Electrolysis

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.

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 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 e.g: 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.
Electrolysis of Aqueous Solutions

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 attracted to positive electrode.

 Either OH– or non-metal ions will lose electrons and oxygen gas or gas of non-metal
in question is released E.g. 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:

o More reactive SO42- → NO3– → OH– → Cl– → Br– → I– 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.
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 binary molten compound

 For a binary 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.

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.
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 and 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
 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 cations that are 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:

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

 E.g: 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.

Ionic half-equations and electrical energy

Ionic Half-equations at the Cathode:

 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 then the greater the voltage.