Topic 2- Quantitative Kinetics

Exercise
1. Sulphur dichloride dioxide, SO2Cl2, decomposes according to the equation:

SO2Cl2(g)  SO2(g) + Cl2(g)

In an experiment, the concentration of the reactant SO 2Cl2 was measured over a period of time. The results are
shown below:

Time/s 0 500 1000 2000 3000 4000

[SO2Cl2]/moldm-3 0.50 0.43 0.37 0.27 0.20 0.15

Plot a graph to show how concentration varies with time and use your graph to calculate the rate of reaction:

a) Initially
b) After 1000 s
c) After 2500 s
d) Explain why the rate of reaction decreases with time.
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e) Work out the rate of reaction when [SO2Cl2]= 0.25 moldm-3. Hence deduce the order of reaction with respect
to SO2Cl2.
f) Hence write the rate equation, calculate a value for the rate constant and give its units.

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2. Hydrogen peroxide, H2O2, decomposes according to the equation:
2H2O2(g)  2H2O(g) + O2(g)
In an experiment, the concentration of the reactant H 2O2 was measured over a period of time. The results are shown
below:
Time/s 0 15 30 60 100 180
[H2O2]/moldm-3 0.40 0.28 0.19 0.07 0.03 0.01
Plot a graph to show how concentration varies with time and use your graph to calculate the rate of reaction:

a) Initially
b) When [H2O2]= 0.20 moldm-3
c) When [H2O2]= 0.10 moldm-3
d) Hence write the rate equation, calculate a value for the rate constant and give its units.

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 3. The decomposition of nitrogen dioxide 2NO 2(g)  2NO + O2(g) was measured and the following data was
collected.

Time, s [NO2], moldm-3

0 0.0100
50 0.00787
100 0.00649
200 0.00481
300 0.00380
400 0.00318
500 0.00275
600 0.00234

Use the graph to determine the order of reaction with respect to nitrogen dioxide and hence deduce the rate
equation for the reaction. Determine the value of k and give its units.

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1. Explain what is meant by the term "rate of reaction".

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2. The initial rates of the reaction 2A + B  2C + D at various concentrations of A and B are given below:

[A] moldm-3 [B] moldm-3 Initial rate /moldm-3s-1

0.01 0.20 0.10
0.02 0.20 0.20
0.01 0.40 0.40
a) What
is the
order of reaction with respect to A and B?

b) What is the overall order of reaction?

c) What is the rate constant?

d) What will be the rate of the reaction if the concentrations of A and B are both 0.01 moldm-3?

3. For the reaction 2NO(g) + H2(g)  N2O(g) + H2O(g), the following rate data were collected:

Initial [NO]/M Initial [H2]/M Initial rate/Ms-1

0.60 0.37 3.0 x 10-3
1.20 0.37 1.2 x 10-2
1.20 0.74 1.2 x 10-2

a. What is the order of reaction with respect to [NO] and [H2]/?

b. What is the overall order of reaction?

c. What is the rate constant

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4. For the reaction PCl3 + Cl2  PCl5, the following data were obtained:

Experiment No. [PCl3]/moldm-3 [Cl2]/ moldm-3 Rate / moldm-3s-1

1 0.36 1.26 6.0 x 10-4
2 0.36 0.63 1.5 x 10-4
3 0.72 2.52 4.8 x 10-3

a. What is the order of reaction with respect to [PCl3] and [Cl2]?

b. What is the overall order of reaction?

c. What is the rate constant

5. Two compounds, X and Y, are known to undergo the reaction

X + 3Y  XY3

Using the experimental results in the table below:

Initial rate of
Initial concentration Initial concentration
EXPERIMENT formation of
of X/moldm-3 of Y/moldm-3
XY3/moldm-3s-1
1 0.100 0.100 0.00200
2 0.100 0.200 0.00798
3 0.100 0.300 0.01805
4 0.200 0.100 0.00399
5 0.300 0.100 0.00601

a. What is the order of reaction with respect to X and Y?

b. What is the overall order of reaction?

c. What is the rate constant

6. The data in the table below relates to the reaction between hydrogen and nitrogen monoxide at 673K.
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)
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 Experiment number Initial concentration Initial concentration Initial rate of
of H2 /moldm-3 of NO /moldm-3 production of N2 /
moldm-3s-1
1 2.0 x 10-3 6.0 x 10-3 6.0 x 10-3
2 3.0 x 10-3 6.0 x 10-3 9.0 x 10-3
3 6.0 x 10-3 1.0 x 10-3 0.5 x 10-3

Deduce the rate equation and calculate the rate constant.

7     (a)     The initial rate of the reaction between compounds A and B was measured in a
series of experiments at a fixed temperature. The following rate equation was deduced.

rate = k[A][B]2

(i)      Complete the table of data below for the reaction between A and B.

Expt Initial [A] Initial [B] Initial rate

/mol dm –3
/mol dm –3
/mol dm s –3 –1

1 4.80 × 10 –2
6.60 × 10 –2
10.4 × 10 –3

2 4.80 × 10 –2
3.30 × 10 –2
 
3   13.2 × 10 –2
5.20 × 10 –3

4 1.60 × 10 –2
  10.4 × 10 –3

(ii)     Using the data for experiment 1, calculate a value for the rate constant, k, and state
its units.

Calculation ..........................................................................................

.............................................................................................................

Units ....................................................................................................
(6)

(b)     State how the value of the rate constant, k, would change, if at all, if the concentration of A
were increased in a series of experiments.

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8.   (a)     The following data were obtained in a series of experiments on the rate of the reaction
between compounds A and B at a constant temperature.
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Experiment Initial concentration Initial concentration Initial rate/mol dm s –3 –1

of A/mol dm –3
of B/mol dm –3

1 0.12 0.15 0.32 × 10 –3

2 0.36 0.15 2.88 × 10 –3

3 0.72 0.30 11.52 × 10 –3

(i)      Deduce the order of reaction with respect to A.

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(ii)     Deduce the order of reaction with respect to B.

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(b)     The following data were obtained in a series of experiments on the rate of the reaction
between NO and O at a constant temperature.
2

 
Experiment Initial concentration Initial concentration Initial rate/mol dm s –3 –1

of NO/mol dm –3
of O /mol dm
2
–3

4 5.0 × 10 –2
2.0 × 10 –2
6.5 × 10 –4

5 6.5 × 10 –2
3.4 × 10 –2
To be calculated

The rate equation for this reaction is

rate = k[NO]2[O ] 2

(i)      Use the data from experiment 4 to calculate a value for the rate constant, k, at this
temperature, and state its units.

Value of k ............................................................................................

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Units of k .............................................................................................

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(ii)     Calculate a value for the initial rate in experiment 5.

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9.          Propanone and iodine react in acidic conditions according to the following equation.

CH COCH + I → ICH COCH + HI

3 3 2 2 3

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 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[CH COCH ][H+]

3 3

(a)     Give the overall order for this reaction.

......................................................................................................................
(1)

(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 mol dm s . –4 –3 –1

 
  initial concentration / mol dm –3

CH COCH
3 3 4.40
I 2 5.00 × 10 –3

H +
0.820

Use these data to calculate a value for the rate constant, k, for the reaction and give its
units.

Calculation ...................................................................................................

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......................................................................................................................

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Units .............................................................................................................
(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.

......................................................................................................................
(1)

10. Hydrogen peroxide is a powerful oxidising agent. Acidified hydrogen peroxide reacts with iodide
ions to form iodine according to the following equation.

H2O2(aq) + 2H+(aq) + 2I−(aq) → I2(aq) + 2H2O(l)

The initial rate of this reaction is investigated by measuring the time taken to produce sufficient
iodine to give a blue colour with starch solution.

A series of experiments was carried out, in which the concentration of iodide ions was varied,
while keeping the concentrations of all of the other reagents the same. In each experiment the
time taken (t) for the reaction mixture to turn blue was recorded.

The initial rate of the reaction can be represented as ( ), and the initial concentration of iodide
ions can be represented by the volume of potassium iodide solution used.

A graph of log10 ( ) on the y-axis against log10 (volume of KI(aq)) is a straight line. The gradient
of this straight line is equal to the order of the reaction with respect to iodide ions.

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 The results obtained are given in the table below. The time taken for each mixture to turn blue
was recorded on a stopclock graduated in seconds.
 
Volume of log10 (volume of
  Expt. Time / s
KI(aq) / cm3 KI(aq)) log10 ( )

  1 5 0.70 71 −1.85

  2 8 0.90 46 −1.66

  3 10 1.00 37 −1.57

  4 15 1.18 25 −1.40

  5 20 1.30 19 −1.28

  6 25 1.40 14 −1.15

(a)     Use the results given in the table to plot a graph of log10 ( ) on the y-axis against log10 (volume of
KI(aq)).

Draw a straight line of best fit on the graph, ignoring any anomalous points.

(b)     Determine the gradient of the line you have drawn. Give your answer to two decimal
places. Show your working.

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(c)     Deduce the order of reaction with respect to iodide ions.

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(d)     A student carried out the experiment using a flask on the laboratory bench. The
student recorded the time taken for the reaction mixture to turn blue. State one way
this method could be improved, other than by repeating the experiment or by
improving the precision of time or volume measurements. Explain why the accuracy
of the experiment would be improved.

Improvement .................................................................................................

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Explanation ....................................................................................................

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11.      (a)     The following data were obtained in a series of experiments on the rate of the reaction
between compounds A and B at a constant temperature.
 
Experiment Initial concentration of Initial concentration of Initial
A/mol dm –3
B/mol dm rate/mol dm s –3 –3 –1

1 0.15 0.24 0.45 × 10 –5

2 0.30 0.24 0.90 × 10 –5

3 0.60 0.48 7.20 × 10 –5

(i)      Show how the data in the table can be used to deduce that the reaction is first-order
with respect to A.

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(ii)     Deduce the order with respect to B.

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(b)     The following data were obtained in a second series of experiments on the rate of the
reaction between compounds C and D at a constant temperature.
 
Experiment Initial concentration of Initial concentration of Initial
A/mol dm –3
B/mol dm –3
rate/mol dm s –3 –1

4 0.75 1.50 9.30 × 10 –5

5 0.20 0.10 To be calculated

The rate equation for this reaction is

rate = k[C]2[D]

(i)      Use the data from Experiment 4 to calculate a value for the rate constant, k, at this
temperature. State the units of k.
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 Value for k ...........................................................................................

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Units of k .............................................................................................

(ii)     Calculate the value of the initial rate in Experiment 5.

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12.      (a)     The initial rate of the reaction between substances P and Q was measured in a series of
experiments and the following rate equation was deduced.

rate = k[P]2[Q]

(i)      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 s –3 –1

1 0.20 0.30 4.8 × 10 –3

2 0.10 0.10  

3 0.40   9.6 × 10 –3

4   0.60 19.2 × 10 –3

(ii)     Using the data from experiment 1, calculate a value for the rate constant, k, and deduce its
units.

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(b)     What change in the reaction conditions would cause the value of the rate constant to
change?

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13.      The rate of the reaction between substance A and substance B was studied in a series of
experiments carried out at the same temperature. In each experiment the initial rate was
measured using different concentrations of A and B. These results were used to deduce the
order of reaction with respect to A and the order of reaction with respect to B.

(a)     What is meant by the term order of reaction with respect to A?

......................................................................................................................

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(b)     When the concentrations of A and B were both doubled, the initial rate increased by a
factor of 4. Deduce the overall order of the reaction.

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(c)     In another experiment, the concentration of A was increased by a factor of three and the
concentration of B was halved. This caused the initial rate to increase by a factor of nine.

(i)      Deduce the order of reaction with respect to A and the order with respect to B.

Order with respect to A .......................................................................

Order with respect to B ........................................................................

(ii)     Using your answers from part (c)(i), write a rate equation for the reaction and
suggest suitable units for the rate constant.

Rate equation .....................................................................................

Units for the rate constant ...................................................................

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14.   (a)     The following table shows the results of three experiments carried out at the same
temperature to investigate the rate of the reaction between compounds P and Q.
 
  Experiment 1 Experiment 2 Experiment 3
Initial concentration of P/mol dm –3
0.50 0.25 0.25
Initial concentration of Q/mol dm –3
0.36 0.36 0.72
Initial rate/mol dm s –3 –1
7.6 × 10 1.9 × 10 3.8 × 10
–3 –3 –3

Use the data in the table to deduce the order with respect to P and the order with respect
to Q.

Order with respect to P ................................................................................

Order with respect to Q ................................................................................

(b)     In a reaction between R and S, the order of reaction with respect to R is one, the order
of reaction with respect to S is two and the rate constant at temperature T has a value of 1

4.2 × 10 mol dm s .
–4 –2 6 –1

(i)      Write a rate equation for the reaction. Calculate a value for the initial rate of reaction
when the initial concentration of R is 0.16 mol dm and that of S is –3

0.84 mol dm . –3

Rate equation ....................…..............................................................

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 Calculation ..........................................................................................

(ii)     In a second experiment performed at a different temperature, T , the initial 2

rate of reaction is 8.1 × 10 mol dm s when the initial concentration of R is 0.76 mol

–5 –3 –1

dm and that of S is 0.98 mol dm . Calculate the value of the rate constant at

–3 –3

temperature T . 2

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(iii)     Deduce which of T and T is the higher temperature.

1 2

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15.          Kinetic studies enable chemists to suggest mechanisms for reactions.

(a)    The following data were obtained in a series of experiments on the rate of the reaction
between compounds A and B at a constant temperature.
 
Experiment Initial concentration of Initial concentration of Initial rate/
A/mol dm –3
B/mol dm –3
mol dm s–3 –1

1 0.12 0.15 0.32 × 10 –3

2 0.36 0.15 2.88 × 10 –3

3 0.72 0.30 11.52 × 10 –3

(i)      Deduce the order of reaction with respect to A.

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(ii)     Deduce the order of reaction with respect to B.

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(b)     The following data were obtained in a series of experiments on the rate of the reaction
between NO and O at a constant temperature.
2

 
Experiment Initial concentration of Initial concentration of Initial rate/
NO/mol dm –3
O /mol dm
2
–3
mol dm s–3 –1

4 5.0 × 10 –2
2.0 × 10 –2
6.5 × 10 –4

5 6.5 × 10 –2
3.4 × 10 –2
To be calculated

The rate equation for this reaction is

rate = k[NO]2[O ] 2

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 (i)      Use the data from Experiment 4 to calculate a value for the rate constant, k, at this
temperature, and state its units.

Value of k ............................................................................................

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Units of k .............................................................................................

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(ii)     Calculate a value for the initial rate in Experiment 5.

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16. Rate = k [A]2 [B]

Correct units for the rate constant in the rate equation above are

A       mol dm−3 s−1

B       mol−1 dm−3 s−1

C       mol2 dm−6 s−1

D       mol−2 dm6 s−1

17. This question is about the reaction between propanone and an excess of ethane-1,2-diol, the
equation for which is given below.

In a typical procedure, a mixture of 1.00 g of propanone, 5.00 g of ethane-1,2-diol and 0.100 g of

benzenesulphonic acid, C6H5SO3H, is heated under reflux in an inert solvent. Benzenesulphonic
acid is a strong acid.

When the concentration of benzenesulphonic acid is doubled, the rate of the reaction doubles. It
can be deduced that

A       the reaction is first order overall.

B       the reaction is third order overall.

C       the reaction is acid-catalysed.

D       units for the rate constant, k, are mol−2 dm6 s−1.

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