Chemistry teacher guide. 3 The manganate(VII) ion is an oxidising agent. The ions are coloured.

a _ Known volumes of known concentrations of all the reagents are mixed and a stop-clock is started. _ At a noted time, a 25 cm3 sample is removed with a pipette and put into a conical flask containing iced water, in order to quench (stop) the reaction. _ The remaining unreacted potassium manganate(VII) in the pipetted sample is then titrated against standard iron(II) sulfate solution until the purple solution goes just colourless. _ At later times, other samples are removed and treated as before. _ The volume of the iron(II) sulfate solution is proportional to the amount of potassium manganate(VII) left in the reaction vessel. b 25 cm3 of a solution of potassium manganate(VII) is mixed with 50 cm3 of water and the intensity of its colour measured using a colorimeter. _ 25 cm3 of the original potassium manganate(VII) solution is mixed with 25 cm3 of sulfuric acid and 25 cm3 of ethanedioic acid solution and a stop-clock is started. _ The mixture is placed in the colorimeter and the intensity of the purple colour of the solution is measured at regular intervals. The intensity of the colour compared with the original intensity is a measure of the concentration of the manganate(VII) ions. eThe potassium manganate(VII) solution is diluted so that its concentration is exactly the same as that in the initial reaction mixture. This allows a comparison to be made between the intensity of the colour and, therefore, the amount of manganate(VII) ions left as the reaction proceeds. c This increase in rate followed by a decrease is caused by one of the products acting as a catalyst. In this experiment the catalyst is the Mn2+ ion. This can be proved by repeating the experiment and adding some Mn2+ ions initially. The fact that the reaction becomes faster shows that the Mn2+ ion is a catalyst. eThe temperature must be kept constant. Many exothermic reactions carried out in a beaker accelerate first before slowing down. This is because the temperature rises, causing the reaction to speed up before slowing down as the reactants are used up. The two most likely rate equations are: rate = k[A][B] and rate = k[A]2 eA possible mechanism for the first suggested rate equation would be: A + B X in a slow, rate-determining step, then X + A products A possible mechanism for the second suggested rate equation would be: 2A X in a slow, rate-determining step, then X + B products (where X is an intermediate in both mechanisms)

The rate equation k[B]2 is possible but highly unlikely two B species would have to react in the first and ratedetermining step, and one B would have to be reformed in a later step. a The clock method for this reaction is as follows: _ In one beaker place known volumes of sodium persulfate solution and sodium thiosulfate solution, plus a few drops of starch solution. _ In another beaker place a known volume of potassium iodide solution. _ Mix the two, start a clock and stir. Stop the clock when the solution turns blue. _ Repeat the experiment with a different volume of sodium persulfate made up to the same total volume with water. _ Repeat the experiment with a different volume of potassium iodide solution, again making up to the same total volume with water. _ As the iodine is produced it reacts with the sodium thiosulfate, until all the sodium thiosulfate has been reacted. The next iodine produced turns the starch dark blue. _ A measure of the rate is b In experiments 1 and 2, [I] remains constant and [S2O8 2] is doubled. The rate doubles (increases by a factor of 21), so the reaction is first order with respect to persulfate, S2O8 2, ions. volume of sodium thiosulfate time taken 2.3 103 1.0 1.0 rate [A][B] concentration s1 (concentration)2 2.2 105 0.20 0.10 rate [C2H5I][KOH] 7.In experiments 2 and 3, [S2O8 2] and [I] are both doubled. The rate increases by a factor of 4. As the reaction is first order with respect to S2O8 2 ions, the rate doubles because of the doubling of [S2O8 2]. Since the rate increases by 2 2, the reaction is also first order with respect to I ions. c The rate equation is: rate = k[S2O8 2][I] Using the values from experiment 1, the rate constant is: k= = 6.3 103 mol1 dm3 s1 eOnly two significant figures are justified as the least accurate data are given to two significant figures. 9 a Since the slope of the tangent equals the rate of reaction, it can be seen that the rate halves as the concentration

of OH ions halves. This means that the reaction is first order (it has a total order of one). b The relative values of the slopes will be identical to those obtained by measuring the change in [OH]. eBecause the 2-bromopropane and the OH ions react in a 1:1 ratio, the concentration of each reagent halves from 0.10 moldm3 to 0.050 moldm3. Thus, it is not possible to tell from these data whether the reaction is first order in OH and zero order in 2-bromopropane or vice versa. c The rate equation is either: rate = k[OH] or rate = k[CH3CHBrCH3] The experiment could be repeated using twice the initial concentration of OH ions but an unaltered concentration of 2-bromopropane. If the first rate equation is correct, the initial slope will be twice as large (rate twice as fast). If the second rate equation is correct, the slope will be unchanged.