Experiment 1

Experiment 1
Object Determination of the rate constant and the energy of activation of the reaction between hydrogen peroxide and hydrogen iodide. Apparatus required: conical flask, thermostat, dry bottle, boiling tube, burette, beakers Chemicals required 2.0 N H2SO4 , 0.4 M KI solution , 0.1 M Na2S2O3 . 5 H2O , 1 vol. H2O2 Theory: The overall reaction between H2O2 and HI which represented by the equation H2O2 + 2 HI = 2 H2O + I2 is kinetically of second order -not, as might be expected, third order. The suggested mechanism is probably as H2O2 + I- = H2O + IO- (slow), IO- + 2 H+ + I- = H2O + I2 (fast) The rate-determining step is the slow stage, Rate [H2O2][I-] (first order with respect to both [H2O2] and [I-]). The order of the reaction with respect to H2O2 can be studied conveniently by choosing conditions such that there is practically constant excess of HI. Then, the rate of the reaction depends only on [H 2O2] and temperature and, hence, the kinetics then follows the first order law, Rate [H2O2]. This is achieved experimentally by continually adding small volumes of sodium thiosulphate solution to remove the iodine as soon as it is liberated and to regenerate iodide according to the reaction 2S2O3-- + I2 = S4O6-- + 2INote that: by using a large volume of solution and adding small amounts of concentrated thiosulphate solution, one can neglect the small increase of volume of the solution and take the concentration of I- ions as constant. The course of the reaction can readily be followed by timing the appearance of iodine (indicated by starch solution) after the addition of a small known volume of thiosulphate solution. The amount of iodine librated by the reaction at a series of times corresponds to the volume of thiosulphate added. The total amount of iodine
librated at infinite time can be determined from a standardization of the hydrogen peroxide used. Thus, it is possible to determine the concentration of hydrogen peroxide at any time, since 1 mol of iodine is librated for every mol of hydrogen peroxide destroyed. The order of the reaction with respect to HI can be determined by determining the first order velocity constant of the reaction with different concentrations of HI. Generally, the rate equation of the overall reaction is Rate = k [H2O2]a [HI]b where, k is the rate constant, a and b are the order with respect to H2O2 and HI, respectively. The rate of this reaction can be determined by allowing the reaction to proceed in the presence of thiosulphate and determining the time taken between mixing of the reactants and the appearance of iodine. The reciprocal of the time interval is a measure of the rate of reaction.
Procedure: 1. Prepare 250 ml of the following solutions: 2.0 N H2SO4 , 0.4 M KI solution , 0.1 M Na2S2O3 . 5 H2O , 1 vol. H2O2 , Freshly prepared starch solution. 2. Into a clean dry conical flask introduce 20 ml of the hydrogen peroxide solution, add about 2 g solid potassium iodide and 10 ml of sulfuric acid. Leave the mixture for about five minutes in a dark place, then titrate the librated iodine with standard sodium thiosulphate solution, and, hence, standardize the hydrogen peroxide solution. Note that: the consumed volume of Na2S2O3 is equivalent to the librated I2 , equivalent to [H2O2] destroyed and equals a. 3. To 50 ml of potassium iodide solution in a dry bottle, add 20 ml of the diluted sulfuric acid and place in a thermostat at about 25 oC. At the same time have 20 ml of hydrogen peroxide solution and 10 ml of the starch solution (in separate boiling tubes) at the same temperature. 4. Arrange the 50 ml burette containing the sodium thiosulphate solution above the flask in the thermostat so that it will deliver directly into the solution, add the starch and hydrogen peroxide solutions (with vigorously shaking) 35
and record the time at which a blue color appears, then add immediately 1 ml of the thiosulphate solution from the burette to discharge the color. 5. Continue the addition of 1 ml aliquots of sodium thiosulphate until the blue color appears until the blue color takes five to six times the initial time to reappear (it is essential that the reaction mixture be shaken continuously). 6. Repeat the experiment at various temperatures in the range 25 to 50 oC. 7. To determine the order of the reaction with respect to hydrogen iodide, repeat the experiment (at 25 oC) now using half and double the amounts of sulfuric acid and potassium iodide in the same total volume of the reaction mixture. Treatment of the experimental data and discussion : 1. The total amount of librated iodine at infinite time can also be determined from the preliminary standardization. Thus, it is possible to determine the concentration of hydrogen peroxide in mole per liter, [H2O2] at each time, (a-x). Note that: x is the volume of Na2S2O3 added. 2. Plot a graph of ln [H2O2] (ln (a-x)) against t, at each temperature to obtain a straight line with a slope of k (rate constant) at constant iodide ion concentration (first order reaction) according to the equation: ln [H2O2] = -k t + B 3. From the values of the rate constant at different temperatures, calculate the activation energy of the reaction from the equation: ln k = -Ea/RT + const. by plotting the values of ln k against 1/T to get a straight line with a slope of Ea/R, then calculate Ea (activation energy).
From the values of the rate constant at different iodide concentrations determine the order of the reaction with respect to hydrogen iodide. The overall reaction will be of a second order.

Experiment 1

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