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Core Topic 3 - Chemical Monitoring and Management
Core Topic 3 - Chemical Monitoring and Management
Core Topic 3 - Chemical Monitoring and Management
However at lower temperatures and with lesser amounts of oxygen and with suitable catalysts,
quite different products are formed. It is important to monitor reaction conditions to ensure
that the yield of the desired product is maximised.
Gather, process and present information from secondary sources about the
work of practising scientists identifying: the variety of chemical occupations,
and a specific chemical occupation for more detailed study
Metallurgical chemist: are scientists who specialise in the properties, applications and
development of metals and alloys in out technological society, They give advice on the
extraction of metals from ores and ways in which they could be combined with other materials
such as polymers or ceramics.
Biochemist: studies the chemical structure and functions of molecules (eg. carbohydrates,
fats, proteins, nucleic acids) in living things. Through their research new medical, industrial
and agricultural products are developed.
Polymer chemist: investigate the properties of large polymeric molecules. They manipulate
their structure to alter their properties in order to produce new and useful plastic products and
materials.
Industrial chemist: study the structure and chemical reactions of materials that can be used
in industry. Their research and development programs lead to the production of a wide variety
of commercial products ranging from petrochemicals, detergents, and plastics to
semiconductors. Industrial chemists may be specialists in analytical chemistry, organic
chemistry or inorganic chemistry. An industrial chemist works in a team. Research ideas are
developed into experimental procedures on a small scale. Consideration in normally given to
factors such as reaction speed, use of catalysts and the position of the reaction equilibrium.
With the aid of chemical engineers, the procedures are scaled up to the industrial production
levels. Chemical monitoring procedures, quality control testing and environmental monitoring
procedures are designed. An industrial chemist works closely with environmental officers and
marketing and management personnel. Planning and organisational skills as well as analytical
and laboratory skills are vital for in industrial chemist.
Ammonia ranks second to sulfuric acid in terms of quantity provided worldwide per year. It is
used to make:
Fertilisers (sulfate of ammonia, ammonium nitrate, urea)
Fibres and plastics (rayon, acrylics, nylon)
Nitric acid, which in turn is used to make fertiliser (ammonium nitrate), dyes, fibres and
plastics, and explosives such as ammonium nitrate, TNT (trinitrotoluene) and nitro-
glycerine (in dynamite)
Household cleaners
Detergents (non-ionic ones).
By the beginning of the twentieth century there was a growing need for an industrial method
of synthesising ammonia. Increasing demands for nitrogenous fertiliser to grow food for
increasing world populations were placing strains on the supply of naturally-occurring Chile
saltpetre (sodium nitrate), the main ‘artificial’ fertiliser at that time. In addition the growing
militancy of Germany was promoting calls for more explosives (generally made from nitric acid
which in turn was mainly produced from saltpetre).
The German, Fritz Haber, in 1908 first developed a method of synthesising ammonia from its
elements, through it was not until 1914 that Carl Bosch successfully converted it into an
industrial process. This synthesis contributed significantly to the German war effort in World
War I in that it insulated German agriculture from any harm caused by interrupted supplies of
saltpetre from South America and it facilitated the production of nitric acid and hence of
explosives.
Identify that ammonia can be synthesised from its component gases, nitrogen
and hydrogen
Describe the synthesis of ammonia as a reversible reaction that will reach
equilibrium
Identify the reaction of hydrogen with nitrogen as exothermic
Explain why the rate of reaction is increased by higher temperatures
Explain why the yield of product in the Haber process is reduced at higher
temperatures using Le Chatelier’s principle
Explain why the Haber process is based on a delicate balancing act involving
reaction energy, reaction rate and equilibrium
Explain that the use of a catalyst will lower the reaction temperature required
and identify the catalyst(s) used in the Haber process
Analyse the impact of increased pressure on the system involved in the Haber
process
This is an equilibrium reaction which at ordinary pressures and temperatures lies well to the
left.
Equilibrium Considerations
Le Chatelier’s principle shows us how to maximise the conversion of nitrogen and hydrogen to
ammonia.
1. If the pressure on a reaction system is increased, the equilibrium moves in the direction
which tends to reduce pressure; that is, the direction which corresponds to a decrease
in the number of moles of gas, since a decrease in the number of moles of gas in a
container of fixed volume leads to a decrease in pressure.
If the pressure on equilibrium mixture of N2 and H2 is increased, the reaction moves to
the right: some N2 and H2 react to form NH3. This happens because that direction
corresponds to a decrease in the number of moles of gas:
4 moles of gas - 2 moles of gas
2. If the temperature is lowered the equilibrium will move in the direction which tends to
increase temperature (release heat). It is exothermic, so if temperature is lowered, it
will move towards the right (form more ammonia).
The percentage conversion of nitrogen to ammonia varies with pressure (at constant
temperature) and temperature (at constant pressure). On equilibrium considerations
alone the reaction should be conducted at high pressure and low temperature.
Rate Considerations
However another consideration is how long will it take for the reaction to reach equilibrium:
that is we need to consider the rate of the reaction. As for most reactions, the rate of the
reaction decreases as temperature decreases. If we lower the temperature in order to move
the equilibrium towards the right, we make the reaction very slow and so it takes a very long
time to reach equilibrium.
One way to increase the rate of reaction is to find a suitable catalyst. Iron is a good catalyst.
While this catalyst does speed up the reaction, the rate is still too slow at room temperature to
be practical. Remember that while a catalyst speeds up a reaction, it does not affect the
position of equilibrium. This is because it speeds up both the forward and reverse reactions.
Hence we have these situations: a low temperature produces a high yield (say 90% conversion
of hydrogen to ammonia), but a very long time (weeks to months) is required to reach
equilibrium, even with a catalyst. A high temperature causes equilibrium to be reach more
quickly (in a few minutes) but the equilibrium yield is extremely low (say 0.1%).
Compromise
Compromise conditions are therefore used. A moderate temperature produces a moderate
yield moderately quickly. Typical conditions for the industrial process, called the Haber
process are:
A temperature of about 700 K (or about 400C) and
A total pressure of about 250 atmospheres.
With a reactant mixture having H2 and N2 in the ratio of 3 : 1, these conditions give an
equilibrium conversion to ammonia of about 40%. The catalyst is magnetite, Fe3O4, with its
surface layer reduced to free iron.
(Re: pic CCHC 193). Reactants pass through the catalyst reactor, then the mixture is cooled to
condense out the ammonia formed: this can be drained off as required. Unreacted gases are
fed back into the catalyst chamber along with incoming fresh reactants. None of the reactant is
wasted. We essentially drive the reaction to a completion by condensing out the reaction
product.
A stoichiometric mixture of hydrogen and nitrogen is used because, as ammonia is formed and
condensed out, left-over reactants can be recycled through the process (with some fresh
reactant mixture added) without any build-up of one reactant over the other.
An important factor in designing an industrial process is energy management. In the Haber
process we would like to use the head released to heat up, at least partially, the incoming
reactants and so minimise our energy costs: this has the added advantage that it stops the
catalyst overheating and so losing activity. This is the reason for the incoming reactants
flowing over the outside of the catalyst chamber entering it.
Carbon monoxide poisons the iron catalyst in the Haber process and so must be removed. This
is done with other catalytic reaction:
Which has the added advantage of producing more hydrogen. The catalyst used is either Fe3O4
at 500C or Cu at 250C.
A complication for the Haber process is that we want a mixture of hydrogen and nitrogen that
does not contain any oxygen (which can react explosively with hydrogen under the conditions
used). Methane us also used to remove oxygen from air (in effect just normal combustion to
CO2 and steam). By adjusting the quantities of methane, steam and air used, this combination
of reactions can be made to product a 3 : 1 mixture of hydrogen and nitrogen. The only
unwanted gas in the mixture is carbon dioxide. This is removed by reaction with a base, if
oxygen has to be excluded and if the reactant mixture has to be recycled through the reactor,
the use of a 3 : 1 mixture is the most efficient way of making ammonia.
Explain why monitoring of the reaction vessel used in the Haber process is
crucial and discuss the monitoring required
Because many different conditions must be maintained for efficient and safe operation of the
Haber process, monitoring is essential. First temperature and total pressure must be
monitored to keep them in the range for optimum conversion of reactants to products: in
addition excessive temperature can damage the catalyst. Then it is essential to monitor the
composition of the incoming gas stream: we need to ensure that the ratio of H2 to N2 is kept at
3 : 1 (to avoid a build-up of one reactant), that oxygen is absent (to avoid risk of explosion)
and that concentrations of carbon monoxide and sulfur-containing species are sufficiently low
to prevent poisoning of catalyst. With a well-maintained plant the catalyst can last up to eight
years. Any build-up of unreactive gases such as argon and methane needs to be watched also
because that can lower the efficiency of the conversion.
In Summary:
Ammonia can be synthesised from nitrogen and hydrogen (equilibrium).
N2(g) + 3H2(g) <--> 2NH3(g) ΔH = –92 kJ/mol
The rate of reaction would be increased by higher temperature, since particles move faster,
causing more collisions and reactions.
But since the reaction is exothermic, an increase in temperature will favour the back reaction
and thus reduce yield of NH3.
Since some changes that would usually be made to the set-up to increase reaction rate and
decrease activation energy shift equilibrium left, there needs to be a delicate balancing of
these factors to compromise between yield and reaction rate.
A catalyst in the reaction lowers activation energy and thus less heat is required for the
reaction to occur. Iron (as surface on magnetite, Fe3O4) is the heterogenous catalyst used (N2
& H2 break apart and react on its surface).
Increased pressure shifts equilibrium right, in order to gain fewer overall moles of gas,
therefore increasing yield in the Haber process.
The Haber process is thus performed with:
approximate temperature 700K, pressure 250atm
catalyst Fe3O4 with Fe surface
the product constantly being condensed and removed (shifting equilibrium
right)
left-over reactants are recycled
incoming reactants heated up by previous reactions by flowing over reaction
chamber (it also stops overheating the catalyst)
Monitoring is required:
Temperature and pressure monitored to keep in optimum range (and not to
damage the catalyst)
H2:N2 :: 3:1 (to avoid build up of one reactant)
Oxygen not present (explosion)
Other contaminants not present (CO or species with S can poison catalyst)
Avoid build-up of unreactive gases (reduces efficiency of reaction)
C c D d products
for reaction aA + bB <--> cC + dD, K
A a B b reactants
This is known as the equilibrium constant, for a particular reaction at particular temperature.
When concentrations of involved species change, the other concentrations adjust in order for K
to remain constant.
A higher number means more to the right in equilibrium.
Hence subbing in numbers for volume, temperature and concentration on the Ammonia
equilibrium will give us different K values.
Deduce the ions present in a sample from the results of these tests
From the above tests, we can deduce the ions present in a sample.
For multiple ions, tests need to be performed in an order, making sure that salts that will not
react are used (ie. NO3– tests with anions). When precipitates form, the reaction needs to be
driven to completion and then the precipitate filtered (or preferably centrifuged off) and the
filtrate tested.
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
Composition:
By volume (& mol): nitrogen 78.11%, oxygen 20.96%, argon 0.93%
Many trace gases and pollutants (ppm concentration), some of which vary from
place to place depending on natural and man-made environments
Identify the main pollutants found in the atmosphere and their sources
Ozone, O3, is a pollutant in the lower atmosphere, is poisonous to most life forms. Causes
respiratory problems, headaches and premature fatigue. It can be creating by passing an
electric current through O2 gas (3O2 -> 2O3).
It is the most harmful component of photochemical smog. Sunlight splits an O atom off
relatively highly concentrations of NO2 from car exhausts, which combines with O2 to form O3
in the air.
In the upper atmosphere (stratosphere), ozone acts as a UV radiation shield. Oxygen gas
shields out short wavelength UV (< 240nm): O2 + UV -> 2O2
These oxygen atoms react with oxygen gas to form ozone, or react with O3 to form O2,
creating a balance in O2 and O3:
These exothermic reactions explain the heat increase with altitude in the stratosphere.
Ozone absorbs the longer wavelength UV radiation (200-300nm): O3 -> O + O2, thus
protecting life on earth from the harmful UV.
A coordinate covalent bond is one where both of a pair of shared electrons come from the
one atom. It is formed when an atom in a bond does not have a full outer shell and the other
does and has an unshared electron pair. It therefore shares this pair with the atom and creates
a coordinate covalent bond.
To form a coordinate covalent bond, 1 atom has a pair of non-bonding electrons, and the other
has to have 2 holes.
Ozone
Compare the properties of the oxygen allotropes O2 and O3 and account for
them on the basis of molecular structure and bonding
Allotropes of oxygen
Oxygen gas, O2 Ozone, O3
Quite reactive Much more reactive (and
Moderate oxidant (quite unstable)
explosive) Powerful oxidant (highly
explosive)
To split requires double-bond to To split requires coordinate
be broken covalent bond to split
O 2 ( g ) 2O( g ) ΔH=+498 O 3 ( g ) O 2 ( g ) O( g )
kJ/mol ΔH=+106
Non-polar kJ/mol
Polar
Colourless gas, pale blue liquid Colourless gas, distinct blue liquid
Odourless Strong, distinctive odour
Essential for all living matter Poisonous (very reactive free
radical O joins onto molecules in
Boils at –183°C organisms)
Sparingly soluble in water Boils at –111°C (150% mass)
More soluble in water
Compare the properties of the gaseous forms of oxygen and the oxygen free
radical
A free radical is an uncharged atom or group of atoms with one or more unpaired electrons.
The oxygen free radical is very reactive, since it has 2 unpaired electrons in 2 outer orbitals.
Because of this high and rapid reactivity, it does not usually exist alone in nature.
Short wavelength UV radiation contains enough energy to break chemical bonds, particularly
double bonds. Many bonds in polymers (biological or not) can be broken by the UV radiation.
In the case of biological molecules (proteins and nucleic acids), their chemical changes caused
by UV creates molecules unable to perform their original function, killing cells in the organism
or causing severe genetic mutation in offspring. To humans they cause increased cancer risk,
damage to the immune system, severe sunburn, and eye cataracts.
CFCs are compounds containing only chlorine, fluorine and carbon. Their (and other
halogenated hydrocarbons, like halons) origins in the atmosphere are from use as refrigerants,
propellants, solvents, and in plastic manufacture.
Identify and systematically name straight chain haloalkanes and alkenes with
up to eight carbon atoms
Identify and name examples of isomers (excluding geometrical and optical) of
haloalkanes up to eight carbon atoms
The only way to stop ozone destruction by CFCs is to stop releasing them to the atmosphere,
because once they are released it is impossible to remove them, and they do not decompose
or get washed out by rain.
International Agreements
Since 1987 there have been several international agreements in which nations have
undertaken to phase out the use of CFCs and other ozone-destroying compounds. The original
agreement was called the Montreal Protocol. The most recent agreement (1992) was to:
Stop using halons by the end of 1994
Cease the manufacture and use of CFCs and 1,1,1-tricholoroethane by 1996
Phase out HCFCs by early in the 21st century
Allow less developed countries some period of grace and provide some financial
assistance to help them phase out CFCs.
Alternatives to CFCs
International agreements (initially the Montreal Protocol) involved many nations in phasing out
the use of CFCs. HCFCs (hydrochlorofluorocarbons) were used as temporary replacements,
whose C-H bond can be broken down in the troposphere, thus causing less to reach the
stratosphere and become destructive to ozone. HFCs (hydrofluorocarbons) lack a C-Cl bond
and thus are not destructive to ozone, but are more expensive and not as efficient as CFCs.
Since CFCs are very slow at diffusing into the stratosphere, they will continue to destroy ozone
for 50-100 years, though restrictions put in place are reducing our emissions and thus will
eventually recover normal atmospheric ozone concentrations.
In the stratosphere ozone come into contact with short wavelength u.v. radiation (before the
ozone has filtered it out) and this short wavelength u.v. breaks a chlorine atom off the CFC
molecule:
The chlorine atom formed then abstracts an oxygen atom from an ozone molecule, forming a
ClO ‘molecule’:
Cl + O3 - ClO + O2
ClO is a free radical and is very reactive with an unpaired electron. ClO reacts with a free
oxygen atom to form a molecule of oxygen, O2 and this regenerates the chlorine atom:
ClO + O - O2 + Cl
This process continues in a cycle, and is a chain reaction. One chlorine atom can destroy
thousands of ozone molecules.
Identify and describe tests that can be used to determine the quality of water
samples as: concentrations of common ions, total dissolved solids, hardness,
turbidity, acidity, dissolved oxygen and biological oxygen demand, and
nitrogen-to-phosphorus ratio
Hardness
Hardness is due to the presence of calcium and magnesium ions in the water. These form
insoluble compounds with soap ions, resulting in a scum on the water surface and around sink
basins. The removal of soap ions from solution reduces the ability of soap to lather.
The test for hardness involves precipitating the calcium and magnesium ions from a known
volume of the water sample with a solution of sodium carbonate (of known concentration),
followed by filtering and drying of the precipitate. Most of the insoluble salt is assumed to be
calcium and the concentration of calcium ions is calculated and reported in parts per million
(ppm).
Turbidity
This can be one measure of the ability of the water to support life. Turbidity results from the
presence of suspended solids in the water. Water with a high turbidity reduces penetration of
light and decreases photosynthesis, which in turn reduces the oxygen concentration.
The test for turbidity is conducted using a turbidity tube standing on a white tile. The tube has
a black cross marked on the base. The water sample is poured into the tube until the cross just
disappears when looking from above.
The use of a turbidity tube is less reliable than a transmittance of light test done with a
colorimeter. The lower reliability is due to variations in human eyesight and the intensity of
background light during testing.
Acidity (pH)
A pH reading below 7 would be expected where there are acid sulfate soils or where there is
acid produced by decomposition of organic matter in stagnant situations. The test can be
conducted with a data logger and pH probe, universal indicator solution or paper, or a pH
meter. If using the universal indicator, comparison with a coloured pH scale provides the pH
value. If it is less than 7, the solution is acidic.
Reaction 1:
Reaction 2:
Reaction 3:
2–
This shows that, for each mole of thiosulfate (S2O3 ) used in the titration, there was 0.25
moles of dissolved oxygen in the original sample.
Nitrogen-to-phosphorus ratio
The nitrogen:phosphorus ratio refers to the total nitrogen level (inorganic and organic nitrogen
in dissolved soluble form and insoluble solid form but not nitrogen gas) and total phosphorus
level (mostly phosphates, hydrogen phosphate, dihydrogen phosphate and polyphosphate
ions). The test is either via volumetric analysis, gravimetric analysis or instrumentally, by
visible light absorption spectroscopy.
The volumetric technique requires the nitrogen to be converted to ammonium sulfate using
sulfuric acid with the addition of excess alkali to produce ammonia gas, which is collected. This
is neutralised by a known volume and concentration of acid in excess. The excess is titrated
with a base to determine the amount of acid that reacted with the ammonia.
The phosphate determination can be done using a gravimetric technique. Sulfuric and nitric
acid mixture converts the phosphorus to phosphate. Addition of a soluble magnesium salt and
ammonia solution precipitates the phosphate as insoluble magnesium-ammonium phosphate-
6-water. This is then collected, dried and calculations are done to determine the amount of
phosphorus. Then the ratio of N:P is calculated and compared with accepted standards for
different types of waterways.
The ions present in natural water bodies (such as rivers, dams and oceans) and their
concentrations depend upon the following factors:
Because of their smaller volumes, rivers and dams are more vulnerable than oceans to
increases in ion concentrations. Nevertheless discharge of poorly treated sewage from big
cities (such as Sydney) and large run-offs from flooded rivers that flow through agricultural
land can affect the ion concentrations in coastal ocean water quite significantly.
Describe and assess the effectiveness of methods used to purify and sanitise
mass water samples
There are several methods used to purify mass water supplies. Most are variations on the
following process:
Water is collected in dams and pumped to a treatment site where the larger solids such
as pieces of plastic are removed by screens. Fine particles suspended in water have
electric charges on their surface that keep the particles from joining together and
becoming large enough to settle as sediment. Separation of fine particulate matter
suspended in water involves the addition of coagulants, such as iron (III) chloride,
FeCl3, to the water. The added FeCl3 overcomes these surface charges so the particles
come together. Iron (III) hydroxide is formed by reaction of FeCl3 and precipitates out
as a floc (flocculant). The floc collects the neutralised particles into large masses that
are more easily filtered. The chloride ions added with the FeCl 3 remain in the water.
They do not have a harmful impact on the water quality. In some instances, after
flocculation the particle size of suspended solids is too fine for filtration through sand
beds and so membrane filters are used. They are more effective than sand filters as
they can have a very small pore size. However membrane filtration is more costly than
sand filtration.
Sanitising mass water supplies involves disinfecting with chlorine gas, Cl2, liquid sodium
hypochlorite solution, NaOCl (aq), or solid calcium hypochlorite, Ca(OCl) 2.
Sedimentation and filtration removes some harmful organisms, such as bacteria,
viruses, cryptosporidium and giardia, but disinfection is needed to ensure
concentrations are acceptably low. In some parts of the water distribution system,
ammonia, NH3, is added to form monochloramine, ClNH2, by reaction with chlorine. This
is a less reactive disinfectant, but lasts much longer in the distribution system.
A few years ago, some water supplies in NSW were contaminated by the
microorganisms, cryptosporidium and giardia. As a result, water supplies are monitored
daily at water treatment plants and throughout each catchment during storms or other
events that cause a rise in stream water levels and could influence water quality. This is
considered effective, as the cost of treatment of all water supplies with membrane
filters would make treatment very expensive.
Microscopic membrane filters have microscopic pores and the use of appropriate sized
filters can avoid the need to chemically treat the water. The filters can be classified as
microfiltration, ultrafiltration, nanofiltration or reverse osmosis membranes depending on the
size of the pore.
The membrane is made from synthetic polymers dissolved in a mixture of solvents and water-
soluble powders of a particular size. The mixture is spread out over a plate and left for the
solvent to dry. The polymer membrane containing particles of water-soluble powder is then
placed in water. The remaining solvent and the powder particles dissolve, leaving a very thin
polymer sheet with definite sized microscopic pores where the water-soluble particles were.
Semi-permeable membranes used in reverse osmosis are either made of cellulose acetate or a
layer of polyamide attached to another polymer. Under pressure these polymers allow the
passage of water molecules but not that of most atoms, ions or other molecules.
Water is made to flow across the membrane not through it. This reduces the blockage factor.
Microfiltration removes protozoans, bacteria, colloids, some colouration and some viruses. The
size of the pore determines which sized particle or organism may pass through the membrane.
The finer the pore size the smaller the particle trapped and the more expensive the
membrane.
Advantages
They can filter out much smaller particles than paper or sand filters can
They filter out virtually all particles larger than their specified pore sizes
They are quite thin and so liquids flow through them fairly rapidly
They are reasonably strong and so can withstand pressure differences across them of
typically 2 to 5 atmospheres
They can be cleaned (back-flushed) and reused
Membrane filters are widely used for filtering both drinking water and treated sewage. No
filters can remove substances that are actually dissolved in the water such as phosphates and
nitrates and heavy metal ions.
Identify the need for collaboration between chemists as they collect and
analyse data
The analysis of local waterways requires the collaboration of a wide variety of chemists and
other scientists. This allows for effective monitoring and management of our waterways.
AAS testing is carried out in a laboratory while simple chemical and physical measurements,
such as pH and temperature, are carried out in the field. A chemist using complex equipment
in the laboratory on water samples needs to have confidence in the sampling techniques used
by field workers collecting the samples.
Gather, process and present information on the range and chemistry of the
tests used to: identify heavy metal pollution of water, and monitor possible
eutrophication of waterways
Heavy metal ions such as Pb2+, Hg2+, Cd2+, Cr2+, Cu2+ and Zn2+ can be identified using the
tests mentioned above.
Eutrophication is the increase in nitrates (NO3-) and phosphates (PO43-) from fertiliser
overuse and sewage. These can be identified using the tests mentioned before.
Gather, process and present information to interpret secondary data from AAS
measurements and evaluate the effectiveness of this in pollution control
Perform first-hand investigations to test for solids in water samples from the
local environment
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 and types of
contaminants, physical and chemical processes used to purify water, and
chemical additives in the water and the reasons for the presence of the
additives