Topic 16 past papers [28 marks]

1. A reaction proceeds by the following mechanism: [1 mark]

step 1: A+A→B
step 2: B+C→ D
Which rate equation is consistent with this mechanism?
A. Rate = k[B]2[C]
B. Rate = k[A]2[B][C]
C. Rate = k[A]2
D. Rate = k[A][C]

Markscheme
C
2. Which graphs show a first order reaction? [1 mark]

A. V and X
B. V and Y
C. W and X
D. W and Y

Markscheme
B
 Bromate and bromide ions react in acidic aqueous solution.
BrO3− (aq) + 5Br− (aq) + 6H+ (aq) → 3Br2 (l) + 3H2O (l)
The following rate data was collected.

3a. Determine the rate expression for the reaction. [2 marks]

Markscheme
BrO3–: 1/first AND Br–: 1/first AND H+: 2/second ✓
«Rate =» k[BrO3−][Br−][H+]2 ✓

M2: Square brackets required for the mark.

3b. Determine the value and unit of the rate constant using the rate [2 marks]
expression in (a).

Markscheme
8.0×10−4
«k = =» 8.0 ✓
0.10×0.10× ( 0.10 ) 2
mol−3 dm9 s−1 ✓

4. What are the units of the rate constant, k, if the rate equation is [1 mark]
Rate = k[A][B]2 ?
A. mol dm−3 s−1
B. dm3 mol−1 s−1
C. dm6 mol−2 s−1
D. dm9 mol−3 s−1

Markscheme
C
5. Which graph is obtained from a first order reaction? [1 mark]

Markscheme
B

This question is about the decomposition of hydrogen peroxide.

6a. Suggest why many chemicals, including hydrogen peroxide, are kept in [1 mark]
brown bottles instead of clear colourless bottles.

Markscheme
decomposes in light [✔]

Note: Accept “sensitive to light”.

Hydrogen peroxide decomposes to water and oxygen when a catalyst such as

potassium iodide, KI, is added.

KI (aq)
2H2O 2 (aq) −−−−→ O2 (g) + 2H2O (l)
6b. In a laboratory experiment solutions of potassium iodide and hydrogen peroxide
[3 marks]
were mixed and the volume of oxygen generated was recorded. The
volume was adjusted to 0 at t = 0.

The data for the first trial is given below.

Plot a graph on the axes below and from it determine the average rate of
formation of oxygen gas in cm3 O2 (g) s−1.
Average rate of reaction:
Markscheme

points correctly plotted [✔]

best fit line AND extended through (to) the origin [✔]

Average rate of reaction:

«slope (gradient) of line =» 0.022 «cm3 O2 (g) s−1» [✔]

Note: Accept range 0.020–0.024cm3 O2 (g) s−1.

6c. Two more trials (2 and 3) were carried out. The results are given below. [2 marks]

Determine the rate equation for the reaction and its overall order, using your
answer from (b)(i).
Rate equation:
Overall order:

Markscheme
Rate equation:
Rate = k[H2O 2] × [KI] [✔]

Overall order:
2 [✔]

Note: Rate constant must be included.

6d. Additional experiments were carried out at an elevated temperature. On [2 marks]
the axes below, sketch Maxwell–Boltzmann energy distribution curves at
two temperatures T1 and T2, where T2 > T1.
 Markscheme

peak of T2 to right of AND lower than T1 [✔]

lines begin at origin AND T2 must finish above T1 [✔]

6e. Apart from a greater frequency of collisions, explain, by annotating your [2 marks]
graphs in (b)(iii), why an increased temperature causes the rate of
reaction to increase.

Markscheme
Ea marked on graph [✔]
explanation in terms of more “particles” with E ≥ Ea
OR
greater area under curve to the right of Ea in T 2 [✔]
6f. MnO 2 is another possible catalyst for the reaction. State the IUPAC name [1 mark]
for MnO 2.

Markscheme
manganese(IV) oxide
OR
manganese dioxide [✔]

Note: Accept “manganese(IV) dioxide”.

6g. Comment on why peracetic acid, CH3COOOH, is always sold in solution [1 mark]
with ethanoic acid and hydrogen peroxide.
H2O 2 (aq) + CH3COOH (aq) ⇌ CH3COOOH (aq) + H2O (l)

Markscheme
moves «position of» equilibrium to right/products [✔]

Note: Accept “reactants are always present as the reaction is in equilibrium”.

6h. Sodium percarbonate, 2Na2CO3•3H2O 2, is an adduct of sodium [2 marks]
carbonate and hydrogen peroxide and is used as a cleaning agent.
Mr (2Na2CO3•3H2O 2) = 314.04
Calculate the percentage by mass of hydrogen peroxide in sodium percarbonate,
giving your answer to two decimal places.

Markscheme
M( H2O 2) «= 2 × 1.01 + 2 × 16.00» = 34.02 «g» [✔]
34.02
«% H2O 2 = 3 × 314.04 × 100 =» 32.50 «%» [✔]

Note: Award [2] for correct final answer.

7. 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
 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]

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]

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]

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