Faraday’s law of electrolysis : Electrolysis is the process of chemical decomposition of an electrolyte by passage of electric current through

its aqueous solution or molten state. The device in which electrolysis is carried out is known as electrolytic cell.
These laws present the relationship between the quantity of electric charge and the amount of the substance deposited at the electrode. These were
given by Faraday in 1834.
First law of electrolysis : This law states that the mass of the substance produced at the electrode (anode or cathode) in the electrolytic cell is
directly proportional to the quantity of electricity passed. The law can be mathematically put as,

W Q , Q is the quantity of electricity

W  It , I is current in amperes

W  ZIt , t is time in seconds, Z is the constant of proportionality called electrochemical equivalent. (E.C.E.)
If I = 1 ampere, t = 1 sec, then m = Z
Thus, electrochemical equivalent may be defined as the mass of the substance produced by passing 1 ampere of current through the electrolyte for
one second.
(1) Passage of 96500 c of electrolysis through electrolyte causes the deposition of one gm equivalent of the product.
(2) Z = E / 96500.
Second law of electrolysis : This law states that when same quantity of electricity is passed through two or more electrolytes connected in
series, then the mass of the substances produced at the electrodes are directly proportional to their equivalent masses or electrochemical
equivalents. For example, if same quantity of electricity produces the product A and B at the respective electrodes of the electrolytic cells connected
in series, then
EQ
W  ZQ 
96500

W1 Z1 E
  1
(Q = same)
W 2 Z 2 E 2

Current efficiency:
amount of subs tan ce actually formed
current efficiency  x100
weight subs tan ce exp ected

Applications of electrolysis :
(i) Determination of equivalent masses of elements, (ii) Electrometallyurgy, (III) Manufacture of non-metals, (iv) Electroplating of metal,
(v) Manufacture of compounds,
(vi) Electroplating – The process of coating an inferior metal with a superior metal by electrolysis.

Preferential discharge theory :

If an electrolyte solution consist of two or more ions and the electrolysis is done then these ions are not discharge at electrode
simultaneously but certain ions are liberate at the electrode in preference to other , this is explain by Preferential discharge theory :
According to this theory ,
When two or more cations are present in solution then the cation with higher value of SRP is preferentially discharged at
cathode
Similarly ,
When two or more anions are present in solution then the anion with higher value of SOP ( low value of SRP) is preferentially
discharged at anode
Discharging order of cation -
+ + +2 + +2 +3 +2 +3 + + +
Li < K < Ca < Na < Mg < Al < Zn < Fe < H < Cu < Ag
Discharging order of anion -
-2 - - - - -
SO4 < NO3 < OH < Cl < Br < I

EX -
(1) Electrolysis of molten NaCl :
 NaCl  Na+ + Cl -

At cathode - at anode -
Na+ + e-  Na 2 Cl -  Cl2 + 2e-
(2) Electrolysis of aq. NaCl ( using pt electrode ) :
Species in solution - Na+ , Cl - , H2O , H + , OH -,
At cathode - ( possible reaction ) -
Na+ + e-  Na (s) E0Na+/Na= -2.71 V [x]
2H2O(l) + 2e-  H2(g) + 2 OH-(aq) E0 H2O/H2 = -0.83 V [√ ]

At anode - ( possible reaction )

2 Cl -(aq)  Cl (g) + 2e 2
-
E0Cl - / Cl2 = -1.36 V [√ ]
2H2O(l)  O (g) + 4H (aq)
2
+
+ 4e
-
E0 H2O/O2 = -1.23 V [x]
At anode according to thermodynamics oxidation of water should takes place but the rate of oxidation of water is very slow and make it faster , some
extra potential ( called over voltage ) difference is applied during electrolysis of NaCl . At this extra voltage , the rate of oxidation of Cl- dominates
over the oxidation of H2O , so , Cl2 is formed at anode and H2 is formed at cathode

Na+ , Cl - At cathode - 2H2O(l) + 2e-  H2(g) + 2 OH-

H2O , electrolysis At anode - 2 Cl
-
 Cl2(g) + 2e-

Net reaction - 2 NaCl + 2H2O(l)  H2(g) + Cl2(g) +2 NaOH

Due to formation of NaOH in solution PH of solution increases
(3)Electrolysis of very dil. NaCl solution (inert electrode ) : Species in solution - Na+ , Cl - , H2O , H + , OH -,
At cathode - ( possible reaction ) -
+
Na (aq) + e
-
 Na(s)
0 +
E Na /Na= -2.71 V [x]
2H2O(l) + 2e-  H2(g) + 2 OH-(aq) E0 H2O/H2 = -0.83 V [√ ]

At anode - ( possible reaction )

2 Cl -(aq)  Cl (g) + 2e 2
-
E0Cl - / Cl2 = -1.36 V [x]
2H2O(l)  O (g) + 4H (aq)
2
+
+ 4e- E0 H2O/O2 = -1.23 V [√ ]
In this condition , there is very less chance of Cl- (less availability ) getting oxidised, so instead H2O will get oxidised
Electrolysis of aq NaCl solution (using Hg electrode) (active electrode ) :
(3)

At cathode - ( possible reaction ) -

Na+(aq) + e-  Na (s) E0Na+/Na= -2.71 V [√]
2H2O(l) + 2e-  H (g) + 2 OH (aq)
2
-
E0 H2O/H2 = -0.83 V [x ]

When Hg electrodes are used instead of Pt , Na+(aq) gets deposited which further react with Hg to form sodium amalgam
Na (s) + Hg (s)  NaHg(s)

At anode - ( possible reaction )

2 Cl (aq)
-
 Cl (g) + 2e 2
- 0 -
E Cl / Cl2 = -1.36 V [√ ]
2H2O(l)  O (g) + 4H (aq)
2
+
+ 4e
- 0
E H2O/O2 = -1.23 V [x]
(5) Electrolysis of aq. CuSO4 solution ( using inert electrode ) :
+2 -2
Species in solution - Cu , SO4 , H2O ,
At cathode - ( possible reaction ) -
+2
Cu + 2e
-
 Cu (s)
0 +2
E Cu /Cu = 0.34 V [√ ]
2H2O(l) + 2e
-
 H2(g) + 2 OH (aq)
- 0
E H2O/H2 = -0.83 V [x ]

At anode - ( possible reaction )

2 SO4 (aq)
-2
 S2O8 (aq)
-2
+ 2e
- 0 -2
E SO4 /S2O8 = -2.01 V [x ]
-2

2H2O(l)  O2(g) + 4H (aq) + 4e

+ - 0
E H2O/O2 = -1.23 V [√]
-----------------------------------------------------------
Net reaction - 2CuSO4 + 2H2O  2Cu(s) + O2(g) + 2H2SO4
+2
In this electrolysis O2 formed at anode and Cu deposited at cathode and solution becomes acidic due to H+ and PH decreases
(5) Electrolysis of aq. CuSO4 solution ( using Cu electrode ) :
+2 -2
Species in solution - Cu , SO4 , H2O
At cathode - ( possible reaction ) -
+2
Cu + 2e
-
 Cu (s) E Cu
0 +2
/Cu = 0.34 V [√ ]
+ 2e  H (g) + 2 OH (aq)
- - 0
2H2O(l) 2 E H2O/H2 = -0.83 V [x ]

At anode - ( possible reaction )

Cu (s)  Cu
+2
+ 2e
- 0
E Cu / Cu
+2
= - 0.34 V [√ ]
2 SO4 (aq)
-2
 S2O8 (aq)
-2
+ 2e
- 0 -2
E SO4 /S2O8 = -2.01 V [x ]
-2

2
2H2O(l)  O2(g) + 4H +(aq) + 4e- E0 H2O/O2 = -1.23 V [x]
(6) Electrolysis of H2SO4solution ( using inert electrode ) :
Species in solution - H+ , SO4-2 , H2O
At cathode - ( possible reaction ) -
2H2O(l) + 2e
-
 -
H2(g) + 2 OH (aq)
0
E H2O/H2 = -0.83 V [√ ] ---------------(i)

At anode - ( possible reaction )

2 SO4-2 (aq)  S2O8-2 (aq) + 2e- E0SO4-2 /S2O8-2 = -2.01 V [x ] ----------(ii)
2H2O(l)  +
O2(g) + 4H (aq) + 4e
-
E0 H2O/O2 = -1.23 V [√ ] ----------------(iii)

Note - for dil H2SO4 reaction (iii) is preferred but at higher concentration of H2SO4 and high current density , reaction (ii) is preferred , when 50% aq.

Solution of H2SO4 is used both reaction (ii) and (iii) occurs simultaneously at anode

BASED QUESTION

1. What weight of copper will be deposited by passing 2 faradays of electricity through a cupric salt (At. Wt. of Cu = 63.5)
(a) 2.0 g (b) 3.175 g (c) 63.5 g (d) 127.0 g
2. How many c.c. of oxygen will be liberated by 2 ampere current flowing for 3 minutes and 13 seconds through acidulated water
(a) 11.2 c.c (b) 33.6 c.c. (c) 44.8 c.c. (d)22.4 c.c.
3. 2.5 faraday of electricity is passed through a solution of CuSO4. The number of gram equivalents of copper deposited on the cathode will be
(a) 1 (b) 2 (c) 2.5 (d) 1.25
+ 2+ 3+
4. On passing 1 Faraday of electricity through the electrolytic cells containing Ag , Ni , Cr ions solution, the deposited Ag ( At.wt. = 108), Ni (At.wt. =
59), Cr (At.wt. = 52) are
Ag Ni Cr
(a) 108 gm 29.5 gm 17.3 gm
(b) 108 gm 59.0 gm 52.0 gm
(c) 108.0 gm 108.0 gm 108.0 gm
(d) 108.0 gm 117.5 gm 166.0 gm
3
5. On the electrolysis of acidified water, if volume of hydrogen liberated is 5.6 cm , then the volume of oxygen liberated is equal to
3 3
(a) 2.8 cm (b) 5.6 cm (c) 8.4 cm3 (d) 11.2 cm3
6. The charge required to liberate 11.5 g sodium from fused sodium chloride is
(a) 0.5 F (b) 1.0 F (c) 1.5 F (d) 96500 Coulombs
7. A 5 ampere is passed through a solution of zinc sulphate for 40 minutes. Find the amount of zinc deposited at the cathode
(a) 40.65 g (b) 4.065 g (c) 0.4065 g (d) 65.04 g
8. What is the amount of chlorine evolved when 2 amperes of current is passed for 30 minutes in an aqueous solution of NaCl
(a) 66 g (b) 1.32 g (c) 33 g (d) 99 g
3+
9. The charge required to deposit 9g of Al from Al solution is (At. Wt. of Al = 27.0)
(a) 3216.3 C (b) 96500 C (c) 9650 C (d) 32163 C
2- 3+
10. The charge required for the reduction of one mole of Cr2O7 ions to Cr is
(a) 96500 C (b) 2  96500 C (c) 3  96500 C (d) 6 96500 C
11. How many atoms of hydrogen are liberated at cathode, when 965 coulombs of charge is passed through water
(a) 6.02  1021 (b) 6.02  1023 (c) 6.02  1019 (d)1 1023/6.02
12 The passage of a constant current through a solution of dilute H2SO4 with ‘Pt’ electrodes liberated 336 cm3 of a mixture of H2 and O2 at S.T.P.
The quantity of electricity that was passed is
(A) 96500 C (B) 965 C (C*) 1930 C (D) 1/100 faraday
Sol. H2O →
H2 + ½ O2
2 × 96500 C 22.4 × 1000 cm3 H2
2 96500 224
2 2 .4 1 0 0 0
C 224 cm3 H2 = 1930 C.

13. A very thin copper plate is electro-plated with gold using gold chloride in HCl. The current was passed for 20 min. and the increase in the
weight of the plate was found to be 2g. [Au = 197]. The current passed was -
(A) 0.816 amp (B) 1.632 amp (C*) 2.448 amp (D) 3.264 amp
Sol. Gold chloride AuCI3
M 2 96500 3
m= 96500 n × I × t = 197  2 0  6 0 = 2.448A.

14 In the electrolysis of an aqueous SnCl2 solution, 4.48 L of chlorine at STP were liberated at the anode. The mass of tin deposited at the cathode
was (M of Sn = 118.5)
(A) 119 g (B) 79.3 g (C) 47.4 g (D*) 23.7 g
15 What must be the concentration of Ag+ in an aqueous solution containing Cu2+ = 1.0 M so that both the metals can be deposited on the cathode
0 0
E 2 E 
Cu Cu Ag Ag
simultaneously. Given that = – 0.34 V and = 0.812 V, T = 298 K
(A) nearly 10–19 M (B) 10–12 M (C*) 10–8 M (D) nearly 10–16 M
16 Electrolytic reduction of 6.15 g of nitrobenzene using a current effeciency of 40% will require which of the following quantity of electricity. [C = 12,
H = 1, N = 14, O = 16]
(A*) 0.75 F (B) 0.15 F (C) 0.75 C (D) 0.125 C

3
Sol.
= 0.05 mole of mitro benzene V.F = 6
6 .1 5
123
electricity of charge required if efficiency is 100% = 0.05 × 6 = 0.3 F
But efficiency is 40%
0 .3
0 .4
charge required = = 0.75.

17 Electrolysis of a solution of HSO 4 ions produces S 2 O 8 . Assuming 75% current efficiency, what current should be
employed to achieve a production rate of 1 mole of S 2 O 8 per hour ?
(A*) 71.5 amp (B) 35.7 amp (C) 142.96 amp (D) 285.93 amp
18 A current is passed through 2 voltameters connected in series. The first voltameter contains XSO4 (aq.) and second has Y2SO4 the relative
atomic masses of X and Y are in the ratio of 2 : 1. The ratio of the mass of X liberated to the mass of Y liberated is
(A*) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) None of the above
Sol. XSO4 (aq.) Y2SO4 (aq.)
M o l.m a s s X 2 m o l. m a s s X m o l. m a s s Y
M o l. m a s s Y 1 2 2
= , eq. wt. of X = eq. wt. of Y =
m as sof Y e q . w t. o f Y m o l.m a s s Y 2
m as sof X e q . w t. o f X m o l.m a s s X 1
= = = 1:1. ×
19.A current of 0.2 A is passed for 10 minutes through 0.05 dm3 of 0.1 M NaCl. If only chlorine is produced at anode and water is reduced to H2 at
cathode, what is the OH¯ concentration in the solution after electrolysis?
600  0 .2
Sol. The number of Faraday = = 1.243 × 10–3.
96500

At the cathode, reaction is H2O + e – ½ H2 + OH¯ →

–3
1.243 × 10 mol of OH¯ are produced.
The concentration = 1.243 × 10-3 / 0.05 = 0.02486 Molar.
20. Find the thickness of the electro deposited silver if the surface area over which deposition occurred was 100 cm2 and a current of 0.2 A flowed
for 1hr with the cathodic efficiency of 80%. Density of
Ag = 10 g/cc (Ag = 108).
1 0 8  0 .2  0 .8  3 6 0 0 1 0 8  0 .2  0 .8  3 6 0 0
9 6 5 0 0 1 0 0 1 0
Sol. Thickness × Area × density = 96500
; Thickness = cm = 6.4 × 10–4 cm

21. An acidic solution of Cu2+ salt containing 0.4 g of Cu2+ is electrolysed until all the copper is deposited. The electrolysis is continued for seven
more minutes with the volume of the solution kept at 100 mL and the current at 1.2 amp. Calculate the volume of gases evolved at NTP during the
entire electrolysis.
Ans. 158.98 ml.
Sol. Anode : 2H2O →
O2 + 4H+ + 4e–. Eº = – 1.13 V. Cathode : Cu2+ + 2e– Cu Eº = 0.34 V. →
2H+ + 2e– H2 → Eº = 0 V.
2H2O + 2e – H2 + 2OH .– → Eº = – 0.83 V.
+
H2O O2 + 2H + 2e . → –

Cu2+ + 2e– → Cu.

____________________________________
H2O + Cu2+ →
O2 + 2H+.
1 1 0 .4
2 2 6 3 .5
moles of Cu deposited = moles of O2 at NTP. Moles of O2 at NTP = × = 3.1496 × 10–3.
After complete electrolysis of Cu.
Charge passed = 1.2 × 7 × 60 = 504 coulomb.
504
96500
Moles of e– = = 5.2228 × 10–3. Moles of H2 at NTP = 2.6114 × 10–3 .
Moles of O2 at NTP = 1.3057 × 10–3.
Total moles of gases at NTP = 7.0667 × 10–3 moles.
Volume of gases evolved at NTP = 158.98 ml.
22. A 300 mL solution of NaCl was electrolysed for 6.00 min. If the pH of the final solution was 12.24, calculate the average current used.

Ans. 1.4 A.
Sol. Anode : 2CI– → Cl2 (g) + 2e– Eº = – 1.36 V

4
Cathods : 2H2O + 2e– →
H2(g) + 2OH– Eº = – 0.83 V
pH = 12.24 [OH–] = 0.0174M
Moles of OH– = 0.3 × 0.0174 = 5.213 × 10–3 moles = Moles of e–
Total charge = 5.213 × 10–3 × 96500 = 503.1 C.
5 0 3 .1
360
It = 503.1 I= = 1.4 A.

Ex. 5600 mL of oxygen at STP is liberated at the anode when 96500 coulombs of electricity is passed through acidified water. Calculate the charge
on an electron.
Sol. 96500 C of electricity liberates 5600 mL of O2 at STP i.e., 1 g eq. of O2 or 6.023 × 1023 electrons.

6.023 × 1023 electrons carry 96500 C.

96500 C
1 electron carries = = 1.603 × 10–19 C
6 . 023  10 23
Ex. If 3 Faradays of electricity are passed through a solution of ferrous bromide, how many grams of iron will be deposited if its atomic weight is 56 ?
Sol. Since 2e are involved in the deposition of Fe (Fe2+ + 2e Fe), the g. eq. wt. of Fe in Fe2+ = 28 g.
or 1F of electricity deposits 28 g of Fe 3F of electricity will deposit = 84 g of Fe.
Ex. The electrochemical equivalent of copper is 0.0003296 g coulomb–1. Calculate the amount of copper deposited by a current of 0.5 ampere
flowing through copper sulphate solution for 50 minutes.
Sol. According to Faraday's first law,
W = I.t.Z.= 0.5 × 50 × 60 × 0.003296 = 0.4944 g
Ex. How many coulomb are required to deposit 28 g Mg on passing through molten MgCl2 in presence of Pt electrodes ?

Sol. 12 g Mg (or 1 equivalent) are deposited by 96500 C

96500
28 g Mg are deposited by = × 28 = 225166.67 C
12
Ex. An electric current is passed through three cells connected in series containing ZnSO4, acidulated water and CuSO4 respectively. What amount

of Zn and H2 are liberated when 6.25 g of Cu is deposited ? Eq. wt. of Cu and Zn are 31.70 and 32.6 respectively.

Sol. Eq. of Cu = Eq. of Zn = Eq. of H2

6 . 25 w w H
Zn 2
= = wZn = 6.43 g and w H 2
= 0.197 g
31 . 70 32 . 6 1

Ex. Calculate the volume of Cl2 at NTP produced during electrolysis of MgCl2 which produces 6.50 g Mg. At.wt. of Mg = 24.3.

Sol. At cathode : Mg2+ + 2e 

 Mg

At anode : 2Cl– 
 Cl2 + 2e

Equivalent of Mg formed at cathode = Equivalent of Cl2 formed at anode

6 .5 w Cl 2
= = 18.99 g
25 . 3 / 2 35 . 5

w 18 . 99
At NTP PV = RT or 1 × V = × 0.0821 × 273 , Volume of Cl2 = 5.99 litre
m 71

Q-Calculate the volume of gas liberated at

anode at NTP from the electrolysis of CuSO4 solution by a current of 2 ampere passed for 10 minutes.

Sol. At cathode : Cu+2 + 2e 

 Cu

At anode :2H2O 
 4H+ + 4e + O2
32 E .i . t 32  2  10  60
E O = =8 W O = = = 0.0995 g
2
4 2
96500 4  96500

0 . 0995  22 . 4
At NTP : Volume of O2 = = 0.0696 litre
32
Q- By passing a certain amount of charge through NaCl solution, 9.2 litre of Cl2 were liberated at S.T.P. When the same
charge is passed through a nitrate solution of metal M, 7.467 g of the metal was deposited. If the specific heat of metal is 0.216 cal/g, what is
formula of metal nitrate ?
Sol. Sp. heat × at. wt. = 6.4

5
 6 .4 wt . of Cl 2
At. wt. of metal = = 29.63 Eq. of metal =
0 . 216 Eq . wt . of Cl 2

and 22.4 litre of Cl2 at S.T.P. weigh = 71 g

71  9 . 2
Eq. of Cl2 = = 0.82
22 . 4  35 . 5
at . wt .
Eq. wt. of metal =
Valency ( n )

7 . 467 n
= 0.82 or n = 3.25 n = 3 ( n is integer)
29 . 63
Q-An acidic solution of Cu+2 salt containing 0.4 g of Cu+2 is electrolysed until all the Cu is deposited. The electrolysis is continued for seven more
minutes with the volume of solution kept at 100 ml and the current at 1.2 ampere. Calculate volume of gases evolved at N.T.P. during
entire electrolysis. At. wt. of Cu = 63.6
Sol. For I part of electrolysis

Anode : 2H2O 
 4H+ + O2 + 4e

Cathode : Cu+2 + 2e 
 Cu
Eq. of O2 formed = Eq. of Cu

0 .4  2
= = 12.58 × 10–3
63 . 6
For II part of electrolysis : Since Cu+ ions are discharged completely and thus further passage of current through solution will lead the
following changes.

Anode : 2H2O 
 4H+ + O2 + 4e

Cathode : 2H2O + 2e 
 H2 + 2OH–
Eq. of H2 = Eq. of O2

i .t 1 . 2  7  60
= = = 5.22 × 10–3
96500 96500
Total Eq. of O2 = 5.22×10–3+12.58 × 10–3 = 17.8 × 10–3
2 Eq. of H2 at NTP= 22.4 litre
or 4 eq. O2 at NTP = 22.4 litre
5.22 × 10–3 Eq. at NTP
22 . 4  17 . 8  10
3

= L = 58.46 ml and
4

22 . 4  17 . 8  10
3

17.8 × 10–3 Eq. O2 at NTP= L= 99.68 ml

4
Note : If salt is CuCl2 than in II part of electrolysis Cl2 gas will liberate.