ELECTROCHEMIST

RY
 ELECTROLYSIS

ELECTROLYSIS IS THE DECOMPOSITION OF

COMPOUND USING ELECTRICITY ===
Electrolyte is an ionic compound which conducts electric
current in molten or aqueous solution, being decomposed in
the process.
Electrode is a rod or plate where electricity enters or leaves
electrolyte during electrolysis. Reactions occur at
electrodes.
Discharge is the removal of electrons from negative ions to
form atoms or the gain of electrons of positive ions to
become atoms.
 Anode is positive electrode connected to positive terminal of d.c. source.
Oxidation occurs here. Anode loses negative charge as electrons flow
towards the battery, leaving anode positively charged. This causes
anion to discharge its electrons here to replace lost electrons and also,
negative charge are attracted to positive charge.
 Cathode is negative electrode connected to negative terminal of d.c.
source. Reduction occurs here. Cathode gains negative charge as
electrons flow from the battery towards the cathode, making cathode
negatively charged. This causes cation to be attracted and gains
electrons to be an atom.
 Anion is negative ion. It’s attracted to anode.
 Cation is positive ion. It’s attracted to cathode.
Electrolysis of Molten Compounds
Molten/aqueous ionic compounds conduct electricity
because ions free to move. In solid state, these ions are held
in fixed position within the crystal lattice. Hence solid ionic
compounds do not conduct electricity.
When molten binary compound is electrolysed, metal is
formed on cathode while non-metal is formed on anode.
Electrolysis of Molten PbBr2
Electrolysis of Molten Compounds
 Electrolysis of Molten PbBr2
 To make molten lead(II) bromide, PbBr2, we strongly heat the solid
until it melts. To electrolyse it, pass current through the molten
PbBr2.
 Ions Present
 Pb2+ and Br-
 Reaction at Anode
 Br-loses electrons at anode to become Br atoms. Br atoms created
form bond together to make Br2 gas.
 2Br-(aq) Br2(g)+ 2e-
 ELECTROLYSIS OF…

MOLTEN LEAD BROMIDE

Pb2+

Br- Br-

ANODE

CATHODE
 ELECTROLYSIS OF…

MOLTEN LEAD BROMIDE

Pb Br Br

Pb2+

Br- Br-

ANODE 2Br- Br2 + 2e- OXIDATION

CATHODE Pb2+ + 2e- Pb REDUCTION

 Reaction at Cathode
 Pb2+ gains electrons at cathode to become Pb atoms becoming
liquid lead (II).
 Pb2+(aq) + 2e- Pb(l)
 Overall Equation
 PbBr2(l) Pb(l) + Br2(g)
EXERCISE 1
(a) The student used 20.0 cm3 of 0.500 mol / dm3 of lithium
hydroxide to prepare the crystals.
Calculate the maximum mass of hydrated lithium nitrate
crystals that could be made.
(b) Predict the products of electrolysis of molten lithium oxide
at the anode (positive
electrode), ................................................................................
.................
the cathode (negative
electrode). ................................................................................
... [2]
 Electrolysis of Aqueous Solution
 Aqueous solutions contain additional H+ and OH- ions of water, totalling 4
ions in the solution – 2 from electrolyte, 2 from water. Only 2 of these are
discharged.
 Electrolysis of aqueous solutions use the theory of selective discharge.
 At cathode
-In CONCENTRATED solutions of nickel/lead compound,
nickel/lead will be discharged instead of hydrogen ions of water
which is less reactive than nickel/lead.
-In VERY DILUTE solutions, hydrogen, copper and silver ions
are preferable to be discharged, according to its ease to be
discharged.
-Reactive ions (potassium, sodium, calcium, magnesium,
aluminium) will NEVER BE DISCHARGED in either
concentrated or dilute condition. Instead, hydrogen ions from
water will be discharged at cathode.
At anode

-In CONCENTRATED solutions, iodine/chlorine/bromine ions
are preferable to be discharged, although it’s harder to
discharged compared to hydroxide ions.
- In VERY DILUTE solutions containing iodide/chloride/bromide
ions, hydroxide ions of water will be discharged instead of
iodide/chloride/bromide, according to ease of discharge.
- Sulphate and nitrate are NEVER DISCHARGED in
concentrated/dilute solutions.
 Concentrated Solutions
Electrolysis of Concentrated NaCl
Ions Present
Na+, H+, OH- and Cl-
Reaction at Anode
Cl- loses electrons at anode to become Cl atoms, although
OH- is easier to discharge. Cl atoms created form covalent
bond together to make Cl2 gas.
 Concentrated Solutions
 2Cl (aq)
- Cl2(g)+ 2e-
 Reaction at Cathode
 H+gains electrons at cathode to become H atoms becoming
hydrogen gas.
 2H+(aq) + 2e- H2(l)
 Overall Equation
 2HCl(l) H2(l) + Cl2(g)
 Note:
any cation and anion left undischarged in solution forms
new bonds between them. E.g. in above, leftovers Na + and OH-
combine to form NaOH.
 Very Dilute Solutions
Electrolysis of Dilute H2SO4
Ions Present
H+, OH- and SO42-

Reaction at Anode
OH- loses electrons at anode to become O2 and H2O.
4OH- (aq) O2(g)+ 2H2O(l) +4e-
Reaction at Cathode
 Very Dilute Solutions
Reaction at Cathode
 H+ gains electrons at cathode to become H atoms becoming hydrogen gas.
 2H+(aq) + 2e- H2(g)
 Overall Equation
 Both equations must be balanced first. The cathode equation is short 2
electrons. Hence, we should first even them by multiplying cathode
equation by 2.
 (2H+ (aq) + 2e- H2(g)) x2
= 4H+(aq) + 4e- 2H2(g)
 Now we can combine the equations, forming:
 4H+(aq) + 4OH+(aq) 2H2(g) + O2(g)+ 2H2O(l)
 4H+
and 4OH+ ions, however, combine to form 4H2O molecules.
Hence:
 4H2O(l) 2H2(g) + O2(g)+ 2H2O(l)
 H2O molecules are formed on both sides. Therefore, they cancel
the coefficients:
 2H2O(l) 2H2(g) + O2(g)
 Since
only water is electrolysed, the sulfuric acid now only
becomes concentrated.
 ELECTROLYSIS OF…

DILUTE SULPHURIC ACID

SO42-

ANODE

CATHODE
 ELECTROLYSIS OF…

DILUTE SULPHURIC ACID

O O
H H
H H
SO42-

ANODE 4OH- 2H2O + O2 + 4e- OXIDATION

CATHODE 4H+ + 4e- 2H2 REDUCTION

 ELECTROLYSIS OF…

DILUTE SULPHURIC ACID

O O
H H
H H
SO42-

This
This electrolysis
electrolysis
ANODE 4OH -
2H2O + O2 + 4e OXIDATIONcan
-
can be
be used
used to
to
deduce the
CATHODE 4H + 4e
+ -
2H2 REDUCTION formula of water
 ELECTROLYSIS OF…

DILUTE HYDROCHLORIC ACID

 ELECTROLYSIS OF…

DILUTE HYDROCHLORIC ACID

Cl-

ANODE

CATHODE
 ELECTROLYSIS OF…

DILUTE HYDROCHLORIC ACID

H H
Cl Cl
Cl-

ANODE 2Cl- Cl2 + 2e- OXIDATION

CATHODE 2H+ + 2e- H2 REDUCTION

 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with carbon electrodes)

 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with carbon electrodes)

SO42-

Cu2+

ANODE

CATHODE
 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with carbon electrodes)

O O

Cu
SO42-

Cu2+

ANODE 4OH- 2H2O + O2 + 4e- OXIDATION

CATHODE 2Cu2+ + 4e- 2Cu REDUCTION

 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with copper anode)

A different reaction
takes place if the anode
is made of copper
 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with copper anode)

SO42-
Cu

Cu2+

ANODE

CATHODE
 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with copper anode)

Cu
SO42-
Cu

Cu2+

ANODE Cu Cu2+ + 2e- OXIDATION

CATHODE Cu2+ + 2e- Cu REDUCTION

 ELECTROLYSIS OF…

AQUEOUS COPPER SULPHATE (with copper anode)

Cu
SO42-
Cu

Cu2+

This
This electrolysis
electrolysis
ANODE Cu Cu2+ + 2e- OXIDATIONcan
can be
be used
used to
to
purify
purify copper
copper or
or
CATHODE Cu2+ + 2e- Cu REDUCTION copper plate
objects
objects
 EXERCISE 3
(a) The student used 15.0 cm3 of 2.00 mol / dm3 sulfuric acid to prepare
the crystals.
Calculate the maximum mass of hydrated copper(II) sulfate crystals
that could be made. [3]
(b) Aqueous ammonia is added to aqueous copper(II) sulfate until the
ammonia is in excess.
What is observed as the aqueous ammonia is added? 2]
(c) An aqueous solution of copper(II) sulfate is electrolysed using inert
electrodes. Predict the products of this electrolysis at
the anode (positive
electrode), .................................................................................................
And the cathode (negative
electrode). .............................................................................................[2]
Electrolysis Using Different Types of Electrodes
 Inert Electrodes are electrodes which do not react with electrolyte
or products during electrolysis. Examples are platinum and
graphite.
 Active Electrodes are electrodes which react with products of
electrolysis, affecting the course of electrolysis. Example is copper.
 Electrolysis of CuSO4 Using Inert Electrodes(e.g. carbon)
Ions Present
 Cu2+ , H+, OH- and SO42-
Reaction at Anode
OH- loses electrons at anode to become O2 and H2O.
4OH - (aq) O2(g)+ 2H2O(l) +4e-
Reaction at Cathode
Cu2+ gains electrons at cathode to become Cu atoms.
Hydrogen ions are not discharged because copper is easier to
discharge.
Cu2+(aq) + 2e- Cu(s)
 Now we can combine the equations, forming:
 2Cu(OH)2(aq) 2Cu(s) + O2(g)+ 2H2O(l)
 Since copper ions in solution are used up, the blue colour fades. Hydrogen and
sulphate ions left forms sulphuric acid.
 Electrolysis of CuSO4 Using Active Electrodes(e.g. copper)
 Ions Present
 Cu2+ , H+, OH- and SO42-
 Reaction at Anode
 Both SO42- and OH- gets attracted here but not discharged. Instead, the copper
anode discharged by losing electrons to form Cu2+. So, the electrode size
decreases.
 Cu(s) Cu2+ (aq) + 2e-
 Reaction at Cathode
 Cu2+ produced from anode gains electrons at cathode to become Cu atoms
becoming copper. Hence, the copper is deposited here and the electrode
grows.
 Cu2+ (aq) + 2e- Cu(s)
 Overall Change
 There is no change in solution contents as for every lost of Cu2+ ions at
cathode is replaced by Cu2+ ions released by dissolving anode. Only the
cathode increases size by gaining copper and anode decreases size by losing
copper. We can use this method to create pure copper on cathode by using
pure copper on cathode and impure copper on anode. Impurities of anode
falls under it.
Electrolysis of CuSO4 Using Active
Electrodes
 COMPOSITION OF WATER

WATER IS AN EXTREMELY POOR CONDUCTOR OF

ELECTRICITY. Dilute sulphuric acid must be added to HOFFMAN
improve Its conductivity. VOLTAMETER

Fill both limbs of a Hoffman Voltameter with water,

(acidified with a small amount of dilute sulphuric acid).
Pass a direct current through the apparatus.

ANODE (+) - a colourless gas collected

- the gas re-lit a glowing splint

CATHODE (-) - a colourless gas collected

- its volume was twice that at anode
- gas exploded with a squeaky pop
when a lighted splint was applied

Conclusion Water can be split into its elements

by passing electricity through it.

water ——> hydrogen (2 vols) + oxygen (1 vol).

 Electroplating
Electroplating is coating an object with thin layer of metal by electrolysis.
This makes the object protected and more attractive.
Object to be plated is made to be cathode and the plating metal is made as
anode. The electrolyte MUST contain plating metal cation.
Plating Iron object with Nickel
Reaction at Anode
Ni2+ discharged from anode into solution. So, the electrode size decreases.
Ni(s) Ni2+(aq) + 2e-
Reaction at Cathode
Ni2+ produced from anode gains electrons at cathode to become Ni atoms
becoming nickel. Hence, the nickel is deposited here and the electrode
grows.
For electroplating, you need:
 -an anode made of the metal that you want to electroplate the object with,
 -ions of the same metal as the anode in solution
 -object to be plated at cathode
 Electroplating is used to make things look better (coating a watch with gold) or to prevent corrosion.
Ni2+(aq) + 2e- Ni(s)
Overall Change
 There is no change in solution contents while iron object receives
nickel deposit.
Creation of Electric Cells by Electrolysis
An electric cell consists of 2 electrodes made of 2 metals of
different reactivity. The cathode is made of more reactive
metal. This is because they have more tendency of losing
electrons. The cathode is made of less reactive metal. The
more further apart the metals in reactivity series, the
higher voltage is created.
 Exercise 4
(a. ) Draw a labelled diagram to show how a steel
rod can be electroplated with copper. [3]

(b.) A 11.09 g sample of an oxide of copper contains

9.86 g of copper. Deduce the empirical formula of
this oxide of copper. [2]
Creation of Electric Cells by Electrolysis
 How the Voltage is Produced
Use an example of zinc and copper as electrodes and
sodium chloride as electrolyte
As zinc is more reactive, it is cathode while copper is anode.
At cathode, Zn atoms in anode loses electrons to form Zn2+
Zn(s) Zn2+(aq) + 2e-

Zn2+ goes into solution while the electrons lost makes the
zinc negative. The electrons flow against conventional
current towards copper anode.
Both Na+ & H+ ions in solution are attracted to the copper
anode due to electrons in it but only H+ ions discharged, due
to selective discharge, to form hydrogen gas.

2H+(aq) + 2e- H2(g)

Hence the overall ionic equation is:
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
which comes from the equation:
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
QUESTION NO. 5
EXTRACTION OF
ALUMINIUM BY
ELECTROLYSIS
 EXTRACTION OF ALUMINIUM

ELECTROLYSIS

Unlike iron, aluminium cannot be extracted using carbon.

(Aluminium is above carbon in the reactivity series)
 EXTRACTION OF ALUMINIUM

ELECTROLYSIS

Unlike iron, aluminium cannot be extracted using carbon.

(Aluminium is above carbon in the reactivity series)

Reactive metals are extracted using electrolysis

 EXTRACTION OF ALUMINIUM

ELECTROLYSIS

Unlike iron, aluminium cannot be extracted using carbon.

(Aluminium is above carbon in the reactivity series)

Reactive metals are extracted using electrolysis

Electrolysis is expensive - it requires a lot of energy…

- ore must be molten (ores have high melting points)

- electricity is needed for the electrolysis process

 EXTRACTION OF ALUMINIUM

RAW MATERIALS

BAUXITE aluminium ore

Bauxite contains alumina (Al2O3 aluminium oxide) plus
impurities such as iron oxide – it is purified before use.
 EXTRACTION OF ALUMINIUM

RAW MATERIALS

BAUXITE aluminium ore

Bauxite contains alumina (Al2O3 aluminium oxide) plus
impurities such as iron oxide – it is purified before use.

CRYOLITE Aluminium oxide has a very

high melting point.
Adding cryolite lowers the
melting point and saves energy.
EXTRACTION OF ALUMINIUM
 EXTRACTION OF ALUMINIUM

THE CELL CONSISTS OF A

 EXTRACTION OF ALUMINIUM

CARBON ANODE

THE CELL CONSISTS OF A CARBON ANODE

 EXTRACTION OF ALUMINIUM

STEEL
CATHODE
CARBON
LINING

THE CELL CONSISTS OF A CARBON LINED

STEEL CATHODE
 EXTRACTION OF ALUMINIUM

MOLTEN
ALUMINA and
CRYOLITE

ALUMINA IS DISSOLVED IN MOLTEN CRYOLITE Na3AlF6

SAVES ENERGY - the mixture melts at a lower temperature
 EXTRACTION OF ALUMINIUM

MOLTEN
ALUMINA and
CRYOLITE

ALUMINA IS DISSOLVED IN MOLTEN CRYOLITE Na3AlF6

aluminium and oxide ions are now free to move
 EXTRACTION OF ALUMINIUM

POSITIVE
ALUMINIUM IONS
ARE ATTRACTED
TO THE
NEGATIVE
CATHODE

CARBON CATHODE

Al3+ + 3e- Al
EACH ION PICKS UP 3 ELECTRONS AND IS DISCHARGED
 EXTRACTION OF ALUMINIUM

NEGATIVE OXIDE
IONS ARE CARBON ANODE
ATTRACTED TO
THE POSITIVE
ANODE

O2- O + 2e-
EACH ION GIVES UP 2 ELECTRONS AND IS DISCHARGED
EXTRACTION OF ALUMINIUM

ELECTRONS

CARBON ANODE

CARBON CATHODE
 EXTRACTION OF ALUMINIUM

ELECTRONS
OXIDATION (LOSS OF
ELECTRONS) TAKES PLACE
AT THE ANODE
CARBON ANODE

ANODE 3O2- 1½O2 + 6e- OXIDATION

 EXTRACTION OF ALUMINIUM

ELECTRONS
OXIDATION (LOSS OF
ELECTRONS) TAKES PLACE
AT THE ANODE

REDUCTION (GAIN
OF ELECTRONS)
TAKES PLACE AT
THE CATHODE CARBON CATHODE

ANODE 3O2- 1½O2 + 6e- OXIDATION

CATHODE 2Al3+ + 6e- 2Al REDUCTION

 EXTRACTION OF ALUMINIUM

ELECTRONS
OXIDATION (LOSS OF
ELECTRONS) TAKES PLACE
AT THE ANODE
CARBON ANODE

REDUCTION (GAIN
OF ELECTRONS)
TAKES PLACE AT
THE CATHODE CARBON CATHODE

ANODE 3O2- 1½O2 + 6e- OXIDATION

CATHODE 2Al3+ + 6e- 2Al REDUCTION

 EXTRACTION OF ALUMINIUM

CARBON DIOXIDE
PROBLEM
THE CARBON
ANODES REACT CARBON ANODE
WITH THE
OXYGEN TO
PRODUCE
CARBON DIOXIDE
 EXTRACTION OF ALUMINIUM

CARBON DIOXIDE
PROBLEM
THE CARBON
ANODES REACT CARBON ANODE
WITH THE
OXYGEN TO
PRODUCE
CARBON DIOXIDE

THE ANODES HAVE TO BE REPLACED AT

REGULAR INTERVALS, THUS ADDING TO THE
COST OF THE EXTRACTION PROCESS
 USES OF ALUMINIUM

THE IMPORTANCE OF ALUMINIUM

LOW DENSITY AND OVERHEAD CABLES

ELECTRICAL CONDUCTIVITY

LOW DENSITY AIRCRAFT BODIES

needs to be an alloyed with
other metals for extra strength

GOOD HEAT CONDUCTIVITY SAUCEPANS

 USES OF ALUMINIUM

THE IMPORTANCE OF ALUMINIUM

LOW DENSITY AND OVERHEAD CABLES

ELECTRICAL CONDUCTIVITY

LOW DENSITY AIRCRAFT BODIES

needs to be an alloyed with
other metals for extra strength

GOOD HEAT CONDUCTIVITY SAUCEPANS

Aluminium is not as reactive as one would

predict from its position in the reactivity series. THIN LAYER
OF OXIDE
This is because a thin layer of oxide quickly
forms on the surface and prevents any further
reaction taking place.
 USES OF ALUMINIUM

THE IMPORTANCE OF ALUMINIUM

LOW DENSITY AND OVERHEAD CABLES

ELECTRICAL CONDUCTIVITY

LOW DENSITY AIRCRAFT BODIES

needs to be an alloyed with
other metals for extra strength

GOOD HEAT CONDUCTIVITY SAUCEPANS

Aluminium is not as reactive as one would

predict from its position in the reactivity series. THIN LAYER
OF OXIDE
This is because a thin layer of oxide quickly
forms on the surface and prevents any further
reaction taking place.

ANODISING puts on a controlled layer of oxide so the metal can be used

for household items such as pans and electrical goods.
 USES OF ALUMINIUM

ANODISING

This puts on a controlled layer of

oxide so that the metal can be + -
used for household items such as
pans and electrical goods.

The aluminium object is made the

anode in the electrolysis of dilute
sulphuric acid.
aluminium
Oxygen given of at the anode object to be cathode
reacts with the aluminium surface, anodised
to build up a very thin film of dilute
oxide. sulphuric
acid
 The END
BY THE APEX
CHEMIST AT THE
VOICE OF SCIENCE
PAPA NYAKUNGU
tnyakungu@gmail.com