1 Hydrogen, H2, reacts with nitrogen monoxide, NO, as shown below:

2H2(g) + 2NO(g) N2(g) + 2H2O(g)

(a) The rate equation for this reaction is:

rate = k[H2(g)][NO(g)]2

The concentration of NO(g) is changed and a rate–concentration graph is plotted.

9.0

8.0

7.0

6.0

initial rate / 5.0

10–4 mol dm–3 s–1
4.0

3.0

2.0

1.0

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
[NO(g)] / 10 mol dm–3
–4

The chemist uses H2(g) of concentration 2.0 × 10–2 mol dm–3.

Using values from the graph, calculate the rate constant, k, for this reaction.

Give your answer to two significant figures and in standard form.

Show your working.

k = .................................... units ............................... [4]

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(b) A chemist investigates the effect of changing the concentration of H2(g) on the initial reaction
rate at two different temperatures.

The reaction is first order with respect to H2(g).

(i) Using the axes below, sketch two graphs of the results.

Label the graphs as follows:

• L for the lower temperature
• H for the higher temperature.

initial rate

0,0
[H2(g)]
[2]

(ii) State the effect of the higher temperature on the rate constant, k.

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(c) The reaction can also be shown as being first order with respect to H2(g) by continuous
monitoring of [H2(g)] during the course of the reaction.

• Using the axes below, sketch a graph to show the results.

• State how you would use the graph to show this first order relationship for H2(g).

[H2(g)]

time

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(d) The chemist proposes a three-step mechanism for the reaction:

2H2(g) + 2NO(g) N2(g) + 2H2O(g)

(i) On the dotted line below, write the equation for step 3.

step 1: 2NO N2O2 fast

step 2: H2 + N2O2 N2O + H2O slow

step 3: .......................................... fast [1]

(ii) Explain why this mechanism is consistent with the rate equation rate = k[H2(g)][NO(g)]2.

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[Total: 11]

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 2 A student carries out an initial rates investigation on the reaction
below.
5I–(aq) + IO3–(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)

From the results, the student determines the rate equation for this reaction:

rate = k [ I–(aq)]2 [ IO3–(aq)] [H+(aq)]2

(a) (i) What is the overall order of reaction?

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(ii) A proposed mechanism for this reaction takes place in several steps.

Suggest two reasons why it is unlikely that this reaction could take place in one step.

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(b) On the rate–concentration graphs below, sketch lines to show the relationship between initial
rate and concentration for IO3–(aq) and H+(aq).

initial rate / initial rate /

mol dm–3 s–1 mol dm–3 s–1

0 0
0 [ IO3–(aq) ] / mol dm–3 0 [ H+(aq) ] / mol dm–3
[2]

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 (c) The table below shows some of the student’s results.

(i) Complete the table by adding the missing initial rates in the boxes.

[ I–(aq)] [ IO3–(aq)] [H+(aq)] Initial rate

/ mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 s–1

Experiment 1 0.015 0.010 0.020 0.60

Experiment 2 0.045 0.010 0.020

Experiment 3 0.060 0.040 0.080

[2]

(ii) Calculate the rate constant, k, for this reaction. Include units.

Give your answer to two significant figures.

k = ............................. units .............................[3]

(iii) The student repeats Experiment 1 using 0.020 mol dm–3 methanoic acid, HCOOH(aq)
(pKa = 3.75), instead of 0.020 mol dm–3 HCl (aq) as a source of H+(aq).

Determine the initial rate in this experiment. Show your working.

initial rate = .................................... mol dm–3 s–1 [3]

[Total: 13]

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3 In aqueous solution, benzenediazonium chloride, C6H5N2Cl, decomposes above 10 °

C
C6H5N2Cl(aq) + H2O(l) C6H5OH(aq) + N2(g) + HCl(aq)

A student investigates the rate of this reaction using an excess of water at 50 °C. The student
takes measurements at intervals during the reaction and then plots his experimental results to
give the graph shown below.

6.0

5.0

4.0

[C6H5N2Cl (aq)]
/ mol dm–3 3.0

2.0

1.0

0
0 20 40 60 80 100 120 140 160 180
time / s

(a) The student uses half-life to suggest the order of reaction with respect to C6H5N2Cl.

(i) What is meant by the half-life of a reaction?

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(ii) Confirm the order of reaction with respect to C6H5N2Cl.

Show your working on the graph.

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 (iii) What would be the effect, if any, on the half-life of this reaction of doubling the initial
concentration of C6H5N2Cl ?

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(b) The student predicts that the rate equation is: rate = k [C6H5N2Cl ].

(i) Using the graph and this rate equation, determine the rate of reaction after 40 s.

Show your working on the graph.

rate = .........................units ................................. [3]

(ii) Calculate the rate constant, k, for this reaction and give its units.

k = ......................... units ................................. [2]

(c) The order of this reaction with respect to H2O is effectively zero.

Explain why.

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[Total: 10]

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4 In aqueous solution, methanoic acid, HCOOH, reacts with bromine, Br2.

HCOOH(aq) + Br2(aq) 2H+(aq) + 2Br –(aq) + CO2(g)

A student carried out an investigation on the rate of this reaction. The student used a large excess
of methanoic acid which ensured that its concentration was effectively constant throughout. During
the reaction, bromine is used up and its orange colour becomes less intense. The intensity of the
bromine colour can be measured with a colorimeter to give the bromine concentration.

The graph below was plotted from the experimental results.

0.010

0.009 ×

0.008 ×

×
0.007
×

0.006

[Br2] / mol dm–3 ×

0.005

×
0.004

0.003 ×

0.002 ×

×
0.001

100 200 300 400 500 600 700

time / s

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In this investigation, a large excess of methanoic acid was used. Under these conditions, the
reaction is effectively zero-order with respect to methanoic acid.

• Using the graph, determine the order of reaction with respect to bromine.

• Using the graph, determine the initial rate of the reaction.

• Calculate the rate constant, k, for the reaction between methanoic acid and bromine under
these conditions.

 In your answer you should make clear how your conclusions fit with the experimental results,
including working shown on the graph and units where appropriate.

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[Total: 9]

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5 In the presence of acid, H+(aq), aqueous bromate(V) ions, Br O3–(aq), react with aqueous bromide
ions, Br–(aq), to produce bromine, Br2(aq).

A student carried out an investigation into the kinetics of this reaction.

(a) Balance the ionic equation for this reaction.

Br O3– + ………Br– + ………H+ ………Br2 + ………H2O

[1]

(b) The student investigated how different concentrations of Br O3–(aq) affect the initial rate of the
reaction.

A graph of initial rate against [Br O3–(aq)] is shown below.

initial rate
/ mol dm–3 s–1

0
0
[BrO3–(aq)] / mol dm–3

The student then investigated how different concentrations of Br–(aq) and H+(aq) affect the
initial rate of the reaction.

The results are shown below.

[Br O3–(aq)] [Br–(aq)] [H+(aq)] initial rate

/ mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 s–1

5.0 × 10–2 1.5 × 10–1 3.1 × 10–1 1.19 × 10–5

5.0 × 10–2 3.0 × 10–1 3.1 × 10–1 2.38 × 10–5

5.0 × 10–2 1.5 × 10–1 6.2 x 10–1 4.76 × 10–5

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• Using the results from the student’s experiments, what conclusions can be drawn about
the kinetics of this reaction? Justify your reasoning.

• Calculate the rate constant for this reaction, including the units.

In your answer you should make clear how your conclusions fit with the experimental
results.

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[Total: 10]

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6 A student investigates the reaction between iodine, I2, and propanone, (CH3)2CO, in the
presence
of aqueous hydrochloric acid, HCl(aq).

The results of the investigation are shown below.

Rate–concentration graph

initial rate
/mol dm–3 s–1

[I2(aq)]
/mol dm–3

Results of initial rates experiments

[(CH3)2CO(aq)] [HCl (aq)] initial rate

experiment
/ mol dm–3 / mol dm–3 / mol dm–3 s–1
1 1.50 × 10–3 2.00 × 10–2 2.10 × 10–9
2 3.00 × 10–3 2.00 × 10–2 4.20 × 10–9
3 3.00 × 10–3 5.00 × 10–2 1.05 × 10–8

(a) Determine the orders with respect to I2, (CH3)2CO and HCl, the rate equation and the rate
constant for the reaction.

Explain all of your reasoning.

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(b) The student then investigates the reaction of hydrogen, H2, and iodine monochloride, ICl.

The equation for this reaction is shown below.

H2(g) + 2ICl(g) 2HCl(g) + I2(g)

The rate equation for this reaction is shown below.

rate = k[H2(g)] [ICl(g)]

Predict a possible two-step mechanism for this reaction. The first step should be the
rate-determining step.

step 1 .......................................................................................................................................

step 2 .................................................................................................................................. [2]

[Total: 11]

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7 Hydrogen, 2,Hreacts with nitrogen monoxide, NO, as shown in the equation below.

2H2(g) + 2NO(g) N2(g) + 2H2O(g)

A chemist carries out a series of experiments and determines the rate equation for this reaction:

rate = k[H2(g)][NO(g)]2

(a) In one of the experiments, the chemist reacts together:

• 1.2 × 10–2 mol dm–3 H2(g)

• 6.0 × 10–3 mol dm–3 NO(g)

The initial rate of this reaction is 3.6 × 10–2 mol dm–3 s–1.

Calculate the rate constant, k, for this reaction. State the units, if any.

k = ……………………… units ……………………… [3]

(b) Predict what would happen to the initial rate of reaction for the following changes in
concentrations.

(i) The concentration of H2(g) is doubled.

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(ii) The concentration of NO(g) is halved.

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(iii) The concentrations of H2(g) and NO(g) are both increased by four times.

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(c) The chemist carries out the reaction between hydrogen and nitrogen monoxide at a higher
pressure.

(i) Explain, with a reason, what happens to the initial rate of reaction.

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(ii) State what happens to the rate constant.

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(d) This overall reaction between hydrogen and nitrogen monoxide takes place by a two-step
mechanism. The first step is much slower than the second step.

Suggest a possible two-step mechanism for the overall reaction.

step 1: .......................................................................................................................................

step 2: .................................................................................................................................. [2]

[Total: 10]

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