CSEC Chemistry

Section A- Principles of Chemistry

9- Electrochemistry
Section A-
Principles of
Chemistry
► States of matter
► Mixtures and separations
► Atomic Structure
► Periodic Table and Periodicity
► Structure and Bonding
► Mole Concept
► Acids, Bases and Salts
► Redox reactions
► Electrochemistry
► Rates of reactions
► Energetics
Objectives
► Conduct investigations leading to the classification of substances
as conductors or non-conductors;
► distinguish between metallic and electrolytic conduction;
► classify electrolytes as strong or weak based on their conductivity;
► define electrolysis, cathode, anode, cation, anion;
► identify ions present in electrolytes;
► predict the electrode to which an ion will drift;
► predict chemical reactions making use of electrochemical series;
► discuss the electrolysis of certain substances;
► define the Faraday constant;
► calculate the masses and volumes of substances liberated during
electrolysis;
► describe industrial applications of electrolysis.
Electrochemistry and the
electrochemical series of metals
► This is the study of electrochemical reactions, which either produce electrical
energy or require electrical energy to proceed).

► The electrochemical series of metals places metals in order of how easily they
lose electrons (ionise), and can be used to predict certain chemical reactions.
► The ability of metal atoms to donate electrons to another reactant increases
going up the series. Therefore, the strength as a reducing agent increases
going up the series.
The electrochemical series of metals
Electrochemical series
Displacement of metals in the
electrochemical series of metals
► The higher a metal in the series, the stronger it is as a
reducing agent, so it donate electrons to metals lower in the
series. The lower metals are then discharged to form atoms.

► E.g. Zn (s) + CuSO4 (aq) 🡪 ZnSO4 (aq) + Cu (s)

► Zn (s) 🡪 Zn2+ + 2 e-
► Cu2+ (aq) + 2e- 🡪 Cu (s)
Displacement of hydrogen in the
electrochemical series of metals
► Metals above hydrogen in the series, displace H+ ions in an
acid, forming hydrogen gas.
► Metals below hydrogen do not react with acids because they
do not displace the H+ ions.

► E.g. Mg (s) + 2HCl (aq) 🡪 MgCl2 (aq) + H2 (g)

► Mg (s) 🡪 Mg2+ (aq) + 2 e-

► 2H+ + 2e- 🡪 H2 (g)
The electrochemical series of non-metals
► The electrochemical series of non-metals places non-metals in order of how easily they gain
electrons, (ionise), and can be used to predict certain chemical reactions.

► The ability of non-metal atoms to ionise and take away electrons from another reactant increases
going up the series. Therefore, the strength as an oxidising agent increases going up the series.
Displacement of non-metals in the
electrochemical series of non-metals
► A non-metal higher in the series displaces a non-metals lower
in the series. The higher non-metal is a stronger oxidizing
agent so it accepts electrons from the ions of the lower
non-metal which then form atoms.

► E.g. Cl2 (g) + 2KI (aq) 🡪 2KCl (aq) + I2 (aq)

► Cl2 (g) + 2e- 🡪 2Cl-

► 2I- (aq) 🡪 I2 + 2e-
Exercise
► If zinc is placed in a solution of copper (II) nitrate, a reaction occurs.
► Explain why a reaction occurs.
► Give a balanced chemical equation and a balanced ionic equation for the reaction.
► What happens to the colour of the copper (II) nitrate solution? Explain why this
occurs.

► Will a reaction occur if zinc is placed in hydrochloric acid?

► Will a reaction occur if some copper turnings are placed in sulfuric acid?

► Will a reaction occur if chorine gas is bubbled into sodium iodide solution?

► Will a reaction occur if bromine solution is added to a solution of potassium

chloride?
Exercise
► For each of the following, predict whether or not a displacement reaction will
occur:
► Aluminium + lead (II) nitrate solution
► Silver + calcium nitrate solution
► Iodine + sodium chloride solution
► Bromine + potassium iodide solution

► Which of the metals in the electrochemical series will release hydrogen gas
when added to hydrochloric acid?

► A metal X was found to displace zinc from zinc nitrate solution, but no
displacement occurred when it was added to magnesium nitrate solution.
Arrange the three metals, X, zinc and magnesium in decreasing order of ease
of ionization.
Electrical Conduction

► Conductors- allow an electric current to pass through.

► e.g. metals, graphite, molten ionic compounds, aqueous solutions of ionic
compounds, acids, alkalis

► Non-conductors- do not allow an electric current to pass through it

► e.g. non-metals (except graphite), plastics, solid ionic compounds, covalent
compounds and aqueous solutions of covalent compounds
Electrical Conduction
Metallic and electrolytic conduction

Conduction in a metal Conduction in an electrolyte

Mobile electrons in the electron pool Mobile ions, which are no longer held
carry the electric current through the together by ionic bonds, carry the
metal electric current through the electrolyte.
The metal remains unchanged The electrolyte decomposes, i.e. it is
chemically. chemically changed.
Electrolytes

► When an ionic compound melts or dissolves in water, the liquid or solution

that forms is known as an electrolyte. Because the ionic bonds have broken
and the ions are free to move, electrolytes are conductors. When an electric
current passes through an electrolyte it decomposes.

► The strength of an electrolyte is determined by the concentration of ions

present.
Strength of electrolytes

► Strong electrolytes are fully ionised when they dissolve in water. Their solutions
contain a high concentration of ions. Examples include aqueous solutions of ionic
compounds, molten ionic compounds, strong acids and strong alkalis.
e.g. H2SO4 (aq) 🡪 2H+ (aq) + SO42- (aq)

► Weak electrolytes are only partially ionised when they dissolve in water. Their
solutions contain a low concentration of ions. Examples include weak acids and weak
alkalis. e.g. CH3COOH(aq) 🡪 CH3COO- (aq) + H+ (aq)
► Pure water is an extremely weak electrolyte. Approximately one in every 5.56 × 108 water
molecules is ionised into H+ and OH− ions at any one time: H2O(l) 🡪 H+ (aq) + OH- (aq)
► The presence of these ions is important when an electric current passes through an
aqueous electrolyte.
Strength of electrolytes
Non-electrolytes

► These are substances which remain as molecules in the liquid state or

dissolved in water, and therefore they do not contain any ions.
Non-electrolytes are non-conductors and include:
► Liquids, e.g. kerosene, gasoline or ethanol.
► Molten covalent substances, e.g. molten wax.
► Solutions of covalent substances, e.g. solutions of glucose or ethanol.
 Electrolysis

The chemical change occurring when an electric current passes through an electrolyte.

Electrolysis is carried out in an electrolytic cell, which has three main components:
► The electrolyte- a molten ionic compound or solution which contains mobile ions.
► A battery or other DC power supply- supplies the electric current.
► Two electrodes- connected to the power supply by wires and are placed in the
electrolyte so that they can carry the current into and out of the electrolyte. (usually
made of an inert material, e.g. graphite (carbon) or platinum, which can conduct
electricity)
► The anode is the positive electrode, connected to the positive terminal of the power supply.
► The cathode is the negative electrode, connected to the negative terminal of the power supply
 Electrolysis
► The negative anions are attracted to the positive anode where they are discharged
to form atoms by losing electrons to the anode: Nn- 🡪 N + ne −
► Oxidation occurs at the anode (Oxidation Is Loss, OIL). The anode behaves as the
oxidising agent.

► The electrons which the anions lose at the anode move through the circuit from
the anode to the positive terminal of the battery. The electrons re-enter the circuit
from the negative terminal of the battery and move from the battery to the
cathode.

► The positive cations are attracted to the negative cathode where they are
discharged to form atoms by gaining electrons from the cathode: Mn+ + ne − 🡪 M
► Reduction occurs at the cathode (Reduction Is Gain, RIG). The cathode behaves as the
reducing agent.
Electrolysis
Electrolysis
 Electrolysis of molten electrolytes
► Molten electrolytes contain two different ions only, a cation and an anion. Both
ions are discharged during electrolysis.

► Electrolysis of molten (fused) lead(II) bromide using inert graphite electrodes

► Ions present in the electrolyte: Pb2+ (l) and Br- (l)
► Events at the anode: The Br - ions move towards the anode where each ion loses an
electron to the anode to form a bromine atom (the ions are discharged). Bromine
atoms immediately bond covalently in pairs to form bromine molecules:
2Br - (l) 🡪 Br2(g) + 2e-
► Red-brown bromine vapour is evolved around the anode.

► Events at the cathode: The Pb2+ ions move towards the cathode where each ion gains
two electrons to form a lead atom (the ions are discharged): Pb2+ (l) + 2e- 🡪 Pb(l)
► Molten lead is formed around the cathode and drips off
Electrolysis of molten electrolytes
Electrolysis of aqueous electrolytes

► An aqueous solution contains at least two different cations and two different
anions because it contains ions from the solute and H+ ions and OH+ ions from
the ionisation of water molecules.

► During electrolysis, one type of cation and one type of anion are discharged in
preference to any others present. This is called preferential discharge.
Factors influencing the preferential
discharge of anions
► The type of anode
► An anode which is not inert(inert-stable, unreactive), e.g. copper, can take part in the
electrolysis process and this affects what happens at the anode. If an active anode is used, the
reaction occurring is the one which requires the least energy. This usually involves the anode
ionising instead of an anion being discharged.

► The concentration of the electrolyte

► The greater the concentration of an ion, the more likely it is to be preferentially discharged.
This rule applies mainly to solutions containing halide ions (Cl− , Br − and I− ions).

► The position of the ion in the electrochemical series

► The lower the ion in the electrochemical series of anions, the more likely it is to be
preferentially discharged. Ions at the top of series are the hardest to discharge because they
are the most stable. Ions at the bottom are the easiest to discharge because they are the least
stable.
Factors influencing the preferential
discharge of anions
Anion

F-

SO42-

NO3-

Cl-

Br-

I-

OH-
Preferential discharge of cations

Cation
► The position of the ion in the electrochemical series influences the K+
preferential discharge of the cations. The lower the ion in the Ca2+
electrochemical series of cations, the more likely it is to be preferentially
discharged. Ions at the top of series are the hardest to discharge because they Na+
are the most stable. Ions at the bottom are the easiest to discharge because Mg2+
they are the least stable.
Al3+
Zn2+
Fe2+
Pb2+
H+
Cu2+
Ag+
Electrolytic cell
Electrolysis of some aqueous solutions
► Dilute sulfuric acid, H2SO4 (aq)

► From H2SO4 : H+ (aq), SO42- (aq); From H2O: H+ (aq), OH- (aq)
► Inert electrodes– carbon or platinum
► Rxn @ anode: OH- ions are preferentially discharged, they are lower in the
electrochemical series than SO42- : 4OH- (aq) 🡪 2H2O(l) + O2(g) + 4e-
Effervescence occurs as oxygen gas is evolved.
► Rxn @ cathode: H+ ions are discharged: 2H+(aq) + 2e- 🡪 H2 (g)
Effervescence occurs as hydrogen gas is evolved.
► Relative proportions of gases: for every 4 mol electrons, 1 mol O 2 and 2 mol
H2 are produced.
► Electrolyte becomes more concentrated: H+ and OH- ions are removed leaving
H+ and SO42- ions in excess, i.e. water is removed.
Electrolysis of some aqueous solutions
► Dilute sodium chloride solution, NaCl(aq)

► From NaCl: Na+ (aq), Cl- (aq); From H2O: H+ (aq), OH- (aq)
► Inert electrodes– carbon or platinum
► At anode: OH- ions are preferentially discharged, they are lower in the
electrochemical series than Cl- : 4OH- (aq) 🡪 2H2O(l) + O2 (g) + 4e-
► Effervescence occurs as oxygen gas is evolved.

► At cathode: H+ ions are preferentially discharged, they are lower in the

electrochemical series than Na+ : 2H+ (aq) + 2e− 🡪 H2 (g)
► Effervescence occurs as hydrogen gas is evolved.

► Relative proportions of gases: for every 4 mol electrons, 1 mol O2 and 2 mol H2 are
produced.
► Becomes more concentrated: H+ and OH- ions are removed leaving Na+ and Cl- ions in
excess, i.e. water is removed.
Electrolysis of some aqueous solutions
► Concentrated sodium chloride solution, NaCl(aq)

► From NaCl: Na+ (aq), Cl- (aq) From H2O: H+ (aq), OH- (aq)
► Inert electrodes– carbon or platinum
► At anode: Cl- ions are preferentially discharged, they are halide ions in a
concentrated solution: 2Cl- (aq) 🡪 Cl2 (g) + 2e-
► Effervescence occurs as chlorine gas is evolved.
► At cathode: H+ ions ;very 2 mol electrons, 1 mol Cl2 and 1 mol H2 are
produced.
► Becomes alkaline: H+ and Cl− ions are removed leaving Na + and OH− ions in
excess, i.e. sodium hydroxide is formed.
Electrolysis of brine
Electrolysis of some aqueous solutions
► Copper(II) sulfate solution, CuSO4 (aq)

► From CuSO4 : Cu2+ (aq), SO42- (aq); From H2O: H+ (aq), OH- (aq)
► Inert electrodes– carbon or platinum
► At anode: OH- ions are preferentially discharged, they are lower in the
electrochemical series than SO42- : 4OH- (aq) 🡪 2H2O(l) + O2(g) + 4e−
► Effervescence occurs as oxygen gas is evolved.
► Electrolyte becomes acidic: Cu2+ and OH- ions are removed leaving H+ and SO42- ions
in excess, i.e. sulfuric acid is formed.

► At cathode: Cu2+ ions are preferentially discharged, they are lower in the
electrochemical series than H+ : Cu2+ (aq) + 2e− 🡪 Cu(s)
► Pink copper is deposited and the cathode increases in size.
► Electrolyte becomes paler blue: blue Cu2+ ions are removed.
Electrolysis of some aqueous solutions
► Copper(II) sulfate solution, CuSO4 (aq)

► From CuSO4 : Cu2+ (aq), SO42- (aq); From H2O: H+ (aq), OH- (aq)
► Anode electrode– active copper; Cathode electrode– carbon, platinum or
copper
► Rxn @ anode: the anode ionises, this requires less energy than discharging
either anion: Cu(s) 🡪 Cu2+ (aq) + 2e-
► Cu2+ ions go into the electrolyte and the anode decreases in size.
► Rxn @ cathode: Cu2+ ions are preferentially discharged, they are lower in the
electrochemical series than H+ : Cu2+(aq) + 2e- 🡪 Cu(s)
► Pink copper is deposited and the cathode increases in size.
► Electrolyte remains unchanged: for every 2 mol electrons, 1 mol Cu2+ ions
enter the electrolyte at the anode, and 1 mol Cu2+ ions is discharged at the
cathode.
Electrolysis of copper-plated key
 Cation Anion

Review Questions K+ F-

Ca2+ SO42-
► Predict whether a displacement reaction will occur when EACH of the
Na+ NO3-
following are mixed and write a balanced equation for EACH reaction that you
predict will occur.
Mg2+ Cl-
► zinc and hydrochloric acid
► iron and zinc chloride solution Al3+ Br-
► aluminium and silver nitrate solution Zn2+ I-
► copper and sulfuric acid
Fe2+ OH-
► iodine and potassium chloride solution
► bromine and sodium iodide solution Pb2+

H+

Cu2+

Ag+
Review Questions
► Distinguish between a conductor and a non-conductor and give TWO named
examples of EACH.

► What is an electrolyte? Give TWO differences between metallic conduction

and electrolytic conduction.

► Distinguish between a strong electrolyte and a weak electrolyte, and give a

named example of EACH.

► Define EACH of the following: electrolysis; anion; cation; anode; cathode

► What THREE factors influence the preferential discharge of anions from

aqueous solutions?
Review Questions
► Draw a labelled diagram of the apparatus used in the laboratory for the
electrolysis of copper (II) sulfate solution using inert graphite electrodes.

► Describe, giving relevant ionic equations, the reactions you would expect to
take place at the electrodes during the electrolysis of dilute sulfuric acid
using inert graphite electrodes, and explain any changes which would occur in
the electrolyte.

► Compare the electrolysis of dilute sodium chloride solution with the

electrolysis of concentrated sodium chloride solution, both using inert
graphite electrodes.
 Quantitative electrolysis
► The movement of electrons through the external circuit from anode to cathode
results in a flow of electrical charge since each electron possesses an extremely
small electrical charge. The quantity of a substance produced at, or dissolved
from, an electrode during electrolysis is directly proportional to the quantity of
electrical charge, or quantity of electricity, which flows through the electrolytic
cell.
► The quantity of electrical charge (Q), is measured in coulombs (C). The quantity
of electrical charge flowing through an electrolytic cell during electrolysis is
dependent on two factors:
► The current (I), which is the rate of flow of the electrical charge. Current is
measured in amperes (known as amps, A).
► The length of time (t) that the current flows for. Time is measured in seconds (s).
Quantitative electrolysis
► quantity of electrical charge (C) = current (A) × time (s)
Q=I×t

► One mole of electrons (6.0 × 1023 electrons), has a total charge of 96 500 C. This
value is known as the Faraday constant.

► The Faraday constant is the size of the electrical charge on one mole of electrons, i.e.
96 500 C mol-1 .

► The following equations show that one mole of electrons is required to discharge one
mole of an ion with a single charge:
► M+ + e- 🡪 M
► or N- 🡪 N + e-
► Using the Faraday constant, it follows that 96 500 C is the quantity of electrical
charge required to discharge one mole of ions with a single charge. The Faraday
constant can be used to calculate the masses of substances and volumes of gases
formed during electrolysis.
 Quantitative electrolysis calculations
►
Quantitative electrolysis calculations
Exercise

► Calculate the volume of oxygen produced at the anode at rtp if an electric

current of 5.0 A is passed through dilute sodium chloride solution for 3 hours,
51 minutes and 36 seconds.
 ►
Exercise
 Industrial applications of electrolysis
► Extraction of metals from their ores
► Electrolysis of the molten ore is used to extract aluminium, and metals above aluminium in the
electrochemical series, from their ores
► Purification of metals (electrorefining)
► Electrolysis is used to convert an impure metal into the pure metal. The anode is the impure metal. The
cathode is a very thin strip of the pure metal. The electrolyte is an aqueous solution containing ions of
the metal being purified. Electrorefining is only suitable to purify metals whose ions are below hydrogen
in the electrochemical series.
► Electroplating
► This is the process by which a thin layer of one metal is deposited on another metal by electrolysis. It is
used to protect the original metal from corrosion, to make it look more attractive or to make an
inexpensive metal object appear more valuable. The anode is a pure sample of the metal being used for
plating. The cathode is the object to be electroplated. The electrolyte is an aqueous solution containing
ions of the metal being used for plating. Only metals whose ions are below hydrogen in the
electrochemical series can be used for plating. Silver, nickel and chromium are the metals most
commonly used.
► Anodising
► Anodising is a process used to increase the thickness of an unreactive oxide layer on the surface of a
metal, usually the aluminium oxide (Al2O3) layer on the surface of aluminium objects. The aluminium
oxide layer is relatively unreactive and adheres to the object, protecting it against corrosion. It also
readily absorbs dyes, so can be attractively coloured. The anode is the cleaned aluminium object, such
as a window frame or saucepan. The electrolyte is usually dilute sulfuric acid.
Industrial applications of electrolysis
Exercise

► Explain why electrolysis is used to extract metals high in the electrochemical

series from their ores.

► Describe how you would purify a sample of silver. Include the equations for
the reactions occurring at the anode and the cathode.

► Give the equations for the reactions that occur at the anode and cathode
during:
► Chromium plating
► Nickel plating
Exercise

► What is the Faraday constant?

► A current of 8.0 amperes flows for 48 minutes 15 seconds through a solution

of copper(II) sulfate. What volume of oxygen, measured at rtp, would be
produced at the anode? What mass of copper would be deposited at the
cathode?

► How long must a steady current of 0.5 amperes flow through the circuit in
order to produce 112 cm3 of chlorine at the anode during the electrolysis of
concentrated sodium chloride solution at stp?
Review Questions

► Write the equations for the reactions occurring at the anode and cathode
during the purification of a lump of silver. Calculate the mass of silver that
could be purified if a current of 2.5 amperes flows for 4 hours 17 minutes 20
seconds during the purification process.

► Explain, giving relevant equations, how electrolysis can be used to

electroplate a spoon with nickel using nickel sulfate solution (NiSO 4(aq)) as
the electrolyte.

► What happens during the process of anodising?