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A2 CHEMISTRY UNIT 4.

3 KINETICS REVISION
1.

(a)

A fixed mass of marble is reacted with dilute hydrochloric acid at a constant temperature.
Explain why the rate of the reaction is increased if the lumps of marble are reduced in size.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

The initial rate of the reaction between substances A and B was measured in a series of
experiments and the following rate equation was deduced.
rate = k[A][B]
(i)

Complete the table of data below for the reaction between A and B.
Expt

Initial [A]
3
/mol dm

Initial [B]
3
/mol dm

0.020

0.020

0.040

0.040

(ii)

0.040

0.060

0.040

Initial rate
3 1
/mol dm s
4

1.210

2.410

0.030
4

7.210

Using the data for Experiment 1, calculate a value for the rate constant, k and state
its units.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(7)
(Total 9 marks)

2.

The hydrolysis of methyl propanoate was studied in acidic conditions at 25C and the rate
equation was found to be
rate = k[CH3CH2COOCH3][H+]
(a)

Use the data below to calculate the value of the rate constant, k, at this temperature.
Deduce its units.
Initial rate of reaction /
3 1
mol dm s
4

1.15 10

Initial concentration of methyl


3
propanoate / mol dm

Initial concentration of
3
hydrochloric acid / mol dm

0.150

0.555

Rate constant .....................................................................................................................


.............................................................................................................................................
.............................................................................................................................................
Units ...................................................................................................................................
.............................................................................................................................................
(3)

(b)

The reaction in part (a) was repeated at the same temperature, but water was added so that
the volume of the reaction mixture was doubled. Calculate the initial rate of reaction under
these conditions.
.............................................................................................................................................
.............................................................................................................................................
(1)
(Total 4 marks)

3.

(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

0.50

0.25

0.25

0.36

0.36

0.72

Initial concentration of P/mol dm

Initial concentration of Q/mol dm


3 1

7.6 10

Initial rate/mol dm s

1.9 10

3.8 10

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 ..............................................................................................
(2)

(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 T1 has a value of
4

6 1

4.2 10 mol dm s .
(i)

Write a rate equation for the reaction. Calculate a value for the initial rate of reaction
3
when the initial concentration of R is 0.16 mol dm and that of S is
3
0.84 mol dm .
Rate equation ...............................................................................................
Calculation .......................................................................................................
.......................................................................................................................

(ii)

In a second experiment performed at a different temperature, T2, the initial


5

3 1

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


3
3
0.76 mol dm and that of S is 0.98 mol dm . Calculate the value of the
rate constant at temperature T2.
.......................................................................................................................
.......................................................................................................................
.......................................................................................................................
(iii)

Deduce which of T1 and T2 is the higher temperature.


.......................................................................................................................
(6)
(Total 8 marks)

4.

(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]
(i)

Complete the table of data below for the reaction between A and B.
Expt

Initial [A]
3
/mol dm

6.60 10

3.30 10

4.80 10

4.80 10

Initial [B]
3
/mol dm

13.2 10
2

1.60 10

Initial rate
3 1
/mol dm s
3

10.4 10

2
2

(ii)

5.20 10

10.4 10

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.
......................
(1)
(Total 7 marks)

5.

Iodine and propanone react in acid solution according to the equation


I2 + CH3COCH3 CH3COCH2I + HI
The rate equation for the reaction is found to be
+

rate = k [CH3COCH3][H ]

(a)

Deduce the order of reaction with respect to iodine and the overall order of reaction.
Order with respect to iodine ...................................................................................
Overall order .........................................................................................................
(2)

(b)

At the start of the experiment, the rate of reaction was found to be


5
3 1
2.00 10 mol dm s when the concentrations of the reactants were as shown below.
Reactant
CH3COCH3
I2
+

Concentration / mol dm
1.50
2

2.00 10

3.00 10

Use these data to calculate a value for the rate constant and deduce its units.
Rate constant .........................................................................................................
................................................................................................................................
................................................................................................................................
Units .......................................................................................................................
(3)

(c)

How can you tell that H acts as a catalyst in this reaction?


................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(Total 7 marks)

6.

The reaction between hydrogen and iodine can be represented by the following equation:
H2(g) + I2(g)

2HI(g)

H = +52 kJ mol

Kinetic data are available for both forward and reverse reactions. A series of experiments to
investigate the kinetics of the forward reaction was carried out at a constant temperature. The
results are shown in Figure 1.
Experiment

Initial concentration
3
of H2 / mol dm

Initial concentration
3
of I2 / mol dm

3.0 10

3.0 10

6.0 10

2.0 10

6.0 10

6.0 10

Initial rate
3 1
/ mol dm s

l.2 10

3.6 10

7.2 10

6
6

Figure 1
(a)

Explain the meaning of each of the following terms:


(i)

rate of reaction;
(1)

(ii)

rate constant;
(1)

(iii)

overall order of reaction.


(2)

(b)

(i)

Use the results in Figure 1 to work out the order of the forward reaction with respect
to both hydrogen and iodine, explaining your reasoning.
(4)

(ii)

Write the rate equation for the reaction between hydrogen and iodine.
(1)

(iii)

Calculate the value of the rate constant for the forward reaction and give its units.
(3)

(c)

The experiment was repeated with the following initial concentrations for reactants:
3

[H2] = 4.0 10 mol dm

[I2] = 5.0 10 mol dm

Calculate the initial rate of the reaction.


(1)
(Total 13 marks)

7.

The second-order rate constant for the reaction of 1-bromopropane with aqueous hydroxide ions was
measured as a function of temperature.
CH3CH2CH2Br(aq) + OH-(aq) CH3CH2CH2OH(aq) + Br-(aq)
The results are shown in the table below.
Temperature/K

1/T/K-1

k/ mol-1dm s

298

0.00336

l.4 10

Temperature/
C
25

3 1

lnk

-8.9

35

3.0 10

45

6.8 10

55

l.4 10

(a) Complete the table above (the first row is done for you)
(b) Plot a graph of lnk against 1/T. Measure the slope (gradient) of the line and hence calculate the
activation energy of the reaction (give your answer to 3 sig figs).
8.

The activation energy of the oxidation of iodide ions by iodate (V) ions can be found by experiment:
The equation for the reaction is:
IO3-(aq) + 5I-(aq) + 6H-(aq) 3I2(aq) + 3H2O(l)
The iodine produced then reacts with the sodium thiosulfate:
I2(aq) + 2S2O32-(aq) 2I-(aq) + S4O62-(aq)
When all the sodium thiosulfate has been used up, the next iodine that is produced forms an intense
blue colour with the starch. The time was recorded when the solution turned intense blue, the
experiments repeated with the same volumes of solutions but at a higher temperature. The results are
shown in the table below:
Time/s

1/time/s-1

ln (1/time)

Temperature/C

135

25

46

40

14

60

Temperature/K

1/Temperature/K-1

(a) Complete the table above


(b) Plot a graph of ln(1/time) on the y axis against 1/T on the x-axis. Measure the gradient of the

line and evaluate the activation energy. (You may assume that the gradient of this line is the
same as that of lnk against 1/T and that its value is Ea/R.

A2 CHEMISTRY KINETICS REVISION ANSWERS


1.

(a)

Increased surface area (1)


more collisions (1)

(b)

(i)

Experiment 2 = 9 6 10

(1)

Experiment 3 = 0 010 (1)


4

Experiment 4 = 8 1 10

(1)

Experiment 5 = 0 035 (1)


(ii)

k=

1.2 10 4

( 0 020)( 0 020)

6 1

(1) = 15 (1) mol dm s (1)

7
[9]

2.

(a)

k = rate/[CH3CH2COOCH3][H ] or
=

1 15 10 4
(0.150)(0.555)

= 1.38 10 to 1.4 10
1

(b)

3 1

mol dm s

ans = rate constant ( 0.150) ( 0.555)


ignore units

= rate constant 0.0208


5
3
5
2.88 10 (1.38 10 gives 2.87 10 )
5
3
5
Allow 2.87 2.91 10 (1.4 10 gives 2.91 10 )
[4]

3.

(a)

order with respect to P is 2


order with respect to Q is 1

(b)

(i)

rate = k[R][S]
(if wrong expression, no further marks)
4
2
rate = (4.2 10 ) 0.16 0.84
5
3 1
= 4.7 10 (mol dm s )
ignore units even if wrong

(ii)

k=

rate
8.110 5
=
[ R ][S] 2 0.76 0.982
4

= 1.1 10
(iii)

1
1
1
1
1
1

T1

1
4

If calculated value for k > 4.2 10 , then answer to (iii) is T2


8

[8]

4.

(a)

(i)

Experiment 2
Experiment 3
Experiment 4

(ii)

k=

2.60 10
2
0.60 10
2
11.4 10

1
1
1

10.4 10 3

(4.80 10 2 )(6.60 10 2 ) 2
= 49.7
(Allow 49.8 and 50)
2

6 1

mol dm s

(b)

No change

1
[7]

5.

(a)

(b)

Order with respect to iodine: 0 (1)


Overall order: 2 (1)

Rate constant: k =
1

2 10 5
4
= 4.4(4) 10 (1)
2
(1.5) (3 10 )

3 1

Units: mol dm s (1)

(c)

Appears in rate equation (1)


OR implied by mention of concentration or order

does not appear in (stoichiometric / overall) equation (1)

2
[7]

6.

(a)

(i)
(ii)
(iii)

change in concentration / amount / mass / volume / (partial) pressure


per unit time / per s (1)
constant of (proportionality) in the rate equation (1)
allow reference to k in rate equation

(i)

sum of
nd
dependent on 2 mark or reference to orders (1)
powers in rate equation (1)
allow reference to annotated rate equation

(b)

(H2) 1 (1)
eg rate trebles as [H2] trebles not rate doubles as [H2] doubles (1)
10

(I2) 1 (1)
eg rate doubles as [I2] doubles (1)
mark these points independently
allow 1 mark for orders if not clear that both are first order
(ii)

rate = k[H2][I2] (1)


must be [H2] not [H]
allow e.c.f from (b)(i)
allow mark for correct answer for (b)(ii), even if (b)(i) wrong

(iii)

rearrange correctly (1)


correct substitution and correct consequential answer (1)
1

3 1

correct units (mol dm s ) (1)


allow e.c.f. from (b)(ii)
allow e.c.f. for incorrect arrangement
(c)

4 10 (1)
allow e.c.f. from (b)(ii) and (b)(iii)
could be worked by ratio from values in table or from rate equation

1
[13]

7.
Temperature/
C

Temperature/K

1/T/K-1

k/ mol-1dm s

25

298

0.00336

l.4 10

35

308

0.00325

3.0 10

45

318

0.00314

6.8 10

55

328

0.00306

l.4 10

3 1

lnk

-8.9

-8.1

-7.3

-6.6

(b) Gradient = -7391


Ea = -slope x R
= -(-7391) x 8.31 = +60090 Jmol-1
Answer = +60KJmol-1 (3 sig figs)

11

8.
Time/s

1/time/s-1

ln (1/time)

Temperature/C

Temperature/K

1/temperature/K-1

135

0.0074

-4.9

25

298

0.00336

46

0.0217

-3.8

40

313

0.00319

14

0.0714

-2.6

60

333

0.00300

(a) Gradient = -6389K


As the gradient = -Ea/R then Ea = -gradient x R
Ea = -(-6389) x 8.31 = +53090 Jmol-1 = +53.1 KJmol-1

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