JURONG PIONEER JUNIOR COLLEGE

2023 JC1 H2 Chemistry (9729)

CHEM COACH (Worksheet 4: Kinetics)

Analysis of Initial Rate Data

1. 2014 JJC Prelim Q1c
In aqueous medium, ammonia reacts with hypochlorite, ClO−, to produce hydrazine.
Hydrazine, N2H4, is commonly used as a rocket propellant in spacecrafts.

2NH3(aq) + ClO−(aq) → N2H4(aq) + Cl−(aq) + H2O(l)

A chemist studied the kinetics of the above reaction at different initial concentrations
of NH3 and ClO−. He obtained the following table of results.

experiment initial [NH3(aq)] initial [ClO−(aq)] initial rate

number / mol dm-3 / mol dm-3 / mol dm-3 s-1
1 1.0 × 10-4 1.0 × 10-4 4.0 × 10-12

2 1.0 × 10-4 0.5 × 10-4 2.0 × 10-12

3 3.0 × 10-4 4.0 × 10-4 4.8 × 10-11

(i) Determine the order of reaction with respect to [NH3] and [ClO−]. Explain your
reasoning.

(ii) Hence write the rate equation for the reaction, and calculate a value for the
rate constant. Include units in your answer.

(i)
Let Rate = k [NH3]a [ClO-]b
Comparing expts 1 & 2, Comparing expts 1 & 2,
[NH3] remains constant.  rate  [ClO-]b [NH3] remains constant.  rate  [ClO-]b
b
When [ClO-] is x2, rate is also x2. (rate)1 4  1.0 
= =
 b = 1 (rate)2 2  0.5 
2 = 2b
 b = 1

Comparing expts 1 & 3,

rate  [NH3]a [ClO-]
a
(rate)3 4.8  10-11  3   4 
= =
(rate)1 4.0  10-12  1   1 
12 = 3a(4)
3 = 3a
 a = 1
Orders of reaction with respect to [NH3] and [ClO-] are both 1.

(ii) rate = k [NH3] [ClO-] Reject: “ rate equation = …..”

From Expt 1 (or any expt), 4.0  10−12 = k (1.0  10-4)( 1.0  10-4)
mol1 dm-3 s–1 = k (mol dm-3)2
k = 4.00  10-4 mol−1 dm3 s–1

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2. 2011 PJC MYE P3 Q2(b)
Since P is used in large excess, [P] remains
P and Q react as follows: P + 2Q → R effectively constant throughout the expt as
Note: [P]0 = initial concentration of P(aq) only a small fraction of P has reacted.
 Rate = k [P]a [Q]b
= k’ [Q]b where k’ = k [P]a = constant
Raterate of reaction/mol
of reaction dm–3-3min
/ mol dm min–1-1
Experiment 1
[X]
[P]00 ==1.50
1.50 mol -3
mol dm–3
0.0080

0.0060 ⚫

0.0040 Experiment 2
⚫ [X]
[P]00 = 0.50 mol dm–3-3
mol dm
0.0020 ⚫
⚫
0 [Q(aq)] / mol
[Y(aq)]/mol -3 –3
dmdm
0 0.010 0.020

(i) Using the graph above, determine the order of reaction with respect to each of the
two reactants, [P] and [Q]. Give your reasoning.

(ii) Hence write down the rate equation for the reaction and state the units for the rate
constant.

(i) From the graph of experiment 1 or experiment 2:

Since the graph is a straight line with a positive gradient passing through the
origin, the rate is directly proportional to [Q]
Hence, order of reaction with respect to [Q] is 1 or rate  [Q].

From the graph,

[Q] / mol dm-3 [P]/mol dm-3 Rate / mol dm-3 min-1
0.020 0.50 0.0020
0.020 1.50 0.0060
Or,
[Q] / mol dm-3 [P]/mol dm-3 Rate / mol dm-3 min-1
0.010 0.50 0.0010
0.010 1.50 0.0030
When [P] is x3, rate is also x3.
 order of reaction with respect to [P] is 1 or rate  [P].

(ii) rate = k [P] [Q] { not “rate equation = ….” }

units for k: mol–1 dm3 min–1

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Analysis of Concentration vs Time Data: Finding order by the graphical method + initial rate
3. [N2013 P3/Q5(c)(d)]
(c) Explain the meaning of the following terms
(i) order of reaction
(ii) Half-life

(c) (i) In an experimentally determined rate equation, rate = k[A]m [B]n,

the order of reaction with respect to [A] and [B] is m and n
respectively. The overall order of reaction is (m+n).
A and B are the reactants.

(ii) Half–life is the time taken for the original concentration (or amount) of a
reactant to be halved.

(d) The Harcourt and Esson reaction is that between hydrogen peroxide and acidified
potassium iodide.
H2O2 + 2I– + 2H+ → 2H2O + I2
The rate of reaction can be followed by measuring the amount of iodine produced
after various times, from which the concentration of H2O2, remaining can be
calculated.
The following reaction mixture was prepared.
initial [H+] = 0.200 mol dm–3
initial [I–] = 0.200 mol dm–3
initial [H2O2] = 0.0200 mol dm–3
The following table shows [H2O2] at various times.

Since H+ and I– are used in large excess,

time / s [H2O2] / mol dm–3
[H+] & [I-] remain effectively constant
0 0.0200 throughout the reaction.
80 0.0167 rate = k [H2O2]a [H+]b [I–]c
183 0.0135 = k’ [H2O2]a
315 0.0103 where k’ = k [H+]b [I–]c = constant
490 0.0071
 A plot of [H2O2] vs time graph gives
760 0.0039 the order of reaction w.r.t. [H2O2].

Plot these data on suitable axes and, showing all your working and drawing clearly
any construction lines on your graph, use your graph to determine:
(i) the order of reaction with respect to [H2O2],
(ii) the initial rate, in mol dm–3 s–1.

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(d) (i)

[H2O2] /mol dm–3

0.005

t½ = 330 s t½ = 335 s

time /s
330 665

[1m] correctly labelled axes + appropriate scale

[1m] all points plotted correctly + smooth curve obtained

(i) From the graph,

330 + 335
(t½)1 = 330 s, (t½)2 = 335 s  t½ = = 332.5 s
2
Since half−lives are  constant, order of reaction w.r.t. [H2O2] is 1.

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(d) (ii)

[H2O2] /mol dm–3

 (0, 0.02)

0.005

t½ = 330 s t½ = 335 s

 (450, 0) time /s
330 450 665

[1m] correctly labelled axes + appropriate scale

[1m] all points plotted correctly + smooth curve obtained

(ii) Initial rate =gradient of tangent at t = 0 s (0, 0.2) & (450, 0)

0.02 - 0
= = 4.44  10-5 mol dm-3 s-1
0 - 450

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Further experiments were carried out by changing [H+] and [I–], but keeping the initial
[H2O2] the same as before. The following results were obtained.

Initial [H+] Initial [I–] Initial rate

/ mol dm–3 / mol dm–3 / mol dm–3 s–1
0.400 0.200 8.4  10–5
0.300 0.200 6.3  10–5
0.200 0.100 2.1  10–5

(iii) Determine the orders with respect to [H+] and [Iဓ]. Explain your reasoning.
(iv) Hence write the rate equation for the reaction, and calculate a value for the
rate constant. Include units in your answer.

Expt initial [H2O2] initial [H+] / initial [I−] / mol initial rate /
/ mol dm−3 mol dm−3 dm−3 mol dm−3 s−1

2 0.0200 0.400 0.200 8.4  10−5

3 0.0200 0.300 0.200 6.3  10−5
4 0.0200 0.200 0.100 2.1  10−5

(iii) Let rate = k [H2O2] [H+]b [I–]c

Comparing experiment 2 & 3, rate  [H+]b

b b
8.4  0.4  4 4 Or, When [H+] is x 4/3, rate is
=   =  b =1
6.3  0.3  3  3  also x 4/3.

Hence order of reaction w.r.t. [H+] is 1.

Comparing experiment 2 & 4, rate  [H+][I-]c

1 c
8.4  0.4   0.2  c
=ဓ    ဓဓ 4 = 2 ( 2 ) ဓဓဓc =1
2.1  0.2   0.1 

Hence order of reaction w.r.t. [I–] is 1.

(iv) rate = k [H2O2] [H+] [I–] ( Reject “rate equation = k …..” )

Using expt 2 (or any one expt),

8.4  10-5 = k ( 0.0200 )( 0.400 )( 0.200 )
mol dm-3 s-1 = k (mol dm-3)3
k = 0.0525 mol-2 dm6 s-1

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Combination of half-life method and initial rates method (2013 PJC CommonTest)

4.
NO2 is an intermediate in the industrial synthesis of nitric acid. This reddish-brown toxic
gas has a characteristic sharp, biting odour and is a prominent air pollutant. One
reaction which occurs in air polluted with nitrogen oxides is shown below.
Since NO2 is used in large excess, [NO2] remains
2NO(g) + O2(g) → 2NO2(g)
effectively constant throughout the expt as only a
small fraction of NO2 has reacted.
 rate = k [NO]a [O2]b
= k’ [O2]b where k’ = k [NO]a = constant

The rate of the reaction was followed by measuring the concentration of remaining
oxygen after fixed time intervals. Two experiments were carried out, starting with
different concentrations of nitrogen monoxide. The following results were obtained.

Experiment 1, Experiment 2,
time/ minutes with [NO] = 0.10 mol dm−3 with [NO] = 0.05 mol dm−3
[O2] / mol dm−3 [O2] / mol dm−3
0 0.0050 0.0050
5 0.0031 0.0045
10 0.0019 0.0040
15 0.0011 0.0036
20 0.0007 0.0032
25 0.0005 0.0029
30 0.0004 0.0026

(i) Using the same axes, plot graphs of [O2] against time for the two experiments on the
grid below.
(ii) Use your graphs to determine the order of reaction with respect to O2 and NO, showing
your working clearly.
(iii) Construct a rate equation for the reaction and use it to calculate a value for the rate
constant, giving its units.

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(i) [O2] / mol dm-3
x
0.0050 

0.0045 

0.0040 


0.0035

x

0.0030


 [NO]=0.05 mol dm-3

0.0025

0.0020
x

0.0015

0.00125
x
0.0010

x
0.0005 x
x [NO]=0.10 mol dm-3

0 5 7.0 10 14.015 20 25 30

t1/2 = 7.0 t1/2 = 7.0

Time / min

(ii) From the graph of [NO] = 0.10 mol dm-3,

(t½)1 = 7.0 min Must show construction lines and
(t½)2 = 7.0 min at least 2 half-lives clearly on the graph.

Since half-lives are constant, reaction is first order w.r.t. [O2].

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(i)
x
0.0050  (0, 0.0050)

0.0045 

0.0040 


0.0035

x

0.0030


 [NO]=0.05 mol dm-3

0.0025 
(23.0, 0.0025)

0.0020
x

0.0015

0.00125
x
0.0010

x
0.0005 x
x [NO]=0.10 mol dm-3
(11.5, 0)
 14.0
11.5
0 5 7.0 10 15 20 25 30

t1/2 = 7.0 t1/2 = 7.0

Time / min

(ii) Draw tangents at t=0 on the two curves.

[O2] [NO] Initial rate

/mol dm-3 /mol dm-3 = gradient of tangent at t = 0

(0, 0.0050) & (11.5, 0)

0.0050 0.10 0.0050 - 0
= 4.35  10-4 mol dm-3 min-1
0 -11.5

(0, 0.0050) & (23.0, 0.0025)

0.0050 0.05 0.0050 - 0.0025

= 1.09  10-4 mol dm-3 min-1
0 - 23.0

When [NO] is x2, rate is x4.

 order of reaction w.r.t. [NO] is 2.

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(iii) Rate = k [O2] [NO]2 ( Reject “rate equation = k …..” )

Using [NO] = 0.10 mol dm-3,

4.35  10−4 = k (0.0050)( 0.10)2
mol dm-3 min-1 = k (mol dm-3)3
k = 8.70 mol−2 dm6 min–1

or, Using [NO] = 0.05 mol dm-3,

1.09  10−4 = k (0.0050)( 0.05)2
mol dm-3 min-1 = k (mol dm-3)3
k = 8.72 mol−2 dm6 min–1

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Deduce rate equation from mechanism of reaction or vice-versa

5. Which suggested mechanism are consistent with the experimentally obtained rate equations?

Rate equation Suggested mechanism

slow
1✓ Rate = k1[NO]2[H2] 2NO(g) + H2(g) N2O(g) + H2O(g)
N2O(g) + H2(g)fast N2 (g) + H2O(g)
The slow step involves two
NO molecules and one H2 From the slow step, rate = k [NO]2 [H2]
molecule colliding together.

2 Rate = k2[H2][I2] H2(g) slow 2H(g)

fast
The slow step involves one 2H(g) + I2 2HI(g)
H2 molecule and one I2
molecule colliding together. From the slow step, rate = k [H2]

3 Rate = k3[HBr][O2] 2HBr(g) + O2(g) slow 2HBrO(g)

fast
The slow step involves one 2HBrO(g) + HBr(g) H2O(g) + Br2 (g)
HBr molecule and one O2
molecule colliding together. From the slow step, rate = k [HBr]2 [O2]

A 1 and 2.
B 2 and 3.
C 1, 2 and 3.
D 1 only.

Ans: D

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Energy profile diagram

6. 2015 A level P3 Q1(b)(i) and (ii)

Menthone can be reduced to menthol by hydrogen with a nickel catalyst. The enthalpy change
for the nickel-catalysed reaction, H, is –80 kJ mol–1, and the activation energy is 42 kJ mol–1.

The reduction goes more quickly if the nickel catalyst is replaced by a platinum catalyst.

Draw a fully labelled reaction pathway diagram for the nickel-catalysed reduction.

On the same axes, draw the reaction pathway diagram for the platinum-catalysed reduction.
Label your line clearly.

Energy / kJ mol-1

Ni-catalysed
reaction Ea(Pt-catalysed rxn) is smaller
than Ea (Ni-catalysed rxn) since
the Pt-catalysed rxn is faster.
Ea=+42 H remains unchanged.

reactants

ဓH=-80

Pt-catalysed products
reaction

progress of reaction

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