Hkdse Chemistry - A Modern View (Chemistry) : Coursebook 4A Suggested Answers

Aristo Educational Press Ltd.
2010
HKDSE CHEMISTRY A Modern View

(Chemistry)
Coursebook 4A
Suggested answers
Chapter 38 Rate of chemical reaction Page
Number
Class Practice 1
Chapter Exercise 4
Chapter 39 Factors affecting rate of reaction
Class Practice 8
Chapter Exercise 11
Chapter 40 Molar volume of gases at room temperature and pressure
(r.t.p.)
Class Practice 14
Chapter Exercise 17
Part Exercise 20
Chapter 41 Dynamic equilibrium
Class Practice 25
Chapter Exercise 27
Chapter 42 Equilibrium constant
Class Practice 30
Chapter Exercise 33
Chapter 43 The effect of changes in concentration and temperature on
chemical equilibria
Class Practice 37
Chapter Exercise 40
Part Exercise 43
HKDSE CHEMISTRY A Modern View (Chemistry) Coursebook 4A
Aristo Educational Press Ltd. 2010 1
Chapter 38 Rate of chemical reaction

Class Practice

A38.1
(a) H
2
+ O
2
(ignition)
(b) K + H
2
O
(c) AgNO
3
solution + NaCl solution

A38.2
(a) (i) Average rate of decrease in mass (g) of Mg =
90s
g 0.36
= 4.0 10
3
g

s
1

(ii) Average rate of decrease in no. of moles of Mg
=
1
1 3
mol g 24.3
s g 10 4.0
= 1.65 10
4
mol s
1

According to the equation, 1 mole of Mg reacts with 2 moles of HCl.
average rate of decrease in concentration of HCl
=
3
1 4
dm
1000
50.0
s mol 10 1.65

2 = 6.60 10
3
mol dm
3
s
1

(Assume the volume of resultant solution to be 50.0 cm
3
.)
(iii) Average rate of increase in volume of H
2
=
s 90
cm 360
3
= 4.0 cm
3
s
1

(b) No. Rate varies during the whole course of the reaction.

A38.3
(a) The rate at A is the slope of the tangent to the curve at this point.
Instantaneous rate at A (t ~ 0) =
min 0 1.6
dm mol 0 6.0
3

= 3.75 mol dm
3
min
1

The rate at B is the slope of the tangent to the curve at this point.
Instantaneous rate at B =
min 0 . 1 3.0
dm mol 7 . 2 5.1
3

= 1.2 mol dm
3
min
1

The rate at C is the slope of the tangent to the curve at this point.
Instantaneous rate at C is zero as the line is horizontal.
(b) At the start of the reaction, the tangent is the steepest. This indicates that the rate
of reaction is the highest at this time. As the reaction proceeds, the slope of the
tangents decreases (point B), until it becomes zero (point C). This indicates that
the rate of reaction becomes lower and lower, until it reaches zero when the
reaction finishes.
(c) Average rate of the reaction =
min 7.0
dm mol 4 5.
3
= 0.77 mol dm
3
min
1

A38.4
(a) Pipette (10.0 cm
3
type)
(b) To quench the reaction. Since hydrochloric acid is used as a catalyst to speed up
the reaction, excess sodium hydrogencarbonate is used to remove the acid and
stop the reaction.
NaHCO
3
(aq) + HCl(aq) NaCl(aq) + CO
2
(g) + H
2
O(l)
(c) (i) 2S
2
O
3
2
(aq) + I
2
(aq) S
4
O
6
2
(aq) + 2I
(aq)
(ii) No. of moles of Na
2
S
2
O
3
(aq) used
= 0.005
1000
6.5
mol = 3.25 10
5
mol
From the equation in (i), mole ratio of S
2
O
3
2
: I
2
= 2: 1.
no. of moles of I
2
present =
2
mol 10 3.25
5
= 1.625 10
5
mol
Concentration of I
2
in the third portion
=
3
5
10 10.0
10 1.625
mol dm
3
= 1.625 10
3
mol dm
3

(d)

A38.5
It is because SO
2
is very soluble in water. The SO
2
generated cannot cause an obvious
volume or pressure change.

A38.6
(a)
Time of reaction t (min) 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Mass of CO
2
produced (g) 0 0.80 1.50 2.05 2.50 2.85 3.05 3.25 3.40
Time of reaction t (min) 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
Mass of CO
2
produced (g) 3.51 3.59 3.64 3.67 3.69 3.70 3.70 3.70 3.70

C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

I
2

(
m
o
l

d
m
3
)

0
Time (min)
(b)

(c) Average rate of reaction =
(min) reaction of time total
(g) produced CO of mass total 2

=
min 7.0
g 3.70
= 0.53 g min
1

A38.7
(a) Since O
2
is the only gas formed, the progress of reaction can be followed by
measuring the volume of O
2
gas collected in a gas syringe at regular time
intervals.
(Use a pipette to withdraw a small but known volume of the reaction mixture and
put it in a conical flask. Quench the reaction by adding excess dilute sulphuric
acid which removes MnO
2
catalyst. Then titrate the small portion of reaction
mixture with standard acidified potassium permanganate solution until the end
point has been reached. Repeat the withdrawal and titration of small portions of
the reaction mixture at regular time intervals. This method measures the change
in the concentration of H
2
O
2
with time.)
(b) Br
2
(aq) is brown in colour. Its colour intensity decreases as Br
2
(aq) is converted
to colourless Br
(aq) during the reaction. The change in colour intensity of the

reaction mixture can be followed by a colorimeter.
(As H
+
(aq) ions are formed during the course of reaction, there will be a change
in pH of the resultant solution. This change in pH can be followed by a pH
meter.)
(c) As there is a decrease in the number of moles of the gases at the product side, the
pressure inside the closed container will change. This can be followed by a
pressure sensor connected to a data-logger.
Time (min)
End of reaction
Total mass of CO
2

produced
Total time of
reaction
M
a
s
s

o
f

C
O
2

p
r
o
d
u
c
e
d

(
g
)

Chapter 38 Rate of chemical reaction

Chapter Exercise

1. rates
2. quickly
3. verage, nstantaneous, urve
4. Average, product, reactant
5. Instantaneous rate, tangent
6. Rate curve
7. steep, steep, horizontal
8. Initial, fastest
9. experiments
10. (a) titrimetric, quenched
(b) olume, pressure, ass, colour, transmittance
11. quench, cooling, diluting, removing
12. data-logger
13. colorimeter
14. C
15. A
16. A
17. B
18. D
19. D
20. D
21. A
22. C
23. B
24. D

25. (a) No. of moles of KMnO
4
used = 0.05
1000
25
mol = 0.00125 mol
No. of moles of K
2
C
2
O
4
used = 0.125
1000
25
mol = 0.003125 mol
Mole ratio of KMnO
4
: K
2
C
2
O
4
= 0.00125 : 0.003125 = 1 : 2.5
The equation indicates that the mole ratio of KMnO
4
: K
2
C
2
O
4
= 2 : 5
= 1 : 2.5.
So, none is in excess. They just react completely.
(b) Since all K
2
C
2
O
4
reacted, its molarity changed from 0.125 M to 0 M in 30 s.
Average rate of decrease in molarity of C
2
O
4
2
=
s 30
M 0.125
= 4.17 10
3
M
s
1

(c) MnO
4
was completely reduced to Mn

2+
in 30 seconds.
Average rate of decrease in molarity of KMnO
4
=
s 30
M 0.05
= 1.67 10
3
M
s
1

From the equation, mole ratio of MnO
4
: Mn
2+
= 1 : 1.
average rate of increase in molarity of Mn
2+
in the mixture
= 1.67 10
3
M s
1

(d) From the equation, mole ratio of MnO
4
: CO
2
= 2 : 10.
no. of moles of CO
2
formed in 30 s = 0.00125 mol 5 = 0.00625 mol
Mass of CO
2
formed in 30 s
= 0.00625 mol (12.0 + 16.0 2) g mol
1
= 0.275 g
Average rate of formation of CO
2
=
s 30
g 0.275
= 0.00917 g s
1

26. (a) (i) Average rate of decrease of CaCO
3
=
s 120
g 2.0
= 0.0167 g s
1

(ii) Average rate of decrease of CaCO
3
in mol s
1

=
3 0 . 16 0 . 12 1 . 40
0167 . 0
+ +
mol s
1
= 1.67 10
4
mol s
1

From the equation, mole ratio of CaCO
3
: HCl = 1 : 2.
average rate of decrease of HCl in mol dm
3
s
1

=
1000
50
2 10 67 . 1
4

mol dm
3
s
1

= 0.00668 mol dm
3
s
1

(b) (i) No. of moles of CaCO
3
used =
3 0 . 16 0 . 12 1 . 40
0 . 2
+ +
mol = 0.0200 mol
No. of moles of HCl used = 2
1000
50
mol = 0.100 mol
Mole ratio of CaCO
3
: HCl = 1 : 5
From the equation, mole ratio of CaCO
3
: HCl = 1 : 2.
hydrochloric acid is in excess.
(ii) From the equation, mole ratio of CaCO
3
: CO
2
= 1 : 1.
rate of production of CO
2
in g s
1

= 1.67 10
4
(12.0 + 16.0 2) g s
1
= 0.00735 g s
1

27. (a) 150 cm
3

(b) At about the 22
nd
minute
(c) Average rate of O
2
produced =
min 22
cm 150
3
= 6.82 cm
3
min
1

(d) From the graph, about 112 cm
3
of O
2
were produced at the 4
th
minute.
When the reaction completed, 150 cm
3
of O
2
were produced.
percentage of H
2
O
2
decomposed at the 4
th
minute =
150
112
100% = 74.7%
(e)

The tangent at the second minute is steeper (has a greater value) than that at
the sixth minute. This suggests that the instantaneous reaction rate at the
second minute is higher than that at the sixth minute.
(f) The graph begins steeply, and slowly levels off until it is horizontal. This is
because as the reaction proceeds, the concentration of the reactant is
decreasing with time, and hence the reaction rate becomes lower and lower.
When all the reactant has turned into products, the rate of reaction becomes
zero.
(g)

28. (a)

(b) (i) It is because carbon dioxide gas escaped from the flask.
(ii) CaCO
3
(s) + 2HCl(aq) CaCl
2
(aq) + H
2
O(l) + CO
2
(g)
(c) It is to prevent the acid spray from spilling out of the conical flask. (Acid
spray will be trapped by the cotton wool.) But it allows the escape of carbon
dioxide gas.
(d) As seen from the curve, the initial rate is lower than expected. This is
because the solution has to be saturated with carbon dioxide gas before the
collected gas
gas syringe
string
hydrogen peroxide solution
Time (min)
V
o
l
u
m
e

o
f

O
2

(
c
m
3
)

Time (min)
L
o
s
s

i
n

m
a
s
s

(
g
)

gas can fully escape from the solution.
(e) 0.540 g
(f) No. of moles of CO
2
formed =
2 0 . 16 0 . 12
540 . 0
+
mol = 0.0123 mol

From the equation in (b)(ii), mole ratio of HCl : CO
2
= 2 : 1.
no. of moles of HCl needed = 0.0123 2 mol = 0.0246 mol
Molarity of HCl =
1000
25
0.0246
M = 0.984 M
29. (a) S
2
O
3
2
(aq) + 2H
+
(aq) SO
2
(g) + H
2
O(l) + S(s)
(b) 1. Gas bubbles evolve and a pungent choking smell can be detected. This
is due to the production of colourless SO
2
gas.
2. The solution becomes cloudy. This is due to the production of creamy
yellow precipitate of sulphur.
(c) As the reaction goes on, more and more sulphur precipitate is formed. When
the solution turns more and more cloudy, the transmittance of light through
the solution also becomes lower. To measure the rate of the reaction, we can
measure the time taken for the cloudy solution to blot out a reference mark
under the beaker of the reaction mixture. The time for blot out is inversely
proportional to the average rate of reaction.

30. As nitrogen (N
2
) is the only gaseous product formed in the reaction, the rate
of reaction can be followed by measuring the volume of N
2
formed with
time.
The volume of N
2
can be measured by using a gas syringe.
If the reaction is performed in a closed container, the rate of reaction can be
followed by measuring the increase in pressure with time.
The pressure inside the closed container can be measured by using a
pressure sensor connected to a data-logger.
If the reaction mixture is put on an electronic balance, the rate of reaction
can be followed by measuring the loss in mass (as a result of the escape of
N
2
) of the mixture with time.


Class Practice

A39.1
1. (a) 2.0 M HCl(aq)
(b) Yes. This is because same mass of zinc strip is used up each time.
(c)

2. (a) The reaction of Mg with 2.0 M hydrochloric acid.
Hydrochloric acid is a strong acid while ethanoic acid is a weak acid. The
H
+
(aq) concentration in 2.0 M HCl(aq) is higher than that in 2.0 M
CH
3
COOH(aq). Since reaction rate increases with an increase in
concentration of a reactant, reaction in 2.0 M HCl(aq) takes a shorter time
to complete.
(b) No. of moles of HCl(aq) and CH
3
COOH(aq) used = MV =
100
50
0 . 2 mol =
0.10 mol
No. of moles of Mg used =
3 . 24
1 . 0
mol = 4.12 10
3
mol
The equation of reaction is
Mg(s) + 2H
+
(aq) Mg
2+
(aq) + H
2
(g)
Mole ratio of Mg : H
+
= 1:2
The amount of HCl(aq) used is in great excess and Mg is the limiting
reagent. As the same mass of Mg is used in the two reactions, the same
amount of hydrogen gas is produced.
0.1 M
Time of reaction (min)
V
o
l
u
m
e

o
f

h
y
d
r
o
g
e
n

c
o
l
l
e
c
t
e
d

(
c
m
3
)

A39.2
(a) 2MnO
4
(aq) + 5C
2
O
4
2
(aq) + 16H
+
(aq) 2Mn
2+
(aq) + 10CO
2
(g) + 8H
2
O(l)
(b) From purple to colourless / disappearance of purple colour.
(c) Add ice to lower the temperature of the water in the water bath.
(d) The average rate of reaction is inversely proportional to the time of the reaction.
That is, average rate
time
1
.
(e)

A39.3
(a) CaCO
3
(s) + 2H
+
(aq) Ca
2+
(aq) + H
2
O(l) + CO
2
(g)
(b) 275 cm
3

(c) The actual volume of CO
2
collected is less than expected. The difference is 85
cm
3
(360 275 cm
3
). It is because some of the carbon dioxide has dissolved in
water and the powdered calcium carbonate used is not pure.
(d)

Temperature (C)
Time
1
(s
1
)
Time (min)
V
o
l
u
m
e

o
f

c
a
r
b
o
n

d
i
o
x
i
d
e

g
a
s

(
c
m
3
)

A
B
(e) As carbon dioxide is formed as the only gaseous product, we can carry out the
reaction in a closed system. The increase in pressure inside the apparatus at
different times can be monitored using a pressure sensor connected to a
data-logger.
As carbon dioxide is formed, it is allowed to escape from the reaction flask. The
decrease in mass of the reaction mixture at different times can be monitored by
weighing with an electronic balance.

A39.4
(a) MnO
2
(s) formed acts as a catalyst in the decomposition of hydrogen peroxide.
(b) Sulphuric acid is used to remove the MnO
2
(s) catalyst in the reaction mixture.
This is to quench the decomposition of H
2
O
2
and allow the analysis of H
2
O
2

concentration in the samples at different time intervals.
Sulphuric acid is also used to acidify the potassium permanganate solution for
the redox reaction with H
2
O
2
.
(c) 6H
+
(aq) + 2MnO
4
(aq) + 5H
2
O
2
(aq) 2Mn
2+
(aq) + 5O
2
(g) + 8H
2
O(l)
(d) and (e)

without MnO
2
(s) catalyst
with MnO
2
(s)

catalyst
Time (min)
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

H
2
O
2

(
M
)


Chapter Exercise

1. oncentration, urface area, emperature, atalyst
2. collide, effective collisions
3. effective
4. oncentration, urface area, emperature, atalyst
5. Catalysts
6. Enzymes
7. A
8. A
9. D
10. B
11. C
12. B
13. D
14. C
15. A
16. B

17. (a)
Sample
Concentration of
Na
2
S
2
O
3
(aq) (M)
Volume of
Na
2
S
2
O
3
(aq)
used (cm
3
)
Volume of
distilled
water added
(cm
3
)
1 0.100 20 0
2 0.075 15 5
3 0.050 10 10
4 0.025 5 15
(b) The amount of HCl(aq) added was the same in all the experiments.
All the experiments were carried out at room conditions.
(c)

Time
1
(s
1
)
Conc. of Na
2
S
2
O
3
(aq) (M)

(d) From the graph, when the rate of reaction was 0.015 s
1
, the concentration
of Na
2
S
2
O
3
(aq) was 0.058 M.
(e) Based on the graph, the rate of the reaction increased when there was an
increase in concentration of Na
2
S
2
O
3
(aq).
(f) When we stopped the stopwatch, there was just enough sulphur precipitate
produced in the solution to mask the cross. The reaction kept going to
produce more sulphur.

18. (a) Zn(s) + 2HCl(aq) ZnCl
2
(aq) + H
2
(g)
(b) No. of moles of Zn used =
0 . 65
1
mol = 0.0154 mol
No. of moles of HCl(aq) present = MV = 2.0
1000
50
mol = 0.100 mol
From the equation in (a), mole ratio of Zn : HCl = 1 : 2
0.0154 mol of Zn requires only 0.0154 2 mol = 0.0308 mol of HCl(aq) for
reaction, so HCl(aq) is in excess. Zn is the limiting reactant.
(c) (i) Initial rate of experiment 2 is higher than that of experiment 1 because
of larger surface area of zinc in the form of powder.
(ii) Volume of H
2
formed is unchanged / the same because the same mass
of Zn is used.
(d)

19. (a) S
2
O
3
2
(aq) + 2H
+
(aq) S(s) + SO
2
(g) + H
2
O(l)
(b) This is the reacting temperature of the experiment. It is necessary to note it
for comparison.
(c) As the reaction proceeds, more and more sulphur precipitate is produced
until it is enough to blot out the cross.
(d) The smell comes from the sulphur dioxide gas produced.
(e) Immerse the small beaker containing the thiosulphate solution in an
ice-water bath.
(f) The longer the time to blot out the cross, the slower the reaction. (The
shorter the time to blot out the cross, the faster the reaction.)
the reciprocal of time (i.e.
time
1
) is a measure of reaction rate.
V
o
l
u
m
e

o
f

H
2
(
g
)

Time
3
(g)

20.
In order to investigate the effect of temperature on rate of chemical
reactions, several experiments should be done. In all the experiments, same
mass of marble chips is allowed to react with same volume but excess of 2
M hydrochloric acid at different temperatures.
As the reaction involves the production of gaseous product, carbon dioxide,
we can collect the gas with a gas syringe and measure the volume of
carbon dioxide gas produced with time.
Knowing the volume of carbon dioxide gas produced with time, we can find
out the rate of carbon dioxide gas produced. By plotting a graph of reaction
rate against temperature, we can understand the effect of temperature on
rate of chemical reactions.
Temperature (C)
Time
1

(r.t.p.)

Class Practice

A40.1
Mg(s) + 2HCl(aq) MgCl
2
(aq) + H
2
(g)
No. of moles of Mg used =
1
mol g 24.3
g 243 . 0

= 0.01 mol
From the equation, mole ratio of Mg : H
2
= 1 : 1,
molar volume of hydrogen at r.t.p. =
mol 0.01
cm 240
3
= 24 000 cm
3
mol
1
or 24.0
dm
3
mol
1

A40.2
1. No. of moles of Cl
2
molecules
=
1 3
3
mol cm 000 24
cm 120

= 0.0050 mol
No. of Cl
2
molecules
= 0.0050 mol 6.02 10
23
mol
1

= 3.01 10
21

2. (a) Volume of nitrogen = 0.1 mol 24.0 dm
3
mol
1

= 2.4 dm
3

(b) No. of moles of CO
2
=
1 23
21
mol 10 02 . 6
10 41 . 2

= 4.00 10
3
mol
Volume of CO
2
= 4.00 10
3
mol 24.0 dm
3
mol
1

= 0.096 dm
3
(96.0 cm
3
)

A40.3
1. From the equation, mole ratio of CO : CO
2
= 2 : 2 = 1 : 1
No. of moles of CO needed = 0.20 mol
volume of CO needed = 0.20 mol 24.0 dm
3
mol
1
= 4.8 dm
3
(4800 cm
3
)
From the equation, mole ratio of O
2
: CO
2
= 1 : 2
No. of moles of O
2
needed = 0.10 mol
volume of O
2
needed = 0.10 24.0 dm
3
= 2.4 dm
3
(2400 cm
3
)

2. (a) (i) 2SO
2
(g) + O
2
(g) 2SO
3
(g)
(from equation) 2 moles 1 mole 2 moles
(By Avogadros Law) 2 volumes 1 volume 2 volumes
15.0 cm
3
? cm
3
? cm
3

By simple proportion, volume of O
2
required =
2
1
0 . 15 cm
3
= 7.5 cm
3

(ii) Volume of SO
3
formed =
1
1
0 . 15 cm
3
= 15.0 cm
3

(b) From the equation, volume ratio of SO
3
: SO
2
= 1 : 1
volume of SO
2
needed = 24.0 cm
3

From the equation, volume ratio of SO
3
: O
2
= 2 : 1
volume of O
2
needed =
2
1
0 . 24 cm
3
= 12.0 cm
3

3. In 100 dm
3
of town gas, volume of H
2
= 49.0 dm
3
, volume of CH
4
= 28.5 dm
3
,
volume of CO = 3.0 dm
3
.
For H
2
and by applying Avogadros Law,
2H
2
(g) + O
2
(g) 2H
2
O(l)
volume ratio 2 1
49.0 dm
3
? dm
3

volume of O
2
needed to react with H
2
=
2
0 . 49
dm
3
= 24.5 dm
3

For CH
4
and by applying Avogadros Law,
CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l)
volume ratio 1 2
28.5 dm
3
? dm
3

volume of O
2
needed to react with CH
4
= 28.5 2 dm
3
= 57.0 dm
3

For CO and by applying Avogadros Law,
2CO(g) + O
2
(g) 2CO
2
(g)
volume ratio 2 1
3.0 dm
3
? dm
3

volume of O
2
needed to react with CO =
2
0 . 3
dm
3
= 1.5 dm
3

Total volume of O
2
needed = 24.5 + 57.0 + 1.5 dm
3
= 83.0 dm
3

A40.4
1. No. of moles of nitrogen gas =
0 . 24
464 . 0
mol = 0.0193 mol
Mass of nitrogen gas = 0.0193 (14.0 2) g = 0.540 g
2. (a) No. of moles of oxygen =
23
21
10 02 . 6
10 204 . 1
mol = 2.00 10
3
mol
Volume of oxygen (at r.t.p.) = 2.00 10
3
24.0 dm
3
= 0.0480 dm
3
(48.0
cm
3
)
(b) Mass of oxygen = 2.00 10
3
(16.0 2) g mol
1
= 0.0640 g

A40.5
1. No. of moles of CO
2
formed at r.t.p. =
000 24
360
mol = 0.0150 mol
From the equation, mole ratio of NaHCO
3
: CO
2
= 2 : 1,
no. of moles of NaHCO
3
needed = 0.0150 2 mol = 0.0300 mol
mass of NaHCO
3
needed = 0.0300 (23.0 + 1.0 + 12.0 + 16.0 3) g = 2.52 g
2. No. of moles of Mg used =
3 . 24
43 . 2
mol = 0.100 mol
No. of moles of HCl(aq) used = 2.0 (
1000
30
) mol = 0.060 mol
Mg(s) + 2HCl(aq) MgCl
2
(aq) + H
2
(g)
From the equation, mole ratio of Mg : HCl = 1 : 2,
0.060 mol of HCl(aq) needs
2
060 . 0
= 0.030 mol of Mg for complete reaction.
Since Mg is in excess, HCl is the limiting reactant.
From the equation, mole ratio of HCl : H
2
= 2 : 1,
no. of moles of H
2
produced =
2
060 . 0
mol = 0.030 mol
Volume of H
2
produced at r.t.p. = 0.030 24.0 dm
3
= 0.72 dm
3

(r.t.p.)

Chapter exercise

1. molar
2. dm
3
mol
1

3. room temperature and pressure, 25, 1, dm
3
mol
1
, cm
3
mol
1

4. molar
5. Avogadros, same
6. volume, temperature, pressure
7. B
8. A
9. A
10. B
11. A
12. B
13. C
14. C
15. C
16. D
17. D
18. (a) No. of moles of propane present =
8) 1.0 3 (12.0
88 . 0
+
mol = 0.0200 mol
Molar volume of propane =
0200 . 0
465
cm
3
mol
1
= 23 250 cm
3
mol
1
(23.25
dm
3
mol
1
)
(b) C
3
H
8
(g) + 5O
2
(g) 3CO
2
(g) + 4H
2
O(l)
From the equation, mole ratio of C
3
H
8
: CO
2
= 1 : 3,
no. of moles of CO
2
formed = 0.0200 3 mol = 0.0600 mol
Volume of CO
2
obtained = 0.0600 23 250 cm
3
= 1395 cm
3

19. (a) No. of moles of SO
2
=
000 24
250
mol = 0.0104 mol
(b) No. of moles of C
2
H
4
=
0 . 24
85 . 0
mol = 0.0354 mol

20. No. of moles of N
2
=
000 24
750
mol = 0.0313 mol
No. of moles of O
2
=
000 24
500
mol = 0.0208 mol
total no. of moles of gases = 0.0313 + 0.0208 mol = 0.0521 mol
(Total volume of gases = (750 + 500) cm
3
= 1250 cm
3
Total no. of moles of gases =
000 24
1250
mol = 0.0521 mol)

21. (a) Volume of H
2
S = 0.5 24.0 dm
3
= 12.0 dm
3

(b) Volume of Cl
2
= 4.2 24.0 dm
3
= 100.8 dm
3

(c) I
2
is a solid at r.t.p.
Density of solid I
2
= 4.93 g cm
3

Mass of 10 mol of I
2
= 10 127 g = 1270 g
Volume of 10 mol of I
2
=
93 . 4
1270
cm
3
= 257.6 cm
3

22. (a) No. of moles of H
2
S =
32.1) 2 (1.0
41 . 3
+
mol = 0.100 mol
No. of moles of Cl
2
=
2) (35.5
10 . 7
mol = 0.100 mol

From the given equation, mole ratio of H
2
S : Cl
2
= 1 : 1,
both reactants are all used up.
As the number of moles of H
2
S : Cl
2
: HCl = 1 : 1 : 2,
no. of moles of HCl formed = 0.100 2 mol = 0.200 mol
mass of HCl = 0.200 (1.0 + 35.5) g = 7.30 g
Volume of HCl (at room conditions) = 0.200 24.0 dm
3
= 4.8 dm
3
(4800
cm
3
)
(b) From the given equation, mole ratio of H
2
S : Cl
2
: HCl = 1 : 1 : 2
By Avogadros Law, volume ratio of H
2
S : Cl
2
: HCl = 1 : 1: 2
100 cm
3
of H
2
S react with 100 cm
3
of Cl
2
to produce 200 cm
3
of HCl at
25C and 1 atm.
(c) No. of moles of S formed =
1 . 32
21 . 3
mol = 0.100 mol
From the given equation, mole ratio of S : Cl
2
= 1 : 1,
no. of moles of Cl
2
needed = 0.100 mol
Volume of 0.100 mol of Cl
2
= 0.100 24.0 dm
3
= 2.4 dm
3
(2400 cm
3
)

23. For methane, CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O(l)
100 cm
3
? cm
3

From the equation, volume ratio of CH
4
: O
2
= 1 : 2,
volume of O
2
needed = 100 2 cm
3
= 200 cm
3

For hydrogen, 2H
2
(g) + O
2
(g) 2H
2
O(l)
200 cm
3
? cm
3

From the equation, volume ratio of H
2
: O
2
= 2 : 1,
volume of O
2
needed =
2
200
cm
3
= 100 cm
3

For carbon monoxide, 2CO(g) + O
2
(g) 2CO
2
(g)
250 cm
3
? cm
3

From the equation, volume ratio of CO : O
2
= 2 : 1,
volume of O
2
needed =
2
250
cm
3
= 125 cm
3

Total volume of O
2
needed = (200 + 100 + 125) cm
3
= 425 cm
3

24. From the given equation (1), volume ratio of NH
3
: O
2
: NO = 4 : 5 : 4,
volume of O
2
needed to oxidize NH
3
to NO = 40
4
5
cm
3
= 50 cm
3

Volume of NO produced = 40 cm
3

From the given equation (2), volume ratio of NO : O
2
= 2 : 1,
volume of O
2
needed to react with NO =
2
40
cm
3
= 20 cm
3

Minimum volume of O
2
needed = (50 + 20) cm
3
= 70 cm
3

25. (a) (i) No. of moles of HCl used = 1.0
1000
50
mol = 0.050 mol
(ii) No. of moles of H
2
formed =
000 24
600
mol = 0.025 mol
(b) Zn(s) + 2HCl(aq) ZnCl
2
(aq) + H
2
(g)
H
2
(g) formed came from the zinc reacted.
From the equation, the mole ratio of Zn : H
2
= 1 : 1,
no. of moles of Zn reacted = 0.025 mol
Mass of Zn reacted = 0.025 65.4 g = 1.635 g
(c) No. of Zn atoms reacted = 0.025 6.02 10
23
= 1.505 10
22

(d) From the equation, mole ratio of ZnCl
2
: H
2
= 1 : 1,
no. of moles of ZnCl
2
formed = 0.025 mol
Molarity of ZnCl
2
(aq) =
3
10 50
025 . 0
mol dm
3
= 0.50 mol dm
3
(M)
Part IX Rate of reaction

Part Exercises

1. C
2. B
3. B
4. A
5. B
6. D
7. B
8. C
9. D
10. A
11. A
12. D
13. C
14. B
15. D
16. C
17. A
18. C
19. B
20. D
21. A

22. (a) The progress of the reaction can be followed by using a colorimeter. The
reactant iodine, I
2
, is brown in colour. The other reactant and all the
products are colourless. The colour intensity of the reaction mixture
decreases as the reaction proceeds.
(b) The progress of the reaction can be followed by determining the volume of
nitrogen gas formed. Only nitrogen is a gas and it is not quite soluble in
water. The volume of gas released from the reaction mixture increases as
the reaction proceeds.
(c) The progress of the reaction can be followed by a chemical method. Known
volumes of the reaction mixture are withdrawn at regular intervals and the
reaction is quenched by lowering the temperature. The concentration of
iodine can be determined by titration with standard thiosulphate (S
2
O
3
2
)
solution.
(d) The reaction can be followed by measuring the time taken when the same
turbidity due to sulphur precipitate appears in the reaction mixture. The
precipitate can mask a reference mark placed underneath the reaction flask.

23. (a) The CO
2
formed is quite soluble in water especially when the pressure of
the closed system is increasing.
(b) 1. By using a colorimeter, we can measure the change in colour intensity
of the reaction mixture with time. As the reaction proceeds, the
concentration of the purple coloured MnO
4
(aq) decreases. Hence, the

colour intensity of the reaction mixture decreases too.
2. By using a gas syringe, we can collect and measure the volume of CO
2

formed with time.
3. By using an electronic balance, we can measure the loss in mass (as a
result of the escape of the CO
2
formed) of the reaction mixture with
time.
(Note: CO
2
is quite soluble in water, so measurements at the start of
the experiment will have some errors.)

24. (a) HCO
3
(aq) + H
+
(aq) H
2
O(l) + CO
2
(g)
(b) Initial rate is the rate of a reaction at the start.
This is the highest rate for the whole reaction because the concentration(s)
of reactant(s) is/are the highest at the beginning of a reaction.
(c) Reaction 3 will have a higher initial rate because for the same concentration,
hydrochloric acid is a stronger acid/ionizes more completely than ethanoic
acid to give a higher concentration of H
+
(aq). Thus, the initial rate is higher.
(d) Reaction 2 will have a higher initial rate because for the same concentration,
sulphuric acid is a dibasic acid/has two ionizable hydrogen atoms per
molecule. As a result, sulphuric acid has a higher concentration of hydrogen
ions. Thus, the initial rate is higher.
(e) No. of moles of NaHCO
3
present = 1 50 10
3
mol = 5 10
2
mol
No. of moles of HCl used = 1
1000
10
mol = 1 10
2
mol
HCl is the limiting reactant, so it is used to calculate the volume of CO
2

formed.
From the equation, mole ratio of HCl : CO
2
= 1 : 1,
no. of moles of CO
2
formed = 1 10
2
mol
Volume of CO
2
formed = 1 10
2
24.0 dm
3
= 0.24 dm
3
(240 cm
3
)
(f)

2
1
P
r
e
s
s
u
r
e

(
k
P
a
)

reaction 3
Time (min)
(g) If the reaction is quite rapid, the use of data-logger can collect enough data
for analysis within a short period of time. Besides, data is stored in digital
format which allows for more convenient analysis and presentation.

25. Na
2
CO
3
nH
2
O(s) + 2HNO
3
(aq) 2NaNO
3
(aq) + CO
2
(g) + (n+1)H
2
O(l)
No. of moles of CO
2
produced =
000 24
600
mol = 0.0250 mol
From the equation, mole ratio of Na
2
CO
3
nH
2
O : CO
2
= 1 : 1,
no. of moles of Na
2
CO
3
nH
2
O = 0.0250 mol
Molar mass of Na
2
CO
3
nH
2
O =
0250 . 0
15 . 7
g mol
1
= 286 g mol
1

286 = (23.0 2 + 12.0 + 16.0 3) + n(1.0 2 + 16.0)
286 = 106 + 18.0n
180 = 18.0n
n = 10

26. (a) Na
2
CO
3
(s) + 2HCl(aq) 2NaCl(aq) + CO
2
(g) + H
2
O(l)
No. of moles of HCl used =
1000
40
2 mol = 0.080 mol
No. of moles of Na
2
CO
3
used =
3) 16.0 12.0 2 (23.0
3 . 5
+ +
mol = 0.050 mol
From the equation, mole ratio of Na
2
CO
3
: HCl = 1 : 2,
0.050 mol of Na
2
CO
3
needs 0.050 2 = 0.10 mol of HCl to react.
HCl is the limiting reactant, so some Na
2
CO
3
is left unreacted.
(b) From the equation in (a), mole ratio of HCl : CO
2
= 2 : 1,
no. of moles of CO
2
evolved =
2
080 . 0
mol = 0.040 mol
Volume of CO
2
evolved at room conditions = 0.040 24.0 dm
3
= 0.96 dm
3
(960 cm
3
)

27. ZnCO
3
(s) + H
2
SO
4
(aq) ZnSO
4
(aq) + H
2
O(l) + CO
2
(g)
No. of moles of ZnCO
3
used =
3) 16.0 12.0 (65.4
5 . 8
+ +
mol = 0.0678 mol
No. of moles of H
2
SO
4
used = 1.20
1000
50
mol = 0.0600 mol
Mole ratio of ZnCO
3
: H
2
SO
4
= 1 : 1,
H
2
SO
4
is the limiting reactant.
From the equation, mole ratio of H
2
SO
4
: CO
2
= 1 : 1,
no. of moles of CO
2
= 0.0600 mol
Volume of CO
2
formed = 0.0600 24.0 dm
3

= 1.44 dm
3
(1440 cm
3
)
28. (a) Volume of oxygen in 500 cm
3
air = 500 20% cm
3
= 100 cm
3
From the equation, volume ratio of CH
3
NO
2
: O
2
= 4 : 3,
volume of CH
3
NO
2
needed =
3
4
100 cm
3
= 133.33 cm
3

(b) From the equation, volume ratio of O
2
: CO
2
: N
2
: H
2
O = 3 : 4 : 2 : 6
volumes of CO
2
, N
2
and H
2
O formed respectively are 133.3 cm
3
,
66.67 cm
3
and 200 cm
3
.
Total volume of gaseous products = 133.33 + 66.67 + 200 cm
3
= 400 cm
3

(c) Total volume of gases consumed = 100 + 133.33 cm
3
= 233.33 cm
3
Overall volume change
= total volume of gaseous products formed total volume of gases
consumed
= 400 233.33 cm
3
= 166.67 cm
3

29. (a) No. of moles of FeS
2
used =
2) 32.1 (56.0
100
+
mol = 0.832 mol
From the given equation, mole ratio of FeS
2
: SO
2
= 4 : 8 = 1 : 2,
no. of moles of SO
2
produced = 0.832 2 mol = 1.664 mol
Volume of SO
2
produced = 1.664 24.0 dm
3
= 39.94 dm
3

(b) From the given equation, mole ratio of FeS
2
: O
2
= 4 : 11,
no. of moles of O
2
used =
4
11
832 . 0 mol = 2.288 mol
Volume of O
2
needed = 2.288 24.0 dm
3
= 54.91 dm
3

Volume of air needed =
20
100
91 . 54 dm
3
= 274.55 dm
3

30. (a) MgCO
3
(s) MgO(s) + CO
2
(g)
CaCO
3
(s) CaO(s) + CO
2
(g)
(b) Let x g and (7.0 x) g be the mass of MgCO
3
and CaCO
3
respectively in the
mixture.
For MgCO
3
,
no. of moles of MgCO
3
decomposed =
3) 16.0 12.0 (24.3 + +
x
mol =
3 . 84
x
mol
From the equation in (a), mole ratio of MgCO
3
: CO
2
= 1 : 1,
no. of moles of CO
2
produced =
3 . 84
x
mol

For CaCO
3
,
no. of moles of CaCO
3
decomposed =
3) 16.0 12.0 (40.1
) (7.0
+ +
x
mol =
100.1
) (7.0 x
mol
From the equation in (a), mole ratio of CaCO
3
: CO
2
= 1 : 1,
no. of moles of CO
2
produced =
100.1
) (7.0 x
mol
Total volume of CO
2
produced
= {(
3 . 84
x
) + [
100.1
) (7.0 x
]} 24 000 cm
3
= 1880 cm
3

Solving for x, x = 4.49
mass of MgCO
3
in the mixture = 4.49 g

31.
The rate of a reaction tells how quickly a chemical reaction occurs. We can
only determine reaction rates by doing experiments. The rate of a chemical
reaction can be followed by measuring the characteristic change in some
physical properties of the reaction with time.
In the decomposition of ammonium nitrite, gaseous product, N
2
, is formed
which can be conveniently collected by using a gas syringe. We can
measure the volume of N
2
gas produced with time.
If the reaction is performed in a closed system, as more and more N
2
is
produced, the higher the pressure inside the reaction vessel. We can
measure the increase in pressure with time by using pressure sensor which
is connected to a data-logger.
As N
2
gas is produced, it will escape into the atmosphere resulting in a loss
in mass of the reaction mixture. If the reaction vessel containing the
reaction mixture is put on an electronic balance, the change in mass with
time can be measured.

Class Practice

A41.1
(a) Yes, it is a reversible reaction. The sign shows that the reaction can
proceed in either direction.
(b) Backward reaction.
(c) Forward reaction: reactants are SO
2
and O
2
; product is SO
3

Backward reaction: reactant is SO
3
; products are SO
2
and O
2

A41.2
(a) (i)

or

Time
H
2
, I
2

HI
Conc.
Time
HI
H
2
, I
2

Conc.
(ii)

(b) As time passes, the colour of the mixture changes from colourless to violet.
The colour intensity keeps on increasing with time. When the equilibrium
state is reached, the colour intensity remains constant.
H
2
+ I
2
2HI
2HI H
2
+ I
2

Reaction
rate
Time

Chapter Exercise

1. rreversible, ompletion
2. eversible, ompletion
3. (a) closed
(b) orward, ackward
(c) equal
(d) eactants, roducts, oncentrations, nchanged, bservable
4. B
5. D
6. A
7. D
8. B
9. C
10. A
11. C

12. (a) (i) 3Fe(s)

+ 4H
2
O(g) Fe
3
O
4
(s) + 4H
2
(g)
Fe
3
O
4
(s) + 4H
2
(g) 3Fe(s)

+ 4H
2
O(g)
(ii) The rates of these two reactions are equal.
(b) 3Fe(s)

+ 4H
2
O(g) Fe
3
O
4
(s) + 4H
2
(g)
(c) Yes.
(d) Equilibrium can only be established in a closed system.
Equilibrium can be reached from either the forward or the backward
direction of the reversible reaction.
At equilibrium, rate of forward reaction is equal to rate of backward
reaction.
At equilibrium, the concentrations of both reactants and products remain
unchanged.

13.

14. (a) Measure the pH of solution with a pH meter. The pH of the solution should
remain constant.
(b) Measure the colour intensity (brown colour of NO
2
(g)) of the reaction
mixture using a colorimeter. The colour intensity of the equilibrium mixture
should remain constant.
OR Measure the pressure of the reaction mixture using a pressure sensor
connected to a data-logger. The pressure of the equilibrium mixture should
remain constant.
(c) Measure the colour intensity (purple colour of I
2
(g)) of the reaction mixture
using a colorimeter. The colour intensity of the equilibrium mixture should
remain constant.

15.

forward
reaction
backward
reaction
R
e
a
c
t
i
o
n

r
a
t
e

Time
Time to reach equilibrium
Y
X
dynamic equilibrium is established
100%
50%
C
o
n
c
e
n
t
r
a
t
i
o
n

Time
16.
Chemical equilibrium only occurs in reversible reactions. e.g. esterification,
thermal decomposition of calcium carbonate, Haber process, etc.
The general equation of chemical equilibrium can be expressed as:
A + B C + D
where the process from A + B C + D is called the
forward reaction, from C + D A + B is called the
backward reaction.
Chemical equilibrium is dynamic in nature during which the rates of
forward and backward reactions are not zero.
Characteristics of dynamic equilibrium:
(a) Only established in closed system with no exchange of materials
between the system and the surroundings.
(b) Can be established by starting from either the forward or the
backward reaction.
(c) The rate of forward reaction is equal to the rate of backward reaction.
(d) The concentrations of both reactants and products remain unchanged
but not zero. Thus, there are no observable changes of the reaction
mixture.

Class Practice

A42.1
The answer is (e) because the amount/concentration of H
2
, I
2
and HI become constant
at (e) and afterwards. (Three H
2
molecules, three I
2
molecules and fourteen HI
molecules)

A42.2
1. (a)
2
eqm 2
eqm 2
2
eqm 2
c
S(g)] H [
] (g) S [ ] (g) [H
K =
(b)
eqm 2 eqm
eqm 2
c
(g)] [Cl CO(g)] [
] (g) [COCl
K =
2. (a) 2NO(g) + O
2
(g) 2NO
2
(g)
(b) 2CH
4
(g) C
2
H
2
(g) + 3H
2
(g)

A42.3
(a) (i) K
c1
=
3
eqm 2 eqm 2
2
eqm 3
(g)] [H (g)] N [
(g)] NH [

(ii) K
c2
=
2
eqm 3
3
eqm 2 eqm 2
(g)] NH [
(g)] [H (g)] N [

(b) K
c1
=
c2
K
1

(c) K
c1
: mol
2
dm
6
K
c2
: mol
2
dm
6

A42.4
(a) and (b) are heterogeneous equilibria.
(a) K
c
= [CO
2
(g)]
eqm
(b) K
c
= [Ag
+
(aq)]
eqm
[Cl
(aq)]
eqm

A42.5
(b), (c), (d), (a)
A42.6
1. K
c
=
2
eqm 4
3
eqm 2 eqm 2 2
(g)] CH [
(g)] [H (g)] H C [

Substituting the equilibrium concentration values into the expression of
equilibrium constant, we have
K
c
=
2 3
3 3 3
) dm mol 0203 0 (
) dm mol 1120 0 )( dm mol 0451 0 (

.
. .

=
6 2
dm mol 154 0

.
2.
CO(g) + 2H
2
(g) CH
3
OH(g)
Concentration (mol
dm
3
)

Initial 0.50 1.00 0
Change 0.15 0.50
= 0.35
2 0.35 = 0.70 +0.35
Equilibrium 0.15 0.30 0.35
K
c
=
2
eqm 2 eqm
eqm 3
(g)] ][H CO(g) [
OH(g)] CH [

Substituting the equilibrium concentration values into the expression of equilibrium
constant,
we have
K
c
=
2 3 3
3
) dm mol 30 . 0 )( dm mol 15 . 0 (
dm mol 35 . 0

=
6 2
dm mol 93 . 25

3.
2HI(g) H
2
(g) + I
2
(g)
Concentration (mol
dm
3
)

Initial
5
4
= 0.8
0 0
Change 2x +x +x
Equilibrium 0.8 2x x x
2
eqm
eqm 2 eqm 2
c
] [HI(g)
] (g) I [ (g)] H [
K =
Substituting the equilibrium concentration values into the equilibrium constant
expression gives
2 3
3 3
) dm mol ) 2 8 . 0 ((
) dm mol )( dm mol (
016 . 0

=
x
x x

Take the square root of both sides of the equation to obtain
) 2 8 . 0 (
) (
126 . 0
x
x
=
Solving for x,
x = 0.0808
Thus,
[H
2
(g)]
eqm
= 0.0808 mol dm
3
[I
2
(g)]
eqm
= 0.0808 mol dm
3
[HI(g)]
eqm
= 0.8 2(0.0808) mol dm
3

= 0.638 mol dm
3


Chapter Exercise

1.
b a
d c
eqm eqm
eqm eqm
[B] [A]
[D] [C]
, concentrations, Equilibrium
2. temperature, initial, equation
3. omogeneous
4. eterogeneous, concentrations
5. osition
6. xtent, ate
7. large, reactant
8. C
9. D
10. B
11. D
12. A
13. A
14. B
15. A
16. C
17. B
18. B
19. C
20. (a) K
c
=
eqm 2
4
eqm
2
eqm 2
2
eqm 2
(g)] [O [HCl(g)]
O(g)] [H (g)] [Cl

(b) K
c
=
2
eqm 2 eqm
(g)] [H [CO(g)]
1

(c) K
c
=
eqm 2
2
eqm 2
2
eqm 2
(g)] [S (g)] [H
S(g)] [H

(d) K
c
=
eqm 2 eqm
eqm 2 eqm 2
O(g)] [H [CO(g)]
(g)] [H (g)] [CO

(e) K
c
=
eqm 2 3
eqm 2
(aq)] ) [Ca(HCO
(g)] [CO

21. (a) K
c
=
eqm
2
4 eqm
2
(aq)] [SO (aq)] Ba [
1
+

Unit of K
c
=
6 2
3 3
dm mol
) dm mol )( dm (mol
1

=
(b) K
c
=
eqm 2
2
eqm
2
eqm
(g)] [Cl NO(g)] [
NOCl(g)] [

Unit of K
c
=
3 1
3 2 3
2 3
dm mol
) dm mol ( ) dm (mol
) dm (mol

=
(c) K
c
=
eqm 2
2
eqm
eqm 2
2
eqm
(g)] [F HCl(g)] [
] (g) Cl [ HF(g)] [

Unit of K
c
=
) dm (mol ) dm (mol
) dm (mol ) dm (mol
3 2 3
3 2 3

i.e. no unit
(d) K
c
=
eqm 4
4
eqm
(g)] Ni(CO) [
CO(g)] [

Unit of K
c
=
9 3
3
4 3
dm mol
dm mol
) dm (mol

=

22. K
c
=
3
2 2
3 3
2
eqm
eqm 2 eqm 2
10 2.07
) 10 (2.2
) 10 )(1.0 10 (1.0

[HI(g)]
(g)] [I (g)] H [

=

23. K
c
=
eqm 2
2
eqm 2
2
eqm 3
(g)] [O (g)] [SO
(g)] [SO
= 10 . 1 dm mol
50 . 1 75 . 1
25 . 2
3 1
2
2
=

mol
1
dm
3

24.
2CO
2
(g) 2CO(g) + O
2
(g)
Concentration (mol
dm
3
)

Initial
1
001 . 0
= 0.001
0 0
Change 0.001 1 10
4
+1 10
4

+
2
1
1 10
4

Equilibrium 9 10
4
1 10
4
5 10
5

K
c
=
2
eqm 2
eqm 2
2
eqm
] [CO
] [O [CO]
=
2 4
5 2 4
) 10 9 (
) 10 5 ( ) 10 1 (

mol dm
3
= 6.2 10
7
mol dm
3

25. (a) Let x be the number of moles per dm
3
of H
2
that react.
H
2
(g) + Br
2
(g) 2HBr(g)
Concentration (mol
dm
3
)

Initial
00 . 2
0 . 4
= 2.0
00 . 2
0 . 4
= 2.0
0
Change x x +2x
Equilibrium 2.0 x 2.0 x 2x
Since K
c
=
eqm 2 eqm 2
2
eqm
(g)] [Br (g)] [H
[HBr(g)]
=
2
2
) 0 . 2 (
) 2 (
x
x
=12.0
Solving for x, x = 1.268
At equilibrium, [H
2
]
eqm
= [Br
2
]
eqm
= 2 1.268 mol dm
3
= 0.732 mol dm
3

[HBr]
eqm
= 2 1.268 mol dm
3
= 2.536 mol dm
3

(b) Let x be the number of moles per dm
3
of H
2
that react.
H
2
(g) + Br
2
(g) 2HBr(g)
Concentration (mol
dm
3
)

Initial
00 . 2
0 . 6
= 3.0
00 . 2
0 . 4
= 2.0
0
Change x x +2x
Equilibrium 3.0 x 2.0 x 2x
Since K
c
=
eqm 2 eqm 2
2
eqm
(g)] [Br (g)] [H
[HBr(g)]

=
) 0 . 2 )( 0 . 3 (
) 2 (
2
x x
x

= 12.0
Solving for x, x = 1.5 or 6.0 (rejected)
At equilibrium, [H
2
]
eqm
= 3.0 1.5 mol dm
3
= 1.5 mol dm
3

[Br
2
]
eqm
= 2.0 1.5 mol dm
3
= 0.5 mol dm
3

[HBr]
eqm
= 2 1.5 mol dm
3
= 3.0 mol dm
3

26. Let x be the number of moles per dm
3
of COCl
2
that react.
CO(g) + Cl
2
(g) COCl
2
(g)
Concentration (mol
dm
3
)

Initial 0 0
0 . 8
20 . 0
= 0.025
Change +x +x x
Equilibrium x x 0.025 x
K
c
=
eqm 2 eqm
eqm 2
(g)] [Cl [CO(g)]
(g)] [CoCl

Substituting the equilibrium concentrations into the expression,
4.7 10
9
=
2
025 . 0
x
x

Since K
c
is large, 0.025 x ~ 0.025
4.7 10
9
=
2
025 . 0
x

Solving for x, x = 2.3 10
6

Equilibrium concentrations are: [CO(g)]
eqm
= [Cl
2
(g)]
eqm
= 2.3 10
6
mol dm
3

[COCl
2
(g)]
eqm
= 0.025 mol dm
3

27. Let x mol dm
3
be the initial concentration of N
2
O
4
and y be the number of moles
per dm
3
of N
2
O
4
that react.
N
2
O
4
(g) 2NO
2
(g)
Concentration (mol dm
3
)

Initial x 0
Change y
+2y
Equilibrium x y = x 1.5 10
3
2y = 3.0 10
3

K
c
=
eqm 4 2
2
eqm 2
(g)] O [N
(g)] [NO

0.2 =
) 10 5 . 1 (
) 10 0 . 3 (
3
2 3

x

Solving for x,
x = 0.00155
Initial concentration of N
2
O
4
(g) is 0.00155 mol dm
3
.

28. K
c
=
eqm 5
eqm 2 eqm 3
] [PCl
(g)] [Cl (g)] [PCl

33.3 =
3
1
eqm 3
10 1.29
) 10 (1.87 (g)] [PCl

[PCl
3
(g)]
eqm
= 0.230 mol dm
3


chemical equilibria
A43.1
(a) (i) The equilibrium position shifts to the right.
(ii) The equilibrium position shifts to the left.
(iii) The equilibrium position shifts to the left.
(b) A: H
2
(g) is added to the equilibrium mixture.
B: HI is removed from the equilibrium mixture.

A43.2
1. The reaction quotient,
(aq)] (aq)][SCN [Fe
(aq)] [FeSCN
Q
3
2
c
+
+
=

[FeSCN
2+
(aq)] =
0 . 2
1020 . 0
mol dm
3
= 0.0510 mol dm
3

[Fe
3+
(aq)] =
0 . 2
0320 . 0
mol dm
3
= 0.0160 mol dm
3

[SCN
(aq)] =
0 . 2
0600 . 0
mol dm
3
= 0.0300 mol dm
3

3 1
3 3
3
c
dm mol 106.25
) dm mol )(0.0300 dm mol (0.0160
dm mol 0.0510
Q

= =
Since Q
c
< K
c
, more products (FeSCN
2+
) will be formed and more reactants
(Fe
3+
and SCN
) will be consumed until Q

c
= K
c
. Hence, the equilibrium position
shifts to the right.
2. (a) Let 2x be the number of moles per dm
3
of HI that decompose.
H
2
(g) + I
2
(g) 2HI(g)
3
)

Initial 0 0
10
40 . 0
= 0.040
Change +x +x 2x
Equilibrium x x 0.040 2x
Substituting equilibrium concentration values into the equilibrium law
expression,

0.00443 , for Solving
) 2 (0.040
49.5
(g)] [I (g)] [H
[HI(g)]
K
2
2
eqm 2 eqm 2
2
eqm
c
=
=
=
x x
x
x

At equilibrium,
[H
2
(g)]
eqm
= 0.00443 mol dm
3

[I
2
(g)]
eqm
= 0.00443 mol dm
3

[HI(g)]
eqm
= 0.040 0.00443 2 mol dm
3
= 0.0311 mol dm
3

(b) After adding 0.10 mol of HI to the reaction vessel, [HI(g)] = 0.0311 +
10
10 . 0
mol dm
3
= 0.0411 mol dm
3


86.07
) dm mol )(0.00443 dm mol (0.00443
) dm mol (0.0411
(g)] (g)][I [H
[HI(g)]
Q
3 3
2 3
2 2
2
c
= = =

Since Q
c
> K
c
, more product (HI) will be consumed and more reactants (H
2

and I
2
) will be formed until Q
c
= K
c
. Hence, the equilibrium position shifts
to the left.
(c) Let 2y be the number of moles per dm
3
of HI that decompose.
H
2
(g) + I
2
(g) 2HI(g)
3
)

Initial 0.00443 0.00443 0.0311 + 0.01
= 0.0411
Change +y +y 2y
Equilibrium 0.00443 + y 0.00443 + y 0.0411 2y
Substituting the new equilibrium concentration values into the equilibrium
law expression,

2
2
eqm 2 eqm 2
2
eqm
c
) (0.00443
) 2 (0.0411
5 49
(g)] [I (g)] [H
[HI(g)]
K
y
y
.
+
=
=

Solving for y, y = 0.00110
At equilibrium,
[H
2
(g)]
eqm
= [I
2
(g)]
eqm
= 0.00443 + 0.00110 mol dm
3
= 0.00553 mol dm
3

[HI(g)]
eqm
= 0.0411 2 0.00110 mol dm
3
= 0.0389 mol dm
3

(d) No, the concentration of HI (0.0389 mol dm
3
) at the new equilibrium
position is still higher than that before the disturbance (0.0311 mol dm
3
).

A43.3
(a) The colour of the mixture becomes bluer, i.e. the equilibrium position shifts to
the right (the product side). As the forward reaction is an endothermic change, an
increase in temperature favours endothermic reaction causing an increase in the
amount of the blue CoCl
4
2
(aq) ions.
(b) The colour of the mixture becomes more pink, i.e. the equilibrium position shifts
to the left (the reactant side). As the backward reaction is an exothermic change,
a decrease in temperature favours exothermic reaction causing an increase in the
amount of the pink Co
2+
(aq) ions.

A43.4
(a) When potassium dichromate is acidified, there is a high concentration of acid,
H
+
(aq). According to the Le Chteliers Principle, the high concentration of
H
+
(aq) shifts the equilibrium position of the system to the right. This leads to the
formation of more orange Cr
2
O
7
2
(aq) ions. So, acidified potassium dichromate
solution is orange in colour.
(b) When sodium hydroxide pellets are added, it neutralizes the acid present. The
concentration of H
+
(aq) is lowered. According to the Le Chteliers Principle, the
system counteracts the change (removal of H
+
(aq)) in a direction to replace the
removed H
+
(aq). This is done by shifting the equilibrium position to the left. As
more Cr
2
O
7
2
(aq) ions are converted to CrO
4
2
(aq) ions, the colour of the
solution changes from orange to yellow.

A43.5
(a) A decrease in volume causes an increase in pressure of the gaseous equilibrium
mixture. According to the Le Chteliers Principle, the equilibrium position of
the system will shift to the side with a decrease in the number of moles of gases.
However, there are equal numbers of moles of gases on both sides of the
equation. So, a change in volume has no effect on the equilibrium position for
this reaction.
(b) It can be concluded that a change in volume has no effect on the equilibrium
position for reactions having the same number of moles of gases on both sides of
the equation.
chemical equilibria

Chapter Exercise

1. osition, equilibrium constant, K
c

2. reaction quotient, equilibrium constant
(a) equilibrium, does not
(b) product, right
(c) reactant, left
3. onstant, osition
4. endothermic, exothermic
5. oncentration, emperature, counteract
6. Le Chteliers Principle, shift
7. yield
8. A
9. D
10. A
11. C
12. C
13. C
14. D
15. C
16. B
17. A
18. A
19. D

20. (a) Shift to the right/product side
(b) Shift to the left/reactant side
(c) Shift to the left/reactant side
(d) No shift in equilibrium position
(e) Shift to the right/product side

21. (a) Fe
3+
(aq) is yellow, SCN
(aq) is colourless and FeSCN

2+
(aq) is dark red.
When the mixture becomes darker red, equilibrium position has shifted to
the product side. When the mixture becomes paler yellow, equilibrium
position has shifted to the reactant side.
(b) CrO
4
2
(aq) is yellow and Cr
2
O
7
2
(aq) is orange. When the mixture becomes
orange, equilibrium position has shifted to the product side. When the
mixture becomes yellow, equilibrium position has shifted to the reactant
side.
(c) NO
2
(g) is brown and N
2
O
4
(g) is colourless. When the mixture becomes pale
brown or yellow, equilibrium position has shifted to the product side. When
the mixture becomes darker brown, equilibrium position has shifted to the
reactant side.

22. Q
c
=
(g)] (g)][H H [C
(g)] H [C
2 2 2
4 2
=
4 . 0 02 . 0
10 2 . 3
4

mol
1
dm
3
= 0.04 mol
1
dm
3

Since Q
c
< K
c
, the equilibrium position shifts to the product side, i.e. to the right.

23. Q
c
=
(g)] (g)][H [CO
O(g)] [CO(g)][H
2 2
2
=
0 . 2 0 . 4
0 . 2 0 . 4
= 1.0
Since Q
c
> K
c
, the reaction will proceed to the reactant side, i.e. to the left.

24. Description (1) applies to Figure 24(b). When H
2
(g) is added, there is a sudden
increase of [H
2
(g)]. When [H
2
(g)] increases, the equilibrium is disturbed. Q
c
is
decreased, so the equilibrium position will shift to the right. This will decrease
[I
2
(g)] and increase [HI(g)].
Description (3) applies to Figure 24(c). The graph shows a decrease in [HI(g)]
and an increase in both [H
2
(g)] and [I
2
(g)]. That is, the equilibrium position has
shifted to the left which is an endothermic process. Increase in temperature
favours the process. Furthermore, there is no sudden change in the
concentrations of all substances, so the pressure of the system has not changed.

25. Low temperatures favour exothermic reaction, i.e. the combination of brown
nitrogen dioxide, NO
2
(g), to form colourless dinitrogen tetroxide, N
2
O
4
(g). That
explains the decrease in colour intensity of the brown haze.
High temperatures favour endothermic reaction, i.e. the decomposition of
colourless N
2
O
4
(g) back to brown NO
2
(g). So the colour intensity of brown haze
increases.

26. Hydroxide ions from sodium hydroxide combine with the hydrogen ions in the
system.
H
+
(aq) + OH
(aq) H
2
O(l)
As the concentration of hydrogen ions in the system decreases, the reaction
quotient Q
c
=
(aq)] O [Cr
(aq)] [H (aq)] [CrO
2
7 2
2 2 2
4
+
will be smaller than K
c
. As Q
c
is smaller
than K
c
, the equilibrium position shifts to the right forming more CrO
4
2
(aq)
which is yellow.

27. A higher concentration of O
2
will shift the equilibrium position towards the
products. Thus, CO is released from the haemoglobin and more HbO
2
will form.

28. (a) According to the Le Chteliers Principle, when there is an increase in
[CO(g)], the system shifts in a direction to lower the [CO(g)]. This is done
by shifting the equilibrium position to the left which can help to remove
some of the added CO.
(b) According to the Le Chteliers Principle, when there is an increase in
[H
2
O(g)], the system shifts in a direction to lower the [H
2
O(g)]. This is done
by shifting the equilibrium position to the right which can help to remove
some of the added H
2
O.
(c) Increasing the reaction volume is equivalent to a decrease in pressure.
According to the Le Chteliers Principle, the system shifts in a direction to
increase the pressure of the system again. This is done by producing more
molecules. Thus, the equilibrium position shifts to the right as there are
larger number of moles of molecules on the right hand side.
(d) According to the Le Chteliers Principle, when there is an increase in
temperature, the system will shift in a direction to absorb the heat added in
order to lower the temperature of the system again. This is done by shifting
the equilibrium position to favour the endothermic change, i.e. to the right.
Part X Chemical equilibrium

Part Exercise

1. C
2. B
3. C
4. D
5. A
6. C
7. B
8. A
9. B

10. COCl
2
(g) CO(g) + Cl
2
(g)
Concentration (mol
dm
3
)

Initial 1.0 0 0
Change 0.028 +0.028 +0.028
Equilibrium 1.0 0.028 =
0.972
0.028 0.028

0.972
(0.028)

(g)] [COCl
(g)] [Cl [CO(g)]
K
2
eqm 2
eqm 2 eqm
c
= =
mol dm
3
= 8.07 10
4
mol dm
3

11. K
c
= [Mg
2+
(aq)]
eqm
[F
(aq)]
2
eqm
= (2.6 10
4
)(5.2 10
4
)
2
M
3
= 7.03 10
11
M
3

12. (a) The forward reaction rate is equal to the backward reaction rate.
Both reactants and products are present and their concentrations remain
unchanged.
(b)
2
eqm 2
eqm 2
2
eqm 2
c
S(g)] [H
(g)] [S (g)] [H
K =
(c) mol dm
3
/M
(d) Let x be the number of moles per dm
3
of H
2
S that decompose.
2H
2
S(g) 2H
2
(g) + S
2
(g)
Concentration (mol
dm
3
)

Initial
1
20 . 0
= 0.20
0 0
Change 2x +2x +x
Equilibrium 0.20 2x 2x x

2
eqm 2
eqm 2
2
eqm 2
c
S(g)] [H
(g)] [S (g)] [H
K = =
2
2
) 2 (0.20
) ( ) 2 (
x
x x

Since equilibrium constant is very small, x is expected to be very small.
Thus, 0.20 2x is almost 0.20.
So, 4.2 10
6
=
2
3
(0.20)
4x

x = 3.5 10
3

[S
2
(g)]
eqm
= 3.5 10
3
mol dm
3

[H
2
(g)]
eqm
= 2 3.5 10
3
mol dm
3
= 7.0 10
3
mol dm
3

(e) The equilibrium position shifts to the left.

13. (a)
PCl
5
(g) PCl
3
(g) + Cl
2
(g)
Concentration (mol
dm
3
)

Initial 1.0 0 0
Change 0.54 1.0
= 0.46
+0.46 +0.46
The changes in concentration of PCl
3
(g) and Cl
2
(g) are plotted with time and
their equilibrium concentration = 0.46 mol dm
3
.

(b) PCl
5
(g) PCl
3
(g) + Cl
2
(g)
Concentration (mol
dm
3
)

Initial 0 0.50 0.30
Change +0.14 0.36 0.50
= 0.14
0.14
The changes in concentration of PCl
5
(g) and Cl
2
(g) are plotted with time and
their equilibrium concentrations = 0.14 mol dm
3
and 0.16 mol dm
3
respectively.
PCl
3
and Cl
2

C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

P
C
l
5
(
g
)

Time

14. (a)
Temperature
(K)
[N
2
]
eqm
[H
2
]
eqm
[NH
3
]
eqm
K
c

500 0.115 0.105 0.439 1448
575 0.110 0.249 0.128 9.6
775 0.120 0.140 0.00439 0.0584
(b) The forward reaction is exothermic. From the table, it is noticed that
increasing temperature decreases the value of K
c
, i.e. the forward reaction is
not favoured. Since increasing temperature favours endothermic reaction,
the forward reaction must be exothermic.

15. (a) K
c
=
2
eqm 3
2
eqm 4 2
eqm 2
4
eqm 2
(g)] [O (g)] H [C
(g)] [O O(g)] [CH

(b) It has the same form as equilibrium constant, K
c
, but Q
c
is calculated from
concentrations at any particular moment, not necessarily at equilibrium. Q
c

is used to predict the shift in equilibrium position.
(c) (i) As Q
c
=
2
3
2
4 2
2
4
2
(g)] [O (g)] H [C
(g)] [O O(g)] [CH
, an increase in [C
2
H
4
(g)] will make Q
c

smaller than K
c
. Thus, the equilibrium position shifts to the product
side, i.e. to the right.
(ii) As Q
c
=
2
3
2
4 2
2
4
2
(g)] [O (g)] H [C
(g)] [O O(g)] [CH
, a decrease in [O
3
(g)] will make Q
c

greater than K
c
. Thus, the equilibrium position shifts to the reactant
side, i.e. to the left.
(iii) As Q
c
=
2
3
2
4 2
2
4
2
(g)] [O (g)] H [C
(g)] [O O(g)] [CH
, a decrease in [O
2
(g)] will make Q
c

smaller than K
c
. Thus, the equilibrium position shifts to the product
side, i.e. to the right.
Cl
2

PCl
5

Time
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

P
C
l
3
(
g
)


16. At A, there should be a sudden decrease in pressure or an increase in volume of
the system. This change favours the formation of more gas molecules by shifting
the equilibrium position to the left producing more C
2
H
4
and H
2
.
At B, there is an increase in temperature of the system. The lines show that both
[C
2
H
4
(g)] and [H
2
(g)] increase while [C
2
H
6
(g)] decreases. The equilibrium
position of the system has shifted to the left which is an endothermic process. An
increase in temperature favours endothermic reaction.
At C, C
2
H
6
(g) is added to the system. This makes the reaction quotient greater
than the equilibrium constant, i.e. Q
c
> K
c
, the equilibrium position shifts to the
reactant side. This lowers [C
2
H
6
(g)] and increases [C
2
H
4
(g)] and [H
2
(g)].

17. (a) Addition of hydrochloric acid increases the concentration of Cl
(aq) ions,
reaction quotient Q
c
=
(aq)] [CuCl
(aq)] (aq)][Cl O) [Cu(H
2
4
4 2
4 2
+
will be greater than the
equilibrium constant, K
c
. Thus, the equilibrium position shifts to the left
producing more CuCl
4
2
(aq), so the solution becomes yellow in colour.
(b) Addition of silver nitrate solution removes Cl
(aq) ions in the system by

precipitation with Ag
+
(aq) ions.
Ag
+
(aq) + Cl
(aq) AgCl(s)
As [Cl
(aq)] decreases, reaction quotient Q

c
=
(aq)] [CuCl
(aq)] (aq)][Cl O) [Cu(H
2
4
4 2
4 2
+

will be smaller than the equilibrium constant, K
c
. Thus, the equilibrium
position shifts to the right producing more Cu(H
2
O)
4
2+
(aq), so the solution
becomes blue in colour.

18. Addition of HCl(aq) removes OH
(aq) in the solution.

H
+
(aq) + OH
(aq) H
2
O(l)
As OH
(aq) is removed, the reaction quotient, Q

c
= [Fe
3+
(aq)][OH
(aq)]
3
,
becomes smaller than the equilibrium constant, K
c
. Thus, the equilibrium
position shifts to the right making more Fe(OH)
3
to dissolve. Then [Fe
3+
(aq)] and
[OH
(aq)] increase and eventually Q

c
becomes the same as K
c
.

19.
SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)
Concentration (mol
dm
3
)

Initial 0.020 0 0
Change 1.2 10
2
+1.2 10
2
+1.2 10
2

Equilibrium 0.020 1.2 10
2

= 8 10
3

1.2 10
2
1.2 10
2

eqm 2 2
eqm 2 eqm 2
c
(g)] Cl [SO
(g)] [Cl (g)] [SO
K = =
) 10 8 (
) 10 2 . 1 )( 10 2 . 1 (
3
2 2

mol dm
3
= 0.018 mol dm
3

20.
eqm 2 eqm
eqm 2
c
(g)] [Cl [CO(g)]
(g)] [COCl
K =
2.9 10
10
=
) 10 )(7.3 10 (1.8
(g)] [COCl
6 5
eqm 2

[COCl
2
(g)]
eqm
= 3.81 mol dm
3

No. of moles of COCl
2
= 3.81 6 mol = 22.86 mol
Mass of COCl
2
= 22.86 (12.0 + 16.0 + 35.5 2) g = 2263 g

21. (a) The equilibrium position does not shift to any direction, so there is no
change in yield of CH
4
.
(b) The equilibrium position shifts to the right, so the yield of CH
4
increases.
(c) The equilibrium position shifts to the right, so the yield of CH
4
increases.
(d) The equilibrium position shifts to the left, so the yield of CH
4
decreases.

Hkdse Chemistry - A Modern View (Chemistry) : Coursebook 4A Suggested Answers

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HKDSE CHEMISTRY A Modern View

(aq) during the reaction. The change in colour intensity of the

was completely reduced to Mn

mol = 0.100 mol

(aq) decreases. Hence, the

HKDSE CHEMISTRY A Modern View (Chemistry) Coursebook 4A

) will be consumed until Q

(aq) is colourless and FeSCN

(aq) ions in the system by

(aq)] decreases, reaction quotient Q

(aq) in the solution.

(aq) is removed, the reaction quotient, Q

(aq)] increase and eventually Q

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