Redox Equilibria a) The total increase in oxidation number of one element must equal the increase in another.

Why: Redox reactions involve the transfer of electrons between chemical species. Oxidation and reduction take place simultaneously, one substance is reduced and the other is oxidised (expressed in half equations). Mg(s) 2Mg2+(aq) + 4eO2 (g) + 4e- 2O2-(aq) b) Redox Titrations - Potassium manganate (VII) estimation of oxidising agents. KMnO4 can act as an oxidant in acidic solution. Procedure (Unit 3): Pipette a known volume of the reducing agent into a conical flask; add an excess of dilute H2SO4. The KMnO4 solution of known concentration is put into the burette and run in until there is a faint pink colour (end point). Use stoichiometry of the reaction to calculate the concentration of the reducing agent. MnO4- (aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l) Ratio 1:5 - Potassium Iodide and Sodium Thiosulphate Procedure: Add a sample of an oxidising agent to excess acidified KI. The oxidising agent liberates iodine, which can then be titrated against a standard sodium thiosulphate solution. When the iodine has faded to pale yellow, add starch indicator and continue to titrate until blue colour disappears. I2 (g) + 2S2O32-(aq) 2I-(aq) + S4O62-(aq) Ration 1:2 c) Standard hydrogen electrode: Hydrogen gas at 1 atm bubbling over a platinum electrode immersed in H+ ions at 25oC. The potential equals zero. This means that other elements can be compared against hydrogen to find the standard value. Standard electrode potential is the electric magnetic frequency (emf) of a cell composed of the standard electrode connected to standard hydrogen electrode. Note: Half equations are written as reduction potentials (electrons on the left). The one with the larger positive value of Eo(SEP) is a more powerful oxidising agent. Eg: Chlorine - Eo = +1.36 Bromine - Eo = +1.07 Therefore chlorine is a stronger oxidising agent than bromine. d) Electrons flow from reductants to the oxidants. In order to know whether a redox reaction will take place physical measurements are taken using half-cells. A typical half-cell consists of a metal in contact with an aqueous solution of its ions and a dynamic equilibrium is reached. Electrons are delocalised throughout the metal strip thus forming an electrode. Eg: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) The reductant (zinc) produces electrons and therefore has a more negative electric potential than the copper electrode. These are connected by a voltmeter, which measures the p.d. across it. The electrons flow towards the copper electrode.

In terms of SEP: In a reaction the half-cell with the more negative SEP will reduce the half-cell with the less negative SEP Ereaction = E of reduced species E of oxidised species SEP for Copper: +0.34 V SEP for Zinc: -0.76 V Ereaction = +0.34 (-0.76) = +1.10 V If Ereaction is positive then the reaction is more likely to occur (thermodynamically unstable) e) Disproportionation is predicted using electrode potentials. For elements existing in three oxidation states, use the data from the half equations to calculate Ereaction. If it is positive, the reaction will occur (rule above). f) Corrosion (rusting in iron) is an electrolytic process caused by the presence of water and oxygen. Some areas become anodic and some become cathodic. - Anodic areas become oxidised (producing Fe2+ + 2e-) - Electrons travel through the metal and reduce oxygen to hydroxide ions - The iron(II) and hydroxide ions form Fe(OH)2(s) - Oxygen oxidises the iron(II) hydroxide to iron (III) oxide rust. Corrosion can be prevented by galvanising with zinc (sacrificial metal) Place a physical barrier between the iron and the environment eg. paint or tin plating g) Storage cells store electrical energy as chemical energy. The reactions are fully reversible and the products are insoluble. Eg. Lead-acid cell consists of lead in a solution of sulphuric acid The negative electrode consists of lead metal: Pb(s) + SO42- PbSO4 (s) + 2eThe positive electrode consists of lead coated with lead (IV) oxide Pb(s) + SO42- + H+(aq) + 2e- PbSO4 (s) + 2H2O(l) The changes that happen as a current flows from the cell produce an insoluble solid, meaning it doesnt dissolve in the electrolyte. When the current is reversed to charge up the cell, the reactions can be reversed.