HSC Chemistry Option Module: Industrial Chemistry

Summary

Industrial Chemistry: 1. Replacements for natural products

x Identify data, gather and process information to identify and discuss the issues
associated with the increased need for a named natural resource that is not a fossil
fuel and evaluate the progress currently being made to solve the problems
identified.

x Discuss the issues associated with shrinking world resources with regard to one
identified natural product that is not a fossil fuel, identifying the replacement
materials used and/or current research in place to find a replacement for the named
material.

Natural product: Rubber

Natural rubber is an elastomer (elastic hydrocarbon polymers) originally derived from latex,
the milky colloid found in some plants. The commercial source of rubber is the Para rubber
tree- rubber therefore a renewable resource.

The uses of rubber are widespread, from household items to many uses in medicine and
industry: tires (the majority is used for this), hoses, belts, matting, flooring, gloves, toy
balloons, rubber bands, pencil erasers, textiles, even spacecrafts.

In addition, the rubber wood can be used as timber for quality furniture and construction once
the tree becomes unviable for rubber production. It is strong, flexible, resistant to microbes
and easy to work with.

Flow Chart for conventional rubber production:

Rubber tree cultivation: tropical countries i.e. South-East Asia, Africa, South America
provide optimum growing conditions, with up to 25 year productive phase

Tapping: Outer layer of bark is cut off and latex is collected in containers supported by wires
attached to the trunk of the tree

Collection: Latex is transferred to air-tight containers for ammoniation (ammonia prevents

latex from coagulating)

Processing: processed into latex concentrate for dipped products, or coagulated under clean
conditions using formic acid

Grading: Rubber is process into various grades (higher grades have size reduction and
cleaning process to remove contaminants)

Final processing and packaging: Rubber is dried, then baled, pelletized and packaged ready
for shipping

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary

Problems with natural rubber

The production of rubber trees has environmental and political issues relating to the
smallholders who grow the crop.

Over 90% of natural rubber production occurs in developing nations with tropical climates
including Thailand, Malaysia, Indonesia, South America and most recently, Africa. A “slash-
and-burn” approach is used, leading to land degradation, air pollution and deforestation. End
of season burn-offs are used to increase plantation area which has seen the emergence of new
diseases previously isolated within the forest.

Rubber growers have little economic incentive to improve the quality of their product as they
have little bargaining power compared to the intermediate traders. As a result, they often
leave contaminants in unrefined rubber in an attempt to be paid more for the weight of the
rubber. Scarcity of land for rubber plantations has led to escalating land prices, leaving
ownership of viable land to a few elite farmers. There are food shortages as the result of land
being used for Rubber plantations rather than crop staples.

Reasons for solutions:

*Some people are severely allergic to proteins in latex products, which can cause
occupational problems esp. in the healthcare industry.
*Rubber plantations in Asia are affected by a fungal disease that could potentially decimate
current production.
*There are also predicted shortages of supply due to economic developments in China and
India
*Today, 75% of rubber production is a synthetic product derived from petroleum. Although
this is a cheap way to produce rubber, petroleum is a non-renewable resource which is rapidly
depleting. Therefore, there is great need for an alternative source of rubber.
* Synthetic rubber is poorer quality and cannot be used for high impact purposes such as
aeroplane tyres and tyres carrying heavy loads.

Solutions to resource shortage

Several substitute plants are being trialled to enhance global production of rubber, the most
promising is a Mexican shrub called guayule. Guayule has the benefits of:

-the potential to reduce environmental effects as it can tolerate more arid conditions
-less likely to cause allergic reactions than latex from rubber trees

2. Equilibrium processes in industrial processes

x Identify data, plan and perform a first-hand investigation to model an equilibrium

reaction

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary

x Choose equipment and perform a first-hand investigation to gather information and

qualitatively analyse an equilibrium reaction

First-hand Investigation: Systems at equilibrium

Aim: To examine the effects of changing reaction conditions on a system at equilibrium

Materials:
Dilute solutions (0.1 M) of:
- Iron (III) chloride
-potassium thiocynate (KSCN)
-potassium chloride (KCl)
-Iron (III) nitrate (Fe[NO3]2)
-sodium hydroxide (NaOH)

Method:
1. Place equal volumes of iron(III) chloride and potassium thiocyanate into a test tube
and allow equilibrium to be established; a blood-red solution will form.
2. Dilute solutions with distilled water until colour lightens
3. Place equal volumes of the diluted solution into five separate test tubes
4. Add a small volume of KCl to the first test tube
5. Repeat step 4 with Iron(III) nitrate for the second test tube
6. Repeat with KSCN for the third test tube
7. Repeat with NaOH for the forth test tube.

Results:

The reaction between Iron(III) chloride and Potassium thiocyanate (KSCN):

FeCl 3( aq )  KSCN ( aq ) œ Fe(SCN  ) 3 ( aq )  3KCl 3( aq )

Chemical Chemical Observation Shift in equilibrium and

added to disturbing regarding colour explanation
FeCl3 and equilibrium
KSCN
KCl KCl Lighter red Increasing the concentration of
one of the products shifts
equilibrium to the right
Fe[NO3]2 Fe[NO3]2 darker red Adding Fe3+ ions increases the
concentration of reactants; shift
to right
KSCN KSCN Darker red Increasing the concentration of
one of the reactants shifts
equilibrium to the right
NaOH NaOH Orange (precipitate) Fe3+ ions react with OH- ions to
form a yellow orange ion
complex; shifts left???

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 HSC Chemistry Option Module: Industrial Chemistry
Summary

Conclusion: Changing the concentrations of reactants and products in an equilibrium, or

adding a substance that will react with either products or reactants, will have an effect on the
equilibrium position. Increasing the concentration of a reactant or a substance that reacts with
a product will shift the equilibrium to favour the products. Conversely, Increasing the
concentration of a product or a substance that reacts with a reactant will shift the equilibrium
to favour the reactants.

x Explain the effect of changing the following factors:

-Concentration
-Pressure
-Volume
-temperature

Le Chatelier’s Principle
When a system that is at equilibrium is changed by altering temperature, concentration of
products and/or reactants or the volume/pressure of gas; the equilibrium shifts to counteract
the effect and return the system to equilibrium

Concentration
An increase in temperature will cause:
-An exothermic reaction to reverse. Products will decompose into reactants i.e. concentration
of products will decrease while concentration of reactants will increase. The reverse occurs if
the temperature of the system is lowered.
-An endothermic reaction to proceed as written. The reverse occurs if the temperature of the
system is increased.

Pressure and volume

An increase in pressure and volume will cause
-changes to occur in gases only
-same effect as decreasing volume of the reaction vessel, as the particles are forced to occupy
less space
-equilibrium favours the side with least number of moles of gas

Concentration
An increase in concentration will cause:
-equilibrium to shift to maintain the molarities of products and reactants i.e. if more reactants
are added, it will shift to produce more product and vice versa.

x Process and present information from secondary sources to calculate K from

equilibrium conditions

The extent to which an equilibrium reaction can be quantitatively defined using the
equilibrium constant, K. When the value of K is large, the equilibrium is towards the product
side. When K is small, it is towards the reactant side.

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 HSC Chemistry Option Module: Industrial Chemistry
Summary
If we define the general homogenous (same chemical state i.e. solid, liquid or gas)
equilibrium reaction as: aA  bB œ cC  dD , then K is defined as:
[products] [C] c [D] d
K , where [ ] denotes concentration in molL-1
[reac tan ts] [A] a [B] b

System at equilibrium

Examples:

1) Consider the equilibrium: 3I 2(g)  6F2(g) œ 2IF5(g)  I 4 F2(g)

At a certain temperature 3.0 moles of F2 and 2.0 moles of I2 are introduced into a
10.0 L container. At equilibrium, the [I4F2] is 0.02 M. Calculate the K for the
reaction.

[IF5 ] 2 [I 4 F2 ] [0.04] 2 [0.02]

K 342.87106... # 343 (3 s.f.)
[F2 ]6 [I 2 ]3 [0.18]6 [0.14]3

Reactants Products
Concentrations I2 F2 IF5 I4F2
(molL-1)
Initial 0.2 0.3 0 0
concentration
Δ concentration -3(0.02) = -0.06 -6(0.02) = -0.12 +2(0.02) = 0.04 +0.02
Equilibrium 0. 1 4 0.18 0.04 0.02
concentration

x Interpret the equilibrium constant expression (no units required) from the chemical
equation of equilibrium reaction

If K is large, the equilibrium lies to the right, so the concentration of products is high and the
reaction almost goes to completion. If K is small, the equilibrium lies to the left, so there is
very little reaction. The size of the K value is an indication of the relative strength of acids
and bases, or the solubility of a substance.

Points to remember:
*When calculating K, disregard any reactants or products in solid or liquid (solvents) state
*the concentrations used refer to the concentrations of reactants and products at equilibrium

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 HSC Chemistry Option Module: Industrial Chemistry
Summary

x Identify that temperature is the only factor that changes the value of the equilibrium
constant (K) for a given equation

The value of K for a given equilibrium is unaffected by changes in concentration or the

addition of a catalyst, which simply increases the rate of both forward and reverse reactions.

For exothermic reactions, K decreases with increasing temperatures as the equilibrium

favours the reactants. Conversely, K increases with decreasing temperatures, as it favours the
products

For endothermic reactions, K increases with increasing temperatures because the equilibrium
favours the products. Conversely, K decreases with decreasing temperatures, as it favours the
reactants

For example, in the oxidation of sulfur dioxide is an exothermic equilibrium:

2SO 2( g )  O 2( g ) œ 2SO 3( g )  heat ,
[SO3 ]2
K=
[O2 ][SO2 ]2

Heating the reaction vessel will shift the equilibrium to the left. This will increase the values
of [O2] and [SO2] and decrease [SO3], therefore K will be smaller. However, if the vessel is
cooled, equilibrium will shift to the right i.e. [SO3] will increase while [O2] and [SO2] will
decrease, so K will be larger.

3. Sulfuric Acid

x Outline three uses of sulfuric acid in industry

Sulfuric acid is one of the most important industrial chemicals, with many applications:

*Used by fertiliser industry (~70% total production) to make ammonium sulfate and
superphosphate
*Removes oxides and grease from steel and iron before galvanising or electroplating
*Dehydration agent i.e. removes water liberated during manufacture of explosives, dyes,
detergents, polymers, esters, electrolysis of sodium chloride solution
*Electrolyte in vehicle batteries
*Used in the production of nitroglycerine for explosives and as a vasodilator (treatment of
heart conditions)

x Describe the processes used to extract sulfur from mineral deposits, identifying the
properties of sulfur which allow its extraction and analysing potential
environmental issues associated with its use

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
Elemental sulfur occurs in deposits near volcanoes, hot springs and underground. It is also
found in ores e.g. PbS, hydrogen sulfide in fossil fuel sources and sulfates in the ocean

Extraction of Sulfur

Frasch Process:
Sulfur is extracted from underground sources by the Frasch process. This process relies on
the following properties of sulfur:

-relatively low melting point (113°C) and boiling point (445°C)

-low density
-insolubility in water

There are 4 main steps:

1. 3 concentric pipes are drilled to the deposit

2. Superheated steam (160°C) under is pumped through the outer pipe, melting the
sulfur
3. Air under high-pressures is pumped through the inner pipe, pushing the low-density
liquid sulfur foam around the middle pipe to the surface
4. The insoluble sulfur is easily separated without the need to evaporate the water.
Slight cooling causes the sulfur to solidify and settle out.
Hot, compressed air

Molten Superheated
sulfur water

Sulfur deposit

Natural gas and petroleum:

Extracted from hydrogen sulfide (H2S) in natural gas and petroleum deposits. The sulfur is
produced in incomplete combustion of H2S:
3H 2 S ( g )  O 2 ( g ) o 2H 2 S ( g )  3S ( g )  SO 2 ( g )

1. The mixture is cooled to condense the sulfur and passed over a heated catalyst:
2H 2S( g )  SO 2 ( g ) o 2H 2 O ( g )  3S( g )

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 HSC Chemistry Option Module: Industrial Chemistry
Summary

2. The mixture is cooled again to condense the remaining sulfur.

Smelting or metal ores

Sulfur may also be released as sulfur dioxide when metal oxide ores are smelted. The general
equation, using M to represent the metal is:
MS(s )  O 2( g ) o M (s )  SO 2( g )

Environmental Issues
Sulfur dioxide readily dissociates with water to form sulphurous and sulfuric acid, thus
producing acid rain. Acid rain lowers the pH of soil and water sources, potentially damaging
the environment and also contributes to chemical weathering of statues and metal. Most of
the sulfur dioxide produced by metal smelting is used to make sulfuric acid and sulfur
dioxide emissions into the atmosphere are strictly controlled by government regulations.

Also produced during mining and smelting is hydrogen sulfide (H2S), a gas more toxic than
cyanide. Soluble substances such as arsenic may be brought to the surface

x Outline the steps and conditions necessary for the industrial production of H2SO4
from its raw materials
x Describe the reaction conditions for the production of SO2 and SO3
x Gather, process and present information from secondary sources to describe the
steps and chemistry involved in the industrial production of H2SO4 and use available
evidence to analyse the process to predict ways in which the output of sulfuric acid
can be maximised

Production of SO2 and SO3

Combustion of sulfur or metal sulfides occurs in a combustion furnace as an exothermic
reaction. Conditions that favour high rate of reaction and yield are high temperature and
surface area (by crushing rock).

Molten sulfur from the Frasch process is filtered to remove impurities and lime (calcium
hydroxide) is added to reduce the acidity, thus preventing corrosion. In the combustion
chamber excess dry oxygen is used to maximise the yield of SO2.

Dry air under

pressure

Combustion
Molten sulfur furnace SO2

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
SO2 derived from smelting of metal ores must be purified and dried before going to the
converter:

O2 SO2
SO2 SO2 Dry
smelter Water Electrostatic Drying SO
scrubber precipitator tower
Metal Steam Steam SO2
Metal sulfide particles
particles

The production of SO3 from SO2 and O2 is an equilibrium reaction involving a compromise
between reaction rate, product yield and economic factors. The following conditions produce
a yield of over 98%:

*High temperatures increase rate of reaction, but the equilibrium is exothermic and high
temperatures may damage the catalyst. 450 - 600°C provides a compromise.
*The vanadium pentoxide or platinum catalyst increases the rate of reaction by lowering the
activation energy for the reaction.
*A multi-stage process is used to convert the SO2 into SO3. With each new stage the
temperature is reduced, thus shifting the equilibrium to the right. This produces a yield of
over 98%.
*Increased pressure shifts the equilibrium to the right, but this is expensive, so pressures of 1-
2 atmospheres are used
*Increasing the concentration of the reactants pushes the reaction to the right. From the
reaction, the stoichiometic ratio of O2:SO2 is 1:2. Industrially, twice as much O2 is used i.e.
1:1 ratio.

Production of H2SO4
Sulfuric acid is manufactured using the contact process. There are 4 main steps involved:

1. Combustion Chamber
Pure sulfur or sulfide ore is combusted in air at 1000°C to produce sulfur dioxide:

S (s )  O 2 ( g ) 1
000q C
o SO 2 ( g ) 'H -300 kJmol -1

2. Converter
Sulfur dioxide is passed into a tower is passed into a tower made of stacked vertical beds of
vanadium pentoxide (V2O5) or platinum catalyst. It is oxidised to sulfur trioxide in an
exothermic equilibrium reaction, with temperatures of 450 - 600°C used as a compromise.
High pressures also shift the reaction to the right.

2SO 2 ( g )  O 2 ( g ) v
anadium pentoxide/platinum
    o 2SO 3( g ) 'H -100 kJmol -1

3. Absorption Tower
Sulfur trioxide cannot immediately be mixed with water, as it forms a fine mist which is
difficult to collect. Instead the gas is bubbled through very concentrated sulfuric acid in
absorption towers to form Oleum (disulfuric acid), H2S2O7.

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 HSC Chemistry Option Module: Industrial Chemistry
Summary

SO 3( g )  H 2SO 4 ( l ) o H 2S2 O 7 ( l )

The sulfuric acid used to dissolve the SO2 must be maintained at 70°C and 98% concentration
to ensure maximum absorption. The concentration is important because at 98%
concentration, the vapour pressure of SO3 above H2SO4 is a minimum. Concentrations greater
than 98% and the water vapour pressure (high vapour pressure at normal temperatures =
volatile) increases sharply, causing the resulting acid mist to evaporate. The acid is also
concentrated at a rate to minimise an increase in concentration

4. Hydration of Oleum:
Oleum is converted into concentrated sulfuric acid by the addition of dilute sulfuric acid and
water. The reaction is highly exothermic, so the acid needs to be cooled before storage.

H 2S2 O 7 ( l )  H 2 O ( l ) o 2HSO 4 ( l )
Traditionally, mild steel was used for the manufacturing equipment. The trend is now to use
Teflon coated piping to reduce contamination of the acid due to iron corrosion.

x Apply the relationship between rates of reaction and equilibrium conditions to the
production of SO2 and SO3

Condition Increase Increase Economic Conditions used

reaction rate Equilibrium factors
yield
Temperature High Low High temp. 450-600°C
temperatures temperatures Expensive and
damages
catalyst
Pressure n/ A High pressures High pressures 1-2 atm.
are expensive
Concentration n/ A Increasing Increasing SO2 Excess O2
of reactants reactant is more O2:SO2 is 1:1
concentration expensive than
increasing O2
Concentration n/ A Removal of n/A Removing SO3 as
of products products it is produced
Other Catalyst n/A Reduces Vanadium
activation pentoxide/platinum
energy and
therefore,
reaction
temperature
Unreacted Recycling back Efficient; Recycling of
gases in reaction maximises Unreacted O2 and
vessel yield SO2

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary

x Perform a first-hand investigation to observe the reactions of sulfuric acid acting as:
-an oxidising agent
-a dehydrating agent

Sulfuric acid as an oxidising agent

The addition of sulfuric acid to zinc metal liberates hydrogen gas.

Sulfuric acid as a dehydrating agent

Addition of sulfuric acid to sugar (sucrose, C12H22O11)

Aim: To observe the reactions of sulfuric acid acting as an oxidising agent and as a
dehydrating agent

Equipment:
-Concentrated sulfuric acid
-Granulated Zinc metal
-matches
-Table sugar (sucrose)
-Glass beaker
-Glass stirring rod

Safety: concentrated sulfuric acid is highly corrosive and toxic and may cause severe burns
to the body. ALWAYS add acid to water, stirring constantly. Use sodium bicarbonate to
neutralise any spills. Wear acid-resistant safety glasses, gloves and aprons at all times. Avoid
inhaling fumes, and use a well-ventilated area, or if possible, a fume cupboard. If contact
with acid occurs, run under cold tap water for at least 15 minutes

Method:
As an oxidising agent:
1) Place a small amount of granulated zinc metal into a glass beaker
2) Slowly add a small volume of concentrated sulfuric acid and place a lid over the
beaker. Zinc bubbles should begin forming on the zinc surface.
3) After several minutes, place a lit match into the beaker. You should hear a loud ‘pop’,
indicating the presence of hydrogen gas

As a dehydrating agent:
1) In a fume cupboard, add a small amount (50 g) of sucrose to a 250mL beaker
2) Slowly pour in concentrated sulfuric acid to just cover the sucrose. After a few
minutes you should observe the beaker becoming hotter,the cusorse reacting to form a
tower of black carbon and sulfur oxide fumes emerging from it.

Results:
As an oxidising agent:
The addition of hot concentrated sulfuric acid to zinc metal liberates sulfur dioxide gas and
water as shown: H 2SO 4 ( aq )  Zn (s ) o ZnSO 4 ( aq )  SO 2 ( g )  H 2 O ( l ) In the process zinc
becomes zinc sulfate i.e. zinc is oxidised (oxidation state changes from 0 to +2).

As a dehydrating agent:

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
The addition of concentrated sulfuric acid to sucrose forms carbon, water and sulfuric acid in
a highly exothermic reaction which causes most of the water to form steam:
H 2 SO 4 ( aq )  C12 H 22 O11 (s ) o 12C (s )  11H 2 O(l)  H 2 SO 4 ( aq )

x Describe and explain the exothermic nature of sulfuric acid ionisation

The ionisation of sulfuric acid is a rapid, highly exothermic reaction. It occurs in two steps:

H 2 SO 4 ( aq ) o H  ( aq )  HSO 4 ( aq ) Kc Ÿ f
- 2-
HSO 4 (aq) œ H  (aq)  SO 4 (aq) K c Ÿ 1.2 u 10  2

In the first dissociation, H2SO4 acts as a strong acid as Kc approaches infinity. In the second
dissociation, HSO4- is a weak acid, so Kc is small.

x Identify and describe safety precautions that must be taken when using and diluting
concentrated sulfuric acid

Diluting sulfuric acid is potentially hazardous due to the vigorous exothermic nature during
ionisation.

Safety Precautions
Wear protective equipment and clothing, especially safety glasses.

ALWAYS ADD ACID TO WATER. Add a small amount at a time, stirring constantly
(sulfuric acid is much denser than water and this may cause a layer of concentrated acid to
form at the bottom, forming a steep temperature gradient). This produces a dilute solution,
releasing only a small amount of heat which can be absorbed by the water. Any splatters that
do occur are more likely to be dilute than concentrated. If spills do occur, clean up with large
amounts of water and sodium hydrogen carbonate (bicarbonate soda).

If water is added to concentrated acid, the heat released will make the water boil violently,
splattering droplets of concentrated acid out of the container. The heat generated may be
enough to crack the container.

x Use available evidence to relate the properties of sulfuric acid to safety precautions
necessary for its transport and storage

Due to its corrosive nature (low pH), it must not be transported with foodstuffs, dangerous-
when-wet substances, oxidising agents, organic peroxides, toxic substances and radioactive
substances.

In high school science labs, dilute sulfuric acid is stored in glass/plastic containers with a
tightly-fitting lid, so that it does not react with moisture in the air. Commercially, it is
transported in its pure molecular form in steel containers as there is no water for it to ionise
and react with the metal. It MUST NOT be stored with foodstuffs, oxidising agents and
organic or combustible materials (it oxidises carbohydrates, causing them to char), or metals

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
(liberates explosive hydrogen gas). Its high vapour pressure means it is volatile, so it must be
stored in well-ventilated areas.

4. Sodium Hydroxide

x Explain the difference between galvanic cells and electrolytic cells in terms of energy
requirements
There are two types of electrochemical cells: galvanic cells and electrolytic cells.

In galvanic cells a redox reaction takes place spontaneously to produce electricity. It consists
of two half cells with separate electrolytes and a salt bridge to complete the circuit.
chemical energy o electrical energy
In galvanic cells, the anode is negative and the cathode positive

In electrolytic cell a compound is decomposed by passing electricity. It is not spontaneous; it

is forced by applying a voltage; electrical energy o chemical energy

In electrolytic cells, the anode is positive potential and the cathode has the negative potential

x Identify, plan and perform a first-hand investigation to identify the products of the
electrolysis of an aqueous solution of sodium chloride

Investigation: Electrolysis of Aqueous Sodium Chloride

Aim: To determine the products of the electrolysis of aqueous sodium chloride or brine

Background: Electrolysis is a process that uses electricity to decompose ionic compounds.

The ion are caused to migrate to the charged electrodes and pure elements will form.
Electrolysis is also used in industry in the purification of active metals such as aluminium and
sodium.

Materials:
-carbon electrodes
-transformer
-brine or salt solution
-phenolphthalein in dropper bottle
-voltameter

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
Carbon Electrode Method:
1/ Place brine solution into a beaker
2/ Place two carbon electrodes into the
beaker and connect to the transformer.
3/ Set to DC 8V and allow the current to
run for a few minutes.
4/ Add drops at the cathode of the circuit,
observe.
5/ Add a few drops at the cathode,
observe.

Voltameter Method:
1/ Place a few drops of phenolphthalein
indicator into a beaker containing
brine solution.
2/ Fill the voltameter with the brine
solution.
3/ Connect to the DC terminal of a
cathode
transformer and allow 8V to flow
anode
through the voltameter.
4/ Observe the voltameter and test the
gases collected above both the
cathode and the anode.

Results:

Equations:
Anode (positive electrode) reaction:
C l  ( aq ) o 1 2 C l 2 ( g )  e  EI - 1 .3 6 V

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 HSC Chemistry Option Module: Industrial Chemistry
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Cathode (negative electrode):
H 2 O (l)  e - o 1 2 H 2 ( g )  OH  ( aq ) EI -0.83 V

Net ionic reaction:

Cl  ( aq )  H 2 O ( l ) o 1 2 Cl 2 ( g )  1 2 H 2 ( g )  OH  ( aq )

Minimum voltage requirement:

1.36  0.83 2.19 V

x Analyse information from secondary sources to predict and explain the different
products of the electrolysis of aqueous and molten sodium chloride

Electrolysis of pure, molten sodium chloride

If pure, molten NaCl undergoes electrolysis, the result is the decomposition of the compound
into its element. Chloride ions are oxidised to form chlorine gas at the anode:
Cl  ( l ) o 1 2 Cl 2 ( g )  e  E I -1.36 V
At the cathode, sodium ions are reduced to form pure sodium metal:
Na  ( l )  e  o Na (s ) E I -2.71 V
E I Total 4.07 V

As there are only 2 species involved, the only products that will form are chlorine gas and
sodium metal.

Electrolysis of aqueous sodium chloride

In an aqueous sodium chloride solution, electrolysis may produce different products because
water can also participate in reactions. There are 2 possible reduction reactions at the
cathode:
Na  ( aq )  e  o Na (s ) E I -2.71 V
H 2 O (l)  e - o 1 2 H 2 ( g )  OH  ( aq ) EI -0.83 V

The water reduction has a significantly lower voltage requirement, so it will proceed. If any
sodium metal did form, it would instantly react with the water anyway.

There are also 2 possible reactions at the anode:

Cl  ( aq ) o 1 2 Cl 2 ( g )  e  EI -1.36 V
  I
H 2 O ( l ) o 1 2 O 2 ( g )  2H ( aq )  2e E -1.23 V

Because the voltage requirements are very similar, the reaction that occurs will depend on the
concentration of the reactants. In a dilute solution, oxygen gas would be produced as there
would be mostly water molecules. In a concentrated solution, however, a mixture of the two
would be produced. In the industrial process to manufacture NaOH, the salt solution used is
so saturated, that pure chlorine gas is produced.

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary

x Outline the steps in industrial production of sodium hydroxide from sodium

chloride solution and describe the reaction in terms of net ionic and full formula
equations
x Distinguish between the three electrolysis methods used to extract sodium
hydroxide:
-mercury process
-diaphragm process
-membrane process

by describing each process and analysing the technical and environmental

difficulties involved in each process

The electrolysis of sodium chloride to produce sodium hydroxide and chlorine is known as a
chloralkali process.

Electrolysis of sodium chloride to produce sodium hydroxide and chlorine is performed using
3 types of electrolytic cells: mercury, diaphragm and membrane cells. The main technical
difficulty in all methods is preventing the chlorine produced contacting (and therefore,
reacting) with the sodium hydroxide or hydrogen.

A saturated brine (NaCl) solution is used in all 3 cells. Impurities are first removed as a
sludge by precipitation reactions:

-Calcium: Ca 2 ( aq )  Na 2 CO 3( aq ) o 2 Na  ( aq )  CaCO 3(s )

-Magnesium: Mg 2 ( aq )  NaOH ( aq ) o MgOH (s )  Na  ( aq )
Fe 2 ( aq )  NaOH ( aq ) o FeOH (s )  Na  ( aq )
-Iron
Fe 2 ( aq )  Na 2 CO 3( aq ) o 2 Na  ( aq )  FeCO 3(s )
2
-sulfate: SO 4 ( aq )  CaCl 2 ( aq ) o CaSO 4 ( s )  2Cl  ( aq )

Despite using different methods, all 3 cells achieve the same overall reaction:
2 NaCl ( aq )  2H 2 O ( l ) o 2 NaOH  Cl 2 ( g )  H 2 ( g )

The Mercury Process

In the mercury cell, titanium coated with a rare earth metal is the anode. A saturated brine
(NaCl) solution floats above cathode, which is a thin layer of mercury at the bottom. Chlorine
gas is oxidised at the anode and pumped away: 2Cl  ( aq ) o Cl 2 ( g )  2e 

Sodium is reduced at the cathode: Na  ( aq )  e  o Na (s ) , where is forms an amalgam (Na/Hg)

with the mercury and is constantly removed.

Electrolysis prevents the amalgam reacting with the brine. The amalgam pumped to a
decomposing vessel where it is reacted with water to form sodium hydroxide and water:
2 Na / Hg  2H 2 O ( l ) o 2 NaOH(aq)  H 2 ( g )  2Hg ( l )

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
Although the mercury is recycled, the mercury cell is being phased out due to concerns of
mercury pollution, particularly of aquatic environments. The NaOH produced is 50% (0.5 M)
concentrated- suitable for commercial purposes.

To Ti anode
Cl2(g) + Cl2(g)

Brine

To Hg cathode
_ H2(g)
Na/Hg
amalga,
NaOH(aq)
Decomposer
Cold water H2O(l)

Mercury cooler
and pump

Hot water

Membrane cell
The Diaphragm Process
In the diaphragm Cell the products of electrolysis are kept apart using a permeable asbestos
diaphragm. This provides a lining for the steel-mesh cathode. The anode is a rod of solid
graphite. Electrolysis occurs when the brine soaks through the asbestos to the cathode.
Hydrogen gas is discharged at the cathode: 2H 2 O ( l )  2e  o H 2 ( g )  2OH  ( aq )

In an aqueous environment the reduction of sodium does not occur. Chlorine gas is
discharged at the anode: 2Cl  ( aq ) o Cl 2 ( g )  2e 

Sodium ions (spectator ions) from the brine are attracted to the cathode and with the
hydroxide ions produced at the cathode, are washed to the bottom where a caustic brine
(NaOH/NaCl) leaves the cell. The NaOH must be concentrated to 50% and the salt removed
via evaporation. The salt may then be reused to form brine.

The overall cell reaction: 2 NaCl ( aq )  2H 2 O ( aq ) o 2 NaOH ( aq )  H 2 ( g )  Cl 2 ( g )

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 HSC Chemistry Option Module: Industrial Chemistry
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Brine
H2(g) Cl2(g)
Asbestos Spend solution
diaphragm Steel-mesh
Graphite cathode
anode
Steam

NaOH solution

This cell is slowly being phased out due to the asbestos used, which poses a serios health
hazard as it is carcinogenic and may cause life-threatening respiratory diseases such as
asbestosis and mesothelioma. Another disadvantage is that is produces low purity NaOH-
only about 12% pure. This is because some of the chloride ions can seep through, thus
contaminating the NaOH.

Membrane Cell
The membrane cell is the most recent cell due to the recent development of high-tech Teflon
membrane. It has a titanium anode (will not react with chlorine gas) and a nickel cathode.
Anode and cathode compartments are separated by an ion exchange that allows water and
positive ions i.e. Na+ to diffuse through, but not negative ions. Brine is pumped into the anode
compartment where chlorine ions are oxidised to form chlorine gas, which is pumped away:
2Cl  ( aq ) o Cl 2 ( g )  2e 

At the cathode, water is reduced to hydrogen gas and hydroxide ions:

2H 2 O ( l )  2e  o H 2 ( g )  2OH  ( aq )

Sodium ions migrate to the cathode compartment where they combine with the hydroxide
ions to form NaOH. Unfortunately, the brine is able to migrate to the cathode compartment,
thus reducing the purity of the NaOH obtained, so further purification is needed. Overall cell
reaction is the same as for the diaphragm cell.

The membrane cell is likely to replace the other two, as it has the least environmental impact
and is very energy efficient as the electrodes can be placed very close to each other. It
produces NaOH of about 30-40% purity (mixture contains NaCl from brine), so further
purification is needed to increase purity to 50%.

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 HSC Chemistry Option Module: Industrial Chemistry
Summary
Ti anode Ni cathode
Cl2(g) H2(g)

Brine in H2O(l)

Na+(aq)

Brine out NaOH(aq)

Property Mercury Cell Diaphragm Cell Membrane cell

Cathode Hg Steel-mesh Nickel
Cathode product Na/Hg amalgam NaOH(aq) NaOH
NaCl(aq) H2(g)
H2(g)
decomposer NaOH n/A
H2(g)
Anode Titanium coated with Titanium/titanium steel-alloy/graphite
rare-earth metal
Anode product Cl2(g)
NaOH purity 50% 12 – 15% ~40%
Operating voltage 4.0 – 4.5 4.0 – 5.0 3.0 – 4.0
Cell temperature 90 – 95 75 – 85 88 – 90
(°C)

Mercury Cell Diaphragm Cell Membrane Cell

Environmental Use of mercury and its Use of asbestos and n/A
Issues disposal: its disposal:
-poses hazard to -expensive to remove
aquatic environments -not readily
decomposed
-small fibres remain
suspended in air for
long periods
Technical Issues Chlorine gas is toxic:
-must wear protective breathing apparatus
-check for leaks
Chemicals used are corrosive to metal surfaces and bricks:
-maintenance is expensive
Hydrogen is highly reactive with chlorine and oxygen:
- check for leaks esp. diaphragm and membrane cells
Mercury is toxic: n/A
-check for leaks
-safe disposal

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 HSC Chemistry Option Module: Industrial Chemistry
Summary
Use of electricity creates heat:
-size of gap between electrodes must be controlled by computer.
-size of gap determines operating voltage and therefore, production
costs
Quality control:
-NaOH concentration (titration)
-impurity metal ions in brine (AAS)
-impurities in Cl2, H2, O2 (gas chromatography)

1. Saponification

Background
Triglycerides
A triglyceride is the general name for a compound containing 3 “fatty acid” molecules joined
to one “glycerol” molecule. Triglycerides are esters.

Fatty acids are long-chain hydrocarbons with a carboxylic (-COOH) group at one end, which
is either saturated or unsaturated.

Schematically, fatty acids can be represented by:

Polar and
hydrophilic/lipophobic
–COOH group
Non-polar and hydrophobic/lipophilic
hydrocarbon chain

Glycerol is a ‘triple alcohol’ i.e. it contains 3 OH- functional groups. Systemically, it is

named ‘propantriol’

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
H
|
H  C  OH
|
Non-polar polar –OH
H  C  OH Hydrocarbon chain functional
| groups
H  C  OH
|
H

Fats and oils are both types of triglycerides. The difference is that fats are solid at room
temperature due to all single C–C bonds, therefore they are said to be saturated. Oils are
liquid at room temperature due to the presence of many double C=C bonds i.e. it is
‘unsaturated’.

x Describe saponification as the conversion in basic solution of fats and oils to glycerol
and salts of fatty acids

Saponification is the reaction in which an ester is ‘hydrolysed’ with a strong base (e.g.
NaOH, KOH) to produce glycerol (alcohol) and salts of fatty acids (carboxylic acid). If the
fatty acid was oleic acid CH 3 (CH 2 )7 CH CH (CH 2 )7 COOH and the base KOH, then the
soap molecule produced would be potassium oleate, CH 3 (CH 2 ) 7 CH CH (CH 2 ) 7 COO  K 
C18H33KO2

x describe the conditions under which saponification can be performed in the school
laboratory and compare these with industrial preparation of soap

The saponification (SAP) value is a measure of the amount of base required to saponify 1
gram of an ester. This value is a measure of the average molecular weight of the all the fatty
acids.

Long-chain fatty acids, found in fats, have low SAP values due to fewer –COOH groups
compared to short-chain fatty acids.

Laboratory Saponification
In the lab, soap can be made by heating a mixture of soap or oil with NaOH or KOH. The
soap produced can be precipitated by using a saturated sodium chloride solution and washed
to remove excess glycerol and base. Dilute acid can be used to neutralise and excess base.

Industrial Saponification
Industrially, soap can be prepared in one stage (Kettle Boiled Batch process) or two stages
(fatty acid neutralisation process). Obvious differences in both of these processes as
compared to laboratory scale are:

-a mixture of fats and oils are used e.g. palm, olive and coconut

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 HSC Chemistry Option Module: Industrial Chemistry
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-huge reaction vessels are used, up to 120 tonnes
-elevated temperatures and pressures (makes water more soluble in fats)
-metal-based catalyst
-the shape size and internal roughness of the reaction Bessel must be considered
-glycerol is removed and used for other purposes

Fatty-acid neutralisation process

This process uses two steps:

The first step hydrolyses the triglycerides to form fatty acids and glycerol, the reverse of
esterification. A zinc-oxide catalyst improves the reaction rate. The fatty acids flow upwards
to a vacuum dryer, while the glycerol/water mixture is pumped away and separated via
distillation.

The second step neutralises the fatty acids with precise amounts of a strong base (determined
from SAP value) to form the sodium/potassium fatty-acid salt (soap).

Kettle Boiled Batch Process

As the name suggests, this process takes place in large, open steel tanks called ‘kettles’. The
reaction mixture is kept constantly boiling via injection of high pressures, which also helps
keep the reaction mixing. Soap from previous reactions is kept to help the water and oil
emulsify. Batch process refers to a reaction where all the reactants (oil, base, salt, catalyst,
water) are added at the beginning and the products removed at the end.

At the end of this process, extra salt is added to help solidify the soap. Extra steam is added
and the mixture settled to remove the glycerol.

The main difference compared to the lab process is the use of high pressure steam to
hydrolyse the fats/oils.

x account for the cleaning action of soap by describing its structure

x explain that soap, water and oil together form an emulsion with the soap acting as
an emulsifier

What is an emulsion?
An emulsion is a mixture formed when two or more normally immiscible substances form a
stable mixture which does not separate. It is not to be confused with a solution, as non of the
molecules are associated with each other. Instead, one of the liquids is evenly dispersed
throughout the other, through the action of another chemical called an emulsifier.

Each emulsion has two different types. For example, if the two liquids were oil and water, the
two emulsions would be:

-oil suspended in water e.g. sorbolene cream

-water suspended in oil e.g. mayonnaise

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 HSC Chemistry Option Module: Industrial Chemistry
Summary
What are surfactants?
Surfactants are chemicals which reduce the surface tension of liquids by adsorbing at the
interface of two different liquids. Surfactants may act as: detergents, wetting agents,
emulsifiers, foaming agents and dispersants. In soaps and detergents, surfactants make it
easier for water to emulsify with oil/ grease.

Soap as an emulsifier
The use of soap as a cleaning agent is dependent on its ability to emulsify dirt/grease in
water. Most dirt is non-polar and oils/grease is non-polar long-chain hydrocarbons. Water is
polar, thus it is immiscible with dirt and grease.

When soap is placed in water and agitated, its ions dissociate (the positive ion takes no part in
the cleaning action). The negative fatty acid ions, called the surfactant (surface acting agent)
do not disperse evenly. Instead, they form clumps with the polar –COOH heads sticking
outwards. The –COOH groups form hydrogen bonds with water. This spherical structure is
called a micelle.

Non-polar lipophilic
Hydrophilic -COOH group
forms hydrogen bonds with hydrocarbon chains
water dissolve triglycerides

Non-polar grease/dirt molecules are encapsulated and dissolved by the non-polar lipophilic
core of the micelle, thus forming an emulsion between water and oil. This emulsion keeps the
grease molecules suspended, which can be carried away by water.

Suspended grease molecule

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 HSC Chemistry Option Module: Industrial Chemistry
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x Distinguish between soaps and synthetic detergents in terms of:
-the structure of the molecule
-chemical composition
-effect in hard water

Detergents are artificial soaps, invented during the 1940’s and have largely replaced soap in
cleaning because they are more powerful emulsifiers and because they can be modified to
specialised applications.

While soaps are made from animal and vegetable oils and manufactured via saponification
(heating triglycerides with a strong base), detergents are derived from petroleum. An alkanol
from petroleum is reacted with Sulfuric acid to a sulfur-containing acid, which is then reacted
with a strong base.

Composition and structure of detergents

The composition of detergents is similar to soaps in that both contain long hydrocarbon chains.
The difference lies in that while soaps are sodium/potassium salts, detergents are hydrocarbons
with a sulfate or sulfonate functional end group.

Structurally, they both contain an ionic or polar head and a non-polar hydrocarbon tail. However
while soaps act only as anionic surfactants, detergents can act as anionic, cationic or non-ionic
surfactants.

Effect in hard water

Hard water contains significant concentrations of magnesium and calcium ions. Soap will not
‘lather’ in hard water as it forms a precipitate ‘scum’ which accumulates on surfaces. Detergents
will lather in hard water and they do not form precipitates.

x distinguish between anionic, cationic and non-ionic synthetic detergents in terms of:
-chemical composition
-uses
Anionic
Anionic detergents contain a negative ion (most commonly sulfate, SO42- or sulfonate SO3-)
as the hydrophilic end of the molecule. The hydrocarbon chain contains a benzene ring at the
ends.

They are primarily used as cleaners for glass and ceramic dishes and clothing and are highly
sudsing. This is due to the fact that these substances have negative surface charges, which
repel the anionic detergents and can be easily washed away, carrying the emulsified
grease/dirt with it. They are usually combined with ionic detergents to provide enhanced
stability.

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 HSC Chemistry Option Module: Industrial Chemistry
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Cationic
Cationic detergents contain a positive ion (usually an ammonia compound). They emulsify
fats well, but are unsuitable for glass and ceramics as they contain negative surface charges.

They are commonly used as fabric softeners and hair conditioners because they reduce static,
thus causing fabric and hair to appear ‘fluffy’. Other uses include germicides, mouthwash and
antiseptic soaps owing to their germicidal properties.

Non-ionic
Non-ionic detergents do not form ions in a solution at all. Instead, they contain hydrophilic
groups (such as oxygen atoms, alcohol groups or polysaccharides) along the hydrocarbon
chain which form hydrogen bonds with water.

They are used for car-washing, cosmetics, dishwashing and froth flotation. One disadvantage
is their loss of solubility in warm water.

O
δ+ δ+

O O
δ- δ-

x solve problems and use available evidence to discuss, using examples, the
environmental impacts of the use of soaps and detergents

Biodegradability
Soaps consists of fatty acids and can therefore be decomposed by bacteria when it enters
sewage or waterways. Therefore, it has no negative impact on the environment.

Early detergents were non-biodegradable as they were made from branched-chain

hydrocarbons which are difficult for bacteria to decompose. This was alleviated in the 1970’s
when straight-chain hydrocarbon detergents were introduced.

The sulfonic acid group found in anionic detergents and non-ionic detergents are highly
biodegradable.

Presence of phosphates
The main environmental impact of detergents was due to the addition of phosphates, as it was
discovered that they aided the effectiveness of detergents. The main problem with the use of
phosphates is their contribution to eutrophication in waterways.

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
Eco-friendly cleaning agents
Eco-friendly cleaning agents use less non-essential chemical additives such as dyes and
fragrances to reduce the toxicity of the detergent.

x gather, process and present information from secondary sources to identify a range
of fats and oils used for soap-making

Oil/fat
Olive oil (oleic acid)
Palm oil (palmitic acid)
Coconut oil (lauric, myristic acid)
Lard (palmitic, stearic, myristic acid)
Tallow (palmitic, oleic, stearic)
Soybean oil (mainly polyunsaturated)
Safflower oil (polyunsaturated)
Shea Oil
Sunflower oil
Rice bran oil
Wheatgerm oil

x Perform a first-hand investigation to carry out saponification and test the product

Experiment: Soap Production

Aim: to make soap by reacting a fat or oil and an alkali

Background: Soaps and other cleaning agents are often produced by the saponification
process. Soap making has been an important industry for many centuries. This reaction
involves the adding of a caustic alkali solution to fats or oils. The ratio of alkali used to fat/oil
depends upon the chemical make-up of the oil.

Mass of alkali (KOH) mass of oil (g) u SAP value of KOH (0.1876)

Materials:
-beaker -olive oil
-potassium hydroxide -boiling chips
-boiling chips -electronic scales
-stirring rod -mould
-heating apparatus -universal indicator
-universal indicator
-hydrochloric acid

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Precautions:
Clean up any spillage and make sure the laboratory is well
ventilated. There is a risk of spitting when the mixture is being
heated. Do not use the soap produced on your skin as there may
be excess KOH.

Method:
1/ Accurately weight 10g of olive oil in a clean beaker.
2/ Calculate the mass of potassium hydroxide needed
according to the equation given above.
3/ Add the potassium hydroxide to the olive oil.
4/ Mix the reactants with a stirring rod.
5/ Add boiling chips to the beaker and gently heat.
6/ Continuously stir the reaction mixture while it is
being heated.
7/ When the soap has formed, wash it thoroughly to
remove any excess hydroxide.
8/ Add 5 drops of universal indicator.
9/ Add hydrochloric acid drop wise till the mixture is neutral.
10/ Place into mould and place in incubator to dry the soap

Conclusion:
What evidence suggests a reaction is occurring?
Macroscopic changes such as the reaction mixture forming a stable, foamy emulsion.

Why was neutralisation necessary?

To remove the excess hydroxide ions produced from the KOH used for the saponification
process

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 HSC Chemistry Option Module: Industrial Chemistry
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x Perform a first-hand investigation to gather information and describe the properties

of a named emulsion and relate these properties to its use.
x Perform a first-hand investigation to demonstrate the effect of soap as an emulsifier

Experiment: The Emulsifying Power of Soaps and Detergents

Aim:
-To examine the production of a soap/stain emulsion
-To compare the emulsifying ability of various commercially available soaps and detergent.

Background:
An emulsion is a mixture of two or more chemicals which under normal conditions would be
immiscible. Another chemical called an emulsifying agent is added to the immiscible
chemicals and allows them to mix. Detergents and soaps act as emulsifying agents when we
use them to clean materials.

Materials:
test tubes
test tube rack
olive oil or other suitable fat or oil
rubber stoppers or corks
a variety of commercially available soaps and detergents

Precautions:
Clean up any spillage and make sure the laboratory is well ventilated. Be careful when
shaking not to spill any of the chemicals.

Method:
Part A: Making an Emulsion
1. Place 10 mL of tap water into two test tubes.
2. Add 2 ml of oil to each test tube.
3. Add a small amount of soap to one of the tubes.
4. Place a rubber stopper or cork on each test tube and shake for 30 seconds.
5. Place both test tubes in a rack and allow to stand.

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 HSC Chemistry Option Module: Industrial Chemistry
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Part B – Testing the Ability of Various Soaps and Detergents:
1. Place 10ml of tap water into as many test tubes as you have soaps and detergents.
2. Add 2mL of oil to each test tube.
3. Add equal mass of different soaps to each one of the tubes. If liquid detergents are used,
equal volumes should be used.
4. Place a rubber stopper or cork on each test tube and shake for 30 seconds.
5. Place both test tubes in a rack and allow to stand.
6. Compare how long each mixture remains an emulsion by timing how long it takes to
separate into layers.

Conclusion and Discussion:

What evidence suggests an emulsion has been produced?
The oil and water formed a homogenous mixture with no distinct oil-water layers

What observations can be used to determine the emulsifying ability of the soaps and
detergents?
The longer it takes for the emulsion to separate back into water and oil layers, the more
powerful its emulsifying ability

How could we gain a better idea as to which of the detergents and soaps were the best
emulsifiers?
Repeat trials using a variety of different types of oils/fats, as well as varying the ratio of water
to oil used.

Why must equal masses or volumes of soaps and detergents be used in the experiment?
To be able to compare the emulsifying abilities of different surfactants, it it necessary to use
equal amounts of the surfactants

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 HSC Chemistry Option Module: Industrial Chemistry
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6. Solvay Process

x Identify the raw materials used in the Solvay process and name the products

Raw materials are sodium chloride (from seawater), ammonia and Calcium carbonate
(limestone). Products are sodium carbonate and calcium chloride (waste product).

2 NaCl ( aq )  CaCO 3(s ) o Na 2 CO 3(s )  CaCl 2 (s )

The overall reaction:
salt brine limestone product waste

x Describe the uses of sodium carbonate

Uses of sodium carbonate:

-manufacture of soap, glass, ceramics, paper, sodium hydroxide and sodium bicarbonate
-petroleum refining
-water softener (removes Mg2+ and Ca2+ ions)
-pollution control (used to scrub exhaust gases to remove sulfur dioxide at power stations)
-cheaper alternative to sodium hydroxide as a general base
-cleaning agent in washing compounds

x Identify, given a flow chart, the sequence of steps used in the Solvay process and
describe the chemistry involved in:
-brine purification
-hydrogen carbonate formation
-formation of sodium carbonate
-ammonia recovery

Brine Purification
Seawater is pumped into shallow ponds, where water is evaporated to leave behind a 30%
concentrated brine. This is a mixture of magnesium and calcium salts, which must be
removed by precipitation.

Ca2+ ions are removed by adding Na2CO3: Na 2 CO 3( aq )  Ca 2  ( aq ) o CaCO 3(s )  2 Na  ( aq )

Mg2+ ions are removed by adding NaOH: 2 NaOH ( aq )  Mg 2  ( aq ) o Mg (OH) 2 (s )  2 Na  ( aq )

A flocculent is added to allow the precipitate to be easily removed.

Hydrogen Carbonate Formation

Crushed limestone is heated in a kiln to produce carbon dioxide and calcium oxide:

CaCO 3(s ) ho

eat
 CO 2 ( g )  CaO (s )

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Coke (carbon) is also present in the kiln, producing more carbon dioxide when heated and
providing heat to decompose the lime:

C ( s )  O 2 ( g ) o CO 2 ( g )

The CaO is used in a later process. The purified brine from the previous step is added to
ammonia (NH4OH). The carbon dioxide from the limestone is bubbled through:

NaCl ( aq )  NH 3( aq )  H 2 O ( l )  CO 2 ( g ) o NH 4 Cl ( aq )  NaHCO 3( aq )

As chloride and sodium are spectator ions, the overall ionic equation:
 
Cl  ( aq )  NH 3( aq )  H 2 O ( l )  CO 2 ( g ) o NH 4 ( aq )  HCO 3 ( aq )

Formation of Sodium carbonate

The ammonium chloride-sodium hydrogen carbonate solution is cooled to 0°C to precipitate
the sodium carbonate, as it is only slightly soluble at lower temperatures:

NaHCO 3( aq ) o NaHCO 3( s )

The mixture is filtered, dried and heated to ~300C to decompose it into sodium carbonate,
water and carbon dioxide:
NaHCO 3(s ) ho
eat
 CO 2 ( g )  H 2 O ( l )  Na 2 CO 3(s )

Ammonia Recovery
Calcium oxide from Hydrogen carbonate formation is dissolved in water to form calcium
hydroxide:
CaO ( s )  H 2 O ( l ) o Ca (OH) 2 ( aq )

When ammonium chloride from hydrogen carbonate formation is added, ammonia gas is
liberated to be reused:
2 NH 4 Cl ( aq )  Ca (OH) 2 ( aq ) o 2 NH 3( g )  H 2 O ( l )  CaCl 2 ( aq )

x Discuss environmental issues associated with the Solvay process and explain how
these issues are addressed

Compared to previous methods, the Solvay process is less polluting as it reuses the products
ammonia and carbon dioxide. However, some environmental issues remain.

Disposal of calcium chloride waste

Calcium chloride has few practical uses in vast quantities. When discharged into the ocean,
there are no noticeable effects. However, when disposed of into rivers/waterways, it can
increase the chloride and calcium ion concentrations to such an extent that local ecosystems

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 HSC Chemistry Option Module: Industrial Chemistry
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are affected. In some areas, the calcium chloride is evaporated and placed in land-fill. This
does not seem to have any effects, but future effects on water supplies are unknown.

Heat (thermal) pollution

As the Solvay process is exothermic and the precipitation of NaHCO3 requires cooling.

This has traditionally been done by using river water as the coolant and simply discharging
the hot water back into the waterway. This can have major effects on aquatic environments as
oxygen is less soluble at higher temperatures.

Modern plants use air-cooling towers and recycle the water instead.

Solid waste
The roasting of limestone in the kiln produces large amounts of silicates, clays as well as
unburnt limestone. Traditionally, this waste was discharged into waterways where it caused
problems by forming a sludge. This waste may be used for bricks or simply as landfill.

Dust Control
Dust is problematic and must be controlled by keeping vehicles in asphalt roadways, using
wetting solution to suppress dust in exposed areas, bag filters in the hydrogen carbonate plant
and installation of dust scrubbing systems.

Noise suppression
Noise is reduced by enclosing noisy areas, using silencers to dampen noise and community
monitoring to identify noise sources.

x Perform a first-hand investigation to assess risk factors and then carry out a
chemical step involved in the Solvay process identifying any difficulties associated
with the laboratory modelling of the step

Investigation: Sodium carbonate production

Aim: To model the production of sodium carbonate by the Solvay process

Materials:
-Large beaker -sodium carbonate (Na2CO3)
-Sintered glass filter -dilute ammonia (NH4OH)
-dry ice/bottled CO2/CO2 from conc. HCl and CaCO3
-Retort stand and ring -ice
-Measuring cylinder -Bunsen burner
-cork/stoppers
-glass/rubber/plastic tubing

Safety: clean up any spillage and ensure good ventilation (ammonia solution is corrosive). As
gas is used, be careful of pressure accumulation. Dry ice ‘burns in contact with skin. Wear
safety glasses at all times.

Method:
1/ Add sodium chloride to an ammonia solution until solution is saturated
2/ Filter the solution to remove excess solid salt

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3/ Place ammonia/salt solution into measuring cylinder
4/ Place marble chips into a conical flask, add concentrated HCl and use the tubing to
bubble CO2 into the ammonia-salt solution.

Measuring cylinder with

Marble chips and ammonia-salt solution
concentrated HCl

5/ Allow the gas to bubble through the solution, but monitor gas inlet as Sodium
hydrogen carbonate may block it

Beaker with ice to aid

precipitation of NaHCO3

6/ Place the measuring cylinder into a large beaker and cool by filling with ice
7/ Use sintered glass filter to filter sodium hydrogen carbonate that precipitates in flask
8/ Place sodium hydrogen carbonate into a clean, dry test tube/crucible
9/ Use Bunsen burner to gently heat the solid until water evaporates
10/ Allow the product to cool

Results: Marble chips and

concentrated HCl

Questions:

1. Write a balanced equation for the reaction

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NaCl ( aq )  NH 3( aq )  H 2 O ( l )  CO 2 ( g ) o NH 4 Cl ( aq )  NaHCO 3(s )
salt brine ammonia water carbon dioxide ammonium chloride sodium hydrogen carbonate

2. Explain why the gas inlet tube must be monitored

NaHCO3 may precipitate at the gas inlet and block it, thus causing an accumulation of CO2
pressure in the flask containing acid and marble chips. As concentrated acid is used, this is a
potential safety hazard.

3. Write a balanced equation for the conversion of the sodium hydrogen carbonate into
sodium carbonate
2NaHCO 3(s)  O 2(g) o H 2 O(l)  CO 2(g)  Na 2 CO 3(s)
sodium hydrogen bicarbonate oxygen water carbon dioxide sodium carbonate

4. Why must the sodium hydrogen carbonate be heated gently?

Carbon dioxide gas is produced, which may cause the mixture to bubble violently

5. Calculate the yield of sodium hydrogen carbonate if 5g of salt was initially used in the
reaction.
5
moles NaCl moles
58.44
5
? moles NaHCO 3 moles
58.44
5
mass NaHCO 3 u 84.008 7.187543... # 7.19 g(2 s.f.)
58.44

6. If 4.5 g of sodium chloride produced 0.9 g of solid sodium carbonate, calculate the
efficiency of the reaction

2 NaCl ( aq )  CaCO 3(s ) o CaCl 2 (s )  Na 2 CO 3(s )

4.5
moles NaCl moles
58.44
1 § 4.5 · 4.5
? moles NaHCO 3 ¨ ¸ moles
2 © 58.44 ¹ 116.88
4.5
mass Na 2 CO 3 u 84.008 3.23439...g
116.88

actual mass Na 2 CO 3
effeciency (%) u 100 27.82592... # 28% (2 s.f.)
calclulated mass Na 2 CO 3

x Process information to solve problems and quantitatively analyse the relative

quantities of reactants and products in each step of the process

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Robert Lee Chin
 HSC Chemistry Option Module: Industrial Chemistry
Summary
x Use available evidence to determine the criteria used to locate a chemical industry
using the Solvay process as an example
Factors which influence the location of a
Solvay plant
x Proximity to raw materials
x Proximity to market for product/transport
links to market
x Proximity to a population centre to
provide a labour force and the community
infrastructure
x Proximity to site for waste disposal
Robert Lee Chin
Example – The Solvay plant in Osborne, SA
x Osborne is located close to the coast. This
allows easy access to sea water, which can be
pumped into ponds for concentration and
purification.
x The hot climate of Adelaide also helps
concentrate the brine
x A limestone deposit is ~50 km away, with a rail
line allowing a deposit each day
x Osborne has excellent rail, road and harbour
connections to supply sodium carbonate to glass
makers throughout Australia
x Proximity to Adelaide means there is a reliable
workforce, schools and shops for workers
x Previously discharged into Port river
x Now being used for landfill, brick manufacture
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 HSC Chemistry Option Module: Industrial Chemistry
Summary

Solvay Process – Flow Chart

Purified Brine Ammoniated Ammonia

30% NaCl, H2O brine NH3(g)

Limestone
CaCO3

Lime Kiln Carbonating tower

CaCO 3( s ) o heat
NaCl ( aq )  NH 3( aq )  CO 2 ( g )  H 2 O ( l )
CaO ( s )  CO 2 ( g ) o NaHCO 3 ( s )  NH 4 Cl ( aq )

H2O CaO
Filter Ammonia recovery
Lime Slaker
Ca (OH) 2 ( aq )  2 NH 4 Cl ( aq ) o
CaO 3( s )  H 2 O ( l )
CaCl 2 ( s )  2H 2 O ( l )  2 NH 3( g )
ho
eat
Ca (OH) 2 ( aq ) Heat

Product Na2CO3(s) Waste product

Sodium carbonate CaCl2

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Robert Lee Chin