1.	Bromine and nitrogen(II) oxide react according to the following equation.
		Br2(g) + 2NO(g) → 2NOBr(g)
	Which rate equation is consistent with the experimental data?

[Br2] / mol dm–3	[NO] / mol dm–3	Rate / mol dm–3 s–1	
0.10	0.10	1.0 × 10–6	
0.20	0.10	4.0 × 10–6	
0.20	0.40	4.0 × 10–6	
A.	rate = k[Br2]2 [NO]
B.	rate = k[Br2] [NO]2
C.	rate = k[Br2]2
D.	rate = k[NO]2
(Total 1 mark)

2.	Which step is the rate-determining step of a reaction?
A.	The step with the lowest activation energy
B.	The final step
C.	The step with the highest activation energy
D.	The first step
(Total 1 mark)

3.	Consider the following graph of ln k against  (temperature in Kelvin) for the second order decomposition of N2O into N2 and O.
		N2O → N2 + O
		
		 K–1
 
(a)	State how the rate constant, k varies with temperature, T.
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(1)

(b)	Determine the activation energy, Ea, for this reaction.
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(3)
 
(c)	The rate expression for this reaction is rate = k [N2O]2 and the rate constant is
0.244 dm3 mol–1 s–1 at 750 °C.
	A sample of N2O of concentration 0.200 mol dm–3 is allowed to decompose. Calculate the rate when 10 % of the N2O has reacted.
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(2)
(Total 6 marks)

4.	The rate information below was obtained for the following reaction at a constant temperature.
		2NO2(g) + F2(g) → 2NO2F(g)

[NO2] / mol dm–3	[F2] / mol dm–3	Rate / mol dm–3 s–1	
2.0 × 10–3	1.0 × 10–2	4.0 × 10–4	
4.0 × 10–3	1.0 × 10–2	8.0 × 10–4	
4.0 × 10–3	2.0 × 10–2	1.6 × 10–3	
	What are the orders of the reaction with respect to NO2 and F2?
A.	NO2 is first order and F2 is second order
B.	NO2 is second order and F2 is first order
C.	NO2 is first order and F2 is first order
D.	NO2 is second order and F2 is second order
(Total 1 mark)

5.	Consider the following reaction.
		2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
	A proposed reaction mechanism is:
	NO(g) + NO(g)  N2O2(g)	fast
N2O2(g) + H2(g) → N2O(g) + H2O(g)	slow
N2O(g) + H2(g) → N2(g) + H2O(g)	fast
	What is the rate expression?
A.	rate = k[H2] [NO]2
B.	rate = k[N2O2] [H2]
C.	rate = k[NO]2 [H2]2
D.	rate = k[NO]2 [N2O2]2 [H2]
(Total 1 mark)

6.	Hydrogen and nitrogen(II) oxide react according to the following equation.
		2H2(g) + 2NO(g)  N2(g) + 2H2O(g)
	At time = t seconds, the rate of the reaction is
		rate = k[H2(g)][NO(g)]2
 
(i)	Explain precisely what the square brackets around nitrogen(II) oxide, [NO(g)], represent in this context.
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(1)
 
(ii)	Deduce the units for the rate constant k.
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(1)
(Total 2 marks)

7.	Which experimental procedure could be used to determine the rate of reaction for the reaction between a solution of cobalt chloride, CoCl2(aq), and concentrated hydrochloric acid, HCl(aq)?
		Co(H2O)62+(aq) + 4Cl–(aq)  CoCl42–(aq) + 6H2O(l)
A.	Measure the change in pH in a given time
B.	Measure the change in mass in a given time
C.	Use a colorimeter to measure the change in colour in a given time
D.	Measure the change in volume of the solution in a given time
(Total 1 mark)

8.	Sodium thiosulfate solution, Na2S2O3(aq), and hydrochloric acid, HCl(aq), react spontaneously to produce solid sulfur, S(s), according to the equation below.
		S2O32–(aq) + 2H+(aq) → S(s) + SO2(aq) + H2O(l)
	A student experimentally determined the rate expression to be:
		rate = k[S2O32–(aq)]2
	Which graph is consistent with this information?

(Total 1 mark)

9.	Alex and Hannah were asked to investigate the kinetics involved in the iodination of propanone.
They were given the following equation by their teacher.
		CH3COCH3(aq) + I2(aq)  CH2ICOCH3(aq) + HI(aq)
	Alex’s hypothesis was that the rate will be affected by changing the concentrations of the propanone and the iodine, as the reaction can happen without a catalyst. Hannah’s hypothesis was that as the catalyst is involved in the reaction, the concentrations of the propanone, iodine and the hydrogen ions will all affect the rate.
	They carried out several experiments varying the concentration of one of the reactants or the catalyst while keeping other concentrations and conditions the same, and obtained the results below.

	Composition by volume of mixture / cm3	Initial rate	
Experiment	1.00 mol dm–3
CH3COCH3(aq)	Water	1.00 mol dm–3
H+(aq)	5.00 × 10–3
mol dm–3 I2 in KI	/ mol dm–3 s–1	
1	10.0	60.0	10.0	20.0	4.96 × 10–6	
2	10.0	50.0	10.0	30.0	5.04 × 10–6	
3	5.0	65.0	10.0	20.0	2.47 × 10–6	
4	10.0	65.0	5.0	20.0	2.51 × 10–6	
 
(a)	Explain why they added water to the mixtures.
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(1)
 
(b)	(i)	Deduce the order of reaction for each substance and the rate expression from the results.
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(2)

(ii)	Comment on whether Alex’s or Hannah’s hypothesis is correct.
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(1)
 
(c)	Using the data from Experiment 1, determine the concentration of the substances used and the rate constant for the reaction including its units.
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(3)
 
(d)	(i)	This reaction uses a catalyst. Sketch and annotate the Maxwell-Boltzmann energy distribution curve for a reaction with and without a catalyst on labelled axes below.

(3)
 
(ii)	Describe how a catalyst works.
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(1)
(Total 11 marks)

10.	The following data were obtained for the reaction between gases A and B.

Experiment	Initial [A] / mol dm–3	Initial [B] / mol dm–3	Initial rate / mol dm–3 min–1	
1	1.0 × 10–3	1.0 × 10–3	2.0 × 10–4	
2	2.0 × 10–3	1.0 × 10–3	2.0 × 10–4	
3	2.0 × 10–3	2.0 × 10–3	4.0 × 10–4	
	Which relationship represents the rate expression for the reaction?
A.	rate = k[B]2
B.	rate = k[A]2
C.	rate = k[A]
D.	rate = k[B]
(Total 1 mark)

11.	Consider the following reaction.
		NO2(g) + CO(g) → NO(g) + CO2(g)
	At T < 227 °C the rate expression is rate = k[NO2]2. Which of the following mechanisms is consistent with this rate expression?
A.	NO2 + NO2  N2O4	fast
N2O4 + 2CO → 2NO + 2CO2	slow
B.	NO2 + CO → NO + CO2	slow
C.	NO2 → NO + O	slow
CO + O → CO2	fast
D.	NO2 + NO2 → NO3 + NO	slow
NO3 + CO → NO2 + CO2	fast
(Total 1 mark)

12.	Consider the following reaction.
		2P + Q → R + S
	This reaction occurs according to the following mechanism.
	P + Q → X	slow
P + X → R + S	fast
	What is the rate expression?
A.	rate = k[P]
B.	rate = k[P][X]
C.	rate = k[P][Q]
D.	rate = k[P]2[Q]
(Total 1 mark)

13.	What happens when the temperature of a reaction increases?
A.	The activation energy increases.
B.	The rate constant increases.
C.	The enthalpy change increases.
D.	The order of the reaction increases.
(Total 1 mark)

14.	(a)	There are four structural isomers with the molecular formula C4H9Br. One of these structural isomers exists as two optical isomers. Draw diagrams to represent the three-dimensional structures of the two optical isomers.
(2)

(b)	All the isomers can by hydrolysed with aqueous sodium hydroxide solution. When the reaction of one of these isomers, X, was investigated the following kinetic data were obtained.

Experiment	Initial [X] /
mol dm–3	Initial [OH–] /
mol dm–3	Initial rate of reaction /
mol dm–3 min–1	
1	2.0 × 10–2	2.0 × 10–2	4.0 × 10–3	
2	2.0 × 10–2	4.0 × 10–2	4.0 × 10–3	
3	4.0 × 10–2	4.0 × 10–2	8.0 × 10–3	
 
(i)	Deduce the rate expression for the reaction.
(3)
 
(ii)	Determine the value of the rate constant for the reaction and state its units.
(2)
 
(iii)	State the name of isomer X and explain your choice.
(2)
 
(iv)	State equations for the steps that take place in the mechanism of this reaction and state which of the steps is slow and which is fast.
(2)
(Total 11 marks)

15.	This question refers to the following reaction.
		X2 + 2Y → 2XY
	The reaction occurs in a series of steps.
	X2 → 2X	slow
X + Y → XY	fast
	What is the rate-determining step for this reaction mechanism?
A.	X2 + 2Y → 2XY
B.	X2 + Y → XY + X
C.	X2 → 2X
D.	X + Y → XY
(Total 1 mark)

16.	This question refers to the following reaction.
		X2 + 2Y → 2XY
	The reaction occurs in a series of steps.
	X2 → 2X	slow
X + Y → XY	fast
	What is the rate expression for this reaction?
A.	rate = k[XY]
B.	rate = k[X2][Y]2
C.	rate = k[X2]
D.	rate = k[2X]
(Total 1 mark)

17.	Consider the following reaction.
		5Br–(aq) + BrO3–(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)
	The rate expression for the reaction is found to be:
		rate = k[Br–] [BrO3–][H+]2
	Which statement is correct?
A.	The overall order is 12.
B.	Doubling the concentration of all of the reactants at the same time would increase the rate of the reaction by a factor of 16.
C.	The units of the rate constant, k, are mol dm–3 s–1.
D.	A change in concentration of Br– or BrO3– does not affect the rate of the reaction.
(Total 1 mark)

18.	The rate expression for a reaction is:
		rate = k [X][Y]
	Which statement is correct?
A.	As the temperature increases the rate constant decreases.
B.	The rate constant increases with increased temperature but eventually reaches a constant value.
C.	As the temperature increases the rate constant increases.
D.	The rate constant is not affected by a change in temperature.
(Total 1 mark)

19.	Consider the following reaction mechanism.
Step 1	H2O2 + I– → H2O + IO–	slow
Step 2	H2O2 + IO– → H2O + O2 + I–	fast
	Which statement correctly identifies the rate-determining step and the explanation?
A.	Step 2 because it is the faster step
B.	Step 1 because it is the slower step
C.	Step 1 because it is the first step
D.	Step 2 because it is the last step
(Total 1 mark)

20.	Nitrogen monoxide reacts at 1280 °C with hydrogen to form nitrogen and water.
All reactants and products are in the gaseous phase.
(i)	The kinetics of the reaction were studied at this temperature. The table shows the initial rate of reaction for different concentrations of each reactant.

experiment	[NO(g)]/
mol dm–3 × 10–3	[H2(g)]/
mol dm–3 × 10–3	Initial rate/
mol dm–3 s–1 × 10–5	
1	5.00	2.00	1.25	
2	10.00	2.00	5.00	
3	10.00	4.00	10.00	
	Deduce the order of the reaction with respect to NO and H2, and explain your reasoning.
(4)
 
(ii)	Deduce the rate expression for the reaction.
(1)
 
(iii)	Determine the value of the rate constant for the reaction from Experiment 3 and state its units.
(2)
(Total 7 marks)

21.	The gas-phase decomposition of dinitrogen monoxide is considered to occur in two steps.
	Step 1:  N2O(g)  N2(g) + O(g)
	Step 2:  N2O(g) + O(g)  N2(g) + O2(g)
	The experimental rate expression for this reaction is rate = k [N2O].
 
(i)	Identify the rate-determining step.
(1)
 
(ii)	Identify the intermediate involved in the reaction.
(1)
(Total 2 marks)

22.	The conversion of CH3NC into CH3CN is an exothermic reaction which can be represented as follows.
		CH3–N≡C  transition state  CH3–C≡N
	This reaction was carried out at different temperatures and a value of the rate constant, k, was obtained for each temperature. A graph of ln k against 1/T is shown below.

(i)	Define the term activation energy, Ea.
(1)
 
(ii)	Construct the enthalpy level diagram and label the activation energy, Ea, the enthalpy change, ∆H, and the position of the transition state.
(3)
 
(iii)	Describe qualitatively the relationship between the rate constant, k, and the temperature, T.
(1)
 
(iv)	Calculate the activation energy, Ea, for the reaction, using Table 1 of the Data Booklet.
(4)
(Total 9 marks)

23.	Two species, P and Q, react together according to the following equation.
		P + Q → R
	The accepted mechanism for this reaction is
		P + P  P2	fast
	P2 + Q → R + P	slow
	What is the order with respect to P and Q?

	P	Q	
A.	1	1	
B.	1	2	
C.	2	1	
D.	2	2	
(Total 1 mark)

24.	The activation energy of a reaction may be determined by studying the effect of a particular variable on the reaction rate. Which variable must be changed?
A.	pH
B.	Concentration
C.	Surface area
D.	Temperature
(Total 1 mark)

25.	Consider the following reaction studied at 263 K.
		2NO(g) + Cl2(g)  2NOCl(g)
	It was found that the forward reaction is first order with respect to Cl2 and second order with respect to NO. The reverse reaction is second order with respect to NOCl.
 
(i)	State the rate expression for the forward reaction.
(1)
 
(ii)	Predict the effect on the rate of the forward reaction and on the rate constant if the concentration of NO is halved.
(2)
 
(iii)	1.0 mol of Cl2 and 1.0 mol of NO are mixed in a closed container at constant temperature. Sketch a graph to show how the concentration of NO and NOCl change with time until after equilibrium has been reached. Identify the point on the graph where equilibrium is established.
(4)
(Total 7 marks)

26.	Consider the following reaction.
		NO2(g) + CO(g) → NO(g) + CO2(g)
	Possible reaction mechanisms are:
Above 775 K:	NO2 + CO → NO + CO2	slow
Below 775 K:	2NO2 → NO + NO3	slow
	NO3 + CO → NO2 + CO2	fast
	Based on the mechanisms, deduce the rate expressions above and below 775 K.
(Total 2 marks)

27.	State two situations when the rate of a chemical reaction is equal to the rate constant.
(Total 2 marks)

28.	Consider the following graph of ln k against  for the first order decomposition of N2O4 into NO2. Determine the activation energy in kJ mol–1 for this reaction.
		
(Total 2 marks)

29.	What is the order of reaction with respect to NO2(g) and F2(g) given the following rate data at a certain temperature?
[NO2(g)] / mol dm–3	[F2(g)] / mol dm–3	Rate / mol dm–3 min–1	
0.1	0.2	0.1	
0.2	0.2	0.4	
0.1	0.4	0.2	

	Order with respect to NO2(g)	Order with respect to F2(g)	
A.	first	first	
B.	first	second	
C.	second	first	
D.	second	second	
(Total 1 mark)

30.	Nitrogen(II) oxide reacts with hydrogen according to the following equation:
	2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
	The table shows how the rate of reaction varies as the concentrations of the reactants are changed.
Experiment	Initial [NO] /
mol dm–3	Initial [H2] /
mol dm–3	Initial rate /
mol (N2) dm–3 s–1	
1	0.100	0.100	2.53×10–6	
2	0.100	0.200	5.05×10–6	
3	0.200	0.100	1.01×10–5	
4	0.300	0.100	2.28×10–5	

(a)	Determine the order of reaction with respect to H2 and with respect to NO.
H2 ................................................................................................................................
NO ..............................................................................................................................
(2)

(b)	Write the rate expression for the reaction.
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(1)
 
(c)	Calculate the value for the rate constant, and state its units using the data from experiment 1.
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(2)

(d)	A suggested mechanism for this reaction is as follows.
	H2 + NO  X	fast step
X + NO → Y + H2O	slow step
Y + H2 → N2 + H2O	fast step
	State and explain whether this mechanism agrees with the experimental rate expression in (b).
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(4)
 
(e)	Explain why a single step mechanism is unlikely for a reaction of this kind.
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(2)
 
(f)	Deduce and explain how the initial rate of formation of H2O compares with that of N2.
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(2)
(Total 13 marks)