=Electrochemistry

Electrolysis

Electrolysis is the decomposition of an ionic compound, when molten or in aqueous solution, by

the passage of an electric current
General principles of electrolysis
 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
Examiner Tips and Tricks
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 by charge
carriers
 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
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

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
Examiner Tips and Tricks
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

Electrolysis of 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
 The ions in brine are:
o Na+ and Cl– ions from the brine / aqueous sodium chloride
o H+ and OH– ions from the water
 When electrolysed, it produces bubbles of gas at both electrodes
o The gases chlorine and hydrogen are produced
o Sodium hydroxide solution is the product remaining in the electrolysis chamber /
container
 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

Electrolysis of dilute sulfuric acid

 Dilute sulfuric acid can be electrolysed using inert electrodes made from platinum or
carbon / graphite
 The ions in dilute sulfuric acid are:
o H+ and SO42– ions from the sufuric acid
o H+ and OH– ions from the water
 When electrolysed, it produces bubbles of gas at both electrodes
o The gases oxygen and hydrogen are produced
 Electrolysing dilute sulfuric acid in a Hoffman voltameter shows that twice as much
hydrogen is produced, compared to oxygen

Product at the negative electrode:

 H+ ions are attracted to the cathode
 The H+ ions gain electrons to form hydrogen gas
Product at the positive electrode:
 OH- ions are attracted to the anode
 They lose electrons and form oxygen gas and water
Examiner Tips and Tricks
 When a gas is produced during electrolysis, you should be able to give the
appropriate gas test:
o Oxygen - if a glowing splint is dipped into a sample of the gas, then the splint will
relight
 o Hydrogen - if a lit splint is dipped into a sample of the gas, then a squaeky pop
will be heard
o Chlorine - if damp litmus paper is dipped into a sample of the gas, it will turn red
and then bleach to a white colour

Electrolysis of aqueous solutions

 Aqueous solutions always have water, H2O, present

 In the electrolysis of aqueous solutions, the water molecules dissociate producing

H2O ⇌ H+ + OH–
H+ and OH– ions:

 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–) are present, the halogen is produced at the anode
o The halide ions lose electrons and forms the halogen (chlorine, bromine or
iodine)
 If there are no halide ions but OH– ions are present, oxygen is produced at the anode
o The hydroxide ions lose electrons and forms oxygen gas (and water)
 In both cases, the other negative ion remains in solution
How concentration affects products at the anode
 The concentration of the solution affects the ion being 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 forms at the anode
 For example:
o For concentrated barium chloride solution :
 Cl– ions are discharged more readily than the OH– ions
 So, chlorine gas is produced at the anode
o For dilute barium chloride solution:
 Only OH– ions are discharged
 So, oxygen is produced at the anode
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:
o The ions of the more reactive metal remain in solution
o This causes the less reactive hydrogen ions, H+, to be discharged
o So, hydrogen will be produced and bubbling will be seen at the cathode
 If the metal is below hydrogen in the reactivity series:
o The less reactive metal ions are discharged
o So, the metal is produced and this will be seen plating onto the cathode
The reactivity series of metals including hydrogen and carbon
Electrolysis of aqueous copper sulfate
 Aqueous copper sulfate contains the following ions:
o Cu2+ and SO42– from the copper sulfate
o H+ and OH– from the water
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
 They 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
o This is because copper ions, Cu2+, are reduced at the cathode and form copper
atoms
 The anode decreases in mass
o This is because copper atoms are oxidised at the anode and form copper
ions, Cu2+
 The gain in mass by the negative electrode is the same as the loss in mass by the
positive electrode
o Therefore, the copper deposited on the negative electrode must be
the same copper ions that are lost from the positive electrode
 This implies that the concentration of the Cu2+ ions in the solution remains constant
Products formed for common aqueous solutions
Aqueous solution - ions present Product at the anode Product at the cathode
Concentrated sodium chloride, NaCl Chlorine gas Hydrogen gas
Dilute sodium chloride, NaCl Oxygen gas Hydrogen gas
Concentrated aqueous copper(II) sulfate, CuSO4 Oxygen gas Copper
Dilute sulfuric acid, H2SO4 Oxygen gas Hydrogen gas

Ionic half equations

  Electrochemistry is concerned with the transfer of electrons
o This is why the definitions of oxidation and reduction are in terms of losing or
gaining electrons, not oxygen
o Oxidation is the loss of electrons
o Reduction is the gain of electrons
 As the ions come into contact with the electrode:
o Electrons are lost or gained
o The ions form neutral substances
o These substances are discharged as products at the electrodes
 At the anode, negatively charged ions lose electrons
o So, oxidation occurs at the anode
 At the cathode, the positively charged ions gain electrons
o So, reduction occurs at the cathode
 Ionic half-equations only show half of what is happening in a reaction involving
electron transfer
o The ionic half-equation for oxidation shows the loss of electrons
o The ionic half-equation for reduction shows the gain of electrons
 Ionic half-equations must have the atoms and charges balanced

Writing ionic half-equations

Metals

 Metals are positive ions, e.g. Li+, Cu2+, Al3+

 If a metal is produced during electrolysis:
o The metal ions will gain electrons to form metal atoms
o The metal ions will be reduced
 The charge on the metal ion indicates the number of electrons that will be gained
o For example:

Li+ + e– → Li

Cu2+ + 2e– → Cu

Al3+ + 3e– → Al

Non-metals

 Non-metals are typically negative ions, e.g. Cl–, Br–, OH–

o The hydrogen ion, H+, is an exception to this

Hydrogen ion / hydrogen half-equation:

 If hydrogen is formed during electrolysis:

o Two hydrogen ions will gain 2 electrons to form hydrogen, H2
 o Hydrogen ions are reduced

2H+ + 2e– → H2

Halide ion / halogen half-equation:

 If a halogen is formed during electrolysis:

o Two halide ions will lose 2 electrons to form the halogen
o Halide ions are oxidised

2X– → X2 + 2e–

Hydroxide ion / oxygen half-equation:

 The ionic half-equation for hydroixde ions forming oxygen is more challenging to balance
o Hydroxide ions lose electrons to form oxygen, O2, and water, H2O
o Hydroxide ions are oxidised

4OH– → O2 + 2H2O + 4e–

Table of reduction and oxidation reactions at the electrodes

Electrolysis of Anode reaction Cathode reaction

Molten lead(II) bromide, PbBr2 2Br– → Br2 + 2e– Pb2+ + 2e– → Pb
Concentrated aqueous sodium chloride, NaCl 2Cl– → Cl2 + 2e– 2H+ + 2e– → H2
Dilute sulfuric acid, H2SO4 4OH– → O2 + 2H2O + 4e– 2H+ + 2e– → H2

Examiner Tips and Tricks

 To help you remember the definitions of oxidation and reduction, use OIL RIG
o Oxidation Is Loss (of electrons) Reduction Is Gain (of electrons)
 To help you remember where oxidation and reduction take place, use a RED CAT and
AN OX
o REDuction at the CAThode
o ANode for OXidation

Electroplating

What is electroplating?

 Electroplating is a process where the surface of one metal is coated with a layer of a
different metal
 The cathode / negative electrode is the object to be electroplated
 The anode / positive electrode is made from the pure metal that will be plated onto the
object
 The electrolyte is an aqueous solution of a soluble salt of the pure metal at the anode
Electroplating a strip of iron 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:
o Tin atoms lose electrons to form tin ions in solution
o The loss of electrons is oxidation
 At the cathode:
o Tin ions gain electrons to form tin atoms
o The gain of electrons is reduction
o The tin atoms are deposited on the strip of iron metal, coating it with a layer of tin

Examiner Tips and Tricks

Extended Tier students 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)

What is electroplating used for?

 Electroplating is done to make metals more resistant to corrosion or damage

o e.g. chromium and nickel plating
o e.g. galvanising - zinc plating / coating, typically done to iron and steel
 It is also done to improve the appearance of metals,
o e.g. coating cutlery and jewellery with silver

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

2H2 + O2 → 2H2O

 The diagram below shows the setup of a hydrogen fuel cell

o The air entering provides the oxygen
o The fuel entering is hydrogen
o 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

 Hydrogen can be produced from water so the process is renewable

 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

 Hydrogen obtained by methods that involve:

o The combustion of fossil fuels releases carbon dioxide and other pollutants into
the atmosphere
o The electrolysis of water requires large amounts of electricity to produce
 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

Examiner Tips and Tricks

You should be able to state advantages and disadvantages of the hydrogen-oxygen fuel cells in
comparison to a petrol engine.