Electrochemistry

O level
August 16, 2024

1 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:
• 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

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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

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:
• Electrons are the charge carriers in the external circuit

• Ions are the charge carriers in the electrolyte

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

2 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.

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

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 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

3 Electrolysis of Aqueous Sodium Chloride and 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:
• Chlorine is used to make bleach
• Hydrogen is used to make margarine

• 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 N a+ and OH – ions remain behind and form the N aOH solution

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 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

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 Diagram showing the test for hydrogen gas

4 Electrolysis of Aqueous Solutions

Aqueous solutions will always have water present (H2 O). In the electrolysis of aqueous solutions, the water molecules
dissociate producing H + and OH – ions:
H2 O ⇌ 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:
• If a concentrated halide solution is being electrolysed, the halogen forms at the anode
• If a dilute halide solution is being electrolysed, oxygen is formed

For example:
• 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
• 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.

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 The reactivity series of metals including hydrogen and carbon

Products formed for Common Aqueous Solutions

Electrolysis of Aqueous Copper(II) Sulfate:

Aqueous copper sulfate contains the following ions: 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:

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 • Cu2+ and H + will both be attracted to the cathode but the less reactive ion will be discharged
• In this case, copper is less reactive than hydrogen
• Copper ions are discharged at the cathode, gain electrons and are reduced to form copper metal
• 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

• OH − ions lose electrons more readily than SO42−

• OH − lose electrons and are oxidised to form oxygen gas
• The half equation for the reaction at the anode is

4OH – ⇌ O2 + 2H2 O + 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

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5 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

6 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
The Half ionic equation of the reaction:
At the Anode ∶ Sn(s) → Sn2+ (aq) + 2e−
At the Cathode ∶ Sn2+ (aq) + 2e− → Sn(s)
Use 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. coating cutlery and jewellery with silver.

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7 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
H2 → 2H + + 2e−
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:
• 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
Note: You should be able to state advantages and disadvantages of the hydrogen-oxygen fuel cells in comparison to a petrol
engine.