Chapter 6: Electrochemistry study of inter-conversion of chemical energy and electrical energy. 6.1 Electrolytes and non-electrolytes 1.

Electrolyte can be molten ionic compound or aqueous solution of ionic compound, acid or alkali. 1. Electrolyte decomposes into its component elements at the electrodes. 2. Non- electrolyte: chemical compounds which do not conduct electricity. 3. In electrolyte, electricity is conducted by freely move ions 4. Example equation:

Electrolysis process: AnBm nAm+ + mBnExample: PbBr2 Pb2+ + 2BrHalf equation for discharge of ions at anode: 1. Bn- B + ne2. Anions are discharged at anode, donating eHalf equation for discharge of ions at cathode 1. An+ + ne- A 2. Cations are discharged at anode, accepting eCombined half equations: An+ + Bn- A + B

a) NaCl ---> Na+ + Clb) H2O ---> H+ + OH6.2 Electrolysis of molten compound 1. Electrolysis : decomposition of electrolyte by electric current 2. Anions anode 3. Cation cathode 4. Graphite or platinum as electrode - Inert - Do not react with electrolyte or product 5. Electrolytic cell:

Example 1: Write the half equation for the discharge of chloride ion Step 1: 2Cl- Cl2 Step 2: 2Cl- Cl2 + 2e-

Example 2: When Lead(II) oxide, PbO is electrolyzed, lead metal and oxygen gas are produced. Write the half equations and overall equation

Prediction of the products of electrolysis of molten electrolytes Example 1: NaCl Na+ + ClElectrode Anode Product Chlorine molecule 2Cl- Cl2 + 2eGreen-yellowish gas Sodium metal atom Na+ + e- Na Grey metal

The lower the position of the ion in the electrochemical series, the easier the ion will be discharged. Example 1: Available of Al3+ ,H+ , O2-, OHIon discharged at anode: 2H+ + 2e- H2 Ion discharged at cathode: 4OH- 2H2O + O2 + 4e-

Cathode

6.3 Electrolysis of Aqueous Solutions 1. Identify anion and cation 2. Solution Vs molten salt of NaCl Ions Cation Anion Solution Na+ H+ Cl- OHMolten Na+ Cl-

B) Concentration of ions in the solution If the concentration of certain ion is higher, the ion is more likely to be discharged Example 1: Electrolysis of CuCl2 solution with carbon electrode Cu Cl2 Cu2+ + ClH2O H+ + OHIf conc. CuCl2 is electrolysed, Cl- will be discharged at anode, whereas Cu2+ will be discharged at cathode. C) Types of electrodes used Common: platinum and carbon Example: Electrolysis of copper(II) sulphate, CuSO4 If carbon as electrode, OH- discharged at the anode If copper as electrode, none of the anion will be discharged. Copper anode dissolves by releasing electrons to form Cu2+ ion Anode : Cu Cu2+ + 2eThe anode mass decreases

Factors that determine the selective discharge of ions at the electrodes 1. Position of ions in the Electrochemical Series 2. Concentration of ions in the solution 3. Types of electrodes used A) Position of ions in the Electrochemical Series

Electrolysis sulphuric acid (aq)

with hydrogen and oxygen gas being given off in a ratio of 2 : 1 .

1. Electrolysis of diluted or concentrated HCl 2. Electrolysis of concentrated sodium chloride solution (Brine) Cathode Na+ and H+ As the hydrogen ion (H+), is lower in the reactivity series than the sodium ions (Na+ ), it accepts electrons more easily. The hydrogen ions (H+) are discharged. 2H+ + 2e ---> H2 Anode

H2SO4 + H2O --> 2H+ + SO42- + H+ + OHCathode Anode SO42- (aq), OH- (aq) OH- + 4e ---> O2 + H2O

2H+ + 2e ---> H2

Both the chloride ions (Cl-) and the hydroxide ions (OH-) migrate to the anode . The chloride ions (Cl-) are preferentially discharged because of their higher concentration

At the Cathode At the Anode

2Cl- ---> Cl2 + 2e

Here we have only one ion, the hydrogen, H+ (aq), and each ion gains an electron to become a hydrogen atom. Two of these newly formed atoms then combine to form a hydrogen gas molecule . Here we have a choice of either sulphate, SO42- (aq), or hydroxide OH- (aq) ions. Hydroxide is easier to discharge, so oxygen gas is given off at the anode.

Note : As the hydrogen ions and chloride ions are discharged, sodium ions and hydroxide ions remain in the solution . The solution becomes sodium hydroxide

6.4 Electrolysis in industries a) extraction of reactive metals - reactive metals like Na, Ca, Mg and Al - exp: Al from Al2O3 Na from NaCl 1. Hall-Heroult process Source: bauxite, containing aluminium ore Electrode: carbon Additive: cryolite (Na3AlF6)

Notes

With electrolysis of aqueous solutions of dilute acids or alkalis, the volume of hydrogen given off at the cathode is roughly twice that of the oxygen gas at the anode. Accordingly, the elements of water are lost and as the electrolysis continues, the concentration of the acid or alkali increases . Essentially, the electrolysis of aqueous sulphuric acid is the electrolysis of water,

6.5 Voltaic cell Al2O3 2Al (l) + 3O (l) Anode : 2O2- O2 + 4eCathode: Al3+ + 3e- Al ___________________________ Overall : 2Al2O3 4Al + 3O2 Note : carbon electrode has to be replaced from time to time as carbon react with oxygen to give CO2 2. Downs process Source : molten NaCl Additive : CaCl, lower mp of NaCl NaCl Na+ + ClAnode : Na+ + e- Na Cathode: 2Cl- Cl2 + 2e_________________________ Overall: 2NaCl 2Na + Cl2 b) Purification of metals Anode: impure metal Cathode: pure metal Electrolyte: ions of the metal to be purified Note: metal is transferred from anode to cathode. Mass of anode is reduced, while mass of cathode is increased. c) electroplating of metals coating surface of metal objects, to prevent corrosion, to improve appearance. Cathode: objects Anode: electroplating metal 1. Immersing two different metals in electrolyte 2. The more electropositive metal releases electrons, acts as anode. 3. The less electropositive metal, accept electrons, as cathode 4. Flow of electrons from anode to cathode through external circuit produces electric current.
5. Types of voltaic cell Primary cell Non-rechargeable Example: - Daniel cell - dry cell - mercury cell - Alkaline cell Secondary cell Rechargeable Example: - lead-acid accumulator - nickel/ cadmium cell
3+ 2-

Daniel cell

1. +ve terminal: Cu (in CuSO4) 2. ve terminal: Zn ( in ZnSO4) Salt bridge: allow ions flow, complete circuit