gm of oxygen combines with 𝑥 gm of metal
8x
∴ 8gm of oxygen will combine with y−x gm of metal
𝑥
Hence equivalent weight of metal = 𝑦−𝑥 × 8

56. A2Ox ⎯→ AClx

3 gm 5 gm
3 5
=
E + 8 E + 35.5
E = 33.25
57. Equivalents of M = equivalents of O2
Wmetal WO2
=
(equivalent mass) metal (equivalent mass) O2

Wmetal
=2
WO 2

Wmetal + WO2 3
 = = 1.5
Wmetal 2

APNI KAKSHA 9
(Physical Chemistry) REDOX EQUIVALENT
EXERCISE # (S-I)
1. (a) Cr O2 Cl2
x + 2(–2) + 2(–1) = 0
x=+6
(b) Mn3O4
3x + 4x(–2) = 0
8
x=+
3
(c) Ca (Cl O2)2
2 + 2(x + (2x – 2)) = 0
x = +3
2−
(d) Zn O 2

x + 2(–2) = –2
x = +2
(e) K4 P2 O7
4 × 1 + 2x + 7x(–2) = 0
x = +5
(f) Fe0.93O
0.93 x – 2 = 0
200
x=
93
(g) K[Co(C2O4)2 (NH3)2]
1 + x + 2x(–2) + 2 × 0 = 0
x=3

MM
10. Eq. wt. of salt =
Totalcationiccharge (n f )
(a) nf = 1
(b) nf = 2
(c) nf = 6

158
11. (a) Eq. wt. = = 31.6
5
158
(b) Eq. wt. = = 52.67
3

APNI KAKSHA 10
(Physical Chemistry) REDOX EQUIVALENT
12. nf (CuS) =6
nf (Cu2S) =8
nf (KMnO4) =5

Redox titration
−
13. gm eq. of SO2 = gm eq. of MnO 4
10
2 × n SO2 = × 0.1 × 5
1000
Milli moles of SO2 = 2.5
14. K 2 Cr2 O 7 + KI ⎯→ Cr3+ + I2
n =6 n =1

meq. of K2Cr2O7 = meq. of KI

mmoles × 6 = 0.1 × 1 × 40
4
mmoles of K2Cr2O7 = = 0.667 mmoles
6

15. Sn + K 2 Cr2 O 7 + HCl ⎯→ SnCl4 + Cr3+

n =4 n =6

equivalent of Sn = equivalent of K2Cr2O7

11.9 1
4 = V
119 10
V = 4 lit

− 2−
16. Equivalents of MnO 4 = eq. of SO 4

18 × 5 = 4X
X = 22.5

4+ 2+
17. Ce + Ce ⎯→ Sn4+ + Cex
n =4− x n =2

m.e. of Ce4+ = m.e. of Sn2+

1 × (4 – x) × 40 = 1 × 2 × 20
x=3

18. SeO2 + CrSO4 ⎯→ Ce3+ + Sex

n =(4− x) n =1

m.e. of SeO2 = m.e. of CrSO4

APNI KAKSHA 11
(Physical Chemistry) REDOX EQUIVALENT
1 × (4 – x) × 10 = 2 × 1 × 20
x=0

19. Moles × 6 = 0.76 × 1

Moles = 0.1266

20. H2O2 + KMnO4 + H+ ⎯→ Mn2+ + O2(g)

n=2 n=5
Number of equivalent of H2O2 = Number of equivalent of KMnO4
N1V1 = N2V2
2 × 0.1 × V = 5 × 0.1 × 1
V = 2.5 litre
= 2500 ml.

x
21. Weight of H2O2 in the mixture = 1 × gm
100
x
mole of H2O2 in the mixture = mole
100  34

H 2 O 2 + KMnO 4 ⎯→ M 2n+ + O2
n =2 n =5

equivalent of H2O2 = equivalent of KMnO4

x
 2 = N × x × 10–3
100  34
20
N= = 0.588
34

−
22. Eq. of MnO 4

= Eq of FeC2O4
5 × nKMnO4 = 3 × 1
3
nKMnO4 =
5
23. V × 0.03 × 6 = 5 × 0.2 × 4
V = 2.22 ml

10 5
24. 0.1 × × 5 = moles ×
1000 3

APNI KAKSHA 12
(Physical Chemistry) REDOX EQUIVALENT
Milli moles = 3 m moles of Br2

25. Fe2O3 do not react with KMnO4

KMnO4 + FeO ⎯→ Fe3+ + Mn+2
equation of KMnO4 = equation of FeO
158
 5 = FeO × 1
158
FeO = 5 WFeO = 360
WFe2O3 = 160 Fe2O3 = 1

1
Mole % of Fe2O3 = × 100 = 16.67
6

100
26. 5 × 0.1 × =x×2
1000
x = 25 × 10–3 moles
= moles of CuO = moles of Cu2O
Milli moles of Cu2+ = 3 × 25 × 10–3 moles
= 75 Milli moles

27. (a) 0.4 × 5 × V = 1 × 2 + 2 × 2

V = 3 lit
(b) 0.2 × 5 × V = 1 × 2 + 2 × 2
V = 6 lit

28. K 2 C2 O 4 · 3H2C2O4·4H2O + MnO−4 + H+ ⎯→ Mn 2+ + CO2

n =8 n =5

−
equivalent of MnO 4 = equivalent of acid oxalate
5.08
0.1 × 5 × V = 8
508
V = 0.16 lit
29. On balancing
As2O5 + 10HCl ⎯→ 2AsCl3 + 2Cl2 + 5H2O
HCl is limiting

APNI KAKSHA 13
(Physical Chemistry) REDOX EQUIVALENT
5
 Moles of Cl2 = ×2
10
=1
Mass of Cl2 = 71 gm

30. Eq. of K2Cr2O7 = Eq. of Fe2+ (initial + back titration)

25 × 0.002 × 6 = 100 × 1 × M + 7.5 × 0.01 × 1
M = 2.25 × 10–4

2.25 10−4  56
ppm = 106 = 126 ppm
100

31. Bleaching powder = CaOCl2

Mohr Salt = (NH4)2SO4 . FeSO4 . 6H2O

CaOCl2 + Fe 2 ⎯→ Cl + Fe
– 3+
nf = 2 n f =1

Fe2+ + KMnO4 ⎯→ Fe3+ + Mn2+

meq of Mohr Salt = meq of CaOCl2 + meq of KMnO4
35 × 1 × 1 = mmoles CaOCl2 × 2 + 30 x 0.1 × 5
m moles of CaOCl2 = 10
mass of chlorine = 10 × 10–3 × 71= 0.71 gm
0.71
% Chlorine = 100 = 7.1 %
10

32. MnO2 + HCl ⎯→ Cl2 + Mn2+

Cl2 + KI ⎯→ I2 + Cl–
I2 + Na2S2O3 ⎯→ I– + Na2 + Na2S4O6
eq of MnO2 = eq of hypo
1 1
n × 2 = 40× 
10 1000
n = 2×10–3

2  10−3  87
% w/w MnO2 = ×100 = 3.48 %
5

APNI KAKSHA 14
(Physical Chemistry) REDOX EQUIVALENT
Acid – Base titration

33. (a) meq. of H3PO4 = meq. of Ca(OH)2

1 × V x 3 = 2 × 30 x 2
V = 40 ml.
(b) meq. of H2SO4 = meq. of Al(OH)3
1 × V = 1 × 3 × 20
V = 60 ml.

34. Let 19 gm mixture contains x moles each of Na2CO3 and NaHCO3.

Therefore
106x + 84x = 19
x = 0.1
Since HCl reacts with mixture as:
HCl + Na2CO3 ⎯→ NaCl + H2CO3
HCl + NaHCO3 ⎯→ NaCl + H2CO3
equivalent of HCl used = equivalent of Na2CO3 + equivalent of NaHCO3
0.1 V = (x × 2) + (x × 1) = 3x
0.1 V = 3 × 0.1
V = 3 lit

35. NaH 2 PO 4 + NaOH ⎯→ Na3PO4 + H2O

n =2 n =1

equivalent of NaH2PO4 = equivalent of NaOH

mole of NaH2PO4 × 'n' factor = M × 'n' factor × V
12
2 = 1 × 1 × V
120
V = 0.2 lit
36. CaCO 3 + HCl ⎯→ CaCl2 + H2CO3
n =2 n =1

KOH+ HCl ⎯→ KCl + H2O

n =1 n =1

equivalent of CaCO3 + equivalent of KOH = equivalent of HCl used

 10 
  2  + (2 × 1 × V) = 1 1 250
 100  1000

V = 25 ml
APNI KAKSHA 15
(Physical Chemistry) REDOX EQUIVALENT

37. Ca(OH)2 + HCl ⎯→ CaCl2 + H2O

NaOH + HCl ⎯→ NaCl + H2O
m.e. of HCl used = m.e. of Ca(OH)2 + m.e. of NaOH
0.5 × 0.5 = m.m. of Ca(OH)2 × 2 + 0.3 × 20
19
m.m. of Ca(OH)2 = m.m.
2
19
wt. of Ca(OH)2 = × 10–3 × 74 gm
2

19 10−3  74
wt % of Ca(OH)2 = 100 = 1.406 %
2  50

APNI KAKSHA 16
(Physical Chemistry) REDOX EQUIVALENT
EXERCISE # (O-II)
6. 3I2 + 6NaOH ⎯→ NaIO3 + 5NaI + 3H2O
3
n-factor = of I2
5
5
n-factor of NaOH =
6
40
Eq. wt. of NaOH = = 48
5/6

−
7. (A) Eq. of MnO 4 = mole × nf

=1×5
Eq. of Fe2+ = 10 × 1 = 10
−
Eq. of MnO 4 < Eq. of Fe2+

(D) Eq. of Cu2S = 2 × 8 = 16

2−
Eq. of Cr2 O7 = 2.66 × 6 = 16
2−
Eq. of Cu2S = Eq. of Cr2 O7

215
8. E MnBr2 = = 12.65
17
240
9. E PbO2 = = 120
2

10. 2MnBr2 + 17PbO2 + 30HNO3 → 2HMnO4 + 2 Pb ( BrO3 )2 + 15 Pb ( NO3 )2 + 14H 2O

The reaction is balanced by the loss or gain of 34 electrons. Hence, E HNO = 30  63 = 55.6
3
34

11. Ba(MnO4)2 nf = (in acidic medium) = 5 × 2 = 10

12. nf of H3PO2
O
acid : no. of replaceable H+ = 1
P
HO H nf = 1
H

+x +3 +3
13. Fe 0.95 O ⎯→ Fe 2 O 3

APNI KAKSHA 17
(Physical Chemistry) REDOX EQUIVALENT
(0.95)

nf =  3 −
2 
x(0.95) = 2 
 0.95 
2
x= nf = 0.85
0.95

M M
Ew = =
n f 0.95

20 20
14. M H 2 O2 = 2 =
22.4 11.2
20 200
× V × 2 = 0.1 ×
11.2 1000
V = 5.675 ml

200 m
15. 0.1 × = ×6
1000 294
m = 0.97 gram

16. 20V H2O2

1L H2O2 liberate 20 O2
20 22.4
11.2 ml H2O2 liberate × 11.2 = = 0.224
1000 100
= 224 ml

N 3− −1
17. NaN3  (charge on N = )
3

N2H2  N 22 − (charge of N = –1)

NO (charge on N = +2)
N2O5  (charge on N = +5)

23 6
18. nf (P4H4) = =
2+3 5
2  10 20 5
n(I2) = = =
2 + 10 12 3
13  2 26
n(Mn3O4) = =
13 + 2 15
4 2 8 4
n(H3PO2) = = =
4+2 6 3
APNI KAKSHA 18
(Physical Chemistry) REDOX EQUIVALENT

19. (A) → (q); (B) → (t); (C) → (r)

APNI KAKSHA 19
(Physical Chemistry) REDOX EQUIVALENT
EXERCISE # (S-II)
1. moles of Fe2O3 = 0.48 gm
0.48
moles of Fe3+ = ×2×10–2 = 6×10–3
160
Fe3+ + Zn ⎯→ Zn2+ + Fe2+
6moles 6moles
meq of Fe2+ = meq of oxidising agent
n 25 ml = 30×0.01×n
1 0.01
6× ×1 = 30× ×n
4 100
n=5

2. Cu + H2SO4 ⎯→ Cu2+ + SO2

f = 2

SO2 + KMnO4 ⎯→ SO42– + Mn2+

f =2 f =5

H 2C2O4 + KMnO4 ⎯→ Mn2+ + CO2

f = 2 f =5

meq of KMnO4 = meq of SO2 + meq of H2C2O4

100 × 0.4 × 5 = meq of SO2 + 25 × 1 × 2
150 = meq of SO2 + meq of Cu
150
moles of Cu =  10 –3
2
WCu = 75 × 10–3 × 63.5

75 10–3  63.5
Weight of sample = 100 = 5 gm
95.25

3. H2O2 + Sn2+ ⎯→ Sn4+ + H2O

f =2

10
H2O2 ⎯→  +
2
2 2
nf = =1
2+2
20
Initial moles of H2O2 =
34

APNI KAKSHA 20
(Physical Chemistry) REDOX EQUIVALENT
moles of H2O2 after the with Sn2+
20 88.2 1
= −
34 1000
= 0.5882 – 0.0882
= 0.5
1 1
Moles of produced O2 = 0.5  =
2 4
1
Volume of O2 at 1 atm 273K =  22.4 = 5.6 lit
4

4. Cu2+ + KI ⎯→ I2 + Cu+
If = 1
I2 + Na2S2O3 ⎯→ Na2S4O6 + I–
meq of Cu2+ = meq of I2 = meq of hypo
20  0.03
moles of Cu 20 ml ×1 = = 6×10–4
1000
1000
moles of Cu in 1 litre = ×6×10–4 = 3×10–2
20
3  10−2  64
% w/w Cu = ×100 = 38.4 %
5

5. KI + KIO3 + HCl → I2 + KCl + H2O

5 KI + KIO + 6HCl → 3 I 2 + 6KCl + 3H2O ....(1)

f =1 f =5 5
f =
3

I + Na 2S2O3 + I– + Na2S2O3
2 ....(2)
f =2 f =1

meq of Na2S2O3 = meq of I2 in 2nd R × n

24 × 0.02 × 1 = 2 × I2

moles of I2 = 0.24
meq of I2 in 1st R × n = meq of KIO3
5
0.24 × = 0.004 × V × 5
3

APNI KAKSHA 21
(Physical Chemistry) REDOX EQUIVALENT
1
10 × 6 × =V
3
20 ml = V
 moles of HCl = 6 × moles of KIO3
24 × M = 6 × 20 × 0.004
MHCl = 0.2

6. Mn3O4 ⎯→ 3Mn2+
x mol 3x mol

KMnO4 + C 2 O 42 − + H+ ⎯→ Mn2+ + CO2

f =5

1.25
Molarity of KMnO4 sol = = 0.25
5
equation of KMnO4 = equation of Mn2+
0.25 × 4 × 3 = 3x × 1
x=1
w 229
% Mn3O4 =  100 = 50%
w 458

2−
7. 4H2O + SCN– ⎯→ SO 4 + HCN + 7H+ + 6e–

I2 + 2e– ⎯→ 2I–
2−
4H2O + SCN– + 3I2 ⎯→ SO 4 + HCN + 7H+

I2 + Na2S2O3 ⎯→ I– + Na2S4O6
meq of I2 = meq of SCN– + meq of hypo
50 × 6 = 2x × 6 + 26 × 1 × 1
x = 2 moles of Ba(SCN)2
2  253
% w/w of Ba(SCN)2 = ×10–3×100 = 25 %
2.024
8. Let the m mole of FeO = x
Let the m mole of Fe2O3 = y

KMnO4 + FeO ⎯→ Fe3+ + Mn2+

n =1
n f =5 f

meq of KMnO4 = m eq of FeO

APNI KAKSHA 22
(Physical Chemistry) REDOX EQUIVALENT
2
× 100 × 5 = x × 1
5
x = 200
Total m moles of Fe3+ after the oxidation = x + 2y
Fe3+ + Zn ⎯→ Fe2+ + Zn2+
Fe2+ + K 2Cr2O7 ⎯→ Fe3+ + Cr3+
n f =6

meq of Fe2+ = meq of K2Cr2O7

2
(x + 2y) × 1 = × 1000 × 6 = 800
15
y = 300
9. Let the m mole of As2O3 = x
As2O5 = y
As2O3 + 2I 2
+ 2 H2O ⎯→ As2O5 + 4H+ + 4I–
nf =4 nf =2

equation of As2O3 = equation of I2

x × 4 = 20 × 0.05
x = 25
Total moles of As2O5 after the P × n = x + y
As2O5 + 4H+ + 4I– ⎯→ As2O3 + 2I2 + 2H2O
nf =4

I2 + Na2S2O3 ⎯→ I– + Na2S4O6
equation of As2O5 = equation of I2 = equation of hypo
1.116
(x + y) × 4 = × 1000 = 4.5
248
x + y = 1.125
y = 0.875
WAS2O3 = 0.25 × 198 × 10–3 = 49.5 × 10–3

WAS2O5 = 0.875 × 230 × 10–3 = 201.25 × 10–3

Total weight = 0.25075 gm

10. n eq NaOH = n eq Oxalate

APNI KAKSHA 23
(Physical Chemistry) REDOX EQUIVALENT
9.15
30 
27  0.12 M y
or = …(1)
1000 1000
n eq KMnO 4 = n eq Oxalate

9.15
30 
36  0.12 M  2z
or = …(2)
1000 1000
From charge conservation,
x + y = 2z …(3)
and molar mass,
M = 39x + y + 88z + 18n … (4)

Solving (1),(2),(3) and (4)

We get, x:y:z = 1 : 3 : 2 and n = 2.

APNI KAKSHA 24
(Physical Chemistry) REDOX EQUIVALENT
EXERCISE # (JEE-MAINS)
1. AgNO3 + KI ⎯→ AgI + KNO3
is not redox
2. CaOCl2 has Cl– & ClO–

3. MnO −4 ⎯→ Mn2+
+6
MnO24−
+4
MnO 2
+3
M 2O3
+2
4. K 4 [Ni(CN) 6 ]

5. KI + K2Cr2O7 ⎯→ Cr+3
+3
6. [Cr(NH 3 ) 4 Cl 2 ]+

7. 2MnO−4 + 5C2O42− + 8H+ ⎯→ 2Mn2+ + 10CO2 + 4H2O

x = 2, y = 5, z = 8

8. 6Na2HASO3 + 2NaBrO3 + 12HCl ⎯→ 2NaBr + 6H3AsO4 + 12NaCl

x : y : Z (lowest ratio of whole number)
6 : 2 : 12
3 :1:6

9. R.A. loose electrons

10. Sn4+ is the oxidizing agent because it undergoes reduction

11. Total e– = 6

12.
+4 +1 +6 0
XeF4 + O 2 F2 ⎯⎯
→ XeF6 + O 2

Redn
Oxidation

APNI KAKSHA 25
(Physical Chemistry) REDOX EQUIVALENT
13. C2O42− + MnO4− + H + ⎯⎯
→ 2CO2 + Mn +2
e– involved in the reaction = 10
e– involved per mole of CO2 = 5

5 30
14.  M 1 =  0.1 2
1000 1000
M = 0.24
 0.24×V×1 = 30×0.2×1
6
V= = 25 mL
0.24

15. 50×0.5×2 = 25×M×1

M=2
50
Moles = M×V = 2×  0.1
1000
Mass = 0.1×40
= 4 gm

16. M×5 = 1×[(1+2) + (6) + (1)]

M×5 = 10
M=2

17. NO +2
N2O +1
NO2 +4
N2O3 +3

18. 2CuBr ⎯→ CuBr2 + Cu

is a disproportion reaction.
19. Eq of H2O2 = Eq of KMnO4
0.316
x×2= ×5
158
x = 5 × 10–3 mol
mH2O2 = 5 × 10–3 × 34 = 0.17gm

APNI KAKSHA 26
(Physical Chemistry) REDOX EQUIVALENT
0.17
%H2O2 = × 100 = 85
0.2
22.

24. Acid + Base ⎯⎯→ Salt + H2O

0.1 M M(OH)2
10ml 0.05 M
30 ml
at equivalence point
equivalent of acid = equivalent of base
0.1 × 10 × n = 30 × 0.05 × 2
n=3

25. MnO2 + HCl ⎯→ Cl2 Mn+2

6 meq 6 meq
= 3m mol
Cl2 + KI ⎯→ Cl– + I2
6 meq 6 meq
I2 + Na2S2O3 ⎯→ I– + Na2S4O6
6 meq 6m mol
= 6meq
−3
%MnO2 = 3 10  87 100
2
= 13.05%
Ans. 13
26. neq. of I2 = neq. of Na2S2O3 = 20 × 0.002 × 1
APNI KAKSHA 27
(Physical Chemistry) REDOX EQUIVALENT
2 × nmol of I2 = 0.4
nmol of I2 = 0.2 m mol
nmol of Cu+2 = 0.2 × 2 × 10–3

+2 0.4 10−3
[Cu ] = −3
= 0.04 = 4 10−2
10 10

Change in oxidation state of Mn is from +7 to +4 which is 3.

APNI KAKSHA 28
(Physical Chemistry) REDOX EQUIVALENT
EXERCISE # (JEE-ADVANCED)
1. Ba(H2PO2)2
 P = +1

2. NO 3− + 4H+ + e– ⎯→ 2H2O + NO
For charge balance 3e–

3. BaO2 + H2SO4 ⎯→ BaSO4 + H2O2

4. 2MnO−4 + 5C2O42− + 16H + ⎯→ 2Mn2+ + 10CO2 + 8H2O

5. Meq. Of H2O2 = Meq. of I2

WH2O2 0.508
  2 1000 =  2 1000
34 254
 WH 2O2 = 0.06g

1
H2O2 ⎯→ H2O2 + O2
2

 34g H2O2 gives 11.2 litres of O2 at STP

11.2
 0.068 g gives =  0.068 = 22.4 mL O2
34
22.4
 Volume Strength of H2O2 = = 4.48 volume
5

6. FeC2O4 + KMnO4 ⎯→ Mn+2 + Fe+3 + C+4

n×5 = 1×3
3
n=
5

7. n×5 = 1×2
2
n=
5

8. Let the total moles of O2 and O3 in the mixture be n.

Applying PV = nRT

APNI KAKSHA 29
(Physical Chemistry) REDOX EQUIVALENT
1×1 = n×0.0821×273
n = 0.044 moles
Moles of O3 = moles of I2 = 1/2 moles of Na2S2O3
1 1 40
=   = 0.002 moles
2 10 1000
Moles of O2 in the mixture = 0.044 – 0.002 = 0.042 moles
Mass of O2 = 0.042×32 = 1.344 g
Mass of O3 = 0.002×48 = 0.096 g
.096
% O3 =  100 = 6.67
1.44
Number of photons required to decompose 0.002 moles of ozone
= 0.002×6.02×1023
= 1.204×1021

9. When nt = 2
i.e. Mn+2 ⎯→ Mn+4

10. The reaction is as follows :

KIO3 + 5KI ⎯→ K2O + 3I2
0.1
Moles of KIO3 = 3 
214

2Na2S2O3 + I2 ⎯→ 2NaI + Na2S4O6

0.1
Moles of Na2S2O3 required = 3  2
214

Number of moles 0.1 1

Molarity = 1000 = 3   2  1000 = 0.0623
volumemL 214 45

11. S8 0
S2F2 +1
H2S –2
12. In CrO2 Cl2 , Cr is in +6

13. Fe3O4 is an equimolar mixture of Fe2O=3 and FeO. Thus, the sample contains Fe2O3, FeO and
impurities. The amount of iodine liberated depends on the amount of Fe2O3 and the entire iron
is converted into Fe2+.

APNI KAKSHA 30
(Physical Chemistry) REDOX EQUIVALENT
Fe3O4 + 2KI + H2SO4 ⎯→ 3FeO + H2O + K2SO4 + I2
Fe2O3 + KI + H2SO4 ⎯→ 2FeO + H2O + K2SO4 + I2
5×11.0 mL of 0.5 M Na2S2O3  55.0 mL of 0.5 N Na2S2O3 soln.
 55.0 mL of 0.5 N I2soln.
 55.0 mL of 0.5 N Fe2O3 soln.
= 27.5×10–3 equivalent Fe3O4 soln.
= 13.75×10–3 mole Fe2O3
2×12.8 mL of 0.25 M KMnO4soln.
 25.6 mL of 1.25 N KMnO4soln.
 25.6 mL of 1.25 N FeO soln.
= 32.0×10–3 equivalent FeO
= 32.0×10–3 moles FeO
Moles of FeO in Fe2O4 = 0.032 – 0.0275 = 0.0045
Mass of Fe3O4 = 0.0045×232 = 1.044 g
Moles of Fe2O3 = 0.0045×232 = 1.044 g
Moles of Fe2O3 existing separtely
= 0.01375 – 0.0045 = 0.00925
1.044
% Fe3O4 =  100 = 34.8
3
148
% Fe2O3 =  100 = 49.33
3

6.3 10
14.  = 0.1 V
126 250
V = 40 mL

15. 2KMnO4 + 3H2SO4 + 5H2O2 ⎯→ K2SO4 + 2MnSO4 + 8H2O

2KMnO4 + 3MnSO4 + 2H2O2 ⎯→ 5MnO2 + 2H2SO4 + K2SO4
MnO2 + Na2C2O4 + 2H2SO4 ⎯→ MnSO4 + Na2SO4 + 2H2O + 2CO2
Millimoles of Na2C2O4 = 10×0.2 = 2
mEq of Na2C2O4 = 4
mEq of MnO2 = 4
mEq of KMnO2 = 4
mEq of H2O2 = 4

APNI KAKSHA 31
(Physical Chemistry) REDOX EQUIVALENT
Millimoles of H2O2 = 2×10–3
0.002
Molarity =  1000M
20
Molarity = 0.1 M

16. Mn+7 ⎯⎯⎯

Acidic
→ Mn+2
Mn+7 ⎯⎯⎯
Neutral
→ Mn+4
Mn+7 ⎯⎯⎯
Basic
→ Mn+6

17. 3Na2CO3 + 3Br2 ⎯→ 5NaBr + NaBrO3 + 3CO2

18. HNO3 (+5)

NO (+2)
NH4Cl (–3)
N2 (0)

19. Household bleach + 2KI ⎯→ I2 + Products

I2 + 2Na2S2O3 ⎯→ Na2S4O6 + 2NaI
Amount of Na2S2O3 used = VM = (48×10–3L)(0.25 mol L–1) = 12×10–3 mol
1
Amount of I2 generated = (12×10–3 mol) = 6×10–3 mol
2
Assuming 1 mol of household bleach products 1 mol I2, we will have
Amount of household bleach in 25 mL solution = 6×10–3 mol

n 6 10−3 mol
Molarity household bleach = = = 0.24M
V 25 10−3 L

20. ClO 3− + 6I– + 6H2SO4 ⎯→ 3I2 + Cl– + 6HSO −4 + 3H2O

22. MnCl2 + K2S2O8 + H2O ⎯→ KMnO4 + H2SO4 + HCl

a mg a mg

+
C2O42− + MnO4− ⎯⎯
H
→ CO2 + Mn 2+
2− −
meq of C 2 O 4 = meq of MnO 4

2×0.255/90 = a×5
a = 1×[55 + 71]
= 126 mg
APNI KAKSHA 32
(Physical Chemistry) REDOX EQUIVALENT

23. Conc. HNO3 oxidises rhombic sulphur (S8) to H2SO4 and itself gets reduced to NO2.
0 +5 +6 +4
S8 + 48HNO3 ⎯⎯
→ 8H 2SO 4 + 48NO 2 + 16H 2O

1 mole of S8 gives 16 moles of H2O

Mass of H2O = 16×18 = 288 gm

24. Chemical reaction of KMnO4 and KI in weakly basic solution is given as

weak
KMnO4 + KI ⟶ MnO2 + I2
Basic

KMnO4 ⟶ MnO2
Oxidation state of Mn
+7 + 4
n-factor of KMnO4 = 3
2I − ⟶ I2
n-factor of I2 is = 2
KMnO4 + KI ⟶ MnO4 + I2
n-factor = 3 n-factor = 2
Equivalents of KMnO4 = Equivalents of I2
n-factor × Number of moles (n) = n-factor × Number of moles (n)
3 × moles of KMnO4 = 2 × moles of I2
3 × 4 = 2 × moles of I2
Moles of I2 = 6 moles

25. 8H + + 5Fe2+ + MnO− → 5Fe3+ + Mn2+ + 4H2 O

For 25ml,
meq of Fe2+ = meq of MnO−
= 12.5 × 0.03 × 5
For 250ml,
mmoles of Fe2+ = 12.5 × 0.03 × 5 × 250/25
moles of Fe2+ = 18.75/1000 mol
= 18.75 × 10−3 mol
= 1.875 × 10−2 mol
x = 1.875

APNI KAKSHA 33
(Physical Chemistry) REDOX EQUIVALENT
Weight of Fe2+ = 1.875 × 10−2 × 56 = 1.05 g
% purity of Fe2+ y = 18.75%
= 1.05/5.6 × 100

26. 8H + + 5Fe2+ + MnO− → 5Fe3+ + Mn2+ + 4H2 O

For 25ml,
meq of Fe2+ = meq of MnO−
= 12.5 × 0.03 × 5
For 250ml,
mmoles of Fe2+ = 12.5 × 0.03 × 5 × 250/25
moles of Fe2+ = 18.75/1000 mol
= 18.75 × 10−3 mol
= 1.875 × 10−2 mol
x = 1.875
Weight of Fe2+ = 1.875 × 10−2 × 56 = 1.05 g
% purity of Fe2+ y = 18.75%
= 1.05/5.6 × 100

H∗
27. KMnO4 ⟶ Mn+2
0
S −2 ⟶ S
∴ ntactor of KMnO4 = 5
ntactor of S −2 (H2 S) = 2
(nKMnO4 × 5) = (5 × 2)H2 S
[(GEN)KMnO4 = (GEP)H2 S ]
∴ nKMnO4 = 2
∴ 2KMnO4 + 3H2 SO4 + 5H2 S → K 2 SO4 + 2MnSO4 + 5 S + 8H2 O
Number of moles of water produced = ' 8 '
Number of moles of electrons involved = 10
∴ x = 8, y = 10 ⇒ (x + y) = 18

APNI KAKSHA 34