Redox Equilibria Standard electrode potential S.H.E. SHE is assigned an electrode potential of 0.00V.

Standard conditions are 1 M solution, 298K temperature, 1 atm pressure. Salt bridge allows ions to move from one half-cell to the other and the high resistance voltmeter measure the potential difference without drawing current from the cell. The electrode potential is defined as the e.m.f of a cell in which the electrode on the left is a standard hydrogen electrode and that on the right is the electrode in question. Cell e.m.f. Of Er = e.m.f. of right-hand electrode and EL = e.m.f. of the left hand (as written on the page), then Ecell = Er-EL. The electron flow is from the most negative/least positive potential half-cell (-ve pole) to the most positive/least negative potential halfcell (-ve pole), i.e. H2/H+ to Cu/Cu2+. (i.e. for Cell Diagram substance oxidised on left, substance reduced on right) If the Ecell is positive then the reaction has the potential to go as written. If it is negative the reaction will work in the reverse reaction. Ecell values close to zero (but positive) may not go because of a high activation energy, or the reaction conditions may not be standard. Multiplying a reaction throughout by a constant does not change the Eo value. So you need to multiple to make electrons balance for the overall equation but not Eo values to do the calculation. Disproportionation This is the simultaneous oxidation and reduction of the same species e.g. 2Cu+ Cu2+ + Cu Oxidation 2Cu+ to Cu2+, Reduction 2Cu+ to Cu. If the Eo value linking the intermediate and lower oxidation state (Cu+ and Cu) is greater than the Eo value linking the higher OS and intermediate (Cu2+ and Cu+) then the intermediate can disproportionate. Reactivity Up the metal reactivity series the half-cell potential voltages becomes more negative and the metal becomes 'more reactive'. Metallic elements react by electron loss (ox. state increase) to form a positive cation (e.g. magnesium ion Mg2+), so, as the electron loss potential increases, so the metallic element's reactivity increases Sodium thiosulphate Na2S2O3 This is a weak reducing agent. Iodine is formed by the oxidation of iodide ion. Iodine dissolves in aqueous solutions of iodide ion to give I3- which is red-brown colour and behaves like I2(aq) and can be titrated directly with thiosulphate. During the titration the red-brown colour of iodine lightens to yellow, when starch is added as an indicator

forming a deep blue complex with the iodine. The titration then continues until the blue solution turns colourless. 2S2O32- + I2 S4O62- + 2IOther methods of calculation This can be worked out by writing out the two equilibria and then drawing an arrow in the direction that the question asks. For example, to predict the reaction between Zn (s) and Fe3+(aq) we write: Fe3+ + e+0.77 V Zn2+ + 2eV Draw the arrow in the direction that the question asks (i.e. with the reactants for each equilibrium being the chemicals in the question) and then subtracting the E values in the direction that the arrow goes. In this case E cell = ( + 0.77 ) - ( - 0.76 ) = +1.53 V OR! For the reaction of copper and silver, the half equations are Cu2+(aq) + 2e_ Cu(s) Eo = + 0.34 V and Ag+(aq) + e_ Ag(s) E = + 0.80 V Careful observation shows that silver is deposited on the silver electrode and the copper electrode starts to dissolve. The reaction with the more positive Eo will proceed in the forward direction. Copper on the left, silver on the right so Ecell = 0.8-0.34 = +0.46V. Overall equation Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s) OR! The anticlockwise rule used to decide in which direction a particular reaction is likely to proceed, write out the two half cells as reductions with the more negative above. If the two are then linked by an anticlockwise circle then the reactions will proceed in the directions shown: Zn2+ + 2e- Zn Zn E = -0.76 Fe2+ E =

Cu2+ + 2e-

Cu

The anticlockwise rule is not an explanation of what happens. Alevel examiners will be looking for something like zinc has the more negative electrode potential, so zinc will be oxidised.