ELECTROLYSIS
Electrolysis is a process of decomposing a substance using electrical energy.
Ionic compounds- conduct by movement of ions. They can only conduct in molten
state (liquid) or when dissolved in water (aqueous) because ions are free to move.
NB; ionic compounds do not conduct in solid state because their ions are strongly
attracted to each other.
An Electrolytic cell.
Cell
+ -
Bulb
Anode Cathode
--------------------
Electrolyte
Electrodes
PARTS OF ELECTROLYTIC CELL
✓ An electrolyte is a compound in solution or molten state which can conduct an
electric current.
✓ Electrodes are electric conducting materials like copper, platinum and carbon
rods. They are the;
Anode-it is connected to the positive terminal of a cell/battery.
It attracts anions during electrolysis.
Cathode- It is connected to the negative terminal of a cell/battery.
It attracts cations during electrolysis.
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They are classified into:
i) Inert electrodes-these are unreactive. .eg. Carbon and Platinum electrodes.
ii) Active/reactive electrodes-They react or are corroded during electrolysis.
ELECTROLYSIS OF MOLTEN LEAD BROMIDE,PbBr2(l)
It is a liquid.
IONS IN LIQUID LEAD (II) BROMIDE
PbBr2 (s) Pb2+( l ) + 2Br-( l )
Cathode and Anode reactions
a) At the cathode (-ve)
Pb2+ ions are attracted and discharged;
Pb2+ + 2e- Pb (s) [Reduction]
b) At the anode (+ve)
Br- ions are attracted and discharged.
2Br- Br2 + 2e- [oxidation]
OBSERVATIONS
Bubbles are produced and a brown gas is seen at the anode because bromine gas is
produced.
OVERALL ELECTROLYSIS EQUATION
Redox reaction; reduction + oxidation
[Cathode + Anode]
Pb2+ + 2e- Pb(s)
Br- Br2 + 2e-
______________________________________________________
．．．． ． ．．． ．． ．
．． ．．．
．
2+ - ．
Pb + 2Br Pb(s) + Br2
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Question
Show the ions in liquid, reaction at the cathode and anode for electrolysis of
molten (liquid) sodium chloride.
Soln
a. At the anode (+ve )
Cl- ions are attracted and discharged.
2Cl- Cl2 + 2e- [oxidation]
b. At the cathode (-ve)
Na+ ions are attracted and discharged.
Na+ + 1e- Na(s) [reduction]
Overall equation
2Na+ + 2e- 2Na(s)
2Cl- Cl2 + 2e-
2Na + 2Cl- 2Na + Cl2
Observation
Bubbles of a yellow gas (Cl2) are produced at the anode.
ELECTROLYSIS OF AQUEOUS SOLUTIONS
Aqueous means dissolves in water. Water takes part during electrolysis of salt
solutions, acids and alkalis because these substances influence water molecules to
separate into hydroxide (OH-) and hydrogen ions (H+).
.eg. H2O (l) H+ (aq) + OH- (aq)
H+ and OH- ions can also be discharged at the electrodes during electrolysis.
Copper (ii) sulphate solution has the following ions;
✓ Cu2+ and SO42- from copper (ii) sulphate.
✓ H+ and OH- ions from water.
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RULES OF SELECTIVE DISCHARGE
a) CATHODE RULES (-ve)
During electrolysis, ions of least reactive metals are selected and discharged first.
e.g
discharged Cu2+ e.g [Cu2+ + 2e- Cu(s) ]
first
H+ eg. [2H+ + 2e- H2 ]
Na+ [Ion of more reactive metal very difficult to discharge]
The above summary is obtained from the electrochemical series which is shown on
below.
ELECTROCHEMICAL SERIES may also be used
ATOM IONS USE
K K+ P-LEASE
Na Na+ S-END
Ca Ca2+ C-HARLIES
Mg Mg2+ M-ONKEYS
Al Al3+ A-ND
Zn Zn2+ Z-EBRAS
Fe Fe2+/3+ I-N
H H+ H-EAVY
Pb Pb2+ L-ARGE
Cu Cu2+ C-AGES
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b) ANODE (+ve)
Halides first (I-, Br-, Cl-, F-,), -for concentrated solutions.
e.g [2Cl- Cl2 + 2e- ]
Hydroxides (OH-) eg. [4OH- 2H2O + O2 + 4e- ]
Others (NO3-, SO42-etc, difficult to discharge)
✓ NB . Ions in high concentration are always discharged first.
Reactive electrodes always form ions in solution during electrolysis.
ELECTROLYSIS OF COPPER (II) SULPHATE SOLUTION using inert
electrodes
Inert electrodes: carbon or platinum
Ions in solution
a. From CuSO4 we have Cu2+ and SO42-
b. From water we have H+ and OH-
At the Anode (+ve)
SO42- and OH- ions migrate to the anode. OH- ions are selectively discharged forming
water and oxygen gas.
4OH- (aq) 2H2O (l) + O2(g) + 4e-
Observation
Bubbles of oxygen gas were produced.
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At the Cathode (-ve)
Cu2+ and H+ ions migrates to the cathode, Cu2+ ions are selectively discharged forming
red-brown copper metal.
Cu2+(aq) + 2e- Cu(s) [red-brown]
Observations
The cathode is coated by red brown colour of copper. The solution gradually charges
from blue to colorless.
NB; The solution becomes acidic because H+ and SO42- ions remain in solution.
OVERALL ELECTROLYSIS REACTION EQUATION
4OH- 2H2O + O2 +4e-
[Cu2+ +2e- Cu (s)] × 2 (multiply by two to cancel electrons)
4OH- 2H2O + O2 + 4e -
2Cu2+ + 4e- 2Cu (s)
-------------------------------------------------------------------
2Cu2+ + 4OH- 2H2O + 2Cu(s) + O2
ELECTROLYSIS OF COPPER(II) SULPHATE SOLUTION using copper
electrodes
NB; copper electrodes are reactive
Ion in solution-
From CuSO4 we have Cu2+ and SO42-
From water we have H+ and OH-
AT THE ANODE (+ve)
SO42- and OH- ions are attracted to the anode.
• the ions remains undischarged
• instead the copper anode is corroded forming copper(ii) ions
.ie. Cu(s) Cu2+ + 2e-
More Cu2+ are formed by the anode hence the solution remains blue.
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AT THE CATHODE (-ve)
Cu2+ and H+ ions are attracted to the cathode. Cu2+ ions are selectively discharged
forming copper.
.ie. Cu2+ + 2e- Cu (s)
OBSERVATION
✓ Anode is corroded
✓ Cathode is coated with red-brown copper.
✓ The solution remains blue or the intensity of the blue colour increases because for every
Cu2+ ions discharged at the cathode, a new Cu2+ is formed at the anode.
NB: Loss in mass by the anode equal to gain in mass by the cathode
ELECTROLYSIS OF DILUTE SULPHURIC ACID OR WATER.
IONS IN SOLUTION;
a) For H2SO4 = 2H+ and SO42-
b) For H2O = H+ and OH-
AT THE ANODE (+ve)
SO42- and OH- ions migrate to the anode. OH- ions are selectively discharged forming
water and Oxygen gas.
4OH- 2H2O + O2 + 4e-
OBSERVATION
Bubbles of oxygen gas produced. More gas is produced at the cathode than anode
(Why?).
AT THE CATHODE (-ve)
H+ ions migrate to the cathode and are discharged forming hydrogen gas.
2H+ + 2e- H2 (g)
OBSERVATION
Bubbles of hydrogen gas produced.
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OVERALL ELECTROLYSIS EQUATION
4OH- 2H2O + O2 + 4e-
[2H+ + 2e- H2 ] × 2
4OH- 2H2O + O2 + 4e-
4H+ + 4e- 2H2
………………………………………………………………..
4OH- + 4H+ 2H2O + O2 + 2H2
NB; The volume of hydrogen gas produced is twice that of oxygen gas. The mole ratio is
2H2: 1O2.
The two gases can be collected using the Hoffmann voltameter.
Hofmann Voltameter.
- +
RE ; concentration can also determine ions to be discharged. .i.e. ions in high
concentration are always preferred than those at low concentration.
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ELECTROLYSIS OF DILUTE AQUEOUS SODIUM CHLORIDE
IONS IN SOLUTION;
From NaCl = Na+ and Cl-
From H2O = H+ and OH-
ANODE (+ve)
Cl- ions OH- ions migrate to the anode OH- ions are selected and discharged (solution is
dilute hence there are more OH- ions than Cl-.
4OH- 2H2O + O2 + 4e-
CATHODE (-ve)
Na+ and H+ ions are attracted. H+ ions are discharged
2H+ + 2e- H2
ELECTROLYSIS OF CONCENTRATED AQUEOUS SODIUM CHLORIDE
(INERT ELECTRODES)
Ions in solution;
From NaCl = Na+ and Cl-
From H2O = H+ and OH-
ANODE (+ve)
Cl- and OH- ions migrate to the anode. Cl- ions are selected and discharged forming
chlorine gas (solution is concentrated hence there are more Cl- ions than OH-.
Observation
Bubbles of a yellow gas produced.
CATHODE
Na+ and H+ ions are attracted. H+ ions are selectively discharged forming hydrogen gas.
2H+ + 2e- H2
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FACTORS AFFECTING PREFERENTIAL DISCHARGE OF IONS
a) CONCENTRATION
Ions in high concentration are always discharged first than those at low concentration.
SOLUTION Ions in solution Anode reaction Cathode reaction
Dilute HCl H+ , Cl- 4OH- 2H2O + O2 + 4e- 2H+ + 2e- H2
+ -
H , OH
Conc. HCl H+ , Cl- 2Cl- Cl2 + 2e- 2H+ + 2e- H2
+ -
H ,OH
b) Types of electrodes used
Reactive electrodes (anode) are corroded during electrolysis.
Example
Solution Ions in sol Electrodes Anode Cathode
2+ 2-
CuSO4 Cu ,SO4 Platinum 4OH- 2H2 + O2 +4e- Cu2+ + 2e- Cu
H+ ,OH- (inert)
CuSO4 Cu2+ SO42- Copper Cu Cu2+ + 2e- Cu2+ + 2e- Cu
H+ , OH-
USES OF ELECTROLYSIS
1. ELECTROPLATING- It is the coating of a metal with a thin layer of another
metal.
REASONS
• to make a metal more attractive
• to prevent rusting/ corrosion of the original metal
Metals commonly used are; silver, copper, gold
STEPS FOR ELECTROPLATING
✓ Make the object ( eg. Ear ring) to be electroplated cathode
✓ Anode should be the same metal you want to electroplate with.
✓ Electrolyte should be a salt solution of a metal used for electroplating.
Example
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Copper plating; the ring becomes the………………, Copper wire
becomes……………the electrolyte is made up of a solution
of………………………………………………………..
Experimental set up
+ -
Bulb
Anode Cathode (ring)
--------------------
Electrolyte ( aq. CuSO4)
Electrodes
2. REFINING/ Purification of metals
EXAMPLE
Refining of copper and gold.
STEPS
✓ Anode should be impure metal.
✓ cathode should be pure metal (e.g copper)
✓ electrolyte should be a salt solution of a metal to be purified (e.g CuSO4 (aq)
Experimental set up.
+ -
Bulb
Anode Cathode ( pure copper)
--------------------
Electrolyte
Electrodes
Reaction equations:
Anode
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Cu Cu2+ + 2e-;
Cathode
Cu2+ + 2e- Cu (s)
NB; Loss in mass of the anode is equal to the gain in mass by the cathode.
3. Extraction of more reactive metals.
Example; ALUMINIUM
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