Electrolysis (i) Molten Ionic Compounds e.

g molten lead(II) bromide using carbon electrodes

Anode Cathode Overall reaction: (ii) Aqueous Ionic Compounds Factors to be considered when predicting the reactions that occur during electrolysis of an aqueous ionic compound. The position of the cation and anion in the electrochemical series The concentration of the electrolyte The nature of the electrolyte The nature of the electrodes

The position in the electrochemical series(ecs) Cations K+ Ca2+ Na+ Mg2+ Zn2+ Fe2+ Ease of discharge of cation increases Anions SO42ClBrIOH-(H2O) Ease of discharge of anion increases

Sn2+ Pb2+ H+(H2O) Cu2+ Ag+

The least electropositive element of the cation of the electrochemical series will be reduced at the cathode. The least electronegative element of the anion at the bottom of the electrochemical will be oxidized at the anode. e.g electrolysis of aqueous potassium chloride using carbon electrodes

At the cathode: K+ (aq) + e 2H2O(l) + 2e K(s) higher in ecs H2(g) +2OH-(aq) lower in ecs

Water will be reduced to hydrogen gas ( K + will not be discharged) At the anode: 2Cl-(aq) 2H2O(l) Cl2(g) + 2e higher in ecs lower in ecs

O2(g) + 4H+(aq) + 4e

Water will be oxidized to oxygen gas( Cl - will not be discharged) Overall electrolytic reaction:

Try completing the table (carbon electrodes are used): Electrolyte Cathode Anode

NaCl(l) Dilute NaCl(aq) CuSO4(aq) H2SO4(aq) Dilute NaOH(aq) Concentration of the electrolyte If the concentrations of the ions which could be discharged at an electrode are very differet, then the ion present in high concentration may be discharged in preference to the others, event though its ease of discharged is unfavorable. e.g electrolysis of concentrated aqueous potassium chloride

At the cathode, hydrogen gas will be discharged. At the anode, chlorine gas will now be discharged instead of oxygen gas regardless of its unfavorable ease of discharge.

Nature of the electrolyte If concentrated aqueous copper (II) chloride is used instead of concentrated aqueous potassium chloride, the products of electrolysis will be different. At the anode, chlorine gas will be formed. At the cathode, Cu2+(aq) + 2e 2H2O(l) + 2e Cu(s) H2(g) + 2OH-(aq) lower in ecs than H+

Copper will be deposited in preference to the evolution of hydrogen gas.

Nature of electrodes If the anode is made of a metal such as silver or copper, the anode may dissolve to form ions in the solution. e.g electrolysis of aqueous copper(II) sulfate using copper electrodes At the anode, copper will dissolve into the solution as copper ions. At the cathode, copper ions will be deposited as copper metal.

(iii)

Industrial Processes

(i)
NaCl solution H2

Electrolysis of Brine using a Diaphragm Cell

Carbon chlorine Spent

Abestos

Steel mesh Steam NaOH as byproduct Anode:2Cl-(aq) Cl2(g) +2e H2 (g) +

Cathode: 2H2O(l)+ 4e 2OH-(aq)

Electrolyte

Anode

Cathode

Purified concentrated aqueous sodium chloride(brine) . (Purification needed to remove Ca2+ and Mg2+ which would precipitate insoluble hydroxides and block the pores of the diaphragm) Graphite or Titanium coated with Ru-Ti oxide The electrolyte is added to the anode compartment. The electrolyte soaks through the diaphragm into the cathode compartment. Electrolysis takes place. Chlorine gas is discharged preferentially due to the high concentration of Cl-. The chlorine gas may be piped from the top of the anode compartment; stored in cylinders. Steel or Nickel Asbestos fibres are deposited in the steel

mesh Diaphragm is porous but separates electrolysis products. Hydrogen gas may be piped out of the cathode compartment Na+ are attracted to the cathode. Na+ combine with the OH- produced to form NaOH. NaOH settles at the bottom of the cell. Overall reaction:

Just a note

Some unreacted sodium chloride will settle at the bottom of the cell, together with the sodium hydroxide. The solution is evaporated. Most of the NaCl crystallizes on cooling, leaving a solution rich in NaOH. (ii) Extraction of Aluminium form Molten Al2O3 or Cryolite Preliminary step Bauxite, Al2O3xH2O, is purified and heated to give aluminium oxide(alumina Al2O3) Alumina has a high melting point, is not readily soluble in water and cannot be an electrolyte.

Preparation of electrolyte: Sodium hexafluoroaluminate(III) (cryolite, Na 3AlF6) is added to Al2O3. Cryolite is used because it It acts as a solvent and an electrolyte Has a much lower melting point than alumina Has a lower vapour pressure than molten aluminium Has a lower density than molten aluminium

Can dissolve sufficient alumina to allow deposition of aluminium at much lower temperature(energy saving)

A little fluorspar is added to lower the melting point further. Small quantity of aluminium fluoride is added to reduce the solubility of the molten aluminium, when formed, in the molten cryolite.

Carbon rods(anode)

Molten cryolite and aluminium oxide

Aluminium tap Molten aluminium Carbon lined box(cathode)

Electrolyte Anode

Alumina and cryolite (Al2O3 and Na3AlF6)

The carbon anode is gradually consumed and needs to be replaced regularly. Cathode

Aluminium settles at the bottom of the cell and is siphoned out

Overall reaction:

Disadvantages of such extraction method: o

(iii)

Electrolytic Purification of Copper

Electrolyte Anode

Aqueous copper(II) sulfate Impure copper

Copper anode dissolves into the electrolyte as Cu 2+ which migrate to the cathode to be reduced to copper. Cathode Pure copper

The anodic sludge may contain traces of precious metals such as gold, silver, platinium which are below copper in the ecs.