IGCSE Chemistry Electrolysis

Electrolysis
Conductivity

There are two types of electric conductors: metallic conductors and electrolytes. In metallic conductors, the electrons are delocalised, and carry the charge. These are solid metals, liquid metals, and graphite. Electrolytes conduct electricity because of free moving ions. If an ionic substance melts or is dissolved, it is an electrolyte. Covalently bonded acids which are dissolved in water are also electrolytes, due to the disassociated ions. Electrolytes have a higher resistance than metallic conductors, and electrolytes are decomposed by the passage of an electric current. This decomposition is called electrolysis.
Ions

There are two ions present in the electrolyte, anions (positive) and cations (negative.) The anion is attracted to the anode (negative electrode) and the cation is attracted to the cathode (positive electrode). There are three main rules used to find the charge of an ion: metal ions, hydrogen ions, and ammonium ions are ALWAYS positive. Non-metal ions are always negative. The size of the charge is equal to the valency of the element.
Products of Electrolysis

The simplest examples of electrolysis involve a molten binary ionic substance. When this is electrolysed, it breaks down into the two electrons from which it is made. The metal (cation) will form at the cathode, and the non-metal (anion) will form at the anode. If the compound is aqueous, the H+ and OH- ions complicate things. These may be discharged as hydrogen and oxygen. When there are two ions of the same type involved in electrolysis, their reactivity is the main factor. The less reactive element will be discharged, as its compound is less stable. The results of electrolysing an ionic compound in aqueous solution can be predicted by using the rules below:
Hydrogen will be discharged at the cathode unless copper, silver or gold ions are present in which case they will be discharged. Oxygen will be discharged at the anode unless chlorine, bromine or iodine are present (in high concentrations), in which case they will be discharged as the halogen.

The electrodes are usually made from platinum or graphite, as they are unreactive.
Electrolysis and Redox

All electrolysis reactions are redox reactions. Oxidation is the loss of electrons, reduction is the gain of electrons (OILRIG). Reduction will take place at the cathode, oxidation at the anode. The redox reactions can be represented by two half equations, which show electrons being lost or gained, represented with the symbol e-. When the two half

equations are combined, the electrons must cancel out, giving an ordinary equation for the whole reaction. Some examples:
Molten Zinc Chloride

As it is molten, the zinc chloride is split into molten zinc and chlorine gas. The positive Zn2+ ions are attracted to the cathode, where they gain two electrons, and are reduced to zinc metal:

Cathod e

Anod e

Dilute Sulphuric Acid

The electrolysis of any acid produces hydrogen and oxygen. Electrolysis of compounds which produce gases is done by a Hoffman voltameter, which collects the gases. The electrolysis occurs at platinum electrodes, and the gas bubbles up into inverted burettes. The volume of hydrogen is double the amount of oxygen, as the formula H2O suggests. The water is electrolysed, the acid is just used as an electrolyte. The hydrogen ions go to the cathode and are reduced, and then pair up as diatomic molecules:

Concentrated Aqueous Sodium Chloride

There are no copper, silver, or gold ions, so hydrogen will be produced at the cathode. The high concentration of chloride ions mean chlorine will be produced as the anode and discharged as chlorine gas.

Aqueous Copper (II) Sulphate Graphite Electrodes

The Cu2+ ions are present in the solution, so they are attracted to the cathode and are reduced to Copper atoms. A salmon pink coating forms on the graphite cathode. No halide ions are present, so oxygen is produced at the anode, as the OH- ions are oxidised.

Electrolysis calculations
It is possible to calculate the amount of a substance produced in electrolysis. The quantities depend on the total number of electrons supplied to the ions, and the charge of the ions. The charge on one mole of electrons is one faraday, and is equal to 96,500 Coulombs. 1 mol e- 1 F = 96500 C Moles of electrons = charge (C) / 96500 The charge which has passed through a circuit can be found using: Q=Ixt Where Q = charge (Coulombs); I = current (Amps); t = time (seconds) e.g. A current of 0.5A is passed through an aqueous solution of copper(II) sulphate for 2 hours. What mass of copper metal is deposited on the cathode? Q=Ixt = 0.5A x 7200s Moles of electrons mol eCu (aq) + 2e
2+ -

= 3600C = charge / 96500 =

Cu(s)

0.0373

2 moles of electrons gives 1 mole of Cu moles of Cu = moles of electrons / 2 = 0.0373 / 2 = 0.0187 mol Cu Mass = moles x molar mass = 0.0187 x 63.5 = 1.19g Mass of copper = 1.19 g e.g. For how long must a current of 0.1A be passed through dilute sulphuric acid in order to produce 240cm3 of oxygen gas? Moles of gas = volume / 24000 = 240/24000 = 0.010 mol O2
4OH (aq)
-

2H2O(l) + O2(g) + 4e

4 moles of electrons give 1 mole Moles of electrons = moles of O2 = 0.040 mol eCharge = moles of e- x 96500 t=Q/I = 3860 / 0.1 time = 643 minutes (3 s.f.)

of O2 x4

= 0.010 x 4 = 3860 C

= 0.040 x 96500 = 38600 s

The Chlor-Alkali Industry

The electrolysis of concentrated sodium chloride solution (brine) produces three important chemicals, chlorine, hydrogen, and sodium hydroxide. The method of

manufacture is called the chlor-alkali industry. This is carried out in a diaphragm (membrane) cell:
chlori ne hydroge n

concentrate d salt solution in

titanium anode

nickel cathode diaphra gm

sodium hydroxide and dilute salt solution out

The electrodes are in separate compartments, partitioned by a permeable diaphragm. At the anode chlorine ions are oxidised, forming chlorine gas, collected from the top:
2Cl (aq)
-

Cl2(g) + 2e
-

At the cathode, hydrogen ions are reduced, to form hydrogen gas, which is also collected at the top of the cell:
2H (aq) + 2e
+
+

H2(g)

The H ions are formed when the water disassociates, and they are removed by the electrolysis. Due to Le Chateliers principle, more water is then disassociated:
H2O(l) H (aq) + OH (aq) .
+ -

The OH- ions are not involved in the electrolysis, and accumulate in the cathode compartment. The Na+ ions are attracted to the cathode, but are not removed by electrolysis, so they remain in solution. The solution in the cathode compartment is now enriched in sodium and hydroxide ions, aka sodium hydroxide solution. The diaphragm stops the hydroxide ions from diffusing back into the anode cell where they would react with the chlorine., as the anode cell has a higher level of solution, meaning the flow is from anode cathode. Some sodium chloride remains in the solution, so the solution is heated till the sodium chloride crystallises out, so it can be removed. Sodium hydroxide is used:
To purify bauxite to make alumina, so aluminium can be extracted. To make soap To break down wood when making paper

To manufacture chemicals

Chlorine is used to make bleach, hydrochloric acid, PVC, and to sterilise water. Hydrogen is used to manufacture ammonia and margarine, and as an alternative power source.