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Industrial Chemistry (Part 2)

4. The industrial production of sodium hydroxide requires the use of electrolysis.

Point 4.1 - Explain the difference between galvanic cells and electrolytic cells in terms of energy
requirements.

A galvanic cell is a cell which uses chemical reactions to produce electrical energy. This occurs
when a spontaneous reaction occurs where oxidation and reduction reactions take place.
Electrons are lost from the anode and travel through a conductive wire (electric current) where it
is absorbed by cathode and reduction takes place.

An electrolytic cell is a cell which uses electrical energy (from a power source e.g. battery) to
produce a chemical reaction. The process of electrolysis forms the basic principle of this cell:
there is a decomposition of a chemical substance by the application of an electric current. Usually
in an electrolytic cell, there are non-spontaneous chemical reactions. An input of electric current
is needed to initiate reactions.

Comparing galvanic and electrolytic cells:

Feature Galvanic Cell Electrolytic Cell


Anode Negative Positive
Cathode Positive Negative
Oxidation At anode At anode
Reduction At cathode At cathode
Flow of electrons Electrons flow through the Electrons flow from negative
conductive wire (external terminal of battery to negative
circuit) from the negative cathode.
terminal (anode) to the
positive terminal (cathode).
Reaction Reactions are spontaneous Reactions are non-
thus EMF (Eo total) is positive spontaneous thus EMF (Eo total)
is negative
Uses In batteries To electroplate metals as well
as purifying metals.

Galvanic Cell -

Electrolytic Cell
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So just to sum up this dot point, an electrolytic cell needs an input of electrical energy (from a
power source such as battery) in order to start a chemical reaction. This is due to the non-
spontaneous nature of the reactions thus resulting in a negative EMF. In a galvanic cell, there is
electrical energy produced from the chemical redox reactions (oxidation and reduction) due to
the movement of electrons.

Point 4.2 - Outline the steps in the industrial production of sodium hydroxide from sodium
chloride solution and describe the reaction in terms of net ionic and full formulae equations.

First of all, salt water is collected from the oceans. However various impurities are present in salt
water. Thus salt water needs to be purified and the contaminants removed. Here are some
equations showing the removal of these impurities in salt water:

Contaminant Removal from sea water


Calcium ions Calcium ions are removed from salt water by reacting
it with sodium carbonate:
CaCl2 (aq) + Na2CO3 (aq) CaCO3 (s) + 2NaCl (aq)_
Magnesium ions Magnesium ions are removed from salt water by
reacting it with sodium hydroxide:
Mg(NO3)2 (aq) + 2NaOH (aq) Mg(OH)2 (s) + 2NaNO3 (aq)
Iron ions Iron ions are removed from salt water by reacting it
with sodium carbonate or sodium hydroxide:
Fe(NO3)2 (aq) + Na2CO3 (aq) FeCO3 (s) + 2NaNO3 (aq)
Fe(NO3)2 (aq) + 2NaOH (aq) Fe(OH)2 (s) + 2NaNO3 (aq)
Sulfate ions Sulfate ions are removed from salt water by reacting it
with calcium chloride:
K2SO4 (aq) + CaCl2 (aq) 2KCl (aq) + CaSO4 (s)

After the removal of these impurities, the salt water (sodium chloride + water) is concentrated.
This can be referred to as saturated brine. Then this brine undergoes electrolysis to produce:

Sodium hydroxide
Hydrogen gas
Chlorine gas

FORMULA EQUATION:

2NaCl (aq) + 2H2O (l) 2NaOH (aq) + H2 (g) + Cl2 (g)

FULL IONIC EQUATION:

2Cl- (aq) + 2H2O (l) 2OH- (aq) + H2 (g) + Cl2 (g) (After cancelling Na+ spectator ion)
Looking at the above reactions, the chlorine ions in the salt water solution are oxidised to form
chlorine gas and the water in the salt water solution is reduced to form hydroxide ions and
hydrogen gas. Electrons are lost from chlorine ions and these electrons are gained by the water
molecules.

Point 4.3 - 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.

Diaphragm Cell:
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The diaphragm cell was the first process used to manufacture sodium hydroxide. Below is a
picture showing the various features of a diaphragm cell:

Key features of a diaphragm cell:


Anode: titanium (to resist chlorine attack)

Cathode: steel mesh (to not react with OH-)

Anode and cathode compartment separated by a porous asbestos diaphragm. The purpose
of this is to prevent the products from mixing.

Anode reaction: 2Cl- (aq) Cl2 (g) + 2e-

Cathode reaction: 2H2O (l) + 2e- 2OH- (aq) + H2 (g)

Electrolyte: brine (salt water)

Description of process:

First of all the concentrated sodium chloride solution is entered into the cell. At the titanium anode,
chlorine ions from solution lose electrons and are oxidised to form chlorine gas. This gas is collected
and removed. At the steel mesh cathode, water molecules are reduced to form hydroxide ions and
hydrogen gas. This gas is also removed. The sodium ions in NaCl solution react with the hydroxide ions
to produce sodium hydroxide (some contamination by NaCl) which is collected.

Technical/Environmental difficulties:

Older diaphragm cells contained asbestos diaphragms. This asbestos can cause severe health
and environmental impacts as it is toxic. Health conditions which arise from exposure to
airborne asbestos fibres are mesothelioma and asbestosis.
A technical difficulty may be a leak in the diaphragm which would cause the hydrogen to
react explosively with chlorine or oxygen. This could be prevented by carefully looking for any
leaks and fixing them.
Another technical difficulty is minimising contact between hydroxide ion and chlorine ion in
solution (because unwanted hypochlorite is formed).
Minimising the amount of chloride that is present in the final hydroxide solution is another
technical difficulty.

Using a lot of electricity in the diaphragm process is a technical difficulty as large electric
currents create heat and magnetic effects.

Mercury Cell:
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The Mercury process was used to produce sodium hydroxide after the diaphragm cell. Below is a
picture showing the various features of a mercury cell:

Key features of a mercury cell:


Anode: titanium (to resist attack)

Cathode: flowing mercury over steel (used to prevent water being reduced, instead allowing
sodium ions to be reduced).

Anode reaction: 2Cl- (aq) Cl2 (g) + 2e-

Cathode reaction: Na+ (aq) + e- Na (l)

Decomposer decomposes mercury/sodium amalgam with water to produce sodium
hydroxide

Electrolyte: brine (salt water)

Description of process:

First of all, brine is flowed slowly through the tank. The mercury cell uses liquid mercury as a cathode
and usually titanium as the anode. The sodium ions are reduced at the cathode and the sodium metal
produced dissolves in the mercury to produce an amalgam. The amalgam flows through the cell until
it arrives at the decomposer where it reacts with water to produce sodium hydroxide:

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


The hydrogen is collected and stored and is a valuable by-product of the reaction. Because mercury
does not react with water, it can be recycled and reused as the cathode. Chlorine gas is produced at
the anode. This is also removed.

Technical/Environmental difficulties:

An environmental problem is the disposal of mercury. Mercury is a very toxic and heavy
metal. If disposed incorrectly (such as in rivers, creeks, down the sink), the mercury might be
consumed by aquatic organisms. This may lead to devastating effects on the organisms
because mercury biomagnifies and bioaccumulates along the food chain. The mercury could
badly injure or kill the aquatic organisms.
As in the diaphragm cell, using a lot of electricity in the mercury cell process is a technical
difficulty as large electric currents create heat and magnetic effects.

Membrane Cell

The membrane cell is the widely used method to produce sodium hydroxide today. Below is a picture
showing the various features of a mercury cell:
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Key features of the membrane cell:

Anode: titanium (to resist attack)


Cathode: steel mesh
An ion-selective, water impermeable membrane made out of a synthetic polymer such as
Teflon. This separates two compartments.

Description of the process:

First of all, brine (concentrated sodium chloride) is entered into anode compartment of the cell and
water is entered into cathode compartment of cell. At the anode, chlorine ions from the brine are
oxidised to form chlorine gas which is collected and removed. At the cathode, water molecules are
reduced to form hydroxide ions and hydrogen gas. The gas is collected and removed. The membrane
does not allow chlorine and hydroxide ions to move into the other compartment. This prevents
contamination of the sodium hydroxide with sodium chloride and the formation of other products
such as sodium hypochlorite (NaOCl). However it allows sodium ions to pass through to cathode
compartment to react with the hydroxide ions to produce sodium hydroxide. This is removed and
further purified.

Technical/Environmental difficulties:

Unlike the other two processes, the hazards of working with mercury and asbestos are avoided. As a
result the membrane process has negligible technical and environmental difficulties.

To sum up this dot point, here is a table comparing all 3 methods:

Feature Diaphragm cell Mercury cell Membrane cell


Anode and reaction In all 3 cells, the anode is titanium and the reaction at the anode is:
2Cl- (aq) Cl2 (g) + 2e-
Cathode and reaction Cathode is steel mesh. Cathode is flowing Cathode is steel mesh.
The reaction at the liquid mercury over The reaction at the
cathode is: steel. The reaction at cathode is:
2H2O (l) + 2e- 2OH- (aq) the cathode is: 2H2O (l) + 2e- 2OH- (aq)
+ H2 (g) + -
Na (aq) + e Na (l) + H2 (g)
NaOH produced with Separate chambers Brine and NaOH mix Membrane will not let
brine or in a separate and have to be OH- or Cl- ions through
chamber? separated. thus in separate
chamber.
Concentration of NaOH Lowest (about 11%) Highest (about 50%) Medium (30-40%)
produced
Expense to operate Expensive Expensive More expensive than
others because it uses
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new technology.
Electrical energy Operating voltage 4-5 Operating voltage 4-4.5 Operating voltage 3-4
volts. volts. volts and may become
lower.
Environmental/health Asbestos is toxic and Mercury is a heavy No asbestos or mercury
problems may causes diseases metal and is toxic. It thus having no
such as asbestosis and bioaccumulates in the environmental/health
mesothelioma. food chain and can problems.
damage kidneys in
humans.

The overall formula equation for all 3 processes is:

2NaCl (aq) + 2H2O (l) 2NaOH (aq) + Cl2 (g) + H2 (g)

Point 4.4 - Identify data, plan and perform a first-hand investigation to identify the products of
the electrolysis of sodium chloride.

Basically different products can be formed when conducting electrolysis of sodium chloride. The
products formed depend on the concentration of the sodium chloride. If dilute NaCl is used,
usually oxygen gas would be produced at the anode and hydrogen gas + hydroxide ions produced
at the cathode. However if concentrated sodium chloride is used, chlorine gas would be produced
at the anode and hydrogen gas + hydroxide ions produced at the cathode.

To identify the substances at each electrode, glowing splint test can be used to identify gas and
litmus paper or universal indicator can be used to identify solution. If in the glowing splint test a
popping noise is heard, then the gas is hydrogen. If the splint reignites, then it is oxygen. If
litmus paper is bleached, solution contains chloride ions and if solution turns universal indicator
purple then there are hydroxide ions present.

Safety includes wearing safety goggles to prevent corrosive sodium hydroxide from splashing into
eyes causing burns and irritations. Experiment should be undertaken in a fume cupboard because
chlorine gas is toxic and can cause respiratory problems and is corrosive.

Point 4.5 - Analyse information from secondary sources to predict and explain the different
products of the electrolysis of aqueous and molten sodium chloride.

In the electrolysis of molten sodium chloride, there are only sodium and chloride ions present.
Thus at the anode the only possible reaction is when the chlorine ions oxidise to form chlorine
gas:

2Cl- (l) Cl2 (g) + 2e-


The only possible reaction at the cathode is when the sodium ions are reduced to form sodium
metal:

2Na+ (l) + 2e- 2Na (l)


FULL EQUATION:

2NaCl (l) Cl2 (g) + 2Na (s)

Thus from the electrolysis of molten sodium chloride it is easy to predict the products formed.
The products formed are: chlorine gas and sodium metal.
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However the electrolysis of aqueous sodium chloride is more complicated due to the presence of
water. The possible anode reactions are: when chloride ions are oxidised to form chlorine gas OR
when water molecules are oxidised to form hydrogen ions + oxygen gas.

If at anode chlorine ions oxidise to form chlorine gas:

2Cl- (l) Cl2 (g) + 2e-


If at anode water molecules are oxidised:

2H2O (l) O2 (g) + 4H+ (aq) + 4e-

However the electromotive force (EMF) for each reaction is different. The reaction with the
highest EMF will most likely proceed (more spontaneous reaction). The E value (using data sheet)
for 1st reaction is -1.36V and 2nd reaction is -1.23V. Theoretically, oxygen would be expected to
form at the anode. However this is not the case. Oxygen is only produced with very dilute NaCl
solutions. With concentrated NaCl solutions chlorine gas is produced instead. This occurs because
of an effect called over voltage and also because the conditions are different to those in which
standard reduction potentials are measured e.g. concentrations of Cl - ions is high, not 1 molL-1.

The possible reactions at the cathode are when sodium ions are reduced to form sodium ions OR
when the water molecules are reduced to form hydroxide ions and hydrogen gas.

If at cathode sodium ions are reduced:

Na+ (aq) + e- Na (s)

If at cathode water molecules are reduced:

2H2O (l) + 2e- 2OH- (aq) + H2 (g)

However like at the anode, the electromotive force (EMF) for each reaction is different. The
reaction with the highest EMF will most likely proceed (more spontaneous reaction). The E value
(using data sheet) for 1st reaction is -2.71V and 2nd reaction is -0.83V. Thus the 2nd reaction will
occur at the cathode since it has a higher E value meaning it is a more spontaneous reaction.

Thus in most cases the products formed are: chlorine gas and hydrogen gas + hydroxide ions.

5. Saponification is an important organic industrial process.

Point 5.1 Describe saponification as the conversion in basic solution of fats and oils to glycerol
and salts of fatty acids.

Saponification is the conversion of fats and oils (large esters of glycerol) in a basic solution to
produce glycerol (1,2,3 propanetriol) and a salt of a fatty acid (soap). Thus because this process
produces soap, it is widely known as a viable method for producing soap, especially in industry.

OVERALL REACTION IN SAPONIFICATION:

Fat/oil + sodium hydroxide glycerol + soap


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Usually the fat or oil is a triglyceride. An example of a common fat which is a triglyceride is
glyceryl tristearate. In the reaction of a triglyceride, the hydroxide present in the sodium
hydroxide (or in some cases potassium hydroxide) breaks the bond between the glycerol and the
alkanoate functional group.

In the reaction of glyceryl tristearate with sodium hydroxide (above), the hydroxide in the sodium
hydroxide breaks the bond between the glycerol and the alkanoate functional group thus forming
the stearate ion: CH3(CH2)16COO-. Now what happens is that this ion is attracted to the sodium ion
from the sodium hydroxide and thus the soap sodium stearate is formed as well as glycerol. The
stearate ion is the fatty acid thus the soap that is formed is the salt of the fatty acid.

Point 5.2 Describe the conditions under which saponification can be performed in the school
laboratory and compare these with industrial preparation of soap.

As part of our course, we have modelled saponification to produce soap. (This experiment is
discussed in more detailed in dot point 5.7).
Basically in a school laboratory, we are limited in resources thus what we did was obtain coconut
oil (as the oil) because its cheap and readily available and added sodium hydroxide to it and
boiled the solution. With constant stirring, we added 2-3 drops of food colouring. After about 10
minutes, we added sodium chloride to precipitate out the soap and we allowed it to cool. Then
we left it to dry and the next day we extracted soap and tested it further.
However In the industrial production of soap, there are many factors which differ from the school
laboratory production of soap.

This is just a brief outline of the industrial production method of soap:

Fatty Acid Neutralisation process:

Initially, the fats and oils are hydrolysed by high pressure steam. This breaks down the
fats into fatty acids and glycerol.
At this point, glycerol is drawn away, purified and sold to the cosmetics industry for use
in creams etc.
The fatty acids are passed into another vessel where they are distilled. This causes the
separation of different fatty acids from each other. At this point, some fatty acids can
be drawn off and sold as individual substances. This also allows the control of the
range of fatty acids (different chain lengths) which are present in a particular soap.
The fatty acids continue into the next reaction vessel where they are mixed with an
alkali (usually sodium hydroxide) and neutralised to form soap in a continuous
process.
The soap is recovered and is then pumped into giant mixers called crutchers where
other desired ingredients are added to it e.g. colours, fragrances.
Finally the soap is rolled into flakes, cast into bars or spray-dried into soap powder.
Now it is ready for commercial use.
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*** Note: In industry there are 2 methods of making soap the batch process or the continuous
process (above).

In the batch process, the raw materials are mixed together in a vessel and allowed to react
together. After the reaction, the desired products are separated from reaction mixture.

In the continuous process, the raw materials are fed in at one end of the industrial plant (or at
various stages along the way) and the products are withdrawn at the other end in a continuous
flow.

Another prominent industrial production of soap is the kettle boiled batch process. In this
method, large amounts of fats/oils, caustic soda (sodium hydroxide) and water are added to a
large open steel tank called a kettle. High pressures and temperatures are used to keep the
reaction boiling. It also keeps the reaction well stirred. At the conclusion of the saponification
reaction, additional salt is added to the mixture to solidify the soap and its washed with steam
to separate glycerol.

PRODUCING SOAP IN SCHOOL LAB vs. INDUSTRIAL PRODUCTION OF SOAP

Factor School laboratory process Industrial process


Raw materials Coconut oil, sodium Mixture of blended fats and oils with sodium
hydroxide, water. These are hydroxide. Some common fats and oils include:
often pure. tallow, coconut oil, palm kernel oil and palm oil.
However these reactants are not pure wastes
e.g. tallow from discarded beef from abattoir.
Blended in exact stoichiometric amounts.
Mixing raw All added at the start. Kettle process: All added at the start
materials Continuously stirred solution Neutralisation process: fats/oils hydrolysed by
with a stirring rod. steam and then fatty acids are neutralised. The
materials are stirred by using steam or
electricity.
Temperature and Standard atmospheric Higher temperature and pressures. Usually
pressure pressure. Temperature about temperatures between 240-270C and
50-80C using Bunsen burner. pressures of about 4.5-5 MPa.
Container 250mL beaker Kettle process: A large open steel tank called a
kettle.
Neutralisation process: reacted in large vessels
and then perfumes, colours added in huge tank
called a crutcher.
Time Reaction in about 1 hour and Washing and setting of soap takes several days.
we left it overnight to solidify
soap.
Disposal of wastes Decanted liquid layer above In both processes, glycerol is removed, purified
soap (mainly glycerol + water and sold to the cosmetics industry for use in
+ excess NaOH) creams. However in neutralisation process
some fatty acids are removed and sold
individually.
Further We added food colouring to Soap washed with steam, colour dyes and
processing the soap. fragrances added, distilled to remove impurities
and vacuum dried.
Then soap cast or stamped into bars, rolled into
flakes or spray dried into powder.
Catalyst Nil Kettle process: metal catalyst
Neutralisation process: zinc oxide
Safety Wear safety goggles and Safety goggles, protective clothing e.g. coats.
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continuously stir.

Point 5.3 Account for the cleaning action of soap by describing its structure

Below is the general structure of a soap molecule:

The zigzag line represents the long hydrocarbon tail which is non polar. The negative circle is the
anion which is present in a soap molecule. The long hydrocarbon tail joined to this anion forms
the fatty acid anion (anion of soap). This anion is polar. Usually to complete the structure of a
soap molecule, a positive ion such as sodium (from sodium hydroxide) reacts with the fatty acid
anion to produce the soap molecule.

First of all, soap is a surfactant meaning that when it enters the water, it decreases the surface
tension of the water. This is because soap contains the long hydrocarbon tail which disrupts the
hydrogen bonding between water molecules thus decreasing the surface tension. Soap has an
effective cleaning action because of its structure.

The first step in soaps cleaning action is shown in the following diagram:

This diagram shows when the soap molecules enter the water. Notice that the positive ion in
soap molecule dissociates in the water and hence does not take part in the cleaning action of
soap.

In the diagram above, we can see that the oil


droplet has been surrounded by the soap
molecules. The long hydrocarbon tails are embedded in the oil molecule because its non polar and
so is the oil droplet thus they interact using dispersion forces. They repel the water molecules as they
are hydrophobic (water hating). However the negative anion sticks out because it is attracted to the
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water molecules at it is charged and polar. The anion forms hydrogen bonds with the water molecules
and thus is hydrophilic (water loving).

In the diagram above, the interaction between the long hydrocarbon tails with the oil droplet and
the anion with the water molecules are strong enough to lift the oil droplet from fabric and thus
leave oil droplet suspended in the water. Note that the soap molecules are able to break up the
oil/dirt forming smaller droplets called micelles. Now the oil droplet is ready to be removed.

Point 5.4 Explain that soap, water and oil together form an emulsion with the soap acting as
an emulsifier.

An emulsion is the dispersion of small droplets of one liquid within another liquid. An example of
an emulsion is soap + water + oil, where the soap acts as the emulsifier a substance which
allows the substances to mix which were previously immiscible.

(This dot point is connected to dot point 5.10)

When oil is added to water (or the other way around), there are two distinct layers formed with
the oil layer sitting on the top because it is less dense than water. These layers dont mix because
the oil is non polar and the water is polar and thus they do not interact (like dissolves only like).

However when soap is entered into the system, there is a cloudy layer observed between the oil
and water layers. This is because the soap molecules interact with the oil molecules (EXPLAINED
ABOVE) and causes the oil molecule to break into smaller droplets called micelles. Thus these are
the small droplets which can be seen suspended in the mixture. After a while, the mixture will
separate into its distinct layers.

There are 2 cases for a soap + water + oil emulsion. The first case is an oil in water emulsion. This
is shown in the diagram below:
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In the diagram above, the oil molecules are surrounded by water thus the hydrophobic
hydrocarbon tails are attracted to the oil droplet (dispersion forces) and the charged anion head is
attracted to the water molecules (hydrogen bonds). The oil micelles do not clump together
because the anionic heads of adjacent soap molecules repel each other (electrostatic attraction).
Thus the soap acts as an emulsifier as it allows the oil droplets to remain suspended in the water
without forming a layer on top.

The other case is the water in oil emulsion. This is shown in the diagram below:

In the diagram above, the water molecules are surrounded by oil thus the hydrophobic
hydrocarbon tails are attracted to the surrounding oil (dispersion forces) and the charged anion
head is attracted to the water molecules (hydrogen bonds). The soap acts as an emulsifier as it
allows the water droplets to remain suspended in the oil without forming a layer.

Point 5.5 Distinguish between soaps and synthetic detergents in terms of: the structure of the
molecule, chemical composition and effect in hard water.

Hard water is the name given to water which has excessive amounts of calcium and magnesium
ions.

Factor Soap Detergent


Structure There are three types of
detergent: anionic, cationic and
non-ionic. These structures are
shown in the next dot point.
Usually has polar head like soap
+ hydrocarbon tail.
Chemical composition Sodium or potassium salts combined Usually hydrocarbons with a
with fatty acids from triglycerides. sulfate, sulfonate or another
hydrophilic group at the end.
Effect in hard water Soap forms a greyish precipitate called Lathers in hard water and does
scum due to the reaction between the not form a precipitate with
soap anions and the calcium + calcium or magnesium ions.
magnesium ions in the water. Thus this
reduces cleaning ability of soap and
reduces lathering.
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Point 5.6 Distinguish between anionic, cationic and non-ionic synthetic detergents in terms
of: chemical composition and uses.

There are namely 3 different types of synthetic detergents: anionic, cationic and non-ionic. The
most common is anionic detergent. The diagrams of these detergents are shown below the
table.

Factor Anionic detergent Cationic detergent Non-ionic detergent


Chemical There is a long hydrocarbon There is a long There is a long
composition tail joined onto a benzene ring hydrocarbon tail hydrocarbon chain
which is attached to a attached to an with many oxygen
sulfonate group (or sulfate ammonium ion atoms in the
group) which is negative which is the positively hydrophilic end. At
hence the name anionic charged head. this end, there is the
detergent. alcohol group OH.
Uses Anionic detergents are used in Cationic detergents Non-ionic detergents
laundry detergents, are used in antiseptic are used in low
dishwashing liquids. soaps, mouthwashes foaming applications
hair conditioners and such as laundry
fabric softeners. detergents, automatic
dishwashers and
cosmetics.
Properties Strongly lathering, more Strongly lathering, Weakly lathering-
effective surfactant than soap. binds strongly to important to prevent
negative surfaces of foam clogging of
wet fabric, water jets in
hydrocarbon tails dishwashers, strong
reduce fibre tangling, alkalis present to
excellent for cleaning dissolve the grease.
plastic products, mild
antiseptic properties.

The structure of anionic detergent:

The benzene ring is attached to the sulfonate anionic head.

The structure of cationic detergent:

The structure of non-ionic detergent:


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Point 5.7 Perform a first hand investigation to carry out saponification and test the product.

Aim: To prepare soap using saponification and compare its properties with a commercial soap and
detergent.

Equipment: Chemicals:

Bunsen burner Sodium hydroxide pellets


Tripod + gauze mat + heatproof mat Coconut oil
10mL measuring cylinder NaCl solid
100mL beaker 1molL-1 sodium chloride solution
Electronic balance Distilled water
Stirring rod Commercial soap
6 test tubes Commercial detergent
Test tube rack Food colouring
Paper towel

Safety:

Wear safety goggles to prevent caustic and corrosive sodium hydroxide from entering
eyes and causing irritants + burns.
Continuously stir boiling solution using stirring rod to prevent the occurrence of
explosion or solution spitting vigorously causing burns to skin + eyes.
Method:

1. Obtain about 2-3 spoonfuls of NaOH pellets and add to 100mL beaker.
2. Add 30mL of distilled water into beaker and dissolve the NaOH.
3. Add 4 teaspoons of coconut oil into the beaker.
4. Gently boil solution using Bunsen burner for about 10 minutes, in the process constantly
stirring with stirring rod.
5. Cool solution by leaving aside for a few minutes.
6. Add about 10g of solid NaCl (measured using electronic balance) to the solution and boil
for another couple of minutes.
7. Add a 2-3 drops of food colouring.
8. Decant the liquid layer on top of the curds and wash the remaining solid with NaCl
solution.
9. Tip the solid (soap) onto a paper towel and leave to dry overnight.
10. Repeat experiment 10 times for more reliable results.

PART B

11. Place half of the soap into test tube 1 and the other into test tube 2.
12. Place about the same amount of commercial soap into test tubes 3 and 4.
13. Place about the same amount of detergent into test tubes 5 and 6.
14. Add 3mL of distilled water to the first test tube of each pair and add 3mL of hard water
to the second test tube in the pair.
15. Shake each test tube vigorously and record observations. Note the height and density of
the froth.

Results/observations:

o In distilled water, our soap foamed a bit.


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o In hard water, precipitate formed.
o Commercial soap frothed a lot in distilled water.
o Commercial soap formed precipitate in hard water.
o Detergent frothed a little bit (more than our soap, less than commercial soap) in distilled
water and to a smaller extent in hard water.

Discussion:

Accuracy We used an electronic balance reading to 2dp and used a measuring cylinder.
However accuracy could be further improved by using an electronic balance which reads to more
decimal places (e.g. 3dp).

Reliability Experiment was not reliable as we did not repeat the experiment 10 times in order
to obtain consistent results. Reliability could be further improved by comparing with other
groups.

Validity Experiment was valid as we produced soap from the saponification reaction between
an oil and sodium hydroxide.

Justify:

o Coconut oil was used as it is readily available, cheap and easy to work with in the lab.
o Rinsed soap with NaCl solution in order to remove excess sodium hydroxide and
precipitate out soap.

Conclusion: We prepared a soap using the saponification reaction and tested it against
commercial soap and detergent. We found that our soap didnt foam as much as the other two
because our soap did not contain any added chemicals.

Point 5.8 Gather, process and present information from secondary sources to identify a range
of fats and oils used for soap making.

Tallow

Tallow is a fat obtained as a by product of beef (and sometimes sheep) processing and is the most
common sort of animal fat used in soap manufacture. It is usually obtained from the wastes
discarded in abattoirs.

Coconut Oil

This oil is obtained from the dried fruit of the coconut palm tree. The fruit is dried and the oil is
pressed out of the dried fruit.

Palm kernel oil

This oil is obtained from the nuts of the palm tree and has similar properties to coconut oil.

Palm oil

This oil is derived from the fleshy fruit of the palm trees rather than the nut. Palm oil has longer
chains than palm kernel oil. This gives it properties similar to tallow.

Point 5.9 Perform a first hand investigation to gather information and describe the properties
of a named emulsion and relate these properties to its uses.
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Mayonnaise:
Mayonnaise is an emulsion of vegetable oil and egg yolks, with the emulsifier being the
lecithin found naturally in the egg yolk.
Its a vinegar and oil emulsion where lecithin stabilises the mixture.

Properties in Relation to Uses:


Mayonnaise is a stable emulsion, due to the strong emulsifying properties of lecithin. It
does not separate into its component liquids even when stored for long periods of time.
This property is useful as it is a food product; it needs to stay in an edible condition,
in storage, for relatively long periods of time.
Mayonnaise also has the property of having a creamy feel, and not feeling oily thus
having a pleasant taste.
Because of the emulsifier, mayonnaise can be used in sandwiches as it is easily spread.

Point 5.10 Perform a first hand investigation to demonstrate the effect of soap as an
emulsifier.

Aim: To demonstrate the effect of soap as an emulsifier.

Equipment:

2 x 250mL large conical flasks


Vegetable oil
Distilled water
Commercial soap

Safety: N/A

Method:

1. Obtain a large conical flask


2. Add about 50mL of distilled water to flask.
3. Add about 50mL of vegetable oil to flask, shake and observe what occurs.
4. Obtain second conical flask and add about 50mL distilled water.
5. Add about 50mL of vegetable oil into the flask.
6. Add 4-5 drops of liquid soap/detergent or a few flakes of solid soap.
7. Shake and observe what happens.

Results/observations:

Water + oil emulsion -

Oil

Water

Soap added
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Cloudy
layer

Discussion:

Accuracy Qualitative experiment

Reliability Should have repeated 10 times for more reliable results.

Validity Valid as we tested aim and observed soaps effect as an emulsifier.

Conclusion:

When soap was added to the water + oil emulsion, a cloudy layer was observed between the
water and oil layers. We also observed tiny oil droplets suspended in the soapy water thus
demonstrating soaps effectiveness as an emulsifier.

Point 5.11 Solve problems and use available evidence to discuss, using examples, the
environmental impacts of the use of soaps and detergents.

Soaps have little impact on the environment because they are made from natural organic
products which are easily broken down by bacteria thus they are biodegradable. They are broken
down into simpler substances such as water and carbon dioxide.

However detergents have significant impacts on the environment. Earlier detergents contained
branched hydrocarbon chains thus it was harder for bacteria to break down resulting in less
biodegradability. When these detergents entered waterways, they caused excessive foaming
resulting in aesthetical and environmental problems. To fix this problem of excess foaming and
depletion in biodegradability, the structure of detergents have changed with new detergents
having linear chains which are much more easily broken down by bacteria thus increasing its
biodegradability. However the disadvantage with these new detergents is that they contain
phosphate builders (e.g. sodium tripolyphosphate Na5P3O10). These builders are added to
enhance the cleaning power of the detergent by increasing the alkalinity and to help soften the
water. However when these detergents are disposed in waterways, there are high levels of
phosphates present. Phosphates are nutrients for vegetation but it high levels in waterways leads
to excessive growth of algae.

This is a huge problem as the algae form a layer on the top of the water, thereby starving the
plants and organisms below essential sunlight. They also use up oxygen in the water and hence
there are depleting levels of oxygen in the water, affecting plants and aquatic organisms such as
fish, crab. When this algae die, they use up more oxygen in the water as they decompose. Thus
eutrophication occurs as a result from the release of these detergents from households and
industries.

To combat the problem of eutrophication caused by these detergents, phosphate builders are
gradually being replaced with chemicals known as zeolites - complex compounds of aluminium,
silicon and oxygen. Zeolites are effective as they soften water and reduce occurrences of
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eutrophication. When added as sodium zeolates in detergent, it replaces calcium ions in the water
but the disadvantage is that they are not as effective in removing magnesium ions. Thus to obtain
optimal water softening, a co-builder (usually a polycarboxylate) is used.

6. The Solvay process has been in use since the 1860s.

Point 6.1 Identify the raw materials used in the Solvay process and name the products.

The Solvay process is an industrial method of producing sodium carbonate from salt solution. The
overall reaction in the Solvay process is shown below:

CaCO3 (s) + 2NaCl (aq) Na2CO3 (s) + CaCl2 (aq)

Thus the raw materials in the Solvay process are the following:

Purified brine (concentrated sodium chloride solution)


Limestone (calcium carbonate)

The products of the process are:

Sodium carbonate
Calcium carbonate

Point 6.2 Describe the uses of sodium carbonate.

Sodium carbonate (Na2CO3) is a white powder and is soluble in water. It is a very important
chemical in industry because of its many useful applications. Some of these are described below:

Manufacture of glass

This is the major use of sodium carbonate. It is heated with silica (sand) and calcium
carbonate to over 1500C where sodium and calcium carbonates decompose into their
oxides. These oxides combine with silica to form silicates which is found in glass.

Softening hard water

Hard water consists of excessive amounts of calcium and magnesium ions. This is a huge
problem when soap is in water as the anion in soap reacts with these ions to produce
unwanted grey precipitates scum. Thus sodium carbonate can be added to the soap to
precipitate out the calcium and magnesium ions, which enhances soaps cleaning ability.

Standard base in volumetric analysis

Pure, anhydrous sodium carbonate is often used as a primary standard in volumetric


analysis e.g. in titrations where it can be used to determine the concentration of an acidic
solution.

Soap manufacture

Sodium carbonate is often reacted with calcium hydroxide to produce sodium hydroxide
which is used to produce soap. Using sodium carbonate is a cheap and efficient process.

Manufacture of sodium hydrogen carbonate


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Sodium carbonate can be reacted with carbon dioxide to produce sodium hydrogen
carbonate (NaHCO3) which is used as baking soda, in chemical spills and in fire
extinguishers.

Point 6.3 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.

Using the diagram above, there are 4 major steps in the Solvay process. Each step is analysed below:

STEP 1: Brine purification + addition of ammonia

Brine is concentrated sodium chloride solution and is mostly found in the oceans salt water.
Brine contains many impurities which are undesirable in the Solvay process. These may include
calcium and magnesium ions. To remove these impurities there are two methods:

Precipitating out the ions by reacting it with either sodium carbonate or sodium
hydroxide.

Ca2+ (aq) + CO32- CaCO3 (s)

Mg2+ (aq) + 2OH- (aq) Mg(OH)2 (s)

Fractional crystallisation where the more soluble contaminants are crystallised out
from the brine solution.

Now this purified brine is entered into a vessel called an ammonia saturator. Here the brine
flows down over many partitions in the ammonia saturator and ammonia (mainly from the
Haber process), is passed up the tower thus dissolving in the brine. The solution is cooled by ice-
cooled water and the result is the formation of ammoniated brine.

STEP 2: Production of sodium hydrogen carbonate

This ammoniated brine is passed into the Solvay tower (also called the carbonator). Here there
is a reaction between the ammoniated brine (consisting of ammonia, water and sodium
chloride) with carbon dioxide which is bubbled through. This carbon dioxide comes from the
decomposition by heat of limestone (calcium carbonate) in a furnace:
Industrial Chemistry (Part 2)

CaCO3 (s) CaO (s) + CO2 (g)


HEAT

The carbon dioxide reacts with water to produce weak carbonic acid which in turn neutralises
ammonia to form ammonium and hydrogen carbonate ions. These hydrogen carbonate ions
react with sodium ions (from the salt) to produce sodium hydrogen carbonate (NaHCO 3).
The reaction mixture is cooled to about 0C which allows the aqueous sodium hydrogen
carbonate to crystallise out leaving ammonium chloride in solution. The overall reaction for this
step is:

NH3 (g) + NaCl (aq) + H2O (l) + CO2 (g) NH4Cl (aq) + NaHCO3 (s)

STEP 3: Formation of sodium carbonate

The solution in the previous step is filtered leaving the filtrate of ammonium chloride. The solid
sodium hydrogen carbonate is collected and heated in a furnace to about 300C. This results in
the formation of sodium carbonate, water and carbon dioxide. The carbon dioxide is recycled and
reused as it is entered into the Solvay tower for the production of NaHCO 3.

2NaHCO3 (s) Na2CO3 (s) + CO2 (g) + H2O (l)


HEAT

STEP 4: Recovery of ammonia

The calcium oxide (lime) which was produced in step 2, is reacted with water to form calcium
hydroxide (slaked lime). This is shown in the equation below:

CaO (s) + H2O (l) Ca(OH)2 (s)

Now refer back to the ammonium chloride filtrate which was also produced in step 2. This is
reacted with the calcium hydroxide to regenerate ammonia:

Ca(OH)2 (s) + 2NH4Cl (aq) CaCl2 (aq) + 2NH3 (g) + 2H2O (l)

This ammonia which is produced from the above reaction is entered into the ammonia saturator
where it dissolves in the brine to once more produce ammoniated brine. The cycle continues

Point 6.4 Discuss environmental issues associated with the Solvay process and explain how
these issues are addressed.

The following are the major environmental concerns associated with the Solvay process:

Disposal of calcium chloride

Calcium chloride is a waste product in the Solvay process and its produced in large
amounts. In some cases, the Solvay plant would sell this waste calcium chloride to
industries where it would be used as a concrete additive, drying agent or to melt ice on the
roads. However the major problem is that the supply of calcium chloride heavily outstrips
the demand for it. As a result, the Solvay plant is forced to dispose of it at nearby landfills
or waterways.

However this increases the level of dissolved salts in waterways, resulting in significant
impacts for the local ecosystems. The aquatic plants and organisms may not be able to
cope with this rise in chloride ion concentration. It causes destruction of vegetation in the
area and also erosion. As a result, Solvay plants have addressed this issue by evaporation
Industrial Chemistry (Part 2)
to dryness of the waste (more expensive method) and disposal in specially designed burial
sites.

Heat release/thermal pollution

Overall, the Solvay process is an exothermic reaction thus excessive amounts of heat are
released into the atmosphere and waterways. This can cause thermal pollution and
significant impacts on organisms especially in waterways. Thermal pollution arises from a
significant temperature rise (of about 5-10C). This temperature change can cause the
destruction of fish eggs and broadly the deaths of aquatic organisms such as frogs and crab
+ fall in levels of dissolved oxygen. In order to reduce this problem, the Solvay plants dilute
their waste water, water from nearby lakes and rivers are added to cool the wastes or
expensive heat diffusers are used.

Mining

The raw materials for the Solvay process are limestone (calcium carbonate) and brine. In
order to obtain these materials, mining needs to be undertaken. This could have
environmental implications such as the destroying of natural habitats and pollution. To
combat this problem, Solvay plants are looking for other sources for these raw materials
e.g. brine from the ocean.

Ammonia loss

Although ammonia in the Solvay process is recycled and reused, there are still noticeable
amounts of ammonia released into the atmosphere. This is a problem as ammonia is a
toxic gas which when inhaled can cause respiratory problems such as asthma and
bronchitis. Thus to reduce this problem, Solvay plants implement good design and careful
monitoring.
Dust

Dust is a problem for people in the vicinity of the Solvay plant and can cause allergies and
respiratory problems such as asthma and bronchitis. This is being addressed by improving
truck loading facilities and upgrading dust suppression systems in the plant.

Point 6.5 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.

We modelled the production of sodium hydrogen carbonate. We obtained a solution of


ammoniated brine, dry ice (source of carbon dioxide) and a conical flask.

Method:

I. Obtained a 500mL conical flask.


II. Add 200mL of ammoniated brine to the conical flask.
III. Add 2 spoonfuls of dry ice into the flask and quickly close the fume cupboard.
IV. Repeat experiment.

Safety:

o Wear safety goggles to prevent poisonous aqueous ammonia from entering into eyes
causing burns + irritants.
o Conduct experiment in a fume cupboard to prevent toxic ammonia gas from being released
into the atmosphere. Ammonia is extremely discomforting to the upper respiratory tract +
lungs and high exposure can cause unconsciousness, narcosis and may lead to death.
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Difficulties:

Oversimplifies process.
Some NaHCO3 crystals formed on the side of the flask.
Only a very small amount of crystals formed.
Small sample.
Conducted in fume cupboard thus it was hard to see reaction.

Justify:

Dry ice was used as it was a source of carbon dioxide as well as allowing the contents in
flask to cool enabling NaHCO3 crystals to form. Dry ice extremely cold at room
temperature.

Reaction:

NH3 (aq) + NaCl (aq) + H2O (l) + CO2 (g) NaHCO3 (s) + NH4Cl (aq)

Point 6.6 Process information to solve problems and quantitatively analyse the relative
quantities of reactants and products in each step of the process.

PROBLEM 1: Find the masses of limestone and brine needed to produce 1 tonne (1000kg) of
sodium carbonate?

STEP 1: WRITE EQUATION

CaCO3 (s) + 2NaCl (aq) Na2CO3 (s) + CaCl2 (aq)

STEP 2: FIND THE NUMBER OF MOLES OF SODIUM CARBONATE

Number of moles = mass (in grams) / molar mass

= (1000000) / 105.99

= 9435 moles

Looking at the mole to mole ratio, NaCl: Na2CO3 = 2:1


Therefore there are 18870 moles of NaCl.

STEP 3: FIND THE MASS

Using the equation n = m/M, the mass of NaCl = 1103 kg (or 1.1 tonnes).

Now using the mole to mole ratio again, we can see that CaCO 3: Na2CO3 is 1:1, therefore there are
9435 moles of limestone.

Therefore the mass of limestone (calcium carbonate) needed = 944 kg (or 0.94 tonnes).

PROBLEM 2: During the preparation of calcium oxide, 1000kg of limestone (calcium carbonate)
is heated. What mass of calcium oxide is produced and calculate the volume of carbon dioxide
produced if the molar volume = 24.5L?

STEP 1: WRITE EQUATION


Industrial Chemistry (Part 2)

CaCO3 (s) CaO (s) + CO2 (g)


HEAT

STEP 2: FIND THE NUMBER OF MOLES OF CALCIUM CARBONATE

The number of moles of calcium carbonate = (1000000) / 100.09 = 9991 moles.

Using the mole to mole ratio, CaCO3: CaO is 1:1 therefore it also has 9991 moles.

STEP 3: FIND THE MASS

The mass of calcium oxide = (9991) x (56.08) = 560kg.

Using the mole to mole ratio again, we can see that there is a 1:1 ratio between calcium
carbonate and carbon dioxide. Therefore there are 9991 moles of carbon dioxide.

Using the equation n = V/Vm, the volume of carbon dioxide produced = 245L.

Point 6.7 Use available evidence to determine the criteria used to locate a chemical industry
using the Solvay process as an example.

The main factors for locating a chemical industry are the following:

Location of raw materials

An industry needs to be located in close proximity to raw materials in order to reduce


transportation costs. The Solvay plant in New York is located near deep brine springs (easy
access to brine) and nearby limestone quarries (to easily mine calcium carbonate).

Disposal of wastes

An industry needs to locate to a place where the disposal of wastes will not have significant
impacts on humans or natural environment. The Solvay plant in Adelaide is located on the
outskirts of Adelaide where the major waste calcium chloride is dumped in designated
landfill areas. This is an important consideration in the Solvay process.

Close proximity to markets

A chemical industry needs to be relatively close to their target markets in order to gain
profits, otherwise they may resort to transport their products to areas long distances away;
thus increasing transportation costs. The Solvay plant at Adelaide is located close enough
to the city and other urban areas to sufficiently provide sodium carbonate to their market.

Availability of a workforce at a suitable cost

This is an obvious major factor as the plant needs workers to operate them at a daily basis.

A note of thanks to:

- Dot point Chemistry


- Spotlight Chemistry
- Conquering chemistry
- HSC Online
Industrial Chemistry (Part 2)

- Chemistry contexts 2
- Macquarie revision guides: Chemistry
- Ahmad Shah Idil