Kinetics 1.

The kinetics of the hydrolysis of the halogenoalkane RCH2Cl with aqueous sodium hydroxide (where R is an alkyl group) was studied at 50 C. The following results were obtained: Experiment 1 2 3 (i) (ii) (iii) (iv) [RCH2Cl] 0.050 0.15 0.10 [OH] 0.10 0.10 0.20 Initial rate/mol dm3 s1 4.0 104 1.2 103 1.6 103

Deduce the order of reaction with respect to the halogenoalkane, RCH2Cl, and with respect to the hydroxide ion, OH, giving reasons for your answers. (4) Hence write the rate equation for the reaction. Calculate the value of the rate constant with its units for this reaction at 50 C. Using your answer to part (ii), write the mechanism for this reaction. (1) (2) (3)
(Total 10 marks)

2. In an experiment to determine the rate of the reaction between persulphate ions and iodide ions in aqueous solution
2 S2O 8 + 2I 2SO 2 4 + I2

the following data were obtained:

Concentration/mol dm 3
S2 O 2 8

I 0.100 0.100 0.200

Initial rate /mol dm3 s 1 0.36 0.72 1.44

0.100 0.200 0.200

(a)

(i) (ii) (iv)

Deduce the order of reaction with respect to each of the reagents and hence write the rate equation for the reaction. (3) With reference to this reaction state what is meant by the overall order of a reaction. (1) (2) Explain why the rate equation cannot be written directly from the stoichiometric equation for the reaction. (1) Suggest a suitable experimental technique that would enable you to determine the rate of the reaction given opposite. (1) Suggest a necessary condition that would help to ensure accurate results. (1) (1)
(Total 10 marks)

(iii) Calculate the rate constant including units.

(b)

(i) (ii)

(iii) Suggest one advantage or disadvantage of your chosen experimental method. (a) (i) Explain what is meant by the following terms. Rate of reaction & Overall order of a reaction (ii) (b)

(2)

Explain why the order of reaction cannot be deduced from the stoichiometric equation for a reaction. (1)

Substitution reactions of halogenoalkanes, can proceed via an SN1 or SN2 mechanism. When 1-bromobutane,

CH3CH2CH2CH2Br, 2-bromobutane, CH3CH2CHBrCH3, and 2-bromo-2-methylpropane, (CH3)3CBr, are reacted separately with aqueous sodium hydroxide solution each gives the corresponding alcohol. (i) (iii) Give the mechanism for the SN1 reaction between 2-bromobutane and hydroxide ions.(3) In an experiment designed to find the mechanism of the reaction between 2-bromo-2methylpropane and hydroxide ions the following data were obtained at constant temperature. Initial concentration of 2-bromo-2-methylpropane /mol dm3 0.10 0.20 0.30 Initial concentration of OH / mol dm3 0.10 0.10 0.20 Initial rate of reaction /mol dm3 s1 1.2 102 2.4 102 3.6 102

Use the data to deduce the rate equation for the reaction of 2-bromo-2- methylpropane with sodium hydroxide solution. (3) (c) Suggest, in outline, a method you could use to follow the progress of the reaction between a bromoalkane and aqueous sodium hydroxide. (3)
(Total 14 marks)

3. Manganate(VII) ions react with ethanedioate ions in acidic solution.

2MnO4 (aq) + 16H (aq) + 5C2O4 (aq) 2Mn (aq) + 8H2O(l) + 10CO2(g)
+ 2 2+

(a)

In a particular experiment 200 cm3 of aqueous potassium manganate(VII), KMnO4, of concentration 0.0500 mol dm3 were mixed with 50.0 cm3 of ethanedioic acid, HOOCCOOH, of concentration 0.500 mol dm3, and 80 cm3 of 1.0 mol dm3 sulphuric acid. (i) (ii) Show by calculation that the starting concentration of the manganate(VII) ions was 3.03 102 mol dm3. The concentration of the manganate(VII) ions was determined over a period of time. Time / s 0 400 800 1200 1600 2000 2400 Concentration of manganate(VII) ions/ mol dm
3

3.03 102 2.98 102 2.86 102 2.75 102 1.90 102 7.50 103 2.50 103

Plot a graph of the concentration of manganate(VII) ions against time and from it determine the initial rate of the reaction and the rate at 1600 s.(5) (b) A second experiment was set up involving the same chemicals in the same concentrations as in experiment 1 but this time some solid manganese(II) sulphate was dissolved in the ethanedioic acid before the potassium manganate (VII) solution was poured in. The plot of the concentration of manganate(VII) ions against time is given below:

(i) (ii)

Determine the order of the reaction with respect to manganate(VII) ions by considering the time taken for the concentration to fall by half, using the concentrations at 0, 800 and 1600 s. (3) Compare this graph with the one you plotted in (a) (ii) and give two pieces of evidence that manganese(II) sulphate is a catalyst for this reaction. (2)
3.5 10 2 3.0 10 2
concentration /mol dm 3

2.5 10 2 2.0 10 2 1.5 10 2 1.0 10 2 5.0 10 3 0 0 400 800 1200 1600 2000 2400 time / s

4. Hydrogen peroxide decomposes to form water and oxygen. (a) (b) Suggest a method for following the rate of this reaction. (2) The reaction is first order with respect to hydrogen peroxide. (i) (ii) Explain what is meant by the term first order. (1)

H2O2(aq) H2O(l) +

1 2

O2(g)

The overall order of the reaction is one. Give the rate equation for the reaction.(1)

(iii) How would you use a graph of hydrogen peroxide concentration against time to show that the reaction is first order? (2) (c) The data in the table show the effect of temperature on the rate of this reaction. T /K 293 302 314 323 (i) (ii) (iii) Rate / mol dm3 s1 1.6 106 4.2 106 14.4 106 33.8 106 1/T /K1 3.41 103 3.31 103 3.19 103 3.10 103 ln(rate) 13.3 12.4 11.1 10.3

On the axes below, sketch graphs for two temperatures, T1 and T2, where T2 is greater than T1, and use them to explain why increasing temperature has a dramatic effect on the rate of this reaction.(4) Plot a graph of ln(rate), on the vertical axis, against 1/temperature, on the horizontal axis, on the grid below.(3) Use your graph and the equation below to calculate the activation energy, EA, for this reaction.

ln(rate) = constant

EA R

(1/T)

where R = 8.31 J K1 mol1

You should include the sign and units with your answer which should be given to two significant figures.(3) 5. This question is about the kinetics of the reaction in which ammonium cyanate, NH4CNO, turns into urea, NH2CONH2, in aqueous solution. NH4CNO(aq) 2CONH2(aq) The table below shows the mass of urea, mt, which formed at different times in a solution of ammonium cyanate of known starting concentration. When the reaction stopped the mass of urea, mfinal, was 20.3 g. Time / min 0 25 50 75 100 150 200 300 (a) (b) (c) Mass of urea, mt /g 0 12.5 15.7 17.1 17.5 18.7 19.1 20.0 mfinal mt/g 20.3 7.8 4.6 3.2 2.8 1.6

Complete the final column of the table.(1) Plot a graph of mfinal mt (on the vertical axis) against time (on the horizontal axis)(2) The graph can be used to work out a rate equation for the reaction. What term in the rate equation for the reaction is proportional to mfinal mt? (1)

(d)

(i) (ii)

Show THREE successive half-life measurements on your graph, and give their values.(2) Use the half-lives to decide whether the reaction is zero order, first order or second order. Explain how you decided the order.(2)

(iii) Suggest a possible rate equation for the reaction. (1) (e) A student thought that water might take part in the rate-determining step of the reaction. (i) (ii) What is meant by the rate-determining step? (1) The solution of ammonium cyanate used in the experiment initially contained 0.35 moles of ammonium cyanate in approximately 1 dm3 (55.5 moles) of water. Is the order you calculated in (d)(ii) an order with respect to ammonium cyanate, or could it include the water as well? Explain your answer. (2)
(Total 12 marks)

6.

(a) (b)

In a rate of reaction experiment between two substances, A and B, the overall order of the reaction was found to be 2. Write three possible rate equations for such a second order reaction between A and B. (3) At a certain temperature the rate of reaction between nitrogen monoxide, NO, and hydrogen, H2, was investigated. The following data were obtained.

[NO]/mol dm3 1.0 1.0 3.0 (i) (ii) (c)

[H2]/mol dm3 1.0 3.0 1.0

Rate/mol dm3 s1 0.02 0.06 0.18

Use the data above to deduce the rate equation for this reaction.(3) Use your answer to (b)(i) above to calculate the value of the rate constant, with units(2)

The investigation described in part (b), above, was repeated, but at a higher temperature, and the rate of the reactions increased. Explain, in terms of particles, why an increase in temperature increases the rate of a reaction. (3) State the effect of an increase in temperature on the value of the rate constant, k. (1) Explain the effect of a catalyst on the rate of a reaction (3) (Total 15 marks)

(d) (e)