5 Redox Solution

HINT & SOLUTION : REDOX EQUIVALENT
EXERCISE # (S-I)
1. (a) K[Co(C2O4)2 (NH3)2]
1 + x + 2x(–2) + 2 × 0 = 0
x=3
(b) K4 P2 O7
4 × 1 + 2x + 7x(–2) = 0
x = +5
(c) Cr O2 Cl2
x + 2(–2) + 2(–1) = 0
x=+6
(d) Mn3O4
3x + 4x(–2) = 0
8
x=+
3
(e) Ca (Cl O2)2
2 + 2(x + (2x – 2)) = 0
x = +3
(f) Zn O22
x + 2(–2) = –2
x = +2
(g) Fe0.93O
0.93 x – 2 = 0
200
x=
93
8
2. (1) + (2) +2 (3) +2.5 (4) –3 (5) +2 (6) +4
3
Nucleus Education-(NURTURE_(UNACADEMY)
(7) +2 (8) +4 (9) +4 (10) +5 (11) -3 (12) +5

(13) +2 (14) –3 (15) +1 (16) +8 (17) +4 (18) +6
(19) +8 (20) +4
3. 8
4. (a) S4O62–(aq) + 6Al (s) + 20 H+  4 H2S (aq) + 6Al3+ (aq) + 6H2O

(b) 6S2O32–(aq) + Cr2O72– (aq) + 14 H+  3 S4O62– (aq) + 2 Cr3+ (aq) + 7H2O
(c) 14ClO3–(aq) + 3As2S3(s) + 18 H2O  14 Cl–(aq) + 6H2AsO4–(aq) + 9HSO4–(aq) + 15H+
(d) 7IO3– (aq) + 6Re (s) + 3H2O 6 ReO4– (aq) + 7I – (aq) + 6H+
(e) 30HSO4–(aq) + As4 (s) + 10 Pb3O4(s) + 26H+  30 PbSO4 (s) + 4H2AsO4– (aq) + 24H2O
(f) 3HNO2(aq) HNO3 + 2NO (g) + H2O
C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Phone: 0744-2799900 Online Partner UNACADEMY 60
(g) 3MnO42– + 4H+  2MnO4– + MnO2 + H2O
(h) 4BCl3 + P4 + 6H2  4BP + 12HCl
(i) 2KMnO4 + 16HCl  2MnCl2 + 5Cl2 + 2KCl + 8H2O
(j) 2KMnO4 + 5H2O2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5O2 + 8H2O
(k) 2KMnO4 = K2MnO4 + MnO2 + O2
(l) Ca(OCl2) + 4KI + 4HCl  2I2 + 4KCl + CaCl2 + 2H2O
(m) 2Cu(NH3)4Cl2 + 7KCN + H2O = K2Cu(CN)3 + 6NH3 + KCNO + 2NH4Cl + 2KCl
5. (a) 3C4H4O62–(aq) + 5ClO3– (aq) + 18 OH–  12 CO32– (aq) + 5 Cl– (aq) + 15H2O
(b) 11Al (s) + 3BiONO3 (s) + 21H2O + 11OH–  3Bi (s) + 3NH3 (aq) + 11Al (OH)4–(aq)
(c) 4H2O2 (aq) + Cl2O7 (aq) + 2OH–  2ClO2– (aq) + 4O2 (g) + 5H2O
(d) Tl2O3 (s) + 4NH2OH (aq) 2TlOH (s) + 2N2 (g) + 5H2O
(e) Cu(NH3)42+ (aq) + S2O42– (aq) + 4OH–  2SO32– (aq) + Cu (s) + 4NH3 (aq) + 2H2O
(f) 3Mn(OH)2 (s) + 2MnO4– (aq)  5MnO2 (s) + 2H2O + 2OH–
(g) 3C2H5OH + 2MnO4– + OH– = 3C2H3O– + 2MnO2 + 5H2O
(h) 2ClO2 + SbO2– + 2OH– = 2ClO2– + Sb(OH)6– + 2H2O
(i) 2MnO4– + 3CN– + H2O 2MnO2 + 3CNO– + 2OH–
MM
6. Eq. wt. of salt =
Totalcationiccharge (nf )
(a) nf = 1
(b) nf = 2
(c) nf = 6
7. 22.4 L of a gas at STP = 1 mole

1
1.12 L of a gas at STP = × 1.12 = 0.05 moles
22.4
Mass of chlorine = moles × molar mass = 0.05 × 71 = 3.55 g
Thus mass of metal = Mass of metal chloride – mass of chlorine = (5.56 – 3.55)g = 2.01 g
3.55 gram of chlorine combine with = 2.01 g of metal
2.01
So 35.5 gram of chlorine combines with = × 35.5 = 20.1 g of metal
3.55
8. nf (CuS) =6
nf (Cu2S) =8
nf (KMnO4) =5
158
9. (a) Eq. wt. = = 31.6
5
158
(b) Eq. wt. = = 52.67
3
10. N1V1 = N2V2
3 × 5 = N2 × 250
N2 = 0.06 N
N
Also M2 = 2 = 0.03 M
2
11. (a) m.e. of H3PO4 – m.e. of Ca(OH)2
1 × V = 2 × 20
V = 40 ml.
(b) m.e. of H2SO4 = m.e. of Al(OH)3
1 × V = 1 × 3 × 20
V = 60 ml.
12. 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
13. NaH2PO4  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 lt
14. 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
15. CaCO3  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  11 250
 100  2  + (2 × 1 × V) = 1000
 
V = 25 ml
16. M eq. of Na2CO3 = M eq. of HCl

w
× 1000 = 50 × 0.1 – 10 × 0.16
106
2
w
% purity = × 100 = 90.1%
1
17. (a) 0.4 × 5 × V = 1 × 2 + 2 × 2

V = 3 lit
(b) 0.2 × 5 × V = 1 × 2 + 2 × 2
V = 6 lit
gm eq. of SO2 = gm eq. of MnO4

18.
10
2 × nSO2 = × 0.1 × 5
1000
Milli moles of SO2 = 2.5
19. Equivalents of MnO4 = eq. of SO24

18 × 5 = 4X
X = 22.5
20. On balancing
As2O5 + 10HCl  2AsCl3 + 5Cl2 + 2H2O
HCl is limiting
5
 Moles of Cl2 = ×5
10
= 2.5
Mass of Cl2 = 177.5 gm
21. 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.
22. Moles × 6 = 0.76 × 1

Moles = 0.1266
100
23. 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
24. Eq. of MnO4
= Eq of FeC2O4
5 × nKMnO4 = 3 × 1
3
nKMnO4 =
5
25. 0.1 × 5 × V = 2 ×  nf I
2
2 10 5
 nf I2 = 
12 3
5
0.1 × 5 × V = 2 ×
3
20
V= lit
3
10 5
26. 0.1 × × 5 = moles ×
1000 3
Milli moles = 3 m moles of Br2
4 2
27. 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
28. SeO2  CrSO4  Ce3+ + Sex
n (4 x) n 1
m.e. of SeO2 = m.e. of CrSO4

1 × (4 – x) × 10 = 2 × 1 × 20
x=0
29. V × 0.03 × 6 = 5 × 0.2 × 4
V = 2.22 ml
30. K2Cr2O7  KI  Cr3+ + I2

n 6 n 1
m.e. of K2Cr2O7 = m.e. of KI

m.m × 6 = 0.1 × 1 × 40
4
m.m. of K2Cr2O7 = = 0.667 m.m.
6
x
31. Weight of H2O2 in the mixture = 1 × gm
100
x
mole of H2O2 in the mixture = mole
100  34
H2O2 + KMnO4  M2n + O2
n 2 n 5
equivalent of H2O2 = equivalent of KMnO4
x
 2 = N × x × 10–3
100  34
20
N= = 0.588
34
1
32. M × 20 × 2 = 30 ×
12
1
M=
16
1
Strength = M × 34 = × 34 = 2.12 gm/lit
16
33. Sn K2Cr2O7 + HCl  SnCl4 + Cr3+

n 4 n 6
equivalent of Sn = equivalent of K2Cr2O7
11.9 1
4 = V
119 10
V = 4 lit
34. K2C2O4 · 3H2C2O4·4H2O + MnO4 + H+  Mn 2 + CO2
n 8 n 5

equivalent of MnO = equivalent of acid oxalate
4
5.08
0.1 × 5 × V = 8
508
V = 0.16 lit
35. 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
36. Meq. of I2 used = 20.10 × 0.05 = 1.005

Let meq. of As2O3 and As2O5 in mixture be a and b respectively.
Addition of I2 to mixture converts As32 into As52 .
Meq. of As2O3 = Meq. of I2 used = Meq. of As52 formed
a = 1.005 …….(i)
After oxidation, the mixture contains all the arsenic in +5 oxidation state, which is then reduced to
As32 by using KI and hypo.
Meq. of As2O3 as As5+ + Meq. of As2O3
= Meq. of I2 liberated = Meq. of hypo used
 1.113 
A+b=   1000
 248 
or a + b = 4.487 …….(ii)
By Eqs. (i) and (ii), we get b = 4.487 – 1.005 = 3.482
 Eq.mass  198 
 Mass of As2O3 =  Meq.  4 
EAs2O3
 1000 
1.005 198
= = 0.0497
4 1000
3.482  230  230 
Mass of As2O5 =
4 1000   EAs2O5
4 
= 0.2002
 Mass of mixture = 0.0497 + 0.2002 = 0.2501 gm

37. Meq of Mohr’s salt

= 35 × 1 × 1 = 35
Meq of KMnO4 = Meq of excess Mohr salt
= 30 × 0.1 × 5 = 15
Meq of Mohr salt reacted with bleaching powder = 35 – 15 = 20
Meq of Cl2 = 20
71
Weight of Cl2 = 20 × 10–3 × = 0.71 g
2
0.71
Percent of Cl2 = × 100 = 7.1%
10
EXERCISE # (S-II)
1. 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
2. Let the m mole of As2O3 = x

As2O5 = y
As2O3 + 2I2 + 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
3. Bleaching powder = CaOCl2

Mohr Salt = (NH4)2SO4 . FeSO4 . 6H2O
CaOCl2 + Fe2  Cl– + Fe3+
nf 2 nf 1
Fe2+ + KMnO4  Fe3+ + Mn2+

meq of Mohr Salt = meq of CaOCl2 + meq of KMnO4
35 × 1 × 1 = millin CaOCl2 × 2 + 30 + 0.1 × 5
m moles of CaOCl2 = 10
man of chlorine = 10 × 10–3 × 71
= 0.71 gm
0.71
% Chlorine = 100 = 7.1 %
10
4. Let the m mole of FeO = x
Let the m mole of Fe2O3 = y
KMnO4 + FeO  Fe + Mn
3+ 2+
n f 5 n f 1
meq of KMnO4 = m eq of FeO

2
× 100 × 5 = x × 1
5
x = 200
Total m moles of Fe3+ after the oxidation = x + 2y
Fe3+ + Zn  Fe2+ + Zn2+
Fe2+ + K 2Cr2 O7  Fe3+ + Cr3+
n f 6
2+
meq of Fe = meq of K2Cr2O7
2
(x + 2y) × 1 = × 1000 × 6 = 800
15
y = 300
5. Cu + H2SO4  Cu2+ + SO2

f  2
SO2 + KMnO4  SO42– + Mn2+

f 2 f 5
H2C2O4 + 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
6. KI + KIO3 + HCl  I2 + KCl + H2O

5 KI + KIO + 6HCl  3 I2 + 6KCl + 3H2O ....(1)
f 1 f 5 5
f 
3
I2  Na 2S2O3 + I– + Na2S2O3 ....(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
1
10 × 6 × = V
3
20 ml = V
 moles of HCl = 6 × moles of KIO3
24 × M = 6 × 20 × 0.004
MHCl = 0.2
7. H2O2 + Sn2+  Sn4+ + H2O

f 2
10
H2O2 
2
2 2
nf = =1
22
20
Initial moles of H2O2 =
34
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
8. Mn3O4  3Mn2+
x mol 3x mol
KMnO4 + C2O42 + 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
9. 4H2O + SCN–  SO24 + HCN + 7H+ + 6e–
I2 + 2e–  2I–
4H2O + SCN– + 3I2  SO24 + 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
10. 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
2
3  10  64
% w/w Cu = ×100 = 38.4 %
5
11. moles of Fe2O3 = 0.48 gm

0.48
moles of Fe3+ = ×2×10–2 = 6×10–3
160
Fe3+ + Zn  Zn2+ + Fe2+
6moles 6moles
2+
meq of Fe = meq of oxidising agent
n 25 ml = 30×0.01×n
1 0.01
6× ×1 = 30× ×n
4 100
n=5
12. 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
EXERCISE # (O-I)
1. A, B & C are disproportionation reaction
1
2. NaN3  N3 (charge on N = )
3
N2H2  N22 (charge of N = –1)
NO (charge on N = +2)
N2O5  (charge on N = +5)
3. On balancing
6HI + 2HNO3  2NO + 3I2 + 4H2O
staichionetriccoefficient of X 5
4. 

staichionetriccoefficient of XO3 1
5. On balancing
3CN– + 7 NO3 + 10H+  10 NO + 3CO2 + 5H2O
6. On balancing
2 KMnO4 + 5 H2O2 + 3 H2SO4  2 MnSO4 + 5 O2 + 8 H2O + K2SO4
Total = 26
7. H2O2  H2O + O2
Oxydation as well as reduction of O atom takes place.
8. All are disproportion reaction
9. Oxidising agent = IO3

Oxidised = Cr(OH)3
(nf)I = 6
10. Ba(SCN)2  Ba2+ + SO24  CO32  NO3


S C  N
0 2 3
nf = 12 + 4 + 16
= 32
11. Only (i) reaction is balanced.
(O.A)
Fe0.9O Fe2O3
12.
% Fe2+ % Fe+3
7 2
=
9 9
Fe+2 
K2Cr2O7
 Fe+3
7
× 0.9
9
7
nf = 1 × × 0.9 = 0.7
9
M 10M
Equivalent mass = 
0.7 7
2
13. Aº  A2Ox
x y
ni
M 2M  16x
Equivalent of M = Equivalent of M2Ox
x y
×x= × 2x
M 2M  16x
x y
=
M 2M 16x
Mn = 8x2 = My
8x 2
M=
yx
M
Eq. wt. of A =
x
2
8x 8x
= 
(y  x)x y  x
Molar mass
14. Equivalent wt. of Acid =
No.of replaceble H ions
15. A2Ox  AClx

3 gm 5 gm
3 5

E  8 E  35.5
E = 33.25
16. Equivalents = Mole  nf
6 1020
= × 1 = 10–3
6 10 23
17. N2  NH3
28
EW(N2 )  = 4.67
6
M
18.
5
19. Equivalents of M = equivalents of O2

Wmetal WO2

(equivalent mass)metal (equivalent mass)O2
Wmetal
=2
WO2
Wmetal  WO2 3
  = 1.5
Wmetal 2
20. Eq. H2SO4 = Eq. Na2CO3

0.125
0.1 × V (lit) = ×2
106
V (ml) = 23.6 ml
21. Eq. (HNO3) = Eq. (NaOH)

M1 n1 V1 = M2 n2 V2
18.9 3.2
× 1 × V1 = × 1 × V2
63 40
V1 4

V2 15
22. x=1
y=1
z=1
25 1.06
23. N  2
1000 106
N = 0.8
24. N V = Mass × nf
50 m
0.2 × = ×2
1000 126
m = 0.63 gm
63 125
25. Eq. (Acid) = × 10 × 2 ×
126 1000
= 1.25
40 125
Eq. (Base) = × 10 × 1 ×
40 1000
= 1.25
Hence neutral
26. In option D ,
4
gm eq KMnO4 = moles of KMnO4 × nf = ×5=4
5
gm eq  H2C2O4 = moles of H2C2O4 × nf = 2 × 2 = 4
Also CO2 produced  4 moles
 4 × 22.7 lit.
27. gm eq. KMnO4 = gm eq  H2O2

n × 5 = 2 × (4)
n = 8/5
28. gm eq. KHC2O4  2H2C2O4 = gm eq. of H2O2

2.8
Moles × 6 = 3 × ×2×2
22.4
Moles = 0.25
m moles = 250
29. nf when acid =1+4=5=x

nf in redox = 2 + 4 + 6 + (4 × 6) + [3 × (1 + 2)]
= 45
30. nf of FeS2 = 11
nf of CuS = 6
20 10 10
× N = 1 × 11 × +2×6×
1000 1000 1000
N = 11.5
31. MnO24  MnO4 + MnO2
Gram eq. of MnO24 = gm eq. of MnO4
 1 2 
1×   = 1 × moles of MnO4
 1 2 
2
Moles of MnO4 =
3
2
Mass of Mn in MnO4 = × 55
3
2
 55
% mass of Mn = 3 × 100
1 55
= 66.66 %
0.678
32. 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
33. (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
34. In option B
Cl2 is reduced to Cl–
35. 0.136 = 6 × moles
Moles = 0.0227
36. N = M × nf
0.6
M= = 0.2
3
5 1
37. NO3  NH2 OH
nf = 6
M
38.
5
39. 1 × 4 = 0.02 × 5 × V (ml)

4 100
= V (ml) = 40 ml
5 2
2
KOH  O30 KO31  O02
40.
Reduced
Oxidized
41. nf = 2
HNO2  N2O / HNO3
42. Since AlCl3 & NaCl are formed

100 × 0.1 × 4 = 0.25 × V (ml)
V = 160 ml
43. HCl + KBrO3 + KBr  Br2

Br2 + S2O32  Br– + S2O62
Gm eq. of HCl = gm eq. of Br2 = gm eq. of Na2S2O3
70 21
 ×M×1= ×2×1
1000 1000
M = 0.6 M
4 0 2 1
44. CHCl2 COOH  2CO2 + H2O + Cl2 (C2 H2 Cl2 O2 )
nf = 6
Moles × 6 = 600
Mole = 100 M moles
100Mmoles 1
For NH3, molesNH3 =
1
= 100 M moles
= 0.1 moles
3 4
45. H2 C2 O4  CO2
a 1 90
×2= 
90 20 1000
81
a=  0.2
400
0.2
% purity = × 100
0.3
= 66%
46. 2mole = 8eq 8eq

K3H(C2O4)2 + KMnO4  CO2
n=4 n=5
1mole=2eq 2eq
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
47. Let V1 & V2 are volumes of KMnO4 in 1st part & 2nd part
Reaction (1) KMnO4 + C2O24 
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
48. Let x gm be pure copper in the sample

ECu2  EI2   I
x
= ×1
63.5
 x 
 63.5 
 
n I2  
2
 x
127
 
n I2  E Na2S2O3
II
x 20
× 2 = 0.1 × ×1
127 1000
x = 0.127 gm
0.127
% Cu in sample = × 100
0.2
= 63.5%
49. E  AsO34  = E(I2)I

1
× 2 = E(I2)I
208
 2  1
n(I2)1 =   /2 =
 208  208
E(I2)II = E(Na2S2O3)
1
× 2 = 0.2 × V (lit)
208
V (ml) = 48.1 ml
50. XeF4 + KI  I2 + Xe + KF
I2 + Na2S2O3  Na2S4O6 + I–
20
x × 10–3 × 4 = × 0.1
1000
x = 0.5
35.5  2
51. % Cl = 100
40  16  (35.5  2)
71
= × 100  55.9%
127
52. KBrO3 + Na2S2O3  Br– + Na2S4O6

0.167 2
N1V1 = N2V2   6 = 45 × N × 10–3  N = N
167 15
53. (I) KIO3 + KI  I2

(II) I2 + S2O32  I– + S4O62
Gm eq. of S2O32 = 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
EXERCISE # (O-II)
1. E HNO3  E NH
4
n×1=2×3
n=6
2. I2 + 60 H–  5 I– + IO3 + 3H2O
n(IO3 ) 1

n(I ] 5
3. Balancing 
AS2O3 + 6 NaOH  Na3ASO3 + Na3AsS3 + 3H2O
x=1
y=6
1
4. H2O2  H2O + O2
2
Vol. of O2 at 27ºC = 500
Vol. of O2 STP
500  273
V=
300
V = 455
35 ml H2O2 give 455 ml O2
1 ml H2O2 give 13 ml O2
Vol. strength = 13 V
5. H2SO4 + H2C2O4 + impurity

n1 n2 n3 moles
n1 n 3
2 2 2 = × 0.1 ……(1)
100 100 1000
n2 4
× 2 = 0.02 × ×5 ……(2)
10 1000
 n1 = 0.028 n2 = 0.002
w1 = 2.744 w2 = 0.18
2.744
% weight of H2SO4 = 100
2.744  0.18 13.185
 40%
6
6. Cr2O72 + An–  Cr+3 + A+x
ECr O2  EAn
2 7
1.68 × 10–3 × 6 = 3.26 × 10–3 × (n + x)

6=2×n+x
3=n+x
x=3–n
0 2 6 0
7. Cl2  S2O32  SO42  Cl  S
nf = 2
(i) moles of S2O32 = M × V
= 0.01 × 50 × 10–3
= 5 × 10–4
= 0.0005
(ii) oxidising agent = Cl2
E = n × nf
= 5 × 10–4 × 2
= 10–3
= 0.001
8. CaCO3  CaO + CO2

n= 0.5 0.5
CO2 + 2NH3 + H2O  (NH4)2CO2
0.5 0.4 0.2
(NH4)2CO3 + 2HCl  2NH4Cl + H2O + CO2
0.2 0.2
Vol. of CO2 = 0.2 × 22.4 = 4.42
3 2 4
9. KMnO4 + H2C2O4  Mn  CO2
EKMnO4  EH2C2O4
M × nf × V = n × nf
50 3 2
M×5× =
1000 1000
24
m=
1000
N = m × nf
5  24 120
N=  = 0.12 N
1000 1000
23 6
10. 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
11. (A)  (q); (B)  (t); (C)  (r); (D)  (t)
12. Ba(MnO4)2 nf = (in acidic medium) = 5 × 2 = 10
13. nf of H3PO2
O
acid : no. of replaceable H+ = 1
P
HO H nf = 1
H
x 3 3
14. Fe0.95 O  Fe2 O3
(0.95)
 2 
x(0.95) = 2 nf =  3  
 0.95 
2
x= nf = 0.85
0.95
M M
Ew = 
n f 0.95
15. 2VO + 3Fe2O3  6FeO + V2O5

x, y = 2, 3
20 20
16. MH2O2  2 
22.4 11.2
20 200
× V × 2 = 0.1 ×
11.2 1000
V = 5.675 ml
200 m
17. 0.1 × = ×6
1000 294
m = 0.97 gram
18. 20V H2O2

1L H2O2 liberate 20  O2
20 22.4
11.2 ml H2O2 liberate × 11.2 = = 0.224
1000 100
= 224 ml
19. Use the reactions

K2CO3 + 2 HCl  H2O + CO2 + 2KCl
NaHCO3 + HCl  H2O + CO2 + NaCl
20. x=y
EXERCISE # (JEE-MAINS)
1. AgNO3 + KI  AgI + KNO3
is not redox
2. CaOCl2 has Cl– & ClO–
3. MnO4  Mn2+

6
MnO24
4
MnO2
3
M2O3
2
4. K4[Ni(CN)6 ]
5. KI + K2Cr2O7  Cr+3
3
6. [Cr(NH3 )4 Cl2 ]
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. (4)
11. Total e– = 6
4 1 6 0
12. XeF4  O2F2 
 XeF6  O2
Redn
Oxidation
13. C2O24  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.
EXERCISE # (JEE-ADVANCED)
1. Ba(H2PO2)2
 P = +1
2. NO3 + 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
 WH2O2  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
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. N1V1 = N2V2
N1 = Normality of H2SO4 = 0.5×2 = 1N
V1 = volume of H2SO4
0.5  2
N2 = Normality of copper (II) carbonate = N
123.5
V2 = Volume of copper (II) carbonate = 1000 mL
0.5  2
Thus, 1.0×V1 = 1000
123.5
Or V1 = 8.09 mL
13. N = M×nf
= 0.3×2  0.6
14. In CrO2Cl2, Cr is in +6
15. 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+.
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
16.   0.1 V
126 250
V = 40 mL
17. 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
Millimoles of H2O2 = 2×10–3
0.002
Molarity = 1000M
20
Molarity = 0.1 M
18. Mn+7 
Acidic
 Mn+2
Mn+7 
Neutral
 Mn+4
Mn+7 
Basic
 Mn+6
19. 3Na2CO + 3Br2  5NaBr + NaBrO3 + 3CO2
20. HNO3 (+5)

NO (+2)
NH4Cl (–3)
N2 (0)
21. 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
5
22. 5I– + ClO3 + H2SO4  Cl2 + HSO4  I2
2
23. ClO3 + 6I– + 6H2SO4  3I2 + Cl– + 6HSO4 + 3H2O
24. MnCl2 + K2S2O8 + H2O  KMnO4 + H2SO4 + HCl

a mg a mg

C2O42  MnO4 
H
 CO2  Mn 2
meq of C2O24 = meq of MnO4
2×0.255/90 = a×5
a = 1×[55 + 71]
= 126 mg
25. Conc. HNO3 oxidises rhombic sulphur (S8) to H2SO4 and itself gets reduced to NO2.
0 5 6 4
S8  48HNO3 
8H2SO4  48NO2 16H2O
1 mole of S8 gives 16 moles of H2O
Mass of H2O = 16×18 = 288 gm

5 Redox Solution

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5 Redox Solution

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HINT & SOLUTION : REDOX EQUIVALENT

(7) +2 (8) +4 (9) +4 (10) +5 (11) -3 (12) +5

4. (a) S4O62–(aq) + 6Al (s) + 20 H+  4 H2S (aq) + 6Al3+ (aq) + 6H2O

7. 22.4 L of a gas at STP = 1 mole

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

13. NaH2PO4  NaOH Na3PO4 + H2O

equivalent of NaH2PO4 = equivalent of NaOH

15. CaCO3  HCl  CaCl2 + H2CO3

KOH HCl  KCl + H2O

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

16. M eq. of Na2CO3 = M eq. of HCl

17. (a) 0.4 × 5 × V = 1 × 2 + 2 × 2

gm eq. of SO2 = gm eq. of MnO4

19. Equivalents of MnO4 = eq. of SO24

22. Moles × 6 = 0.76 × 1

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

30. K2Cr2O7  KI  Cr3+ + I2

m.e. of K2Cr2O7 = m.e. of KI

33. Sn K2Cr2O7 + HCl  SnCl4 + Cr3+

36. Meq. of I2 used = 20.10 × 0.05 = 1.005

 Mass of mixture = 0.0497 + 0.2002 = 0.2501 gm

37. Meq of Mohr’s salt

2. Let the m mole of As2O3 = x

equation of As2O3 = equation of I2

Total weight = 0.25075 gm

3. Bleaching powder = CaOCl2

Fe2+ + KMnO4  Fe3+ + Mn2+

meq of KMnO4 = m eq of FeO

5. Cu + H2SO4  Cu2+ + SO2

SO2 + KMnO4  SO42– + Mn2+

H2C2O4 + KMnO4  Mn2+ + CO2

meq of KMnO4 = meq of SO2 + meq of H2C2O4

WCu = 75 × 10–3 × 63.5

6. KI + KIO3 + HCl  I2 + KCl + H2O

I2  Na 2S2O3 + I– + Na2S2O3 ....(2)

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

7. H2O2 + Sn2+  Sn4+ + H2O

10. Cu2+ + KI  I2 + Cu+

11. moles of Fe2O3 = 0.48 gm

12. MnO2 + HCl  Cl2 + Mn2+

8. All are disproportion reaction

9. Oxidising agent = IO3

10. Ba(SCN)2  Ba2+ + SO24  CO32  NO3

11. Only (i) reaction is balanced.

15. A2Ox  AClx

19. Equivalents of M = equivalents of O2

20. Eq. H2SO4 = Eq. Na2CO3

21. Eq. (HNO3) = Eq. (NaOH)

27. gm eq. KMnO4 = gm eq  H2O2

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

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

39. 1 × 4 = 0.02 × 5 × V (ml)

42. Since AlCl3 & NaCl are formed

43. HCl + KBrO3 + KBr  Br2

46. 2mole = 8eq 8eq

H2C2O4 + KMnO4  CO2 + Mn2+

48. Let x gm be pure copper in the sample

49. E  AsO34  = E(I2)I

52. KBrO3 + Na2S2O3  Br– + Na2S4O6

53. (I) KIO3 + KI  I2

5. H2SO4 + H2C2O4 + impurity

1.68 × 10–3 × 6 = 3.26 × 10–3 × (n + x)

8. CaCO3  CaO + CO2

11. (A)  (q); (B)  (t); (C)  (r); (D)  (t)