NSS Chemistry Part 13 Industrial Chemistry - I
NSS Chemistry Part 13 Industrial Chemistry - I
NSS Chemistry Part 13 Industrial Chemistry - I
(aq) + 2 H
+
(aq) + CO
2
(g)
(i) Suggest an experimental method to follow the change in concentration of Br
2
(aq) in the reaction mixture.
Give a reason for your suggestion.
The table below lists the experimental data obtained at a certain temperature:
Run
Volume used / cm
3
Initial rate for the
disappearance of
Br
2
(aq) / mol dm
3
s
1
0.010 M Br
2
(aq) 0.20 M HCO
2
H(aq) H
2
O( )
1 2.0 10.0 8.0
1.2 10
5
2 4.0 10.0 6.0
2.4 10
5
3 8.0 10.0 2.0
4.8 10
5
(ii) Suggest how the initial rate for the disappearance of Br
2
(aq) can be found.
(iii) Why is it necessary to keep the concentration of HCO
2
H(aq) much higher than that of Br
2
(aq)?
(iv) Deduce the order of the reaction with respect to Br
2
(aq).
(v) Suggest how the order of the reaction with respect to HCO
2
H(aq) can be determined.
(9 marks)
20
20. [HKAL 2006 II Q3a]
An experiment is conducted, at 293 K, to study the kinetics of the decomposition of H
2
O
2
(aq) in the presence
of peroxidase, an enzyme.
2H
2
O
2
(aq)
peroxidase
H
2
O(l) + O
2
(g)
(i) Outline a chemical method to follow the change in concentration of H
2
O
2
(aq) in the reaction mixture at
different times (t).
(ii)# The table below lists the results obtained:
t / minutes 0 5 10 20 30 50
[H
2
O
2
(aq)]
(arbitrary units)
46.1 37.1 29.8 19.6 12.3 5.0
By plotting a suitable graph, show that the decomposition is first order with respect to H
2
O
2
(aq). Hence,
calculate the rate constant at 293 K.
(iii) Is it possible to determine experimentally the rate constant for the above decomposition at 353 K? Explain.
(9 marks)
21
21. [HKAL 2008 II 2a]
The gaseous reaction below takes places at 750
o
C in a closed container with a fixed volume.
(g) N O(g) 2H 2NO(g) g) ( H 2
2 2 2
+ +
(i) Suggest an experimental method that can be used to follow the concentration of (g) N
2
in the
reaction mixture. Briefly explain the principle of your suggested method.
(ii) The table below lists three sets of experimental data of the reaction at 750
o
C:
Experiment
Initial concentration / mol dm
3
Initial rate for the
formation of g) ( N
2
/ mol
-1 -3
s dm
(g) H
2
NO(g)
1 0.010 0.0250 0.500
2 0.005 0.0250 0.250
3 0.010 0.0125 0.125
Deduce the rate equation for the reaction, and calculate its rate constant at 750
o
C.
(iii) Is the reaction an elementary reaction? Explain.
(6 marks)
22. [HKAL 2009 II 2a]
An experiment was devised to study the kinetics of the following acid
Four runs of the experiment were conducted at the same temperature, and the reaction mixtures used were
prepared according to the table below:
Run
0.02 M I
2
(aq)
1 50.0
2 50.0
3 50.0
4 50.0
In each run, 10.0 cm
3
of the reaction mixture was withdrawn at regular time intervals and added to excess
NaHCO
3
(aq). When effervescence subsided, the resulting mixture was titrated against
using starch solution as indicator. The graph below shows the plot of the titre against time for each run.
(i) What is the purpose of adding the reaction mixture to excess NaHCO
(ii) Deduce the reaction order with respect to Iodine.
(iii) Deduce, by plotting another graph, the reaction order with respect to propanone.
(iv) Suggest how the reaction order with respect to H
22
An experiment was devised to study the kinetics of the following acid-catalysed reaction:
Four runs of the experiment were conducted at the same temperature, and the reaction mixtures used were
prepared according to the table below:
Volume used /cm
3
1.0 M
CH
3
COCH
3
(aq)
H
2
O()
5.0 20.0
10.0 15.0
15.0 10.0
20.0 5.0
of the reaction mixture was withdrawn at regular time intervals and added to excess
(aq). When effervescence subsided, the resulting mixture was titrated against
using starch solution as indicator. The graph below shows the plot of the titre against time for each run.
What is the purpose of adding the reaction mixture to excess NaHCO
3
(aq) before each titration?
Deduce the reaction order with respect to Iodine.
Deduce, by plotting another graph, the reaction order with respect to propanone.
Suggest how the reaction order with respect to H
+
(aq) can be determined.
catalysed reaction:
Four runs of the experiment were conducted at the same temperature, and the reaction mixtures used were
1.0 M H
2
SO
4
(aq)
25.0
25.0
25.0
25.0
of the reaction mixture was withdrawn at regular time intervals and added to excess
(aq). When effervescence subsided, the resulting mixture was titrated against standard Na
2
S
2
O
3
(aq)
using starch solution as indicator. The graph below shows the plot of the titre against time for each run.
(aq) before each titration?
Deduce, by plotting another graph, the reaction order with respect to propanone.
(11 marks)
23
24
Activation Energies
23. [HKAL 1989 I Q2c]
The Maxwell-Boltzmann distribution of molecular speeds of a gas at 1250 K is shown in the diagram below:
speeds/ ms
-1
percentage
of
molecules
(i) Sketch on the diagram a graph of the probable distribution of molecular speeds of the same gas at 298K.
(ii) Explain why there is a distribution of speeds.
(4 marks)
(i)
(ii)
25
24. [HKAL 1991 II Q3a]
For the reaction 2XY(g) X
2
(g) + Y
2
(g),
the rate constant is 3.91 10
-4
mol
-1
dm
3
s
-1
at 370
o
C and 4.05 10
-2
mol
-1
dm
3
s
-1
at 470
o
C.
Generally the rate constant of a reaction is related to the temperature by k = A exp(-E
a
/RT).
Calculate
(i) the activation energy,
(ii) the rate constant at 450
o
C.
[Gas constant, R = 8.314 JK
-1
mol
-1]
(6 marks)
25. [HKAL 1992 I Q2e]
The diagram below gives the Maxwell-Boltzmann energy distribution of a system of molecules at two
temperatures:
Ea
Energy
Relative no. of
molecules with a
particular energy
T1
T2
where T2 > T1 and Ea is the activation
energy of a reaction
What do the shaded areas of the curves represent and why are they different at different temperatures?
(2 marks)
The shaded area under either one of these curves corresponds to the amount of molecules that collide with
kinetic energy which is greater than the activation energy (Ea).
As temperature increases, the average kinetic energy of the molecules will increase, therefore, the amount of
molecules with kinetic energy which is greater than the activation energy (Ea) also increase.
26
26. [HKAL 1996 I Q1b]
Carbon-14,
14
C, is radioactive, emitting particles.
(i)# Write an equation for the decay of
14
C.
(ii) A charcoal sample from the ruins of an ancient settlement was found to have a
14
C/
12
C ratio 0.60 times that
found in living organisms.
(1) Explain why the
14
C/
12
C ratio in the charcoal sample is smaller than that in living organisms.
(2) Given that the half-life for the decay of
14
C is 5730 years, calculate the age of the charcoal
sample.
Note: The integrated form of the rate expression for radioactive decay can be represented by the
following equation:
log
.
10
1
2
0 301 N
N t
t
o
t
=
where N
o
is the initial number of radioactive nuclei;
N
t
is the number of radioactive nuclei at time t;
t
1
2
is the half-life for the decay.
(iii) All radioactive decay has zero activation energy. Comment on the effect of temperature upon the rate of
decay.
(5 marks)
(i)
(ii) (1)
(2)
(iii)
27
27. [HKAL 1998 II Q3a]
The table below lists the rate constants, k, at different temperatures, T, for the first order decomposition of a
dicarboxylic acid, CO(CH
2
CO
2
H)
2
, in aqueous solution:
CO(CH
2
CO
2
H)
2
(aq)
CH
3
COCH
3
(aq) + 2CO
2
(g)
T /K 273 293 313 333 353
k /s
-1
2.46 10
-5
4.75 10
-4
5.76 10
-3
5.48 10
-2
?
(i) Determine the activation energy for the reaction by plotting an appropriate graph.
(ii) Estimate the rate constant of the reaction at 353 K and hence calculate the half-life of the reaction at
the same temperature.
(iii) Suggest a method to monitor the progress of the reaction.
(9 marks)
28
28. [HKAL 1998 II Q3b]
The exothermic reaction
E(g) E(g) (1)
is a single stage reaction.
(i) Sketch curves to show the distribution of molecular kinetic energy of the reactant, E(g), at two
different temperatures.
(ii) With reference to your answer in (i), explain why the rate of reaction (1) increases with temperature.
(iii) In the presence of a catalyst, C, reaction (1) will proceed at a faster rate via the following mechanism:
E(g) + C(g) EC(g)
EC(g) C(g) + E(g) (EC is the reaction intermediate.)
Sketch labeled energy profiles for the conversion of E(g) to E(g), with and without the catalyst.
Explain why reaction (1) proceeds faster in the presence of the catalyst.
(8 marks)
(i)
29
29. [HKAL 2000 I Q7b]
Without giving any experimental detail, outline what measurements have to be taken in order to determine
the activation energy of a reaction.
(3 marks)
Keeping the (initial) concentrations of the reagents unchanged, carry out the experiment at different
temperatures and determine the corresponding (initial) rate.
(ii)
(iii)
30
30. [HKAL 2002 II Q3a]
An experiment was conducted to study the hydrolysis of benzenediazonium chloride at 298K and 1 atm.
C
6
H
5
N
2
+
Cl
-
(aq) + H
2
O(l) C
6
H
5
OH(aq) + N
2
(g) + HCl(aq)
The progress of the hydrolysis was followed by measuring the volumes of N
2
(g), v, liberated at different time, t.
The table below lists the experimental results.
t / s 0 5 10 15 25 3600 5400
v / cm
3
0 33 56 73 92 110 110
a. By plotting a suitable graph, show that the hydrolysis is first order with respect to benzenediazonium
chloride.
b. Using your graph in (a), determine the rate constant of the hydrolysis at 298K.
c. Suggest how the activation energy of the hydrolysis can be determined.
(You are not required to give the experimental details.)
(8 marks)
31
32
31. [HKAL 2004 I Q3a]
a Consider the following system, which comprises two single step reactions.
(k
1
and k
1
are the rate constants.)
(i) Write the respective rate equations for the forward and backward reactions.
(ii) Sketch a labeled energy profile for the forward reaction.
(iii) Predict with explanation, whether k
1
or k
1
will increase to a greater extent when the temperature of the
system is increased.
(4 marks)
32. [HKAL 2008 I 3a(iii)]
Which one of the following graphs represents the distribution of molecular speeds of one mole of a gas at
two different temperatures T
1
and T
33. [HKAL 2010 I 1b]
A student made the following remark:
The rate of an elementary gaseous reaction increases with temperature because the average kinetic energy of
the reactant molecules increases with temperature
Is the explanation provided by the student regarding the increase in reaction rate appropriate ?
Elaborate your answer.
Ans: C
33
Which one of the following graphs represents the distribution of molecular speeds of one mole of a gas at
and T
2
, where T
2
> T
1
?
A student made the following remark:
The rate of an elementary gaseous reaction increases with temperature because the average kinetic energy of
the reactant molecules increases with temperature.
Is the explanation provided by the student regarding the increase in reaction rate appropriate ?
Which one of the following graphs represents the distribution of molecular speeds of one mole of a gas at
The rate of an elementary gaseous reaction increases with temperature because the average kinetic energy of
Is the explanation provided by the student regarding the increase in reaction rate appropriate ?
(3 marks)
34
Catalysts
34. [HKAL 1991 I Q2b]
The energy profiles of the reaction
A(g) + B(g) C(g)
under two different catalysts X and Y are represented below.
Reaction coordinate
Energy
System with catalyst X
A, B
C
Reaction coordinate
Energy
System with catalyst Y
A, B
C
a. What is the effect of increasing temperature on the equilibrium of each system?
b. What is the effect of decreasing pressure on the equilibrium of each system?
c. Compare the effect of increasing temperature on the rate of reaction in the two systems.
d. Why could the use of a different catalyst change the order of the reaction?
(7 marks)
35
35. [HKAL 1994 Essay]
Write an essay to account for the fact that at 750K and 200 atmosphere pressure, the energetically favourable
formation of ammonia
N
2
(g) + 3H
2
(g) 2NH
3
(g)
proceeds very slowly, but in the presence of an iron surface it proceeds at a much faster rate.
(20 marks)
36
36. [HKAL 2002 I Q7b]
Devise an experiment, using chemicals and apparatus commonly available in a school laboratory, to show
that the reaction of peroxodisulphate(VI) ions with iodide ions can be catalyzed by iron(III) ions.
S
2
O
8
2-
(aq) + 2I
-
(aq) 2SO
4
2-
(aq) + I
2
(aq)
(5 marks)