Electrochemistry

Electrolysis
Electrolysis is the process of decomposing (or splitting up) a substance by passing an electric
current
through it. The substance which is being decomposed is called the electrolyte
Electrolyte
An electrolyte is a substance which conduct electricity in fused (molten) or in solution and is
thereby decomposed

Examples of electrolytes

 Aqueous sulphuric acid

 Aqueous hydrochloric acid
 Aqueous nitric acid
 Aqueous sodium chloride
 Aqueous sodium hydroxide
 Aqueous carbonic acid
 Aqueous ethanoic acid

Strong electrolyte
It is a substance which ionizes completely and produces a lot of ions in solution which are able to
carry out an electric current rapidly.

Examples of strong electrolytes

 Aqueous sodium hydroxide

 Aqueous sodium chloride

 Aqueous copper (II) sulphate

 Aqueous hydrochloric acid

 Aqueous sulphuric acid

 Aqueous nitric acid

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Weak electrolyte
It is a substance which ionizes partially and it conducts electric current only slightly and
therefore undergoes slight decomposition
Examples of weak electrolytes
 Carbonic acid

 Organic acids e.g. ethanoic acid

Non electrolyte
It is a substance which does not conduct electricity I fused or in solution state
Examples of non-electrolytes
 Sugar solution

 Ethanol

 Petrol

 Benzene

 Tetra chloromethane
 They do not conduct electricity because they exist only in form of molecules and not
capable of ionization
Conductor
It is a solid substance that allows electricity to pass through without decomposing e.g. all metals
Non conductor
Alternative term: Insulator
It is a solid that does not conduct electricity e.g. plastics, wood and glass

Electrodes: piece of metal or graphite where oxidation or reduction takes place. They are
conductors that allows electricity in and out of an electrolyte

Anode (+ve): electrode where oxidation occurs. It is a positively charged electrode. It is an

electrode connected to the positive terminal of the power supply.

Cathode (-ve): electrode where reduction occurs It is a negatively charged electrode

It is an electrode connected to the negative terminal of the power supply

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Binary compounds consist of only two elements, molten means in liquid state.e.g. molten lead
(II) bromide, molten sodium chloride, molten aluminium oxide etc

Electrolysis of molten binary ionic compounds always produce:

d) Metals at the cathode by reduction.

e) Non- metals at the anode by oxidation.

Passing an electric current through molten sodium chloride decomposes the material into sodium
metal and chlorine gas. Care must be taken to keep the products separated to prevent the
spontaneous formation of sodium chloride
Cations
They are positively charged ions
Example
Cation Formula of cation

Aluminium ion Al3+

Calcium ion Ca2+

Hydrogen ion H+

Magnesium ion Mg2+

Sodium ion Na+

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Anions
They are negatively charged ions
Example

Anion Formula of anion

Bromide ion Br-

Chloride ion Cl-

Hydroxide ion OH-

Iodate ion I-

Sulphate ion SO42-

The ionic theory

The ionic theory states that: The electrolytes contain ions and when no current is passing, the
ions wander about randomly in the solution. If the electric circuit is closed, the cathode
immediately becomes negatively charged and the anode becomes positively charged. The anode
attracts negatively charged ions while the cathode attracts the positively charged ions.

The selective order of discharge of ions

The discharge of ions varies from one electrolyte set up to another. When two or more ions of
similar charge are present under similar conditions in a solution e.g. H+ and Na+ or OH- and
SO42- , one is preferentially selected for discharge. The ion selected for discharge of competing
ions depends on the following factors:
 The position of ions in the electrochemical series

 The concentration of ions in solution

 The nature of electrodes

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1. Position of ions or radicals in the electrochemical series
Ions are arranged in the order of decreasing order of stability and amount of energy they require
for them to get discharged from an aqueous solution when an electric current is made to flow
through the solution. The arrangement is called electrochemical series. Note that the
electrochemical series is slightly different from the reactivity series of metals.

Most stable ions Increase in stability and require energy least stable ions

K+, Ca2+, Mg2+, Al3+, Zn2+, Fe2+, Pb2+, H+, Cu2+, Ag+, SO42-, NO3-, Cl-, Br-, I-, OH-

The ions of very reactive metals such as potassium, sodium, calcium, magnesium and aluminium
are more stable in solution and hence require more energy to be liberated as compared to the ions
of less reactive metals such as copper, silver, mercury and gold.

Therefore, when the ion of a more reactive metal is competing for discharge against the ion of a
less reactive metal, the less stable ion requiring lower energy for discharge is liberated in
preference to the more stable ion. Positive ions will be discharged at the cathode and negative
ions at the anode. For example, H+ will be discharged at the cathode in preference to Na+ since
H+ are less stable and require lower energy for discharge. Equally, the OH- will be discharged at
the anode in preference to SO42- since the OH- are less stable and require lower energy for
discharge.

2. Concentration of ions in aqueous solution

Concentration has no effect on the selective discharge of metal cations. However, the
concentration of anions is the principle factor that determines which anions will be liberated
regardless of their position in the electrochemical series. The anion with the highest
concentration is selectively discharged from the solution in preference to the one whose
concentration is lower regardless of their position in the electrochemical series. For example, in
the electrolysis of concentrated sodium chloride, both OH- and Cl- are present. The Cl- are
discharged in preference to OH- owing to the high concentration of Cl- in solution despite Cl-
requiring more energy than OH-. This is the only case in which the order of discharge as stated
by the electrochemical series is reversed.

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3. Nature of electrodes
Inert or unreactive electrodes such as platinum and graphite (Carbon) have no effect on the
selective discharge of competing ions on their surfaces. However, active electrodes such as
copper, mercury and most metals have an effect on the preferential discharge of competing ions.
An active electrode selectively discharges more stable ions in preference to less stable ions. For
example, in the electrolysis of sodium chloride solution using inert electrodes, H+are discharged
at the cathode in preference to Na+. However, when the mercury cathode has been used, Na+ are
selectively discharged to form sodium Amalgam (NaHg) in preference to the H+.

Electrolysis of lead (II) bromide

Ions present in lead (II) bromide
Pb2+ and Br−
At the cathode
Lead (II) ions, Pb2+, move to the cathode where they gain electrons to become lead atoms
Pb2+ +2e Pb
Lead is given off as a liquid
At the anode
The bromide ions, Br-, each lose one electron to form bromine atoms. They pair as molecules
Br2- Br2 + 2e
Bromine is given off as a gas

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Electrolysis of acidified water
Pure water is a weak electrolyte. It only partially ionizes. Therefore, it is a poor conductor of
electricity. The addition of hydrochloric acid or sulphuric acid makes it a strong electrolyte.
Hoffman apparatus

Ions present in aqueous sulphuric acid

H+ and SO42- : from sulphuric acid
H+ and OH- : from water
At the cathode
Hydrogen ions, H+, are attracted to the cathode where they are discharged as hydrogen gas
2H+(aq) + 2e → H2(g)
2 volumes of hydrogen gas are produced

At the anode
Hydroxide ions, OH-, and sulphate ions, SO42- are attracted to the anode. But the OH- are
preferred for discharge due to their position in the electrochemical series

4OH−(aq) → 2H2O(l) + O2(g) + 4e

1 volume of oxygen is produced

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Electrolysis of sodium chloride
Concentrated sodium chloride is called brine

Ions present in aqueous sodium chloride

Na+ and Cl- : from sodium chloride
H+ and OH-: from water
At the anode
Chloride ions, Cl-, are discharged in preference to hydroxide ions, OH- due to the concentration
factor.
2Cl−(aq) → Cl2(g) + 2e
At the cathode
Hydrogen ions, H+, are discharged in preference to sodium ions, Na+.
2H+(aq) + 2e → H2(g)

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The sodium ions, Na+ , and hydroxide ions, OH- , that remain solution combine to form sodium
hydroxide and electrolyte gradually becomes alkaline due to the presence of sodium hydroxide,
NaOH.

Electrolysis of aqueous copper (II) sulphate

(a) Using copper electrodes

Ions present in aqueous copper (II) sulphate

Cu2+ and SO42- : from copper (II) sulphate
H+ and OH- : from water
At the cathode
Copper (II) ions gain two electrons and deposited as copper atoms on the cathode.
Cu2+ + 2e → Cu
The copper cathode grows as copper atoms are deposited
At the anode
Copper atoms lose two electrons and enter the solution as copper (II) ions
Cu(s) → Cu2+(aq) + 2e

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(b) Using an inert electrode e.g. carbon (graphite)
At the cathode
Copper (II) ions, Cu2+ are liberated in preference to hydrogen ions, H+, to form copper metal
because Cu2+require less energy for discharge than H+. Hydrogen ions remain in solution
Cu2+(aq) + 2e → Cu(s)

At the anode
Hydroxide ions, OH−, from water are discharged in preference to sulphate ions, SO42-, to produce
oxygen gas because they require less energy for discharge and are more concentrated than
sulphate ions. The sulphate ions remain in solution
4OH−(aq) → 2H2O(l) + O2(g) + 4e

The hydrogen ions and sulphate ions that remain solution combine to form sulphuric acid. As
aqueous copper (II) sulphate solution is electrolyzed using inert electrode, its blue colour
disappears due to the removal of copper (II) ions and the solution becomes acidic

Industrial application of electrolysis

1. Electrolysis is used in extraction of very reactive metals such as potassium, sodium,
magnesium, calcium and aluminium

2. Electrolysis is used in the refinery and purification of metals such as copper and zinc.

3. Electrolysis is used in the electroplating metals. Electroplating is the art of covering the
surface of a metal with a thin adherent metal coating by means of electrolysis. Electroplating is
done to protect the surface of the base metal against corrosion or for a purely decorated effect.
Metals that may be used for electroplating include nickel, silver, gold, chromium, zinc, tin etc.
The object to be electroplated is used as the cathode and is immersed in a solution containing
ions of the metal to be plated. When an electric current passes through the solution, metal ions
that migrated to the cathode are reduced, depositing on the object as free metal. The metal
deposited on the object is replaced in the solution by using an anode of the same metal.

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Anode reaction
Nickel dissolves at the anode and replenishes the solution
Ni(s) Ni2+(aq) + 2e
Cathode reaction
Nickel plated on the object
Ni2+(aq) 2e Ni(s)
4. Sodium hydroxide, chlorine gas and hydrogen gas are manufactured on a large scale by
electrolysis of brine in the mercury cathode cell.
Faraday’s laws of electrolysis
Faraday’s first law of electrolysis
The law states that: The mass of a substance produced at the electrode during electrolysis is
directly proportional to the quantity of electricity passing through the electrolyte .

m∞Q
m ∞ It
Q = It
m = mass[g]
I = current [A]
t = time [s]
Q = charge (quantity of electricity) [Coulombs, C]

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Example
1. A current of 0.4A flows for about 1500 seconds. Calculate the quantity of electricity.

Solution
Q = It
Q = 0.4A x 1500s
Q = 675C

Faraday’s second law of electrolysis

The law states that: When the same quantity of electricity is passed through different electrolytes
the number of moles of the element deposited is inversely proportional to the charges on the ions
of the element.
Note
1 Faraday = 1 mole of electrons = 96500C

Example
1. Calculate the charge on an ion X if 5.4g is deposited by a current of 5A passing for 3 hours 13
minutes. [ Ar of X = 27]

Solution
Q X MM
q=
mX F
¿ X MM
q=
mXF

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 0.5 A X [ ( 60 X 60 X 3 )+ ( 60 X 13 ) ] s X 27 g/mol
q=
5.4 g X 96500 C/mol
q=3
2. How many moles of electron are required to produce 2.7g of aluminium by electrolytic
Charge on ion X = X3+ or X3
reduction?
Solution
Al3+ + 3e → Al
3mol of electron → 27g
X → 2.7g
3 mol of electron X 2.7 g
x=
27 g
x = 0.3 mol of electron
Calculations involving molar volumes
The volume of one mole of any gas is:
 24dm3 (24000cm3) at r.t.p
 22.4dm3 (22400 cm3) at s.t.p

Example
1. 0.2 faradays of electricity were passed through a solution of dilute sulphuric acid. Calculate
the volume of the gases produced or evolved measured at r.t.p at the anode and cathode.

Solution
At the anode oxygen gas is produced.
4OH−(aq) → 2H2O(l) + O2(g) + 4e
1F → 1 mol of ẽ
x → 4 mol of ẽ
1 F X 4 mol
x=
1mol
x = 4F
4F → 24dm3
0.2F → x
3
0.2 F X 24 dm
x=
4F
x = 1.2dm3
At the cathode hydrogen gas is produced
2H+(aq) + 2e → H2(g)
1mol of ẽ → 1F
2mol of ẽ → x
1 F X 2 mol
x=
1 mol
x = 2F
2F → 24dm3
0.2F → x
3

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 0.2 F 24 dm
x=
2F
x = 2.4dm3 BY MR PHIRI P

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