Electrolysis

Terms used in electrolysis

Electrolysis is the decomposition of an electrolyte in molten state or aqueous solution by electricity. An electrolyte is a substance which conducts an electric current in molten state or aqueous solution, and is decomposed by electricity. The anode is the electrode where oxidation occurs. It is the electrode connected to the positive terminal of the d.c. supply. The cathode is the electrode where reduction occurs. It is the electrode connected to the negative terminal of the d.c. supply.

Terms used in electrolysis

An anion is a negative ion and is attracted to the anode. A cation is a positive ion and is attracted to the cathode. An ammeter is an instrument used to measure the electric current passing through a circuit. Electric current is measured in ampere (A). A variable resistor (or rheostat) is used to vary the resistance and then regulate the current.

Electrolysis

Factors affecting electrolysis

The position of ions in the electrochemical series. The concentration of ions in the solution. The nature of the electrodes.

Position of cations in the e.c.s.

Position of anions in the e.c.s.

Case 1: Electrolysis of molten lead(II) bromide

Nichrome wire Electrode (-) Molten lead(II) bromide

Electron flow

Nichrome wire Electrode (+)

Case 1: Electrolysis of molten lead(II) bromide

Solid lead(II) bromide does not conduct electricity because the ions are not mobile. Molten lead(II) bromide contains mobile ions.
Cation Pb2+() Anion Br-()

Case 1: Electrolysis of molten lead(II) bromide

Electron flow Nichrome wire Electrode (-) Nichrome wire Electrode (+)

Molten lead(II) bromide

Case 1: Electrolysis of molten lead(II) bromide

At cathode, lead(II) cations receive electrons, they undergo reduction and discharge to form lead atoms. Pb2+() + 2e Pb()

Case 1: Electrolysis of molten lead(II) bromide

At anode, bromide anions give up electrons, they undergo oxidation and discharge to form bromine atoms. 2Br-() Br2() + 2e

Case 1: Electrolysis of molten lead(II) bromide

Bromine atoms then join in pair to form bromine molecules.

Case 2: Electrolysis of acidified water using platinum electrodes

Although water is known to be poor electrical non-conductor, it actually ionizes slightly to give hydrogen ions and hydroxide ions. H2O() H+(aq) + OH(aq) Pure acids are covalent compounds. However they ionize in water. HCl(g) + water HCl(aq) + HCl(aq) H (aq) + Cl (aq)

Case 2: Electrolysis of acidified water using platinum electrodes

Cation H+(aq) Anion OH-(aq)

Case 2: Electrolysis of acidified water using platinum electrodes

At cathode, hydrogen ions receive electrons, they undergo reduction and discharge to form hydrogen gas.
2H+(aq) + 2e H2(g)

Case 2: Electrolysis of acidified water using platinum electrodes

At anode, hydroxide ions give up electrons, they undergo oxidation and discharge to form oxygen gas.
4OH-(aq) O2(g) + 2H2O() + 4e

Case 2: Electrolysis of acidified water using platinum electrodes

2H+(aq) + 2e H2(g) (1) 4OH-(aq) O2(g) + 2H2O() + 4e (2) (1)x2: 4H+(aq) + 4e 2H2(g) (3) (2)+(3): 4OH-(aq) + 4H+(aq) O2(g) + 2H2O() + 2H2(g) 4H2O() O2(g) + 2H2O() + 2H2(g)

Overall equation: 2H2O() O2(g) + 2H2(g)

Case 2: Electrolysis of acidified water using platinum electrodes

Dilute acid is added to provide more mobile ions so as to increase the conductivity of the water. The concentration of dilute acid increases at the end as water is consumed in the electrolysis.

Case 3: Electrolysis of dilute sodium chloride solution using carbon electrodes

Cation H+(aq) Na+(aq)

Anion OH-(aq) Cl-(aq)

Case 3: Electrolysis of dilute sodium chloride solution using carbon electrodes

The sodium ions and hydrogen ions move towards the cathode. At the cathode, the position of hydrogen ions in the electrochemical series is lower than that of sodium ions. Hydrogen ions are preferentially discharged (reduced) to form colourless hydrogen gas. + 2H (aq) + 2e H2(g)

Case 3: Electrolysis of dilute sodium chloride solution using carbon electrodes

The chloride ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of chloride ions. Hydroxide ions are preferentially discharged (oxidized) to form colourless oxygen gas. 4OH (aq) O2(g) + 2H2O() + 4e

Case 3: Electrolysis of dilute sodium chloride solution using carbon electrodes

Overall reaction: 2H2O() O2(g) + 2H2(g)

Water ionizes continuously to replace the hydrogen ions discharged at the cathode. Thus there is an excess of hydroxide ions near the cathode and the solution there becomes alkaline. Water ionizes continuously to replace the hydroxide ions discharged at the anode. Thus there is an excess of hydrogen ions near the anode. The solution there becomes acidic.

Case 3: Electrolysis of dilute sodium chloride solution using carbon electrodes

If a few drops of universal indicator are added to the sodium chloride solution, the solution near the cathode will turn blue while that near the anode will turn red. The sodium chloride becomes more concentrated as water is consumed in the electrolysis.

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

Cation
H+(aq)

Anion
OH-(aq)

Cu2+(aq) SO42-(aq)

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

The copper(II) ions and hydrogen ions move towards the cathode. At the cathode, the position of copper(II) ions in the electrochemical series is lower than that of hydrogen ions. Copper(II) ions are preferentially discharged (reduced) to form brown copper metal. 2+ Cu (aq) + 2e Cu(s)

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

The sulphate ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of sulphate ions. Hydroxide ions are preferentially discharged (oxidized) to form colourless oxygen gas. 4OH (aq) O2(g) + 2H2O() + 4e

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

Overall reaction:
2Cu2+(aq) + 4OH(aq) 2Cu(s) + O2(g) + 2H2O()

Water ionizes continuously to replace the hydroxide ions discharged at the anode. Thus there is an excess of hydrogen ions near the anode. The solution there becomes acidic. If a few drops of universal indicator is added into the solution, red colour appears around anode.

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

The blue colour of the solution fades out because the concentration of copper(II) ions decreases. Copper(II) ions and hydroxide ions are consumed in the electrolysis. Hydrogen ions and sulphate ions remain in the solution. Thus the solution eventually becomes sulphuric acid.

Case 4: Electrolysis of dilute copper(II) sulphate solution using carbon electrodes

After a few minutes, cathode is coated with copper. If the polarities of cells are then reversed, anode is coated with copper. The factor of electrode should be considered as in case 8.

Case 5: Electrolysis of dilute sodium iodide solution using carbon electrodes

Cation H+(aq) Na+(aq) Anion OH-(aq) I-(aq)

Case 5: Electrolysis of dilute sodium iodide solution using carbon electrodes

The sodium ions and hydrogen ions move towards the cathode. At the cathode, the position of hydrogen ions in the electrochemical series is lower than that of sodium ions. Hydrogen ions are preferentially discharged (reduced) to form colourless hydrogen gas. + 2H (aq) + 2e H2(g)

Case 5: Electrolysis of dilute sodium iodide solution using carbon electrodes

The iodide ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of chloride ions. However, the concentration of iodide ions is much greater than that of hydroxide ions. Iodide ions are preferentially discharged (oxidized) to form iodine. 2I-(aq) I2(aq) + 2e

Case 5: Electrolysis of dilute sodium iodide solution using carbon electrodes

Overall reaction: 2H+(aq) + 2I(aq) H2(g) + I2(aq) The solution near the cathode becomes alkaline. The iodine produced at the anode dissolves in the solution. Therefore a brown colour develops around the anode.

Case 5: Electrolysis of dilute sodium iodide solution using carbon electrodes

Hydrogen ions and iodide ions are consumed in the electrolysis. Sodium ions and hydroxide ions remain in the solution. The solution eventually becomes sodium hydroxide solution.

Case 6: Electrolysis of conc. sodium chloride solution using carbon electrodes

Cation H+(aq) Na+(aq)
Conc.

Anion OH-(aq) Cl-(aq)

Case 6: Electrolysis of conc. sodium chloride solution using carbon electrodes

The sodium ions and hydrogen ions move towards the cathode. At the cathode, the position of hydrogen ions in the electrochemical series is lower than that of sodium ions. Hydrogen ions are preferentially discharged (reduced) to form colourless hydrogen gas. + 2H (aq) + 2e H2(g)

Case 6: Electrolysis of conc. sodium chloride solution using carbon electrodes

The chloride ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of chloride ions. However, the concentration of chloride ions is much greater than that of hydroxide ions. Chloride ions are preferentially discharged (oxidized) to form chlorine gas. 2Cl-(aq) Cl2(g) + 2e

Case 6: Electrolysis of conc. sodium chloride solution using carbon electrodes

Overall reaction: 2H+(aq) + 2Cl(aq) H2(g) + Cl2(aq) Water ionizes continuously to replace the hydrogen ions discharged at the cathode. Thus there is an excess of hydroxide ions near the cathode. The solution there becomes alkaline. The chlorine gas formed at the anode dissolves in the solution. The solution there becomes acidic and has a bleaching effect.

Case 6: Electrolysis of conc. sodium chloride solution using carbon electrodes

Hydrogen ions and chloride ions are consumed in the electrolysis. Sodium ions and hydroxide ions remain in the solution. Eventually, the solution becomes sodium hydroxide solution.

Case 7: Electrolysis of conc. sodium chloride solution using mercury electrodes

Cation

Anion

H+(aq)
Na+(aq) Hg()

OH-(aq)
Cl-(aq) Hg()

Case 7: Electrolysis of conc. sodium chloride solution using mercury electrodes

The sodium ions and hydrogen ions move towards the cathode. At the cathode, the position of hydrogen ions in the electrochemical series is lower than that of sodium ions. However, sodium ions are preferentially discharged (reduced) to form sodium metal. The sodium metal formed dissolves in the mercury to form a sodium amalgam.
Na+(aq) + e + Hg(l) Na/Hg(l) sodium amalgam

Case 7: Electrolysis of conc. sodium chloride solution using mercury electrodes

The sodium amalgam then reacts with water to form sodium hydroxide and hydrogen.
2Na/Hg(l) + 2H2O(l) 2NaOH(aq) + H2(g) + 2Hg(l)

Case 7: Electrolysis of conc. sodium chloride solution using mercury electrodes

The chloride ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of chloride ions. However, the concentration of chloride ions is much greater than that of hydroxide ions. Chloride ions are preferentially discharged (oxidized) to form chlorine gas. 2Cl-(aq) Cl2(g) + 2e

Case 7: Electrolysis of conc. sodium chloride solution using mercury electrodes

Overall reaction:
2Na+(aq) + 2Cl(aq) + 2Hg(l) 2Na/Hg(l) + Cl2(g)

Sodium ions and chloride ions are consumed in the electrolysis. Thus the sodium chloride solution becomes more and more dilute. This reaction is very important in the manufacture of chlorine bleaching solution.

Case 8: Electrolysis of dilute copper(II) sulphate solution using copper electrodes

Cation

Anion

H+(aq) OH-(aq) Cu2+(a q) Cu(s) SO42(aq) Cu(s)

Case 8: Electrolysis of dilute copper(II) sulphate solution using copper electrodes

The copper(II) ions and hydrogen ions move towards the cathode. At the cathode, the position of copper(II) ions in the electrochemical series is lower than that of hydrogen ions. Copper(II) ions are preferentially discharged (reduced) to form brown copper metal. 2+ Cu (aq) + 2e Cu(s)

Case 8: Electrolysis of dilute copper(II) sulphate solution using copper electrodes

The sulphate ions and hydroxide ions move towards the anode. At the anode: the position of hydroxide ions in the electrochemical series is higher than that of sulphate ions. However, copper is a stronger reducing agent than hydroxide ions and thus more easily oxidized. The copper anode dissolves to form copper(II) ions (oxidized). Cu(s) Cu2+(aq) + 2e

Case 8: Electrolysis of dilute copper(II) sulphate solution using copper electrodes

Overall reaction: Cu(s) Cu(s) anode cathode The net effect is the transfer of copper from the anode to the cathode. The rate at which copper deposits on the cathode is equal to the rate at which the copper anode dissolves.
Increase in mass of cathode = decrease in mass of anode

Case 8: Electrolysis of dilute copper(II) sulphate solution using copper electrodes

The concentration of copper(II) ions in the solution remains the same. The blue colour of the solution does not change.

Comparing a chemical cell and an electrolytic cell

Comparing a chemical cell and an electrolytic cell

Chemical cell
Function A device for generating electricity from chemical reactions. Electrons flow from negative electrode to the positive electrode through the external circuit. Circuit is completed by the movement of mobile electrons.

Electrolytic cell
A device for bringing out chemical changes by electricity. Cations discharge and gain electrons at cathode, while anions discharge and give up electrons at anode. Circuit is completed by the movement of mobile ions.

Direction of electricity

Comparing a chemical cell and an electrolytic cell

Chemical cell
Reactions at positive electrode Reactions at negative electrode Reduction (Cathode)

Electrolytic cell
Oxidation (anode)

Oxidation (anode)

Reduction (Cathode)

Commercial uses of electrolysis

Manufacture of hydrogen, chlorine and sodium hydroxide and bleaching solution Refining of copper Electroplating Extracting reactive metals Aluminium anodization

Manufacture of bleaching solution

Manufacture of bleaching solution

At the anode: 2Cl(aq) Cl2(g) + 2e + At the cathode: Na (aq) + e + Hg(l) Na/Hg(l)
sodium amalgam

The sodium amalgam then flows into a second cell and reacts with water to form sodium hydroxide, hydrogen and mercury. Mercury is then recovered and then pumped back into the reaction chamber. 2Na/Hg(l) + 2H2O(l) 2NaOH(aq) + H2(g) + 2Hg(l)

Manufacture of bleaching solution

This process also produces waste which contains poisonous mercury compounds. These waste products will cause serious pollution problems if they are discharged into rivers and seas.

Refining of copper

Refining of copper

Copper ore contains a few impurities mostly silver, gold, platinum, iron and zinc reduce the electrical conductivity of copper significantly. anode: impure copper cathode: very pure copper electrolyte: copper(II) sulphate solution and sulphuric acid

Refining of copper

Iron and zinc are more reactive than copper. They form ions more readily than copper. At anode, iron and zinc give up electrons first. Then copper gives up electrons to form copper(II) ions. 2+ Zn(s) Zn (aq) + 2e Fe(s) Fe2+(aq) + 2e 2+ Cu(s) Cu (aq) + 2e

Refining of copper

Impurities such as silver, gold and platinum settle at the bottom of the container. At the cathode, the position of copper(II) ions in the electrochemical series is lower than that of hydrogen ions. Copper(II) ions are preferentially discharged (reduced) to form brown copper metal. 2+ Cu (aq) + 2e Cu(s)

Refining of copper

Overall reaction: Cu(s) Cu(s) anode cathode

Refer to case 8

Electroplating

Electroplating

Electroplating is the coating of an object with a thin layer of a metal by electrolysis. Cathode: object to be plated Anode: plating metal Electrolyte: a solution of a compound of the plating metal

Electroplating

Objects may be electroplated with copper, nickel, chromium, gold or silver. Typical example: electroplating of copper

Pollution problems of electroplating

The electroplating industry produces many toxic waste by-products.

acids and alkalis cumulative poisons of heavy metals and ions (such as nickel, chromium and mercury) toxic cyanides.

Solutions

Controlling the pH value of effluents

The pH value of acidic effluents can be controlled by adding sodium carbonate. The pH value of alkaline effluents can be controlled by adding sulphuric acid. Add sodium hydroxide solution to the effluents to form insoluble metal hydroxides. The solid is then filtered off.

Treatment of heavy metal compounds

Solutions

Treatment of poisonous chromium waste

Poisonous chromium(VI) compounds are reduced to non-toxic chromium(III) compounds by sodium sulphite. Sodium hydroxide solution is then added to the chromium(III) compounds to form solid chromium(III) hydroxide. The solid is then filtered off.

Extraction of reactive metals

Reactive metals such as K, Na, Ca, Mg and Al are extracted from its ores by electrolysis of molten metal ores. Metal ions are attracted to the cathode and reduced to form metal. Mn+(l) + ne- M(s)

Anodization of aluminium

Aluminium oxide is a protective oxide layer. It does not react with acids and alkalis. However, natural occurring aluminium oxide layers are thin and unevenly distributed. Anode: Al Cathode: circular sheet of steel Electrolyte: dilute sulphuric acid

Anodization of aluminium

At anode: 4OH-(aq) O2(g) + 2H2O() + 4e Oxygen is then reacted with aluminium anode to form a thick protection oxide layer. 4Al(s) + 3O2(g) 2Al2O3(s) Aluminium oxide can be dyed.