Kinetics HL - Set 2 [171 marks]

1. What is the intercept on the y-axis when a graph of lnk is plotted against [1 mark]
1
on the x-axis?
T

ln k = − RETa + ln A
A. lnA

B. − ERa
C. − ERa
D. Ea

Markscheme
A

Examiners report
[N/A]

2. What is the effect of increasing temperature on the rate constant, k? [1 mark]

A. The rate constant does not change.
B. The rate constant decreases linearly.
C. The rate constant increases exponentially.
D. The rate constant increases proportionally with temperature.

Markscheme
C

Examiners report
[N/A]
3. Which pair of statements explains the increase in rate of reaction when [1 mark]
the temperature is increased or a catalyst is added?

Markscheme
C

Examiners report
[N/A]

4. Which is true of an Arrhenius plot of ln k (y-axis) against 1 ? [1 mark]

T
A. The graph goes through the origin.
B. The activation energy can be determined from the gradient.
C. The intercept on the x-axis is the activation energy.
D. The intercept on the y-axis is the frequency factor, A.

Markscheme
B

Examiners report
[N/A]
5. Which of the terms in the Arrhenius equation takes into account the [1 mark]
orientation of the molecules?
−Ea
k = Ae RT
A. A
B. Ea
C. R
D. T

Markscheme
A

Examiners report
[N/A]

6. What happens to the rate constant, k, and the activation energy, Ea , as [1 mark]
the temperature of a chemical reaction is increased?

Markscheme
D

Examiners report
[N/A]
7. The rate constant for a reaction is determined at different temperatures. [1 mark]
Which diagram represents the relationship between the rate constant, k ,
and temperature, T , in K ?

Markscheme
C

Examiners report
This question could be answered if students knew that the relationship
between k and T is exponential (as stated in A.S. 16.3.1), but it was not
necessary that students recalled the Arrhenius equation. Candidates found the
question difficult, having only 46% correct answers.
 A mixture of 1.00 mol SO2(g), 2.00 mol O 2(g) and 1.00 mol SO 3(g) is placed in a
1.00 dm3 container and allowed to reach equilibrium.
2SO2(g) + O2(g) ⇌ 2SO3(g)

8a. Nitrogen oxide is in equilibrium with dinitrogen dioxide. [1 mark]

2NO(g) ⇌ N2O 2(g) Δ HΘ < 0
Deduce, giving a reason, the effect of increasing the temperature on
the concentration of N2O 2.

Markscheme
[N2O 2] decreases AND exothermic «thus reverse reaction favoured»

Accept “product” for [N2O 2].

Do not accept just “reverse reaction favoured/shift to left” for
“[N2O 2] decreases”.
[1 mark]

Examiners report
[N/A]
8b. A two-step mechanism is proposed for the formation of NO 2(g) from [2 marks]
NO(g) that involves an exothermic equilibrium process.
First step: 2NO(g) ⇌ N2O 2(g) fast
Second step: N2O 2(g) + O2 (g) → 2NO2(g) slow
Deduce the rate expression for the mechanism.

Markscheme
ALTERNATIVE 1:
«from equilibrium, step 1»
[N2O2]
Kc =
[NO]2
OR
[N2O 2] = Kc[NO]2
«from step 2, rate «= k1[N2O 2][O2] = k2K[NO]2[O2]»
rate = k[NO]2[O2]

ALTERNATIVE 2:
«from step 2» rate = k2[N2O 2][O2]
k1
«from step 1, rate(1) = k1[NO]2 = k–1[N2O 2], [N2O 2] = [NO]2»
k−1
k1
«rate = k [NO]2[O2]»
k−1 2
rate = k[NO]2[O2]

Award [2] for correct rate expression.

[2 marks]
 Examiners report
[N/A]

8c. The rate constant for a reaction doubles when the temperature is [2 marks]
increased from 25.0 °C to 35 °C.
Calculate the activation energy, Ea, in kJ mol−1 for the reaction using section 1 and
2 of the data booklet.

Markscheme
«ln
k1
k2
= Ea
R
( T12 − 1
T1
)»
T2 = «273 + 35 =» 308 K AND T1 = «273 + 25 =» 298 K
Ea = 52.9 «kJ mol–1»

Award [2] for correct final answer.

[2 marks]

Examiners report
[N/A]
 Reaction kinetics can be investigated using the iodine clock reaction. The
equations for two reactions that occur are given below.
Reaction A: H2 O2 (aq) + 2I− (aq) + 2H+ (aq) → I2 (aq) + 2H2 O(l)
2−
Reaction B: I2 (aq) + 2S2 O 3(aq) → 2I− (aq) + S4 O2− 6 (aq)
Reaction B is much faster than reaction A, so the iodine, I2 , formed in reaction A
2−
immediately reacts with thiosulfate ions, S2 O 3 , in reaction B, before it can react
with starch to form the familiar blue-black, starch-iodine complex.
In one experiment the reaction mixture contained:
5.0 ± 0.1 cm3 of 2.00 mol dm−3 hydrogen peroxide (H2 O2 )
5.0 ± 0.1 cm3 of 1% aqueous starch
20.0 ± 0.1 cm3 of 1.00 mol dm−3 sulfuric acid (H2 SO4 )
20.0 ± 0.1 cm3 of 0.0100 mol dm −3 sodium thiosulfate (Na2 S2 O 3 )
50.0 ± 0.1 cm3 of water with 0.0200 ± 0.0001 g of potassium iodide (KI) dissolved
in it.
After 45 seconds this mixture suddenly changed from colourless to blue-black.

9a. The concentration of iodide ions, I− , is assumed to be constant. Outline [1 mark]

why this is a valid assumption.

Markscheme
KI/I− /potassium iodide/iodide (ion) (rapidly) reformed (in second stage of
reaction);
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9b. For this mixture the concentration of hydrogen peroxide, H2 O 2 , can also [2 marks]
be assumed to be constant. Explain why this is a valid assumption.

Markscheme
amount (in mol) of H2 O 2 /hydrogen peroxide ≫ amount (in mol)
Na2 S2 O3 /S2 O2−
3 /sodium thiosulfate/ thiosulfate (ion);
Accept amount (in mol) of H2O 2/hydrogen peroxide ≫ amount (in mol)
KI/I–/potassium iodide/iodide (ion).
Accept “H2O 2/hydrogen peroxide is in (large) excess/high concentration”.
(at end of reaction) [H2 O 2 ] is only slightly decreased/virtually unchanged;
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9c. Explain why the solution suddenly changes colour. [2 marks]

Markscheme
all Na2 S2 O3 /sodium thiosulfate/S2 O2−
3 /thiosulfate consumed/used up;
Accept “iodine no longer converted to iodide”.
(free) iodine is formed / iodine reacts with starch / forms iodine-starch
complex;
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9d. Calculate the total uncertainty, in cm3 , of the volume of the reaction [1 mark]
mixture.

Markscheme
(5 × 0.1) = (±)0.5(cm3 );

Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.
9e. Calculate the percentage uncertainty of the concentration of potassium [1 mark]
iodide solution added to the overall reaction mixture.

Markscheme
(±)0.7(%);
Comprises both mass of KI = ± 0.5% and volume of KI = ± 0.2%.

Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9f. Determine the percentage uncertainty in the concentration of potassium [1 mark]

iodide in the final reaction solution.
 Markscheme
0.5 + 0.7 = (±)1.2%;
Sum of (i) and (ii) (percentage uncertainty of total volume = absolute
uncertainty as 100 cm3).

Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9g. The colour change occurs when 1.00 × 10−4 mol of iodine has been [4 marks]
formed. Use the total volume of the solution and the time taken, to calculate the
rate of the reaction, including appropriate units.
Markscheme
total volume 0.100(dm3 )/100(cm3 );
(change in concentration = 1.00×10−4
0.100
=) 1.00 × 10−3 (mol dm3 );

(rate = 1.00×10−3
45
=) 2.2 × 10−5 ;
Award [3] for the correct final answer.
mol dm−3 s−1 ;

Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.
 The activation energy can be determined using the Arrhenius equation, which is
given in Table 1 of the Data Booklet. The experiment was carried out at five
different temperatures. An incomplete graph to determine the activation energy of
the reaction, based on these results, is shown below.

9h. State the labels for each axis. [2 marks]

x-axis:
y-axis:

Markscheme
1
x-axis: Temperature / T1 /T−1 ;
Ignore units.
y-axis: ln rate/log e rate / ln rate constant/log e rate constant / ln k/log e k;
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9i. Use the graph to determine the activation energy of the reaction, in [3 marks]
kJ mol−1 , correct to three significant figures.

Markscheme
−Ea
gradient = R
;
−4.00 −4.80
gradient = = −8333/ = = −8276;
(3.31×10−3−2.83×10−3) (3.41×10−3−2.83×10−3)
−1 −1
Ea = ( 8.31×8333
1000
) = 69.3(kJ mol )/ = ( 8.31×8276
1000
) = 68.8(kJ mol );
Award [3] for correct final answer.
Accept values from 65.0 to 73.0 kJ mol –1.
Deduct [1] for final answer in J mol–1.
Deduct [1] for final answer not to 3 significant figures.
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

9j. In another experiment, 0.100 g of a black powder was also added while [2 marks]
all other concentrations and volumes remained unchanged. The time
taken for the solution to change colour was now 20 seconds. Outline why you
think the colour change occurred more rapidly and how you could confirm your
hypothesis.

Markscheme
acting as a catalyst / black powder reacts with thiosulfate ions / solid dissolves
to give blue-black solution;
Accept any other valid suggestion which will make colour change more rapid.
For catalyst: amount/mass of black powder remains constant / no
new/different products formed / activation energy decreased;
For other suggestions: any appropriate way to test the hypothesis;
Award [1] for valid hypothesis, [1] for appropriate method of testing the
stated hypothesis.
 Examiners report
This question explored basic chemical concepts in the context of a practical
situation. Whilst this is one frequently carried out during practical courses,
none of the questions depended on prior knowledge. Students varied
significantly in their ability to interpret the information given to answer parts
(a) to (c), but very few could correctly carry out the propagation of
uncertainties required in part (d). An encouraging number were able to carry
out the rate calculation required in part (e). It was surprising how many
students, though unable to identify the axes of the Arrhenius graph given in
part (f), were still able to interpret it to correctly calculate the activation
energy. Part (g) was deliberately open ended and elicited a number of
interesting responses, though frequently the tests proposed would not in fact
confirm the suggested hypothesis.

To determine the activation energy of a reaction, the rate of reaction was

measured at different temperatures. The rate constant, k, was determined and
ln k was plotted against the inverse of the temperature in Kelvin, T −1 . The
following graph was obtained.

10a. Define the term activation energy, Ea . [1 mark]

 Markscheme
minimum energy needed to react/start a reaction / energy difference between
reactants and transition state;

Examiners report
The idea of activation energy being a minimum was seldom communicated.
Few were able to follow through all the mathematics to find Ea by a graphical
method and those that did had often omitted 10−2 in their calculations. The
answers were often poorly set out so it was difficult to assess the award of part
marks; indeed, many candidates seemed to hope that a correct answer would
somehow emerge from a mass of incomprehensible figures.

10b. Use the graph on page 8 to determine the value of the activation [2 marks]
−1
energy, Ea , in kJ mol .

Markscheme
gradient of the line: –63;
Accept –60 to –65.
Ea (= −R × gradient) = 0.52(kJ mol−1 );
Accept 0.50 to 0.54.
 Examiners report
The idea of activation energy being a minimum was seldom communicated.
Few were able to follow through all the mathematics to find Ea by a graphical
method and those that did had often omitted 10−2 in their calculations. The
answers were often poorly set out so it was difficult to assess the award of part
marks; indeed, many candidates seemed to hope that a correct answer would
somehow emerge from a mass of incomprehensible figures.

10c. On the graph on page 8, sketch the line you would expect if a catalyst is [1 mark]
added to the reactants.

Markscheme
gradient of the line less steep (less negative);
Accept any position as long as gradient less steep.

Examiners report
The idea of activation energy being a minimum was seldom communicated.
Few were able to follow through all the mathematics to find Ea by a graphical
method and those that did had often omitted 10−2 in their calculations. The
answers were often poorly set out so it was difficult to assess the award of part
marks; indeed, many candidates seemed to hope that a correct answer would
somehow emerge from a mass of incomprehensible figures. The gradient of
the graph for (c) was generously marked; all candidates had to do was to
realize that the catalyst would lower the activation energy and thus the
gradient would be less negative. As long as a line with less negative gradient
was drawn, the mark was awarded.

Na S O (aq) HCl(aq)
 Sodium thiosulfate solution, Na2 S2 O 3 (aq), and hydrochloric acid, HCl(aq), react
to produce solid sulfur as in the equation below.

S2 O2− +
3 (aq) + 2H (aq) → S(s) + SO 2 (g) + H2 O(l)

The following results to determine the initial rate were obtained:

11a. Deduce, with a reason, the order of reaction with respect to each [2 marks]
reactant.

Markscheme
2−
experiments 1 and 2 ([S2 O 3 ] remains constant) change in [H+ ] does not
affect the rate so zero order with respect to H+ (aq) / OWTTE;
2−
experiment 1/2 and 3 ([H+ ] has no effect) [S2 O 3 ] is halved and rate is also
2−
halved so first order with respect to [S2 O 3 ] / OWTTE;
Accept explanation given in mathematical terms.
Award [1 max] if both [S2O 32–] is first order, and [H+] is zero order are stated
without reason.
 Examiners report
The interpretation of orders of rate from experimental data was well
understood, and explained. Calculations of both the value and units of Kc were
also done well. Very few candidates produced an acceptable equation for the
rate determining step, many did not realise the importance of balancing both
the number of atoms and charge on both sides. The required careful
explanation of how Ea is determined from experimental data was lacking, too
often a vague description of using gradient and R without context was
considered sufficient by many candidates.

11b. State the rate expression for this reaction. [1 mark]

Markscheme
rate = k[S2 O2−
3 ];

Examiners report
The interpretation of orders of rate from experimental data was well
understood, and explained. Calculations of both the value and units of Kc were
also done well. Very few candidates produced an acceptable equation for the
rate determining step, many did not realise the importance of balancing both
the number of atoms and charge on both sides. The required careful
explanation of how Ea is determined from experimental data was lacking, too
often a vague description of using gradient and R without context was
considered sufficient by many candidates.
11c. Determine the value of the rate constant, k, and state its units. [2 marks]

Markscheme
0.18;
s−1 ;

Examiners report
The interpretation of orders of rate from experimental data was well
understood, and explained. Calculations of both the value and units of Kc were
also done well. Very few candidates produced an acceptable equation for the
rate determining step, many did not realise the importance of balancing both
the number of atoms and charge on both sides. The required careful
explanation of how Ea is determined from experimental data was lacking, too
often a vague description of using gradient and R without context was
considered sufficient by many candidates.

11d. State an equation for a possible rate-determining step for the reaction. [1 mark]
 Markscheme
S2 O2− 2−
3 → S + SO 3 ;
Accept any balanced equation that starts with only one S2O 32–.
Equations must be balanced in terms of number of atoms and charge.

Examiners report
The interpretation of orders of rate from experimental data was well
understood, and explained. Calculations of both the value and units of Kc were
also done well. Very few candidates produced an acceptable equation for the
rate determining step, many did not realise the importance of balancing both
the number of atoms and charge on both sides. The required careful
explanation of how Ea is determined from experimental data was lacking, too
often a vague description of using gradient and R without context was
considered sufficient by many candidates.

11e. Suggest how the activation energy, Ea , for this reaction may be [3 marks]
determined.

Markscheme
determine rate at a range of temperatures (while keeping concentrations
constant);
calculate k for each temperature;
plot graph of ln k against T −1 ;
−Ea
gradient is R
/OWTTE;
 Examiners report
The interpretation of orders of rate from experimental data was well
understood, and explained. Calculations of both the value and units of Kc were
also done well. Very few candidates produced an acceptable equation for the
rate determining step, many did not realise the importance of balancing both
the number of atoms and charge on both sides. The required careful
explanation of how Ea is determined from experimental data was lacking, too
often a vague description of using gradient and R without context was
considered sufficient by many candidates.

Nitrogen dioxide and carbon monoxide react according to the following equation:
NO 2(g) + CO(g) ⇌ NO(g) + CO2(g) ΔH = –226 kJ
Experimental data shows the reaction is second order with respect to NO 2 and
zero order with respect to CO.

12a. State the rate expression for the reaction. [1 mark]

Markscheme
«rate =» k [NO2]2

Accept rate = k [NO2]2[CO]0.

[1 mark]

Examiners report
[N/A]
12b. The following mechanism is proposed for the reaction. [1 mark]

Step I NO2 (g) + NO2 (g) → NO(g) + NO3 (g)

Step II NO3 (g) + CO(g) → NO2 (g) + CO2 (g)
Identify the rate determining step giving your reason.

Markscheme
«step» I AND CO does not appear in the rate law expression
OR
«step» I AND only «2 molecules of» NO2 appears in rate expression

Do not allow ECF from (i).

[1 mark]

Examiners report
[N/A]

12c. State one method that can be used to measure the rate for this reaction. [1 mark]
 Markscheme
«IR or UV-vis» spectroscopy
OR
colorimetry
OR
colour change «over time»

Accept GC/gas chromatography.

[1 mark]

Examiners report
[N/A]

12d. Sketch the relationship between the rate of reaction and the [1 mark]
concentration of NO2.
 Markscheme

Curve must go through origin.

[1 mark]

Examiners report
[N/A]

12e. The Arrhenius equation, k = Ae− REaT , gives the relationship between the [1 mark]
rate constant and temperature.
State how temperature affects activation energy.

Markscheme
activation energy is independent of temperature

Accept “no relationship”.

[1 mark]
 Examiners report
[N/A]

Calcium carbonate reacts with hydrochloric acid.

CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)

13a. Outline two ways in which the progress of the reaction can be [2 marks]
monitored. No practical details are required.

Markscheme
Any two of:
loss of mass «of reaction mixture/CO2»
«increase in» volume of gas produced
change of conductivity
change of pH
change in temperature

Do not accept “disappearance of calcium carbonate”.

Do not accept “gas bubbles”.
Do not accept “colour change” or “indicator”.
[2 marks]

Examiners report
[N/A]
 The results of a series of experiments in which the concentration of HCl was varied
are shown below.

13b. Suggest why point D is so far out of line assuming human error is not the [1 mark]
cause.
 Markscheme
reaction is fast at high concentration AND may be difficult to measure
accurately
OR
so many bubbles of CO2 produced that inhibit contact of HCl(aq) with CaCO3(s)
OR
insufficient change in conductivity/pH at high concentrations
OR
calcium carbonate has been used up/is limiting reagent/ there is not
enough calcium carbonate «to react with the high concentration of HCl»
OR
HCl is in excess
OR
so many bubbles of CO2 produced that inhibit contact of HCl(aq) with CaCO3(s)

[1 mark]

Examiners report
[N/A]

13c. Draw the best fit line for the reaction excluding point D. [1 mark]
 Markscheme

straight line going through the origin AND as close to A, B, C as is

reasonably possible
[1 mark]

Examiners report
[N/A]

13d. Suggest the relationship that points A, B and C show between the [1 mark]
concentration of the acid and the rate of reaction.
 Markscheme
«directly» proportional

Accept “first order” or “linear”.

Do not accept “rate increases as concentration increases” or
“positive correlation”.
[1 mark]

Examiners report
[N/A]

13e. Deduce the rate expression for the reaction. [1 mark]

Markscheme
rate = k [H+]

Accept “rate = k [HCl]”.

[1 mark]

Examiners report
[N/A]
13f. Calculate the rate constant of the reaction, stating its units. [2 marks]

Markscheme
0.02
s–1

[2 marks]

Examiners report
[N/A]

13g. Predict from your line of best fit the rate of reaction when the [1 mark]
concentration of HCl is 1.00 mol dm−3.

Markscheme
20.5 × 10–3 «mol dm–3 s–1»

Accept any answer in the range 19.5–21.5.

[1 mark]

Examiners report
[N/A]
13h. Describe how the activation energy of this reaction could be [3 marks]
determined.

Markscheme
ALTERNATIVE 1:
carry out reaction at several temperatures
1
plot T against log rate constant

Ea = – gradient × R

ALTERNATIVE 2:
carry out reaction at two temperatures

determine two rate constants

OR
determine the temperature coefficient of the rate

use the formula ln k1

k2
= Ea
R
( T12 − 1
T1
)

−Ea
Accept “gradient = R ” for M3.

Award both M2 and M3 for the formula ln rate = R ( 1 − 1 ).

rate 1 Ea
2 T2 T1

rate 1 − Ea ( 1 − T1 )
Accept any variation of the formula, such as rate = e R T 1 2 .
2

[3 marks]
 Examiners report
[N/A]

Chemical kinetics involves an understanding of how the molecular world changes

with time.

14a. (i) Define the term rate of reaction. [4 marks]

(ii) Temperature and the addition of a catalyst are two factors that can affect the
rate of a reaction. State two other factors.
(iii) In the reaction represented below, state one method that can be used to
measure the rate of the reaction.

ClO− − +
3 (aq) + 5Cl (aq) + 6H (aq) → 3Cl 2 (aq) + 3H2 O(l)
Markscheme
(i) change in concentration of reactant/product with time / rate of change of
concentration;
Increase can be used instead of change for product or decrease can be used
instead of change for reactant.
Allow mass/amount/volume instead of concentration.
Do not accept substance.
(ii) concentration;
particle size / surface area;
light;
pressure;
Allow pH.
(iii) (measuring electrical) conductivity / (measuring) pH;
Accept other suitable method.

Examiners report
This was the most popular question in Section B of the paper. Part (a) was very
well answered.
 A catalyst provides an alternative pathway for a reaction, lowering the activation
energy, Ea .

14b. (i) Define the term activation energy, Ea . [4 marks]

(ii) Sketch the two Maxwell–Boltzmann energy distribution curves for a fixed
amount of gas at two different temperatures, T1 and T2 (T2 > T1 ). Label both
axes.
Markscheme
(i) minimum/least/smallest energy needed (by reactants/colliding particles) to
react/start/initiate a reaction;
Allow energy difference between reactants and transition state.
Minimum/least/smallest required for the mark.
(ii) x-axis label: (kinetic) energy/(K)E and y-axis label: probability/fraction of
molecules/particles / probability density;
Allow number of molecules/particles for y-axis.
correct shape of a typical Maxwell–Boltzmann energy distribution curve;
Do not award mark if curve is symmetric, does not start at zero or if it crosses
x-axis.
two curves represented with second curve for T2 > T1 to right of first curve,
peak maximum lower than first curve and after the curves cross going to the
right, T2 curve needs to be above T1 curve as illustrated;
M2 and M3 can be scored independently.

Examiners report
In (b) (i), some candidates failed to mention minimum/least/smallest energy in
the definition of activation energy. In part (ii), again candidates often dropped
easy marks here for poor representations of the Maxwell-Boltzmann energy
distribution curves. In some cases the curves were drawn symmetrically,
which was incorrect. In addition, incorrect labels were often given for the x-
and y-axes. Some candidates mixed these curves up with enthalpy level
diagrams. It was nice to see more candidates giving a more precise label for
the y-axis as probability/fraction of molecules rather than just number of
molecules. The latter was allowed but is less precise (although does tend to be
used in many IB textbooks).

→
 Sketch graphical representations of the following reactions, for X → products.

14c. (i) Concentration of reactant X against time for a zero-order reaction. [3 marks]

(ii) Rate of reaction against concentration of reactant X for a zero-order reaction.

(iii) Rate of reaction against concentration of reactant X for a first-order reaction.

Markscheme

(i) ;

(ii) ;

(iii) ;

Examiners report
Part (c) however was very well answered.
 For the reaction below, consider the following experimental data.

2ClO2 (aq) + 2OH− (aq) → ClO− −

3 (aq) + ClO 2 (aq) + H2 O(l)

14d. (i) Deduce the rate expression. [5 marks]

(ii) Determine the rate constant, k, and state its units, using the data from
Experiment 2.
(iii) Calculate the rate, in mol dm−3 s−1 , when
[ClO2 (aq)] = 1.50 × 10−2 mol dm−3 and [OH− (aq)] = 2.35 × 10−2 mol dm−3 .
 Markscheme
(i) second order in ClO2 and first order in OH− ;
rate = k[ClO2 ]2 [OH− ];
Award [2] for correct final answer.
(ii) k = 2.30 × 102 /230;
mol−2 dm6 s−1 ;
(iii) 1.22 × 10−3 /0.00122(mol dm−3 s−1 );

Examiners report
In part (d), many candidates also scored highly though the units of k in (ii) did
cause a problem for some candidates.

Another reaction involving OH− (aq) is the base hydrolysis reaction of an ester.
CH3 COOCH2 CH(aq) + OH− (aq) → CH3 COO− (aq) + CH3 CH2 OH(aq)

14e. Apply IUPAC rules to name the ester, CH3COOCH 2CH3(aq). [1 mark]

Markscheme
ethyl ethanoate;
Do not allow ethyl acetate.

Examiners report
In (e) (i), the most common mistake was candidates stating ethyl methanoate
instead of ethyl ethanoate.
14f. Describe qualitatively the relationship between the rate constant, k, [1 mark]
and temperature, T.

Markscheme
as temperature/T increases, (value of) rate constant/k increases
(exponentially);
Do not allow answers involving ln k from the Arrhenius equation.
Do not allow T directly proportional to k.

Examiners report
In part (ii), a number of candidates stated incorrectly that T is directly
proportional to k, which is incorrect. Proportionality is a concept embedded in
AS 11.3.1 in Topic 11, and may be worth some further discussion in the light
of the Arrhenius Equation.
14g. The rate of this reaction was measured at different temperatures and [4 marks]
the following data were recorded.

Using data from the graph, determine the activation energy, Ea , correct to three
significant figures and state its units.
 Markscheme
slope = −5.6 × 103 / − 5600(K);
Ea = −slope × R/slope = −Ea /R;
Ea ( = 5.60 × 103 K × 8.31J K−1 mol−1 ) = 4.65 × 104 (J mol−1 )/46.5(kJ mol−1 )
;
Accept answers in range 4 .60 × 104 Jmol−1 to 4.67 × 104 (J mol −1 ).
J mol−1 /kJ mol−1 ;
Accept J or kJ.
Unit mark can be scored independently but correct Ea values with incorrect
units scores only [3 max] (for example 46.5 J mol −1 ).
Award [4] for correct final answer.

Examiners report
The most difficult part of Q6 however involved (e) (iii). Very few candidates
scored full marks here and simply did not know how to manipulate the
equation to get the activation energy. Others even gave incorrect units.

A two-step mechanism has been proposed for the following reaction.

Step 1: ClO− (aq) + ClO− (aq) → ClO− −

2 (aq) + Cl (aq)
Step 2: ClO− − − −
2 (aq) + ClO (aq) → ClO 3 (aq) + Cl (aq)

14h. Deduce the overall equation for the reaction. [1 mark]

 Markscheme
3ClO− (aq) → ClO− −
3 (aq) + 2Cl (aq);
Ignore state symbols.

Examiners report
One respondent stated that part (f) (ii) would be difficult for candidates. (f)
certainly did prove challenging and the rate expression for step two was often
given incorrectly. This question became a good discriminating question in
Section B. However the better students did manage to score all three marks in
part (f).

14i. Deduce the rate expression for each step. [2 marks]

Step 1:
Step 2:

Markscheme
− 2
Step 1: rate = k[ClO ] ;
− −
Step 2: rate = k[ClO2 ][ClO ];
Penalize missing k once only.
Examiners report
One respondent stated that part (f) (ii) would be difficult for candidates. (f)
certainly did prove challenging and the rate expression for step two was often
given incorrectly. This question became a good discriminating question in
Section B. However the better students did manage to score all three marks in
part (f).
15a. (i) State the full electron configuration of Fe. [8 marks]
(ii) State the abbreviated electron configuration of Fe3+ ions.
(iii) Cyanide ions, CN− , can act as ligands. One complex ion that involves the
3−
cyanide ion is [Fe(CN)6 ] . Identify the property of a cyanide ion which allows it
to act as a ligand, and explain the bonding that occurs in the complex ion in terms
3−
of acid–base theory. Describe the structure of the complex ion, [Fe(CN)6 ] .

(iv) Explain why complexes of Fe3+ are coloured.

 Markscheme
(i) 1s2 2s2 2p6 3s2 3p6 3d6 4s2 /1s2 2s2 2p6 3s2 3p6 4s2 3d6 ;
5
(ii) [Ar]3d ;
(iii) lone pair of electrons (on C);
CN− acts as a Lewis base / Fe3+ acts as a Lewis acid;
dative covalent/coordinate bond formed (between CN− and Fe3+ );
ligands occupy an octahedral shape around central metal ion / coordination
number of Fe3+ is 6;
(iv) d sub-level splits (into two sets of orbitals of different energy) / ΔE;
colour due to electron transitions between (split) d orbitals;

Examiners report
Most candidates had no difficulty with the full electron configuration of Fe in
(a) but many could not write the abbreviated electron configuration of Fe3+ ,
losing 3d electrons ahead of 4s. Some G2 comments suggested that the word
abbreviated caused problems, but this is stated in the teacher‘s notes and
most candidates seemed to have no difficulty with the term. Descriptions of
cyanide ions acting as ligands were particularly well expressed but some
candidates had difficulty explaining why Fe3+ ions are coloured, referring to
excited orbitals emitting light.

The reaction between carbon monoxide, CO(g), and nitrogen dioxide, NO 2 (g) ,
was studied at different temperatures and a graph was plotted of ln k against 1 .
T
The equation of the line of best fit was found to be:

1
ln k = −1.60 × 104 ( ) + 23.2
T
 1
/10−3 K−1
T

15b. (i) The Arrhenius equation is shown in Table 1 of the Data Booklet. [6 marks]
Identify the symbols k and A.
k:
A:
(ii) Calculate the activation energy, Ea , for the reaction between CO(g) and
NO2 (g).
(iii) Calculate the numerical value of A.
Markscheme
(i) k:
rate constant;
A:
Arrhenius constant / frequency/pre-exponential factor;
−Ea
(ii) gradient = R
/Ea = −gradient × R;
(= −(−16) × 8.31) = +133(kJ mol−1 )/1.33 × 105 (J mol−1 );
(iii) ln A = (intercept ony- axis = ) 23.2 ;
A = 1.190 × 1010 ;
 Examiners report
In part (c) most candidates identified the symbols of the Arrhenius equation.
Many calculated the activation energy, although several calculated the
gradient from the graph rather than using the equation of the line of best fit.
(This was accepted, but made the question much harder than intended.)
Several candidates also calculated the numerical value of A correctly.

BF3 (g) reacts with NH3 (g) to form F3 BNH3 (g) according to the equation below.
BF3 (g) + NH3 (g) → F3 BNH3 (g)

16a. Identify the type of bond present between BF3 and NH3 in F3 BNH3 (g) [2 marks]
and state another example of a compound with this type of bonding.

Markscheme
dative (covalent)/coordinate;
+
carbon monoxide/CO / hydronium (ion)/ H3 O / ammonium (ion)/NH+ 4 /
aluminium chloride/Al2 Cl6 / any relevant transition metal complex (e.g.
[Ni(NH3 )6 ]2+ );
Accept AlCl3.

Examiners report
(i) was usually well done.
16b. The table below shows initial rates of reaction for different [3 marks]
concentrations of each reactant for this reaction at temperature, T.

Deduce the rate expression, the overall order of the reaction and determine the
value of k, the rate constant, with its units, using the data from Experiment 4.

Markscheme
rate = k[BF3 ][NH3 ];
second (order)/2°;
k = 3.40 dm3 mol−1 s−1 ;
Allow units of L mol–1s–1 or M–1s–1.
Units required for mark.

Examiners report
some did not answer the question which asked for the overall order of the
reaction. Some candidates also got their units incorrect. A few G2 comments
mentioned the fact that the data was quite complicated as there was no
experiment with [NH3 ] constant. It is true that the maths here may appear
more challenging than normal, but candidates should be able to handle this
type of data and in fact a significant number of the better candidates did score
full marks on this question.

H (g)
 The following is a proposed mechanism for the reaction of NO(g) with H2 (g).
Step 1: 2NO(g) → N2 O2 (g)
Step 2: N2 O2 (g) + H2 (g) → N2 O(g) + H2 O(g)

16c. Identify the intermediate in the reaction. [1 mark]

Markscheme
N2 O 2 ;

Examiners report
This was well answered.

16d. The observed rate expression is rate = k[NO]2 [H ] . Assuming that the [1 mark]
2
proposed mechanism is correct, comment on the relative speeds of the two steps.

Markscheme
([H2 ] appears in rate expression so) step 2 rate-determining/rds/slow step;
Allow “since step 1 involves 2NO and step 2 involves H 2 and as all 3 molecules
are involved in rate expression, then two steps must have approximately
same rate” / OWTTE.
 Examiners report
This was well answered.

16e. The following two-step mechanism has been suggested for the reaction [2 marks]
of NO 2 (g) with CO (g), where k2 ≫ k1 .

k1
Step 1 NO2 (g) + NO2 (g) −
→ NO(g) + NO3 (g)
k2
Step 2: NO3 (g) + CO(g) −
→ NO2 (g) + CO2 (g)
Overall: NO2 (g) + CO(g) → NO(g) + CO2 (g)
2
The experimental rate expression is rate = k[NO 2 ] . Explain why this mechanism
produces a rate expression consistent with the experimentally observed one.

Markscheme
(k2 ≫ k1 so) step 1 rate-determining/rds/slow step;
two molecules of NO 2 involved in step 1 consistent with rate expression / rate
2
of overall reaction must equal rate of step 1 which is rate = k1 [NO 2 ] /
OWTTE;

Examiners report
Although most candidates stated that the rds was step 1, many struggled with
the explanation.

H (g) I (g)
16f. HI(g) decomposes into H2 (g) and I2 (g) according to the reaction below. [4 marks]
2HI(g) → H2 (g) + I2 (g)
The 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 is
T
shown below.
1
T
/10−3 K−1

Calculate the activation energy, Ea , for the reaction using these data and Table 1
of the Data Booklet showing your working.
Markscheme
Ea = −R × m;
measurement of gradient from two points on line;
Accept a gradient in range –2.14 × 104 K to –2.27 × 104 (K).
correct answer for Ea ;
correct units kJ mol−1 /J mol−1 corresponding to answer;
Allow kJ or J.
A typical answer for Ea = 1.85 × 102 kJmol–1.
Allow answers for Ea in range 1.75 × 102 kJmol–1 to 1.91 × 102 kJmol–1.
Award [4] for correct final answer with some working shown.
Award [2 max] for correct final answer without any working shown.

Examiners report
Although this question has been asked on a number of recent papers,
candidates really struggled with this graphical based format. All sorts of
mistakes were made, including gradients, units etc. Some did not even know
how to approach the question.

1
 Consider the following graph of ln k against 1 (temperature in Kelvin) for the
T
second order decomposition of N2 O into N2 and O.

N2 O → N2 + O

1
/10−3 K−1
T

17a. State how the rate constant, k varies with temperature,T . [1 mark]

Markscheme
k increases with increase in T /k decreases with decrease in T ;
Do not allow answers giving just the Arrhenius equation or involving lnk
relationships.

Examiners report
This question on chemical kinetics was very poorly answered by candidates. In
(a), many candidates simply gave the Arrhenius equation and failed to
describe the explicit relationship between k and T .
17b. Determine the activation energy, Ea , for this reaction. [3 marks]

Markscheme
gradient = −Ea /R;
−30000(K) = −Ea /R;
Allow value in range –28800–31300 (K).

Examiners report
(b) was answered very poorly and although some candidates had an idea
about the gradient expression, most were out by a factor of 100 in their final
answer and many totally ignored units.

2
17c. The rate expression for this reaction is rate = k[N2 O]2 and the rate [2 marks]
constant is 0.244 dm3 mol−1 s−1 at 750 °C.
A sample of N2 O of concentration 0.200 mol dm −3 is allowed to decompose.
Calculate the rate when 10% of the N2 O has reacted.

Markscheme
0.9 × 0.200 = 0.180(mol dm−3 );
rate = (0.244 × (0.180)2 =) 7.91 × 10−3 mol dm−3 s−1 ;
Award [2] for correct final answer.
Award [1 max] for either 9.76 × 10–3 moldm–3s–1 or 9.76 × 10–5 moldm–3s–1.

Examiners report
In (c), the most common error related to the 10% reduction and units also
proved challenging.

18. What happens when the temperature of a reaction increases? [1 mark]

A. The activation energy increases.
B. The rate constant increases.
C. The enthalpy change increases.
D. The order of the reaction increases.
 Markscheme
B

Examiners report
[N/A]

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

Markscheme
D

Examiners report
[N/A]

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 Cl 2 and second
order with respect to NO. The reverse reaction is second order with respect to
NOCl.

20a. State the rate expression for the forward reaction. [1 mark]
 Markscheme
rate = k[NO]2 [Cl2 ];

Examiners report
In part (a) the rate expression was correctly stated although some confused
this with an equilibrium constant expression.

20b. Predict the effect on the rate of the forward reaction and on the rate [2 marks]
constant if the concentration of NO is halved.

Markscheme
rate of reaction will decrease by a factor of 4;
no effect on the rate constant;

Examiners report
Only the better candidates realized that the rate of reaction will decrease by a
factor of four and there will be no effect on the rate constant.

20c. 1.0 mol of Cl 2 and 1.0 mol of NO are mixed in a closed container at [4 marks]
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.
 Markscheme

y axis labelled concentration/mol dm−3 and x axis is labelled time/s;

gradient for [NO];
gradient for [NOCl] will be equal and opposite;
equilibrium point identified / two curves level off at same time;

Examiners report
Although most candidates were able to correctly sketch the concentration
versus time graph many forgot to label the axes or include units.

20d. Consider the following reaction. [2 marks]

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.

Markscheme
Above 775 K: rate = k[NO2 ][CO];
Below 775 K: rate = k[NO2 ]2 ;
 Examiners report
Part (b) was well answered and candidates demonstrated a good
understanding of rate expressions based on reaction mechanism.

20e. State two situations when the rate of a chemical reaction is equal to [2 marks]
the rate constant.

Markscheme
zero order reaction;
all concentrations are 1.0 mol dm−3 ;

Examiners report
The better candidates were able to figure out that the rate of a chemical
reaction is equal to the rate constant when all concentrations are
1.0 mol dm−3 or for a zero order reaction.

20f. Consider the following graph of ln k against 1 for the first order [2 marks]
T
decomposition of N2 O4 into NO2 . Determine the activation energy in kJ mol−1
for this reaction.
 Markscheme
9.2−8.4
slope = = −6.67 × 103 ;
(3.53−3.65)×10−3

(Ea = 6.67 × 103 × 8.31)

55.4 (kJ mol−1 );
Accept in range 55.0 – 56.0
Award [1] if 55454 (J) stated
Award [2] for the correct final answer

Examiners report
Most candidates had difficulty in calculating activation energy from the graph
−1 −1
in part (d) and some gave the answer in J mol instead of kJ mol which
showed that they missed this instruction in the question.

Consider the following equilibrium reaction.

Cl2 (g) + SO2 (g) ⇌ SO2 Cl2 (g) ΔH Θ = −84.5kJ

In a1.00 dm3 closed container, at 375 °C, 8.60 × 10−3 mol of SO2 and
8.60 × 10−3 mol of Cl2 were introduced. At equilibrium, 7.65 × 10−4 mol of
SO2 Cl2 was formed.

20g. Deduce the equilibrium constant expression, Kc , for the reaction. [1 mark]

Markscheme
[SO2Cl2]
(Kc ) = [Cl2][SO2]
;

Ignore state symbols.

Square brackets [ ] required for the equilibrium expression.
 Examiners report
In part (e), the equilibrium constant expression was correctly stated by the
majority but calculating the value ofKc proved to be difficult.

20h. Determine the value of the equilibrium constant, Kc . [3 marks]

Markscheme
7.84 × 10−3 mol of SO2 and 7.84 × 10−3 mol of Cl2 ;
7.84 × 10−3 mol dm−3 of SO2 , 7.84 × 10−3 mol dm−3 of Cl2 and
7.65 × 10−4 mol dm−3 of SO2 Cl2 ;
12.5;
Award [1] for 10.34
Award [3] for the correct final answer

Examiners report
A large number of candidates obtained the incorrect answer of 10.34 as a
result of using the initial concentrations of the reactants instead of equilibrium
concentrations.

20i. If the temperature of the reaction is changed to 300 °C, predict, stating [3 marks]
a reason in each case, whether the equilibrium concentration of SO 2 Cl 2
and the value of Kc will increase or decrease.

Markscheme
value of Kc increases;
[SO2 Cl2 ] increases;
decrease in temperature favours (forward) reaction which is exothermic;
Do not allow ECF.
 Examiners report
[N/A]

20j. If the volume of the container is changed to 1.50 dm 3 , predict, stating a [3 marks]
reason in each case, how this will affect the equilibrium concentration of SO 2 Cl 2
and the value of Kc .

Markscheme
no effect on the value of Kc / depends only on temperature;
[SO2 Cl2 ] decreases;
increase in volume favours the reverse reaction which has more gaseous
moles;
Do not allow ECF.

Examiners report
The application of Le Chatelier’s principle was handled well by the majority
with minor omissions such as not using the term gaseous particles in part (iv).

20k. Suggest, stating a reason, how the addition of a catalyst at constant [2 marks]
pressure and temperature will affect the equilibrium concentration of
SO2 Cl2 .

Markscheme
no effect;
catalyst increases the rate of forward and reverse reactions (equally) / catalyst
decreases activation energies (equally);
 Examiners report
Some candidates stated that the addition of a catalyst does not affect the
value of Kc or the position of equilibrium, which did not answer the question
and scored no marks because they had not commented on the concentration
of SOCl2 . Some candidates correctly stated that a catalyst increases the rate
of forward and reverse reactions equally.

21a. Define the term rate of reaction. [1 mark]

Markscheme
decrease in concentration/mass/amount/volume of reactant with time /
increase in concentration/mass/amount/volume of product with time / change
in concentration/mass/amount/volume of reactant/product with time;

Examiners report
Surprisingly, the rate of reaction was only correctly defined by approximately
50% of candidates in (a) (i).

21b. State an equation for the reaction of magnesium carbonate with dilute [1 mark]
hydrochloric acid.

Markscheme
MgCO3 (s) + 2HCl(aq) → MgCl2 (aq) + CO2 (g) + H2 O(l);
Ignore state symbols.

Examiners report
The equation for the reaction of magnesium carbonate with dilute hydrochloric
acid was not well answered (part (ii)), and often candidates did not write
correct formula or forgot to include water as a product.
21c. The rate of this reaction in (a) (ii), can be studied by measuring the [1 mark]
volume of gas collected over a period of time. Sketch a graph which shows how
the volume of gas collected changes with time.

Markscheme

Plot starts at the origin and levels off.

No mark awarded if axes are not labelled.

Examiners report
Part (iii) was well answered by most candidates.

21d. The experiment is repeated using a sample of hydrochloric acid with [4 marks]
double the volume, but half the concentration of the original acid. Draw
a second line on the graph you sketched in part (a) (iii) to show the results in this
experiment. Explain why this line is different from the original line.

Markscheme
new curve reaches same height as original curve;
new curve less steep than original curve;
volume of gas produced is the same because the same amount of acid is used;
reaction is slower because concentration is decreased;

Examiners report
Part (iv) was well answered by most candidates, although the weaker
candidates often only scored two or three marks.
 Nitrogen monoxide reacts at 1280 °C with hydrogen to form nitrogen and water.
All reactants and products are in the gaseous phase.

21e. The kinetics of the reaction were studied at this temperature. The table [4 marks]
shows the initial rate of reaction for different concentrations of each
reactant.
Deduce the order of the reaction with respect to NO and H2 , and explain your
reasoning.

Markscheme
(from experiments 1 and 2 at constant [H2 ] ), [NO] doubles, rate quadruples;
hence, second order with respect to NO;
(from experiments 2 and 3 at constant [NO]), [H2 ] doubles, rate doubles;
first order with respect to H2 ;
Allow alternative mathematical deductions also.

Examiners report
Part (b) (i) was well answered and many candidates scored all four marks.
Some candidates used a simple mathematical approach and those that
followed this method typically were able to deduce the order correctly.

21f. Deduce the rate expression for the reaction. [1 mark]

Markscheme
rate = k[NO]2 [H2 ];

Examiners report
For (ii) most candidates were able to write the rate expression for the reaction.

21g. Determine the value of the rate constant for the reaction from [2 marks]
Experiment 3 and state its units.
 Markscheme
k (= (10.00 × 10−5 )/(10.00 × 10−3 ) (4.00 × 10−3 )) = 2.50 × 102 ;
2

Do not penalize if Experiments 1 or 2 are used to determine k.

mol−2 dm6 s−1 ;

Examiners report
In (iii), determining the value of the rate constant and its corresponding units
was difficult for many candidates and only the better candidates scored both
marks. Many mistakes were seen in the units.

The gas-phase decomposition of dinitrogen monoxide is considered to occur in

two steps.
k1
Step 1: N2 O(g) −
→ N2 (g) + O(g)
k2
Step 2: N2 O(g) + O(g) −
→ N2 (g) + O2 (g)
The experimental rate expression for this reaction is rate = k[N2 O].

21h. Identify the rate-determining step. [1 mark]

Markscheme
step 1 / equation showing step 1;

Examiners report
Part (c) (i) was usually well answered.

21i. Identify the intermediate involved in the reaction. [1 mark]

 Markscheme
O (atom) / oxygen atom;
Do not allow oxygen or O2.

Examiners report
A common mistake for (ii) involved candidates writing O2 instead of O.

The conversion of CH3 NC into CH3 CN 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.

21j. Define the term activation energy, Ea . [1 mark]

Markscheme
(minimum) energy needed for a reaction to occur / difference in energy
between the reactants and transition state;

Examiners report
The definition of activation energy was well answered.
21k. Construct the enthalpy level diagram and label the activation energy, [3 marks]
Ea , the enthalpy change, ΔH , and the position of the transition state.

Markscheme

correct position of activation energy;

correct position of ΔH and H(CH3 NC)/reactant line above H(CH3 CN)
product line;
Accept ΔE instead of ΔH on diagram if y-axis is labelled as energy.
Do not penalize if CH3NC and CH3CN are not labelled on diagram.
correct position of transition state;
Allow [2 max] if axes are not labelled on diagram.

Examiners report
Part (ii) was a question where most candidates scored at least one/two marks
although perfect answers were less common. Reasons leading to the loss of
marks included: absence of axes, incomplete libelling of axes and the
incorrect identification of the position of the transition state.

21l. Describe qualitatively the relationship between the rate constant, k, and [1 mark]
the temperature, T .

Markscheme
as temperature/T increases rate constant/k increases (exponentially);
 Examiners report
Parts (iii) and (iv) were very poorly answered for such a fundamental topic. All
sorts of errors were evident, including incorrect gradients, inability to
rearrange the Arrhenius Equation etc.

21m. Calculate the activation energy, Ea , for the reaction, using Table 1 of [4 marks]
the Data Booklet.

Markscheme
from graph gradient m = − ERa ;
measurement of gradient from chosen points on graph;
Units of m are K. Do not penalize if not given, but do not award mark for
incorrect units.
Value of m is based on any two suitable points well separated on the plot.
correct answer for Ea ;
correct units corresponding to answer;
Note: A typical answer for Ea = 1.6 × 102 kJ / kJmol–1.

Examiners report
Even the better candidates struggled greatly with this question, even though
this comes straight from AS 16.3.2.

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