Chem 54 (2nd) PDF

Chapter 54
Industrial processes
54.1 Production of fertilizers
54.2 Chloroalkali industry
54.3 Production of methanol
54.4 Social, economic and environmental considerations of
industrial processes
Learning goal
After studying this chapter, you should be able to:
54.1
• describe the importance of fertilizers to our world
• describe feedstock, principles, reaction conditions, procedures and products for processes
involved in the production of ammonia
• describe the process of the conversion of ammonia to fertilizers
• explain the physicochemical principles involved in the production of ammonia
• explain how industrial processes such as the Haber process often involve a compromise between
rate, yield and economic considerations
54.2
• describe the importance of the chloroalkali industry
• explain the underlying chemical principles involved in mercury cell process and membrane cell
process of the chloroalkali industry
54.3
• describe the importance of methanol
• recognize the significance of the conversion of methane to methanol
• describe feedstock, reaction conditions, procedures and products for processes involved in the
manufacturing of methanol via syngas
• discuss the advancement of the methanol production technology
54.4
• discuss social, economic and environmental considerations of industrial processes as illustrated
by the Haber process, the chloroalkali industry or the manufacturing of methanol via syngas
Chapter 54 Industrial processes
Many chemical products we use in daily life are developed from industrial processes that make use of
the natural resources. For example,
• the main component in the air

can be used to make fertilizers,
• the salt in the ocean can be used

to make chlorine bleach,
• the main component in the natural gas can be converted

to methanol which is a starting material of many other
chemicals such as plastics, drugs, paints and adhesives.
A natural gas production platform
Think about...
Which substance in the air can be used as the raw material to make fertilizers?
Nitrogen
Which substance in the ocean can be used as the raw material to make chlorine bleach?
Sodium chloride solution
Which substance in natural gas can be used as the raw material to make methanol?
Methane
After studying this chapter, you should be able to answer the above questions.
chlorine bleach 氯漂白劑 adhesive 黏合劑

methanol 甲醇
54 Industrial processes

PowerPoint
Nutrients for healthy plant growth
We need food for energy and for growth. Plants are our fundamental food
source. We eat a variety of plants directly. These are mainly crops,
including fruits, vegetables and cereals (e.g. wheat, rice). We also need
livestock and poultry for their meat, milk and eggs. These animals feed
on grass or cereals. So in this way, we are eating plants indirectly. See
Figure 54.1.
(a)
(b)
Figure 54.1 (a) Fruits.

(b) Vegetables. (c) A wheat
field. (d) Livestock feed on
grass. (c) (d)
Plants need certain nutrients to grow well, particularly nitrogen,

Note 1 phosphorus and potassium. Plants need them in large quantities and N1
Phosphorus is needed by plants to +
absorb aqueous solutions of their compounds (e.g. in the form of NH4 ,
make nucleic acids, phospholipids
– 2– +
and several proteins. NO3 , HPO4 and K ) through roots (Figure 54.2).
Figure 54.2 Plants absorb aqueous

solutions of the nutrients for growth
through their roots.
cereal 穀類 poultry 家禽
livestock 牲畜 wheat 小麥
3 54
XIII Industrial chemistry
H20 Example 54.1

Understanding the importance of nitrogen
(a) Plants need nitrogen from the soil to make proteins. What are proteins?
(b) Why is nitrogen essential to life?
(c) Can plants use free nitrogen present in the air? If not, how do plants obtain nitrogen to make
proteins? CE2000(I)9(c)(ii)
Solution
(a) Proteins are natural polymers built from monomers called amino acids. An amino acid has the
general formula H2NCH(R)COOH. Different amino acids have different R-groups. There are only
about 22 different amino acids, from which an infinite number of proteins can be built.
(b) Nitrogen is essential to life because all living things contain proteins and all proteins contain
nitrogen.
(c) Most plants cannot use free nitrogen in the air. They can only use fixed nitrogen, that is, nitrogen
chemically combined in compounds such as ammonium nitrate, ammonium sulphate, etc.
The importance of fertilizers

Today, there are over seven billion people on the Earth and the growing
Note 2 population needs more and more food. One way of solving the food N2
This website gives the instant
number of births and number of
problem is to grow more crops. However, when the same crops are
deaths in the world. grown in the same field for many years, the nutrients in the soil will
be exhausted. The soil may become short of one or more types of
nutrients. Fertilizers are added to the soil to replace the nutrients
used up by plants.
Key point
Fertilizers are added to the soil to provide important nutrients to
enhance healthy plant growth. They are usually inorganic salts that
contain one or more of the elements nitrogen, phosphorus and
potassium.
Nitrogenous fertilizers
There are several types of fertilizers. The most important one is
nitrogenous fertilizers. The nitrogen in the soil can be replenished by
adding nitrogenous fertilizers.
amino acid 氨基酸 inorganic salt 無機鹽

54 4 ammonium nitrate 硝酸銨 natural polymer 天然聚合物
exhausted 耗盡
replenish 補充
ammonium sulphate 硫酸銨 nitrogenous fertilizer 氮肥
fertilizer 肥料
Learning tip Nitrogenous fertilizers are usually nitrates or ammonium salts.

Aqueous ammonia is Ammonium nitrate NH4NO3 is the most widely used fertilizer. It is
volatile. Besides, it is so soluble in water and can be easily absorbed by plants. It also has a high
alkaline that it will
change the soil pH.
nitrogen content (35% by mass). In the form of granules, it can be easily
Therefore, it is not very stored and transported (Figure 54.3).
convenient and
common to apply
aqueous ammonia to
the soil directly.
Figure 54.3 (a) Ammonium

nitrate granules (b) Bags of
ammonium nitrate fertilizer (a) (b)
Other common nitrogenous fertilizers are ammonium sulphate

(NH4)2SO4, sodium nitrate NaNO3 and urea (NH2)2CO.
Class practice 54.1

The following pack of 5-3-8 NPK fertilizer contains 5% nitrogen, 3%
phosphorus and 8% potassium.
A54.1
(a) HNO3(aq) + NH3(aq) NH4NO3(aq)
(b) (i) Percentage by mass of nitrogen in ammonium
nitrate
14.0 × 2
= × 100% = 35%
14.0 × 2 + 1.0 × 4 + 16.0 × 3
(ii) Assume that all the nitrogen in the fertilizer
comes from ammonium nitrate.
Mass of nitrogen in 50 g of fertilizer
= 50 g × 5% = 2.5 g
Mass of ammonium nitrate in 50 g of fertilizer
2.5 g
= = 7.14 g
35%
(c) Potassium hydroxide is very corrosive. Besides, it is
too alkaline that it may change the pH of the soil.
A NPK fertilizer for potted plants
(a) Nitrogenous fertilizers are most often manufactured by neutralization of

an acid and an alkali. Write an equation for such a reaction to
manufacture ammonium nitrate.
(b) The pack of fertilizer has a net weight of 50 g.
(i) Calculate the percentage by mass of nitrogen in ammonium nitrate.
(ii) Calculate the mass of ammonium nitrate in this pack of NPK.
(c) Suggest why potassium sulphate but not potassium hydroxide is used in
the fertilizers.
sodium nitrate 硝酸鈉 granule 顆粒

urea 脲 volatile 具揮發性的
5 54
CE2000(I)9(d)
AL2006(I)9
AS2010(I)11
DSE2014(2)1(c)(i),(vi)
Production of ammonia — Haber process
E
XTRA
Do you know? Ammonia is the basic chemical used for the production of nearly all
S
forms of nitrogenous fertilizers such as ammonium nitrate, ammonium

Mainland China has
the largest proportion sulphate and urea. Millions of tonnes of ammonia are produced worldwide
(about 29%) of every year. Ammonia is the second largest synthetic chemical in terms of
worldwide production
of ammonia.
its annual production. Most of the ammonia produced (about 80%) is used
to make nitrogenous fertilizers.
Figure 54.4 shows the growth in worldwide ammonia production that

reflects the increased use of fertilizers.
Think about Think about
There is a rapid
Can you suggest a increase in the world
reason for the rapid population during this 140 000
increase in worldwide period. In order to
Production mass (1000 tonnes)
production of grow more crops for 120 000
ammonia from 1947 to food in a given period

2007? of time, a large supply 100 000
of nitrogenous
fer tilizer is needed. 80 000
Haber process was invented and adopted by large

industrial plants to manufacture nitrogenous fertilizers 60 000
using ammonia as the feedstock.

40 000
Figure 54.4 Worldwide 20 000
production of ammonia
0
from 1947 to 2007.
1940 1950 1960 1970 1980 1990 2000 2010
Note 3 Year
In the Haber process, 450°C, 200 atm and iron catalyst are the most commonly used conditions for the
manufacture of ammonia. There may be variations in different manufacturers.
Ammonia is produced industrially by the Haber process, named

after a German chemist called Fritz Haber (Figure 54.5). The process
involves direct combination of nitrogen and hydrogen at 400–450°C and
N3
200 atm in the presence of finely divided iron as the catalyst.
finely divided iron
–1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
400–450°C,
Figure 54.5 Fritz Haber
200 atm
(1868–1934). His invention
in synthesizing ammonia is CE2000(II)10 DSE2012(2)1(a)(i)(1)
an important contribution to
humans. He was awarded Feedstock for the Haber process
the Nobel Prize for
Chemistry in 1918. Source of nitrogen CE2000(II)10
* Book 1, Section 2.4, p.14 Nitrogen is obtained by *fractional distillation of liquid air. The liquid
air is fractionally distilled to separate out the nitrogen.
fractional distillation 分餾法

54 6 Haber process 哈柏法
feedstock 原材料
A54.2 Class practice 54.2

(a) Nitrogen
(b) Fractional distillation of liquid air The boiling points of argon, nitrogen and oxygen are –186°C, –196°C and
(c) When the liquid air is warmed up
–183°C respectively.
slowly, liquid nitrogen will boil off
as gas first. (a) Which of the three gases has the lowest boiling point?
(b) Suggest a method to separate the three gases from air.
(c) Briefly describe how nitrogen is separated from air by the method in (b).
Sources of hydrogen DSE2012(2)1(a)(ii) DSE2014(2)1(c)(ii)
(1) Steam-methane reforming N4
Learning tip Hydrogen is mainly produced by reacting methane (in natural

More about the steam- gas) with steam over a nickel(II) oxide catalyst at 700–1000°C and
methane reforming will
10–20 atm. The process is usually called the steam-methane
be discussed in
Section 54.3. reforming.
NiO
–1
Note 4 CH4(g) + H2O(g) 3H2(g) + CO(g) ∆H = +206 kJ mol
Remind students that it is easier to
700–1000°C,
recall the reaction and equation by
10–20 atm
memorizing the name of the
reaction.
The mixture of hydrogen and carbon monoxide produced is
known as synthesis gas (or simply syngas). The production of
hydrogen can be further increased by the following reaction, known
Note 5 as the water-gas shift reaction. N5
The water-gas shift reaction not
–1
only can increase the production of CO(g) + H2O(g) CO2(g) + H2(g) ∆H = –41 kJ mol
H2, it can also adjust the mole ratio
of CO and H2 in the syngas to meet
the requirement of other industrial (2) Electrolysis of brine CE2000(II)10
reactions. This will be discussed
more in the manufacture of Hydrogen is one of the products in the electrolysis of brine.
methanol using syngas in Section
54.3.
(3) Cracking of petroleum
Hydrogen is obtained as a by-product from cracking of petroleum.
Class practice 54.3

A54.3
1. (a) Hydrogen is produced at the
cathode.
1. Hydrogen can be obtained by the electrolysis of brine.
+
(b) 2H (aq) + 2e
–
H2(g) (a) State whether hydrogen is produced at the anode or at the cathode.
2. (a) Cracking is the process of (b) Write a half equation for the production of hydrogen at the electrode.
breaking down large molecules
(usually long-chain molecules 2. Hydrogen can also be obtained by the cracking of petroleum.
of carbon compounds) into
smaller ones.
(a) What is meant by ‘cracking’?
(b) C12H26 4C3H6 + H2 (b) Write an equation for the production of hydrogen during the cracking
of C12H26, which produces propene and hydrogen only.
cracking 裂解作用 steam-methane reforming 蒸汽–甲烷重整作用

electrolysis 電解 synthesis gas/syngas 合成氣體/合成氣
7 54
nickel(II) oxide 氧化鎳(II) water-gas shift reaction 水–煤氣轉移反應

The Haber process CE2000(II)10 CE2003(I)6(b)

CE2002(II)25 AS2011(II)6
Note 6
‘Poison the catalyst’ means to
Nitrogen and hydrogen are mixed in the ratio of 1:3 by volume. The
reduce the effectiveness of the gaseous mixture is dried and purified. This is necessary because any
catalyst.
impurities (such as sulphur and its compounds) present would poison the N6
Note 7
Compression of gases helps
catalyst used in the process. The gaseous mixture is then compressed in N7
increase the concentration of the compressor and preheated in a heat exchanger before they enter
reactant particles in the catalytic
chamber which can increase the the catalytic chamber.
rate of reaction.
In the catalytic chamber, nitrogen and hydrogen combine in a

Learning tip
‘Yield’ means ‘how much
reversible reaction to give ammonia at 400–450°C and 200 atm in the
product can be presence of finely divided iron as catalyst. The percentage yield of
obtained compared to
ammonia is about 15% under these conditions.
the theoretical
maximum amount if the –1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
reaction goes to 100%’.
1 volume 3 volumes 2 volumes
Note 8 The mixture (ammonia, unreacted nitrogen and hydrogen) leaving the N8
The cost of the Haber process can
be reduced if the unreacted
catalytic chamber is cooled in the heat exchanger. The heat released from
nitrogen and hydrogen are the exothermic reaction is used to preheat nitrogen and hydrogen before
recycled and hot product gases
are used to warm up the they enter the catalytic chamber.
reactants.
Ammonia (b.p. –33°C) is then liquefied under pressure in the

condenser and collected in the storage tank. The unreacted nitrogen and
hydrogen are recycled. Figure 54.6 shows a flow diagram for the Haber
process. Figure 54.7 shows a modern Haber process plant.
DSE2014(2)(1)(c)(v)
Volume ratio of
N2 : H2 = 1 : 3
Catalytic
N2 H2
Chamber
(400–450°C) NH3, unreacted
hot compressed N2 & H2
N2 & H2
heat cool liquid
clean dry up down NH3 Storage
Purifier and Condenser
Compressor Tank
Drier N2 & H2
Heat exchanger
unreacted N2 & H2
compressed Recycling
N2 & H2 (200 atm) Pump
Figure 54.6 A flow diagram for the Haber process.
catalytic chamber 催化室 heat exchanger 換熱器

54 8 compressor 加壓器 percentage yield 百分產率
poison 毒化
liquefy 液化
recycle 回收
Figure 54.7 A modern Haber process plant.
Key point
The starting point in the manufacture of fertilizers is the manufacture
of ammonia (from nitrogen and hydrogen) by the Haber process:
finely divided iron
–1
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
400–450°C,
200 atm
Physicochemical principles and economic

Simulation
(Haber process)
considerations involved in the Haber process
The operating conditions employed in the Haber process involve a
DSE2014(2)1(c)(iv) compromise between the rate of reaction, the yield and economic
considerations. To explain this, it is necessary to consider the production
cost in the chemical industry and the factors that affect a chemical
equilibrium.
Pressure DSE2012(2)1(a)(iii)
Consider the chemical equilibrium in the Haber process:
N2(g) + 3H2(g) 2NH3(g)
Four moles of gaseous reactants produce only two moles of a gaseous

product. Since there are a greater number of moles of gases on the
left-hand side of the equation, an increase in pressure will cause the
equilibrium position to shift 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. This increases the amount of ammonia produced per unit
time.
chemical equilibrium 化學平衡 compromise 協調
equilibrium position 平衡位置
9 54
However, to withstand very high pressures (e.g. 1000 atm), the

construction and maintenance costs for the plant are high. As a
compromise, 200 atm is the typical pressure used in the process.
Temperature DSE2012(2)1(a)(iii)
The formation of ammonia from nitrogen and hydrogen is an exothermic

Think about
–1
Why does a reaction reaction (∆H = –92 kJ mol ). A low temperature favours an exothermic
proceed slowly at reaction. Hence, a low temperature increases the yield of ammonia.
low temperatures?
However, at low temperatures, the reaction proceeds slowly. This lowers
Think about
the amount of ammonia produced per unit time.
At low temperatures, the average
kinetic energy of the reactant
As a compromise, a moderately high temperature (400–450°C) is often
particles is low and the particles
move slowly. Besides, not many used. This ensures that more ammonia can be produced in a given period
reactant particles have energy that
of time.
is equal to or greater than activation
energy at low temperatures.
Consequently, there will be a small
number of effective collisions per Catalyst DSE2012(2)1(a)(i)(2) N9
unit time, so the reaction proceeds
slowly. A catalyst has no effect on the position of equilibrium and hence does
not increase the yield of ammonia. In the Haber process, the catalyst
Note 9
A catalyst increases the rates of speeds up the reaction and shortens the time for the reaction to
both forward and backward reach equilibrium. Therefore, more ammonia can be produced in a
reactions to the same extent. It will
not shift the equilibrium position. given period of time. Then a lower operating temperature can be used.
Thus, the use of catalyst will not
This lowers the cost of energy consumption.
change the yield of the chemical
process.
The iron catalyst is in finely divided form which greatly increases
the surface area of the catalyst. Hence, this improves its catalytic effect.
Key point
As a summary, the optimum (most suitable) conditions for producing
ammonia are:
• 200 atm,
• 400–450°C and
• with the use of finely divided iron as catalyst.
The percentage yield of ammonia is about 15% under the optimum

conditions. Although the percentage yield is not high, the product can be
obtained more quickly at such moderately high temperatures and
pressures.
exothermic reaction 放熱反應

54 10 optimum 最適當的
withstand 承受
H20 Example 54.2

Understanding the effects of pressure and temperature on the percentage yield of ammonia
The graph below shows the effects of pressure and temperature on the percentage yield of ammonia in
the Haber process.
100 200°C
300°C
Percentage yield of ammonia
80
400°C
N10
60 Note 10
500°C
To answer (a), students can draw a
vertical straight line on the graph at
40 any pressure and find out the effect
of temperature on the percentage
600°C yield of ammonia at constant
20 pressure.
To answer (b), just choose any one
curve (constant temperature) and
look at the effect of pressure on
the percentage yield of ammonia
0 200 400 600 800 1000 at constant temperature.
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 above, what pressure has to be maintained at 500°C to give a 40% yield of
ammonia?
(d) According to the graph above, what is the maximum operating temperature that gives a 85%
or more yield of ammonia at 500 atm?
DSE2012(2)1(a)(iv)
(e) Suggest ONE way that can further increase the yield of ammonia in the process.
DSE2014(2)1(c)(v)
(f) State how ammonia is isolated from unreacted nitrogen and hydrogen when they come out from
the catalytic chamber.
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) Remove ammonia from the equilibrium mixture continuously. This shifts the equilibrium position
to the product side and thus further increases the yield of ammonia.
N2(g) + 3H2(g) 2NH3(g)
(f) Condense ammonia so that it becomes a liquid.
Try Chapter Exercise Q26
isolate 分離
11 54
H20 Example 54.3

Calculating the percentage yield of ammonia
If 28 kg of nitrogen reacts with 18 kg of hydrogen in the Haber process, 5 kg of ammonia is
produced.
(a) What is the theoretical yield of ammonia?
(b) What is the percentage yield of ammonia?
(Relative atomic masses: H = 1.0, N = 14.0)
Solution
(a) N2(g) + 3H2(g) 2NH3(g)
Mass of reactants 28 kg 18 kg
3 3
28 × 10 g 18 × 10 g
Number of moles –1 –1
(14.0 × 2) g mol (1.0 × 2) g mol
= 1000 mol = 9000 mol
Since 1 mole of N2 only reacts with 3 moles of H2, H2 is in excess while N2 is the limiting
reactant.
From the equation, mole ratio of N2 : NH3 = 1 : 2
 number of moles of NH3 produced = 1000 mol × 2 = 2000 mol
–1
Theoretical yield of NH3 = 2000 mol × (14.0 + 1.0 × 3) g mol
= 34 000 g
= 34 kg
actual yield of NH3
(b) Percentage yield of NH3 = × 100%
theoretical yield of NH3
5 kg
= × 100%
34 kg
= 14.7%
Class practice 54.4

A54.4
(a) (i) The forward reaction is
exothermic. A lower temperature
Sulphuric acid is manufactured by the Contact process. The following shows an
favours the exothermic reaction important step in the process:
which causes the equilibrium –1
position to shift to the right, 2SO2(g) + O2(g) 2SO3(g) ∆H = –196 kJ mol
producing more sulphur trioxide.
Vanadium(V) oxide is used as the catalyst for this step. If 320 g of sulphur
(ii) Since there is a smaller number
of moles of gas on the right- dioxide reacts with excess oxygen at 450°C and 1 atm, 360 g of sulphur trioxide
hand side of the equation, a is produced.
higher pressure will cause the
(a) Using the principle of chemical equilibrium, explain why
equilibrium position to shift to
the right, producing more (i) a lower temperature increases the yield of sulphur trioxide,
sulphur trioxide. (ii) a higher pressure increases the yield of sulphur trioxide.
(Cont’d)
Contact process 接觸法 sulphur trioxide 三氧化硫

54 12 sulphur dioxide 二氧化硫 vanadium(V) oxide 氧化釩(V)
A54.4 (Cont’d)
(b) (i) Number of moles of SO2 used
320 (b) (i) Calculate the theoretical yield of sulphur trioxide.
= mol
32.1 + 16.0 × 2
= 4.99 mol (ii) Calculate the percentage yield of sulphur trioxide.
From the equation, mole ratio (c) Explain why the reaction is not carried out at too low temperatures and
of SO2 to SO3 = 1 : 1.
 number of moles of SO3 too high pressures in the industrial plant.
formed = 4.99 mol (d) State and explain the effect of catalyst on the yield of sulphur trioxide.
Theoretical yield of SO3
(Relative atomic masses: O = 16.0, S = 32.1)
= 4.99 × (32.1 + 16.0 × 3) g
= 399.7 g
Experiment 54.1 Experiment Workbook 5
PowerPoint Experiment Investigating the catalytic oxidation of ammonia

Video In this experiment, you are going to investigate the catalytic oxidation of
(ii) Percentage yield of SO3 ammonia and find out whether it is an endothermic or an exothermic reaction.
360 g
= × 100% = 90.1%
399.7 g
(c) If temperature is very low, the XTRA
E Historical note
S
reaction will be too slow that a

longer time is needed to reach
The first Haber process plant
equilibrium. If pressure is very
high, the construction and The first Haber process plant was built by
maintenance costs for the catalytic BASF (a leading chemical company till today).
chamber and pipes that can It opened in September 1913 in Germany. The
withstand high pressure will be
plant was originally built to manufacture
very high.
(d) The use of catalyst has no effect ammonia for producing fertilizers. However,
on the yield of sulphur trioxide. This soon after the World War I began, the plant
is because the catalyst increases was expanded to convert ammonia into nitric
both forward and backward
reaction rates to the same extent
acid for making explosives.
The first Haber process plant in
but it does not shift the equilibrium Germany.
position.
Production of fertilizers from ammonia

Ammonium nitrate
Ammonium nitrate is a commonly used nitrogenous fertilizer. It is made
by neutralizing nitric acid with ammonia.
AL2000(II)2(e)(i) Industrial production of nitric acid — the Ostwald process

CE2001(I)8(b)
CE2002(II)42 Nitric acid is manufactured by the catalytic oxidation of ammonia. The
AL2006(I)9
raw materials for the manufacture are ammonia, air and water.
The reactions involved are:

(1) Ammonia (from the Haber process) is oxidized by air using platinum
as catalyst to form nitrogen monoxide. 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
catalytic oxidation 催化氧化作用 nitrogen monoxide 一氧化氮 explosive 炸藥

neutralization 中和作用 Ostwald process 奧斯托惠爾特法
13 54
(2) Nitrogen monoxide reacts with oxygen (in air) to form nitrogen
AS2006(B)10(a)(iii)
dioxide.
–1
2NO(g) + O2(g) 2NO2(g) ∆H = –117 kJ mol
(3) Finally, nitrogen dioxide is dissolved in water in the presence of air to

form nitric acid.
4NO2(g) + O2(g) + 2H2O() 4HNO3(aq)
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)
Figure 54.8 A flow diagram for the manufacture of nitric acid.
Manufacture of ammonium nitrate from nitric acid

The nitric acid manufactured neutralizes the ammonia, producing
ammonium nitrate solution.
NH3(aq) + HNO3(aq) NH4NO3(aq)
The resultant solution of ammonium nitrate can be sold directly. The

solution may also be further concentrated and converted into granules.
The solid fertilizers are generally supplied to customers in bags.
Some fertilizer factories are really huge and consist of several plants
side by side (Figure 54.9). Ammonia is made in one plant while nitric
acid is made in another plant. Therefore, the ammonia and nitric acid
produced from these plants can be fed to the nearby fertilizer plant
Figure 54.9 A fertilizer factory.
conveniently.
absorption chamber 吸收室 nitrogen dioxide 二氧化氮

54 14 nitric acid 硝酸 oxidation chamber 氧化室
A flow plan of a fertilizer factory is shown in Figure 54.10.

0.2 pt
N2
Ammonia
NH3
Plant
H2
NH4NO3
O2 (fertilizer)
Nitric Acid
HNO3
Plant
H2O
Figure 54.10 A flow plan of a fertilizer factory that manufactures ammonium nitrate.
Ammonium sulphate
Ammonium sulphate solution is produced by reacting sulphuric acid with
ammonia.
2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
Note 11 The solution is evaporated to give ammonium sulphate crystals. These

Structural formula of urea:
crystals are dried in a drier before packing in bags. Then they are delivered
O
to customers.
C
H2N NH2 Urea N11
Think about
Urea fertilizers are produced by reacting aqueous ammonia with carbon
Do you remember dioxide to form ammonium carbamate, which is then dehydrated to form
the meaning of urea.
‘dehydration’?
2NH3(aq) + CO2(g) H2NCOONH4(aq)
Think about ammonium carbamate
‘Dehydration’ is a chemical change in which
hydrogen and oxygen are eliminated in a ratio H2NCOONH4(aq) (NH2)2CO(aq) + H2O()
of 2 : 1 from a compound. urea
H20 Example 54.4

Conversion of ammonia to nitrogenous fertilizers
Ammonia is a colourless gas with a characteristic pungent smell. It can be used to produce nitrogenous
fertilizers like ammonium nitrate.
(a) Draw three-dimensional structures to show the shapes of an ammonia molecule and an
ammonium ion.
(b) To produce ammonium nitrate, the ammonia is first converted to nitric acid by an industrial
process.
cont’d
ammonium carbamate 氨基甲酸銨

dehydration 脫水作用
15 54
(i) Write the chemical equation for the first step of this industrial process.
(ii) Explain whether this is a redox reaction.
(c) Write the chemical equation for the manufacture of ammonium nitrate from ammonia and nitric
acid.
(d) State ONE potential hazard of ammonium nitrate.
(e) Hence, or otherwise, suggest ONE safety precaution when transporting or storing ammonium
nitrate.
Solution
(a) Ammonia molecule: Ammonium ion:
N H
H H
H
N
H H
H
(b) (i) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

(ii) Yes. It is a redox reaction. The oxidation number of nitrogen increases from –3 to +2. The
oxidation of oxygen decreases from 0 to –2.
(c) NH3(aq) + HNO3(aq) NH4NO3(aq)
(d) Ammonium nitrate is explosive.
(e) Keep ammonium nitrate away from heat or fire.
Try Chapter Exercise Q27
Class practice 54.5 AS2002(B)10(a)(iii)
A54.5 1. (a) What is the percentage by mass of nitrogen in

1. (a) (i) Percentage by mass of nitrogen in urea
(i) urea, (NH2)2CO,
14.0 × 2
= × 100%
14.0 × 2 + 1.0 × 4 + 12.0 + 16.0 (ii) ammonium nitrate, NH4NO3 and
= 46.7%
(iii) ammonium sulphate, (NH4)2SO4?
(ii) Percentage by mass of nitrogen in
ammonium nitrate (b) Which fertilizer has the highest nitrogen content?
14.0 × 2
= × 100% (Relative atomic masses: H = 1.0, C = 12.0, N = 14.0, O = 16.0,
14.0 × 2 + 1.0 × 4 + 16.0 × 3
= 35% S = 32.1)
(iii) Percentage by mass of nitrogen in
ammonium sulphate 2. Ammonium sulphate is a nitrogenous fertilizer. It is not combustible but
14.0 × 2 can be dangerous at high temperatures. At high temperatures, ammonium
=
14.0 × 2 + 1.0 × 8 + 32.1 + 16.0 × 4
× 100% sulphate is converted to ammonium pyrosulphate, (NH4)2S2O7, which
= 21.2% further decomposes to give an alkaline gas, sulphur dioxide, water and
(b) Urea
2. (a) Ammonia
nitrogen.
(b) 3(NH4)2S2O7 2NH3 + 6SO2 + 9H2O + 2N2 (a) Suggest what the alkaline gas is.
(c) Ammonium sulphate should be stored in a (b) Write an equation for the thermal decomposition of ammonium
cool place.
pyrosulphate.
(c) Suggest ONE safety precaution for the storage of ammonium
sulphate.
ammonium pyrosulphate 過硫酸銨

54 16 thermal decomposition 熱分解作用
Reading to learn
Read the article below and answer the questions that follow.
The importance of 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 natural processes
that can be described as nitrogen fixation.
Lightning triggers the reaction between nitrogen and oxygen in the atmosphere to form nitrogen
oxides — nitrogen monoxide (NO) and nitrogen dioxide (NO2). Both oxides combine with water vapour
to form nitric acid (HNO3). Nitric acid is then carried to the ground in rain and snow, where it is converted
to nitrites and nitrates.
Reading to learn
1. N2(g) + O2(g) 2NO(g)
2. There is a steady supply of bacteria in the soil used
for nitrogen fixation. The process is more reliable.
On the contrary, nitrogen fixation by lightning
depends very much on the ‘unpredictable’ weather.
3. Yes. It fixes free nitrogen in air to nitrogen-containing
compounds that can be utilized by plants.
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 peas, beans and the soya plant, can convert
nitrogen into nitrates. They are known as nitrogen-fixing bacteria.
Questions
1. Write the equation for the reaction between nitrogen and oxygen to form nitrogen monoxide.
2. Suggest ONE advantage of nitrogen fixation by bacteria over nitrogen fixation by lightning.
3. Is the Haber process a nitrogen fixation process? Explain briefly.
STSE connections 54.1

PowerPoint
The need for mass production of fertilizers
With the expansion of world population (which is over seven billions today!), more crops are required for
food. Crops are repeatedly harvested from the same place and the soil thus becomes less fertile.
Without the sufficient supply of fertilizers,

the soil would eventually become infertile.
nitrogen oxides 氮氧化物 fertile 肥沃 pea 豌豆

harvest 收割 soya plant 黃豆
17 54
nitrogen fixation 固氮作用 trigger 引發

Traditionally, farmers collected animal waste and manure as fertilizers. However, these sources are not
reliable and cannot meet the increasing demand of the crops. Today, many farmers use fertilizers. The mass
production of fertilizers becomes extremely important. Otherwise, many more people in the world would be
starving! It is estimated that by 2015, world fertilizer consumption will reach nearly 190 million tonnes each
year.
STSE connections 54.1
No. Healthy and good crops need traces of other elements which may not be applied to
Question for discussion: the soil together with the most common fertilizers such as nitrogenous fertilizers.
Do you think that the use of man-made fertilizers can solve the problem completely? Give your reasons.
54.2 Chloroalkali industry AL2008(I)9
PowerPoint
Importance of chloroalkali industry
Think about In ‘Part I Planet Earth’, we have learnt that salt from the ocean is an
Sea water is an
important natural resource on the Earth. We can obtain common salt
important source of
sodium chloride. Why (sodium chloride) from sea water. Brine (concentrated sodium chloride
is it not used directly solution) is the raw material for chloroalkali industry. It produces
as the feedstock in
chloroalkali industry? sodium hydroxide, chlorine and hydrogen by electrolysis.
CE2004(II)36 DSEPP2012(2)1(c)(iii)
Think about Key point AL2009(I)3(a)(iv) DSE2014(2)1(a)(iv)
Sea water contains not only
sodium chloride, but also electrolysis
other dissolved minerals.
brine sodium hydroxide + chlorine + hydrogen
Therefore, sea water is not a electrolysis
suitable raw material for 2NaCl(aq) + 2H2O() 2NaOH(aq) + Cl2(g) + H2(g)
chloroalkali industry.
Note 12
Hydrogen and chlorine react to form hydrogen chloride. Dissolving
Chlorine bleach is made by
dissolving chlorine gas in cold, hydrogen chloride in water produces hydrochloric acid.
dilute sodium hydroxide solution. At
high temperature (about 70°C), H2(g) + Cl2(g) 2HCl(g)
–
OCl ion will disproportionate to
– –
form Cl and ClO3 ions. water
–
i.e. 3OCl (aq)
–
ClO3 (aq) + HCl(g) HCl(aq)
–
2Cl (aq)
(Note: disproportionate means one Chlorine can be bubbled into sodium hydroxide solution to produce
chemical species is simultaneously
oxidized and reduced.) chlorine bleach.
Cl2(g) + 2NaOH(aq) NaCl(aq) + NaOCl(aq) + H2O() N12
DSEPP2012(2)1(c)(ii)
bleaching solution
– – –
or Cl2(g) + 2OH (aq) Cl (aq) + OCl (aq) + H2O()
–
Bleaching solution contains hypochlorite ions (OCl (aq)) as the active
ingredient.
brine 鹽水 hypochlorite ion 次氯酸根離子

54 18 chloroalkali industry 氯鹼工業 sodium hydroxide 氫氧化鈉
hydrochloric acid 氫氯酸
The products of the chloroalkali industry have a wide range of

applications. Table 54.2 lists some uses of these products.
CE2007(II)41
Hydrogen Chlorine Sodium hydroxide
To make margarine To sterilize swimming pool water To make soaps
To be used as a rocket fuel To make plastics such as PVC To make drain cleaner
To make fertilizers To make solvent such as the To neutralize acidic effluents

thinner used in correction fluids from factories
Chlorine and hydrogen Sodium hydroxide and chlorine
To make hydrochloric acid To make chlorine bleach
Table 54.2 Some uses of the products from the chloroalkali industry.
drain cleaner 通渠劑 pesticide 殺蟲劑

margarine 人造牛油 sterilize 消毒
19 54
Working principles of chloroalkali industry

XTRA
E Do you know?
S
Imagine that the electrolysis of brine is carried out in the simple container
In 2011, there were
about 10 million as shown below (Figure 54.11). 0.2 pt
tonnes of chlorine and
11 million tonnes of
chlorine hydrogen
sodium hydroxide
produced from the
chloroalkali industry in
Europe.
– +
graphite
brine Cl H
– +
Cl H
– +
OH Na
– +
OH Na
anode cathode
Figure 54.11 A simple set-up

for electrolysis of brine.
Hydrogen is produced at the cathode and chlorine is produced at

–
the anode. As electrolysis goes on, hydroxide ions, OH (aq), accumulate
Note 13 in the solution. The solution therefore gradually changes to sodium
–
In general, OH (aq) ions are hydroxide solution. However, if this simple set-up were applied in the
preferentially discharged because
it is a stronger reducing agent than industrial production of sodium hydroxide, chlorine and hydrogen, three
–
Cl (aq) ions. Concentration effect problems would arise:
accounts for the preferential
–
discharge of Cl (aq) ions when
1. Hydrogen and chlorine would mix together. This mixture is explosive
brine is electrolysed.
under sunlight.
Think about 2. The chlorine formed would dissolve in the electrolyte, reacting
What are the products
directly with the sodium hydroxide solution.
formed from the
reaction between 3. As chloride ions are consumed, hydroxide ions would be discharged.
chlorine and sodium
hydroxide?
This produces oxygen which contaminates chlorine. N13
As a result, the basic design of the electrolytic cell for the chloroalkali
Think about
Chlorine reacts with sodium industry is to separate the anodic and cathodic reactions of the
hydroxide to give sodium
hypochlorite, sodium chloride
electrolysis, and allow them to proceed at the same time. This prevents the
and water. products at the electrodes from mixing together. Besides, the sodium
hydroxide formed is continuously flowing out of the cell in order to avoid
the formation of oxygen.
The flowing mercury cell and the membrane cell are two widely used
technologies in the chloroalkali industry.
anode 陽極 flowing mercury cell 流汞電解池

54 20 cathode 陰極 membrane cell 薄膜電解池
contaminate 污染
electrolyte 電解質
Electrolysis of brine by using a flowing mercury cell

In the flowing mercury cell (Figures 54.12 and 54.13), the electrolysis
takes place in a cell with a slightly sloping base. 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.
titanium anodes
chlorine
Animation
Figure 54.12 Flowing mercury cells (Electrolysis of brine using a
in a chloroalkali plant. flowing mercury cell)
brine used brine
sodium
Think about flow of mercury
hydrogen amalgam
What are the advantages
mercury cathode N14
and disadvantages of
using titanium and
graphite respectively as
the anode?
Think about water

Titanium will not corrode but it is
expensive.
Graphite is cheap but it will sodium
corrode/break down easily mercury hydroxide
especially under high voltage. recovered
Figure 54.13 Electrolysis of brine in a flowing mercury cell.

Note 14
Both the brine (fresh) and
mercury (recycled) are fed into At the anode (titanium or graphite):
the flowing mercury cell. The
continuous supply of brine is to – –
2Cl (aq) Cl2(g) + 2e (oxidation)
make sure that the concentration
–
of Cl (aq) ions is more or less
–
the same all the time. Cl (aq) ions are preferentially discharged (oxidized) to form chlorine gas
as the main product. Chlorine gas produced is led away through pipes. It is
then washed, dried, liquefied under pressure and stored in steel cylinders.
At the cathode (mercury):

+ –
Na (aq) + e + Hg() Na/Hg() (reduction)
sodium amalgam
Learning tip +
Na (aq) ions are preferentially discharged (reduced) to form sodium metal.
Sodium amalgam is
It immediately dissolves in the mercury cathode to give a sodium/
a liquid alloy of
sodium in mercury. mercury alloy called sodium amalgam. This alloy is carried away before it
reacts with water.
alloy 合金 reduction 還原作用 sloping 傾斜的

oxidation 氧化作用 sodium amalgam 鈉汞齊
21 54
The sodium amalgam flows into another tank, where it reacts with
water to form hydrogen and sodium hydroxide solution. Mercury is
recovered and pumped back to the electrolytic cell. See Figure 54.13
again.
Note 15 2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg() N15

Flowing mercury cell allows the sodium amalgam
formation of Cl2, H2 and NaOH at
different places so that Cl2 and H2
will not mix and react, while Cl2 will The flowing mercury cell has the advantage of producing
not dissolve in NaOH.
concentrated sodium hydroxide solution of high purity. However,
mercury is poisonous. Serious environmental problems arise if mercury
leaks from the flowing mercury cell.
Key point
The redox reactions that take place during the electrolysis of brine
using a flowing mercury cell:
+ –
Reduction (at cathode): Na (aq) + e + Hg() Na/Hg()
– –
Oxidation (at anode): 2Cl (aq) Cl2(g) + 2e
Electrolysis of brine using a membrane cell

The membrane cell is an electrolytic cell in which an ion-permeable
membrane is used to separate the cathode and anode compartments. This
prevents the products from mixing together. Nickel is used as the cathode
while titanium is used as the anode. See Figures 54.14 and 54.15.
Figure 54.14 Membrane cells
in a chloroalkali plant.
chlorine hydrogen
Animation
(Electrolysis of brine using
anode cathode
Learning tip a membrane cell)
The ion-permeable
membrane is a polymer brine water
+
membrane. It works on Na
+
the ion-exchange Na
+
principle, allowing only Na +
– H
cations to pass through. 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.
cation 陽離子 ion-permeable membrane 離子透性膜

54 22 ion exchange 離子交換
At the anode (titanium):

– –
2Cl (aq) Cl2(g) + 2e (oxidation)
–
Cl (aq) ions are preferentially discharged (oxidized) at the anode to form
+
chlorine gas, leaving an excess of Na (aq) ions in the resultant solution.
At the cathode (nickel):

+ –
2H (aq) + 2e H2(g) (reduction)
– –
or 2H2O() + 2e H2(g) + 2OH (aq)
DSEPP2012(2)1(c)(i)
+
H (aq) ions from water are preferentially discharged (reduced) in the
–
cathode compartment, forming hydrogen gas. OH (aq) ions accumulate in
the cathode compartment.
The ion-permeable membrane in the membrane cell allows the passage

+ – –
of Na (aq) ions but not that of Cl (aq) or OH (aq) ions. The used brine is
simply removed from the anode compartment. The resultant solution in
the cathode compartment is sodium hydroxide solution containing no
sodium chloride impurity. It is composed of about 30–35% sodium
hydroxide by mass.
The membrane cell represents a more advanced technology than the

flowing mercury cell. It does not contain poisonous mercury. Besides, it
requires a lower voltage to operate than the flowing mercury cell.
Key point
The redox reactions that take place during the electrolysis of brine
using a membrane cell:
+ –
Reduction (at cathode): 2H (aq) + 2e H2(g)
– –
or 2H2O() + 2e H2(g) + 2OH (aq)
– –
Oxidation (at anode): 2Cl (aq) Cl2(g) + 2e
Comparison of the flowing mercury cell and the

membrane cell used in the chloroalkali industry
Table 54.3 shows a comparison between the flowing mercury cell and the
membrane cell used for the electrolysis of brine in the chloroalkali
industry.
23 54
Flowing mercury cell Membrane cell

Anode Titanium or graphite Titanium
Cathode Mercury (flowing) Nickel
Brine Brine
Electrolyte
(flowing through the cell) (flowing through 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 54.3 A comparison of the flowing mercury cell and the membrane cell.
H20 Example 54.5

Understanding the underlying chemical principles involved in the chloroalkali industry
The diagram below represents a simplified set-up to simulate the industrial preparation of chlorine,
hydrogen and sodium hydroxide by a flowing mercury cell.
chlorine
electrode P
concentrated sodium
chloride solution
platinum wire
mercury electrode
After passing a current through a concentrated sodium chloride solution for some time, chlorine
was liberated at electrode P. When the mercury layer was run into cold water, an alkaline solution and
a colourless gas were obtained.
(a) Which electrode is the cathode?
(b) Name a suitable material for electrode P. Explain your choice.
(c) With the aid of a chemical equation, account for the formation of chlorine from electrode P.
cont’d
54 24
(d) (i) Suggest the product formed at the mercury electrode.

(ii) Write an equation to show the formation of the alkaline solution when the mercury layer was
run into the cold water.
(iii) Name the alkaline solution.
(e) Suggest TWO potential hazards in this experiment.
(f) State TWO advantages of using a membrane cell over flowing mercury cell for the industrial
preparation of chlorine, hydrogen and sodium hydroxide.
Solution
(a) Mercury electrode
(b) Graphite. The electrode has to be an inert electrode. (Note: Platinum cannot be used even though
it is quite inert because chlorine produced can attack it.)
–
(c) Electrode P is the anode. Cl (aq) ions are preferentially discharged because the concentration of
–
Cl (aq) ions is high.
– –
2Cl (aq) Cl2(g) + 2e
(d) (i) Sodium amalgam or Na/Hg()
(ii) 2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg()
alkaline
solution
OR 2Na(s) + 2H2O() → 2NaOH(aq) + H2(g)

alkaline
solution
(iii) Sodium hydroxide solution

(e) Mercury may vaporize in the laboratory. Prolonged inhalation may lead to mercury poisoning.
Chlorine vapour is toxic.
(f) The use of membrane cell for the industrial preparation of chlorine, hydrogen and sodium
hydroxide is more energy-efficient and causes less environmental impact.
A54.6
Class practice 54.6
–
(a) At the anode, Cl (aq) ions are
preferentially discharged to form Membrane cell is one of the electrolytic cells used in the chloroalkali
chlorine gas because the industry. In the cell, an ion-permeable membrane is used to separate the
–
concentration of Cl (aq) ions is very
high.
cathode and anode compartments so that hydrogen and chlorine produced
–
2Cl (aq) Cl2(g) + 2e
–
will not mix together.
+
At the cathode, as H (aq) is lower
+ +
than Na (aq) in the E.C.S., H (aq)
(a) With the help of half equations, explain the formation of hydrogen and
ions are preferentially discharged to chlorine in the membrane cell.
form hydrogen gas.
+ – (b) Explain the formation of sodium hydroxide solution in the cell.
2H (aq) + 2e H2(g)
–
(b) Cl (aq) ions are preferentially (c) Suggest an impurity that will be present in the resultant solution if the ion-
discharged at the anode, leaving an
+ permeable membrane is not used in the cell.
excess of Na (aq) ions around anode.
+
As H (aq) ions are preferentially
+ –
discharged at the cathode, water molecules ionize continuously to replenish the H (aq) ions discharged, leaving an excess of OH (aq) ions
+ – – +
around cathode. As the membrane is permeable to Na (aq) ions but not OH (aq) and Cl (aq) ions, the Na (aq) ions can go into the cathode
–
compartment while OH (aq) ions are kept in the cathode compartment. Eventually, sodium hydroxide solution forms.
(c) Sodium chloride
25 54
STSE connections 54.2 PowerPoint
Environmental damages caused by careless disposal of mercury from industry

The Chisso Corporation was located in Kumamoto, Japan and the company 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 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 unexpectedly
developed symptoms of mercury poisoning. The illness was then known as the ‘Minamata Disease’. The
symptoms of the ‘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 be
crazy when they began to uncontrollably shout.

Note 16
PowerPoint Methanol reacts with carbon monoxide to form
Importance of methanol acetic acid (carbonylation of methanol). Refer to
Book 5 Chapter 55 in more detail.
H Methanol (CH3OH) (Figure 54.16) is a colourless liquid with a boiling

point of 65°C. It is highly toxic and flammable. However, methanol is
H C OH
also a very important chemical. It is one of the top ten chemicals
H produced globally. In 2011, there were over 90 methanol production
Figure 54.16 Structural plants worldwide which produce over 45 million tonnes of methanol
formula of methanol. N16 per year.
Methanol can be used as feedstock to produce a wide variety of

chemicals in the chemical industry, as a source of fuel and as a solvent.
XTRA
E Historical note
S
The production of As feedstock for the chemical industry DSE2012(2)1(b)(i)

methanol actually started in
the 1800s when people Methanol can be used as a feedstock for the production of other carbon
tried to get methanol from
wood. They did this by compounds such as methanal (or formaldehyde), ethanoic acid (acetic
heating wood until a liquid acid), dimethyl ether (DME) and methyl tertiary butyl ether (MTBE).
was distilled. This explains
why methanol is also known
as wood alcohol.
acetic acid 醋酸 methanal 甲醛

54 26 dimethyl ether 二甲醚 methanol 甲醇
mercury poisoning 汞中毒
Minamata Disease 水俁病
paralysis 癱瘓
victim 受害者
ethanoic acid 乙酸 methyl tertiary butyl ether 甲基三級丁基醚
formaldehyde 蟻醛
• Formaldehyde is used for the manufacture of various kinds of

AL2009(I)10 synthetic polymers e.g. phenol-formaldehyde (also known as
bakelite). See Figure 54.17.
Note 17
The monomer of PVA is vinyl • Acetic acid can be converted to chemicals such as polyvinyl acetate N17
acetate (CH2=CHOCOCH3) which
is prepared from ethene by reaction (PVA). It can be used to make water-based paints, paper coatings
with oxygen and acetic acid over a and glues. See Figure 54.18.
palladium catalyst.
• Dimethyl ether (DME) has the structural formula of:
C C C C
O O
H H
C C H C O C H
O CH3 O CH3
H H
It should be not confused with the
related polymer polyvinyl alcohol
It has replaced chlorofluorocarbons (CFCs) as aerosol spray N18,
which is also called PVA. Strictly
N19
speaking, PVAc is a better propellant. See Figure 54.19.
abbreviation for polyvinyl acetate
and PVOH for polyvinyl alcohol. • Methyl tertiary butyl ether (MTBE) has the structural formula of: N20
CH3
Note 18
Remind students that
CH3 C O CH3
chlorofluorocarbons is a family of
CH3
carbon compounds (not a single
compound) containing chlorine
It is a petrol additive which is added to petrol to improve the
and fluorine. They deplete the
upper ozone layer of the Earth combustion efficiency of petrol. This reduces the amount of harmful
which protects our Earth from the
exhaust emissions from motor vehicles. See Figure 54.20.
harmful ultraviolet radiation from
the Sun.
Figure 54.17 A pressure Figure 54.18 PVA is the Figure 54.19 DME is an Figure 54.20 MTBE is a
cooker with bakelite handle. key ingredient of white glue. aerosol spray propellant. common petrol additive.
Note 19
Aerosol refers to a system of
colloidal particles dispersed in a
gas, smoke or fog.
As a source of fuel
Note 20
Transportation fuel
MTBE is a petrol additive which is
used as an oxidizing agent to
Methanol is combustible. It can be used directly or blended with other
oxidize the carbon monoxide gas petroleum products (e.g. petrol) as a clean fuel in motor vehicles.
that cars produce.
chlorofluorocarbon (CFC) 氯氟碳化合物 polyvinyl acetate (PVA) 聚醋酸乙烯酯 aerosol spray 噴霧 petrol additive 汽油添加劑
phenol-formaldehyde 酚甲醛樹脂 synthetic polymer 合成聚合物 bakelite 電木 propellant 推進劑
27 54
Fuel for fuel cells

Recently, methanol has been widely considered to be the fuel in some fuel
cells (Figure 54.21). Methanol can be obtained as a very pure product. This
greatly reduces the risk of contaminating the fuel cell catalyst. Besides,
methanol is a liquid under room conditions. Therefore, it can be handled
much the same way as conventional fuels like petrol and diesel oil.
Figure 54.21 A methanol-based
fuel cell supplies electricity to this
MP3 player, which runs for around As a solvent
3
60 hours on a 10 cm charge of
concentrated methanol. Methanol is added to ethanol to give methylated spirit which is used as
an industrial solvent.
Figure 54.22 below shows the distribution of different uses of

methanol.
making used as fuel

formaldehyde 35%
38%
Figure 54.22 A pie chart showing the others used as solvent making acetic acid
distribution of different uses of methanol. 7% 8% 12%
Significance of the conversion of methane to

methanol
Methane is the major component of natural gas. Although natural gas
is abundant, major natural gas resources are usually found in remote parts
of the world. Transportation of the gas becomes too expensive. Some of
the natural gas found along with petroleum is even simply burnt off in
the oil fields (Figure 54.23).
Note 21
Typical composition of natural gas (before it is refined): N21
CH4 (70–90%), C2H6 + C3H8 + C4H10 (0–20%), CO2 (0–8%)
Figure 54.23 Some of the natural

gas found along with petroleum is
burnt off in the oil field.
fuel cell 燃料電池

54 28 methylated spirit 加甲醇酒精
However, the most promising solution is to convert methane to

methanol on the spot. It becomes much easier to store and transport.
Today, about 90% of the methanol produced comes from methane.
Manufacturing methanol
Methanol is manufactured industrially from methane by a three-stage
process.
Note 22 Stage 1 Steam-methane reforming to give syngas N22

The name ‘Steam-methane
reforming’ can help students recall Stage 2 Compression of synthesis gas and conversion to methanol
what reactants are used to make
syngas. Stage 3 Distillation of liquid products to give pure methanol.
1. Steam-methane reforming to give syngas

Firstly, natural gas is treated to remove any sulphur impurity present
Note 23 (i.e. desulphurization). Then methane (main component of natural gas) N23
To remove sulphur, the gas is
passed through a bed of zinc oxide reacts with steam under moderate pressures of about 10–20 atm and at
(ZnO) pellets. Zinc oxide reacts temperatures around 700–1000°C in the presence of nickel(II) oxide
with sulphur compounds to form
zinc sulphide. (NiO). This steam-methane reforming reaction is highly endothermic.
NiO
–1
CH4(g) + H2O(g) CO(g) + 3H2(g) ∆H = +206 kJ mol
700–1000°C, 1 : 3
10–20 atm
Learning tip
After the reaction, both steam and syngas are collected. The steam is
Syngas is a mixture
of hydrogen (H2) and removed and condensed. The water is recycled and the dry syngas is ready
carbon monoxide for the compression stage.
(CO) in various
proportions.
2. Compression of syngas and conversion to methanol
In 1966, ICI (one of the world’s major paints companies) introduced the
use of Cu/ZnO/Al2O3 catalyst (a mixture of Cu, ZnO and Al2O3) for the
conversion of syngas to methanol. A temperature of about 250°C and a
pressure of about 50–100 atm are used.
Cu/ZnO/Al2O3
–1
Note 24 CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol N24
Remind students about the 1 : 2 250°C,
different mole ratios of CO and H2 50–100 atm
in the syngas produced and that
DSE2012(2)1(b)(ii)
used in the production of CH3OH.
Water-gas shift reaction is used to
adjust the mole ratio. The
application of the reaction is
explained in Example 54.6(d) on
p.31.
desulphurization 脫硫作用 syngas 合成氣
steam-methane reforming 蒸汽–甲烷重整作用
29 54
Think about It is worth noting that the conversion of syngas to methanol involves
Why do you think a a decrease in the number of moles of gases (from 3 moles to 1 mole). The
pressure of 50–100 atm process is favoured by high pressures. In addition, the production of
and a temperature of
250°C are used even
methanol is favoured at low temperatures because the overall reaction is
though the conversion exothermic.
is favoured by high
pressures and low
temperatures?
After the conversion, the product mixture is cooled so that methanol
condenses. Thus, methanol is separated from the unreacted gases. The
Think about unreacted gases and the heat from the conversion are recycled.
To withstand very high pressure, the
catalytic chamber and the pipes have
to be strengthened. This requires a
very high cost to construct and
3. Distillation of liquid products to give pure methanol
maintain the industrial plant.
The conversion of syngas to methanol The crude methanol collected from the above conversion contains
is favoured by low temperature.
methanol, water and traces of by-products. It is stored temporarily in a
However, at low temperatures, the
reaction proceeds slowly. This lowers crude storage tank. Pure methanol can be obtained by distillation.
the amount of methanol produced
per unit time. As a compromise
between the cost, yield and rate of The whole process of the manufacture of methanol from natural gas is
reaction, a pressure of 50–100 atm summarized in Figure 54.24.
and a temperature of 250°C are used
for the manufacture of methanol.
steam
Steam- syngas Compression

natural methane and Distillation methanol
gas reforming conversion
desulphurization syngas recycled
Figure 54.24 A simplified flow diagram for the manufacture of methanol from natural gas.
Key point
Methanol is manufactured by the following reactions:
NiO
CH4(g) + H2O(g) CO(g) + 3H2(g)
700–1000°C,
10–20 atm
Cu/ZnO/Al2O3
CO(g) + 2H2(g) CH3OH(g)
250°C,
50–100 atm
by-product 副產物
54 30
H20 Example 54.6

Understanding the advancement of the methanol production technology DSE2012(2)1(b)(iii)
In 1923, a German chemist Matthias Pier, developed a method to convert syngas into methanol. In
his method, syngas was compressed in the presence of ZnO/Cr2O3 as catalyst. Under extremely
vigorous conditions, i.e. a temperature of about 400°C and a pressure around 300 atm, the syngas
could be converted to methanol.
(a) Write the chemical equation for the conversion from syngas into methanol.
(b) State the changes in operating conditions for methanol production via syngas from Matthias Pier’s
method in 1923 to ICI’s method in 1966.
(c) Explain the advantages of the advancement in operating conditions in terms of economic
considerations.
(d) Steam-methane reforming produces CO and H2 in the ratio of 1 : 3. In 1999, a water-gas shift
reaction, in which H2 reacted with CO2, was introduced to adjust the ratio.
(i) What is the significance of adjusting the ratio of CO and H2?
(ii) Write the chemical equation for the water-gas shift reaction.
(e) Conversion of biomass to syngas has become more widely used. State ONE advantage of using
biomass instead of natural gas.
Solution
(a) CO(g) + 2H2(g) CH3OH(g)
(b) In Matthias Pier’s method in 1923, ZnO/Cr2O3 catalyst was used. The operating pressure was
about 300 atm and the operating temperature was about 400°C.
In ICI’s method in 1966, Cu/ZnO/Al2O3 was used as the catalyst. The operating pressure ranged
from 50–100 atm and the operating temperature was about 250°C.
(c) Using a better and more efficient catalyst can reduce energy consumption and eventually lower
the running cost of the plant.
The maintenance cost for the converters and pipes that can withstand high pressures is lower.
The use of a lower temperature consumes less fuel.
(d) (i) The conversion from syngas into methanol requires CO and H2 in a ratio of 1 : 2. If the ratio
of 1 : 3 from steam-methane reforming is not adjusted, there will be insufficient CO or excess
H2 for the conversion.
(ii) CO2(g) + H2(g) CO(g) + H2O(g)
(e) The biomass is a renewable feedstock.
water-gas shift reaction 水–煤氣轉移反應

31 54
Reading to learn
Read article below and answer the questions that follow.
Latest development of the methanol manufacturing process

At present, the majority of methanol is produced from natural gas in large manufacturing plants. In fact,
methanol can be made from a number of renewable feedstock.
• Some methanol manufacturing plants are built to use landfill methane gas as a feedstock for
methanol production.
• Some plants have digesters installed that can treat 25 tonnes of pig manure per day to produce
syngas.
• Some plants have converters that convert biomass (e.g. rice straw) to syngas.
• Recently, a team of scientists at the University of Texas at Arlington (UTA) has developed a method
of converting carbon dioxide to methanol using CuO–Cu2O nanowires in the presence of sunlight.
Methanol can be used to drive car engines, electric
sunlight
turbines and used in fuel cells. A lot of researches are
being conducted to explore its potential as an alternative CH3OH
to fossil fuels. CO2
+ –
Reading to learn H,e
1. New equipments that can handle biomass and animal manure
nanowire
(e.g. to gasify biomass and digest animal manure) are needed. A
large area is also needed to grow plants and rear animals.
2. Methanol can be produced from renewable resources. Besides,
combustion of methanol produces less harmful products.
3. Sunlight is unlimited and it is a free resource.
Questions
1. What are the limitations for the development of methanol production by biomass and animal manure?
2. Why do people regard methanol as a good alternative to fossil fuels?
3. Suggest TWO advantages of converting CO2 to CH3OH using sunlight.
Class practice 54.7

A54.7 1. Methanol can be made industrially by the following reaction.
1. (a) Methanal/ethanoic acid/ –1
dimethyl ether/methyl tertiary CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol
butyl ether (MTBE)
(a) Name ONE carbon compound that is produced from methanol in
(b) (i) Steam-methane reforming
chemical industry.
(b) Syngas is used to make methanol. It is produced from the reaction
between methane and steam.
CH4(g) + H2O(g) 3H2(g) + CO(g)
(i) Name the process for the formation of syngas.
(Cont’d)
fossil fuel 化石燃料

54 32 alternative 替代品
biomass 生物量
pig manure 豬糞
rice straw 稻米
nanowire 納米線 turbine 渦輪機
A54.7 (Cont’d)
(b) (ii) 1 : 2
(iii) 1 : 3
(c) CO2(g) + H2(g) CO(g) + H2O(g)
(ii) What is the mole ratio of CO to H2 used for the production of
(d) Since the conversion of syngas into
methanol is exothermic, the heat methanol?
released can be used to preheat the (iii) What is the mole ratio of CO to H2 in the syngas produced?
syngas before it enters the methanol
converter.
(c) Write an equation for the water-gas shift reaction that helps adjust the
After the conversion of syngas into mole ratio of CO to H2 in syngas.
methanol, unreacted syngas can be
separated from product mixture and
(d) Apart from the operating conditions such as temperature, pressure
recycled. and catalyst, suggest THREE ways that can make the methanol
Remove the methanol from the synthesis via syngas more economical.
product mixture continuously. This
shifts the equilibrium position to the 2. Syngas can be produced by incomplete combustion of biomass, i.e.
product side and thus further
increases the yield of methanol.
burning in a limited supply of oxygen. Before the process, the biomass
2. (a) If the supply of oxygen is sufficient, has to be dried.
the biomass will burn completely to (a) Explain why a limited supply of oxygen is used in the above
give carbon dioxide and water
instead. production of syngas.
(b) Any TWO: (b) State TWO advantages of using biomass to produce syngas.
Biomass is a renewable raw material.
(c) State TWO disadvantages of using biomass to produce syngas.
It is biological material that derived
from living things. It can be replenished 2. (c) Biomass is not a cheap raw material because the costs for growing plants and rear animals are
in a much shorter time compared to quite high.
natural gas. Hence, it potentially never Unlike natural gas, which is already a gas, biomass has to be gasified before it is used to produce
runs out. OR syngas. Energy, new equipments are needed for gasification and this adds cost to the production.
The use of biomass reduces landfills.
And this can help to turn waste into
Table 54.4 below shows a summary of the industrial processes
something much useful. OR discussed in this chapter.
Biomass may be more readily available than natural gas
to countries that do not have its own oil fields.
Industrial process Raw material(s) Optimum conditions/Principle Product(s)

Production of • Nitrogen (from air) 1. Haber process (to make Ammonium nitrate
fertilizers • Hydrogen (from ammonia):
natural gas) 200 atm, 400–450°C, Fe as
catalyst
2. Ammonia then reacts with
nitric acid
Chloroalkali Brine (concentrated Electrolysis by using a flowing Chlorine, sodium

industry sodium chloride mercury cell or a membrane cell hydroxide and
solution) hydrogen
Production of Methane (from natural 1. Steam-methane reforming to Methanol

methanol gas) produce syngas:
10–20 atm, 700–1000°C, NiO
catalyst
2. Conversion of syngas to
methanol:
50–100 atm, 250°C,
Cu/ZnO/Al2O3 as catalyst
Table 54.4 A summary table of the industrial processes involved in the production of fertilizers, the chloroalkali industry
and the production of methanol.
33 54
Activity 54.1
PowerPoint Studying an industrial process and controlling the production of a chemical
plant
In this activity, you are going to use computer modelling to study an industrial
process and to control the production of a chemical plant.
Activity 54.2
PowerPoint ‘It is desirable to set up local industrial plants for the production of chlorine’
In this activity, the teacher will organize two debating teams from the class. One
team is for the above motion and the other is against. At the end of the debate,
you are required to make a summary of different viewpoints on the motion.
STSE connections 54.3 PowerPoint
Bhopal disaster
In 1984, a pesticide plant of the Union Carbide Corporation in Bhopal of India, accidentally released about
40 tonnes of the lethal gas ‘methyl isocyanate’. It was believed that half a million people were exposed to the
gas and 20 000 people died as a result of the exposure.
Survivors of the disaster gathered in front of the

Union Carbide factory one day after the lethal gas
leak. Their eyes and lungs had been badly damaged
after exposure to the gas.
It was a terrible day according to a survivor who said, ‘It felt like somebody had filled our bodies up with
red chillies. Our tears were coming out and our noses were watering.’ The gas burnt the tissues of their eyes
and lungs and attacked their nervous systems. Some people even lost control of their bodies. Urine and faeces
ran down their legs. The Bhopal disaster was one of the world’s worst industrial disasters.
methyl isocyanate 異氰酸甲酯

54 34 disaster 災難
exposure 接觸
lethal 致命的
survivor 生還者
54.4 Social, economic and environmental

PowerPoint considerations of industrial processes
Other than chemical principles, it is also necessary to consider the
economic, social and environmental aspects of industrial processes.
Economic considerations AS2003(c)14
The economic aspect is related to the cost of producing the industrial

products. The factors to be considered include:
• fixed costs including the investment on buildings, machinery,

equipment, storage tanks, etc. (See Figure 54.25),
• costs for maintenance and to cover depreciation (depreciation

happens because chemical plants often operate under severe/ corrosive
Figure 54.25 Investment on conditions),
buildings, machinery and equipment
• costs of fuel, feedstock and other necessary chemicals,
is necessary when setting up an
industrial plant. • costs for land and labour,
• cost for removal of chemical waste.
Manufacturers always try to lower the cost of production of

chemicals. This can be achieved by using cheap feedstock in the
processes. For example, in the Haber process, the use of natural gas
instead of petroleum as the source of hydrogen lowers the cost of
feedstock. As a result, the cost of ammonia production is lower.
Besides, the use of catalysts can also help lower the cost of fuel.
Catalysts speed up chemical reactions. For example, finely divided iron
catalyst is used in the Haber process. Therefore, a lower operating
temperature can be used and thus consumes less fuel.
In addition, the recycling of unreacted feedstock or heat energy

during the processes also greatly lowers the production cost.
Social considerations
When a chemical company decides to set up an industrial plant in a
place, there will be a great impact to the community. The industrial plant
creates job opportunities for the people in that place. It may help raise
the economy of the surrounding areas.
depreciation 折舊
machinery 機械
35 54
At the same time, a good transport network is essential for N25
transportation of raw materials, products and labour. This may improve

the existing transport network of the community. On the contrary, this
may also be a burden to the existing transport network (Figure
54.26).
Environmental considerations AS2003(c)14
Chemical products
Some chemical products are potential hazards. They may enter and
Figure 54.26 The increased interact with the environment, especially when accidents happen. Care
number of trucks for transporting
raw materials and products may
must be taken to store and handle these chemicals. For example,
add burden to the traffic.
• In the Haber process, the ammonia produced is toxic. It is mainly
Note 25 stored under pressure in liquid form. Safety precautions in handling
Apart from transport network of and storing liquid ammonia have to be followed strictly.
the community, there are other
fundamental facilities and systems • Chlorine is also a potential hazard from the chloroalkali industry. It is
needed such as communication
systems, power stations and highly toxic, and strict precautions are necessary to minimize risk to
schools. workers and possible leakages during its handling.
• Methanol is highly toxic and flammable. The greatest hazard

involved in storing and handling methanol is the risk of fire or
explosion.
Chemical wastes
Chemical industries are likely to produce chemical wastes and cause
pollution problems. Chemical wastes from these plants are usually
toxic, flammable or explosive. These wastes should be reduced or treated
by appropriate waste treatment facilities.
For example, pollutants emitted to the atmosphere from the Haber

process and the preparation of its feedstock include nitrogen oxides,
sulphur dioxide, carbon monoxide, carbon dioxide, hydrogen sulphide,
methane, ammonia, particulates and volatile organic compounds (VOCs).
The levels of these pollutants can be reduced if suitable measures are

Note 26
Low-NOx burners are designed to taken. Some examples are given below.
control fuel and air mixing at each
burner in order to create larger and • The amount of nitrogen oxides released can be reduced by using
more branched flames. Peak flame
temperature is thereby reduced,
low-NOx burners. N26
and results in less NOx formation.
explosive 爆炸性的 particulates 懸浮粒子

54 36 flammable 易燃的 toxic 有毒的
burden 負擔
potential hazard 潛在危險
hydrogen sulphide 硫化氫 volatile organic compound (VOC) 揮發性有機化合物
• The amount of sulphur dioxide in the flue gas can be expected to be

significantly reduced if natural gas is used instead of coal as the energy
source.
• Carbon dioxide can be recycled and converted to methanol and

other fuels by using advanced technologies.
In Hong Kong, for example, the Waste Disposal (Chemical Waste)

Regulation in Hong Kong has been enacted since 1992 to introduce
complete controls on chemical waste. Besides, the Environmental
Protection Department enforces the regulation by ensuring that the
handling of chemical wastes is done by licensed waste collectors and
disposal facilities (Figure 54.27).
There is an increasing amount of legislation to ensure the safe

performance of chemical operations. Furthermore, manufacturers and
Figure 54.27 The Chemical Waste chemists are developing ‘greener’ chemical processes to minimize the
Treatment Centre (CWTC) in Tsing
potential pollution problems. This has led to the development of a branch
Yi is a licensed disposal facility in
Hong Kong. of chemistry called green chemistry. Details of green chemistry will be
introduced in Chapter 55.
green chemistry 綠色化學 legislation 立法

37 54
Key terms
PowerPoint
English term Chinese translation Page

1. brine 鹽水 18
2. catalytic oxidation 催化氧化作用 13
3. chloroalkali industry 氯鹼工業 18
4. dimethyl ether 二甲醚 26
5. ethanoic acid 乙酸 26
6. fertilizer 肥料 4
7. flowing mercury cell 流汞電解池 20
8. green chemistry 綠色化學 37
9. Haber process 哈柏法 6
10. membrane cell 薄膜電解池 20
11. methanal 甲醛 26
12. methanol 甲醇 26
13. methyl tertiary butyl ether 甲基三級丁基醚 26
14. nitrogenous fertilizer 氮肥 4
15. sodium amalgam 鈉汞齊 21
16. steam-methane reforming 蒸汽–甲烷重整作用 7
17. synthesis gas/syngas 合成氣體/合成氣 7
18. water-gas shift reaction 水–煤氣轉移反應 7
54 38
Progress check
PowerPoint
Can you answer the following questions? Put a ‘✓’ in the box if you can. Otherwise, review the relevant
part on the page as shown.
Page
1. What are nitrogenous fertilizers? 4
2. What is the Haber process? 6
3. What is the feedstock for the Haber process? How are they obtained? 6–7
4. What are the operating conditions for the Haber process? 8
5. What are the physicochemical principles and economic considerations involved in the
9–10
Haber process?
6. How are nitrogenous fertilizers produced? 13–15
7. What is chloroalkali industry? 18
8. What are the working principles used by the chloroalkali industry? 20
9. How does the flowing mercury cell differ from the membrane cell? 24
10. What is the importance of methanol? 26
11. What is the significance of methanol synthesis from methane? 29
12. What is the feedstock used to manufacture methanol? 29
13. What are the operating conditions of methanol synthesis from syngas? 29–30
14. What are the social, economic and environmental considerations of industrial
35–37
processes?
39 54
Summary
PowerPoint
1. Fertilizers provide important nutrients such as nitrogen, phosphorus and potassium to enhance
healthy plant growth.
2. Ammonia is the raw material used to make nitrogenous fertilizers.
3. Ammonia is manufactured 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 is obtained by fractional distillation of liquid air and hydrogen is
obtained from steam-methane reforming using natural gas.
–1
The mixture of hydrogen and carbon monoxide produced is known as synthesis gas (or simply
syngas).
5. High pressures and low temperatures increase the yield of ammonia at equilibrium. However,
high pressures require a high cost to construct and maintain the equipment. Low temperatures
increase the time to reach equilibrium. As a result, the optimum conditions of the Haber
process are set at 200 atm and 400–450°C.
6. Ammonium nitrate can be produced by neutralizing ammonia with nitric acid. Nitric acid is
manufactured by the catalytic oxidation of ammonia in the Ostwald process.
Pt catalyst
–1
4NH3(g) + 5O2(g) 4NO(g) + 6H2O() ∆H = –907 kJ mol
–1
2NO(g) + O2(g) 2NO2(g) ∆H = –117 kJ mol
4NO2(g) + O2(g) + 2H2O() 4HNO3(aq)
7. Ammonium nitrate, ammonium sulphate and urea are the common nitrogenous fertilizers.
54.2 Chloroalkali industry
8. The chloroalkali industry produces sodium hydroxide, chlorine and hydrogen by electrolysis of
brine.
2NaCl(aq) + 2H2O() 2NaOH(aq) + Cl2(g) + H2(g)
9. Electrolysis of brine using a flowing mercury cell:

+ –
At the cathode: Na (aq) + e + Hg() Na/Hg()
– –
At the anode: 2Cl (aq) Cl2(g) + 2e
Sodium hydroxide forms in the flowing mercury cell by reacting sodium amalgam with water.
2Na/Hg() + 2H2O() 2NaOH(aq) + H2(g) + 2Hg()
54 40
10. Electrolysis of brine using a membrane cell:

+ – – –
At the cathode: 2H (aq) + 2e H2(g) or 2H2O() + 2e H2(g) + 2OH (aq)
– –
At the anode: 2Cl (aq) Cl2(g) + 2e
Sodium hydroxide formed in the membrane cell does not contain sodium chloride as impurity
+
because the membrane selectively allows the passage of Na (aq).
11. ethanol is a very important chemical as it can be used as feedstock to produce a wide variety of
M
chemicals in the chemical industry, as a source of fuel and as a solvent.
12. The manufacture of methanol involves three steps: 31. (a) Natural gas
(b) CH4(g) + H2O(g) CO(g) + 3H2(g)
(a) Steam-methane reforming to give syngas 700–1000°C, 10–20 atm, use NiO as catalyst
(c) CO(g) + 2H2(g) CH3OH(g)
NiO
–1
700–1000°C, 10–20 atm 31. (d) Methane is the main component of natural gas which
is usually burnt off in the oil fields. But it is a great
(b) Compression of syngas and conversion to methanol wastage of natural resources. It is not easy or
Cu/ ZnO/ Al2O3 convenient to store and transport the gas. These
–1 problems are solved when methane is converted to
CO(g) + 2H2(g) CH3OH(g) ∆H = –90 kJ mol liquid methanol. Furthermore, methanol can be turned
250°C, 50–100 atm into a wide variety of other chemicals which can be
used in making different types of consumer products.
(c) Distillation of liquid products to give pure methanol.
54.4 Social, economic and environmental considerations of industrial processes
13. Other than chemical principles, it is also necessary to consider the economic, social and
environmental aspects of industrial processes.
32. (a) When brine is electrolysed, hydrogen ions are preferentially discharged at the cathode to give hydrogen.
+ –
2H (aq) + 2e H2(g)
(b) N2(g) + 3H2(g) 2NH3(g)
400–450°C, 200 atm, use finely divided iron as catalyst
(c) CO(g) + 2H2(g) CH3OH(g)
(d) (i) Syngas is a mixture of hydrogen and carbon monoxide.
(ii) Carbon monoxide is present in the syngas, which is also one of the raw materials to produce methanol. Hence, there is no need to find a source
of carbon monoxide for the production. OR
Chlorine and sodium hydroxide are also major products of chloroalkali industry. Production of hydrogen only for methanol production using
electrolysis of brine will produce more chlorine and sodium hydroxide than needed. The cost of disposing of excess chlorine and sodium
hydroxide is very high.
(e) Advantage:
There is no need to transport the hydrogen (a flammable gas) over a long distance from the chloroalkali plant to the Haber process plant. This
reduces the risk of any accident during transportation. OR
This creates many job opportunities for local people. OR
Existing transport network around the industrial plants will be improved for the transportation of fuel, feedstock, products and labour into and out
of the plants.
Disadvantage:
The two big plants will usually produce a lot more wastes to pollute the environment at the same site.
33. (a) Cu/ZnO/Al2O3
(b) CH4(g) + H2O(g) CO(g) + 3H2(g)
(c) (i) Exothermic. As the temperature decreases (from 325°C to 125°C), the equilibrium concentration of methanol increases. As a decrease in
temperature favours an exothermic reaction, the forward reaction should be exothermic.
(ii) If the temperature is low, the reaction will proceed very slowly. As a result, it will take a long time for the reaction to reach equilibrium.
(iii) The equilibrium concentration of methanol will increase if pressure increases. Since there is a smaller number of moles of gas on the right-
hand side of the equation, a high pressure will cause the equilibrium position to lie mainly on the product side.
However, if a very high pressure is used, the cost of construction and maintenance of the catalytic chamber and pipes that can withstand a
high pressure would also be very high.
41 54
Concept map
PowerPoint
Complete the following concept map.
Hydrogen Chlorine Sodium hydroxide
products Flowing mercury cell

raw material cells used
Brine Chloroalkali industry
Membrane cell
INDUSTRIAL PROCESSES
Production of fertilizers Production of methanol
basic chemical Fractional

N2 distillation of
Haber
liquid air
process
NH3
Syngas
H2 H2, CO
(H2, CO)
compression,
Cu/ZnO/Al2O3
then distillation
H2SO4 CO2 HNO3 Steam-methane CH3OH

reforming
(NH4)2SO4 (NH2)2CO NH4NO3 uses
Methane from • as feedstock for the

natural gas chemical industry
• as a source of fuel
• as a solvent
(Hints: brine, chlorine, fuel, membrane cell, methane, (NH2)2CO, NH3, NH4NO3, (NH4)2SO4, syngas)
54 42
Chapter exercise
Fill in the blanks 7. The f lowing
m ercury
cell and
embrane
the m cell are commonly used
Section 54.1 membrane
in the chloroalkali industry. The
1. Plants need certain nutrients in large quantities
itrogen hosphorus
cell is more economical and environmentally
such as n ,p and
otassium
friendly because the cell does not contain
p to support their healthy growth.
poisonous mercury and it requires a
lower
2. A mmonia
is the raw material to make voltage to operate.
nitrogenous fertilizers. It is produced industrially
Haber Section 54.3
by the process which combines Methane
itrogen ydrogen 8. is the major component of
n and h directly feedstock
400–450 200 natural gas. It can be used as to
at °C and
produce a wide variety of chemicals, as a source
atmospheric pressures (atm) in the presence of fuel solvent
iron of and as a .
finely divided as the catalyst.
9. Methanol is manufactured industrially from
3. In the Haber process, nitrogen comes from the
fractional distillation methane by:
of liquid air. Hydrogen
Steam-methane reforming
mainly comes from the steam-methane reforming (a) to give
synthesis gas
in which methane
(in natural gas) reacts (or syngas).
steam nickel(II) oxide syngas
with over a (b) Compression of and
methanol
catalyst at 700–1000°C and 10–20 atm. conversion to .
Distillation
(c) of liquid products to give
4. The Haber process usually operates at methanol
high low pure .
pressures and
temperatures in order to get an acceptable
percentage yield of ammonia which is a
Multiple-choice questions
rate
compromise between of Section 54.1
yield economic
reaction, and
10. What is the mass of nitrogen in 1.0 kg of
considerations.
ammonium nitrate?
catalytic
5. Nitric acid is manufactured by the (Relative atomic masses: H = 1.0, N = 14.0,
oxidation
of ammonia. The raw materials for O = 16.0)
ir 10. Percentage by mass of N in NH4NO3
the manufacture are ammonia, a A. 0.18 kg 14.0 × 2
ater = × 100% = 35%
and w . 14.0 × 2 + 1.0 × 4 + 16.0 × 3
B. 0.35 kg Mass of nitrogen in 1.0 kg of ammonium nitrate
C. 0.47 kg = 1.0 kg × 35% = 0.35 kg
Section 54.2 B
D. 0.63 kg
6. In the chloroalkali industry, concentrated
brine
sodium chloride solution ( ) is 11. Which of the following gases is/are the
odium
the raw material to produce s component(s) of syngas?
ydroxide hlorine
h , c and (1) Methane
h ydrogen by e lectrolysis . (2) Hydrogen
(3) Carbon monoxide
A. (1) only
B. (2) only
C. (1) and (3) only 11. Refer to p.7 of chapter
D
D. (2) and (3) only 54 for details.
43 54
29
12. Consider the Haber process: 16. Consider the following set-up used to oxidize
N2(g) + 3H2(g) 2NH3(g) ∆H = –92 kJ mol
–1 ammonia in the presence of red hot platinum
wire.
Which of the following actions can shift the
equilibrium position to the right? oxygen
glass rod
(1) Increasing the pressure
(2) Increasing the temperature
(3) Adding a catalyst 12. (2): increasing temperature shifts the equilibrium
position to the left because the backward reaction is
A. (1) only endothermic. platinum wire
B. (2) only (3): a catalyst increases the rates of both forward and
C. (1) and (3) only backward reactions to the same extent. It does not
change the equilibrium A
D. (2) and (3) only
position.
concentrated NH3(aq)
13. Iron is the catalyst used in the Haber process.
Which of the following statements about the
The platinum wire can be kept red hot
action of iron in the process is/are correct?
throughout the reaction. Which of the following
(1) It increases the rate of forward reaction more
is a possible reason for this?
than that of the backward reaction.
A. Ammonia reacts with oxygen exothermically
(2) It shortens the time to reach equilibrium.
and the heat given out keeps the platinum
(3) It shifts the equilibrium position to the
wire red hot.
product side.
B. Oxygen supports the burning of platinum
A. (1) only
wire and makes it red hot.
B. (2) only
C. Ammonia reacts with platinum wire to give a
C. (1) and (3) only
B
large amount of heat and keeps it red hot.
D. (2) and (3) only
D. Nitrogen monoxide formed reacts with
14. If 12.8 g of NH3 is completely oxidized to HNO3, platinum wire to give a large amount of heat
what is the theoretical yield of HNO3? that keeps it red hot.
A
(Relative atomic masses: H = 1.0, N = 14.0,
O = 16.0) 14. Number of moles of NH3 used Questions 17 and 18 refer to the following reaction in
12.8
A. 27.7 g =
14.0 + 1.0 × 3
mol = 0.753 mol the production of urea:
B. 47.4 g As 1 mole of NH3 forms 1 mole of HNO3, number 2NH3 + CO2 X (NH2)2CO + H2O
C. 66.5 g of moles of HNO3 formed is also 0.753 mol.
Theoretical yield of HNO3 B
17. Which of the following is the possible formula of
D. 94.5 g
= 0.753 × (1.0 + 14.0 + 16.0 × 3) g = 47.4 g X?
15. Which of the following statements about the A. H2NCONH4
production of ammonium nitrate from nitric acid B. H2NCOONH2
and ammonia is INCORRECT? C. H3NCOONH3 17. Refer to p.15 of chapter
D
A. The reaction is exothermic. D. H2NCOONH4 54 for details.
B. The reaction is a redox reaction.

18. If 17.0 g of NH3 is used in the reaction and 24.0 g
C. Ammonia is manufactured by the Haber
of urea is produced, what is the percentage yield of
process.
urea for the reaction?
D. Nitric acid is manufactured by the catalytic
(Relative atomic masses: H = 1.0, C = 12.0,
oxidation of ammonia.
B N = 14.0, O = 16.0)
18. Number of moles of NH3 used
15. There is no change in the oxidation number of every element in A. 60% 17.0
= mol = 1 mol
the reaction. Hence, this is not a redox reaction. B. 70% 14.0 + 1.0 × 3
From the equation, mole ratio of NH3 to urea
C. 80%
= 2 : 1. C
D. 90%
 number of moles of urea produced = 0.5 mol
Theoretical mass of urea produced
= 0.5 × (14.0 × 2 + 1.0 × 4 + 12.0 + 16.0) g = 30.0 g
54 44 24.0 g
Percentage yield of urea = × 100% = 80%
30.0 g
Section 54.2 A. (1) and (2) only

19. Which of the following statements about the B. (1) and (3) only
flowing mercury cell is/are correct? C. (2) and (3) only 22. Refer to p.23 of chapter 54
for details. D
D. (1), (2) and (3)
(1) Titanium is used as the cathode.
(2) The electrolyte is brine. Section 54.3
(3) Hydrogen ions are preferentially discharged
23. Which of the following statements about the
at the mercury electrode.
steam-methane reforming to give syngas are
A. (1) only 19. (1): mercury is used as the
cathode.
correct?
B. (2) only +
(3): Na (aq) ions are (1) The ratio of CO to H2 is 1 : 3.
C. (1) and (3) only preferentially discharged
B (2) The reaction is endothermic.
D. (2) and (3) only when mercury is used as
the cathode. (3) Platinum metal is used as the catalyst.
Questions 20 to 22 refer to the electrolysis of brine A. (1) and (2) only
using a membrane cell. B. (1) and (3) only
20. Which of the following statements about the C. (2) and (3) only 23. Nickel(II) oxide is used as
D. (1), (2) and (3) A
membrane used in the membrane cell are the catalyst.
correct?
24. The manufacture of methanol from syngas is
(1) The membrane is permeable to all ions. an equilibrium reaction as shown in the
(2) The membrane separates the cathode and equation below:
anode compartments.
CO(g) + 2H2(g) CH3OH(g)
(3) The membrane separates the hydrogen and –1
∆H = –90 kJ mol
chlorine formed.
A. (1) and (2) only Which of the following combinations of
B. (1) and (3) only temperature and pressure favours the production
20. The membrane is
C. (2) and (3) only permeable to cations only.
of methanol?
C
D. (1), (2) and (3) It is selectively permeable.
A. Low temperature and low pressure
B. High temperature and high pressure
21. Which of the following statements correctly
C. Low temperature and high pressure
explains how sodium hydroxide solution is C
D. High temperature and low pressure
produced in the membrane cell?
+
A. Na (aq) ions are discharged at the cathode to 25. Which of the following hazard warning labels
form sodium which then reacts with water should be put on a container of methanol?
to form NaOH(aq). 21. Refer to p.23 of chapter 54
+
for details. (1) (2)
B. Na (aq) ions are allowed to pass through the
membrane to the cathode compartment of
–
the cell which has an excess of OH (aq) ions.
–
C. OH (aq) ions are allowed to pass through the
membrane to the anode compartment of the (3)
+
cell which has an excess of Na (aq).
+
D. Na (aq) ions displace the hydrogen atoms in
water to form NaOH(aq). B
A. (1) and (2) only

22. Which of the following are the advantages of a
B. (1) and (3) only
membrane cell over a flowing mercury cell?
C. (2) and (3) only
(1) The sodium hydroxide solution obtained A
D. (1), (2) and (3)
contains no sodium chloride.
(2) It does not involve the use of poisonous
mercury.
(3) It requires a lower voltage to operate.
45 54
29
26. (a) (i) 200°C and 1000 atm
(ii) Exothermic. As shown in the graph, low temperatures favour the production of ammonia. Since low
Structured questions temperature favours exothermic reaction, the formation of ammonia from nitrogen and hydrogen is
exothermic.
Section 54.1 (iii) 25%
26. (a) The graph on the right shows the percentage

yield of ammonia obtained by reacting a
100 200°C
1 : 3 by volume of nitrogen and hydrogen at 300°C
different temperatures and pressures.
N2(g) + 3H2(g) 2NH3(g) 80
Percentage yield of NH3

400°C
(i) From the graph, at what temperature and
pressure is the percentage yield of 60
500°C
ammonia highest?
(ii) From the graph, deduce whether the
40
formation of ammonia from nitrogen and
hydrogen is exothermic or endothermic. 600°C
(iii) What is the percentage yield of ammonia 20

at 400°C and 250 atm?
(iv) From your answers in (i) and (iii), explain
why many industrial plants applying this 0 200 400 600 800 1000
reaction are operated at 400°C and 250 Pressure (atm)
atm.
(b) In the industrial manufacture of ammonia,
explain
(i) why the gases are purified before being passed into the reaction chamber.
(ii) how the ammonia can be separated from the mixture of gases obtained.
(c) Ammonia manufactured is used to make ammonium sulphate for use as a fertilizer.
(i) Write the equation for the reaction used to make ammonium sulphate from ammonia.
(ii) State and explain the effect of adding ammonium sulphate on the pH of the soil.
27. Urea ((NH2)2CO) is a nitrogenous fertilizer produced by reacting carbon dioxide with ammonia to form
ammonium carbamate (H2NCOONH4), which is then dehydrated to form urea.
(a) Draw three-dimensional structures to show the shape of urea. 27. (a) O
(b) Explain why urea is highly soluble in water.

C
(c) Write an equation for the reaction between carbon dioxide and ammonia.
N N
(d) Predict, with a reason, whether the reaction in (c) is exothermic or endothermic.
H H
H H
(e) Write an equation for the dehydration of ammonium carbamate.
(f) Apart from urea, name TWO other nitrogenous fertilizers.
26. (a) (iv) It is a compromise between rate of reaction, yield and economic considerations. If the temperature is very low, the reaction proceeds
slowly. This lowers the amount of ammonia produced per unit time. If the pressure is very high, the construction and maintenance
costs for the catalytic chamber and pipes that can withstand high pressure will be very high. As a result, 400°C and 250 atm are
used.
(b) (i) Impurities will ‘poison’ the catalyst and thus affect the catalytic effectiveness.
(ii) Liquefy the ammonia by applying pressure.
(c) (i) 2NH3(aq) + H2SO4(aq) (NH4)2SO4(aq)
(ii) The pH of the soil decreases because the aqueous solution of ammonium sulphate is acidic.
27. (b) This is because extensive hydrogen bonds form between urea molecules and water molecules.
(c) CO2(g) + 2NH3(aq) H2NCOONH4(aq)
(d) Exothermic. This is because CO2 is acidic while NH3 is alkaline. The reaction between them is neutralization.
(e) H2NCOONH4(aq) (NH2)2CO(aq) + H2O()
54 46 (f) Ammonium nitrate and ammonium sulphate
Section 54.2
28. Diaphragm cell was once used to replace the flowing mercury cell in the chloroalkali industry. The diagram
below shows the structure of a diaphragm cell.
28. (d) The diaphragm is permeable to all ions including
+ –
28. (a) There is a risk of mercury leakage from chlorine hydrogen Na (aq) and Cl (aq) ions, so the resultant solution
the flowing mercury cell which can contains sodium chloride.
+
cause serious environmental problem. (e) The membrane used is permeable to Na (aq) ions but
– – +
Diaphragm cell has no such problem not Cl (aq) and OH (aq) ions, so Na (aq) ions can go
–
because mercury is not used. into the cathode compartment while OH (aq) ions are
brine kept in the cathode compartment. Hence, the resultant
solution contains NaOH(aq) but not NaCl(aq).
titanium anode steel cathode
(f) To convert vegetable oil into solid fat in making
– –
(b) (i) 2Cl (aq) Cl2(g) + 2e margarine/to make fertilizers/to make hydrochloric
+ –
(ii) 2H (aq) + 2e H2(g) acid/as a rocket fuel
(c) It is used to keep the chlorine and used brine
sodium hydroxide apart so that they
porous asbestos diaphragm
will not react.
(a) Suggest ONE reason of replacing the flowing mercury cell with the diaphragm cell.
(b) Write the half equation for the reaction taking place at the
(i) titanium anode and
(ii) steel cathode.
(c) Suggest the function of the porous asbestos diaphragm in the cell.
(d) Explain why the resultant solution contains a little amount of sodium chloride.
(e) The small amount of sodium chloride can be excluded if the membrane cell is used. Explain the
function of the membrane in the membrane cell.
(f) State TWO uses of hydrogen formed in the chloroalkali industry.
29. The production of caustic soda (NaOH) and chlorine (Cl2) is one of the world’s most important industries.
In the chloroalkali industry, brine is electrolysed in a membrane cell as shown below.
–
29. (a) Positive 29. (e) Cl (aq) ions are preferentially discharged at electrode A
– – +
(b) 2Cl (aq) Cl2(g) + 2e d.c. source and Na (aq) ions pass through the membrane to the
(c) Toxic cathode compartment. Thus, the concentration of used
+
29. (d) As H (aq) ions are brine is lower than that of the original brine.
preferentially discharged at chlorine hydrogen
electrode B, water molecules
ionizes continuously to
+
replenish the H (aq) ions used brine sodium hydroxide
discharged, leaving an solution
–
excess of OH (aq) around A B
electrode B. Furthermore, 29. (f) Agree. Combustion of hydrogen gives water as
the membrane allows the only product which is not harmful.
+ –
Na (aq) ions but not OH (aq)
–
and Cl (aq) ions to pass brine water
+
through. Thus, Na (aq) ions can go into the cathode compartment
–
while OH (aq) are kept in the cathode compartment. Hence, sodium
membrane
hydroxide solution forms.
(a) State the polarity of electrode A.

(b) Write a half equation for the reaction that occurs at electrode A.
(c) Chlorine is stored in steel cylinders. Name the hazard warning label which should be put on these
cylinders.
(d) Explain the formation of sodium hydroxide solution in the cell.
(e) Account for the difference in concentrations of the original brine and used brine.
(f) Hydrogen is one of the products in the chloroalkali industry. A student states that the hydrogen
produced can help reduce air pollution as it is a non-polluting fuel. Comment on his/her statement.
47 54
29
30. (a) 2CH3OH() + 3O2(g) 2CO2(g) + 4H2O()
+ –
(b) CH3OH(aq) + H2O() CO2(g) + 6H (aq) + 6e
(c) Advantage: methanol is a liquid which is easier to handle than hydrogen gas.
Section 54.3 Disadvantage: methanol is toxic.
30. Methanol can provide energy by direct combustion. It can also be used as a fuel in fuel cells.
(a) Write a chemical equation for the combustion of methanol.
(b) In a fuel cell, aqueous methanol is oxidized to give carbon dioxide and hydrogen ions. Write a half
equation for the reaction involved.
(c) Hydrogen can also be used as a fuel in fuel cells. Suggest ONE advantage and ONE disadvantage of
using methanol over hydrogen as fuel in fuel cells.
(d) Suggest the hazard warning labels that should be put on a cylinder of methanol.
(e) Besides using as a fuel, suggest ONE other use of methanol. 30. (d) Toxic, flammable
31. Methane is used to make syngas in the steam-methane reforming process. Syngas is then converted to
methanol. (Answers on p.54-41.) 30. (e) To make other chemicals such as methanal/ethanoic acid/dimethyl ether
(DME)/methyl tertiary butyl ether (MTBE), etc. OR
(a) What is the major source of methane? As an industrial solvent to make methylated spirit.
(b) Write the equation for the steam-methane reforming to make syngas. State the conditions commonly
used in the industry.
(c) Write the equation for the conversion of syngas to methanol.
(d) What is the significance of converting methane to methanol?
32. It is suggested that the chloroalkali industry can provide the raw material, hydrogen, for the Haber process
and the manufacture of methanol. (Answers on p.54-41.)
(a) With the help of a chemical equation, explain how hydrogen is produced in the chloroalkali industry.
(b) Write an equation for the reaction in the Haber process. State the conditions commonly used
industrially.
(c) Write an equation for the manufacture of methanol that consumes hydrogen.
(d) The steam-methane reforming is commonly used to make syngas for the production of methanol.
(i) What is syngas?
(ii) Suggest ONE advantage of using syngas as the raw materials to produce methanol over obtaining
hydrogen from the chloroalkali industry.
(e) Suggest ONE advantage and ONE disadvantage of setting up the Haber process and chloroalkali
industrial plants together at the same site.
(Hint: You can consider the social, economic or environmental aspect.)
33. Methanol is produced industrially by the catalytic conversion of syngas (a mixture of CO and H2) at a
temperature of 250°C and a pressure of 50–100 atm. The equation for the equilibrium reaction is as follows:
(Answers on p.54-41.) CO(g) + 2H2(g) CH3OH(g)
(a) What is the catalyst used in the above reaction?
(b) Syngas is made from the steam-methane reforming. Write an equation for the reaction.
(c) The graph on the right shows the change in
Concentration of methanol (mol dm )
–3
concentration of methanol in the reaction chamber 125°C

with time at three different temperatures under the
225°C
same pressure.
(i) State and explain whether the reaction is 325°C
exothermic or endothermic.
(ii) Explain why the process is NOT carried out at
125°C though a higher equilibrium concentration
of methanol is obtained at lower temperatures.
(iii) Predict and explain the effect of high pressure on
Time (s)
the equilibrium concentration of methanol. Hence,
explain the use of pressure of 50–100 atm in the industry.
54 48

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Chapter 54

• describe the process of the conversion of ammonia to fertilizers

• explain the physicochemical principles involved in the production of ammonia

• recognize the significance of the conversion of methane to methanol

• discuss the advancement of the methanol production technology

• the main component in the air

• the salt in the ocean can be used

• the main component in the natural gas can be converted

A natural gas production platform

chlorine bleach 氯漂白劑 adhesive 黏合劑

54.1 Production of fertilizers

Figure 54.1 (a) Fruits.

Plants need certain nutrients to grow well, particularly nitrogen,

Figure 54.2 Plants absorb aqueous

H20 Example 54.1

The importance of fertilizers

amino acid 氨基酸 inorganic salt 無機鹽

Learning tip Nitrogenous fertilizers are usually nitrates or ammonium salts.

Figure 54.3 (a) Ammonium

Other common nitrogenous fertilizers are ammonium sulphate

Class practice 54.1

A NPK fertilizer for potted plants

(a) Nitrogenous fertilizers are most often manufactured by neutralization of

sodium nitrate 硝酸鈉 granule 顆粒

forms of nitrogenous fertilizers such as ammonium nitrate, ammonium

Figure 54.4 shows the growth in worldwide ammonia production that

production of grow more crops for 120 000

ammonia from 1947 to food in a given period

Haber process was invented and adopted by large

using ammonia as the feedstock.

Figure 54.4 Worldwide 20 000

Ammonia is produced industrially by the Haber process, named

fractional distillation 分餾法

A54.2 Class practice 54.2

Sources of hydrogen DSE2012(2)1(a)(ii) DSE2014(2)1(c)(ii)

(1) Steam-methane reforming N4

Learning tip Hydrogen is mainly produced by reacting methane (in natural

Class practice 54.3

cracking 裂解作用 steam-methane reforming 蒸汽–甲烷重整作用

nickel(II) oxide 氧化鎳(II) water-gas shift reaction 水–煤氣轉移反應

The Haber process CE2000(II)10 CE2003(I)6(b)

In the catalytic chamber, nitrogen and hydrogen combine in a

Ammonia (b.p. –33°C) is then liquefied under pressure in the

Figure 54.6 A flow diagram for the Haber process.

catalytic chamber 催化室 heat exchanger 換熱器

Figure 54.7 A modern Haber process plant.

Physicochemical principles and economic

Consider the chemical equilibrium in the Haber process:

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

Four moles of gaseous reactants produce only two moles of a gaseous

However, to withstand very high pressures (e.g. 1000 atm), the

The formation of ammonia from nitrogen and hydrogen is an exothermic

The percentage yield of ammonia is about 15% under the optimum

exothermic reaction 放熱反應

H20 Example 54.2

H20 Example 54.3

Class practice 54.4

Contact process 接觸法 sulphur trioxide 三氧化硫

Experiment 54.1 Experiment Workbook 5