Electrolysis

Basics

• When an electric current is passed through a molten ionic compound the compound
decomposes or breaks down
• The process also occurs for aqueous solutions of ionic compounds
• Covalent compounds cannot conduct electricity hence they do not undergo electrolysis
• Ionic compounds in the solid state cannot conduct electricity either since they have no
free ions that can move and carry the charge

Key terms

• Electrode is a rod of metal or graphite through which an electric current flow into or out
of an electrolyte
• Electrolyte is the ionic compound in molten or dissolved solution that conducts the
electricity
• Anode is the positive electrode of an electrolysis cell
• Anion is a negatively charged ion which is attracted to the anode
• Cathode is the negative electrode of an electrolysis cell
• Cation is a positively charged ion which is attracted to the cathode
Electrolysis of molten compounds eg: Lead (II) Bromide:

Diagram showing the electrolysis of lead (II) bromide

Method:

• Add lead (II) bromide into a beaker and heat so it will turn molten, allowing ions to be
free to move and conduct an electric charge
• Add two graphite rods as the electrodes and connect this to a power pack or battery
• Turn on power pack or battery and allow electrolysis to take place
• Negative bromide ions move to the positive electrode (anode) and lose two electrons to
form bromine molecules. There is bubbling at the anode as brown bromine gas is given
off
• Positive lead ions move to the negative electrode (cathode) and gain electrons to form a
grey lead metal which deposits on the surface of the electrode

Reaction at electrodes:

Electrolysis: General Principles

Rules

• Aqueous solutions will always have water (H2O)

• H+ and OH- ions from the water are involved as well

Positive electrode (anode)

• OH- ions and non-metal ions (anions) are attracted to the positive electrode
• Either OH- or non-metal ions will lose electrons and oxygen gas or gas of non-metal in
question is released, eg. chlorine, bromine, nitrogen
• The product formed depends on which ion loses electrons more readily, with the more
reactive ion remaining in solution

A reactivity series of anions is shown below:

More reactive SO42- → NO3- → Cl- → Br- → I-→ OH- Less reactive
Negative electrode (cathode)

• H+ and metal ions attracted to the negative electrode but only one will gain electrons
• Either hydrogen or metal will be produced
• If the metal is above hydrogen in reactivity series, then hydrogen will be produced and
bubbling will be seen at the cathode
 The reactivity series of metals including hydrogen and carbon

Concentrated and dilute solutions

• Concentrated and dilute solutions of the same compound give different products
• For anions, the more concentrated ion will tend to get discharged over a more dilute ion

Electrolysis of molten compound

• For a molten compound of a metal and a nonmetal, the cathode product will always be
the metal
• The product formed at the anode will always be the non-metal
Electrolysis of Aqueous Solutions

Diagram showing the electrolysis of aqueous solutions

Method:

• Add aqueous solution into a beaker

• Add two Graphite rods as the electrodes and connect this to a power pack or battery
• Turn on power pack or battery and allow electrolysis to take place
Electrolysis: Reactions at the Electrodes
Determining what gas is produced

• If the gas produced at the cathode burns with a 'pop' when a sample is lit with a lighted
splint then the gas is hydrogen
• If the gas produced at the anode relights a glowing splint dipped into a sample of the gas
then the gas is oxygen
• The halogen gases all produce their own colours (bromine is red-brown, chlorine
is yellow-green and fluorine is pale yellow)

Products of Electrolysis & Charge Transfer

Copper refining

• The electrolysis of CuSO4 using graphite rods produces oxygen and copper
• By changing the electrodes from graphite to pure and impure copper, the products can be
changed at each electrode
• Electrolysis can be used to purify metals by separating them from their impurities
• In the set-up, the impure metal is always the anode, in this case the impure copper
• The cathode is a thin sheet of pure copper
• The electrolyte used is an aqueous solution of a soluble salt of the pure metal at the
anode, e.g: CuSO4
• Copper atoms at the anode lose electrons, go into solution as ions and are attracted to the
cathode where they gain electrons and form now purified copper atoms
• The anode thus becomes thinner due to loss of atoms and the impurities fall to the
bottom of the cell as sludge
• The cathode gradually becomes thicker

Electrolysis of halide solutions

• We have seen that cation lower down on the reactivity series tend to be discharged in
preference to more reactive cations
• The same occurs for anions which can be arranged in order of ease of discharge:

More reactive SO42- → NO3- → OH- → Cl- → Br- → I- Less reactive

• Eg. in a concentrated aqueous solution of barium chloride, the Cl- ions are discharged
more readily than the OH- ions, so chlorine gas is produced at the anode
• If the solution is dilute however only the OH- ion is discharged and so oxygen would be
formed

Transfer of Charge

• During electrolysis the electrons move from the power supply towards the cathode
• Positive ions within the electrolyte move towards the negatively charged electrode which
is the cathode
• Here they accept electrons from the cathode and either a metal or hydrogen gas is
produced
• Negative ions within the electrolyte move towards the positively charged electrode which
is the anode
• If the anode is inert (such as graphite or platinum), the ions lose electrons to the anode
and form a nonmetal or oxygen gas
• If the anode is a reactive metal, then the metal atoms of the anode lose electrons and go
into solution as ions, thinning the anode

Diagram showing the direction of movement of electrons and ions in the

electrolysis of NaCl
Ionic Half-Equations & Electrical Energy

• Reduction occurs at the cathode as the positive ions gain electrons

Electrochemical cells

• An electrochemical cell is a source of electrical energy

• The simplest design consists of two electrodes made from metals
of different reactivity immersed in an electrolyte and connected to an external circuit
• A common example is zinc and copper
• Zinc is the more reactive metal and forms ions more easily, releasing electrons as its
atoms form ions
• The electrons give the more reactive electrode a negative charge and they then flow
around the circuit to the copper electrode
• The difference in the ability of the electrodes to release electrons causes a voltage to be
produced
• The greater the difference in the metal's reactivity, the greater the voltage
Electrochemical cell made with copper and magnesium. These metals are further apart
on the reactivity series than copper and zinc and would hence produce a greater voltage
Electroplating

• Electroplating is a process where the surface of one metal is coated with a layer of a
different metal
• The metal being used to coat is a less reactive metal than the one it is covering
• The anode is made from the pure metal used to coat
• The cathode is the object to be electroplated
• The electrolyte is an aqueous solution of a soluble salt of the pure metal at the anode

A piece of iron being electroplated with tin. The electrolyte is tin(II)

chloride, a water-soluble salt of tin

Uses of electroplating

• Electroplating is done to make metals more resistant to corrosion or damage, e.g:

chromium and nickel plating
• It is also done to improve the appearance of metals, e.g: silver plating cutlery

Conductors & insulators

• Conductors of electricity allow electrical charge to pass through them easily

• Conductors can be:
o Solids such as metals or graphite
o Liquids such as molten lead bromide or molten metals
o Solutions such as sodium chloride solution
• Copper is used extensively in electrical wiring as it is an excellent conductor and
is malleable and easy to work with
 • Aluminium is used in overhead cables which are reinforced with a steel core
• The steel core provides extra strength and prevents the cable from breaking under its own
weight
• Although not as good a conductor as copper, it is less dense and cheaper than copper

Insulators

• Insulators resist the flow of electricity and do not conduct

• Most insulators are solids of plastic, rubber or ceramic
• Plastics are used as insulators and are placed around electrical wiring and for some tool
and machine handles
• Ceramics are used in very high voltage lines where contact between the power line and
the metal of the pylon would be dangerous

Hydrogen-Oxygen fuel cell

In the cell, three components are separated from each other by two graphite electrodes.
The fuel (hydrogen) is supplied into the negative electrode(anode) while the oxidant(oxygen) is
supplied into the positive electrode(cathode).

Ionic half-equation at the anode:

H2(g) + 2OH-(aq) → 2H2O(l) + 2e-
Ionic half-equation at the cathode:
O2(g) + 2H2O(l) + 4e- → 40H-
Overall equation
2H2(g) + O2(g) → 2H2O
Pros👍
• Do not emit any air pollutants and only water is produced
• High energy efficiency of about 70%
• Can operate continuously if the flow of O2(g) and H2(g) can be maintained
Cons👎
• Materials used to make the electrodes are expensive
• Manufacturing of the cells results in the production of toxic by-products
• The fuel(hydrogen) needed can only be produced cheaply by fossil fuels
• Do not work well at low temperatures *if the temperature drops below 0˚C, the cell will
freeze
• Safety concerns as high-pressure tanks are required to store the hydrogen