54

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Industrial processes

Haber process is the main industrial process for production of

ammonia. Over 80% of the ammonia produced is used in making
Chapter preview nitrogenous fertilizers.

54.1 Importance of fertilizers

54.2 Manufacture of ammonia by the Haber process
54.3 Compromise between reaction rate, yield and economic considerations in the
Haber process
54.4 Production of fertilizers from ammonia
54.5 Importance of the chloroalkali industry
54.6 Chemical principles involved in the chloroalkali industry
54.7 Social, economic and environmental considerations of the chloroalkali industry
54.8 Importance of methanol
54.9 Manufacture of methanol

Prior knowledge & Quick review

(For Chapter 54)
 All answers
Importance of industrial processes

Many synthetic products we use in daily life are made from natural resources using industrial processes.
For example,

• nitrogen in the air is used to

make fertilizers;

• dissolved sodium chloride in the

oceans is used to make chlorine
bleach;

• methane in natural gas is converted to methanol which

can be used as a feedstock to produce other chemicals
such as ethanoic acid and methanal.

A natural gas production platform

Think about...
1 How can nitrogen be converted to fertilizers?

2 How can sodium chloride be converted to chlorine bleach?

3 What chemical processes are involved in the conversion of natural gas to methanol?


After studying this chapter, you should be able to answer the above questions.

chlorine bleach 氯漂白劑 methanol 甲醇

fertilizer 肥料
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54.1 Importance of fertilizers

Increasing demand for food crops

The world population has exceeded 7 billions and is still expanding. With
the rapid increase in the world population, the demand for food
increases rapidly. Food crops such as rice, maize and wheat (Figure 54.1)
need certain elements, particularly nitrogen, phosphorus and
potassium, to grow well.

Figure 54.1 Wheat is the main

ingredient in bread, noodles,
biscuits and cereals.

Nitrogenous fertilizers
Nitrogen is essential for the formation of proteins for plant growth.
–
Plants can absorb nitrogen from the soil as nitrates (NO3 ). However, in
many places, natural processes cannot provide sufficient amounts of
nitrates for crop growth. Synthetic fertilizers are used as a source of
nitrogen in these places.
Learning tip
Excessive use of fertilizers Nitrogenous fertilizers are often produced in the form of nitrates
such as ammonium – +
(NO3 ) or ammonium salts (NH4 ). Ammonium nitrate (NH4NO3) is
nitrate leads to nitrate
contamination of water. one of the most widely used nitrogenous fertilizers. It is soluble in water
This may cause increased and can be easily absorbed by plants. Moreover, it has high nitrogen
growth of algae.
content (35% by mass). See Figure 54.2.

Caution
Ammonium nitrate is explosive.
Do not heat solid ammonium
nitrate or ammonium nitrate
solution to dryness.

Figure 54.2 (a) A bag of ammonium

nitrate fertilizer. (b) Ammonium nitrate
granules, which are easily stored and
transported
(a) (b)

ammonium nitrate 硝酸銨 billion 十億

nitrogenous fertilizer 氮肥 cereal 穀物
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Other common nitrogenous fertilizers include ammonium sulphate
((NH4)2SO4) and urea ((NH2)2CO).

Class practice 54.1

5-3-8 NPK fertilizers refer to fertilizers that contain 5% nitrogen (N), 3%
phosphorus (P) and 8% potassium (K).

A pack of NPK fertilizer for potted plants

(a) Nitrogenous fertilizers are generally produced by neutralization of an acid
with an alkali. Write the chemical equation for the neutralization involved
in producing ammonium nitrate.
(b) The pack contains 50 g of 5-3-8 NPK fertilizer.
(i) Calculate the percentage by mass of nitrogen in ammonium nitrate.
(ii) Assuming that ammonium nitrate is the only nitrogen-containing
substance in the pack, calculate the mass of ammonium nitrate in
the pack.
(Relative atomic masses: H = 1.0, N = 14.0, O = 16.0)

STSE issue 54.1

Mass production of fertilizers
With the increase of the world’s population, lots of crops are grown for food. When crops are grown on the
same field for many years, the nutrients in the soil will be depleted. The soil becomes short of one or more
types of nutrients. Fertilizers are added to the soil to replenish the nutrients consumed by crops.

When crops are grown on the same

field repeatedly, the nutrients are
constantly taken away from the soil.
Eventually the soil will become infertile.

Traditionally, farmers use animal waste and manure as fertilizers. However, these sources are not reliable
and cannot meet the increasing demand for crops. Nowadays, synthetic fertilizers are widely used. If not, many
people in the world would suffer from food shortage crisis. In 2022, the world demand for fertilizers can reach
200 million tonnes yearly.

ammonium sulphate 硫酸銨 deplete 消耗 infertile 貧瘠

112 urea 脲 food shortage crisis 糧食短缺危機
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54.2 Manufacture of ammonia by the Haber
process

Learning tip Millions of tonnes of ammonia (NH3) are produced worldwide yearly.
• Mainland China has Most of the ammonia produced (over 80%) is used in making nitrogenous
the largest proportion fertilizers. See Figure 54.3.
(about 29%) of
worldwide production
of ammonia.
• Other uses of ammonia other uses
include making (18%)
fertilizer
chemicals, explosives,
(82%)
plastics and
pharmaceuticals.

Figure 54.3 Different uses of ammonia. (Source of data: Potashcorp public company, 2013)

Development of the Haber process

In 1909, Fritz Haber (Figure 54.4), a German chemist, discovered the
transformation of atmospheric nitrogen to ammonia which can be used to
produce nitrogenous fertilizers and explosives. By 1913, the chemical
company BASF turned the discovery into an industrial process. Then
ammonia was produced industrially by the Haber process, named after
Fritz Haber.

The process involves the reaction between nitrogen and hydrogen at

400–450°C and 200 atm in the presence of finely divided iron as the
Figure 54.4 Fritz Haber
(1868–1934) catalyst.

finely divided iron –1

N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
400–450°C,
200 atm

Nitrogen can be obtained from fractional distillation of liquid air.

Learning tip Hydrogen can be obtained from cracking of naphtha or electrolysis of
More about steam brine. It can also be produced by steam reforming of natural gas. This
reforming of natural
reaction gives hydrogen as one of the products.
gas will be discussed in
Section 54.9.

Haber process 哈柏法 BASF 巴斯夫 pharmaceutical 藥物

steam reforming 蒸汽重整<作用> Fritz Haber 弗里茨․哈柏
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Industrial procedure for the Haber process
Figure 54.5 shows a modern chemical plant for carrying out the Haber
process.

Figure 54.5 A modern chemical plant

for the Haber process

The industrial procedure for the Haber process can be represented by

the flow diagram in Figure 54.6.

Catalytic
N2 H2 Volume ratio of
Chamber
N2 : H2 = 1 : 3
(400–450°C)
NH3, unreacted
hot compressed N2 & H2
N2 & H2
heat cool liquid
clean dry up down NH3 Storage
Purifier and Compressor Condenser
Tank
Drier N2 & H2
Heat Exchanger
unreacted N2 & H2
compressed Recycling
N2 & H2 (200 atm) Pump

Figure 54.6 A flow diagram for the industrial procedure of the Haber process

Learning tip Nitrogen and hydrogen are mixed in a volume ratio of 1 : 3. The gaseous
The gaseous mixture is mixture is purified and dried. It is then compressed in a compressor and
purified because any preheated in a heat exchanger before it enters a catalytic chamber.
impurities (such as
sulphur and its
compounds) would In the catalytic chamber, nitrogen and hydrogen combine to give
poison the catalyst. ammonia at 400–450°C and 200 atm in the presence of finely divided iron
as the catalyst. The yield of ammonia is about 15% under such conditions.
–1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
1 volume 3 volumes 2 volumes

The resultant mixture leaving the catalytic chamber is very hot. The
mixture then goes to the heat exchanger, which heats up the incoming
nitrogen and hydrogen while the mixture gets cooled down. This process
saves energy.
catalytic chamber 催化室 purifier 淨化器
114 compressor 加壓器 recycling pump 回流泵
heat exchanger 換熱器
 Industrial processes 54
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The resultant mixture is then cooled to condense ammonia
(b.p.: –33.3°C) to liquid. Ammonia is separated out and collected in the
storage tank. The unreacted nitrogen and hydrogen are recycled.

Key point
The Haber process for the manufacture of ammonia:
finely divided iron –1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
400–450°C,
200 atm

Example 54.1

Understanding the industrial procedure for the Haber process

The equation below shows the reaction involved in the industrial production of ammonia, which takes
place in the presence of finely divided iron.
–1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
(a) The gaseous mixture introduced into the catalytic chamber contains nitrogen and hydrogen in
1 : 3 volume ratio. Suggest a disadvantage of NOT following this volume ratio.
(b) All chemical plants for the Haber process have a heat exchanger. Explain the importance of the
heat exchanger from economic aspect.
(c) Suggest an advantage of separating ammonia from the resultant mixture by condensation.

Solution
(a) An excess of one reactant means that some reactant will pass the catalytic chamber without
reaction. Then there will be a waste of space in the catalytic chamber.
(b) As the reaction is exothermic, the heat produced can be recycled to preheat the mixture of
hydrogen and nitrogen before they enter the catalytic chamber. This can save energy, and thus
the production cost.
(c) Ammonia is easily liquefied while unreacted nitrogen and hydrogen are not. Then ammonia can
be separated easily from the resultant mixture by condensation.

Example 54.2

Calculating the yield of ammonia produced

In a Haber process, 336 kg of nitrogen reacts with 80 kg of hydrogen to give 70 kg of ammonia.
(a) Determine, by calculation, the limiting reactant in the reaction.
(b) Calculate the theoretical yield, in kg, of ammonia.
(c) Calculate the percentage yield of ammonia.
(Relative atomic masses: H = 1.0, N = 14.0)
Cont’d

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Solution
(a) N2(g) + 3H2(g) 2NH3(g)
336 × 1000 g
Number of moles of N2 = –1
= 12 000 mol
(14.0 × 2) g mol
80 × 1000 g
Number of moles of H2 = –1
= 40 000 mol
(1.0 × 2) g mol
From the equation, mole ratio of N2 to H2 = 1 : 3.
12 000 mol of N2 requires 36 000 mol of H2 for complete reaction. Hence, N2 is the limiting
reactant.
(b) From the equation, mole ratio of N2 to NH3 = 1 : 2.
 number of moles of NH3 produced = 12 000 × 2 mol = 24 000 mol
–1
Theoretical yield of NH3 = 24 000 mol × (14.0 + 1.0 × 3) g mol = 408 000 g = 408 kg
actual yield of NH3
(c) Percentage yield of NH3 = × 100%
theoretical yield of NH3
70 kg
= × 100%
408 kg
= 17.2%

Class practice 54.2

Ammonia is manufactured by the Haber process, which used nitrogen and
hydrogen as the feedstocks.
(a) Write the chemical equation for the formation of ammonia from nitrogen
and hydrogen.
(b) A recycling process is practised in the manufacture of ammonia. What is/
are recycled in the Haber process? Explain the importance of such practice
from an economic perspective.
(c) Explain why the mixture of nitrogen and hydrogen must be dry and free
from impurities.

54.3 Compromise between reaction rate, yield

and economic considerations in the Haber
process
Manufacturers aim at maximizing the yield of the desired product and
minimizing the cost and time for its production. This involves a
compromise between the rate of reaction, the yield and economic
considerations. The reaction conditions in the Haber process are a result
of such a compromise.

compromise 協調
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Pressure at 200 atm
Consider the following chemical equilibrium in the Haber process:

N2(g) + 3H2(g) 2NH3(g)

4 moles 2 moles

Since there are a smaller number of moles of gases on the right-

hand side of the equation, an increase in pressure will shift the
equilibrium position to the right. Hence, a high pressure increases the
yield of ammonia. Furthermore, a high pressure also increases the
concentration of the gaseous mixture and speeds up the reaction.

However, the construction cost and maintenance cost of pipelines

and reaction chambers that can withstand a high pressure are both
high. As a compromise, 200 atm is chosen as the operating pressure for the
process.

Temperature at 400–450°C
The forward reaction of the Haber process is exothermic.
–1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol

Decreasing the temperature will shift the equilibrium position to the

right, and thus increase the yield of ammonia. However, decreasing the
temperature will decrease the rate of reaction.

As a compromise, the operating temperature of the process is set at

400–450°C. At this temperature range, both the reaction rate and the yield
of ammonia are not too low.

Using a catalyst
The reaction has very high activation energy as strong N≡N bonds have
to be broken. The use of iron catalyst in the Haber process provides an
Learning tip alternative pathway with lower activation energy. The catalyst speeds
A catalyst has no effect up the reaction. Therefore, more ammonia can be produced in a given
on the equilibrium period of time.
position and will not
increase the yield of
ammonia. The iron catalyst used is in finely divided form. This greatly
increases the surface area of the catalyst, and thus improves its catalytic
effect.

catalyst 催化劑 equilibrium position 平衡位置

chemical equilibrium 化學平衡 exothermic 放熱的
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Example 54.3
Integrated
Effects of pressure, temperature and catalyst on the percentage yield of ammonia
The graph below shows how pressure and temperature affect the percentage yield of ammonia in the
Haber process.

200°C
Percentage yield of ammonia 300°C

400°C

500°C

600°C

Pressure / atm

(a) At constant pressure, what is the effect of temperature on the percentage yield of ammonia?
(b) At constant temperature, what is the effect of pressure on the percentage yield of ammonia?
(c) According to the graph, what pressure has to be maintained at 500°C in order to give a 40% yield
of ammonia?
(d) According to the graph, what is the maximum temperature that gives a 85% or more yield of
ammonia at 500 atm?
(e) In a Haber process operating at 400°C and 200 atm, the gaseous mixture is allowed to leave the
catalytic chamber before it contains about 20% ammonia, i.e. the theoretical yield of ammonia.
Suggest the purpose of doing this.

Solution
(a) The higher the temperature, the lower is the percentage yield of ammonia.
(b) The higher the pressure, the higher is the percentage yield of ammonia.
(c) 600 atm
(d) 300°C
(e) It takes a relatively long time for the system to reach equilibrium (with the highest percentage yield
of ammonia). By allowing the gaseous mixture to leave the catalytic chamber before reaching the
yield of about 20% ammonia, the total amount of NH3(g) produced per unit time increases.

percentage yield 百分產率

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Class practice 54.3

Sulphuric acid is manufactured by the Contact process, which involves the
following reversible reaction.
–1
2SO2(g) + O2(g) 2SO3(g) ∆H = –196 kJ mol
Vanadium(V) oxide is used to catalyse this reaction. If 450 kg of sulphur dioxide
reacts with excess air at 450°C and 1 atm, the percentage yield of sulphur
trioxide is 98%.
(a) Explain, using the concepts of chemical equilibrium, why each of the
following changes can increase the yield of sulphur trioxide.
(i) Lowering the reaction temperature
(ii) Increasing the pressure
(b) Explain why the following reaction conditions are NOT adopted.
(i) A very low reaction temperature
(ii) A very high pressure
(c) Calculate the actual yield, in kg, of sulphur trioxide produced.
(d) Chemical plants for the Contact process are designed to have a
continuous flow of reactants into the catalytic chamber. Explain why this
increases the yield of sulphur trioxide.
(e) State the effect of catalyst on the yield of sulphur trioxide. Explain your
answer.
(Relative atomic masses: O = 16.0, S = 32.1)

54.4 Production of fertilizers from ammonia

The production of fertilizers from feedstock can be represented by the flow
chart below.

Haber process
Feedstock: Bulk chemical: Synthetic products (fertilizers):
N2, H2 NH3 NH4NO3, (NH4)2SO4, (NH2)2CO

Figure 54.7 A flow chart showing the production of fertilizers from feedstock

Ammonia produced from the Haber process is transported to fertilizer

factories. Using different reagents and different methods of production,
nitrogenous fertilizers such as ammonium nitrate (NH4NO3),
ammonium sulphate ((NH4)2SO4) and urea ((NH2)2CO) are produced.
They are then converted to granules, packed in bags and sold to customers.

nitrogenous fertilizer 氮肥
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Production of ammonium nitrate
Ammonium nitrate is produced by reacting nitric acid with ammonia.

Manufacture of nitric acid

Nitric acid is manufactured by catalytic oxidation of ammonia. Figure
54.8 shows a flow diagram for the manufacture of nitric acid.

air NH3 (from Haber process)

air air water

Catalytic chamber NO Oxidation chamber NO2 Absorption

(with Pt catalyst at (mixing and HNO3
chamber
900°C and 8 atm) cooling)

Stage 1 Stage 2 Stage 3

Figure 54.8 A flow diagram for the manufacture of nitric acid

Stage 1 (in catalytic chamber)

Ammonia (from the Haber process) reacts with oxygen (in air) to form
nitrogen monoxide in the presence of platinum catalyst. A temperature of
900°C and a pressure of 8 atm are used as the reaction conditions. The
reaction is highly exothermic.
Pt –1
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) ∆H = –970 kJ mol
900°C, 8 atm

Experiment 54.1 Stage 2 (in oxidation chamber)

Investigating the Nitrogen monoxide reacts with oxygen (in air) to form nitrogen dioxide.
catalytic oxidation of
–1
ammonia 2NO(g) + O2(g) 2NO2(g) ∆H = –117 kJ mol

Experiment video Stage 3 (in absorption chamber)

Investigating the
Nitrogen dioxide is dissolved in water in the presence of air to form nitric
catalytic oxidation
of ammonia acid.
4NO2(g) + O2(g) + 2H2O() 4HNO3(aq)

Production of ammonium nitrate from nitric acid

Learning tip
Nitric acid can also be Most of the nitric acid manufactured (over 80%) reacts with ammonia to
used to make explosives. produce ammonium nitrate.

NH3(aq) + HNO3(aq) NH4NO3(aq)

ammonium nitrate

absorption chamber 吸收室 catalytic oxidation 催化氧化<作用/反應>

120 ammonium nitrate 硝酸銨 nitric acid 硝酸
catalytic chamber 催化室
 Industrial processes 54
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Many fertilizer manufacturers have several other plants built next to
one another. Therefore, the ammonia and nitric acid produced from
separate plants can be conveniently fed to the nearby fertilizer plants
where ammonium nitrate is produced.

Industrial processes are usually continuous. It is more economical to

keep the plants running, instead of producing individual batches of
fertilizers.

Production of ammonium sulphate

Ammonium sulphate is produced by reacting sulphuric acid with
ammonia.
2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
ammonium sulphate

Production of urea
Urea is produced by reacting aqueous ammonia with carbon dioxide
to form ammonium carbamate, which is then dehydrated to form urea.

2NH3(aq) + CO2(g) H2NCOONH4(aq)

ammonium carbamate

H2NCOONH4(aq) (NH2)2CO(aq) + H2O()

urea

Example 54.4
Integrated
Conversion of ammonia to nitrogenous fertilizers
Ammonia is used for the production of nitrogenous fertilizers such as ammonium nitrate and
ammonium sulphate.
(a) To produce ammonium nitrate, ammonia is first converted to nitrogen monoxide by an industrial
process.
(i) Write the chemical equation for the reaction in this step.
(ii) Explain, in terms of oxidation number changes, whether the reaction in (i) is a redox reaction.
(b) To produce ammonium sulphate, ammonia is allowed to react with sulphuric acid. Write the
chemical equation for this reaction.
3
(c) 
Calculate the theoretical volume, in dm , of ammonia, measured at room temperature and
pressure, required to produce 13.20 g of solid ammonium sulphate.
(Relative atomic masses: H = 1.0, N = 14.0, O = 16.0, S = 32.1; molar volume of gas at room
3 –1
temperature and pressure = 24 dm mol )

Cont’d

ammonium carbamate 氨基甲酸銨 urea 脲

ammonium sulphate 硫酸銨
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Solution
(a) (i) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
(ii) That is a redox reaction because the oxidation number of nitrogen increases from –3 to +2.
The oxidation number of oxygen decreases from 0 to –2.
(b) 2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
(c) Number of moles of (NH4)2SO4 produced
13.20 g
= –1
[(14.0 + 1.0 × 4) × 2 + 32.1 + 16.0 × 4] g mol
= 0.0999 mol
From the equation, mole ratio of (NH4)2SO4 to NH3 = 1 : 2.
 number of moles of NH3 required
= 0.0999 × 2 mol
= 0.200 mol
Theoretical volume of NH3 needed
3 –1
= 0.200 mol × 24 dm mol
3
= 4.8 dm

Class practice 54.4

The flow chart below outlines the four main stages in the production of
ammonium nitrate from ammonia.

Stage 1 Stage 2 Stage 3

ammonia nitrogen monoxide nitrogen dioxide nitric acid
catalyst X

Stage 4

ammonium nitrate

(a) (i) Write the chemical equation for the reaction in Stage 1.
(ii) Name catalyst X.
(b) Write the chemical equation for the reaction in Stage 2.
(c) What chemical(s) is/are needed to convert nitrogen dioxide to nitric acid
in Stage 3?
(d) Calculate the theoretical mass, in g, of ammonium nitrate produced when
3
2.0 dm of NH3(g) reacts with excess nitric acid.
(Relative atomic masses: H = 1.0, N = 14.0, O = 16.0; molar volume of gas at
3 –1
room temperature and pressure = 24 dm mol )

ammonium nitrate 硝酸銨

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Reading to learn

Nitrogen fixation

Plants cannot directly use nitrogen from the air. They absorb nitrates from the soil and use the nitrogen
to produce proteins. Nitrogen fixation is any process that converts elemental nitrogen to a nitrogen-
containing compound (e.g. ammonium compound and nitrate). There are a number of nitrogen-fixing
natural processes.

Lightning triggers the reaction between nitrogen and oxygen in the atmosphere to form nitrogen
oxides, namely nitrogen monoxide (NO) and nitrogen dioxide (NO2). Nitrogen oxides react with water in
the atmosphere to form nitrous acid (HNO2) and nitric acid (HNO3). These acids are then carried to the
ground by rain and snow, where they are converted to nitrites and nitrates.

Lightning provides the activation

energy for the reaction between
atmospheric nitrogen and oxygen
to form nitrogen oxides.

Besides, certain bacteria in the roots of plants, such as beans, can convert nitrogen into nitrates. They
are known as nitrogen-fixing bacteria.

Questions
1. Write the chemical equation for the reaction between nitrogen and oxygen to form nitrogen monoxide.
2. Suggest one advantage of fixing nitrogen by bacteria over that by lightning.
3. Is the Haber process a nitrogen fixation process? Explain briefly.

History corner
Production of fertilizer from Chilean nitrate mineral
Prior to the development of the Haber
process, European countries imported
nitrate-containing minerals from Chile to
produce nitrogenous fertilizers. These
minerals contain 6–10% sodium nitrate.
After the minerals were mined and crushed,
the sodium nitrate in minerals was extracted
and crystallized. These crystals contained Chilean nitrate mineral
about 98% of sodium nitrate. The nitrate
provided a nitrogen source for crop growth.

nitrogen fixation 固氮作用 bean 豆類

sodium nitrate 硝酸鈉 Chilean 智利的
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54.5 Importance of the chloroalkali industry

Sodium chloride (NaCl) is found naturally in large amounts in sea water or
in underground deposits. It is often obtained either by evaporating sea
water (Figure 54.9) or by mining underground deposits (Figure 54.10).

Figure 54.9 A salt evaporation pond for extracting sodium Figure 54.10 An underground salt mine
chloride from sea water in Thailand

Learning tip Concentrated sodium chloride solution (brine) is the raw material in
Chlor denotes chlorine the chloroalkali industry. Electrolysis of brine produces three
and alkali denotes an
important chemicals, sodium hydroxide, chlorine and hydrogen. Table
alkali metal, such as
sodium. 54.1 shows some uses of these chemicals.

Chemical Uses

• making chlorine bleach

Sodium hydroxide • making soap
• making drain cleaner

• making hydrochloric acid

• making chlorine bleach
Chlorine
• making polyvinyl chloride (PVC)
• making insecticides and pesticides

• making ammonia
Hydrogen • making hydrochloric acid
• making margarine

Table 54.1 Some uses of sodium hydroxide, chlorine and hydrogen

Key point
electrolysis
brine sodium hydroxide + chlorine + hydrogen
electrolysis
2NaCl(aq) + 2H2O() 2NaOH(aq) + Cl2(g) + H2(g)

brine 鹽水 sodium chloride 氯化鈉 deposit 沉積層

124 chloroalkali industry 氯鹼工業 pond 池塘
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Class practice 54.5
Chlorine, hydrogen and sodium hydroxide are the main products of the
chloroalkali industry. They are produced as bulk chemicals which can be
further processed to give a wide range of synthetic products such as
hydrochloric acid, chlorine bleach, etc.
(a) Identify one main product from above that is used in each of the following
applications.
(i) Making margarine
(ii) Making PVC
(iii) Making drain cleaner
(b) Chlorine bleach is made by dissolving chlorine gas in cold dilute sodium
hydroxide solution.
(i) Complete the following equation for the reaction involved in the
production of chlorine bleach.
Cl2(g) + 2NaOH(aq) (aq) + (aq) + H2O()
(ii) Name the active ingredient in chlorine bleach.

54.6 Chemical principles involved in the

chloroalkali industry
Consider the electrolysis of brine
in the laboratory using the set-up hydrogen chlorine
shown in Figure 54.11:
electrolytic cell
During electrolysis,
+
Learning tip • hydrogen ions H (aq) (from concentrated
graphite sodium chloride
In water, there are small water) are discharged at the electrodes
+ solution
amounts of H (aq) and cathode, forming hydrogen
–
OH (aq) ions coming
from the slight ionization gas H2(g).
of H2O(). –
i.e. H2O()
+
H (aq) + • chloride ions Cl (aq) (from e
– –
e
–
OH (aq) dissolved sodium chloride) are
discharged at the anode, Figure 54.11 Set-up for the electrolysis
forming chlorine gas Cl2(g). of brine using graphite electrodes

+
• sodium ions Na (aq) (from dissolved sodium chloride) and hydroxide
–
ions OH (aq) (from water) stay behind. The resultant electrolytic
solution eventually becomes concentrated in sodium hydroxide.

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However, the following shortcomings would arise in the above

Learning tip electrolytic cell.

A mixture of H2(g) and • The hydrogen and chlorine formed would mix and react to form
Cl2(g) can be explosive.
hydrogen chloride gas.
H2(g) + Cl2(g) 2HCl(g)
• The chlorine formed would react directly with the sodium hydroxide
solution formed in the electrolytic solution.
Cl2(g) + 2NaOH(aq) NaOCl(aq) + NaCl(aq) + H2O()

In the chloroalkali industry, the electrolytic cell used is specially

designed so that the products at the anode and cathode are separated.
This prevents the products from mixing. The flowing mercury cell
and the membrane cell are two of the common electrolytic cells used in
the chloroalkali industry. See Figures 54.12 and 54.13.

Figure 54.12 Flowing mercury cells in a chloroalkali plant Figure 54.13 Membrane cells in a chloroalkali plant

Flowing mercury cell

Figure 54.14 shows a schematic diagram of a flowing mercury cell for the
electrolysis of brine.

chlorine titanium anodes

brine used brine

flow of mercury
hydrogen
mercury cathode
sodium
amalgam

sodium
hydroxide
water
Figure 54.14 Electrolysis
of brine in a flowing mercury
cell pump mercury recovered

flowing mercury cell 流汞電解池

126 membrane cell 薄膜電解池
 Industrial processes 54
TE All answers
The flowing mercury cell has a slightly sloping floor. Mercury is
used as the cathode. It flows down the floor of the cell. Titanium or
graphite is used as the anode. Brine flows through the cell during
electrolysis.

At the anode (titanium or graphite):

– –
2Cl (aq) Cl2(g) + 2e (oxidation)
Think about it
–
What are the advantages Cl (aq) ions are discharged (oxidized) to give chlorine gas. The chlorine
and disadvantages of
gas produced is led away through pipes. It is then liquefied under pressure
using (i) titanium and
(ii) graphite as the and stored in steel cylinders.
anode?
At the cathode (mercury):
+ –
Na (aq) + e + Hg() Na/Hg() (reduction)
sodium amalgam

+
Na (aq) ions are discharged (reduced) to give sodium metal, which
dissolves in the mercury cathode to give a liquid sodium/mercury alloy
called sodium amalgam.

The sodium amalgam then flows to a separate reactor, where it reacts

with water to form sodium hydroxide solution and hydrogen gas.
Mercury is recovered and pumped back to the electrolytic cell. See
Figure 54.14 again.

2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg()

sodium amalgam

The sodium hydroxide solution produced from the flowing

mercury cell has a high purity. Although the mercury is recovered for
reuse, some of it may leak to the environment. This causes serious
environmental problems as mercury is poisonous.

Key point
The reactions that take place during the electrolysis of brine using a
flowing mercury cell:
– –
Oxidation (at anode): 2Cl (aq) Cl2(g) + 2e
+ –
Reduction (at cathode): Na (aq) + e + Hg() Na/Hg()

Membrane cell
Compared with a flowing mercury cell, a membrane cell does not use
mercury which is poisonous. Besides, it operates at a lower voltage.
Less energy is required.
sodium amalgam 鈉汞齊
127
XIII Industrial Chemistry
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Figure 54.15 shows the schematic diagram of a membrane cell for the
electrolysis of brine.

chlorine hydrogen

anode cathode

brine water
+
Na
+
Na
+
Na +
– H
Cl +
titanium anode – H nickel cathode
Cl – –
Cl OH
–
OH
used sodium
brine hydroxide
ion-permeable membrane

Figure 54.15 Electrolysis of brine in a membrane cell

In the membrane cell, the anode and cathode compartments are

separated by an ion-permeable membrane. This ion-permeable
+ – –
membrane allows the passage of Na (aq) ions but not Cl (aq) or OH (aq)
ions. Nickel is used as the cathode while titanium is used as the anode.

At the anode (titanium):

– –
2Cl (aq) Cl2(g) + 2e (oxidation)
–
Cl (aq) ions are discharged (oxidized) to form chlorine gas, leaving an
+
excess of Na (aq) ions in the electrolytic solution.

At the cathode (nickel):

+ –
2H (aq) + 2e H2(g) (reduction)
– –
or 2H2O() + 2e H2(g) + 2OH (aq)
+
H (aq) ions from water are discharged (reduced) to form hydrogen gas.
–
OH (aq) ions will accumulate in the cathode compartment. The excess
+
Na (aq) ions in the anode compartment will migrate through the ion-
permeable membrane to the cathode compartment to balance the excess
negative charge there.

The used brine is removed from the anode compartment. The

resultant solution in the cathode compartment is sodium hydroxide
solution with no or least sodium chloride impurity.

128
 Industrial processes 54
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Key point
The reactions that take place during the electrolysis of brine using a
membrane cell:
– –
Oxidation (at anode): 2Cl (aq) Cl2(g) + 2e
+ –
Reduction (at cathode): 2H (aq) + 2e H2(g) or
– –
2H2O() + 2e H2(g) + 2OH (aq)

Example 54.5

Understanding the chemical principles involved in the electrolysis of brine

The set-up shown in the diagram below can be used to simulate the industrial production of chlorine,
hydrogen and sodium hydroxide using a flowing mercury cell.

chlorine

electrode P
concentrated sodium
chloride solution
platinum wire

mercury electrode

After passing electricity through the electrolytic cell for some time, chlorine is produced at electrode
P. Upon running the mercury electrode into cold water (not shown in the diagram), an alkaline solution
and a colourless gas are produced.
(a) Which electrode in the set-up is the cathode?
(b) Suggest a material suitable for making P.
(c) With the aid of a half equation, account for the formation of chlorine at P.
(d) (i) The product formed at the mercury electrode can dissolve in mercury to form an alloy.
Name this alloy.
(ii) Write the chemical equation for the reaction that occurs when the mercury electrode is run
into the cold water.
(iii) What is the alkaline solution produced?
(e) State TWO potential hazards of using a flowing mercury cell for the electrolysis of brine.

Solution
(a) Mercury electrode
(b) Graphite or titanium
Cont’d

129
XIII Industrial Chemistry
All answers TE
– –
(c) P is the anode. Cl (aq) ions are preferentially discharged at P because the concentration of Cl (aq)
–
ions is much higher than that of OH (aq) in the electrolytic solution.
– –
2Cl (aq) Cl2(g) + 2e
(d) (i) Sodium amalgam
(ii) 2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg()
(iii) Sodium hydroxide solution
(e) Mercury may vaporize during the electrolysis. Prolonged inhalation may lead to mercury
poisoning. Besides, chlorine is toxic.

Table 54.2 compares a flowing mercury cell with a membrane cell for
the electrolysis of brine.

Flowing mercury cell Membrane cell

Anode Titanium or graphite Titanium

Cathode Mercury (flowing) Nickel

Brine Brine
Electrolyte
(flowing through the cell) (flowing through the anode compartment)
– –
Anodic reaction 2Cl (aq) Cl2(g) + 2e
+ –
+ –
2H (aq) + 2e H2(g)
Cathodic reaction Na (aq) + e + Hg() Na/Hg() – –
or 2H2O() + 2e H2(g) + 2OH (aq)

Separation between
cathode and anode None Ion-permeable membrane
compartments

Table 54.2 Comparison of a flowing mercury cell with a membrane cell

Class practice 54.6

Flowing mercury cells and membrane cells are two kinds of electrolytic cells
commonly used in the chloroalkali industry. In these cells, brine is electrolysed
to give chlorine, sodium hydroxide and hydrogen as the main products.
(a) State the raw material used in the chloroalkali industry.
(b) Write the overall equation for the electrolysis of brine in the chloroalkali
industry.
(c) Give TWO advantages of using membrane cells over using flowing
mercury cells in chloroalkali plants.

130
 Industrial processes 54
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54.7 Social, economic and environmental
considerations of the chloroalkali industry
There was once a chloroalkali plant in Hong Kong. It was located at Tsing
Yi Island. The plant had stopped operating since 1996. One of the reasons
was the high operation costs of the plant.

Other than the chemical principles involved in the industrial processes,

it is necessary to consider the social, economic and environmental
aspects of setting up a chemical plant. The following points have to be
considered when setting up a chloroalkali plant.

Availability of resources and costs

• Is the plant close to the source of raw materials?
It costs more if raw materials are transported over long distances. It would
be preferable to choose the site of the chloroalkali plant near the sea.

• Is there an inexpensive fuel and electricity supply?

Coal, petroleum or natural gas may be used as fuel. The choice of a fuel
depends on its price. Electricity is used during electrolysis of brine. The
cost of electricity has to be considered too.

• Are land and labour available and affordable?

A chemical plant usually occupies a large area. There should be adequate
land resources at reasonably low price. Besides, there should be a
good supply of skilled labour nearby and the wage cost should be low
enough to support the operation.

Demand and transport

• Are there available markets nearby?
If there is demand for the products in nearby regions, this will reduce
the cost of delivering products to customers.

• Is there a good transport network?

A good transport network is essential for delivery of the products to
customers and for the convenience of workers. Hence, it would be
important to build the chemical plant near a port, or close to a railway or
major roads.
chloroalkali industry 氯鹼工業
131
XIII Industrial Chemistry
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Environmental considerations and impacts
Activity 54.1 • Are the costs for pollution control high?
‘Is it desirable to set up Nowadays, stricter regulations are set on the handling of chemical wastes
a chloroalkali plant in
Hong Kong?’ and harmful emissions from chemical plants. The cost of waste disposal
In this activity, the teacher and that for compliance with water and air pollution control would
will divide the class into
be high.
two groups. One group is
for the above motion and
the other is against. At • What pollution problems would arise?
the end of the debate,
both sides are required to
There will be air, water and noise
make a conclusion on
different viewpoints. pollution if there is leakage of raw
materials and spillage or emissions of
wastes (Figure 54.16).

Figure 54.16 Chemical wastes

discharged without proper treatment
cause serious water pollution.

STSE issue 54.2

Hazards relating to the improper disposal of mercury from industry
The Chisso Corporation was located in Kumamoto, Japan. It mainly produced petrochemicals and plastics.
From 1932 to 1968, the company dumped an estimated 27 tonnes of mercury compounds into Minamata Bay.
Minamata was a small factory town near Kumamoto. Most of the factories in there were dominated by the
Chisso Corporation.

A woman held a victim of ‘Minamata

Disease’ in Minamata, Japan, in 1973.

Starting from the 1950s, thousands of people whose diet included fish from the bay were found to have
developed symptoms of mercury poisoning. The illness was then known as ‘Minamata Disease’. The symptoms
of ‘Minamata Disease’ included sensory problems in the hands and feet, damage to vision and hearing,
weakness, and in extreme cases, paralysis and death. Furthermore, some victims were thought to have suffered
mental illness when they began to uncontrollably shout.

Chisso Corporation 智索株式會社 Minamata Bay 水俁灣

132 compliance 遵守 paralysis 麻痺
Kumamoto 熊本市
 Industrial processes 54
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54.8 Importance of methanol
Methanol (CH3OH) (b.p.: 64.6°C) is a colourless liquid under room
conditions. It is toxic and flammable but has a wide range of uses. The
structural formula of methanol is:

In industry, methanol is converted into different chemical feedstocks

and products. Figure 54.17 shows the distribution of these feedstocks and
products.
dimethyl ethene and propene
ether 10%
methanal 10%
29% ethers (e.g. MTBE)
10%

methyl methylpropenoate
2%
chloromethanes
2%
methanamine petrol
Figure 54.17 Distribution of chemical 3% 10%
biodiesel
feedstocks and products produced solvents others ethanoic acid
4%
from methanol 5% 6% 9%

As feedstock to produce chemicals

Methanol is a one-carbon compound which can act as a starting
material to make carbon compounds with larger numbers of carbon.
Learning tip
These carbon compounds can be used to manufacture consumer and
• Manufacture of acetic
acid from methanol industrial products.
will be discussed in
Section 55.4. Methanol can be used as a
• The structural formula feedstock to produce chemicals such
of dimethyl ether
(DME) is:
as acetic acid (ethanoic acid) and
formaldehyde (methanal). These
chemicals are in turn used in making
products like synthetic polymers,
• The structural formula adhesives, foams and paints. Methanol
of methyl tertiary butyl can also be converted to dimethyl ether
ether (MTBE) is:
(DME) and methyl tertiary butyl ether
(MTBE) which are used to produce Figure 54.18 DME is an aerosol
spray propellent.
aerosol spray propellent (Figure 54.18)
and petrol additive respectively.

acetic acid 醋酸 methanol 甲醇 adhesive 黏合劑 foam 泡沫

dimethyl ether 二甲醚 methyl tertiary butyl ether 甲基三級丁基醚 aerosol spray propellent 噴霧器推進劑 petrol additive 汽油添加劑
133
methanal 甲醛
XIII Industrial Chemistry
All answers
As a fuel for motor vehicles
Methanol is a liquid fuel. It can be
easily handled and transported.
Think about it Methanol can be used on its own
What are the advantages as a fuel for motor vehicles
and disadvantages of
using methanol as a fuel (Figure 54.19) or blended into
compared with petrol? petrol to produce a clean fuel.

Figure 54.19 A methanol powered bus in

New York City

As a fuel for fuel cells

Methanol is a liquid over a broad
temperature range (–97.6°C to direct methanol
fuel cell
64.7°C), covering all conditions in
Learning tip which fuel cells operate. Methanol
Refer to ‘Extended can be used as a fuel for many
learning 31.1: Direct different fuel cells, ranging from
methanol fuel cell
(DMFC)’ in Book 3B, fuel cells to power vehicles to
p.101 for the working portable fuel cells for electronic
principle of DMFC.
devices (Figure 54.20).
Figure 54.20 A direct methanol fuel cell
(DMFC) is powering a compact disc (CD)
player.

For making biodiesel

Learning tip Methanol is used to convert triesters such as vegetable oils and
Triesters can be used
to make soap by animal fats into biodiesel.
saponification as
discussed in Book 4B,
Chapter 46.

KOH

a triester methanol a biodiesel glycerol

biodiesel 生物柴油 petrol 汽油

134 fuel cell 燃料電池 saponification 皂化<作用/反應>
glycerol 甘油 triester 三酯
methanol 甲醇
 Industrial processes 54
54.9 Manufacture of methanol

Significance of the conversion of natural gas to

methanol
Learning tip
Natural gas consists Natural gas is an abundant raw material in the Earth’s crust, and the
mainly of methane
majority of natural gas resources are found, together with petroleum, in
(about 70–90%).
remote regions. Storage and transportation of natural gas require
special tanks and pipelines which are very expensive to build. Some of
the natural gas obtained in oil fields is burned (Figure 54.21) directly or
simply released into the atmosphere.

One of the solutions is to convert natural gas to methanol in

chemical plants near the oil fields. Methanol is a liquid which is easier to
store and transport. Moreover, methanol is more reactive than
methane. It is more suitable for use as a starting material for the
production of fuels and other useful chemicals.

Processes involved in the manufacture of methanol

Figure 54.21 Burning of
natural gas at an oil field
from natural gas
Figure 54.22 shows a flow diagram for the manufacture of methanol from
natural gas.

natural gas

desulphurization for removal of any

sulphur impurities
crude
steam Steam syngas Synthesis of methanol Methanol
CO2 reforming methanol distillation

pure methanol

Figure 54.22 A flow diagram for the manufacture of methanol from natural gas

The manufacture of methanol involves three main processes:

1. Production of syngas by steam reforming of natural gas
2. Synthesis of methanol
3. Purification of methanol by distillation

steam reforming of natural gas 天然氣的蒸汽重整<作用> oil field 油田

syngas 合成氣
135
XIII Industrial Chemistry
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1. Production of syngas by steam reforming of natural gas
Natural gas (its main component is methane) is mixed with steam under
30 atm, heated to around 700–1000°C and then passed over nickel(II) oxide
(NiO) catalyst. This process is known as steam reforming. Synthesis gas
or syngas is produced in the process. Syngas is a mixture consisting
mainly of H2(g) and CO(g).
NiO –1
CH4(g) + H2O(g) CO(g) + 3H2(g) ∆H = +206 kJ mol
700–1000°C, 1 : 3
30 atm

2. Synthesis of methanol
The conversion of syngas to methanol involves the use of Cu/ZnO/Al2O3
catalyst (a mixture of Cu, ZnO and Al2O3) under 50–100 atm and about
250°C.
Cu/ZnO/Al2O3
–1
CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol
1 : 2 250°C,
50–100 atm

The conversion of syngas to methanol requires CO(g) and H2(g) in

mole ratio of 1 : 2. As the production of syngas generates CO(g) and H2(g)
in mole ratio of 1 : 3, a shift reaction, as shown below, is used to increase
the amount of CO(g) and reduce the amount of H2(g).
–1
CO2(g) + H2(g) CO(g) + H2O(g) ∆H = –41 kJ mol

After the conversion of syngas to methanol, the methanol produced

is separated from the unreacted gases. The unreacted gases and the heat
produced from the conversion are recycled.

3. Purification of methanol by distillation

The crude methanol collected from the above conversion contains
methanol, water and traces of by-products. Pure methanol can be obtained
by distilling the crude methanol.

Key point
Methanol is manufactured by the following reactions:
NiO
CH4(g) + H2O(g) CO(g) + 3H2(g)
700–1000°C,
30 atm

Cu/ZnO/Al2O3
CO(g) + 2H2(g) CH3OH(g)
250°C,
50–100 atm

shift reaction 轉移反應 synthesis gas/syngas 合成氣體/合成氣

136 steam reforming 蒸汽重整<作用>
 Industrial processes 54
TE
Example 54.6
Integrated
Understanding the physiochemical principles involved in the manufacture of methanol via
syngas
Consider the following flow diagram about the production of methanol via syngas.
Process 1: Process 2: Process 3:

Steam Compression and Distillation of crude

reforming of conversion of syngas methanol to obtain
natural gas to produce methanol pure methanol

(a) (i) State the main component of natural gas.

(ii) Write the chemical equation for the steam reforming of natural gas in Process 1.
(b) The syngas produced is compressed and its components are allowed to react as described below.
Cu/ZnO/Al2O3 –1
CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol
250°C, 50–100 atm
(i) Draw a labelled energy profile for the formation of methanol from syngas. (Note: you are
NOT required to label the catalysts in the energy profile.)
(ii) Explain, by using the concepts of chemical equilibrium and reaction rate, why it is necessary
to compress the syngas before it enters the catalytic chamber.
(iii) (1) Would increasing or decreasing the temperature favour the formation of methanol?
Suggest a reason.
(2) Justify, in terms of chemical equilibrium and reaction rate, the temperature (250°C) used
in the conversion is a compromise.
Solution
(a) (i) Methane
(ii) CH4(g) + H2O(g) CO(g) + 3H2(g)
(b) (i) (ii) The conversion of syngas to methanol
involves a decrease in number of moles of
gases. Thus, high pressure shifts the
Potential energy

equilibrium position to the right to produce

more methanol.
Also, increasing the pressure makes the
–1
∆H = –90 kJ mol
particles crowded. This increases the
frequency of effective collisions and hence the
reaction rate.
Reaction coordinate

(iii) (1) Decreasing the temperature favours the formation of methanol because the forward
reaction is an exothermic reaction.
(2) Too low a temperature leads to very slow reaction and takes a long time for the system to
reach equilibrium.
Too high a temperature favours the backward reaction, which is an endothermic reaction.
This reduces the yield of methanol.

physiochemical 物理化學
137
XIII Industrial Chemistry
All answers
Class practice 54.7
Methanol is an important bulk chemical that is used in making a wide variety
of synthetic products. Traditionally, the substance for making methanol is
syngas which is made from methane.
(a) (i) What is syngas?
(ii) Write the chemical equation for the production of syngas from
methane.
(iii) What is the mole ratio of CO to H2 in the syngas produced?
(b) (i) Write the chemical equation for the production of methanol from
syngas.
(ii) What is the mole ratio of CO to H2 used in the production of methanol?
(c) A shift reaction is adopted to adjust the mole ratio of CO to H2 in syngas
for effective production of methanol.
(i) Write the chemical equation for the shift reaction.
(ii) Explain the significance of the shift reaction in the methanol
production.
(d) Name one carbon compound that is produced from methanol in chemical
industry and state one of its uses.

Advancement of the methanol production

technology
The conversion of methane to methanol has quite a long history. In 1923,
a German chemist, Matthias Pier, developed a method to convert syngas
to methanol. In 1966, ICI, one of the world’s major paint manufacturers,
developed the method mentioned on p.136. Table 54.3 shows a comparison
of the two methods.

Method
Year Catalyst used Operating pressure Operating temperature
developed by

Matthias Pier 1923 ZnO/Cr2O3 300 atm 400°C

ICI 1966 Cu/ZnO/Al2O3 50–100 atm 250°C

Table 54.3 Comparing Matthias Pier’s method and ICI’s method for the conversion of syngas to methanol

The ICI’s method uses a more efficient catalyst and operates at a

much lower pressure and temperature. Hence, the construction cost
and maintenance cost of pipelines and reaction chambers that can
withstand high pressures are lower. The use of a lower temperature also
saves energy.

ICI 帝國化學工業
138 Matthias Pier 馬提亞斯․皮爾
 Industrial processes 54
TE All answers
Apart from using the improved operating conditions, scientists are
still investigating into developing more efficient and sustainable ways
of producing methanol.

Direct conversion of methane to methanol

With the use of zeolite (Figure 54.23) as catalyst at atmospheric pressure
and around 200°C, methane can be converted directly to methanol. No
by-products form in this reaction.

1 zeolite
CH4(g) + O2(g) CH3OH()
2 ~200°C, 1 atm

Microbial reactions
Figure 54.23 Zeolite stones
Methane can be oxidized to methanol by some microbes (e.g. yeast and
bacteria). These microbes provide enzymes for oxidation. The oxidation
uses renewable feedstock and has higher energy efficiency.

New sources of renewable feedstock

Learning tip Methane collected from landfills can be used as a renewable feedstock
The installation of for methanol production. Besides, biomass (e.g. pig manure and rice straw)
digesters can convert is another renewable feedstock that can be converted to syngas. Then
tonnes of pig manure
to syngas daily. syngas can be converted to methanol (Figure 54.24).

Figure 54.24 Rice straw can be

used as a renewable feedstock of
syngas for methanol production.

Class practice 54.8

Methanol can be produced industrially by the reaction as shown below.
–1
CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol
Unconsumed hydrogen from chemical industries is allowed to react with
carbon monoxide to produce methanol.
Explain why this methanol production technology is considered as an
advancement.

biomass 生物量 digester 消化器 rice straw 稻草

zeolite 沸石 microbe 微生物 sustainable 可持續的
139
XIII Industrial Chemistry
All answers
Reading to learn

Producing methanol from carbon dioxide captured from the atmosphere

Carbon dioxide is a greenhouse gas that causes global warming. Scientists have been working hard to
capture carbon dioxide from the atmosphere and convert it to methanol using a catalyst in solution form.
The CO2-to-methanol conversion requires a temperature of 150°C. Scientists are facing the challenge of
finding a catalyst which is stable at this temperature.
In 2017, a research team led by a chemistry professor at the
University of Southern California, USA, developed a stable catalyst
based on ruthenium metal. With the new catalyst, about 79% of the
carbon dioxide captured from the atmosphere can be converted to
methanol. The crude product is a methanol-water mixture, from
which methanol can be separated by distillation.
Ru(s)
CO2(g) + 3H2(g) CH3OH(g) + H2O() Emissions from industrial plants
150°C
contain carbon dioxide.

Questions
1. Suggest one benefit of the CO2-to-methanol conversion process to the environment.
2. Why is it important to develop a catalyst that will not be easily decomposed at elevated temperatures?

Chemistry in daily life

Methanol as a ship fuel

In recent years, some research studies have shown that methanol is a promising
alternative fuel for ships. Methanol burns cleanly in ship engines with lower
emissions of nitrogen oxides (NOx) and suspended particulates compared with
traditional ship fuels (e.g. fuel oil). Besides, methanol gives no sulphur dioxide
in combustion as it is sulphur-free.

Furthermore, methanol is biodegradable. It dissolves readily in water and

can be oxidized to methanoic acid through enzymatic reaction by most micro-
organisms, which is eventually converted to carbon dioxide. This means that
any methanol accidentally spilled on the sea could be removed in a much
shorter time. The environmental impact of methanol spillage would be less
harmful than that of equivalent oil spillage.

Methanol may be an alternative

fuel for greener shipping.

biodegradable 生物可降解的 methanol 甲醇 equivalent 相等的

140 fuel oil 燃料油 methanoic acid 甲酸
 Industrial processes 54
TE
Chapter review
Progress check

Chapter review
After studying this chapter, you should be able to:
describe the importance of fertilizers to our world
describe the feedstock, principles, reaction conditions, procedures and products for processes
involved in the manufacture of ammonia
explain the physicochemical principles involved in the manufacture of ammonia
explain how industrial processes such as the Haber process often involve a compromise between
rate, yield and economic considerations
describe the process of the conversion of ammonia to fertilizers
describe the importance of the chloroalkali industry
explain the underlying chemical principles involved in flowing mercury cell process and
membrane cell process of the chloroalkali industry
discuss the social, economic and environmental considerations of industrial processes as
illustrated by the chloroalkali industry
describe the importance of methanol
recognize the significance of the conversion of methane to methanol
describe the feedstock, reaction conditions, procedures and products for processes involved in
the manufacture of methanol via syngas
discuss the advancement of the methanol production technology

e-Dictionary
Key terms (For Chapter 54)
Page Page
1. catalytic oxidation 催化氧化<作用/反應> 120 6. methanol 甲醇 133
2. chloroalkali industry 氯鹼工業 124 7. nitrogenous fertilizer 氮肥 111
3. flowing mercury cell 流汞電解池 126 8. sodium amalgam 鈉汞齊 127
4. Haber process 哈柏法 113 9. steam reforming 蒸汽重整<作用> 136
5. membrane cell 薄膜電解池 126 10. synthesis gas/syngas 合成氣體/合成氣 136

141
 XIII Industrial Chemistry

Key concepts
54.1 Importance of fertilizers
Chapter review

–
1. Nitrogenous fertilizers are often produced in the form of nitrates (NO3 ) or ammonium salts
+
(NH4 ). Ammonium nitrate (NH4NO3) is one of the most widely used nitrogenous fertilizers.

54.2 Manufacture of ammonia by the Haber process

2. Ammonia is used in making nitrogenous fertilizers.

3. Ammonia is produced industrially by the Haber process:

finely divided iron –1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
400–450°C,
200 atm

4. In the Haber process, nitrogen can be obtained from fractional distillation of liquid air. Hydrogen
can be obtained from cracking of naphtha or electrolysis of brine. It can also be produced by
steam reforming of natural gas.

54.3 Compromise between reaction rate, yield and economic considerations in the Haber
process

5. High pressures and low temperatures increase the yield of ammonia at equilibrium. However,
operating at high pressures requires a high cost for the construction and maintenance of
pipelines. Operating at low temperatures decreases the reaction rate. As a compromise, the
operating pressure and temperature of the Haber process are chosen at 200 atm and 400–450°C
respectively.

54.4 Production of fertilizers from ammonia

6. Ammonium nitrate is produced by reacting nitric acid with ammonia.

NH3(aq) + HNO3(aq) NH4NO3(aq)

7. Nitric acid is manufactured by catalytic oxidation of ammonia.

Pt –1
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) ∆H = –970 kJ mol
900°C, 8 atm
–1
2NO(g) + O2(g) 2NO2(g) ∆H = –117 kJ mol
4NO2(g) + O2(g) + 2H2O() 4HNO3(aq)

8. Ammonium sulphate is produced by reacting sulphuric acid with ammonia.

2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)

9. Urea is produced by reacting aqueous ammonia with carbon dioxide to form ammonium
carbamate, which is then dehydrated to form urea.
2NH3(aq) + CO2(g) H2NCOONH4(aq)
ammonium carbamate

H2NCOONH4(aq) (NH2)2CO(aq) + H2O()

urea

142
 Industrial processes 54
54.5 Importance of the chloroalkali industry

10. Concentrated sodium chloride solution (brine) is the raw material in the chloroalkali industry.

Chapter review
11. The electrolysis of brine produces three important chemicals, sodium hydroxide, chlorine and
hydrogen.
electrolysis
2NaCl(aq) + 2H2O() 2NaOH(aq) + Cl2(g) + H2(g)

54.6 Chemical principles involved in the chloroalkali industry

12. Electrolysis of brine using a flowing mercury cell:

– –
At the anode: 2Cl (aq) Cl2(g) + 2e
+ –
At the cathode: Na (aq) + e + Hg() Na/Hg()
Sodium amalgam reacts with water to form sodium hydroxide solution and hydrogen gas.
2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg()

13. Electrolysis of brine using a membrane cell:

– –
At the anode: 2Cl (aq) Cl2(g) + 2e
+ – – –
At the cathode: 2H (aq) + 2e H2(g) or 2H2O() + 2e H2(g) + 2OH (aq)

54.7 Social, economic and environmental considerations of the chloroalkali industry

14. Other than the chemical principles involved in the industrial processes, it is necessary to
consider the social, economic and environmental aspects of setting up a chemical plant.

54.8 Importance of methanol

15. Methanol can be used as a feedstock to produce chemicals, as a fuel for motor vehicles and fuel
cells, and for making biodiesel.

54.9 Manufacture of methanol

16. The manufacture of methanol involves three processes:

(a) Production of syngas by steam reforming of natural gas
NiO –1
CH4(g) + H2O(g) CO(g) + 3H2(g) ∆H = +206 kJ mol
700–1000°C, 1 : 3
30 atm

(b) Synthesis of methanol

Cu/ZnO/Al2O3
–1
CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol
1 : 2 250°C,
50–100 atm

(c) Purification of methanol by distillation

143
 Chapter review

144
XIII
Concept map
Complete the concept map by filling in the items listed below:

brine, chlorine, fuel, membrane cell, methane, (NH2)2CO, NH3, NH4NO3, (NH4)2SO4, syngas

(b)
Hydrogen Sodium hydroxide
Industrial Chemistry
All answers

products Flowing mercury cell

(a) raw material cells used
Chloroalkali industry
TE

(c)

INDUSTRIAL PROCESSES

Production of fertilizers Production of methanol

Fractional
basic chemical N2 distillation of
liquid air basic chemical
(d) Haber process

(h)

H2 H2, CO
(H2, CO)
catalytic oxidation compression,
Cu/ZnO/Al2O3 then distillation

H2SO4 1. CO2 HNO3 Steam reforming CH3OH

2. H2O
uses
(e) (f) (g)
(i)
from • as a feedstock to produce chemicals
natural gas • as a (j) for motor vehicles and fuel cells
• for making biodiesel
 Industrial processes 54
TE All answers
Chapter exercise
A. Fill in the blanks
Section 54.2 Section 54.5
1. is the feedstock for making 5. Concentrated solution
nitrogenous fertilizers. It is produced industrially by (brine) is the raw material in the chloroalkali
the Haber process which combines nitrogen and industry. The electrolysis of brine produces
hydrogen directly at °C and , and

Chapter exercise
atm in the presence of finely .
divided as the catalyst.
Section 54.6
2. In the Haber process, nitrogen is obtained from 6. cells and
of liquid air. Hydrogen cells are two kinds of electrolytic cells commonly
can be obtained from of used in the chloroalkali industry.
naphtha or of brine. It can also
Section 54.8
be produced by steam reforming of natural gas.
7. is the major component of
3. In the Haber process, nitrogen and hydrogen are
natural gas. It can be used as to
mixed in a volume ratio of . The
produce chemicals, as a for
mixture is and dried. Then it is
motor vehicles and fuel cells. Methanol is also used
compressed in a compressor and preheated in a
for making .
before it enters a catalytic
chamber. The gaseous mixture leaving the catalytic Section 54.9

chamber is cooled to ammonia 8. The manufacture of methanol from natural gas

to a liquid and then separate it out. The unreacted involves three main processes:
nitrogen and hydrogen are . (a) Production of by

Section 54.4 of natural gas

4. Nitric acid is manufactured by (b) of methanol

of ammonia. The feedstocks for the (c) Purification of methanol by
manufacture are ammonia, (in air)
and water.

B. Practice question
Section 54.9
9. State the operating conditions and suitable catalyst(s) for each of the following industrial processes.
(a) Haber process: N2(g) + 3H2(g) 2NH3(g)
(b) Catalytic oxidation of ammonia: 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
(c) Steam reforming of natural gas: CH4(g) + H2O(g) CO(g) + 3H2(g)
(d) Conversion of syngas to methanol: CO(g) + 2H2(g) CH3OH(g)

145
 XIII Industrial Chemistry
All answers
C. Multiple-choice questions
Section 54.3 14. If 12.8 g of NH3 is completely oxidized to HNO3,
10. Consider the following reversible reaction: what is the theoretical yield of HNO3?
–1 (Relative atomic masses: H = 1.0, N = 14.0, O = 16.0)
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
A. 27.7 g
Which of the following actions would cause the
B. 47.4 g
equilibrium position to shift to the right?
C. 66.5 g
(1) Increasing the pressure D. 94.5 g
(2) Increasing the temperature
(3) Adding a catalyst Direction: Q15 and Q16 refer to the following reactions
Chapter exercise

A. (1) only in the production of urea.

B. (2) only 2NH3 + CO2 X (NH2)2CO + H2O
C. (1) and (3) only
15. Which of the following is the possible formula of X?
D. (2) and (3) only
A. H2NCONH4
11. Which of the following reactions are redox? B. H2NCOONH2
(1) N2(g) + 3H2(g) 2NH3(g) C. H3NCOONH3
(2) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) D. H2NCOONH4
(3) 4NO2(g) + O2(g) + 2H2O() 4HNO3(aq)
16. If 17.0 g of NH3 gives 24.0 g of urea, what is the
A. (1) and (2) only percentage yield of urea?
B. (1) and (3) only
(Relative atomic masses: H = 1.0, C = 12.0, N = 14.0,
C. (2) and (3) only
O = 16.0)
D. (1), (2) and (3)
A. 60.0%
Section 54.4 B. 70.0%
12. Which of the following nitrogen compounds are C. 80.0%
commonly used as fertilizers? D. 90.0%

(1) Sodium nitrite Section 54.6

(2) Ammonium nitrate
17. Which of the following changes takes place at the
(3) Urea
negative electrode of a membrane cell?
A. (1) and (2) only + –
A. Na + e Na
B. (1) and (3) only – –
B. 2Cl Cl2 + 2e
C. (2) and (3) only – –
C. 4OH O2 + 2H2O + 4e
D. (1), (2) and (3) – –
D. 2H2O + 2e H2 + 2OH
Direction: Q13 and Q14 refer to the following series of
18. Which of the following statements about the
conversions for the production of nitric acid from
membrane in a membrane cell are correct?
ammonia.
(1) The membrane is permeable to both cations
NH3 NO NO2 HNO3 and anions.
13. Which of the following correctly shows the changes (2) The membrane separates the cell into cathode
in oxidation number of nitrogen in these and anode compartments.
conversions? (3) The membrane prevents the hydrogen and
A. 0 +2 +4 +6 chlorine formed from mixing.
B. –3 +2 +4 +5 A. (1) and (2) only
C. +3 –2 –4 –5 B. (1) and (3) only
D. –3 +4 +2 +5 C. (2) and (3) only
D. (1), (2) and (3)

146
 Industrial processes 54
All answers
19. Which of the following are advantages of using Section 54.9
membrane cells over using flowing mercury cells in 21. Which of the following equations represents a shift
the chloroalkali industry? reaction for adjusting the composition of syngas?
(1) The sodium hydroxide solution obtained A. CH4(g) + H2O(g) 3H2(g) + CO(g)
contains no sodium chloride. B. CO2(g) + H2(g) CO(g) + H2O(g)
(2) They do not involve the use of poisonous C. 2H2(g) + O2(g) 2H2O(g)
mercury. D. C(s) + H2O(g) CO(g) + H2(g)
(3) Less energy is required for operation.
A. (1) and (2) only 22. The production of methanol from syngas involves
B. (1) and (3) only the following reversible reaction:

Chapter exercise
C. (2) and (3) only CO(g) + 2H2(g) CH3OH(g)
–1
D. (1), (2) and (3) ∆H = –90 kJ mol

Section 54.8 Which of the following combinations of temperature

20. Which of the following are the uses of methanol? and pressure favours the production of methanol?

(1) As a solvent A. Low temperature and low pressure

(2) As a feedstock for producing ethanoic acid B. High temperature and high pressure
(3) As an ingredient in alcoholic drinks C. Low temperature and high pressure
D. High temperature and low pressure
A. (1) and (2) only
B. (1) and (3) only
C. (2) and (3) only
D. (1), (2) and (3)

D. Structured question
Section 54.9
23. In chemical industry, methanol is produced from the reaction between carbon monoxide and hydrogen in a mole
ratio of 1 : 2.
(a) Write the chemical equation for the production of methanol from carbon monoxide and hydrogen. (1 mark)
(b) (i) Describe how a mixture of carbon monoxide and hydrogen can be produced from natural gas.
(ii) Write the chemical equation for the reaction involved in (b)(i), and state the mole ratio of carbon monoxide
and hydrogen in the gaseous mixture produced.
(3 marks)
(c) Consider the following shift reaction:
CO2(g) + H2(g) CO(g) + H2O(g) ∆H < 0
(i) State the effect of increasing the concentration of CO2(g) on this equilibrium system.
(ii) Explain why the shift reaction can make the industrial production of methanol more efficient.
(3 marks)

147
 XIII Industrial Chemistry

Exam practice
A. Structured questions
Section 54.2
1. Explain why the Haber process significantly contributes to crop yield increase.
(1 mark)
(HKDSE 2019 Paper 2 Q1a(i))
Section 54.4
2. (a) The graph below shows the percentage yield of ammonia when nitrogen and hydrogen react in a mole ratio of
1 : 3 at different temperatures and pressures.

N2(g) + 3H2(g) 2NH3(g)

200°C
300°C
Exam practice

Percentage yield of NH3

400°C

500°C

600°C

Pressure / atm

(i) From the graph, find the temperature and pressure combination that gives the highest percentage yield of
ammonia.
(ii) Deduce whether the formation of ammonia from nitrogen and hydrogen is exothermic or endothermic.
(iii) What is the percentage yield of ammonia at 400°C and 200 atm?
(iv) Justify, with reference to equilibrium position, reaction rate and/or production cost, the Haber process
operating at 400°C and 200 atm is a compromise.
(5 marks)
(b) In the Haber process,
(i) explain why it is necessary to purify and dry the gaseous reactants before passing them into the catalytic
chamber.
(ii) state how ammonia can be separated from the resultant mixture after it leaves the catalytic chamber.
(2 marks)
(c) Ammonia is used in making synthetic fertilizers such as ammonium sulphate.
(i) Write the chemical equation for the production of ammonium sulphate from ammonia.
(ii) State and explain the effect of adding ammonium sulphate on the soil pH.
(3 marks)
148
 Industrial processes 54
3. Nowadays in industry, a solid catalyst vanadium(V) oxide is used for the conversion of SO2(g) to SO3(g).
(a) The reactants need to be purified before passing into the reaction chamber containing the catalyst. Why?
(1 mark)
(b) The operation conditions are set at 450°C and 1 atm to achieve a 96% conversion. Suggest why it is NOT
preferable to further increase the conversion percentage by each of the following methods:
(i) lowering the temperature of the reaction system
(ii) increasing the pressure of the reaction system
(2 marks)
(c) In order to increase the conversion percentage, one of the reactants used is in slight excess. From the perspective
of feedstock, which of SO2(g) or O2(g) would be in slight excess? Explain your answer. (1 mark)
(HKDSE 2017 Paper 2 Q1b(ii))

Section 54.6
4. The diagram below shows a flowing mercury cell used in the chloroalkali industry.

gas X
anode (carbon)

Exam practice
brine used brine
resultant
mixture Z
cathode (mercury sodium
circulating in the cell) gas Y hydroxide
solution
water

pump

(a) (i) What is gas X?

(ii) Write the half equation for the reaction that occurs at the carbon anode.
(iii) State one daily product that is manufactured from X.
(3 marks)
(b) (i) Write the half equation for the reaction that occurs at the mercury cathode.
(ii) The product of electrolysis formed at the cathode will dissolve in mercury. Name the resultant mixture Z.
(2 marks)
(c) (i) What is gas Y?
(ii) Write the chemical equation for its formation from the resultant mixture in (b)(ii).
(2 marks)
(d) Both chlorine bleach and hydrochloric acid are products of the chloroalkali industry. Explain why these two
products should NOT be stored together. (1 mark)

149
 XIII Industrial Chemistry

5. Membrane cells are a type of electrolytic cells used in the chloroalkali industry. The diagram below shows the
structure of a membrane cell.

gas P gas Q

concentrated H2O()
NaCl solution

titanium nickel
electrode electrode

dilute NaCl solution R

solution

ion-permeable
compartment X compartment Y
membrane
Exam practice

(a) What are gases P and Q respectively? (2 marks)

(b) With the help of half equations, explain the formation of P and Q in the membrane cell. (4 marks)
(c) Which one is the anode compartment, X or Y? (1 mark)
(d) State TWO functions of the ion-permeable membrane. (2 marks)
(e) (i) What is solution R?
(ii) Explain the formation of R in the cell.
(3 marks)
(f) Chlorine bleach can be made from two of the products in the chloroalkali industry.
(i) Write the ionic equation for the reaction involved in making chlorine bleach.
(ii) Name the active ingredient of chlorine bleach.
(2 marks)

6. A chloroalkali chemical plant uses membrane electrolytic cells to produce hydrogen, chlorine and sodium hydroxide.
(a) With the help of chemical equations, briefly describe how hydrogen, chlorine and sodium hydroxide are
produced in a membrane electrolytic cell. (4 marks)
(b) Sodium hypochlorite (NaOCl) can be made from the products obtained in the membrane electrolytic cell.
Write a chemical equation for its formation. (1 mark)
(HKDSE 2019 Paper 2 Q1b(i)–(ii))

Section 54.9
7. (a) Write the chemical equation for the formation of syngas from methane. (1 mark)
(b) Syngas can be obtained from the conversion of biomass. Suggest why it is considered as an advancement of
the methanol production technology. (1 mark)
(HKDSE 2019 Paper 2 Q1a(ii))

150
 Industrial processes 54
8. Catalytic conversion of syngas (a mixture of CO and H2) at 250°C and 50–100 atm produces methanol. The
equation for the reaction involved is as follows:

CO(g) + 2H2(g) CH3OH(g)

(a) What catalyst is used in the above reaction? (1 mark)

(b) Syngas is produced from the steam reforming of natural gas. Write the chemical equation for the production.
(1 mark)
(c) The graph below shows the variation of concentration of methanol in the catalytic chamber with time at three
different temperatures under the same pressure.

–3
Concentration of methanol / mol dm

125°C

225°C

325°C

Exam practice
Time / min

(i) Deduce whether the above reaction is exothermic or endothermic.

(ii) Explain why 125°C is NOT chosen as the operating temperature for the process though it gives the
highest equilibrium concentration of methanol.
(iii) Predict and explain the effect of an increase in pressure on the equilibrium concentration of methanol.
Hence, explain why the conversion is NOT operated at pressures lower than 50 atm or higher than
100 atm.
(5 marks)

9. Methanol is an important compound in the chemical industry. It can be produced industrially from syngas by a
process carried out at 250°C and 50–100 atm in the presence of a mixture of catalysts.
(a) By considering the number of carbon atoms in methanol, suggest why methanol is an important compound
in the chemical industry. (1 mark)
(b) Syngas is a mixture consisting mainly of carbon monoxide and hydrogen. It can be produced from the reaction
between compound X and steam.
(i) Suggest what X may be, and state a natural source of X.
(ii) Write the chemical equation for the reaction involved in making syngas.
(3 marks)
(c) Write the chemical equation for the production of methanol from syngas, and suggest the mixture of catalysts
used. (2 marks)
(d) From an economic perspective, state an advantage of using catalysts in the industrial production of methanol.
(1 mark)

151
 XIII Industrial Chemistry

10. Chloroalkali industry can provide hydrogen, which is a feedstock for the Haber process and the manufacture of
methanol.
(a) With the help of a half equation, explain how hydrogen is produced in the chloroalkali industry. (2 marks)
(b) Write the chemical equation for the production of ammonia in the Haber process. State the conditions
commonly used. (2 marks)
(c) Write the chemical equation for the manufacture of methanol that uses hydrogen as one of the feedstocks.
(1 mark)
(d) Steam reforming of natural gas is commonly adopted for making syngas which in turn, is used to produce
methanol.
(i) What is syngas?
(ii) Suggest one advantage of using hydrogen (present in syngas) as the feedstock to produce methanol over
using hydrogen produced from the chloroalkali industry.
(2 marks)
(e) Suggest one advantage and one disadvantage of building an industrial plant for the Haber process and one
for the chloroalkali industry within the same region. You are required to consider the social, economic or
environmental aspect. (2 marks)
Exam practice

11. Methanol is an important chemical in industry and can be produced from methane. The production can be
considered as separated into two stages.
(a) State one potential hazard of methanol. (1 mark)
(b) Other than natural gas, suggest one source of methane. (1 mark)
(c) In the first stage, CH4(g) reacts with H2O(g) to form CO(g) and H2(g), and equilibrium would be attained. The
graphs below show the percentage conversion of CH4(g) at equilibrium under different conditions.
percentage conversion of CH4(g)

percentage conversion of CH4(g)

at a constant temperature
at a constant pressure

temperature / °C pressure / atm

Graph 1 Graph 2

(i) With reference to Graph 1, explain whether the forward reaction is endothermic or exothermic.
(ii) With reference to Graph 2, explain, with the aid of a chemical equation, the effect of pressure on the
percentage conversion of CH4(g).
(4 marks)
(d) In the second stage, CO(g) reacts with H2(g) to form methanol. Write a chemical equation for the reaction.
(1 mark)
(HKDSE 2021 Paper 2 Q1c)

152
Answers to Chapter exercise (c) The –OH groups in L-ascorbic acid can
form hydrogen bonds with water molecules. 1
Chapter 50 (d) Glucose/D-glucose 1
16. (a) Citrus fruits (e.g. oranges, lemons,
A. Fill in the blanks (p.18)
grapefruits, etc.) 1
1. raw materials; bulk chemicals
OR
2. raw materials; energy; by-products; wastes
Vegetables (e.g. tomatoes. broccoli,
3. natural gas; petrochemicals
potatoes, etc.) (1)
4. Reichstein
(b) Glucose is renewable. 1
5. two-step fermentation
(c) Vitamin C can be produced on a large scale
B. Multiple-choice questions (p.18) in a relatively short time. 1
6. D (d) (i) Enzymes can speed up the
7. C fermentation. 1
Option (C): chlorine bleach is a synthetic product. (ii) The reaction conditions, e.g.
8. A temperature and pH, need to be
9. C controlled carefully for fermentation
10. D using enzymes. 1
11. A
12. B Chapter 51
13. C A. Fill in the blanks (p.51)
1. rate equation
C. Structured questions (p.19)
2. (b) orders of reaction; experiments
14. (a) (i) Petroleum 1
3. rate constant; concentration
(ii) Yes. This is because one of the
4. concentration; straight; slope
hydrogen atoms in benzene is replaced
5. square; rate constant
by a –CH=CH2 group. 1
6. initial rate
(b) Styrene can be used in the production of
polystyrene and styrene-based materials B. Practice questions (p.51)
(e.g. acrylonitrile-butadiene-styrene (ABS), 7. (a) Order of reaction with respect to S: 2
styrene-acrylonitrile (SAN), styrene- Overall order of reaction: 2
–1 3 –1
butadiene rubber (SBR) and styrene- Unit of the rate constant (k1): mol dm min
butadiene latex). 1 (b) Order of reaction with respect to T: 1
Polystyrene is used to make polystyrene Order of reaction with respect to U: 2
foam, composite materials, polystyrene film, Overall order of reaction: 3
–2 6 –1
etc. Hence, styrene is a building block of a Unit of the rate constant (k2): mol dm min
wide variety of synthetic products. 1 8. (a) No effect
15. (a) Condensation/elimination 1 (b)
(b) Chiral carbon atoms in the structure of KGA:
–3
[NO2(g)] / mol dm

1 Time / min
Chiral carbon atoms in the structure of (c) Rate = k[NO2(g)]
2

L-ascorbic acid:
C. Multiple-choice questions (p.52)
9. B
10. D
T1
1
 11. C (c) Substitute the results of Trial 1 into the rate
Option (A): although P does not appear in the rate equation,
–6 –3 –1 –3 2
equation, it takes part in the reaction because it is 3.6 × 10 mol dm s = k × (0.30 mol dm )
–6 –3 –1
one of the reactants. The rate equation shows that 3.6 × 10 mol dm s
k= –3 2
increasing [P] has no effect on the reaction rate. (0.30 mol dm )
–5 –1 3 –1
Option (B): the rate of reaction quadruples when = 4.0 × 10 mol dm s 2
[Q] is doubled. (1 mark for the correct numerical answer; 1
Option (D): the rate constant may have a unit of mark for the correct unit)
–1 3 –1
mol dm s . (d) Substitute the new initial concentration of
–3
12. D XY, i.e. 0.75 mol dm , into the rate equation,
–5 –1 3 –1 –3 2
13. A Rate = 4.0 × 10 mol dm s × (0.75 mol dm )
–5 –3 –1
14. A = 2.25 × 10 mol dm s
As the rate doubles when the concentration of X is Comparing the new initial rate with that of
doubled, the order of reaction with respect to X is Trial 1, the initial rate of reaction increases
1. The rate of reaction increases by a factor of 8 by a factor of
–5
when both the concentrations of X and Y are 2.25 × 10
–6 = 6.25 1
doubled. This suggests that doubling the 3.6 × 10
concentration of Y leads to an increase in the rate OR
by a factor of 4. Thus, the order of reaction with Compared with Trial 1, the initial
respect to Y is 2. concentration of XY increases by a factor of
15. A 0.75
1 = 2.5. As the reaction is second
Rate = k[X] 2 1 0.30
1 1 1 order with respect to XY, the initial rate will
Rate1 = k[2X] 2 = k × 2 2 × [X] 2 = k × 2 × [X] 2 2
increase by a factor of 2.5 = 6.25. (1)
16. C
19. (a) The reaction is first order with respect to W
Substitute the data into the rate equation,
2 because a straight line passing through the
Rate = k[X][Y]
–3 –1 –3 –3 2 origin is shown in the graph of rate against
0.90 mol dm s = k × (0.20 mol dm ) × (0.30 mol dm )
–3 –1 [W]. 1
0.90 mol dm s
k= –3 –3 2 (b) Rate = k[W] 1
(0.20 mol dm ) × (0.30 mol dm )
–2 6 –1 (c) Slope of the line = k
= 50 mol dm s –3 –1
(0.020 – 0) mol dm s
= –3
D. Structured questions (p.53) (0.060 – 0) mol dm
–1
17. (a) This is to ensure that the concentrations of = 0.333 s 2
–
both H2O2(aq) and I (aq) remained more or (1 mark for the correct numerical answer; 1
less constant throughout the reaction. mark for the correct unit)
+ 2 –
Hence, the concentration of H (aq) was the 20. (a) Rate = k[ClO2(aq)] [OH (aq)] 1
only factor to be varied in the experiment. 1 (b) 3 1
(b) Order of reaction with respect to H2O2(aq): 0 (c) The reaction rate will triple. 1
1 (d) The reaction rate will increase by a factor of
2
–
Order of reaction with respect to I (aq): 0 1 2 × 2 = 8. 1
+
(c) Rate = k0[H (aq)] 1 21. (a) Substitute the results of Trial 1 into the rate
18. (a) From Trials 1 and 2, when the initial equation,
–3 –1
concentration of XY is doubled, the initial 0.1584 mol dm min
–3 –3 2
rate quadruples. Hence, the order of = k × 1.5 mol dm × (2.0 mol dm )
–3 –1
reaction with respect to XY is 2. 1 0.1584 mol dm min
k= –3 –3 2
(b) Rate = k[XY]
2
1 1.5 mol dm × (2.0 mol dm )
–2 6 –1
= 0.0264 mol dm min 2
(1 mark for the correct numerical answer; 1
mark for the correct unit)

T2
 (b) Substitute the results of Trial 2 into the rate 23. (a) (i)
log [HCHO(g)]
equation,
–3 –1
0.3168 mol dm min
–2 6 –1 –3 2
= 0.0264 mol dm min × x × (2.0 mol dm )
–3 –1
0.3168 mol dm min
x= –2 6 –1 –3 2
0.0264 mol dm min × (2.0 mol dm )
x = 3.0 1
Substitute the results of Trial 3 into the rate
equation,
–2 6 –1 –3
y = 0.0264 mol dm min × 1.5 mol dm ×
–3 2
(3.0 mol dm )

log (initial rate)

y = 0.3564 1
Substitute the results of Trial 4 into the rate
equation,
–3 –1
1.2672 mol dm min
–2 6 –1 –3 2
= 0.0264 mol dm min × 3.0 mol dm × z
–3 –1
1.2672 mol dm min
z= –2 6 –1 –3
0.0264 mol dm min × 3.0 mol dm
z = 4.0 1
– –
22. (a) (i) CH3CH2Cl + OH CH3CH2OH + Cl 1
(ii) No. This is because its concentration is
much higher than that of CH3CH2Cl. Its
concentration would be more or less
constant throughout the reaction. 1 1
(b) From Trials 1 and 2, at the same initial (ii) (1) Order of reaction with respect to
–
concentration of OH , the initial rate doubles HCHO(g) = x
when the initial concentration of CH3CH2Cl x = slope of the line
is doubled. Hence, the order of reaction with (–7.4) – (–8.4)
= 1
respect to CH3CH2Cl is 1. 1 (–1.0) – (–1.5)
From Trials 2 and 3, at the same initial =2 1
concentration of CH3CH2Cl, the initial rate ∴ the order of reaction with
doubles when the initial concentration of respect to HCHO(g) is 2.
–
OH is doubled. Hence, the rate of reaction (2) y-intercept of the line = log k
–
with respect to OH is 1. 1 log k = –5.4
–6 –1
(c) Rate = k[CH3CH2Cl][OH ]
–
1 k = 4.0 × 10 mol
3 –1
(d) Substitute the results of Trial 1 into the rate dm s 2
2
equation, (b) Rate = k[HCHO(g)] 1
–4 –3 –1
4.0 × 10 mol dm s
–4 –3
= k × 0.50 × 10 mol dm × 0.10 mol dm
–3
Chapter 52
–4 –3 –1
4.0 × 10 mol dm s A. Fill in the blanks (p.79)
k= –4 –3 –3
0.50 × 10 mol dm × 0.10 mol dm 1. Activation energy
–1 3 –1
= 80 mol dm s 2 2. Energy profile; reaction coordinate
(1 mark for the correct numerical answer; 1 3. activated complex (or transition state)
mark for the correct unit) 4. activation; Maxwell-Boltzmann distribution; frequency
5. rate constant
E
6. – a
2.3 R

T3
 B. Practice questions (p.79) C. Multiple-choice questions (p.80)
7. 12. C
activated complex 13. D
Potential energy

14. B
Ea 15. C
16. B
reactants Option (A): the number of particles would not
∆H
increase again at the high end of kinetic energy.
products
Option (C): kinetic energy is zero when there are
Reaction coordinate
no particles in the system. Hence, the curve starts
Ea 1 1 at the origin.
8. log k1 – log k2 = ( – )
2.3 R T2 T1 Option (D): theoretically, there is no maximum
Ea 1 1
log 0.163 – log 0.348 = ( – ) kinetic energy. Its value can be infinite.
2.3 × 8.31 510 500
–1 –1 17. A
Ea = 160 539 J mol = 161 kJ mol
18. C
Ea 1 1
9. log k1 – log k2 = ( – ) 19. C
2.3 R T2 T1
–2 Ea 1 1 Option (C): according to the Arrhenius equation,
log 1.32 × 10 – log 1.64 = ( – ) –
Ea
2.3 × 8.31 548 473 k = Ae RT , the rate constant decreases exponentially
–1 –1
Ea = 138 338 J mol = 138 kJ mol with decreasing temperature.
Ea 1 1
10. log k1 – log k2 = ( – )
2.3 R T2 T1 Chapter 53
Ea 1 1 A. Fill in the blanks (p.102)
log k – log 4k = ( – )
2.3 × 8.31 100 + 273 30 + 273
–1 –1
1. (a) small
Ea = 18 579 J mol = 18.6 kJ mol
(b) selective
Ea
11. (a) log k = log A – (c) surface area
2.3 RT
(b) (d) chemically
(e) poisoned
1
/ × 10 K 5.00 3.33 2.50 2.00 1.67 1.43 1.25
–3 –1
2. activation energy
T
3. same; position
log k –0.627 –0.521 –0.469 –0.437 –0.415 –0.399 –0.388
4. enzymes
(c) 1 –3
/ × 10 K
–1
T B. Multiple-choice questions (p.102)
5. C
(1): this reaction occurs inside hydrogen-oxygen
fuel cells where platinum or nickel electrodes can
act as a catalyst to speed up the reaction.
log k (3): concentrated H2SO4 acts as a catalyst in
esterification.
6. B
7. D
8. B
By using the points (0.00195, –0.435) and 9. C
(0.005, –0.627), the slope 10. B
–0.627 – (–0.435) 11. D
= = –62.95
0.005 – 0.00195 12. D
E 13. D
∴ – a = –62.95
2.3 R (1): biological catalysts, i.e. enzymes, are used.
–1
Ea = 62.95 × 2.3 × 8.31 J mol
–1 (2): nickel, platinum or palladium can be used as
= 1203 J mol
–1 the catalyst.
= 1.20 kJ mol
(3): finely divided iron is used as the catalyst.
T4
14. B Chapter 54
(1): it should be carried out in the absence of A. Fill in the blanks (p.145)
oxygen, not carbon dioxide. 1. Ammonia; 400–450; 200; iron
(2): enzymes can be sensitive to changes in pH, 2. fractional distillation; cracking; electrolysis
which would affect its effectiveness. Enzymes can 3. 1 : 3; purified; heat exchanger; condense; recycled
work best only within specific pH ranges. 4. catalytic oxidation; oxygen
(3): it should be carried out between 25°C and 5. sodium chloride; chlorine; hydrogen; sodium
40°C in a closed system. hydroxide
C. Structured questions (p.104) 6. Flowing mercury; membrane
15. (a) It is produced when nitrogen and oxygen 7. Methane; feedstock; fuel; biodiesel
in the air combine at high temperatures in 8. (a) syngas; steam reforming
car engines. 1 (b) Synthesis
N2(g) + O2(g) 2NO(g) 1 (c) distillation
(b) (i) Platinum or rhodium 1 B. Practice question (p.145)
(ii) Depositing the catalyst on the 9. (a) Operating conditions: 400–450°C, 200 atm
honeycomb structure of a catalytic Catalyst: finely divided Fe
converter can provide a larger surface (b) Operating conditions: 900°C, 8 atm
area for the catalysis to occur. 1 Catalyst: Pt
As a result, more carbon monoxide (c) Operating conditions: 700–1000°C, 30 atm
and nitrogen monoxide can adsorb Catalyst: NiO
onto the catalytic surface and react (d) Operating conditions: 250°C, 50–100 atm
per unit time. Hence, the conversion of Catalysts: Cu/ZnO/Al2O3
these gases to harmless gases will
proceed faster at the same C. Multiple-choice questions (p.146)
temperature. 1 10. A
(c) 2CO(g) + 2NO(g) 2CO2(g) + N2(g) 1 11. D
(d) Lead compounds in the car exhaust can 12. C
‘poison’ the metal catalyst in the catalytic 13. B
converter and inhibit its action. 1 14. B
16. (a) Hydrogenation/addition reaction 1 From the given information, 1 mol of NH3 gives
(b) Nickel (Also accept platinum or palladium 1 mol of HNO3
as the answer.) 1 Theoretical yield of HNO3
(c) (i) It represents the proportion of 12.8 g –1
= –1 × (1.0 + 14.0 + 16.0 × 3) g mol
molecules with kinetic energy greater (14.0 + 1.0 × 3) g mol
than Ea. 1 = 47.4 g
(ii) In the presence of a catalyst, the 15. D
reaction proceeds through an 16. C
alternative pathway with lower From the given information, 2 mol of NH3 gives
activation energy. 1 1 mol of (NH2)2CO
This increases the proportion of Theoretical yield of (NH2)2CO
17.0 g 1
molecules with kinetic energy greater = –1 × × [(14.0 + 1.0 × 2) ×
(14.0 + 1.0 × 3) g mol 2
than Ea in the gaseous reaction system –1
2 + 12.0 + 16.0] g mol
(the shared area in the above curve
= 30.0 g
becomes larger). 1
Percentage yield of(NH2)2CO
There is an increase in the frequency
24.0 g
of effective collisions. Thus, the rate of = × 100% = 80.0%
30.0 g
the reaction increases. 1 17. D

T5
 18. C Chapter 55
The membrane is permeable to cations but not A. Fill in the blanks (p.177)
anions. It is a selectively permeable membrane. 1. hazardous
19. D 2. Sustainable development
(1): the sodium hydroxide solution obtained 3. (a) renewable
contains no or least sodium chloride impurities. (b) solvents
20. A (c) energy
(3): methanol is poisonous. (d) wastes
21. B (e) accidents
22. C 4. desired; reactants
D. Structured question (p.147) 5. (a) atom economy
23. (a) CO(g) + 2H2(g) CH3OH(g) 1 (b) Nitrogen
(b) (i) Mix natural gas with steam under (c) non-toxic
30 atm, heat the gaseous mixture to (d) solvent
around 700°C to 1000°C, and then (e) energy
pass it over the NiO catalyst. 1 B. Practice questions (p.177)
(ii) CH4(g) + H2O(g) CO(g) + 3H2(g) 1 6. Atom economy of the production by benzene
Mole ratio of CO(g) to H2(g) in the oxidation
gaseous mixture produced = 1 : 3. 1 (12.0 × 4 + 1.0 × 2 + 16.0 × 3) g
(c) (i) Increasing the concentration of CO2(g) = × 100%
[(12.0 × 6 + 1.0 × 6) + (16.0 × 2) × 9 ] g
causes the equilibrium position to shift 2
to the right/product side, producing 98.0 g
= × 100%
more CO(g) and H2O(g). 1 (78.0 + 144.0) g
(ii) Methanol is produced from the reaction = 44.1%
between CO(g) and H2(g) in a mole Atom economy of the production by but-1-ene
ratio of 1 : 2. However, the reaction oxidation
mentioned in (b)(ii) generates a (12.0 × 4 + 1.0 × 2 + 16.0 × 3) g
= × 100%
gaseous mixture (syngas) with CO(g) [(12.0 × 4 + 1.0 × 8) + (16.0 × 2) × 3] g
98.0 g
and H2(g) in a mole ratio of 1 : 3. 1 = × 100%
(56.0 + 96.0) g
Shift reaction can be used to adjust
= 64.5%
the mole ratio of H2(g) to CO(g) in the
syngas by reducing the amount of H2(g)
and increasing the amount of CO(g). 1

7. Atom economy of Reaction I

(12.0 × 10 + 1.0 × 8 + 16.0 × 4) × 200 g
= × 100%
[(12.0 × 8 + 1.0 × 6 + 16.0 × 4) × 200 + (12.0 × 2 + 1.0 × 6 + 16.0 × 2) × 200] g
38 400.0 g
= × 100%
(33 200.0 + 12 400.0) g
= 84.2%
Atom economy of Reaction II
(12.0 × 10 + 1.0 × 8 + 16.0 × 4) × 200 g
= × 100%
[(12.0 × 8 + 1.0 × 4 + 16.0 × 2 + 35.5 × 2) × 200 + (12.0 × 2 + 1.0 × 6 + 16.0 × 2) × 200] g
38 400.0 g
= × 100%
(40 600.0 + 12 400.0) g
= 72.5%
∴ Reaction I has a higher atom economy.

T6
C. Multiple-choice questions (p.178) respectively. Hence, Reaction (1) uses the
8. D least hazardous reactants. 1
9. A 19. (a) The reaction involved in the alternative
10. C method is carried out at a higher
11. D temperature. Hence, it is less energy
12. C efficient. 1
Option (A): enzymes are biological catalysts which (b) The reagent (70% HNO3) and catalysts
are renewable, non-toxic and biodegradable. (MoO3/SiO2) used in the alternative method
Moreover, using enzymes in a synthesis can reduce are less hazardous (the conc. HNO3 and
fuel consumption because enzymes only work at conc. H2SO4 used in the traditional method
ambient temperatures. are corrosive.) 1
Option (B): most organic solvents are hazardous
to environment. Some of them are even toxic or
carcinogenic. Answers to Exam practice
13. D
14. C Chapter 50
15. B A. Multiple-choice questions (p.20)
16. D 1. D
D. Structured questions (p.180) B. Structured questions (p.20)
17. (a) Methanol can be produced by steam 2. (a) Dietary supplements (e.g. vitamin C tablets)/
reforming of natural gas, followed by food and drinks (e.g. bottled soft drinks, corn
compression of the syngas produced at a flakes)/personal care products (e.g. acne
high temperature, pressure and in the facial wash) 1
presence of catalysts. 1 (b) D-sorbitol and L-sorbose 1
It can also be produced by oxidation of (c) Enzymes are used in the fermentation and
methane by microbial reactions (e.g. using they can be denatured easily at high
yeast and bacteria). 1 temperatures, leading to the loss of
(b) CH3OH(l) + CO(g) CH3COOH(l) 1 catalytic activities. 1
(c) Operating temperature: 150–200°C (d) Any one of the following:
Operating pressure: 30–60 atm 1 • Method 2 uses less hazardous chemicals. 1
Catalysts used: HI, Rh (In Method 1, the CH3COCH3 used is
(d) All the atoms in the reactants (CH3OH and flammable; the acid used is irritating, and
CO) are converted to the desired product the KMnO4 used is strongly oxidizing,
(CH3COOH) in the main reaction. 1 while the oxygen used in Method 2 is
(e) (i) Iridium/Ir 1 harmless.)
(ii) Iridium is more selective in carbonylation • Method 2 uses a catalyst (Ni). (1)
of methanol. Side reactions are less (Catalysts can be regenerated at the end
likely to take place. Therefore, CATVIA of the reaction. Hence, less waste is
process produces less waste. 1 produced.)
The smaller amounts of side products
(e.g. CH3I) formed make the purification Chapter 51
of acetic acid easier. Therefore, less
A. Multiple-choice questions (p.56)
energy is needed for separating and
1. C
purifying the acetic acid when CATIVA 1 2
(2): new reaction rate = k[J(g)][ K(g)]
process is used. 1 2
1 2
18. (a) This indicates that all the reactant atoms = k[J(g)][K(g)]
4
are converted to the desired product in ∴ the reaction rate decreases by a factor of 4
these reactions. 1 when [K(g)] is halved while [J(g)] is kept constant.
2
(b) N2(g) and H2(g) are non-toxic, while CO(g) (3): new reaction rate = k[3J(g)][3K(g)]
2
and CH3OH(l) are poisonous and toxic = 27k[J(g)][K(g)]
T7
 2. C From Trials 1 and 2, at the same initial
1 2 3 2 – –
rate2 = k[ NO(g)] [3Br2(g)] = k[NO(g)] [Br2(g)] concentrations of BrO3 (aq) and I (aq), the
2 4
3 relative initial rate doubles when the initial
rate2 = rate1 +
concentration of H (aq) is doubled. Hence,
4 +
the order of reaction with respect to H (aq)
B. Structured questions (p.56)
is 1. 1
3. HKDSE 2021 Paper 2 Q1a(iii)
(c) Repeat Trial 1 using the same initial
4. HKDSE 2019 Paper 2 Q1a(iii) – –3
concentrations of I (aq) (i.e. 0.10 mol dm )
5. (a) + –3
and H (aq) (i.e. 0.10 mol dm ) but a
–
doubled initial concentration of BrO3 (aq)
–3
(i.e. 0.20 mol dm ) under the same
–3

experimental conditions. Then measure the

[NH3(g)] / mol dm

relative initial rate of the reaction. 1

If the relative initial rate is 2, the order of
–
reaction with respect to BrO3 (aq) is 1. 1
– – 2 +
(d) Rate = k[BrO3 (aq)][I (aq)] [H (aq)] 1
(e) Substitute the results into the rate equation,
–3 –3 –1
2.4 × 10 mol dm s
–3 –3 2 –3
= k × 0.20 mol dm × (0.10 mol dm ) × 0.10 mol dm
–3 –3 –1
t/s
2.4 × 10 mol dm s
2 k= –3 –3 2 –3
0.20 mol dm × (0.10 mol dm ) × 0.10 mol dm
(1 mark for the correct line; 1 mark for the –3 9 –1
= 12 mol dm s 2
correct labelling of the two axes)
(1 mark for the correct numerical answer; 1
(b) [NH3(g)] decreases linearly with time,
mark for the correct unit)
indicating that the rate of the decomposition
7. (a) Taking logarithm of the rate equation gives:
is constant throughout the reaction. Hence,
log (rate) = log k + x log [O3(g)]
the order of reaction with respect to NH3(g)
Taking the logarithm of the experimental
is 0. 1
results provided, we get the following data
Rate = k 1
which can be used to plot the graph.
(c) k = rate of decomposition of NH3(g)
∆[NH3(g)] log [O3(g)] –2.90 –2.73 –2.60 –2.43 –2.30
=–
∆t
–3 log (initial rate) –6.10 –5.92 –5.80 –5.62 –5.49
(0.00127 – 0.00150) mol dm
=–
(250 – 0) s log [O3(g)]
–7 –3 –1
= 9.2 × 10 mol dm s 2
(1 mark for the correct numerical answer; 1
mark for the correct unit)
6. (a) Measure the colour intensity of the reaction
mixture at regular time intervals by using a
colorimeter. 1
This is because I2(aq) is brown in colour and
is the only coloured species in the reaction. log (initial rate)
The colour intensity of the reaction mixture
will increase with time. 1
(b) From Trials 1 and 3, at the same initial
– +
concentrations of BrO3 (aq) and H (aq), the
relative initial rate quadruples when the initial
–
concentration of I (aq) is doubled. Hence,
–
the order of reaction with respect to I (aq)
2
is 2. 1

T8
 (1 mark for the correct line; 1 mark for the (c)
correct labelling of the two axes)

–1
Initial rate / mol dm s
–3.19 – (–5.92)

–3
(b) Slope of the line = x = 1
0 – (–2.73) H
=1 1
y-intercept of the line = log k L
log k = –3.19
–4 –1
k = 6.46 × 10 s 2
(1 mark for the correct numerical answer; 1 –3
[H2(g)] / mol dm 2
mark for the correct unit)
(1 mark for each correct line)
8. (a) If the reaction is first order with respect to
9. (a) As the reaction proceeds, the concentration
NO(g), the graph provided should be a
of indicator J decreases and the (pink)
straight line, but not a curve, passing
colour intensity of the reaction mixture
through the origin. 1
decreases with time. 1
(That is, the initial rate should be directly
(b) A much higher concentration of J(aq)
proportional to the concentration of NO(g).)
2 should be used so that its concentration is
(b) Plot a graph of initial rate against [NO(g)] .
more or less constant throughout the
If the reaction is second order with respect
reaction. 1
to NO(g), the graph should give a straight
(c) From Trials 1 and 2, when the concentration
line passing through the origin. 1 –3
of NaOH(aq) is halved (from 0.20 mol dm
–3
Point P Q R to 0.10 mol dm ), the initial slope
2 –5
[NO(g)] / × 10 mol dm
2 –6
0.4 2.5 3.6 (representing the initial rate of the reaction)
–3 –3 –1 also halves (from 0.12 to 0.06). Hence, the
Initial rate / × 10 mol dm s 0.65 4.2 6.0 –
order of reaction with respect to OH (aq)
is 1. 1
(d) Any FOUR of the following points:
• Carry out the experiment several times (or
three times) by mixing the same volume
–1
Initial rate / × 10 mol dm s

but different initial concentrations of J(aq)

–3

with a fixed volume of a much higher

concentration of NaOH(aq). 1
–3

• Keep the concentration of NaOH(aq) and

the temperature (or experimental
conditions) the same in the different trials. 1
• Follow the progress of the reaction in
each trial by measuring the absorbance
of the reaction mixture at regular time
intervals using a colorimeter. 1
• Plot graphs of the absorbance against
2 –5
[NO(g)] / × 10 mol dm
2 –6 time for different trials. Determine the
2 initial slope of each curve. 1
(1 mark for the correct line; 1 mark for the • Compare the initial slopes of each curve
correct labelling of the two axes) at different initial concentrations of J(aq)
to determine the order of reaction with
respect to J(aq). 1
10. HKDSE 2020 Paper 2 Q1c(i)–(iv)

T9
 Chapter 52 As the temperature increases, there is a
A. Structured questions (p.82) larger proportion of particles having kinetic
1. HKDSE 2021 Paper 2 Q1a(i) energy greater than Ea. 1
2. (a) This increases the frequency of effective
collisions. Hence, the reaction rate
increases. 1
Potential energy

2
5. (a) Rate = k[N2O(g)] 1
(b) (i) By using the points at (0, 0) and
–4
(0.02, 11 × 10 ), the rate constant at
973 K
–4 –3 –1
(11 × 10 – 0) mol dm s
= 2 –6 1
Reaction coordinate (0.02 – 0) mol dm
–1 3 –1
= 0.055 mol dm s 1
(1 mark for the correct shape of energy profile;
(ii) By using the points at (0, 0) and
1 mark for the correct indication of the Ea and –4
(0.01, 24 × 10 ), the rate constant at
∆H of the reaction; 1 mark for the correct
1023 K
labelling of the two axes.) –4
(24 × 10 – 0) mol dm s
–3 –1

(b) (i) = 2 –6 1
(0.01 – 0) mol dm
–1 3 –1
1 = 0.24 mol dm s 1
(ii) Any TWO of the following: Ea 1 1
(c) log k1 – log k2 = ( – )
• It contains partially broken and 2.3 R T2 T1
partially formed bonds. 1 Ea 1 1
log 0.055 – log 0.24 = ( – ) 1
2.3 × 8.31 1023 973
• It is highly unstable (and can never –1 –1
Ea = 243 458 J mol = 243 kJ mol 1
be isolated.) 1
6. (a) It is the minimum amount of energy
• It has the highest energy among all
required for a chemical reaction to occur. 1
types of chemical species in the
(b)
reaction system. (1)
(c) Activation energy for the forward reaction
Potential energy

–1 –1
= (182 – 9) kJ mol = 173 kJ mol 1
3. HKDSE 2020 Paper 2 Q1a(iii)
4. (a) x: Number of particles (or molecules) 1
y: Kinetic energy 1
(b) T2
Any one of the following explanations: Reaction coordinate
3
• This is because the distribution of
OR
molecular kinetic energies of the
gaseous reaction system is wider at T2. 1
• This is because the proportion of
Potential energy

particles having higher kinetic energies

is greater at T2. (1)
(Accept other correct explanations.)
(c) The area under each curve represents the
total number of particles in the gaseous
reaction system. 1 Reaction coordinate (3)
There is no change in the total number of
(1 mark for the correct shape of energy profile;
particles in the gaseous reaction system
1 mark for the correct indication of the Ea and
when the temperature is changed. 1
∆H of the reaction; 1 mark for the correct
(d) It represents the increased proportion of
labelling of the two axes.)
particles having kinetic energy greater than
Ea . 1

T10
 (c) By using the points (0.00165, –0.25) and Hence, the order of reaction with respect to
(0.00185, –2.00), the slope iodide ions is 1.
(–2.00) – (–0.25) (c)
= = –8750
0.00185 – 0.00165
E curve for the repeated

–3
∴ – a = –8750

Concentration of iodine / mol dm

2.3 R experiment X
–1
Ea = 8750 × 2.3 × 8.31 J mol 1
–1
= 167 239 J mol
–1
= 167.2 kJ mol 1
Y
Chapter 53
A. Multiple-choice questions (p.105)
1. D
Option (B): as the forward reaction is exothermic,
an increase in temperature causes the equilibrium
Time / s
position to shift to the reactant side so as to remove 1
heat. (d) Step 1: S2O (aq) + 2Fe (aq)
2– 2+
2SO (aq) +
2–
8 4
Option (C): catalysts do take part in chemical 2Fe (aq) 1
3+

reactions. In a catalytic process, the catalyst forms 3+ –

Step 2: 2Fe (aq) + 2I (aq) I2(aq) +
an intermediate with a reactant, which is then 2+
2Fe (aq) 1
regenerated by reacting with another reactant. This 4. (a) (i) In Step 1, the oxidation number of
also explains why catalysts are not consumed in vanadium decreases from +5 to +4. 1
chemical reactions. In Step 2, the oxidation number of
2. B vanadium increases from +4 to +5. 1
A catalyst increases the rates of both the forward (ii) It acts as a catalyst that speeds up the
and backward reactions of a reversible reaction to conversion of SO2 to SO3. 1
the same extent. Thus, it has no effect on the (b)
equilibrium position of the reaction. In other words,
it does not affect the composition of an equilibrium
with catalyst
mixture.
without catalyst
Potential energy

B. Structured questions (p.106)

3. (a) Measure the colour intensity (or
absorbance) of the reaction mixture by
using a colorimeter. 1
OR
Titrate a known volume of a small portion of
the reaction mixture (quenched) against Reaction coordinate
4
standard sodium thiosulphate solution, (1 mark for showing of exothermic reaction;
using starch solution as the indicator. The 1 mark for the two energy profiles i.e., one with
solution changes from dark blue to catalyst and another one without catalyst;
colourless at the end point. (1) 1 mark for the labelling of reactants (2SO2(g) +
(b) At t = 100 s, the concentration of iodine, O2(g)) and product (2SO3(g)); 1 mark for the
–3
as shown by curve X, is 0.0114 mol dm labelling of the two axes)
and that shown by curve Y is 5. HKDSE 2020 Paper 2 Q1c(v)
–3
0.0057 mol dm . 1 6. (a) (i) 2CO(NH2)2 + 4NO + O2
This shows that the concentration of iodine 4N2 + 4H2O + 2CO2 1
formed is halved for the same time interval (ii) Number of moles of urea
when the initial concentration of iodide 10.0
= mol
ions is also halved. 1 12.0 + 16.0 + (14.0 + 1.0 × 2) × 2
= 0.167 mol 1
T11
 From the equation in part (i), mole Besides, alcoholic drinks containing
ratio of CO(NH2)2 to NO is 1 : 2. ethanol manufactured by Reaction (2) may
∴ maximum number of moles of NO contain hazardous wastes (e.g. H3PO4). 1
reacted
= 0.167 mol × 2 = 0.334 mol 1 Chapter 54
Maximum mass of NO removed A. Structured questions (p.148)
= 0.334 × (14.0 + 16.0) g = 10.0 g 1 1. HKDSE 2019 Paper 2 Q1a(i)
(b) (i) Reaction only takes place on the 2. (a) (i) 200°C and 1000 atm 1
surface. 1 (ii) The graph shows that the percentage
7. (a) C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g) 1 yield of ammonia decreases with
(b) Ethanol 1 increasing temperature at constant
(c) It provides the enzymes (or biological pressure. Since an increase in
catalysts) that speed up the fermentation of temperature favours the endothermic
glucose. 1 change of an equilibrium system, the
(d) Pressure will build up inside the conical forward reaction is exothermic. 1
flask after a few days. 1 (iii) 20% 1
(e) At such a high temperature, the enzymes in (iv) As shown from the graph, decreasing
yeast are denatured and lose their the temperature favours the formation
catalytic activities. 1 of ammonia (or can increase the
(f) Ethanol is oxidized to ethanoic acid by the percentage yield of ammonia). However,
actions of oxygen and bacteria in the air. 1 if the temperature is too low, the
8. (a) Cracking of heavy petroleum fractions 1 reaction will occur very slowly and it
(b) takes a long time for the reaction
system to reach equilibrium. 1
with catalyst As shown from the graph, increasing
without catalyst
the pressure favours the formation of
Potential energy

ammonia (or can increase the

percentage yield of ammonia). However,
if the pressure is too high, the
construction cost and maintenance
cost of pipelines and reaction chambers
that can withstand a high pressure
Reaction coordinate would be very high. 1
4
Hence, the Haber process operating at
(1 mark for the energy profile of the catalysed
400°C and 200 atm is a compromise
reaction; 1 mark for the energy profile of the
between reaction rate, yield and
uncatalysed reaction; 1 mark for the labelling
economic considerations.
of the reactants (CH2=CH2 + H2O) and product
(b) (i) Impurities in the gaseous reactants
(CH3CH2OH); 1 mark for the labelling of the
may ‘poison’ the catalyst and inhibit its
two axes)
action. 1
(c) Reaction (1) has to be carried out between
(ii) Cool the resultant mixture to condense
25°C and 40°C (or at a relatively low
ammonia to liquid. 1
temperature) because enzymes can be
(c) (i) 2NH3(aq) + H2SO4(aq)
denatured easily at high temperatures. 1
(NH4)2SO4(aq) 1
On the contrary, Reaction (2) has to be
(ii) The pH of the soil decreases. 1
carried out at 300°C (or at a relatively high
Aqueous solution of ammonium
temperature). 1
sulphate is (weakly) acidic. It can
(d) Alcoholic drinks containing ethanol
neutralize any alkaline substances in
manufactured by Reaction (1) can have the
the soil. 1
desired flavour originating from the raw
material used. 1
T12
 +
3. HKDSE 2017 Paper 2 Q1b(ii) net flow of Na (aq) ions from
4. (a) (i) Chlorine/Cl2 1 compartment X to Y. (1)
– –
(ii) 2Cl (aq) Cl2(g) + 2e 1 • The resultant solution eventually
(iii) Chlorine bleach/insecticides/ becomes concentrated in sodium
pesticides 1 hydroxide in compartment Y. (1)
–
(Accept other daily products that are (f) (i) Cl2(g) + 2OH (aq)
– –
manufactured from chlorine.) Cl (aq) + OCl (aq) + H2O(l) 1
+ –
(b) (i) Na (aq) + e + Hg(l) Na/Hg(l) 1 (ii) Sodium hypochlorite 1
(ii) Sodium amalgam 1 6. HKDSE 2019 Paper 2 Q1b(i)–(ii)
(c) (i) Hydrogen 1 7. HKDSE 2019 Paper 2 Q1a(ii)
(ii) 2Na/Hg(l) + 2H2O(l) 8. (a) Cu/ZnO/Al2O3 1
2NaOH(aq) + H2(g) + 2Hg(l) 1 (b) CH4(g) + H2O(g) CO(g) + 3H2(g) 1
(d) Chlorine bleach can react with hydrochloric (c) (i) The graph shows that the concentration
acid to give toxic chlorine gas. 1 of methanol decreases with increasing
5. (a) P: chlorine/Cl2 1 temperature at constant pressure.
Q: hydrogen/H2 1 Since an increase in temperature
–
(b) At titanium electrode, Cl (aq) ions are favours the endothermic change of an
preferentially discharged (oxidized) to form equilibrium system, the forward
Cl2(g) because its concentration is much reaction is exothermic. 1
–
higher than that of OH (aq). 1 (ii) If the operating temperature is lower
– –
2Cl (aq) Cl2(g) + 2e 1 than 125°C, the reaction may proceed
+
At nickel electrode, H (aq) ions are (very) slowly. This takes a long time for
preferentially discharged (reduced) to form the reaction system to reach
H2(g) because it is a stronger oxidizing equilibrium. 1
+
agent than Na (aq). 1 (iii) Since there are a greater number of
+ –
2H (aq) + 2e H2(g) 1 moles of gases on the left-hand side of
(c) X 1 the equation, an increase in pressure
(d) It separates the cell into two compartments causes the equilibrium position to shift
so that the hydrogen and chlorine formed to the right/product side. 1
would not mix together and react. 1 If the conversion is operated at a
+ –
It only allows Na (aq) ions but not Cl (aq) pressure lower than 50 atm, the
–
and OH (aq) ions to pass through. 1 concentration of methanol obtained will
(e) (i) Sodium hydroxide 1 be (very) low. 1
(ii) Any TWO of the following points: If the conversion is operated at a
–
• Cl (aq) ions are preferentially pressure higher than 100 atm, the
discharged at the titanium electrode construction cost and maintenance
+
to give Cl2(g). Meanwhile, H (aq) ions cost of pipelines and catalytic
are preferentially discharged at the chambers that can withstand a high
nickel electrode to give H2(g). 1 pressure will be (very) high. 1
+
• Na (aq) ions (from dissolved sodium 9. (a) As methanol is a one-carbon compound, it
chloride) stay behind in compartment can be used as the starting material to
–
X, and OH (aq) ions (from water) make other carbon compounds with larger
continuously form (at nickel number of carbon atoms. 1
electrode) in compartment Y. 1 (b) (i) X is methane. 1
• The membrane only allows cations A natural source of X is natural gas/
but not anions to pass through. As landfill gas/biomass. 1
there is a higher concentration of (ii) CH4(g) + H2O(g) CO(g) + 3H2(g) 1
cations in compartment X (because (c) CO(g) + 2H2(g) CH3OH(g) 1
anions are removed), there will be a Cu/ZnO/Al2O3 1

T13
 (d) With the use of catalysts, the conversion of Any one of the following disadvantages:
syngas to methanol can be carried out at • Chlorine (a toxic gas), ammonia (a toxic
a lower temperature and pressure. This gas) and hydrogen are hazardous, so
saves energy and reduces the construction having both industrial plants built within
cost and maintenance cost of the pipelines the same region may increase the risk of
and reaction chambers that can withstand accidents, and the cost of safety control
a high pressure. 1 will be higher. 1
10. (a) When brine is electrolysed in a membrane • Having both industrial plants built within
cell, H2O(l) is reduced to form H2(g) and the same region may generate more
–
OH (aq) at the cathode. 1 wastes, and this can create a more
– –
2H2O(l) + 2e H2(g) + 2OH (aq) 1 significant environmental impact. As a
OR result, the cost of pollution control will
When brine is electrolysed in a membrane be higher. (1)
+
cell, H (aq) is reduced to form H2(g) at the 11. HKDSE 2021 Paper 2 Q1c
cathode. (1)
+
2H (aq) + 2e
–
H2(g) (1) Chapter 55
(b) N2(g) + 3H2(g) 2NH3(g) 1 A. Structured questions (p.181)
Operating temperature: 400–450°C 1. (a) CH3COOCH2CH3 1
Operating pressure: 200 atm 1 OR
Catalyst used: finely divided iron
(c) CO(g) + 2H2(g) CH3OH(g) 1 (1)
(d) (i) It is a mixture consisting mainly of H2(g) (b) Any one of the following:
and CO(g). 1 • It has a pleasant fruity smell. 1
(ii) Carbon monoxide is present in the • It is a good solvent for organic
syngas, which is one of the feedstocks substances. (1)
for producing methanol. Hence, there is (c) (i) C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g) 1
no need to find a source of carbon (ii) It provides the enzymes (or biological
monoxide for the production. 1 catalysts) that speed up the
OR fermentation of glucose. 1
Chlorine and sodium hydroxide are also (iii) CH3OH(l) + CO(g) CH3COOH(l) 1
the main products of the chloroalkali (iv) Method I is greener because (any one
industry. Production of hydrogen only of the following):
for methanol production by electrolysis • The glucose solution (feedstock) is
of brine will produce more chlorine and harmless but the methanol and
sodium hydroxide than necessary. The carbon monoxide (feedstocks) used
cost of disposing of chlorine and in Method II are toxic and poisonous
sodium hydroxide would be high. (1) respectively. 1
(e) Any one of the following advantages: • Biological catalysts (from the yeast
• It creates more jobs for people living near and bacteria) are used. They pose
the two industrial plants. 1 less harm to the environment
• There is no need to transport the compared to the inorganic catalysts
hydrogen (a flammable gas) over a long (HI, Ir) that used in Method II. (1)
distance from the chloroalkali plant to the • The wastes produced are
ammonia production plant. Hence, it can biodegradable but the wastes
reduce transportation cost and the risk produced (e.g. CH3I) in Method II
of any accidents caused. (1) are not. (1)
• The existing transport network around OR
the two industrial plants will be improved Method II is greener because (any one
for the transportation of fuel, feedstock, of the following):
products and labour into and out of the
T14 plants. (1)
 • The main reaction has an atom using additional chemical reagents
economy of 100%, but it is not for such as dilute H2SO4 or dilute HNO3.
Method I. (1) Hence, less waste would be produced. 1
• Compared to Method I, the ethanoic
acid produced is more concentrated.
Therefore, the separation and Answers to Part exercise
purification of the ethanoic acid
consumes less energy. (1) Chapter 55
• It does not consume food (glucose) A. Multiple-choice questions (p.183)
but Method I does. (1) 1. D
2. Route II is greener. 2. C
• In terms of waste prevention: Step 1 is reduction because H2 is added to
Compared with Route I (H3PO4, SO2, H2O2, D-glucose.
2+
Fe ), fewer reagents are used in Route II Step 2 is oxidation because an –OH group in
(E. coli bacteria, H2O). Hence, less waste D-sorbitol is converted to a ketone group.
would be produced. 1 Step 3 is oxidation because an –OH group in
• In terms of hazardous nature of the reactants L-sorbose is converted to a carboxyl group.
and reagents used: Step 4 is condensation because the carboxyl
The starting material (glucose) used in group of 2-keto-L-gulonic acid (KGA) reacts with
Route II is harmless, while that (benzene) one of its –OH groups to give an ester group, with
used in Route I is carcinogenic. 1 the elimination of small molecules (H2O).
OR 3. C
Less hazardous reagents and solvents (E. coli 4. D
bacteria, H2O) are used in Route II but 5. C
corrosive H3PO4, toxic SO2 and corrosive 6. C
(when concentrated) or irritating (when dilute) 7. B
H2O2 are used in Route I. (1) Ea 1 1
log k1 – log k2 = ( – )
• In terms of using renewable feedstock: 2.3 R T2 T1
52 × 1000 1 1
Benzene is produced from petroleum, which log k – log 1.5k = ( – )
2.3 × 8.31 25 + 273 + T 25 + 273
is a non-renewable resource. In contrast,
1 52 000 1 1
glucose can be obtained from plants, which log ( ) = ( – )
1.5 2.3 × 8.31 298 + T 298
is a renewable resource. 1 T = 5.86
3. (a) Iron/Fe 1 8. C
(b) 400–450°C, 200 atm 1 (2): one of the 12 principles of green chemistry is
(c) Room temperature and pressure (or using catalysts.
ambient conditions) 1 (3): generally, the fewer steps in an industrial
Enzymes work only at ambient conditions. 1 process, the fewer chemicals are needed and
OR eventually, less waste is produced.
At high temperatures, enzymes are 9. C
denatured and lose their catalytic
activities. (1) B. Structured questions (p.185)
(d) (i) With the use of the synthesized 10. (a) From Trials 1 and 2, at the same initial
catalyst, nitrogen fixation can be [CO], the initial rate doubles when the
carried out at much lower initial [Hb] is doubled. Hence, the order of
temperatures and pressures. This can reaction with respect to Hb is 1. 1
save fuel and energy, and thus the From Trials 2 and 3, at the same initial
production cost. 1 [Hb], the initial rate triples when the initial
(ii) With the use of the synthesized [CO] is tripled. Hence, the order of reaction
catalyst, N2 can be converted to NH4
+
with respect to CO is 1. 1
ions on its own without the need of
T15
 m
(b) 2 1 1=2
(c) Rate = k[Hb][CO] 1 ∴m=0
11. (a) Withdraw small portions of the reaction Thus, the order of reaction with
mixture using a pipette at regular time respect to X is 0. 1
intervals. 1 (ii) Let the rate equation be rate =
n
Quench the reaction in the small portions k[alkali][W] , where n is the order of
by pouring them into ice-cold distilled reaction with respect to W.
water. 1 By substituting the given data into the
Titrate the alkali present in the quenched rate equation, we have
–3 m n
portions against standard hydrochloric acid 1.2 × 10 = k (0.040)(0.010) (0.40) ....(1)
–3 m n
using phenolphthalein as an indicator. The 2.4 × 10 = k (0.080)(0.010) (0.40) ....(2)
–3 m n
colour of the indicator will change from 3.6 × 10 = k (0.120)(0.020) (0.40) ....(3)
–3 m n
pink to colourless at the end point. 1 2.4 × 10 = k (0.160)(0.020) (0.20) ....(4)
(b) (i) (1) This is to ensure that the Dividing (3) by (4),
–3 m n
concentration of X was more or 3.6 × 10 k (0.120)(0.020) (0.40)
–3 = m n
less the same throughout the 2.4 × 10 k (0.160)(0.020) (0.20)
reaction, and the concentration of 3 3 0.40 n
= ( )
the alkali would be the only factor 2 4 0.20
n
2=2
to be varied in the experiment. 1
∴n=1
(2) A very small amount of W (the
Thus, the order of reaction with
catalyst) is sufficient to increase
respect to W is 1. 1
the rate of reaction to a great –3 –3 –1 –3 –3
(d) 2.4 × 10 mol dm s = k (0.160 mol dm )(0.20 mol dm )
extent. 1 –3 –3 –1
2.4 × 10 mol dm s
(ii) The reaction is first order with respect k= –3 –3
(0.160 mol dm )(0.20 mol dm )
to the alkali because a straight line –1 3 –1
= 0.075 mol dm s 2
passing through the origin is shown in
(1 mark for the correct numerical answer;
the graph of (initial) rate against initial
1 mark for the correct unit)
[alkali]. 1
12. HKDSE 2018 Paper 2 Q1c
(iii) The irregular results show that the
13. (a) The reaction starts slowly because it
(initial) rate is higher than expected. 1
involves effective collisions between two
Since the reaction is exothermic, the
kinds of negatively charged ions. 1
temperature of the reaction mixture
More energy is needed for them to
increases as the reaction proceeds.
approach and collide with each other
The reaction goes faster at higher
because they will repel each other. 1
temperatures. 1 – 2+ +
(b) (i) MnO4 (aq) + 4Mn (aq) + 8H (aq)
(c) (i) Let the rate equation be rate = 3+
m n 5Mn (aq) + 4H2O(l) 1
k[alkali][X] [W] , where m and n are 2– 3+
C2O4 (aq) + 2Mn (aq)
the order of reaction with respect to X 2+
2Mn (aq) + 2CO2(g) 1
and that of W. 2+
(ii) Mn (aq) can provide an alternative
By substituting the given data into the
pathway with lower activation energy
rate equation, we have –
–3 m n for the reaction between MnO4 (aq)
1.2 × 10 = k (0.040)(0.010) (0.40) ....(1) 2–
–3 m n and C2O4 (aq) in an acidic medium to
2.4 × 10 = k (0.080)(0.010) (0.40) ....(2)
–3 m n occur. 1
3.6 × 10 = k (0.120)(0.020) (0.40) ....(3)
–3 m n 14. HKDSE 2019 Paper 2 Q1c
2.4 × 10 = k (0.160)(0.020) (0.20) ....(4)
15. (a) It acts as a catalyst to speed up the
Dividing (3) by (1),
–3 m n reaction. 1
3.6 × 10 k (0.120)(0.020) (0.40)
–3 = m n (b) Reaction (II) can be carried out at a much
1.2 × 10 k (0.040)(0.010) (0.40)
0.020 m lower pressure (or atmospheric pressure).
3=3( ) This can greatly save the construction cost
0.010

T16
 and maintenance cost of the pipelines and (ii) Boots’ method consists of many steps,
reaction chambers that have to withstand a so many chemicals may be used.
high pressure. 1 Eventually, a considerable amount of
(c) Poisonous feedstock (CO) is used in wastes would be produced. 1
Reaction (I), while no poisonous feedstocks Since Boots’ method consists of many
are used in Reaction (II). 1 steps, many (reaction) intermediates
Reaction (I) is less energy efficient are produced. Hence, a large amount
because it is carried out at a higher of energy is needed for the separation
temperature and pressure. 1 and purification of ibuprofen. 1
(d) Any one of the following: (b) (i) Number of carbon atoms wasted
(Correct example: 1 mark; correct = 10 + 4 – 12 = 2 1
explanation: 1 mark) Number of hydrogen atoms wasted
• Oxidation of methane to methanol by = 14 + 6 – 16 = 4 1
microbial reactions. This oxidation uses Number of oxygen atoms wasted
renewable feedstock and has higher =3–1=2 1
energy efficiency. 2 (Note: molecular formula of acid
• Production of methanol from methane anhydride, (CH3CO)2O, and that of the
collected from landfills and biomass. product of Step 1 are C4H6O3 and
This production uses renewable C12H16O respectively.)
feedstock. 2 (ii) Atom economy of Step 1
16. HKDSE 2017 Paper 2 Q1c 176.0 g
= × 100% = 74.6% 1
17. HKDSE 2018 Paper 2 Q1b (134.0 + 102.0) g
18. HKDSE 2020 Paper 2 Q1b (Note: relative molecular masses:
19. (a) Two-stage fermentation process for vitamin 2-methylpropylbenzene = 134.0; acid
C production is considered as a green anhydride = 102.0; product of Step 1
process because: = 176.0)
• The raw material (glucose) is a (c) Steps 2 and 3 1
renewable resource. 1 (d) Any TWO of the following:
• Bacteria is used to ferment D-sorbitol to • Catalysed reactions usually take place at
L-sorbose and then to 2-keto-L-gulonic lower temperatures. Hence, this can
acid (KGA). Hence, fewer reagents and reduce energy consumption. 1
solvents are used, and the chance of • Catalysts are often very selective in
producing harmful wastes would be actions. This selective property of
smaller. 1 catalysts reduces the formation of side
(b) CATIVA process for acetic acid production products. 1
is considered as a green process because • Catalysts are used in very small amounts
(any TWO of the following): and can be regenerated at the end of
• Methanol (the feedstock) can be reaction. Hence, it would not cause
produced from renewable resources like significant waste problems. (1)
biomass. 1
• The main reaction has an atom economy
of 100%. 1 Answers to Revision test
• Iridium and hydrogen iodide are used as
the catalysts. Hence, less energy is Chapter 55
required to operate the process. (1) A. Multiple-choice questions (p.192)
20. (a) (i) Percentage yield 1. C
= 90% × 90% × 90% × 90% × 90% × 90% 2. A
= 53.1% 1

T17
 3. D respect to (CH3)3CBr(aq) is 1. 1
–
From Trials 1 and 2, at the same initial [NO2 (aq)], From Trials 1 and 3, the initial rate
the initial rate increases by a factor of 1.5 when the triples when the initial [(CH3)3CBr(aq)]
+ –
initial [NH4 (aq)] is increased by a factor of 1.5. is tripled and the initial [OH (aq)] is
Hence, the order of reaction with respect to doubled. Now that the order of
+
NH4 (aq) is 1. reaction with respect to (CH3)3CBr(aq)
+
From Trials 1 and 3, at the same initial [NH4 (aq)], is 1, increasing the initial
the initial rate quadruples when the initial [(CH3)3CBr(aq)] by 3 times leads to an
–
[NO2 (aq)] is doubled. Hence, the order of reaction increase in initial rate by 3 times. This
–
with respect to NO2 (aq) is 2. means that doubling the initial
–
4. C [OH (aq)] does not change the initial
2
Rate = k[P][Q] rate. Hence, the order of reaction with
–
1 2 12 2 1 2 respect to OH (aq) is 0. 1
Rate1 = k[2P][ Q] = 2 × ( ) = k[P][Q] = k[P][Q]
2 2 2 (ii) Rate = k[(CH3)3CBr(aq)] 1
5. C (iii) Substitute the results of Trial 1 into the
Ea 1 1
log k1 – log k2 = ( – ) rate equation,
2.3 R T2 T1 –2 –3 –1 –3
50.0 × 1000 1 1 1.2 × 10 mol dm s = k × 0.20 mol dm
log 0.035 – log k2 = ( – ) –2
1.2 × 10 mol dm s
–3 –1
2.3 × 8.31 350 298 k=
k2 = 0.705 0.20 mol dm
–3

6. D = 0.06 s
–1
2
Ea 1 1
log k1 – log k2 = ( – ) (1 mark for the correct numerical answer;
2.3 R T2 T1
k Ea 1 1 1 mark for the correct unit)
log 1 = ( – )
k2 2.3 R T2 T1 12. (a) The rate constant of the reaction at 25°C is
k 250 × 1000 1 1 equal to the slope of the line. By using the
log 1 = ( – )
k2 2.3 × 8.31 320 300 points at (0,0) and (0.0015, 5.0 × 10 ),
–13

k1 –3 –13
(5.0 × 10 – 0) mol dm s
–3 –1
= 1.88 × 10 k=
k2 (0.0015 – 0) mol dm
–3

k1 –10 –1
= 531 = 3.33 × 10 s 2
k2
(1 mark for the correct numerical answer;
7. A
1 mark for the correct unit)
8. D
Ea 1 1
9. C (b) log k1 – log k2 = ( – )
2.3 R T2 T1
10. C –10
log 3.33 × 10 – log k2
B. Structured questions (p.194) 115 × 1000 1 1
= ( – ) 1
11. (a) Substitution (reaction) 1 2.3 × 8.31 40 + 273 25 + 273
–10
(b) (i) It is the instantaneous rate of a log 3.33 × 10 – log k2
reaction at time t = 0 (the starting time 115 × 1000 1 1
= ( – )
×
2.3 8.31 313 298
of the reaction). 1 –9
k2 = 3.09 × 10 1
(ii) As the reaction proceeds, the
∴ the rate constant of the reaction at 40°C
concentrations of the reactants –9 –1
is 3.09 × 10 s .
decrease. The concentrations of the
reactants at time t = 0 (initial
concentrations of the reactants) are
known because the reaction has not
started yet. 1
(c) (i) From Trials 1 and 2, at the same initial
–
[OH (aq)], the initial rate doubles when
the initial [(CH3)3CBr(aq)] is doubled.
Hence, the order of reaction with

T18
 (c) (b) Any TWO of the following:
• The reaction has an atom economy of
100%. 1
• The reaction takes place in the gas phase.
Hence, no solvent is used. 1
• A mixture of Cu, ZnO and Al2O3 are used
–1

as the catalysts to speed up the reaction. (1)

mol dm s
–3

25°C
–13
Rate / × 10

Temperature lower
than 25°C

–3
[CH3Cl] / mol dm
1
13. (a) Trial I
Ea 1
Arrhenius equation: log k = log A – ( ) 1
2.3 R T
When a reaction has smaller Ea, the slope
Ea
of the line (– ) would be smaller. 1
2.3 R
(b) Trial I 1
(c) A catalyst increases the rate of a reaction
by providing an alternative pathway with
lower activation energy. 1
(d)
Number of particles

proportion of particles
having kinetic energy
greater than Ea

Ea’ Ea Kinetic energy

1
In the presence of a catalyst, the reaction
proceeds through an alternative pathway
with lower activation energy (Ea’). This
increases the proportion of particles with
kinetic energy greater than the Ea in the
gaseous reaction system. There is an
increase in frequency of effective collisions.
Thus, the rate of reaction increases. 1
14. (a) CO(g) + 2H2(g) CH3OH(g) 1

T19