Electrolysis: Basics

●  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

Diagram Showing the Electrolysis of

Lead (II) Bromide
Video- Electrolysis of molten compounds
https://www.youtube.com/watch?v=iPJIFgOkIUA (Long duration)

https://www.youtube.com/watch?v=ilNOpROacf0 (Short duration)

Aluminium extraction

https://www.youtube.com/watch?v=mvDHeYI-a00
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

Reaction at electrodes:
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:

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
The reactivity series of metals including hydrogen and carbon
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

Electrolysis of aqueous solutions

Diagram showing the electrolysis of

aqueous solutions
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
Video- Electrolysis of aqueous solutions
https://www.youtube.com/watch?v=GrgYXk_NCec

Electrolysis of brine
https://www.youtube.com/watch?v=N_HQGiC9OJE
Electrolysis of halide solutions
●  We have seen that cations 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:
More reactive SO42- → NO3– → OH– → Cl– → Br– → I– Less reactive
●  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
Electrolysis: Reactions at the Electrodes
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)
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 copper
●  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
Ionic half-equations at the cathode

●  Reduction occurs at the cathode as the positive ions gain electrons

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
Applications of Electrolysis
Electrolysis is used in various processes which are industrially important

1.  Extraction of reactive metals like sodium,magnesium ,calcium etc from

their ores.

2.Electrolytic extraction of aluminium from bauxite [Hall Heroult Process]

using alumina (aluminium Oxide) and Cryolite.

3. Chlor alkali process to manufacture chlorine gas and sodium hydroxide.

4. Electrolysis of water to get oxygen and hydrogen gases.

5.Electrorefining of metals like copper.

6.Electroplating of metals and alloys with gold,silver,chromium,nickel etc.

Electrolytic extraction of aluminium from bauxite [Hall Heroult Process] using alumina
(aluminium Oxide) and Cryolite.
Video- Electrolysis of aqueous solutions
https://www.youtube.com/watch?v=GrgYXk_NCec

Brine

https://www.youtube.com/watch?v=N_HQGiC9OJE&t=139s
Chlor alkali process to manufacture chlorine gas and sodium hydroxide.
Electrolysis of water
to get oxygen and
hydrogen gases.
Electrorefining of metals like copper.
Video- Electrolytic refining of copper
https://www.youtube.com/watch?v=qqmKqpA61GI
Electroplating of metals and alloys with gold,silver,chromium,nickel etc.
Electroplating Principle - Video
https://www.youtube.com/watch?v=JrZQQqYVVIs

Electroplating lab demo,industrial process

https://www.youtube.com/watch?v=U9Y8xclePOw

Anodising

https://www.youtube.com/watch?v=UIeE2i1pTn0

https://www.youtube.com/watch?v=1yaBrMNZHBw

Hydrogen fuel cells

https://www.youtube.com/watch?v=5_lDGna9MBM