REACTION KINETICS 1 An energy profile diagram of a chemical reaction is given below:

(a) Give the expression that represents activation energy without a catalyst for (i) the forward reaction (ii) the backward reaction (b) Give the expression that represents activation energy with a catalyst for (i) the forward reaction (ii) the backward reaction (c) By what amount has the introduction of a catalyst reduced the activation energy of the (i) forward reaction (ii) backward reaction 2 Case 1 : The chemical reaction of the decomposition of hydrogen peroxide solution is catalysed by manganese(IV) oxide powder. Case 2 : In the chemical process of producing sulphur trioxide involving sulphur dioxide and oxygen as reactants, nitrogen monoxide is used as a catalyst. Identify the type of catalyst used and give reasons for your answer. Two reactions P and Q are carried out by a researching student. Reaction P occurs fast while Q is a slow reaction. Q requires a higher temperature. (i) Which of the two reactions has a higher rate constant? (ii) Why does Q require a higher temperature? (iii) Which of the two has a higher activation energy? A reaction mechanism is summarised below: Step I : P + 2Q R (slow) Step II : R + S T (fast) (a) Which step determines the rate equation? (b) Write the rate equation of the above reaction. (c) Give the order of reaction with respect to : i. P ii. Q (d) What is the order of the above reaction? Sketch the shape of n ( [ n
[ ] ([ ] [ ] ]

) versus t on the axes given below:

The table below shows the results of a series of experiments conducted to determine the order of reaction. Based on the results, answer the questions that follow: Experiment [P]/mol dm-3 [Q]/mol dm-3 [R]/mol dm-3 Initial rate/ mol dm-3s-1 1 0.12 0.1 0.2 1.4 103 2 0.12 0.2 0.2 2.8 103 3 0.12 0.2 0.1 3.5 103 4 0.24 0.2 0.2 2.8 103 (a) Derive the order of reaction of (i) P (ii) Q (iii) R (b) From your answer of part (a), deduce the rate equation of the above reaction. (c) Calculate the rate constant for the above equation. State its unit in your answer.

The rate equation for the oxidation of iodide ions by hydrogen peroxide is Rate = k[H2O2] [I-] [H+]0 (a) What is the order of reaction with respect to (i) H2O2 (ii) I(iii) H+? (b) What is the overall order of the reaction? The equation for the decomposition of N2O5 is N2O5(g) 2NO2(g) + O2(g) The reaction above is of the first order. (a) Write the rate equation for the reaction above. (b) At 55C, when the initial concentration of N2O5 is 0.020 mol dm-3, the rate of decomposition of N2O5 is 3.4 10-2 mol dm-3 s-1. Calculate the rate constant at 55C. (c) Calculate the time taken for the concentration of N2O5 to be reduced to 0.010 mol dm-3. Sucrose undergoes hydrolysis as represented by the following equation C12H22O11 + H2O 2C6H12O6 The rate of hydrolysis of sucrose at 300C is determined in an experiment by measuring the concentration of sucrose at regular time intervals. The graph of concentration against time is shown below:

(a) What is the order of the hydrolysis reaction with respect to sucrose? (b) Determine the rate constant of the reaction if the rate of hydrolysis is independent of water. (c) What is the initial rate of hydrolysis if the initial concentration of sucrose is 40.5 g dm-3? 10 The rate constant of a first order reaction is 2.5 10-6 s-1. The initial concentration of the reactant is 0.15 mol dm-3. What is the value of the initial rate in mol dm-3 s-1? The half-life for the radioactive decay of carbon-14 is 5730 years. (a) Calculate the rate constant for the decay. (b) What time will elapse before of the carbon-14 has decayed? The data below was obtained from the reaction A + B C at 28C. Experiment 1 2 3 Initial rate (mol dm-3s-1) 6.3 25.2 25.2 [A] (moldm-3) 0.05 0.10 0.10 [B] (mol dm-3) 0.05 0.05 0.10

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(a) Find the rate equatin of the reaction. (b) Find the rate constant at 28C. (c) Find the initial rate of the reaction when the initial concentration of A and B are 0.20 mol dm-3 and 0.30 mol dm-3 respectively. 13 The variation in the rate constant, k at two different temperatures for the reaction 2HI(g) H2(g) + I2(g) is given in the following table: Temperature (C) 283 356 K (mol-1 dm3 s-1) 3.52 10-7 3.02 10-5 (a) Calculate the activation energy of the reaction. (b) What is the rate constant at 293C? Comment on your result. 14 The decomposition of dinitrogen pentoxide is given below: 2N2O5(g) 4NO2(g) + O2(g) The rate constants for the above decomposition are 3.7 10-5 s-1 and 1.4 10-4s-1 at 298 K and 308 K respectively. (c) Calculate the activation energy for this reaction. (d) Calculate the rate constant at 328 K.

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