Chemical Monitoring and Management

Robert Evans is a chemist in plastics industry under the branch of polymer chemistry.
- His role is synthesising and studying the physical and chemical properties of polymers based
on different catalysts, temperatures and pressures. He constantly monitors equipment to
ensure the required conditions are maintained.
- A chemical principle in his work is that the level of branching of the polymers affect its
rigidity. A high level of branching leads to lower compaction and lower dispersion forces
which make a flexible polymer. The intramolecular interactions between polymer chains,
cross links, also affects flexibility where the stronger the cross links, the more rigid the
polymer is.

As chemists specialise in particular branches and many chemical problems requires expertise from
many branches, there is a need for collaboration between chemists.

Chemical reactions, where reactants form different products under different conditions need
monitoring. Combustion for example produces different products under different levels of oxygen.
With an excess of oxygen, the combustion of octane will undergo complete combustion:
25
8 18() + 2() 82() + 92 ()
2
With a limited supply of oxygen, octane will undergo incomplete combustion
28 18() + 232() 152() + () + 182 ()
Thus the level of oxygen must be monitored as unfavourable products decrease efficiency of engines
and increases pollution.

The work of practising scientists include:

Variety of Chemical Occupations
- Analytical quantitative and qualitative analysis of substances.
- Physical Physical aspects of chemistry such as reaction rate and structure of compounds
- Organic Carbon based compounds such as hydrocarbons, sugars and fats.
- Inorganic Other compounds such as metals and their extraction.
- Other branches such as environmental, industrial, nuclear and pharmaceutical
An Environmental chemist reviews compliance with government regulations about:
- Water treatment systems
- Environmental noise
- Contaminated waste and classifying waste for disposal
- Levels of gas stack emissions
- Answers questions and enquiries/complaints

Ammonia has many important industrial uses:

- Fertilisers (ammonium and nitrate salts)
- Reactant in the production of nitric acid
- Fibres and polymers
- Explosives
- Stabiliser in the rubber industry
- Pharmaceuticals
It is synthesised from its component gases, nitrogen and hydrogen

2() + 32() 23() 3 4() < 0

As the forward reaction is exothermic, if the temperature is increased, in accordance with LCP the
equilibrium system will shift to counteract the change and favour the endothermic reaction. This
favours the reverse reaction and shift the equilibrium left, reducing yield.
However when temperature is increased, the number of particle collisions also increases which
increases the rate of reactions in both directions of the equilibrium.
Thus, the temperature of the reaction must be balanced between reaction rate and yield to
maximise production of ammonia over time. The industry uses approximately 450oC.

As the reactants have 4 gaseous moles and the product has 2 gaseous moles, pressure will also
affect the equilibrium. If the pressure is increased, in accordance with LCP the equilibrium system
will shift to counteract the change and favour the reaction that produces less gaseous moles, that is
more yield. Industry uses approximately 250atm and does not use higher pressures as it will be
expensive and difficult to maintain.

A magnetite (Fe3O4(s)) surface catalyst is used that is highly porous with a large surface area. It
reduces the activation energy required for the reaction by providing an alternate path way. Its large
surface area provides a location which increases the reaction rate. Thus less energy is required and
the cost is reduced. It does not affect equilibrium position and only increases rate of reaction.

Nitrogen and hydrogen in the ratio of 1:3 are pumped into reaction vessel and synthesised into
ammonia. The ammonia and any leftover reactants are pumped are then pumped into a condenser,
which liquefies and removes the ammonia. The unused reactants are then pumped back to the
reaction vessel to be reused. By continually removing the ammonia, the equilibrium is forced to the
right and almost to completion, with accordance to LCP.

The Haber process must be monitored to ensure the reaction takes place safely and at a high yield:
- Temperature 450oC
- Pressure 250 atm
- Reactant concentration 1:3
- Purity of gases
- Yield greater than 50%
- Presence of oxygen may cause mixture to explode
- CO and Sulphides degrade magnetite catalyst and prevent it from working properly.

The Haber process was developed in 1908, where two chemists, Fritz Haber (an academic) and Karl
Bosch (industrial chemist) pioneered the development of high-pressure equipment and efficient
catalysts required to make the process viable, which allowed for the mass production of ammonia by
1914.
At the start of WW1 Germany was dependent upon the Chilean saltpetre for the nitrogen
compounds required for explosives. When the Allied blockade of South American ports cut of this
supply, the Haber-Bosch process allowed Germany to produce the needed explosives and fertilisers
and is widely believed to have prolonged the war.
Since then however, it has increased fertiliser production and led to increased crop yields globally,
providing food for millions.
+ -
Provided a stable source of food for billions H2(g) is derived from natural gas which is non-
renewable.
NH3(g) leaks are dangerous and a potent
greenhouse gas.
Increased use of fertilisers could lead to
nitrates entering water systems and cause Algal
blooms.

Solubility Rules:

Soluble Compounds
Group 1 Ammonium Salts Nitrates Halides Sulphates
EXCEPTIONS - - - Ag+, Hg2+, Ag+, Hg2+, Pb2+,
Pb2+, Cu+, Ca2+, Ba2+
Insoluble Compounds
Carbonates and Phosphates Sulphides Hydroxides
EXCEPTIONS Group 1, Ammonium Salt Group 1|2, Group 1, Ammonium
Ammonium Salts Salts, Ba2+, Ca2+

Identifying Ions:

In a Flame Test a platinum wire is cleaned with concentrated HCl (6.0M) and heated until red to
ensure no other cations are present.
- Barium || Apple Green
- Calcium || Brick Red
- Copper || Emerald Green
- Lead || Blue-White
- Sodium || Yellow
- Potassium || Lilac

Precipitation Reactions (Cations):

- Pb2+ forms white precipitate with Cl- and yellow with I-
- Ba2+ forms white precipitate with SO42-
- Ca2+ forms white precipitate with SO42- and F-
- Cu2+ forms blue precipitate with OH-
- Fe2+ forms green-brown precipitate with OH- which decolourises with MnO4-
- Fe3+ forms brown precipitate with OH- and forms deep red with SCN-

Precipitation Reactions (Anions):

- CO32- forms carbon dioxide bubbles with HNO3
- SO42- forms fine white precipitate Ba(NO3)2
- PO43- forms white precipitate with Ba(NO3)2 and brown with Fe(NO3)3
- Cl- forms white precipitate with AgNO3 and photo-decompose into silver powder.
Lead needs to be monitored in society as it is a toxic heavy metal and is dangerous to humans and
the environment. It is a neurotoxin and bio-accumulates (builds up in the body) and bio-magnifies
along the food chain. It causes:
- Behavioural and intellectual development problem in children.
- Brain damage and neurological disease.
- Comas
- Seizures
- Death
Lead can be released into the environment in a number of ways:
- Was a constituent in petrol and paints
- Pipes made from lead

Atomic Absorption Spectroscopy is a method in determining the concentration of metal ions and has
a precision from 1ppm to 1ppb. This works on the principle that each element has a unique
absorption spectrum (will only absorb certain wavelength of light due to unique electron
configuration). Thus the specific wavelength will be absorbed by the tested element and the
concentration can be found by comparing the original intensity to the exiting intensity of the light.

Lamp: Source of light for metal being tested, emits specific wavelength.
Flame: Where the sample is vaporised.
Lens: Focuses the incoming light towards the monochromator.
Monochromator: Separates incoming light into specific wavelengths and directs desired wavelength
to photomultiplier.
Photomultiplier: Measures the intensity of the specific light.
Computer: Processes the difference in intensity to calculate absorbance and concentration.

AAS can detect very small concentrations of various metal ions known as trace elements which are
necessary for the functioning of living organisms. AAS has been a very important tool in improving
the understanding the functions of the human body (with trace elements such as zinc, cobalt and
copper) by studying cellular activity for example Cu is vital in red blood cell formation and iron is
essential for haemoglobin function. It also allows the discovery of previously unknown trace
elements for bodily function and detect levels of harmful metals in the body (Pb).
Limitations:
- Requires the test element to be known beforehand.
- Cant distinguish between isotopes and transitional metals.
- Equipment is very expensive.
Sulfate Concentration in Fertiliser Practical

1. Weight 3 grams of crushed fertiliser.

2. Dissolve in 100mL of 0.1M HCl with stirring rod. (Removes CO32- and PO43-)
3. Filter off insoluble material (Any other precipitates will reduce accuracy).
4. Add slowly excess BaCl2 (Precipitates BaSO4).
5. Filter solution through sintered glass crucible (BaSO4 is very fine so filter paper might let the
precipitate pass).
6. Dry precipitate to remove any water.
7. Cool precipitate to ensure it does not absorb water.
8. Weight precipitate.

Sources for Error:

- Not all sulphate precipitates || Add BaCl2 slowly and multiple times.
- Other precipitates form || Add HCl
- Sample weighed still contained water || Dry, cool and weight. Repeat this procedure
multiple times for reliability.

Calculation Method:
Mass(BaSO4) || n(BaSO4) || Molar ratio 1:1 || Mass(SO4) || Mass(SO4) Mass(BaSO4) for percentage

The atmosphere is a layer of gas surrounding Earth, with pressure decreasing with altitude. The
layers of the atmosphere are:
- Troposphere (0 15km): Temperature decreases as Earth radiates heat with altitude
resulting in convection currents which allow weather patterns to occur.
- Stratosphere (15 50km): Temperature increases with altitude due to the exothermic
reactions in the formation of ozone and oxygen. Because of the temperature gradient, there
is little vertical mixing of gases and hence the layer is very stable.
- Mesosphere (50 85km): Temperature decreases with altitude and is where most meteors
burn up.
- Thermosphere (80 600km): Temperature increases with altitude and is where the high
energy particles from the sun are absorbed. It includes the ionosphere and the
magnetosphere.

There are 3 main gases which make up the atmosphere:

N2 (78.08%) || O2 (20.95%) || Ar (0.93%)
In addition there are also some trace gases such as CO2, Ne, He, Kr, CH4.

The main pollutants in the lower atmosphere are:

Source Pollutant
Combustion reactions in cars, factories, planes NO3, NO2, NO, CO2, CO, C
Metal extraction, smelting factories, coal SO2
Aerosols such as deodorant and hair sprays CFCs
Livestock mainly cows CH4
Carbon Oxides are released from combustion reactions and volcanic activity and CO is a poisonous
gas that reduces the amount of oxygen that reaches oxygen. CO2 also increases the greenhouse
effect.
Particulates are small airborne particles such as soot and asbestos which are produced from
combustion (forest fires) and metal extraction. It results in respiratory problems and smog.
Nitrogen Oxides are formed as the result of heat produced by combustion or lightning and can lead
to photochemical smog and acid rain.
Sulfur Oxides are formed from volcanoes and the smelting of sulphide related ores and can lead to
acid rain.
Chlorofluorocarbons dont have a natural source and damages the ozone cycle leading to holes in
the ozone layers.

Ozone is an allotrope of oxygen with 3 oxygens per molecule. In the troposphere it is considered a
pollutant as it is a respiratory irritant, toxic to all living organisms. If it is inhaled, the single bond can
break and released an oxygen free radical within the respiratory system which damages normal
biological function of the lungs causing generic mutation or cell membrane damage to cells. It is
formed through:

2() () + ()
() + 2() 3()

In the stratosphere however it is a very important gas as it protects living organism from the harmful
effects of UV light from the sun and allows beneficial UV light to enter.
- UV-A is beneficial as it allows photosynthesis and vitamin D production.
- UV-B and UV-C causes skin cancers and DNA mutations in the nuclear of cells.

It absorbs harmful UV through the natural ozone cycle:

3() () + 2()

2() 2 ()
As oxygen radicals are very reactive, they react again to reform oxygen and ozone exothermically.
() + 2() 3()
3() + () 22()
Since energy is required to break these bonds, energy is released when the bonds are reformed in
the form of heat which is what heats the stratosphere.

A coordinate covalent bond is formed when one atom provides all the shared
electrons. In the case of ozone, the third oxygen atom gains 8 valence
electrons through the second oxygens electrons and does not provide any
electrons of its own. Once a coordinate covalent bond is formed, it is
indistinguishable from ordinary covalent bond. Another species with this bond
is carbon monoxide.
Comparison of allotropes of oxygen

Oxygen Radical Oxygen Ozone Reason

o
Boiling Point ( C) n/a -117 -76 Ozone is polar
Density n/a low High Ozone had more mass but
same volume
Solubility n/a low high Ozone is polar
Stability Very low high low Ozone has additional single
bond which is easier to
break
Reactivity Very high low High Ozone is unstable and prone
Strong oxidant Strong oxidant to photo disassociation
Polarity non non polar Resonance effect

Chlorofluorocarbons are compounds that contain carbon, chlorine and fluorine and halons include
bromine as well. They were first created in 1928 when there was a need to find a cheap alternative
to refrigerants as they are very stable, inert, non-toxic and non-flammable. Common uses are:
- Propellant in aerosol cans
- Foaming agent in foam plastics
- Refrigerant
- Cleaning agents
- Electrical fire extinguisher

As CFCs are very stable they are not broken down in the troposphere and slowly diffuse into the
stratosphere where the UV radiation allows it to decompose and form radicals.

3 () () + 2 ()
It then reacts with an ozone molecule and strips it of an oxygen:
() + 3() () + 2()
() + () () + 2()
This new radical reacts with another oxygen radical forming an oxygen molecule and reforms the
original chlorine radical. The above two reactions occur in a cycle, slowly depleting the stratosphere
of Ozone, forming it into oxygen.
This creates an Ozone Layer and allows harmful UV light to enter the troposphere which has
resulted in incidence of sunburn and skin cancer, increased risk of cataracts, lowered immune
response, reduced plant growth and increased damage to many synthetic materials such as PVC.

The Ozone Monitoring Instrument, a satellite is able to monitor levels of ozone, various CFCs and
many other pollutants. It uses a series of imaging tools to examine the radiation that hits the
atmosphere and is a specialised form of spectroscopy

The Montreal Protocol (1987) was taken to alleviate the problem:

- Completely phase out CFCs by 2010
- Short term use of HCFCs as a substitute until 2040. HCFCs are more susceptible to break
down in the troposphere and so are less of a risk in entering the stratosphere where they
still have the same potential as CFCs.
 - The long term goal is to use HFCs which rapidly breakdown in troposphere and do not
contain any bromine or chlorine, the radicals that destroy the ozone layer. Hence they do
not have the capacity to damage the ozone layer but they are expensive to produce.

Water quality can be determined by considering:

Total Dissolved Solids

TDS is the mass of all solids dissolved in a unit volume of water. It can be measured through
- Evaporation and weighing the mass of the remaining solid.
- Electrical conductivity as the free moving ions can carry charge. The greater the conductivity,
the greater the ion concentration.
Hardness
Hardness is the concentration of Ca2+ and Mg2+ ions in water. Hard water forms a grey scum with
soap and normal water forms a lather.
Turbidity
Turbidity is the measure of suspended particles in water which decrease its clarity. High turbidity
makes water very murky and blocks the UV rays required for photosynthesis for plants in the water,
decreasing dissolved oxygen levels. It can be measured through:
- A secchi disk which is lowered into the water until the black and white quadrants are
indistinguishable. The depth recorded is converted to NTU, with clean water less than 3NTU.
Acidity
Acidity of the water must be kept in certain ranges as many organisms only survive in particular pH
ranges and clean water is between 6.5 8.5 pH. It can be measured using a pH meter.
Dissolved Oxygen
DO comes from absorbance of oxygen from the air at the surface of the water and from
photosynthesis of aquatic plants. The oxygen is consumed by aerobic organisms and can further
decrease with thermal pollution as heat decreases solubility of oxygen. It can be measured through:
- Winkler Titration method
- Dissolved oxygen sensor
Biological Oxygen Demand
BOD is a measure of the concentration of dissolved oxygen needed by the aerobic bacteria which
breakdown organic matter in the water. A high BOD indicates that water is polluted. It can be
measured by allowing this microorganisms to oxidise organic matter in a sealed, dark environment
at 25oC for 5 days and then measuring the difference in DO levels.

The factors that affect ion concentrations are:

Industrial
- Acidic rain leaches metal ions such Ca2+ and Mg2+ from soil. These ions can be washed into
waterways
- Industrial effluent where waste is dumped into waterways without treatment and many
heavy metal ions can enter waterways.
Agricultural
- Rainfall on land with fertiliser causes the run-off water to contain a large amount of PO43-,
SO42- and NO3- , which encourages algal blooms.
- When land is cleared for agriculture, the water is able to carry more sediment with it such as
K+, Ca2+, SO42- and Cl-.
Mass water sanitation begins with water being collected in catchments and goes through the
following processes for purifications:
- Catchment monitoring: minimises the amount of toxins that enter catchments through
banning land clearings, industrial and agricultural activity near the catchment areas.
- Screenings: Water passes through several filters which get progressively smaller to filter out
large particle such as bottles and sticks.
- Aeration: Water is sprayed into the air to increased DO levels which oxides any iron and
manganese salts to be removed later.
- Flocculation and Coagulation: FeCl3 is added to precipitate ions in the water. These
precipitates then coagulate other minute particles in the water, into insoluble clumps called
flocs.
- Sedimentation: The flocs are allowed to settle at the bottom of the tank, forming a sludge
which is then systematically removed.
- Filtration: The water is passed through a series of sand, gravel and charcoal filters which
decreases turbidity.
- Chlorination: The water is disinfected of micro-organisms such as E.coli and Giardia, by
adding a strong oxidant like chlorine gas.
- pH Adjustment: The ideal pH of water is 6.5 - 8.5 and to adjust it buffering chemicals such as
carbonates and hydroxides are added. Acidic water can cause the structural degradation of
pipes and other water distribution systems
- Fluoridation: Fluoride ions are added to prevent tooth decay and better protect teeth.

This method is used in Australia and has a very high standard globally that is effective in producing
sufficient amounts of water to meet demands of large cities. However in mid-1998 Giardia and
Cryptosporidium was detected in waterways as a result from heavy rainfall that followed a drought
period as it washed in a large amount of organism matter and micro-organisms. This could have
been prevented if the water was sterilised with ozone instead of chlorine however this is much more
expensive.

A Microscopic Membrane Filter consists of a thin sheet of a synthetic polymer

(polypropylene) which contains very small pores, diameter of 0.2 micrometres, that
are large enough to allow water molecules to pass through but small enough to
restrict micro-organisms. The water is passed across the membrane surface (which
prevents blocking) and is pulled through the filter using high pressure pumps or
gravity.

Eutrophication is the process where a body of water becomes enriched with

phosphate and nitrate nutrients to an extent that induces algal blooms which is
accelerated by thermal pollution. This results in low DO levels and lead to the death
of aerobic life in water systems (fish and bacteria). As phosphate is in a lower
concentration than nitrate (1:10) it is the limiting factor in algae and plant growth.
Algae will multiply rapidly, covering the water in a green scum, reducing sunlight penetration. The
BOD will increase as the aerobic bacteria will attempt to decompose the organic matter and the
decreased sunlight will inhibit photosynthesis in the water and further decrease DO.