Electrolysis

1. Electrolysis: decomposition of a compound in solution or molten state by passing

electricity through it.
2. Conductor: a solid substance that allows electricity to pass through it.
3. Non-conductor or insulator: a solid substance that does not allow electricity to
flow through it.
4. Electrolyte: a substance which, when dissolved or molten, conducts electricity and
is decomposed by it.
5. Non-electrolyte: a compound which cannot conduct electricity, be it in molten or
solution state.
6. Electrode: a graphite or metal pole (rod) or plate through which the electric current
enters or leaves the electrolyte.
7. Cathode: a negative electrode which leads electrons into the electrolyte.
8. Anode: a positive electrode which leads electrons out of the electrolyte.
9. Ion: a positively or negatively charged atom or radical (group of atoms).
10. Cation: a positive ion which moves to the cathode during electrolysis.
11. Anion: a negative ion which moves to the anode during electrolysis.
12. The electrolytic cell (voltameter): The apparatus in which electrolysis is carried
out is called electrolytic cell or voltameter
EVALUATION:
1) Define the term electrolysis
2) Differentiate between electrolytes and ions
3) State the functions of voltameter and electrodes
4) Define voltameter, electrodes and Hoffman voltameter
5) State Faradays two laws of electrolysis
Electrolysis of acidified water

A Hofmann voltameter is an apparatus for electrolyzing

water. It consists of three joined upright cylinders, usually glass. The inner cylinder is open at
the top to allow addition of water which contains a low concentration of a compound such
as sulfuric acid to improve conductivity and complete the circuit . A platinum electrode is placed
inside the bottom of each of the two side cylinders, connected to the positive and negative
terminals of a source of electricity. When current is run through Hofmann's voltameter,
gaseous oxygen forms at the anode and gaseous hydrogen at the cathode. Each gas displaces
water and collects at the top of the two outer tubes. The tubes which collect the product gases are
usually graduated, so that the volume of gas can be measured. the two-to-one ratio of the
volumes of hydrogen and oxygen gas produced by the apparatus illustrates the chemical formula
of water, H2O.

- H+ ions are attracted to the cathode, gain electrons and form hydrogen gas
- OH- ions are attracted to the anode, lose electrons and form oxygen gas. The overall
balanced equation for the process is: 2H2O(l) → 2H2(g) + O2(g)

EVALUATION:

(i) Explain the process of electrolysis of acidulated water

(ii) Explain the chemical equations
(iii) Explain the resultant effect of the process in the formation of water
(iv) Draw Hoffman voltameter in electrolysis of acidulated water

ELECTROLYSIS OF CUPPER (II) SULPHATE SOLUTION: Whenever copper sulfate or

CuSO4 is added to water, it gets dissolved in the water. As CuSO4 is an electrolyte, it
splits into Cu+ + (cation) and SO4 − − (anion) ions and move freely in the solution. The Cu+ +
ions (cation) will be attracted towards cathode. On reaching the cathode, each Cu+ + ion
will take electrons from it and becomes neutral copper atoms. Similarly, the SO4 − −
(anion) ions will be attracted by anode. So SO4 − − ions will move towards anode where
they give up two electrons and become SO4 radical. But since SO4 radical cannot exist in
the electrical neutral state, it will attack copper anode and will form copper sulfate. In
the above process, after taking electrons the neutral copper atoms get deposited on the
cathode. At the same time, SO4 reacts with copper anode and becomes CuSO4 but in
water it cannot exist as single molecules instead of that CuSO4 will split into Cu+ +, SO4 − −
and dissolve in water. So, it can be concluded that, during electrolysis of copper sulfate
with copper electrodes, copper is deposited on cathode and same amount of copper is
removed from anode. If during electrolysis of copper sulfate, we use platinum
electrode instead of copper, then electrolysis reactions will be little bit different.
Actually, SO4 cannot react with platinum and in this case the SO4 will react with water
of the solution and will form sulfuric acid and liberate oxygen at the anode.
CuSO4 (aq) → Cu2+ (aq) + SO42-(aq)

H2O⇔ H+ + OH–.

Cathode reaction: Cu2+(aq) + 2e- → Cu(s)

Anode reaction (If inert electrode like platinum is used instead of copper anode): 2H2O(l) →
O2(g) + 4H+(aq) + 4e-

Faradays first law of electrolysis: the amount of substance (m) deposited

or dissolved at the electrodes is directly proportional to the quantity of
electricity (Q) passed through the electrolyte.
Mathematically, m ∝ Q or m = zQ
where, z=electrochemical equivalent
Q = I.t hence, m = z.I.t
Faradays 2nd law of electrolysis: If the same quantity of electricity is
passed through different electrolytic cells, connected in series, the amounts
of substances deposited or liberated at the electrodes are directly proportional
to their chemical equivalent weights.
Mathematically, m1/m2 = E1/E2
Example 1: In the electrolysis of copper sulphate solution, a current of 3A is
passed through the electrolyte for 2hours. Given that the e.c.e of copper is
3.2 x 10-4gc-1, what is the mass of copper deposited at the cathode? Solution,
M = zIt = 3.2 x 10-4 x 3 x 2 x60x60
= 7.1g
Example 2: A cathode of initial mass 10g weighs 10.05g after a current of
3A passes through the voltameter for 10mins. Calculate e.c.e of the metal
deposited
Solution:m = zIt thus z = m/It
z = 10.05/3 x 10 x 60 = 5.57X 10-3gc-1
Example 3: a copper and a silver voltameter are connected in series, and
at the end of a period of time, 5g of copper was deposited, calculate the mass
of silver deposited at the same time. Chemical equivalent of copper = 31.5.
chemical equivalent of silver = 108. Solution: 5.0/mass of silver =31.5/108.
Thus, 108x5/31.5 = 17.4g = mass of silver deposited
EVALUATION:
(i) Explain the process of electrolysis of copper sulphate solution with copper and
platinum electrodes
(ii) Explain the chemical equations involved
(iii) Explain the resultant effect of the process in the color of the solution
(iv) Solve numerical questions on the relationship between the mass of substances
released at the electrodes and the quantity of electric charge passed through the
electrolyte (according to Faraday’s first and second law of electrolysis)
 Electrolysis Applications

1) Electrorefining – Purification of Metals

An aqueous solution of the metal salt with the impure metal as the anode and the pure
metal as the cathode is electrolyzed. The pure metal of more than 99% purity deposits
on the cathode, and the impurities are collected at the bottom as mud. Copper and
nickel are some examples of the metal purified by electrorefining.
2) Electroplating
The object to be coated is made of the cathode. An aqueous solution of the metal salt to
be coated is the electrolyte. The same metal or any inert metal can be the anode. In
electrolysis, metal ion from the electrolyte deposit on the object. The loss of metal ions
in the solution will be compensated if the same metal is made the anode.

Uses of Electroplating
• Improving the thickness of the metal surface.
• enhancing the appearance of the substance.
• to optimize a material’s resistance towards corrosion.
• Enhancing the electrical conductivity like plating a copper layer on an electrical
component.
• Minimizing Friction.
• Improving wear resistance.
• Improving surface uniformity.
3) Electro-forming
Electroforming is a process of making a replica of objects using electrolysis. The object
to be replicated is pressed in wax to make a mold. Graphite powder is coated uniformly
to make it conductive. This is used as a cathode, and the salt of the metal to be
deposited is taken as the electrolyte. After getting the required coating by electrolysis,
the wax and the graphite are melted away.
4) Manufacture of Pure Gases and pure metals
Pure hydrogen and oxygen are obtained by the electrolysis of acidified water. High
percentage of hydrogen for commercial use is manufactured in this way. Also, pure K,
Na and Al are obtained by electrometallurgy which is to extract them electrolytically from
their ores.
5) Manufacture of Compounds
Compounds like sodium hydroxide, potassium chloride, heavy water etc., are
manufactured by electrolysis.
EVALUATION:
(I) Explain electroplating of metal with appropriate diagram
(II) Explain purification of metals
(III) Explain electrolytic production of metals from their compounds
(IV) State chemical equations involved in the electrolytic extraction of metals from
their ores