HSC CHEMISTRY MODULE THREE

Chemical Monitoring
and Management
The chemical industry
The Haber process
Monitoring ions
Atmospheric chemistry
Monitoring water quality

AC electric motors

Roy Fu

The chemical industry

Outline the role of a
chemist employed in
a named industry or
enterprise, identifying
the branch of
chemistry undertaken
by the chemist and
explaining a chemical
principle that the
chemist uses. (1.1.1)
Gather, process and
present information
from secondary
sources about the
work of practising
scientists identifying:
- the variety of
-----chemical
=----------occupations
- a specific chemical --occupation for a ------more detailed study
(1.2.1)

There are many different branches of chemistry including:

Analytical chemistry; the determination of what substances are in a sample
and how much of each is present.
Physical chemistry; the study and measurement of physical aspects of
compounds and reactions such as rates of reaction/kinetics and the
structure and bonding in compounds.
Environmental chemistry; the study of how substances interact in the
environment and the monitoring of pollutants in air, water and soil.
Polymer chemistry; the development of new polymers, working out how
polymerisation occurs and how to make it more efficient and studying the
properties of polymers.
Nuclear chemistry; the production and uses of radioisotopes for medicine
and industry and the study of the fundamental nature of nuclear reactions.

Luke (not his real name) is an analytical chemist at Qenos, an Australian chemical
manufacturing company in Botany Bay.
This company makes ethylene by the thermal cracking of ethane and then
polymerises it to form polyethylene. It also sells some ethylene to other companies
that make ethylene oxide, ethylene glycol, non-ionic surfactants and other plastics.
Luke has many roles as an analytical chemist. He must:
Monitor the quality of ethylene and polyethylene products, particularly
checking the nature and amount of any impurities present.
Monitor waste water and gaseous emissions to ensure environmental
standards are met.
Collaborate with process engineers at the cracking furnace to adjust
operating conditions for yield optimisation.
Ensure instruments are calibrated and are operating properly.

Gas-Liquid chromatography (GLC) is a chemical principle used by Luke in his

analysis. This technique involves a gas mobile phase being vaporised into a stream
of He carrier gas that flows over a liquid stationary phase coated onto the GLC
column.

The gaseous components will dissolve in the stationary phase and then evaporate
back out of it at differing rates. The solubility of the gas will depend on its polarity
relative to the stationary liquid.
More soluble components will have longer retention times through the column as
they move through the column more slowly.
A separation is achieved and a detector measures the amount of each component
as it emerges from the GLC column. A graph or chromatogram is produced which
can be analysed.

Identify the need for

collaboration
between chemists as
they collect and
analyse data. (1.1.2)

The height of the peak and the area under the peak/integral provides a measure for
the relative proportions of each component.

Since chemistry is such a board discipline, chemists will specialise in particular

branches of chemistry. However, many chemical problems in the real world require
expertise from many branches of chemistry and science.
Solving complex problems will require chemists with different specialities and thus
it is essential that chemists collaborate and communicate with each other.
For example, environmental chemists may collaborate with analytical chemists to
monitor pollutant levels and if there are excessive levels, they may collaborate to
deduce a possible source of the contamination such as an industrial plant. They may
then collaborate with industrial chemists to reduce these excessive emissions.

Describe an example
of a chemical reaction
such as combustion,
where reactants form
different products
under different
conditions and thus
would need
monitoring. (1.1.3)

Combustion reactions produce different products under different conditions.

In a plentiful supply of oxygen, complete combustion occurs which produces carbon
dioxide and water only.

If there is insufficient oxygen, incomplete combustion will occur which produces

any combination of water, carbon monoxide and soot.

Carbon monoxide is a toxic gas even at low ppm concentrations as it

combines preferentially with haemoglobins in the red blood cells 200
times better than oxygen. This reduces the efficiency of the red blood cells
ability to carry oxygen, leading to suffocation.
Soot is carcinogenic; it may cause cancer.
Because of the toxic nature of these 2 products, combustion reactions must be
monitored to ensure that there is an ideal air : fuel ratio so that the production of
these substances is avoided.
Combustion can also release acidic oxides such as sulfur dioxide, unburnt
hydrocarbons, particulates and lead. The emission of these substances must also be
monitored for environmental and health reasons.
Finally, since incomplete combustion releases less energy than complete
combustion, it is necessary to monitor combustion reactions to ensure that the
maximum energy output from the reaction is achieved.

The Haber process

Identify and describe
the industrial uses of
ammonia. (2.1.1)

Ammonia is used to make:

Fertilisers in the form of ammonium nitrate or ammonium sulfate as a
source of nitrogen for plants.
Nitric acid from the Ostwald process which is used for explosives such as
TNT, synthetic dyes, fibres and plastics.
Sodium carbonate from the Solvay process which is used to make glass.
Household cleaners and detergents

Identify that ammonia

can be synthesised
from its component
gases, nitrogen and
hydrogen. (2.1.2)

Ammonia can be produced in an exothermic equilibrium reaction:

At ordinary temperatures and pressures, this equilibrium lies well to the left.

When the temperature is increased, Le Chateliers principle predicts that the

equilibrium will shift left towards the heating absorbing endothermic reaction in an
attempt to decrease the temperature. Thus, the yield of ammonia is reduced.

The collision theory predicts that the rate of a reaction depends on the frequency
of successful collisions between reactant particles. Successful collisions involve
the reactants particles colliding with enough KE to overcome activation energy so
that products can be formed.
Higher temperatures results in an increase in the average KE of the reactant
particles. This in turn leads to an increased reaction rate as the frequency of
collisions will increase and the proportion of reactant particles colliding with
will also increase.

Describe that
synthesis of ammonia
occurs as a reversible
reaction that will
reach equilibrium.
(2.1.3)
Identify the reaction
of hydrogen with
nitrogen as
exothermic. (2.1.4)
Explain why the yield
of product in the
Haber process is
reduced at higher
temperatures using Le
Chateliers principle.
(2.1.6)
Explain why the rate
of reaction is
increased by higher
temperatures. (2.1.5)

Explain that the use of

a catalyst will lower
the reaction
temperature required
and identify the
catalyst(s) used in the
Haber process. (2.1.8)

A catalyst increases the rate of reaction by providing an alternative reaction

pathway with lower , sometimes via the formation of an intermediate.

By increasing the rate of reaction with a catalyst, lower temperatures can be used
in the Haber process.
The catalyst used in the Haber process is powdered magnetite (
fused
with
,
and
.

Analyse the impact of

increased pressure on
the system involved in
the Haber process.
(2.1.9)

When the pressure on the system is increased, Le Chateliers principle predicts that
the equilibrium will shift right to produce less moles of gas in an attempt to
decrease gas pressure. Thus, the yield of ammonia increases.
Higher pressures also results in an increased reaction rate since the number of
reactant particles per unit volume will increase, allowing for more successful
collisions to occur between reactant particles.
Thus, high pressures favour both yield and reaction rate in the Haber process.

Explain why the Haber

process is based on a
delicate balancing act
involving reaction
energy, reaction rate
and equilibrium.
(2.1.7)

Explain why
monitoring of the
reaction vessel used
in the Haber process
is crucial and discuss
the monitoring
required. (2.1.10)
Gather and process
information from
secondary sources to
describe the
conditions under
which Haber
developed the
industrial synthesis of
ammonia and
evaluate its
significance at that
time in world history.
(2.2.1)

Compromise conditions are used in the Haber process in order to achieve a high
yield of ammonia relatively quickly at a reasonable cost. Most of these conditions
can be predicted using Le Chateliers principle and the collision theory:
Moderate temperatures (450 C) is used to give moderate yields
moderately quickly. If temperatures are too high, there will be a fast
reaction rate BUT the yield of ammonia will be compromised and the
catalyst may get damaged. Conversely, if temperatures are too low, there
will be a high yield BUT the rate of reaction will be too slow.
High pressures (25 MPa) are used to improve yield and kinetics. Even
though it is preferable to have pressure to be as high as possible, this is not
done due to economic and safety considerations.
A powdered magnetite catalyst fused with
,
and
is used to
increase the rate of reaction. Sulfur compounds,
and
may poison
the catalyst so it is essential to ensure the input gases are not contaminated
with these compounds. It is also important to monitor the particle size of
the catalyst to ensure it has a high SA so that it can make contact with the
reactants.
A 3:1 stoichiometric ratio of
is used so that left-over reactants can
be recycled without the build up of one reactant over another. This
maximises the efficiency of the process.
Ammonia product is liquefied under pressure upon formation to drive the
equilibrium towards the right to increase the yield of ammonia.
Heat released by the reaction is recycled by using it to heat up any
incoming reactants to minimise energy costs. This also prevents the catalyst
from overheating and losing activity.
Eventually, about 98% of the reactants are converted into ammonia with these
conditions.

Chemical engineers need to perform a vast range of monitoring activities to ensure

quality control. The temperature, pressure, supply of nitrogen and hydrogen,
removal of ammonia, heat exchange and activity of the catalyst must be monitored
to ensure the plant is functioning efficiently and safely.

The Haber process was first developed by Fritz Haber in 1905. Using lower
temperatures, high pressure and an osmium catalyst, Haber was able to produce
100 g of ammonia. Carl Bosch later scaled the process up to industrial levels.
The Haber process was extremely significant during this time.
The rising world population has caused an increase in demand for nitrogen
based fertilisers to increase agricultural crop yields but there was a limited
and dwindling supply of natural fertilisers such Chilean saltpetre and guano.

With the Haber process, synthetic fertilisers could be readily produced and
this allowed for sufficient food production to sustain the growing
population.
Early in WW1, the Allied naval blockaded the Atlantic sea routes from Chile
and this prevented Germany from importing Chilean saltpetre for use in
agriculture and in the manufacture of explosives and gunpowder.
Consequently, the Haber process allowed synthetic fertilisers to be
produced to grow the crops needed to sustain the German population
during WW1. Furthermore, the Haber process paved the way for efficient
nitric acid production which allowed Germany to manufacture explosives
for its war effort. Indeed, the Haber process may have prolonged WW1,
resulting in more deaths.

Monitoring ions
Deduce the ions
present in a sample
from the results of
tests. (3.1.1)

Perform a first-hand
investigation to carry
out a range of tests,
including flame tests
to identify the
following ions:
- phosphate
- sulfate
- carbonate
- chloride
- barium
- calcium
- lead
- copper
- iron
(3.2.1)

There are 3 qualitative tests that can be done to identify ions; colour of solution,
flame tests and precipitation tests. These tests can only identify the species present
in a sample.
Colour of solution
The colour of solution can be used to quickly make a reasonable guess on which
ions are present.
Ion

,
-

Colour of solution

Blue
Pale green (may be colourless if dilute)
Yellow brown (nearly colourless if dilute)
Colourless

This test is generally not very reliable because many salt solutions are colourless.
Flame Tests
Some cations produce distinctive colours when their salts are volatilised in a blue
Bunsen flame. This flame test can be used to identify the presence of certain
cations.
Ion

Flame colour
Blue green
Brick red
Apple green
Yellow
Light purple

The following method can be used to perform a flame test:

1. Clean a Pt wire by dipping it in
HCl and heating it with a Bunsen flame.
2. Repeat step 1 until no colour comes from the wire. This must be done to
remove any
which produces an intense yellow flame colour that may mask
other colours.
3. Dip the Pt wire into the sample.
4. Place it into the Bunsen flame and observe the colour of the flame.

Advantages of the flame test includes:

Quick and cheap to do.
Helps confirm precipitation test.

Disadvantages:
Only gives qualitative information.
Can only be used to identify certain cations and is completely useless on
anions.
Cannot distinguish between ions of the same element (eg.
and
).
Not suitable for assessing solutions with more than 1 cation as the
contamination will make it difficult to identify individual cations.
Cannot be used to identify toxic heavy metals like lead due to safety issues.

The reason why cations produce characteristic flame colours lies in the electron
shell structure of an atom. When a sample is vaporised in a flame, the outershell
electrons of the cation may absorb a quantum of energy and are excited to
higher energy levels. Excited electrons are unstable and they release energy as light
with a particular frequency when they return to the ground state. Atoms of each
element have different energy levels and the frequency of the light emitted by an
element is given by with

Precipitation tests
Precipitation tests can be used to identify the ions in a solution. These tests revolve
around the formation of distinctively coloured precipitates or metal complexes.
The solubility rules are required here.
Insoluble

,
,
-

If the unknown solution contains more than 1 cation/anion, we must prevent the
ions from cross reacting; for example, both
give a white precipitate
with
. Once an ion forms a precipitate and is identified, it must be removed
by precipitating it to excess and then filtering it out to ensure it will not interfere
with subsequent tests. Further tests are then performed on the filtrate.
Cations
To identify the cations present in a solution, the following sequence may be
followed:

Further confirmatory tests can also be used:

will form a canary yellow precipitate with

solution

decolourises acidified potassium permanganate (

)
forms a blood red complex ion with potassium thiocyanate (

Anions
To identify anions in a solution, the following sequence may be used:

Note: While
can precipitate with either
with
under acidic conditions.

or

, it will not precipitate

Further tests can also be used here:

A solution with
will have pH > 7.
If effervescence of gas does occur after the first step, whether or not the
gas is
can be confirmed with limewater.
turns limewater from
colourless to milky due to the formation of a precipitate.

Gather, process and

present information
to describe and
explain evidence for
the need to monitor
levels of one of the
above ions in
substances used in
society. (3.2.2)

Advantages of precipitation tests:

Can identify both cations and anions.
More reliable than simple flame tests.

Disadvantages:
Only gives qualitative information.
Very time consuming and cumbersome.
Need to have appropriate reagents available.

Lead is a toxic heavy metal that can cause a vast range of adverse health effects if
exposed to it:
The effects of acute lead poisoning includes: muscle weakness, loss of
appetite, abdominal pain, nausea and constipation.
Chronic lead poisoning may lead to anaemia, kidney disease, impaired
memory and concentration peripheral neuropathy.
In children, it may also cause retarded intellectual development and
behavioural problems.
Because of these health effects, it is essential to monitor the levels of Pb in
substances used in society to ensure that people are not exposed to harmful
concentrations of Pb.
The main exposures to Pb includes:
Lead-based paints in older homes.
Soil and water that has been contaminated by old leaded petrol.
Smelting of lead ores.
According to the NHMRC, the recommended blood lead levels is less than 0.1 ppm
and drinking water should have less than 0.01 ppm of Pb.

Identify data, plan,

select equipment and
perform first-hand
investigations to
measure the sulfate
content of lawn
fertiliser and explain
the chemistry
involved. (3.2.3)
Analyse information
to evaluate the
reliability of the
results of the above
investigation and to
propose solutions to
problems
encountered in the
procedure. (3.2.4)

Acidified
forms a canary yellow precipitate with ammonium
molybdate.
precipitate dissolves in excess
to form a colourless complex ion.

Determining amounts of concentrations of specific substances in a sample is called

quantitative analysis.
Gravimetric analysis is a form of quantitative analysis which involves the weighing
of materials and determining the percentage composition (by mass) of elements in
compounds or components of a mixture.
In the context of ions, gravimetric analysis is basically a quantitative extension of
precipitation tests.
FHI Sulfate content in a fertiliser
Aim: To determine the sulfate content of a fertiliser by gravimetric analysis.
Safety Issues:
is a toxic solution and HCl is highly corrosive.
Method:
1. Accurately weigh out 0.60 g of powdered fertiliser into a beaker.
2. Pour distilled water into the beaker and stir until the fertiliser is dissolved.
3. Add 10 drops of concentrated
.
4. Heat the mixture with a hotplate until it just boils.
5. Slowly add excess
dropwise into the beaker. Stir with a glass rod after
each addition and note any cloud formation as
strikes the solution.
6. Gently re-boil the mixture for 5 minutes to coagulate the precipitate.

7. Allow the mixture to cool.

8. Weigh some dry filter paper and record the mass obtained.
9. Set up a filtration apparatus and filter off the precipitate. Alternatively, a
sintered glass crucible may be used.

10. Ensure all the precipitate is transferred by rinsing the beaker with water.
11. Rinse the precipitate with distilled water and ethanol.
12. Dry the precipitate in a drying oven until constant mass is attained and then
weigh it.

Results:
Fertiliser
Mass (g)

Analysis:
The precipitation reaction that occurs is represented by:

Describe the use of

atomic absorption
spectroscopy (AAS) in
detecting
concentrations of
metal ions in
solutions and assess
its impact on scientific
understanding of the
effects of trace

0.5010

Glass sintered crucible Glass sintered crucible

with dried precipitate
20.2052
20.7351

Discussion:
If the method was followed carefully, both accurate and valid results should be
obtained. To assess the reliability of the results, the method should be repeated
several times to see if consistent results are obtained.

Problems and solutions:

Underestimation of sulfate content:

can form as very small particles that can pass through the filter. To
overcome this problem, the precipitate was formed slowly in a hot solution
which causes the particles to be large. The particle size was then further
increased by digesting the mixture. Finally, the solution was cooled
before the filtration step to increase the insolubility of the precipitate.
Some
may be lost by dissolution if the volume of wash water is too
great.

can also be lost via spillage when transferring from beaker to funnel.

Overestimation of sulfate content:

may be contaminated with adsorbed impurities due to the large SA

of the small particles. HCl is added initially to prevent any
and/or
from precipitating with
. Also, the precipitate is rinsed with
distilled water after filtration to remove any excess
impurities.
The
precipitate may not have completely dried so it may still contain
water when it is weighed. To prevent this error, the precipitate was dried to
a constant mass in a drying oven.

Conclusion: The percentage by mass of sulfate in a fertiliser was found to be

43.54%.

Atomic absorption spectroscopy (AAS) is a very sensitive instrumental technique

that can measure the concentration of ions in a sample.
The key principle of AAS is that each element only absorbs and emits specific
wavelengths of light.
The sample that is being analysed is vaporised in flames to convert molecules,
compounds and ions into atoms. A hollow cathode ray lamp is then used to emit
specific wavelengths of light that are known to be absorbed by the element being
measured. The lamp uses the element itself as the cathode to produce a set of
unique emission wavelengths. As the sample absorbs the specific wavelengths of
light emitted by the lamp, the light intensity will drop. A filter selects 1 wavelength

elements. (3.1.2)

of light to analyse and the intensity of the light detected is measured with and
without the sample in the flame. This ratio is used to calculate absorbance.

Gather, process and

present information
to interpret
secondary data from
AAS measurements
and evaluate the
effectiveness of this
in pollution control.
(3.2.5)

Absorbance is directly proportional to the concentration of the metal ion in the

sample.

To obtain the concentration of the metal ion, a calibration curve is constructed

using a series of standard solutions.
(ppm)
Absorbance
(dimensionless)

1
5
10
25
50
0.0065 0.0275 0.0555 0.1395 0.2790

The concentration of the metal ion can then be determined by interpolation from
the calibration curve.
It is also possible to extrapolate the graph to obtain a concentration but this may
result in an invalid concentration since it assumes that the graph will continue to
have the same trend. It is more preferable to simply use a wider range of standard
solutions so interpolation can be done.

AAS can be used to monitor toxic heavy metal pollution in soil and water. AAS is
extremely effective here since toxic heavy metals such as Pb, Hg and Cd are often
present at only minute levels. This helps to ensure public health as it prevents
poisonings (eg. the Minamata disease which occurred due to the release of Hg in
industrial wastewater that accumulated in seafood).
AAS can also be used to monitor essential trace elements.
Trace elements are elements that are required by living organisms in very small
amounts (typically 1-100 ppm). Any deficiencies may lead to diseases. Common
trace elements in humans include Fe for haemoglobin production and function, Co
for DNA synthesis, Zn for enzyme functions and DNA binding proteins and I for
thyroid hormone production.
Older analytical techniques such as gravimetric analysis and volumetric analysis
were not sensitive enough to measure the concentration of trace elements. In fact,
before AAS was invented, deficiency diseases could not be explained. For example,
people suffering from iron deficiency anaemia had symptoms including fatigue, hair
loss and dizziness but these symptoms could not be explained. Since AAS is much
more sensitive and specific compared to these older analytical techniques, it has
greatly developed the scientific understanding of trace elements in living
organisms:
It has helped to identify trace elements and elucidate their biological roles.
Any deficiencies can be detected in blood or urine and then rectified.
AAS has also improved agricultural productivity as it can be used to identify
soils and pastures that lack micronutrients such as Mn, B and Mo. Trace
elements can then be included in fertilisers to improve crop growth and
animal health.
While AAS has the advantage of being very accurate and sensitive, there are some
limitations:
The AAS machine is expensive and lacks portability which is required for
field testing.
Different lamps are required for each element so the cations of interest
must be known.
Generally cannot be used to analyse anions.
Cannot differentiate between ions of the same element (eg.
and
).

Atmospheric chemistry
Describe the
composition and
layered structure of
the atmosphere.
(4.1.1)

The atmosphere is the thin layer of gases that surrounds the Earth.
The composition of the atmosphere is essentially constant at all altitudes:
Gas
Nitrogen
Oxygen
Argon
Carbon dioxide

Identify the main

pollutants found in
the lower atmosphere
and their sources.
(4.1.2)

The atmosphere consists of 5 layers. From Earths surface outwards, these are the
troposphere, stratosphere, mesosphere, thermosphere and exosphere.

The boundaries between each layer are marked by changes in the temperature
gradient.
The troposphere is the region of the atmosphere closest to Earth in which
temperature decreases as altitude increases. It extends from sea level to an altitude
of about 15 km. In the troposphere, gases are well mixed due to convection
currents and this gives rise to weather.
The stratosphere extends from an altitude of about 15-50 km and here,
temperature increases as the altitude increases. In the stratosphere, there is limited
vertical mixing of gases so it is very dry and very stable. It contains the ozone layer
which is most concentrated at an altitude of around 25 km. Gas diffusion into and
out of the stratosphere via the tropopause is very slow.
The thermosphere and the mesosphere are the 2 outer layers of the atmosphere
and they have very low gas pressures. They both contain the ionosphere where
many atoms and molecules are ionised into gaseous ions.
Pollutant
Carbon monoxide

Volatile organic
compounds
Ozone
d

Concentration (%v/v)
78.1
20.9
0.93
0.037

Sources
Incomplete combustion in motor vehicles, bushfires
and cigarettes.
Unburnt fuels from vehicles, industry.

Formed as part of photochemical smog.

Describe ozone as a
molecule able to act
both as an upper
atmosphere UV
radiation shield and a
lower atmosphere
pollutant. (4.1.3)

Describe the
formation of a
coordinate covalent
bond. (4.1.4)

Demonstrate the
formation of
coordinate covalent
bonds using Lewis
electron dot
structures. (4.1.5)

Compare the
properties of the
oxygen allotropes
and
and
account for them on
the basis of molecular
structure and
bonding. (4.1.6)

In the troposphere, ozone is a pollutant. Ozone is very toxic at concentrations

greater than 20 ppm. It is a very powerful oxidising agent and thus can disrupt
biochemical reactions in the body by attaching oxygen free radicals to unsaturated
biological molecules. It causes eye irritation, breathing difficulties, headaches and
premature fatigue. Ozone is also poisonous to plants and readily attacks plastics
and rubber, causing them to deteriorate.
In the stratosphere however, ozone is protective as it acts as a radiation shield that
prevents damaging short wavelength UV radiation from reaching Earths surface.
A coordinate covalent bond is a covalent bond in which both of the shared
electrons came from the same atom. Once formed, a coordinate covalent bond is
identical to a normal covalent bond.
When a coordinate covalent bond is formed, there is a partial transfer of charge
from one atom to another.
A covalent bond symbol with an arrow tip ( ) can be used to designate a
coordinate covalent bond.

The formation of a coordinate covalent bond can be demonstrated with Lewis dot
diagrams:

Ozone contains a coordinate covalent bond and there are 2 possible Lewis
structures for it:

The 2 bonds in ozone are actually identical. The actual structure of ozone is a hybrid
of the resonance structures above:

Allotropes are different structural forms of an element in the same state.

Oxygen exists in 2 allotropic forms;
(diatomic oxygen) which is an odourless and
colourless gas and
(ozone) which is a pale blue gas with a sharp odour.
Ozone has a bent shape and contains dipoles due to its coordinate covalent bond;
it is a polar molecule. On the other hand, diatomic oxygen is linear and does not
contain dipoles so it is a non-polar molecule. Thus, ozone contains dipole-dipole
attractions whereas diatomic oxygen only contains weak dispersion forces. This
results in diatomic oxygen and ozone having different physical properties; ozone
has a much higher MP/BP and is much more soluble in water than diatomic
oxygen. Also, ozone is denser than oxygen because it is 1.5x heavier than oxygen.

The double bond in diatomic oxygen has a high bond energy; it is very strong.

The bond dissociation energy in ozone is much lower so the O O bond in ozone is
labile.
Because of this diatomic oxygen is much less reactive and more stable than ozone.

Compare the
properties of the
gaseous forms of
oxygen and the
oxygen free radical.
(4.1.7)

Identify the origins of

chloroflurorcarbons
(CFCs) and halons in
the atmosphere.
(4.1.8)

A free radical is a neutral atom or molecule with one or more unpaired valence
electron.
The dot notation () can be used to represent a free radical.
The oxygen free radical is formed by the splitting of diatomic oxygen.

The oxygen free radical is very reactive and unstable compared to diatomic oxygen
because of the presence of an unpaired electron and an incomplete valence shell. In
fact, the oxygen free radical is even more reactive than ozone.

A haloalkane is a compound in which one or more hydrogen atom of an alkane has

been replaced by a halogen atom.
Chloroflurocarbons (CFCs) are haloalkane molecules in which all the hydrogen
atoms have been replaced by fluorine and/or chlorine atoms.

Halons are haloalkane molecules in which all the hydrogen atoms have been
replaced by bromine, chlorine and/or fluorine atoms.

CFCs were originally used to replace toxic ammonia gas as a refrigerant in fridges
and air conditioners. They were also used as propellants in spray cans, blowing
agents to make expanded plastics and solvents for cleaning electrical circuit boards.
In many of these uses, CFCs were released directly into the atmosphere since it was
believed they were safe due to their inert and non-toxic nature.
The properties of CFCs that made them so useful includes: very inert, low solubility
in water, low MP/BP, readily liquefies upon compressions, non-toxic and
non-flammable.
Halons were used in fire extinguishers due to their fire retardant properties. They
are dense, non-toxic and non-flammable liquids.

Identify and name

examples of isomers
(excluding
geometrical and
optical) of
haloalkanes up to
eight carbon atoms.
(4.1.9)

Discuss the problems

associated with the
use of CFCs and
assess the
effectiveness of steps
taken to alleviate
these problems.
(4.1.10)
Present information
from secondary
sources to write the
equations to show
the reactions
involving CFCs and
ozone to demonstrate
the removal of ozone
from the atmosphere.
(4.2.1)
Present information
from secondary
sources to identify
alternative chemicals
used to replace CFCs
and evaluate the
effectiveness of their
use as a replacement
for CFCs. (4.2.3)

Isomers are compounds with the same molecular formula but different structural
formula.
An example is
:

When dealing with isomers, focus on arranging the halogen substituents. Also, be
wary that isomers with 4 or more carbons are not all linear.
To name haloalkanes, IUPAC nomenclature rules are used:
Count the longest carbon chain.
Name all substituents using prefixes where necessary and arrange in
alphabetical order.
Add numbering positions such that the sum is minimised. If the same sum is
obtained despite using different numbering positions, give the lowest
number to the halogen that is cited first as a prefix.
The inertness and low water solubility of CFCs that made them useful has become a
major problem. Because of these 2 properties, CFCs are not destroyed in the
troposphere and are not washed out by rain. Instead, they slowly diffuse into the
stratosphere where high energy UV radiation initiates reactions that destroy ozone.
The produced

essentially acts as a catalyst for the destruction of ozone.

is then regenerated when

reacts with an oxygen free radical in the
stratosphere. This precipitates a chain reaction.

One
can destroy thousands of ozone molecules before it is removed from the
stratosphere by other processes. These series of reactions were proposed by
Rowland and Molina, hence the Rowland-Molina hypothesis.
Similar reactions occur with halons involving
CFCs and halons have high ozone depletion potential (ODP).

Depletion of the ozone layer is a major concern since it will lead to more UV-B and
UV-C reaching the Earths surface. These high energy photons would cause many
issues:
Sunburns and skin cancers due to DNA damage.
Cataracts due to the breakdown of lens proteins.
Suppressed immune responses and so more diseases in general.
Reduced growth in some plants.
Damage to polymers like PVC.

The only way to stop ozone destruction by CFCs is to stop releasing them into the
atmosphere since it is practically impossible to remove them. Because CFCs can no
longer be used, alternative substances have been made to replace them.
Hydrochloroflurocarbons (HCFCs) were the first replacement to CFCs. These
compounds contain C H bonds which make them more readily broken down in the
troposphere by free radicals and atoms. Only a small portion of HCFCs can reach the
stratosphere so they have much a lower ODP than CFCs. Nevertheless, their ODP is
still relatively significant since they contain C Cl bonds and thus they are only
temporary replacements for CFCs. An example of a HCFC is
.

Analyse the
information available
that indicates changes
in atmospheric ozone
concentrations,
describe the changes
observed and explain
how this information
was obtained. (4.1.11)

Hydrofluorocarbons (HFCs) are regarded as the long term CFC replacements and
are now widely used as refrigerants. Like HCFCs, they are also broken down in the
troposphere but in addition, they have an ODP of zero since they contain no C Cl
or C Br bonds. An example of a HFC is
.
Unfortunately, HFCs are more expensive than CFCs and both HCFCs and HFCs are
potent greenhouse gases. Despite this, both are extremely effective replacements
for CFCs as they have similar properties to CFCs but have much lower ODPs due to
their structure.
The Montreal Protocol (1987) was the first international treaty to phase out CFCs
and other ozone depleting substances (ODS).
Many targets have been met even ahead of time because of the widespread
adoption and global cooperation. This has allowed for various amendments to be
made to accelerate the phase out.
While it will start take several decades for ozone levels to recover, the Montreal
Protocol has been very effective as the use of ODS is dropping and the ozone hole is
starting to stabilise.
There are many instruments that can be used to measured ozone levels in the
stratosphere.
Ground based UV spectrophotometers point vertically upwards towards the
atmosphere. It then measures the intensity of light at a wavelength known to be
absorbed by ozone and then compares this to the intensity of light at wavelengths
that are not absorbed by ozone. This comparison gives a measure of the total ozone
per unit area of Earth surface at that location in Dobson units (DU).
The total ozone mapping spectrophotometer (TOMS) and ozone mapping
instruments (OMI) are satellite based spectrophotometers that work similarly to
ground based UV spectrophotometers. However, these devices are placed on board
a satellite where it scans through the atmosphere as the satellite orbits to measure
ozone levels as a function of altitude and geographical location.
Aerial spectrophotometers can also be used. Instruments are carried up to the
stratosphere on a He balloon where the concentration of ozone is measured as a
function of altitude.
There is direct evidence that indicates ozone levels are dropping:
The British Antarctic Survey at Halley Bay noted a 10% drop in stratospheric
ozone levels in spring 1976 and a 50% drop by 1985.
The evidence above correlates with independent data measured by TOMS.

There is also indirect evidence:

Levels of
were measured in the Airborne Antarctic Ozone Experiment
in 1987. This experiment identified a significant correlation between the
formation of
and a decline in ozone levels; it was consistent with the
Rowland-Molina hypothesis.

The Montreal Protocol and its amendments have caused ODS such as CFCs
to be replaced with non-ozone depleting substances. This has resulted in
the partial recovery of the ozone hole so it indicates that substances like
CFCs have indeed caused the destruction of ozone.
Studies of skin cancer shows that in the period 1987 2000, there has been
a 66% increase in skin cancer in the second half of this interval compared to
the first half. This correlates with the 56% reduction of ozone recorded over
the same period.

Monitoring water quality

Identify that water
quality can be
determined by
considering:
- concentration of ----- common ions
- total dissolved
solids
- hardness
- turbidity
- acidity
- dissolved oxygen
- and biochemical ---- oxygen demand
(5.1.1)
Perform first-hand
investigations to use
qualitative and
quantitative tests to
analyse and compare
the quality of water
samples. (5.2.1)

In scientific terms, the criteria used to assess water quality include: concentration of
ions, total dissolved solids, hardness, turbidity, pH, dissolved oxygen and the
amount of biochemical oxygen demand.
Concentration of common ions
The most common cations in water are
. There are also
some trace metals (eg.
,
) and heavy metals (eg.
,
).
These ions can affect water taste, hardness and toxicity.
AAS is widely used to monitor these cations; gravimetric analysis and volumetric
analysis are generally not used since they are not sensitive enough.
The most common anions in water are
. These can
affect water taste and pH.
Gravimetric analysis can be used to monitor these ions.

can be used to precipitate

while
can be used to
precipitate
.
The precipitate formed is then weighed and the concentration of the ion
can be calculated.
Volumetric analysis can also be used.

can be titrated with

using a
indicator.

can be titrated with standardised HCl.

Alternatively, ion-selective electrodes can be used. The voltage measured by these
galvanic cells is related to the concentration of a particular ion in the water.
Total dissolved solids
Total dissolved solids (TDS) is the mass of dissolved solids per unit volume of water.
Most of the dissolved solids in water are ionic compounds so TDS can be a measure
of salinity.
TDS can affect water taste, use of water for irrigation, survival of fish and DO levels.
High TDS in waterways can result from waterways being too close to the ocean or
from human activities that lead to rising water tables and soil erosion such as
farming practices, land clearing and over-irrigation.
The TDS in a water sample can be measured by first filtering off any suspended
solids and then evaporating the water to dryness and weighing the residue left
behind. This method tends to be unreliable with clean water.
Modern instrumental techniques use a conductivity probe and meter to measure
the electrical conductivity of a water sample to approximate TDS. The probe and
the meter must be calibrated with standard solutions before it is used. This method
gives a reasonable approximation of the TDS in a water sample since most of the
dissolved solids will be ionic compounds. While this technique is faster and
portable, it becomes less accurate at higher TDS levels.
Hardness
Water with appreciable amounts of
and/or
is called hard water. Water
with very low concentrations of these 2 ions is called soft water.
The
and
in hard water precipitates with soap molecules forming a
scum that sticks to clothes and sinks. This effectively removes soap from solution
and hence disrupts its cleaning action.
A qualitative test for hardness involves the use of soap. Soap is added to a water
sample and then shaken in a stoppered test tube. This is then compared to positive
and negative controls (2 shaken test tubes containing soap and water that is known
to be soft or hard). The amount of lather formed is a qualitative indicator of the
hardness of the sample; the more lather formed, the softer the water.

Alternatively, hardness can be monitored quantitatively via titration with EDTA

solution. In a
buffer solution, EDTA reacts with both
and
in
a 1:1 ratio. Eriochrome Black T is used as the indicator in this titration.
Because there is no distinction between
and
with this method, hardness
is expressed as equivalent
in
.
AAS can also be used to monitor hardness by measuring
and
individually. Note that the concentration obtained for
with AAS will be lower
than the one obtained by EDTA titration since EDTA solution also reacts with
.
Turbidity
Turbidity is a measure of the cloudiness or lack of transparency in a water body. It is
measured in nephelometric turbidity units (NTU).
Turbidity occurs due to small insoluble suspended solids in the water that scatters
light and makes the water appear cloudy.
High levels of turbidity will give the water an unpleasant appearance and taste.
It also reduces the penetration of sunlight through the water which is essential for
aquatic plants for photosynthesis.
Increased levels of turbidity can arise naturally from soil erosion especially after
heavy rains and floods. This natural process is greatly accelerated by human
activities such as land clearing, farming practices and mining.
Secchi disks can be used to measure relative turbidity of water. The disk is lowered
into the water sample until it just becomes invisible. The dept at which this occurs is
an inverse measure of the turbidity of the water; the shorter the length of the
string, the higher the turbidity.

Turbidity tubes can also be used. The sample of water is slowly added to the tube
until the mark at the bottom of the tube just becomes invisible. The turbidity can
then be read off the tube.

Gravimetric analysis can also be used to measure the total suspended solids and
hence turbidity. The suspended solids in a sample of water are filtered off and the
dry mass of the residue is then measured. This is quite effective on dirty water in
the environment but it is not practical on drinking water because it contains
particles that are too small to be filtered off.
A more exact measure of turbidity uses a nephelometer. This instrumental
technique measures the intensity of light scattered at
to the incident light. The
more turbid the water, the more scattering occurs. Turbidity is then measured
relative to distilled water (0 NTU) and formazin (100 NTU) standards.

Acidity
Water is considered to be polluted if the pH is outside the range of 6.5 8.5.
The pH of the water may disrupt the acid base balance in aquatic organisms and
may lead to death if severe.
Possible sources of too acidic water include industrial waste, acid rain, fertiliser runoff and sulfide ore mines.
If the water is too basic, the cause may be industrial wastes or nearby limestone
rocks.
Narrow range universal indicator pH papers can be used to approximate the pH of
water.
Alternatively, a calibrated pH meter is used which gives an exact pH value.
Dissolved oxygen
Dissolved oxygen (DO) is the amount of oxygen (mg) dissolved in 1 L of water at a
fixed temperature.
Aquatic plants undergo photosynthesis to produce oxygen which can then dissolve
in the water.
Some oxygen also dissolves into the water directly from the atmosphere. This
process is assisted by turbulent water flow.
High DO levels are vital for the survival of aquatic organisms. It is required for the
respiration of aquatic organisms and for the decomposition of organic matter by
aerobic bacteria. If DO levels get too low (less than 4 5 ppm), aquatic organisms
will experience metabolic stress and anaerobic bacteria will decompose organic
matter into toxic and malodorous products.
The main cause of low DO levels in natural water is high organic waste discharges.
This includes poorly treated sewage and wastes from farms and meat processing
plants. Other causes may be high salinity, high water temperatures due to thermal
pollution or eutrophication.
The Winkler titration method can be used to determine the DO in a water sample.
The 1:4 ratio between

and

can then be used to calculate DO.

Identify factors that

affect the
concentrations of a
range of ions in
solution in natural
bodies of water such
as rivers and oceans.
(5.1.2)

Alternatively, an electrolytic DO sensor can be used. Dissolved oxygen from the

sample diffuses across a membrane and is reduced to water at the platinum
cathode. At a constant voltage, the current flow through this cell is proportional to
the DO concentration.

Biochemical oxygen demand

The biochemical oxygen demand (BOD) of a water body is the amount of DO
required by aerobic bacteria to completely break down the organic matter in the
water.
BOD is a measure of organic waste pollution. In general, a waterway is considered
to be polluted if the BOD > 4 5 ppm.
To monitor BOD, the 5-day BOD test can be used. A water sample is divided into 2
samples. The DO of the 1st sample is measured while the 2nd sample is incubated in
a dark air-free container at
for 5 days. 5 days is usually sufficient for natural
organic waste to be decomposed in non-polluted water ways. Also, the sample is
held in the dark to prevent any photosynthetic algae from producing oxygen. The
DO of the 2nd sample is then measured and the BOD can be calculated using:

If the water is polluted, the above method will not work because all the available
DO will be consumed in less than 5 days. Polluted water samples are analysed by
either diluting the sample with a standard nutrient solution with a known
or
by re-aerating the sample with oxygen gas periodically and then measuring the new
DO each time.

The ion concentrations in a water body can be affected by the following factors; the
pathway from rain to water body, frequency and volume of rain, characteristics of
the water, nearby human activities and the type of water body.

Pathway from rain to water body

Rain contains some
. When rain runs off bushland into
streams, some
and
can be picked up from natural nutrients on the
surface and perhaps some
and
from decomposing minerals.
Rain can also percolate to underground aquifers where it will dissolve even more
ions such as
and
.
Frequency and volume of rain
Heavy or more frequent rain will carry more ions into the water body though the
extra volume of water may cause ion concentrations to decrease.

Gather, process and

present information
on the range of tests
used to:
- identify heavy metal
--pollution of water
- monitor possible ---eutrophication of ----waterways
(5.2.2)

Characteristics of the water

More acidic rain can cause the leaching of ions such as
and
from soils and
bedrocks into the water body.
Waters with higher temperatures will cause more minerals to dissolve.
Higher rates of water evaporation will increase ion concentrations.
Nearby human activities
Land clearing and mining generally leads to more water rapidly running across
disturbed lands and into water bodies. This facilitates the dissolution of a variety of
ions.
The use of fertilisers in farms may lead to fertiliser run-off when rainwater carries
this fertiliser form the soil into water bodies. This often increases the levels
of
,
and
.
Discharges of raw and/or treated sewage will increase the concentration of many
ions, particularly
and
. Industrial effluents and rubbish dumps may be
a source of heavy metal ions.
Type of water body
Oceans are less affected by changes in ion levels than smaller water bodies due to
the large volume of water present.
Heavy metals
Heavy metals are metals with high atomic masses such as Pb, Hg and Cd.
They bioaccumulate up the food chain within tissues of living organisms and are
generally toxic.
The common sources of heavy metals are industrial wastes (eg. Pb paints and Hg
cell) and runoff from contaminated soils near roads and landfills.
To monitor heavy metals, the following sequence may be used:

Alternatively, instrumental techniques can be used which are generally more

sensitive and accurate. These include AAS, ion-selective electrodes and mass
spectrometry.

Describe and assess

the effectiveness of
methods used to
purify and sanitise
mass water supplies.
(5.1.3)
Gather, process and
present information
on the features of the
local town water
supply in terms of:
- catchment area
- possible sources of --contamination in -----this catchment
- chemical tests -------available to ------------determine levels ----

1.
2.
3.

4.

Eutrophication
Eutrophication occurs when a water body is enriched with nutrients to the point
where rapid proliferation of algae/plant life occurs (an algal bloom).
Eutrophication mostly occurs due to high levels of phosphate and nitrate. These 2
ions are the growth liming nutrients for plants.
Common sources of nitrates and phosphates include excess fertiliser run-off from
farms, animal wastes, phosphate builders in laundry detergents and raw sewage.
Algal blooms are not only aesthetically unpleasant but they also cause DO levels to
drop dramatically:
The green scum reduces UV penetration so there will be less
photosynthesis.
Algal blooms hinder the diffusion of oxygen from the air to the water.
On the death of the algae, oxygen is used by aerobic bacteria to decompose
their remains.
Other adverse effects include:
Algae may clog up irrigation pumps and give the water an unpleasant taste.
They lead to the build-up of sediments in the water body due to dead algae.
Blue green algae called cyanobacteria can produce toxins that can kill
livestock and cause serious illness in humans.
To monitor eutrophication, phosphate and nitrate levels are monitored by a
colorimetric method. Colorimetry involves measuring the absorbance of light at a
certain wavelength passing through a solution.
To monitor phosphate, acidified ammonium molybdate is added to a water
sample. If phosphate is present then a canary-yellow precipitate will form.
A quantity of ascorbic acid is then added to the precipitate to form an
intense blue complex. The concentration of phosphate is then determined
by colorimetry relative to standards.
To monitor nitrate levels, the water sample is passed through a tube of
granulated Cd/Cu to reduce nitrate ions into nitrite ions. Sulfanilamide and
N-napthalenediamine is then added to the solution to form an intense
pink purple azo-dye. The concentration of nitrate is then measured
colorimetrically against known standards.
DO and BOD levels can also be measured to monitor eutrophication; low DO and
high BOD levels may indicate possible eutrophication but these tests should be
used in conjunction with the phosphate and nitrate tests.
Water purification is done to remove contaminants from raw water to produce
water suitable for human use.
There are 2 major goals in water purification:
Clarification; making the water clear, colourless and odourless.
Sanitation; removing harmful microbes from the water.
The steps are as follows:
Screening: Large objects such as fish and plant debris are removed using screens
that act as sieves.
Aeration: Air is bubbled into the water to help remove colour and odour by
oxidising
and
to insoluble products.
Lime softening: Lime (CaO) is added so that the water becomes slightly alkaline for
the next step. Soda ash (
) is then added to soften the water by removing
and
by precipitation reactions.
Flocculation:
or
are added as coagulants to create a gelatinous
precipitate to help remove suspended solids.

The suspended particles adsorb onto the precipitate and form flocs. This process
is aided by the addition of cationic polymers.
5. Sedimentation: The water is then transferred into the settling tanks where the flocs

--and types of -----------contaminants

- physical and -----------chemical processes --used to purify water
- chemical additives --in the water and the
--reasons for the -------presence of these ----additives
(5.2.3)

settle to the base of the tank to form a sludge. These are periodically removed.
6. Filtration: Water is filtered through layers of sand and gravel to remove any
remaining particulates. Crushed anthracite coal can also be used as a filter to
adsorb organic matter and improve the odour and taste of the water.
7. pH adjustment: The pH is readjusted with hydrated lime or soda ash to prevent the
scaling and corrosion of water distribution pipes.
8. Disinfection: The filtered water is disinfected with 1-2 ppm of
.
The produced hypochlorous acid kills bacteria and some viruses and protozoa.
Sometimes, ammonia is then added to produce monochloramine, which is a longer
lasting disinfectant.
In rare cases, ozone can also be used which is very effective against both bacteria
and viruses.
9. Fluoridation: About 1 ppm of fluoride (in the form of
) is added to
strengthen tooth enamel and reduce tooth decay.

Screening, the second part of flocculation, sedimentation and filtration are the
physical processes used to purify water.
Aeration, lime softening, the first part of flocculation, pH adjustment, disinfection
and fluoridation are the chemical processes used to purify water.
Overall, these methods are very effective for purifying water since ADWG criteria is
consistently met.
The screens remove large objects quickly, coagulants and sand filters removes
colours, odours and most suspended particles and chlorination removes almost all
bacteria and some viruses.
There are some problems though. Chlorination is NOT foolproof; it may not kill
extremely fine pathogens. The Giardia and Cryptosprordium outbreak in 1998 is
proof of this. Also, adding
to water will decrease its pH and excessive amounts
can affect human health so
levels must be closely monitored.
Taking all factors into consideration however, the water purification process is
generally both fast and reliable. With better catchment management and consistent
monitoring, the present treatment methods should be sufficient to produce water
suitable for human use.
A catchment is the drainage area for all the rainfall going into a water body or a
storage reservoir.
The Sydney catchment covers over 16000
to the south and west of Sydney
and consists of 5 major systems, each with its own reservoir and water filtration
plant.
The largest reservoir in Sydney is Warragamba Dam. Warragambas catchment
covers 9050
and has Coxs and Wollondilly as 2 major rivers. Areas closest to
the dam, making up 30% of the total catchment, are restricted special areas of

Describe the design

and composition of
microscopic
membrane filters and
explain how they
purify contaminated
water. (5.1.4)

unspoilt bushland. Most of the rest of the catchment consists of cleared farming
land and some small and large towns.
Sources of contamination includes:
Agriculture; water run-off from agricultural lands can contain fertiliser,
faecal matter and organophosphate/organochlorine pesticides.
Mining; water can flow into abandoned mines where it will leach ions such
as
and
.
Animals; native and feral may contaminate the water with their faeces or by
dying and decaying within the water. This leads to the contamination of the
water with pathogens and parasites.
The contaminants can be monitored with chemical tests that have already been
described.
A microscopic membrane filter is a thin film of synthetic polymer with uniformly
sized pores.
The common polymers used for these filters are polypropylene,
polytetrafluoroethylene and polysulphone.
Microscopic membrane filters are an alternative method for purifying water supply.
They can be produced in sheet or capillary forms.
Advantages of microscopic membrane filters include:
They have uniform holes that reliably filter out very small particles such as
pathogens that are not killed by chlorination.
They filter out water fairly quickly as the membranes are thin and can
withstand high pressures.
They can be cleaned easily by black-flushing and then reused.
Disadvantages:
They are very expensive so it cannot be used to purify mass water supplies.
Pleated sheet membrane filter
This consists of a 100
membrane that is folded or spirally wounded around a
central core. It is help in place with mesh and plastic outer casing to form a
cartridge.
The cartridge is mounted in a water pipe where water will flow across the
membrane (NOT perpendicularly) to avoid the clogging up of the pores.

Since the pores are very tiny (0.2

), larger particles and pathogens cannot pass
through the filter.
High fluid pressures (2-5 atm) are maintained to accelerate the filtration process.

Capillary membrane filters

These consists of porous material made into hollow capillaries with an outer
diameter of 500
, an inner diameter of 200
and pore sizes of around
0.2-0.5
.
For each capillary, dirty water flows along the outside through the wall of the
capillary and clean water transverses the pores and emerges inside.
Many capillaries are bundled together to make a filtering unit with a large SA.