ELECTROCHEMISTRY

LEARNING OUTCOMES

 Describe investigations leading to the classification of substances as conductors or non-

conductors.
 Distinguish between metallic and electrolytic conduction
 Define electrolysis, cathode, anode, cation and anion
 Define electrolytes as strong and weak based on their conductivity
 Predict the electrode to which an ion will drift
 Define oxidation and reduction reactions including reactions at electrodes
LEARNING OUTCOMES

 Predict chemical reactions making use of electrochemical series

 Identify ions present in electrolytes
 Discuss the electrolysis of certain substances.
 Define Faraday constant.
 Calculate the masses and volumes of substances liberated during. electrolysis.
 Describe industrial applications of electrolysis.
Conductors and Electrolytes

 The movement of electrically charged particles through a medium constitutes an electric

current. The medium of conduction is known as a conductor.
 Electrolytes can conduct electricity in their molten and aqueous
 states. E.g. Metals
 Non-conductors like plastic, ceramic and rubber can be used as insulation materials.
 Eg. The plastic coating on copper wires
Electrical Conductions in Conductors

 Electrical conductions in conductors can be explained through how the atoms are
bonded.
 In metals, the electrons become delocalised due to overlapping orbitals of the tightly
packed atoms in the crystal lattice.
 The valence electrons of each atom are loosely held as they are relatively distant from the
nucleus. Thus they can be easily separated and move about randomly throughout,
conducting electricity.
 The only non-metal that conducts electricity is graphite.
 In graphite, not all electrons are used in bonding. Thus, the free electrons can move along
the layers and carry the electric current.
The Ionic Theory

 The ionic theory proposes that it is the presence of freely-moving charged particles called
ions in the electrolyte that allows electrolysis to occur.

 These ions are only mobile when the electrolytes are in molten or aqueous state.

 These free moving ions arise only when an ionic solid melts or dissolves in water or
when certain polar covalent compounds dissolve in water and their molecules ionise
(dissociate into freely moving ions).
What is Electrolysis ?

 Electrolysis is a process by which a substance is broken up into its components by the

passage of electricity through it.
 The substance must be an ionic compound and must be molten or dissolved in water in
order for the ions to be mobile.
 A direct current must be used for electrolysis.
 During this process, electrical energy is changed into chemical energy.
Electrolysis

 One electrode is connected to the positive terminal of the battery. It is called the anode.
Oxidation occurs here.
 The other electrode is connected to the negative terminal of the battery. It is called the
cathode. Reduction occurs here.
 An electrolyte is a substance that is being electrolysed.
 An electrolyte is able to conduct electricity due to the presence of mobile ions.
 Positive ions are known as cations.
 Negative ions are known as anions
Selective Discharge of Ions

 At the cathode:
 Positive ions from the electrolyte are discharged if they are H+ ions or ions of less reactive
metals such as Cu2+ , Pb2+ or Ag+ .
 Positive ions of reactive metals such as Na+ , K+ and Ca2+ are not discharged in the presence
of water. Instead, H+ ions from water are discharged and H2 gas is produced.
 At the anode:
 Negative ions from the electrolyte are discharged if they are halide ions such as I- , Br - , and
Cl- .
 SO4 2- and NO3 - ions are not discharged. Instead, OH- ions from water are discharged and O2
gas is produced.
Selective Discharge of Ions

 The table shows the electrode products from solutions of ions, assuming the solutions are
fairly concentrated.
Inert and Reactive Electrodes

 Inert electrodes do not react with the product produced or dissolved in the electrolyte.
 Carbon and platinum are examples of inert electrodes.
 Reactive electrodes can react or dissolve in the electrolyte.
 Copper, silver and mercury are examples of reactive electrodes.
Electrolysis of Molten Compounds

 When electricity passes through the molten ionic compound, the positive ions will
migrate to the negative electrode, also known as cathode, while the negative ions will
migrate to the positive electrode, known as anode.
 At the cathode, the positive ions will gain electrons and become metal atoms while the
negative ions will lose electrons at the anode and become non-metallic atoms.
 At the Cathode Sodium ions gain electrons and become sodium atoms, sodium ions are
discharged: Na+ (l) + e- Na (l)
 At the Anode Chloride ions lose electrons and become chlorine gas, chloride ions are
discharged: 2Cl- (l) Cl2 (g) + 2e-
Electrolysis of Molten Compounds
Electrolysis of Molten Lead (II) Bromide (PbBr2)

 Electrolysis is not possible with solid lead(II) bromide.

 This is because the ions are held in a three-dimensional lattice, unable to move freely to
the electrodes. Melting enables the ions to become mobile and to travel to the respective
electrodes.
 At the cathode (-) molten lead is formed:
 Pb2+(l) + 2e-→ Pb(l)
 At the anode, gaseous bromine is evolved:
 2Br-(l)- 2e- → Br2(g)
QUICK REVIEW!

1. What is meant by (i) cathode, (ii) anode ?

2. What is meant by an electrolyte? What type of compounds must
electrolytes be?
3. During electrolysis, to which electrode do:
(a) the positive ions of the electrolyte move to;
(b) the negative ions of the electrolyte move to?
4. Predict the products formed when the following substances (in the
molten state) are electrolysed.
QUICK REVIEW 1!

Compound Product at Anode Product at Cathode

Potassium chloride, KCl
Calcium fluoride, CaF2
Electrolysis of Solutions

 When solutions are electrolysed, gases are usually produced.

 The gases produced can be collected in test tubes to be identified later by simple tests.
 The electrolysis of solutions is more complicated than electrolysis of molten compounds,
because the products at the electrodes can come from the electrolyte as well as from
water.
Electrolysis of Dilute H2SO4

 Pure water will not conduct electricity, so some dilute sulphuric acid is added to make it
conduct electricity.
 The electrolysis of dilute sulphuric acid is therefore essentially the same as the
electrolysis of water.
Electrolysis of Dilute H2SO4
Electrolysis of Dilute H2SO4

 Dilute sulphuric acid contains H+ , SO4 2- and OH- ions.

 At the cathode:
 H + ions take in electrons to become H2 molecules; H+ ions are discharged
 2H+ (aq) + 2e- H2 (g)
 Dilute sulphuric acid contains H+ , SO4 2- and OH- ions.
 H + ions take in electrons to become H2 molecules;
 H+ ions are discharged:
 4OH- (aq) O2 (g) + 2H2O(l) + 4e-
Electrolysis of Dilute H2SO4

 Overall reaction: 2H2O(l) 2H2 (g) + O2 (g)

 At the cathode: 2 volumes of hydrogen are produced.
 At the anode: 1 volume of oxygen is produced.
 The electrolysis of dilute solutions is essentially the same as the electrolysis of water.
Electrolysis of Dilute Sodium Chloride
Solution

 The ions present in the solution are: Na+ , Cl- (from sodium chloride) and H+ , OH- (from
water).
 At the cathode:
 Both Na+ and H+ are attracted here, but due to their relative positions in the reactivity series, H+ ions
are preferentially discharged:
 2H+ (aq)+ 2e-  H2 (g)
 At the anode:
 Both Cl- and OH- are attracted here, but due to the lower position of the hydroxide ions in the reactivity
series, they are preferentially discharged:
 4OH- (aq)  O2 (g) + 2H2O(l) + 4e-
 Overall reaction: 2H2O(l)  2H2 (g) + O2 (g) [ Electrolysis of water ]
Electrolysis of Concentrated Sodium Chloride
Solution

 The ions present in the solution are: Na+ , Cl- and H+ , OH.
 At the cathode:
 Both Na+ and H+ are attracted here, but due to their relative positions in the reactivity series,
H+ ions are preferentially discharged:
 2H+ (aq) + 2e-  H2 (g)
 At the anode:
 Both Cl- and OH- are attracted here, but due to the high concentration of the chloride ions,
chloride ions are preferentially discharged:
 2Cl- (aq)  Cl2 (g) + 2e-
Electrolysis of Concentrated Sodium Chloride
Solution

 Overall reaction: Hydrogen gas is produced at the cathode and chlorine gas is produced
at the anode.
 The Na+ and OH- ions left in the solution combine to form sodium hydroxide, thus
making the solution alkaline.
Electrolysis of Solutions
Electrolysis of CuSO4 Solution

 Using copper (reactive) electrodes.

 The ions present in the solution are: Cu2+ , SO4 2- , H + and OH- .
 At the cathode:
 Cu2+ ions are discharged in preference over the H+ ions: Cu2+ + 2e-  Cu
 At the anode:
 Neither SO4 2- nor OH- ions are discharged. Instead the copper anode dissolves in the solution
and produces electrons:
 Cu  Cu2+ + 2e-
Electrolysis of CuSO4 Solution

 During the electrolysis the total concentration of the CuSO4 solution remains unchanged.
The cathode increases in mass while the anode decreases in mass proportionately.
Electrolysis of CuSO4 Solution: Using Copper
(Reactive) Electrodes

 During the electrolysis the concentration of the H+ and SO4 2- ions increases, and hence
the solution becomes more acidic.
 This process essentially transfers copper metal from the anode to the cathode.
 This process is used in the industry for the purification of impure copper to obtain pure
copper.
 Quick Check 2!!

1. Place in order the ease of discharge of the following cations (starting from the easiest first): Ca2+, Na+ , H+ ,
Al3+, Mg2+, K+ , Cu2+, Pb2+, Ag+ .
2. Place in order the ease of discharge of the following anions (starting from the easiest first): Br- , Cl- , NO3 - , OH-
, I- , SO4 2-
3. (a) State the products obtained when a solution of dilute sulphuric acid is electrolysed using platinum electrodes.
(b) Write the ionic equations for the reactions taking place at thecathode and anode.
 QUICK REVIEW 2!!

4. (a) State the products obtained when a concentrated solution of sodium chloride is electrolysed using inert
electrodes.
(b) Write the ionic equations for the reactions taking place at the cathode and anode.
5. (a) State the products obtained when a solution of sodium hydroxide is electrolysed using platinum electrodes.
(b)Write the ionic equations for the reactions taking place at the cathode and anode
Faraday’s Law of Electrolysis

 The Faraday constant, F, is the quantity of electricity carried by one mole of electrons
and is equivalent to 96500 C mol-1 .
 The amount of a substance deposited on each electrode of an electrolytic cell is directly
proportional to the quantity of electricity passing through the cell.
 The quantity of electricity contained in a current running for a specified time can be
calculated by Q= l x t
Faraday’s Law of Electrolysis: Example 1

 Calculate the amount of charge transferred when a 5 A current is used for 2 minutes
during electrolysis.
 2 minutes = 2 × 60 = 120 s (always convert time to seconds!!)
 Q=IxT
 Charge = current × time
 Charge = 5 × 120 = 600 C
 Q = 600 C
Faraday’s Law of Electrolysis: Example 2

 Sodium and chlorine are produced during the electrolysis of molten sodium chloride:
 Na+ + e– → Na
 2Cl– → Cl2 + 2e–
 9,650 coulombs of charge pass. Calculate the amount of sodium and chlorine produced.
[1 F (faraday) = 96,500 C].
 Number of moles of electrons = 9,650 ÷ 96,500 = 0.1 mol
 1 mol of electrons are needed to produce 1 mol of sodium - so 0.1 mol of sodium is
produced.
 2 mol of electrons are needed to produce 1 mol of chlorine - so 0.05 mol (0.1 ÷ 2) of
chlorine is produced.
Faraday’s Law of Electrolysis: Example 3

 Bromine is produced during the electrolysis of molten lead(II) bromide:

 2Br– → Br2 + 2e–
 A current of 13.4 A was used for 0.5 hours. Calculate the mass of bromine produced. [1 F
= 96,500 C. Ar of Br2 = 160].
APPLICATIONS OF
ELECTROCHEMISTRY

 Electroplating
 Anodising
 Electrorefining
Electroplating

 Electroplating is the process in which a metallic object is coated with another metal by
electrolysis.
 This is useful for coating a cheaper metal with a more expensive one, such as copper or
silver.
Electroplating with Copper

 The electrolyte is copper(II) sulphate (CuSO4 )solution.

 The object to be plated is made the cathode; copper is made the anode.
 At the cathode:
 Cu2+ ions are discharged as copper metal is deposited on the object:
 Cu2+(aq) + 2e  Cu(s)
 At the anode:
 Copper dissolves:
 Cu(s)  Cu2+(aq) + 2e-
 There is a net transfer of copper from the anode to the cathode. The concentration of the CuSO4
solution remains unchanged.
Electroplating with Other Metals

 Many metallic objects can be electroplated in the same way.

 The object is made the cathode and the metal used for electroplating is made the anode.
The electrolyte is a solution of ions of the metal used for the plating.
 Electroplating can be used to protect iron objects from corrosion by covering it with a
less reactive metal like chromium or copper.
 Electroplating also makes the object more attractive and increases its value e.g. plating it
with gold, silver and platinum.
Examples of Electroplating
Anodising

 Anodising is the process of making the oxide layer on the surface of the aluminium thicker. This
will protect the aluminium even better.
 The aluminium object is made the anode while the cathode could be copper or lead or aluminium.
 The electrolyte used is either dilute sulphuric acid or dilute chromic (V) acid.
 When current is applied, the water in the electrolyte breaks down and oxygen is deposited at the
anode.
 4OH- – 4e- → 2H2O (l) + O2 (g)
 This oxygen then combines with the aluminium to form aluminium oxide and thus provides a
protective layer for the aluminium.
 This layer prevents corrosion and also can absorb dyes which can be permanently fixed by
treatment with boiling water.
Electrorefining of Copper

 This is a process in which the purity of metals such as copper, is improved.

 Copper of high quality is needed for important purposes, such as wiring.
 The electrolyte used is a mixture of copper (II)sulphate and sulphuric acid.
 The impure copper is made the anode.
 A strip of pure copper is made the cathode.
Electrorefining of Copper

 At the anode:
 Cu(s) – 2e- → Cu2+(aq)
 Copper atoms leave the anode and enter the solution as copper ions.
 At the cathode:
 Cu2+(aq) + 2e → Cu(s)
 Copper ions are discharged and deposited on cathode.
 Summary: copper leaves the anode and is deposited on the cathode.
 Anode mud is a mixture of gold and other impurtiies that collect at the bottom of the
anode.
QUICK REVIEW 3!!

1. State two uses of electrolysis in the industry.

2. (a) What is electroplating? (b) State two advantages of electroplating an iron object with
chromium.
3. A metal spoon is to be coated with silver. Sketch a diagram to show how you would set
up the electrolytic cell for this to be carried out. Label the material that can be used for
the cathode and anode. Also state a suitable solution for the electrolyte