Electrolysis: General Principles

 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

Particles in ionic compounds are in fixed position in the solid state but can move around when
molten or in solution

Key terms used in a simple electrolytic cell

 Electrode is a rod of metal or graphite through which an electric current flows into or out
of an electrolyte
 Electrolyte is the ionic compound in a 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
 The basic set-up of an electrolytic cell

 Metals and hydrogen form positively charged ions and so either a metal or hydrogen gas
is formed at the cathode
 Non-metals form negatively charged ions and so non-metals (except hydrogen) are
formed at the anode

Exam Tip

Use the PANIC mnemonic to remember which electrode is the positive and which is the
negative:

Positive (is) Anode Negative Is Cathode

 Electrolysis: Charge Transfer
 During electrolysis, current needs to flow around the circuit
 In order for this to occur, charge must be transferred around the circuit (current is a
measure of the rate of flow of charge) by charge carriers
 The power supply provides the cathode with a supply of electrons, causing it to become
negatively charged
 Positive ions (cations) in the electrolyte move towards the cathode where they gain
electrons
 Negative ions (anions) in the electrolyte move towards the anode where they lose
electrons
 The electrons move from the anode back towards the power supply
 So, in a complete circuit:
o Electrons are the charge carriers in the external circuit
o Ions are the charge carriers in the electrolyte

Diagram showing the direction of movement of electrons and ions in the electrolysis of NaCl
Electrolysis of Molten Compounds
 A binary ionic compound is one consisting of just two elements joined together by ionic bonding
 When these compounds undergo electrolysis they always produce their corresponding elements
 To predict the products made at each electrode, first identify the ions
 The positive ion will migrate towards the cathode and the negative ion will migrate towards
the anode
 Therefore, the cathode product will always be the metal, and the product formed at
the anode will always be the non-metal
Example: Electrolysis of molten lead(II) bromide
Method:
 Add lead(II) bromide into a beaker and heat it 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 the power pack or battery and allow electrolysis to take place
 Negative bromide ions move to the positive electrode (anode) and each loses one electron 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
Diagram showing the electrolysis of lead(II) bromide
Worked example
Identify the product formed at the anode and cathode during the electrolysis of molten potassium
chloride.
Answer
 The ions present are potassium (K+) and chloride (Cl-)
 The chloride ions are attracted to the anode and form chlorine gas
 The potassium ions are attracted to the cathode and form potassium metal
Exam Tip
Remember electrodes need to be inert such as graphite or platinum so that they don’t participate in a side
reaction with the electrolyte.
Electrolysis of Aqueous Sodium Chloride & Dilute Sulfuric Acid
Aqueous sodium chloride
 Brine is a concentrated solution of aqueous sodium chloride
 It can be electrolysed using inert electrodes made from platinum or carbon/graphite
 When electrolysed, it produces bubbles of gas at both electrodes as chlorine and hydrogen are
produced, leaving behind sodium hydroxide solution
 These substances all have important industrial uses:
o Chlorine is used to make bleach

o Hydrogen is used to make margarine

o Sodium hydroxide is used to make soap and detergents

Product at the Negative Electrode:

 The H+ ions are discharged at the cathode as they are less reactive than sodium ions
 The H+ ions gain electrons to form hydrogen gas
Product at the Positive Electrode:
 The Cl– ions are discharged at the anode
 They lose electrons and chlorine gas forms
 The Na+ and OH– ions remain behind and form the NaOH solution
Diagram showing the products of the electrolysis of aqueous sodium chloride
Dilute sulfuric acid
 Dilute sulfuric acid can be electrolysed using inert electrodes made from platinum or
carbon/graphite
 Bubbles of gas are seen at both electrodes
Product at the Negative Electrode
 H+ ions are attracted to the cathode, gain electrons and form hydrogen gas
Product at the Positive Electrode
 OH- ions are attracted to the anode, lose electrons and form oxygen gas and water
Determining what gas is produced
 If the gas produced at the anode relights a glowing splint dipped into a sample of the gas then the
gas is oxygen
Diagram showing the test for oxygen gas
 If the gas produced at the anode bleaches damp litmus paper then the gas is chlorine

Diagram showing the test for chlorine gas

 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
 Diagram showing the test for hydrogen gas

Electrolysis of Aqueous Solutions

 Aqueous solutions will always have water present (H2O)
 In the electrolysis of aqueous solutions, the water molecules dissociate producing H+ and
OH– ions:

H2O ⇌ H+ + OH–

 These ions are also involved in the process and their chemistry must be considered
 We now have an electrolyte that contains ions from the compound plus ions from the
water
 Which ions get discharged and at which electrode depends on the relative reactivity of
the elements involved
 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

Positive Electrode (anode)

 Negatively charged OH– ions and non-metal ions are attracted to the positive electrode
 If halide ions (Cl-, Br-, I-) and OH- are present then the halide ion is discharged at the
anode, loses electrons and forms a halogen (chlorine, bromine or iodine)
 If no halide ions are present, then OH- is discharged at the anode, loses electrons and
forms oxygen gas
 In both cases the other negative ion remains in solution
 The concentration of the solution also affects which ion is discharged:
o If a concentrated halide solution is being electrolysed, the halogen forms at the
anode
 o If a dilute halide solution is being electrolysed, oxygen is formed
 For example:
o For a concentrated solution of barium chloride, the Cl- ions are discharged more
readily than the OH- ions, so chlorine gas is produced at the anode
o If the solution is dilute however only the OH- ion is discharged and so oxygen
would be formed

Negative Electrode (cathode)

 Positively charged H+ and metal ions are attracted to the negative electrode but only one
will gain electrons
 Either hydrogen gas or metal will be produced
 If the metal is above hydrogen in the reactivity series, then hydrogen will be produced
and bubbling will be seen at the cathode
 This is because the ions of the more reactive metal will remain in the solution, causing
the ions of the least reactive metal to be discharged
 Therefore, at the cathode, hydrogen gas will be produced unless the positive ions from
the ionic compound are less reactive than hydrogen, in which case the metal is produced
The reactivity series of metals including hydrogen and carbon

Products formed for Common Aqueous Solutions

 Electrolysis of Aqueous Copper(II) Sulfate
Electrolysis of Aqueous Copper Sulfate

 Aqueous copper sulfate contains the following ions:

o Cu2+, SO42-, H+ and OH-

Using graphite electrodes:

Apparatus for the electrolysis of copper(II)sulfate using inert / passive graphite electrodes

Product at the Cathode:

 Cu2+ and H+ will both be attracted to the cathode but the less reactive ion will be
discharged
 o In this case, copper is less reactive than hydrogen
o Copper ions are discharged at the cathode, gain electrons and are reduced to form
copper metal
o The half equation for the reaction at the electrode is:

Cu2+ + 2e- → Cu

Product at the Anode:

 SO42- and OH- are both attracted to the anode

o OH- ions lose electrons more readily than SO42-
o OH- lose electrons and are oxidised to form oxygen gas
o The half equation for the reaction at the anode is

4OH– ⟶ O2 + 2H2O + 4e–

Using copper electrodes:

Apparatus for the electrolysis of copper(II)sulfate using active copper electrodes

Observations at the anode and cathode

  The cathode increases in mass while the anode decreases
 This occurs as copper atoms are oxidised at the anode and form ions while copper ions
are reduced at the cathode, forming copper atoms
 The gain in mass by the negative electrode is the same as the loss in mass by the positive
electrode
 Therefore the copper deposited on the negative electrode must be the same copper ions
that are lost from the positive electrode
 That implies that the concentration of the Cu2+ ions in the solution remains constant

Ionic Half Equations

 In electrochemistry we are mostly concerned with the transfer of electrons, hence the definitions
of oxidation and reduction are applied in terms of electron loss or gain rather than the addition or
removal of oxygen
 Oxidation is when a substance loses electrons and reduction is when a substance gains
electrons
 As the ions come into contact with the electrode, electrons are either lost or gained and they
form neutral substances
 These are then discharged as products at the electrodes
 At the anode, negatively charged ions lose electrons and are thus oxidised
 At the cathode, the positively charged ions gain electrons and are thus reduced
 Ionic half equations show the oxidation and reduction of the ions involved
 It is important to make sure the charges are balanced
Table of Reduction and Oxidation Reactions at the Electrodes
.

Exam Tip
To help you remember the definitions of oxidation and reduction use OIL RIG
Oxidation Is Loss (of electrons) Reduction Is Gain (of electrons)

Electroplating
 Electroplating is a process where the surface of one metal is coated with a layer of a different
metal
 The anode is made from the pure metal you want to coat your object with
 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

 Example: coating a strip of iron metal with tin:

A piece of iron being electroplated with tin. The electrolyte is tin(II) chloride, a water-soluble salt of tin
 At the anode: Tin atoms lose electrons to form tin ions in solution
 At the cathode: Tin ions gain electrons to form tin atoms which deposit on the strip of iron
metal, coating it with a layer of tin
Uses of electroplating
 Electroplating is done to make metals more resistant to corrosion or damage
o e.g, chromium and nickel plating
  It is also done to improve the appearance of metals,
o e.g. coating cutlery and jewellery with silver

Exam Tip
You may be asked to write the ionic half equations for the reaction at each electrode. For the example
above, these would be:
At the anode: Sn (s) → Sn2+ (aq) + 2e-
At the cathode: Sn2+ (aq) + 2e- → Sn (s)

Hydrogen Fuel Cells

 A fuel is a substance which releases energy when burned
 Hydrogen is used as a fuel in rocket engines and in fuel cells to power some cars
 A fuel cell is an electrochemical cell in which a fuel donates electrons at one electrode and
oxygen gains electrons at the other electrode
o H2 → 2H+ + 2e–

o O2 + 4e– → 2O2–

 The hydrogen-oxygen fuel cell produces electricity by combining both elements, releasing
energy and water
 The overall equation for the reaction within a hydrogen fuel cell is:
hydrogen + oxygen → water
 The diagram below shows the setup of a hydrogen fuel cell
 The air entering provides the oxygen
 The fuel entering is hydrogen
 The only chemical product made is water
Diagram showing the movement of hydrogen, oxygen and electrons in a hydrogen-oxygen fuel cell
Advantages & Disadvantages of Hydrogen Fuel Cells
 Hydrogen-oxygen fuel cells are becoming more common in the automotive industry to replace
petrol or diesel engines
Advantages
  They do not produce any pollution: the only product is water whereas petrol engines
produce carbon dioxide, and oxides of nitrogen
 They release more energy per kilogram than either petrol or diesel
 No power is lost in transmission as there are no moving parts, unlike an internal combustion
engine
 Quieter so less noise pollution compared to a petrol engine
Disadvantages
 Materials used in producing fuel cells are expensive
 Hydrogen is more difficult and expensive to store compared to petrol as it is very flammable and
easily explodes when under pressure
 Fuel cells are affected by low temperatures, becoming less efficient
 There are only a small number of hydrogen filling stations across the country
 Hydrogen is often obtained by methods that involve the combustion of fossil fuels, therefore
releasing carbon dioxide and other pollutants into the atmosphere
Exam Tip
You should be able to state advantages and disadvantages of the hydrogen-oxygen fuel cells in
comparison to a petrol engine.