Rate Equations and Kp

Rate Equations and Kp

8 Areas outside the will not be scanned for marking 3 Propanone and iodine react in acidic conditions according to the following equation. C 3 COC 3 + I 2 IC 2 COC 3 + I A student studied the kinetics of this reaction using hydrochloric acid and a solution containing propanone and iodine. From the results the following rate equation was deduced. rate = k[c 3 COC 3 ][ + ] 3 (a) Give the overall order for this reaction.. 3 (b) When the initial concentrations of the reactants were as shown in the table below, the initial rate of reaction was found to be 1.24 10 4 mol dm 3 s 1. initial concentration / mol dm 3 C 3 COC 3 4.40 I 2 5.00 10 3 + 0.820 Use these data to calculate a value for the rate constant, k, for the reaction and give its units. Calculation...... Units... (3 marks) 3 (c) Deduce how the initial rate of reaction changes when the concentration of iodine is doubled but the concentrations of propanone and of hydrochloric acid are unchanged.. (08) WMP/Jan10/CEM4

9 Areas outside the will not be scanned for marking 3 (d) The following mechanism for the overall reaction has been proposed. Step 1 C 3 COC 3 + + C + C O C 3 Step 2 C + C O C 3 C C C 3 + + O C 3 Step 3 C C C 3 + I 2 IC 2 C + I O O + Step 4 IC 2 C O O + C 3 IC 2 C C 3 + + Use the rate equation to suggest which of the four steps could be the rate-determining step. Explain your answer. Rate-determining step... Explanation.... (2 marks) 3 (e) Use your understanding of reaction mechanisms to predict a mechanism for Step 2 by adding one or more curly arrows as necessary to the structure of the carbocation below. Step 2 C + C O C 3 C C C 3 + + O 8 Turn over (09) WMP/Jan10/CEM4

16 6 (a) In the presence of the catalyst rhodium, the reaction between NO and 2 occurs according to the following equation. 2NO(g) + 2 2 (g) N 2 (g) + 2 2 O(g) The kinetics of the reaction were investigated and the rate equation was found to be rate = k[no] 2 [ 2 ] The initial rate of reaction was 6.2 10 6 mol dm 3 s 1 when the initial concentration of NO was 2.9 10 2 mol dm 3 and the initial concentration of 2 was 2.3 10 2 mol dm 3. 6 (a) (i) Calculate the value of the rate constant under these conditions and give its units. Calculation... Units... (3 marks) 6 (a) (ii) Calculate the initial rate of reaction if the experiment is repeated under the same conditions but with the concentrations of NO and of 2 both doubled from their original values. (16) WMP/Jun11/CEM4

17 6 (b) Using the rate equation and the overall equation, the following three-step mechanism for the reaction was suggested. X and Y are intermediate species. Step 1 NO + NO X Step 2 X + 2 Y Step 3 Y + 2 N 2 + 2 2 O Suggest which one of the three steps is the rate-determining step. Explain your answer. Rate-determining step... Explanation... (2 marks) (Extra space)... 6 Turn over for the next question Turn over (17) WMP/Jun11/CEM4

2 Section A Answer all questions in the spaces provided. 1 The rate of hydrolysis of an ester X (COOC 2 C 2 C 3 ) was studied in alkaline conditions at a given temperature. The rate was found to be first order with respect to the ester and first order with respect to hydroxide ions. 1 (a) (i) Name ester X. 1 (a) (ii) Using X to represent the ester, write a rate equation for this hydrolysis reaction. 1 (a) (iii) When the initial concentration of X was 0.024 mol dm 3 and the initial concentration of hydroxide ions was 0.035 mol dm 3, the initial rate of the reaction was 8.5 x 10 5 mol dm 3 s 1. Calculate a value for the rate constant at this temperature and give its units. Calculation... Units... (3 marks) 1 (a) (iv) In a second experiment at the same temperature, water was added to the original reaction mixture so that the total volume was doubled. Calculate the initial rate of reaction in this second experiment. (02) WMP/Jan11/CEM4

3 1 (a) (v) In a third experiment at the same temperature, the concentration of X was half that used in the experiment in part 1 (a) (iii) and the concentration of hydroxide ions was three times the original value. Calculate the initial rate of reaction in this third experiment. 1 (a) (vi) State the effect, if any, on the value of the rate constant k when the temperature is lowered but all other conditions are kept constant. Explain your answer. Effect... Explanation... (2 marks) 1 (b) Compound A reacts with compound B as shown by the overall equation The rate equation for the reaction is A + 3B AB 3 rate = k[a][b] 2 A suggested mechanism for the reaction is Step 1 A + B AB Step 2 AB + B AB 2 Step 3 AB 2 + B AB 3 Deduce which one of the three steps is the rate-determining step. Explain your answer. Rate-determining step... Explanation... (2 marks) 11 Turn over (03) WMP/Jan11/CEM4

4 2 Gases P and Q react as shown in the following equation. 2P(g) + 2Q(g) R(g) + S(g) The initial rate of the reaction was measured in a series of experiments at a constant temperature. The following rate equation was determined. rate = k[p] 2 [Q] 2 (a) Complete the table of data for the reaction between P and Q. Experiment Initial [P] / mol dm 3 Initial [Q] / mol dm 3 Initial rate / mol dm 3 s 1 1 2.5 10 2 1.8 10 2 5.0 10 5 2 7.5 10 2 1.8 10 2 3 5.0 10 2 5.0 10 5 4 5.4 10 2 4.5 10 4 (3 marks) (Space for working)... 2 (b) Use the data from Experiment 1 to calculate a value for the rate constant (k) at this temperature. Deduce the units of k. Calculation... Units... (3 marks) 6 (04) WMP/Jun12/CEM4

2 Section A Answer all questions in the spaces provided. 1 The initial rate of the reaction between two gases P and Q was measured in a series of experiments at a constant temperature. The following rate equation was determined. rate = k[p] 2 [Q] 1 (a) Complete the table of data below for the reaction between P and Q. Experiment Initial [P] / mol dm 3 Initial [Q] / mol dm 3 Initial rate / mol dm 3 s 1 1 0.20 0.30 1.8 10 3 2 0.40 0.60 3 0.60 5.4 10 3 4 0.90 12.2 10 3 (3 marks) (Space for working)... (02) WMP/Jan12/CEM4

3 1 (b) Use the data from Experiment 1 to calculate a value for the rate constant k and deduce its units. Calculation... Units... (3 marks) 1 (c) Consider the graphs E, F, G and below. k k k k E T F T Write in the below the letter of the graph that shows how the rate constant k varies with temperature. G T T 7 Turn over (03) WMP/Jan12/CEM4

2 Section A Answer all questions in the spaces provided. 1 This question involves the use of kinetic data to calculate the order of a reaction and also a value for a rate constant. 1 (a) The data in this table were obtained in a series of experiments on the rate of the reaction between compounds E and F at a constant temperature. Experiment Initial concentration of E / mol dm 3 Initial concentration of F / mol dm 3 Initial rate of reaction / mol dm 3 s 1 1 0.15 0.24 0.42 10 3 2 0.45 0.24 3.78 10 3 3 0.90 0.12 7.56 10 3 1 (a) (i) Deduce the order of reaction with respect to E. (Space for working)... 1 (a) (ii) Deduce the order of reaction with respect to F. (Space for working)... (02) WMP/Jun13/CEM4

3 1 (b) The data in the following table were obtained in two experiments on the rate of the reaction between compounds G and at a constant temperature. Experiment Initial concentration of G / mol dm 3 Initial concentration of / mol dm 3 Initial rate of reaction / mol dm 3 s 1 4 3.8 10 2 2.6 10 2 8.6 10 4 5 6.3 10 2 7.5 10 2 To be calculated The rate equation for this reaction is rate = k[g] 2 [] 1 (b) (i) Use the data from Experiment 4 to calculate a value for the rate constant k at this temperature. Deduce the units of k. Calculation... Units... (3 marks) 1 (b) (ii) Calculate a value for the initial rate of reaction in Experiment 5. 6 Turn over (03) WMP/Jun13/CEM4

2 Section A Answer all questions in the spaces provided. 1 (a) The data in the following table were obtained in two experiments about the rate of the reaction between substances B and C at a constant temperature. Experiment Initial concentration of B / mol dm 3 Initial concentration of C / mol dm 3 Initial rate / mol dm 3 s 1 1 4.2 10 2 2.6 10 2 8.4 10 5 2 6.3 10 2 7.8 10 2 To be calculated The rate equation for this reaction is known to be rate = k[b] 2 [C] 1 (a) (i) Use the data from Experiment 1 to calculate a value for the rate constant k at this temperature and deduce its units. Calculation... Units... (3 marks) (Extra space)... 1 (a) (ii) Calculate a value for the initial rate in Experiment 2. (02) WMP/Jan13/CEM4

3 1 (b) The data in the following table were obtained in a series of experiments about the rate of the reaction between substances D and E at a constant temperature. Experiment Initial concentration of D / mol dm 3 Initial concentration of E / mol dm 3 Initial rate / mol dm 3 s 1 3 0.13 0.23 0.26 10 3 4 0.39 0.23 2.34 10 3 5 0.78 0.46 9.36 10 3 1 (b) (i) Deduce the order of reaction with respect to D. 1 (b) (ii) Deduce the order of reaction with respect to E. Question 1 continues on the next page Turn over (03) WMP/Jan13/CEM4

4 1 (c) The compound (C 3 ) 3 CBr reacts with aqueous sodium hydroxide as shown in the folfollowing equation. (C 3 ) 3 CBr + O (C 3 ) 3 CO + Br This reaction was found to be first order with respect to (C 3 ) 3 CBr but zero order with respect to hydroxide ions. The following two-step process was suggested. Step 1 (C 3 ) 3 CBr (C 3 ) 3 C + + Br Step 2 (C 3 ) 3 C + + O (C 3 ) 3 CO 1 (c) (i) Deduce the rate-determining step in this two-step process. 1 (c) (ii) Outline a mechanism for this step using a curly arrow. 8 (04) WMP/Jan13/CEM4

8 3 (a) Table 1 shows the results of three experiments to investigate the rate of reaction between compounds A and B dissolved in a given solvent. All three experiments were carried out at the same temperature. Table 1 Experiment 1 Experiment 2 Experiment 3 Initial concentration of A / mol dm 3 1.60 10 2 2.40 10 2 3.60 10 2 Initial concentration of B / mol dm 3 4.20 10 2 6.30 10 2 6.30 10 2 Initial rate / mol dm 3 s 1 8.00 10 5 1.80 10 4 4.05 10 4 3 (a) (i) Deduce the order of reaction with respect to A. Tick ( ) one. [1 mark] Order of reaction with respect to A 0 Tick ( ) 1 2 3 (a) (ii) Deduce the order of reaction with respect to B. Tick ( ) one. [1 mark] Order of reaction with respect to B 0 Tick ( ) 1 2 (08) WMP/Jun14/CEM4

9 3 (b) The reaction between two different compounds, C and D, is studied at a given temperature. The rate equation for the reaction is found to be rate = k[c][d] 2 3 (b) (i) When the initial concentration of C is 4.55 10 2 mol dm 3 and the initial concentration of D is 1.70 10 2 mol dm 3, the initial rate of reaction is 6.64 10 5 mol dm 3 s 1. Calculate the value of the rate constant at this temperature and deduce its units. [3 marks] Calculation... Units of rate constant... 3 (b) (ii) The experiment in Question 3 (b) (i) is repeated at the same temperature but after the addition of extra solvent so that the total volume of the mixture is doubled. Deduce the new initial rate of reaction. [1 mark] 6 Turn over for the next question Turn over (09) WMP/Jun14/CEM4

2 Section A Answer all questions in the spaces provided. 1 Gases A and B react as shown in the following equation. 2A(g) + B(g) C(g) + D(g) The initial rate of the reaction was measured in a series of experiments at a constant temperature. The following rate equation was determined. rate = k[a] 2 An incomplete table of data for the reaction between A and B is shown in Table 1. Table 1 Experiment Initial [A] / mol dm 3 Initial [B] / mol dm 3 Initial rate / mol dm 3 s 1 1 4.2 10 3 2.8 10 3 3.3 10 5 2 7.9 10 3 2.8 10 3 3 5.6 10 3 1.8 10 4 1 (a) Use the data from Experiment 1 to calculate a value for the rate constant, k, at this temperature. Deduce the units of k. [3 marks] Calculation....... Units.... (02) WMP/Jun15/CEM4

3 1 (b) Use your value of k from Question 1(a) to complete Table 1 for the reaction between A and B. (If you have been unable to calculate an answer for Question 1 (a), you may assume a value of 2.3 This is not the correct answer.) [2 marks] 1 (c) The reaction is zero order with respect to B. State the significance of this zero order for the mechanism of the reaction. [1 mark]... 6 Turn over for the next question Turn over (03) WMP/Jun15/CEM4

17 6 The initial rate of the reaction between gases D and E was measured in a series of experiments at a constant temperature. The results are shown in Table 1. Table 1 Expt Initial [D] / mol dm 3 Initial [E] / mol dm 3 Initial rate / mol dm 3 s 1 1 1.25 10 2 5.81 10 1 1.16 10 2 2 1.88 10 2 8.73 10 1 3.92 10 2 3 1.88 10 2 1.75 1.57 10 1 6 (a) Deduce the order of reaction with respect to D and the order with respect to E. [2 marks] Order with respect to D Order with respect to E Space for working 6 (b) Suggest why initial rates of reaction are used to determine these orders rather than rates of reaction at other times during the experiments. [1 mark] 6 (c) State how the initial rate is obtained from a graph of the concentration of the product against time. [2 marks] 5 Turn over (17) WMP/Jun16/CEM4

18 7 The reaction between propanone and iodine in the presence of hydrochloric acid was studied at a constant temperature. C 3 COC 3 + I 2 C 3 COC 2 I + I The following rate equation was deduced. rate = k [C 3 COC 3 ][ + ] 7 (a) Suggest why the order with respect to iodine is zero. [1 mark] 7 (b) In an experiment the initial concentrations of propanone, iodine and hydrochloric acid were as shown in Table 2. The initial rate of reaction in this experiment was 8.64 10 7 mol dm 3 s 1. Table 2 Initial concentration / mol dm 3 C 3 COC 3 5.82 10 2 l 2 1.78 10 3 + 4.76 10 1 Use the data in Table 2 and the rate equation to calculate a value for the rate constant at this temperature. Give units with your answer. [2 marks] (18) WMP/Jun16/CEM4

19 7 (c) A series of experiments was carried out using concentrations of propanone approximately 100 times the concentrations of iodine and hydrochloric acid. Suggest the rate equation under these conditions. Explain your answer. [2 marks] 5 Turn over for the next question Turn over (19) WMP/Jun16/CEM4