Electrolysis

• It is the process of decomposition of electrolytes by passing electricity through

its aqueous solution or molten form.
• Electrolytic cell: The cell in which chemical change is brought by the
application of electrical energy is called electrolytic cell. In such cell two
electrodes are dipped in the same electrolytic solution in the same container.
The electrode connected to positive terminal of battery is called anode and that
connected to negative terminal of battery is called cathode.
• Galvanic cell: The cell in which electrical energy is produced as a result of
chemical reaction is called galvanic cell. In such cell two electrodes with their
respective electrolytes are usually set up in two container. The two containers
are connected by salt bridge. Anode is negative and cathode is positive electrode
in such cell.
Redox reaction in electrolysis:
• Electrolysis involves either the generation of current as in galvanic cell (or voltaic
cell) or the consumption of electricity to cause electrochemical reactions as in most
of the electrolytic cell.
• During electrolysis, anions, being negatively charged ions, migrate towards the
positively charged electrode (anode) and cations, being positively charged ions,
migrate towards the negatively charged electrode (cathode).
• Oxidation of anions take place at anode and reduction of cations at cathode.
• The oxidation reaction at anode and the reduction reaction at cathode go side by side
and complete the net reaction undergoing on the system.
There are two aspects of electrolysis:
i. Qualitative aspect of electrolysis: It includes the normal phenomenon of electrolysis like
factors affecting the electrolysis, the fate of electrolysis, choice of electrodes,
concentration of electrolytic solution, presence of impurities, etc. The products obtained
during electrolysis depend upon the following factors:
 Nature of electrolytes
 State of electrolytes (Molten state or aqueous state)
 Concentration of electrolyte solution
 Nature of electrodes (Attackable or non- attackable)
 Charge density flown during electrolysis.
• Illustration with examples
i. Electrolysis of molten NaCl in presence of graphite or Pt: The electrodes that do not take
part in oxidation reduction reaction with electrolyte solution are called non- attackable
electrodes eg. Pt, graphite. When electricity is passed through molten NaCl then the ions
are discharged at the corresponding electrodes
NaCl ⇌ Na+ + Cl-
At anode (Oxidation): 2Cl- → Cl2 +2e-
At cathode (Reduction): Na+ + e- → Na
Cell reaction: 2NaCl → 2Na + Cl2
As a result of electrolysis of molten NaCl, chlorine is obtained at anode and sodium is
obtained at cathode.
[The potential at which ions are converted into neutral atom is called discharge potential]
ii. Electrolysis of aqueous NaCl solution in presence of platinum electrode: When
electricity is passed through aqueous NaCl solution, both cations (Na + and H+ ions) move
towards the cathode. Out of these two , H+ ion has lower discharge potential than Na + ion
(if the electrode is inert), Hence, H + ions are discharged in preference to Na+ ions.
Similarly, both Cl- and OH- ions move towards anode. Out of these two, Cl - has lower
discharge potential and is discharged in preference to OH - ions.
NaCl ⇌ Na+ + Cl-
H2O ⇌ H+ + OH-
At anode (Oxidation): 2Cl- → Cl2 +2e-
At cathode (Reduction): 2H+ + 2 e- → 2H2 b
Cell reaction: NaCl + H2O → NaOH + H2 + Cl2
Therefore, when aqueous solution of NaCl is electrolyzed, Cl 2 is obtained at anode and
H2 is obtained at cathode.
iii. Electrolysis of aqueous NaCl solution using graphite anode and mercury cathode:
NaCl ⇌ Na+ + Cl-
H2O ⇌ H+ + OH-
When mercury is used as cathode, the discharge potential of H+ ion will be high and
it is discharged only at high voltage. In this condition Na+ ion will be discharged in
preference to H+ ion.
Out of Cl- and OH- ions, Cl- ions have lower discharge potential and are discharged in
preference to OH- ions.
At anode (Oxidation): 2Cl- → Cl2 + 2e-
At cathode (Reduction): 2Na+ + 2 e- → 2Na
Thus obtained Na reacts with Hg of cathode and forms amalgam.
Na + Hg → NaHg
iv. Electrolysis of CuSO4 solution using non - attackable electrodes (Pt electrode):
CuSO4 ⇌ Cu++ + SO4--
H2O ⇌ H+ + OH-
Since discharge potential of OH- is less than that of SO4--, OH- are discharged in
preference to SO4--.
At anode (Oxidation): 4OH- → 2H2O + O2 + 4e-
Since discharge potential of Cu++ is less than that of H+, Cu++ is discharged in
preference to H+.
At cathode (Reduction): 2Cu++ + 4 e- → 2Cu
Therefore, oxygen is released at anode (or water is oxidized at anode) and copper is
deposited at cathode.
v. Electrolysis of CuSO4 solution using attackable electrodes (i.e, Cu electrode):
CuSO4 ⇌ Cu++ + SO4--
H2O ⇌ H+ + OH-
At Cu-cathode: Cu++ ion undergoes reduction to Cu in preference to H+ as
Cu++ + 2 e- → Cu (Reduction half)
At Cu-anode: Cu atom of anode undergoes oxidation to Cu++ in preference toSO4--
and OH- ions as
Cu – 2e- → Cu++ (Oxidation half)
The overall effect is Cu-anode is erroded and Cu-cathode is grown up in size.
 Quantitative aspect of electrolysis: It includes about the amount of substance decomposed
ii.
or deposited or liberated in electrolysis process.
• The quantitative relationship between the amount of electricity passed and the mass of ion
discharged in the voltameter was first investigated by Michael Faraday and gave the
following two laws in 1833.
Faraday’s first law of electrolysis:
• It states that the amount of substance discharged or liberated at the electrode during
electrolysis is directly proportional to the quantity of electricity (charge) passed through the
electrolyte solution.
According to this law,
Amount of substance discharged (m)  charged supplied (Q)
or, m = ZQ
or, m = ZIt [ Charge (Q) = current (I) x time (t) ]
where, Z = proportionality constant and known as electrochemical equivalent(ECE)
m = amount (mass) of substance discharged
Electrochemical equivalent (ECE):
We have, m = ZIt
If 1 ampere current is passed through the electrolyte solution for 1 sec (i.e. one coulomb
charge) then, m = Z. Hence, electrochemical equivalent of a substance is defined as the mass
of substance (in gram) deposited or liberated by the passage of one coulomb charge.
Faraday: The quantity of charge required to discharge or deposit one equivalent of any
substance is called Faraday. In terms of electrons it is defined as the charge carried by one
mole of electrons.
1 Faraday = Charge carried by 1 mole of electrons
= Charge on one electron x Avogadro’s No.
= 1.602 x 10-19 C x 6.023 x 1023
= 96488 C ( 96500 C)
Chemical equivalent
The amount of substance in gram liberated or deposited by passing 96500 coulomb charge is
called chemical equivalent or equivalent weight (E).
Significance of the laws of electrolysis
• 1 Faraday (96500 coulomb) charge deposits 1 gram equivalent of any substance. Let
E be the equivalent weight of a substance
i.e. 96500 coulomb deposits E g of substance
1 coulomb deposits g of substance
By definition ECE, Z =
Unit of Z is gram coulomb-1 or gram ampere-1 sec-1
Therefore, Faraday’s first law (m=ZIt) can also be mathematically expressed as, m=
One of the significance of the Faraday’s first law of electrolysis is that it helps to
calculate the electrochemical equivalent (ECE) of chemical substance.
Faraday’s second law of electrolysis:

• It states that when same quantity of electricity is passed through different electrolytic
solution connected in series, the mass of substance deposited or liberated at the
respective electrodes is directly proportional to its chemical equivalent or equivalent
weight. According to this law,
Mass of substance discharged (m)  chemical equivalent (E)
mE
or,
For two different substances

Where, m1 and m2 are the mass of two substances having chemical equivalent E 1 and E2
respectively deposited during electrolysis by passing same quantity of charge.
Relation between electrochemical equivalent (Z) and chemical equivalent (E):

From Faraday’s first law of electrolysis,

For two different substances in the voltameter if same quantity of charge is passed.
m1 = Z1Q …..(i)
m2 = Z2Q …..(ii)
Dividing equation (i) by (ii), we get
= …..(iii)
From Faraday’s second law of electrolysis, = …..(iv)
From equation (iii) and (iv)
=
Or, Z  E
Numerical problems
• 5 ampere current is passed through a voltameter containing CuSO4 solution for 15
minutes (having Cu-electrode). (a) calculate the mass of copper metal deposited. (b)
If mass of each electrode is 5g initially what will be the masses of anode and cathode
after electrolysis? (c) What will be the mass of Cu metal deposited if current
efficiency is only 75%?
(a) Total quantity of electricity (Q) = Current x time in second
=5A x (15x60)sec
=4500coulomb
Atomic mass of Cu =63.5
Equivalent mass of Cu = =31.75
• We know, 96500 coulomb charge deposits 31.75g of Cu
4500coulomb charge deposits
Alternately,
m=

(b) After electrolysis mass of anode is decreased and mass of cathode is increased
Mass of anode = 5 – 1.48 = 3.52g
Mass of cathode = 5+ 1.48 = 6.48g
(c) If current efficiency is 75%
The quantity of electricity (Q)= Current X time in second X current efficiency
Q = 5A X (15 X60 sec) X =3375coulomb
96500coulomb charge deposits 31.75g of Cu
3375coulomb charge deposits X 3375g =1.110g of Cu
• Calculate the number of coulomb of electricity required
(a) To discharge 0.3mol of Zn2+
(b) To deposit 4g of Mg from MgSO4
Solution: Zn++ + 2e- → Zn
1mol 2mol
1mole of Zn++ is discharged by 2 moles of electrons
0.3 mole of Zn++ is discharged by 2 X 0.3 moles of electrons
= 0.6 moles of electrons
We know,1mole of electrons = 96500coulomb
0.6 mole of electrons = 0.6 X96500coulomb
= 57900coulomb
[Alternatively, m = = where 1mol of Zn++ =65.3g and Eq. wt. = 32.65
0.3mol of Zn++ = 0.3 X 65.3g =19.59g]
(b) 1g equivalent of Mg = 12
Since, 1g equivalent of metal is deposited by 96500coulomb of charge
12g of Mg is deposited by 96500 coulomb
4g of Mg is deposited by X 4 = 32166.66 C

Alternatively,
[ m = =where m = 4g, E = 12]