HSC CHEM

BOS: 28218087

Research Assessment Task (Notes)

1. Chemical Monitoring and Management - Section 5
Identify that water quality can be determined by considering:

Concentrations of common ions

Total dissolved solids
Hardness
Turbidity
Acidity
Dissolved oxygen and biochemical oxygen demand

Good quality drinking water:

Contains only small quantities of dissolved substances
Colourless and clear
Odourless and pleasant taste
Low salt content, pH close to 7
Domestic water should be soft
Good quality environmental water:
Adequate concentrations of dissolved oxygen (photosynthesis + survival)
Lesser levels of oxygen-consuming substances
Relatively free of suspended solids (interferes with photosynthesis)
Low nitrate + phosphate concentration (promotes algal blooms and eutrophication)
Concentration of common ions:
Potable water (water fit for drinking) must have low ion concentration avoid unpalatable taste + harmful effects
Ion concentration in sea water usually high compared to fresh water (Na+ and Cl- most abundant)
Note: Ion concentration in fresh water variable e.g. some rivers + lakes have high Ca2+
(limestone rocks ions dissolve when water runs through)
Common Ion Source

Effect

Test (Presence)

Chloride

Dissolved from Soil by

rainwater

Increases salinity kills

vegetation

Gravimetric Analysis:

Increased by land clearing

Brought to surface by rising
water tables

Gives water salty taste

Acidified sample heated and silver nitrate

slowly added insoluble silver chloride
precipitate (AgCl)
Volumetric Analysis (Mohr Method):
Titration against silver nitrate (AgNO3)
solution + potassium chromate indicator
AgNO3(aq) + Cl-(aq) AgCl(s) + NO3-(aq)

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Sulfate

BOS: 28218087
Soils and underground rocks
Brought to surface by ground
water + rising water table

Phosphate

Gives water bitter and medicinal Gravimetric Analysis:

taste
Water sample acidified with nitric acid
Causes diarrhoea + dehydration remove CO3- and HCO3- ions
in both humans and animals

Drops of Ba(NO3)2 added: white

precipitate (BaSO4), sample goes turbid
presence of sulphate ions

Fertilisers from farms

Essential for aquatic life;

Qualitative:

Household Detergents

Excess however fertilises

waterways algal blooms +
eutrophication

Precipitation of magnesium ammonium

phosphate: Warm with solution of
ammonium molybdate + nitric acid
yellow precipitate
Quantitative:
Colorimeters: filters to select wavelength of
light
- More elaborate: spectrophotometers

Magnesium
+

Leeching from soil (rainwater) Soaps will not lather

causes industrial pipes to block
Found within limestone rocks
Affects laundry
- CaCO3

Test (Hardness of Water):

Volumetric titration used within ammonia,
ammonium ion buffer

Calcium

Heavy Metals: Lead - Discarded car batteries Lead - Damages nervous system Atomic Absorption Spectrometry (AAS):
- Leaded contamination

Most common + preferred technique

of soil
Lead
- Washed from air
Inexpensive; however
during rain
- Initial set up costs very high
+
Mercury

Mercury - Industrial Processes Mercury - Damages nervous

system

+
Cadmium

Aluminium

Cadmium - Zinc smelting

- Sewerage
treatment

Cadmium - Bones porous

- Liver damage

Mobilised in soil by
increasing acidity

Toxic to plants correlation to

acid rain

Same as above

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BOS: 28218087

Total Dissolved Solids:

Abbr. (TDS): Total mass of all solids dissolved in unit volume of water
- Nearly all are ionic substances i.e. salts; potable water TDS < 500ppm
- Often quoted in mgL-1 or ppm
- Common ions: Na+, Mg2+, Ca2+, K+, Fe2+, Al3+
Fresh water contains less dissolved solids compared to salt water
- Salts more soluble than oxygen
- Total amount of TDS in freshwater fluctuates over time (influx of rainwater + seawater)
Factors contributing to TDS:
- Tidal flows
- Erosion
- Sewage and chemical runoff

TDS is related to water quality as clean water is relatively free of contaminants;

- Large amount of dissolved solids indicates unclean waste affects dissolved oxygen + aquatic life negatively
- >1000ppm degraded waterway i.e. water has limited value for irrigation
- High sodium levels: salinity problems (rivers and lakes)
- High potassium levels: leaching of burns or decaying plant remains (freshwater)
High salt concentrations are detrimental to crop growth affects crop yield
- Causes: Rise of groundwater to land surface from
- Removal of deep-rooted vegetation
- Continued flood irrigation of agricultural land
- Land-clearing
- Solutions: Management + minimisation
Testing Procedures:
TDS by evaporation (Destructive test):
Take specific volume of water (filter suspended solids) and weigh
Evaporate to dryness and then weigh the solid left
- Relatively inaccurate + suitable only for large TDS (Turbulent bubbling and spitting during evaporation
requires considerable care for accuracy)
Conductivity Measurement (Non-destructive test):
Nearly all solid dissolved in water is ionic (salts form ions in water conduct electricity)

- Measuring electrical conductivity can measure TDS

- Reasonable approximation in most cases

Modern instrumental methods use a conductivity probe and data logger

TDS (ppm) = 0.65 x conductivity in mS cm-1 (microsiemens/cm)
Standardise the meter with a standard solution and measure conductivity sample of water
- Accurate at low ion concentrations but drops off as salinity increases

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Hardness:
Hard Water: water containing significant concentrations of Ca2+, Mg2+, and Al3+ (together with HCO3-, SO42-, Cl-)

- Temporary Hard Water: Ca2+ and HCO3- ions can be softened by boiling
CaCO3 (s) + CO2 (g) + H2O (l) Ca2+ (aq) + 2HCO3- (aq)

- Permanent Hard Water: Mg2+ rather than calcium ions cannot be softened by boiling
Note: Hence water hardness measured by determining total concentration of calcium and magnesium ions in water
Expressed as milligrams of calcium carbonate (CaCO3) per litre
Hardness in domestic water is undesirable
- Soaps do not lather in hard water (soap is sodium stearate, a salt of the carboxylic acid, stearic acid)
Calcium and magnesium salts of stearic acid insoluble in water
Precipitates as grey scum on water surfaces + produces scale deposits in baths and sinks reduces efficiency

Factors contributing to hardness:

- Types of rocks that the water flows over (e.g. limestone)
Porous limestone soils acidic due to high levels of CO2 . Acidic water seeps through cracks and dissolves
CaCO3 produces solution of calcium hydrogen carbonate
- Industrial influences e.g. cement dust, run off
Testing Procedures:
Qualitative Test - stoppered test tube with flakes of soap solution
Water samples shaken in stoppered test tubes with flakes of soap or soap solution
After strong agitation for 1 minute, test tubes left to stand
- Soft water produces significant lather
- Hard water produces scum on surface + wont form bubbles
Ca2+ + 2CH3(CH2)16COO Ca(CH3(CH2)16COO)2 (s)
Quantitative Tests
EDTA Titration (Volumetric):
Both Ca2+ and Mg2+ ions in ammonia, ammonium ion buffer to form complex with EDTA (metal-EDTA complex)
M2+ + [EDTA]4 M-EDTA2EDTA: Quadruply charged anion [EDTA]4 (Ethylenediamine tetra-acetic acid) reacts in 1:1
stoichiometric ratio
Water
titrated
against
EDTA with indicator Eriochrome Black T (EBT)

Atomic Absorption Spectrometry (AAS):

Calcium ions determined first with a calcium lamp and calcium standards for calibration graph
Repeated with magnesium ions, lamp and standards
Total hardness is calculated by combining these 2 pieces of separate data

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Turbidity:
Define: A measure of the cloudiness or lack of transparency of water
Caused by suspended solids present
High concentrations of suspended solids increases turbidity:
- Scatters and reduces light penetration into water, lowering rate of photosynthesis and dissolved oxygen

- Unpleasant taste and colour

- Blocks gills of aquatic organisms and smothers small plants decrease in plant growth and impacts larger organisms

- Small particles in upper layer of water absorb infra-red radiation (sunlight) raising water temperature
Factors contributing to turbidity:
- Physical forces (naturally heavy floods + rains)
Rain running across grasslands picks up suspended matter
Rapid flows agitates water stirs up sediment
- Industrial run-off
- Land clearing and Farming
Loose earth exposed to rain
Testing Procedures:
Quantitative Tests:
Total Suspended Solids (TTS):
Determined gravimetrically by filtering the water sample (provided the filter has small pores)
Filter 1L of sample + measure dry mass (milligrams) of suspended solids in filter

- Freshwater streams should be <20mg/L

Useful for dirty water but not practical on drinking water (small amounts of dissolved substances)
Secchi Disk:
Disk painted black and white with string attached is lowered into body of
water until cross/mark can no longer be seen when viewed through
underwater viewer at surface
Water depth measured is inversely proportional to turbidity; calibration
graph used whilst string gives relative measure of NTU
NTU: Nephelometric Turbidity Units
Provides
logarithmic value

Convenient + portable (Adv.)

Low reliability than colorimeter (Disadv.)

- Variations in human eyesight

Nephelometer:
Measurement: Extent to which light is scattered by suspended particles in liquid

- 90 o of original path (sample, if clear should not scatter any light at this angle)
- More scattering more turbid

Calibrated using standard colloidal polymer suspension + distilled water

- If sample is too turbid: systematic dilutions required

- Turbidity calculated through comparison with this graph

More exact

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Acidity:
Define: The tendency of a medium to hydronate a specific reference base
- Measurement of concentration of hydrogen ions
- pH of water good indicator of its health
Clean, potable water should have pH in the range of 6.5 - 8.5
- Anything above/below indicates source of pollution (e.g. fertiliser run-off, industrial waste, acid drainage)
- Acidic water: Sour taste
- Basic water: Bitter taste
Changes in pH greatly affect usability of water + ability to harbour life:
- Decreased pH <6 enhances solubility of toxic metals disrupts enzyme function
- Increased pH >9 causes ammonia poisoning in aquatic organisms (Ammonium ions in water Ammonia)
Aquatic life tolerate only certain pH range
- Water tanks & pipes corroded by low/high pH
Factors contributing to acidity:
- Acidic water:
Acid rain
Urban and mining residue e.g. sulfide ore exposure
Organic decomposition (peat areas with high rates slightly acidic)

- Alkaline water:
Dissolved limestone soils slightly alkaline (pH > 7)
CO32-(aq) + H2O(l)

HCO3-(aq ) + OH-(aq)

Industrial waste discharge local change

Note: Waste discharge can be acidic or alkaline
Testing Procedures:
pH Paper (Destructive Test):
pH paper dipped into sample of water within container provided with test kit
After ~5 minutes colour change compared to pH chart

- Alternatively, indicator also can be used

Provides an estimate (lowered accuracy), though narrow range charts give better accuracy
pH meter/probe (Non-destructive Test):
Sample of water assessed using data logger + pH meter
pH Meter: Contains glass electrodes which are ion-sensitive; must be properly maintained + calibrated with
buffers otherwise invalid results
Most common + simplest way to measure pH

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Dissolved Oxygen:
Abbr. (D.O): Levels of molecular oxygen dissolved in water
- Measure of mg (O2) dissolved in 1L of water at fixed temperature (usually 20 - 25 C)
Two sources of Dissolved Oxygen in water:

- Atmosphere (mixed by turbulence created by wind, water flow + thermal currents)

- Photosynthesis (algae, plants, phytoplankton)
Dissolved Oxygen provides good indicator of water quality:
- O2 sensitive to temperature + organic wastes
- High D.O vital for sustaining life:
Aquatic organisms (respiration)
Levels <5 ppm respiratory distress, water body decays + undesirable characteristics

Factors affecting dissolved oxygen:

- Increasing amount of O2:

- More surface area (SA) in contact with air
- Decreasing amount of O2:
- Heat pollution (water temperature rises solubility decreases)
- Eutrophication (excessive growth higher B.O.D)
- Organic waste (increases decomposition process)
Testing Procedures:
Electrolysis Method: - polarographic oxygen probe
Fact: Rate of electrolysis of substance is proportional to its concentration under following conditions:
Constant voltage
Constant electrode surface area + separation between electrodes
Oxygen diffuses from sample through permeable membrane to anode for electrolysis
Anode: O2 (aq) + 4H+ (aq) + 4e-(aq)
Cathode: Ag (s) +

Cl-

(aq)

2H2O (l)

AgCl (s) + e- (aq)

Current flow converted into concentration

Volumetric Titration: - Winkler method
1. Oxygen present reduced by alkaline solution of Manganese Ions (Mn2+) to form precipitate
2Mn4+ (aq) + 4OH-(aq) + O2 (aq) 2MnO(OH)2 (S)
2. Precipitate is dissolved in concentrated sulphuric acid to produce Mn4+ ions, which oxidise iodide into iodine
MnO(OH)2 (s) +2I-(aq) + 4H+(aq) I2 (aq) + Mn2+(aq) +3H2O(aq)
3. Titration against sodium thiosulfate using starch indicator
I2 + 2S2O32- 2I- + S4O62-

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Biochemical Oxygen Demand:

Abbr. (B.O.D) : Measure of the capacity of organic matter in a water sample to consume oxygen
- I.e. concentration of oxygen needed for the complete breakdown of organic matter in water by bacteria
- Hence measures organic pollution (particularly due to aerobic respiration)
High Biochemical Oxygen Demand is detrimental:
- Bacteria decomposing wastes dissolved oxygen decreases
Insufficient oxygen for aquatic life
Iron salts oxidised
Discolouration + smell
- Ponds + slow-moving streams without water flush stagnant and toxic
- Samples >4 ppm considered polluted
Factors affecting biochemical oxygen demand:
Note: Same factors which affect dissolved oxygen
- Aeration of stream water (rapids) acceleration decomposition
- Chlorine
Inhibits/kills microorganisms which decompose material

Testing Procedures
5 Day B.O.D Test (BOD5)
Measures change in D.O over 5 day period when sample left in the dark + filled closed incubation bottle at 20oC

- Usually 1L of sample
- More commonly done on unpolluted water
- Oxygen consumed quality of water

Note: Dark prevent photosynthetic algae from releasing O2

BOD5 = (Dissolved Oxygen)0 days (Dissolved Oxygen)5 days
Polluted samples: Systematic dilution or re-aeration (run out of dissolved oxygen)
Respirometer
Sample placed in special bottle containing pressure sensor in lid
Oxygen depletion replacement diffusion into water (air in bottle)
Net reduction in pressure = B.O.D; readouts up to 400 000 ppm calculated
Relatively newer method

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BOS: 28218087

Identify factors that affect the concentrations of a range of ions in solution in natural bodies of water such
as rivers and oceans
Factors affecting concentration of ions:
Pathway (Rain Water Body):
Rain contains very few ions:

- Dissolved CO2: Carbonate

- Sea spray: Na+, Cl-, SO42-

Rain runs off bushland into streams:

- Small amounts of nitrates + phosphates picked up (natural nutrients on surface)

- Possible small amounts of Ca2+ and Mg2+ (decomposing minerals)

Rain-water occasionally soaks into ground + flows through underground aquifers into a stream:

- Increased amounts: Ca2+, Mg2+, SO42-, Cl- and CO32-

Dissolving from soils and rocks

Rain-water occasionally percolates down to deep underground aquifers (artesian basins) and comes to surface
centuries later:

- Much higher levels of Ca2+, Mg2+, SO42-, Cl- and CO32- May contain other ions: Fe3+, Mn2+, Cu2+ and Zn2+
Water Temperature:
Minerals dissolve faster at high temperatures
pH of Rain:
Water from acid rain better able to leach certain ions from soils it passes over/through

- Ca2+, Mg2+ and Fe3+ concentrations increase

Human Activity (Nature + Amount):

Land clearing leads to water running rapidly across disturbed land into streams:

- Increases sediment loads turbidity

- Facilitates dissolution: Na+, K+, Ca2+, Mg2+, SO42, Cl and CO32

Agriculture leads to fertiliser run-off:

- Increase in water: NO3- and PO43- \

Industrial Effluents:
Raw and/or treated sewage is discharged into rivers and oceans:

- Increase: NO3- and PO43 Uncontrolled monitoring can discharge heavy metal ions into water bodies:

- Increase: Pb2+, Hg2+, Cd2+, Cr2+, Cu2+ and Zn2+

Leaching (Rubbish Dumps, Rocks + Soils):
Poorly designed rubbish tips allow rain and storm-water to flow + seep through

- Termed: Leaching
- Dangerous Cations: Cd2+, Hg2+, Pb2+
Aquatic Organisms:
Marine organisms e.g. shelled invertebrates use ions to make exoskeletons

- Change ion concentrations of Ca2+ and CO32-

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Describe and assess the effectiveness of methods used to purify and sanitise mass water supplies
Water is used for many purposes:
- Drinking and cooking
- Washing and irrigating
- Industrial Applications
Methods to purify + sanitise:

Process

Explanation

Screening

Metal screens remove large solid particles (e.g. twigs + leaves)

Coagulation (Flocculation)

Water contains fine suspended particles (clay colloids):

- Cannot settle (repulsion between negative surfaces) precipitate by flocculation

Water is mixed with Iron (III) Chloride:

- Coagulant encourages suspended solids + micro-organisms to bind and form large

particles

- Water circulated in flocculation tank, gently stirred to help precipitate form

Traps suspended solids + removes colour

OR
Alum (Al2(SO4)3) added, often with lime (Ca(OH)2):

- Gelatinous precipitate of aluminium hydroxide formed Ca(OH)2

- Ca(OH)2 raises pH encourage precipitate formation
- Adsorption: Suspended solids, precipitated iron + bacteria stick to [aluminium hydroxide]
Al3+(aq) + 3H2O(l) Al(OH)3(s) + 3H+(aq)

Sedimentation (Clarification)

Treated water allowed to stand in settling (sedimentation) tanks:

- Flocs settle to bottom, forming sludge + settled water

- Sludge reused as compost
- ~95% impurities removed
Filtration

Settled water passed through granular filters (often sand, gravel + anthracite coal)

- Removes most of the remaining suspended solids

- Granulated anthracite has high carbon content adsorb dissolved organic matter
- Water is clear (< 0.5 NTU) + free of coloured matter
Alternative: Membrane filters
- More costly than sand-bed filtration

- More effective (smaller pore size)

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Disinfection (Sanitising)

BOS: 28218087
Gaseous chlorine gas added to filtered water disinfection

- Reacts with water to produce hypochlorous acid

- Kills bacteria + microbes (e.g. E. Coli)

Term: Chlorination

Cl2 (g) + H2O(l)

HOCl (aq) + H+ (aq) + Cl- (aq)

Alternative: Sodium Hypochlorite

NaOCl(aq) + H2O(l)

HOCl (aq) + H+(aq) + Cl- (aq)

Alternative: Ammonia
- Reacts with chlorine Monochloramine (NH2Cl)
- Weaker oxidising agent
- More chemically stable (lasts longer through transport)
Alternative: Ozone
- Electric spark passed through clean dry air or O2
- Strong oxidising agent effective + positive impact (colour, odour, taste)
- Highly sensitive to turbidity Not used extensively in Australia
Fluoridation

Fluorine added in form of compounds e.g. sodium hexafluorosilicate (Na2SiF6)

Na2SiF6 (aq) + 4H2O 2Na+(aq) + 6F(aq) + H4SiO4 (aq) + 4H+

- Not added as safety measure, rather reduce incidence of tooth decay

Fluorine acts in complementary ways to reduce tooth decay:

- Interacts with tooth enamel denser lattice, stronger + resistant

- Presence in plaque and saliva: Remineralisation (repairing small defects in tooth)
- Interferes with acid-producing bacteria (bactericide)
pH Correction

pH of water adjusted with buffers:

- Lime: Ca(OH)2 added with CO2 to form sodium hydrogen carbonate buffer
Alternative: Soda Ash
Suitable pH range: 7 - 8.5

- Reduce and prevent scaling + corrosion of water distribution pipes

Assessment of Effectiveness:
Flocculation:
Very effective at removing fine suspended particles attracting bacteria + viruses to surface

(Research: 99.9% Bacteria and 99% viruses)

Removes some of organic matter washed up as soils + vegetation (water travels from rain to catchment area)
Responsible for brown discolouration and odour
Cost effective and relatively fast

Sand Filtration:
Removes high proportion of particulate matter in water after flocculation
Sufficiently fast: Produces volume of treated water required for big cities
Does not remove extremely small particles (suspended solids too fine after flocculation)
Leaves some taste + odour

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Chlorination:
Cost-effective way of removing most pathogens (disease-causing agents)
Does not remove all organisms

Giarda and Cryptosporidium Scare:

100 + casualties in 1998, Warragamba Dam Sydney householders advised to boil water

Possible formation of hazardous disinfection by products e.g. trihalomethanes

Risk is far less than microbial contamination
Chlorination still warranted (minimum disinfection concentrations)

Overall:
There are flaws in methods used to purify and sanitise water (contamination can still occur)
1998 Sydney contamination scare (Giarda and Cryptosporidium)

Methods are still highly effective in sanitising mass water supplies to produce high quality potable water
Recommendations: Membrane filters and Ozone sterilisation
Cost a lot; development further increase in water quality

Describe the design and composition of microscopic membrane filters and explain how they purify
contaminated water
Membrane Filter: A thin film of synthetic polymer through which there are pores (small holes) of fairly uniform size
- Polymer: Polypropylene
Pore size of ~ 0.2 m diameter allow water molecules but not bigger molecules + harmful microorganisms through

- Able to remove molecules of carbon compounds + particles of sub cellular size

- Term: Partially permeable

Membrane filtration uses gravity, vacuum/pressure pumps or centrifugal force

Forces liquid through membrane
Smaller pore size greater energy required for filtration

Depth Membrane:
- Simplest type
- Sheet of porous polymer pleated (folded) around a central rigid core + held with surrounding mesh
Cartridge placed in suitable housing; filters water as it flows through

Hollow-fibre Membrane:
- Porous material made into hollow capillaries (thin, hollow tubes)
Outside diameter: 500 m
Inside diameter: 200 m
Pore size: 0.2 - 0.5 m

- Large number of capillaries bundled together

filtering unit with large SA

- Cleaning: Air blown from clean side (dislodge trapped particles washed away by dirty water on outside)
-

Able to filter bacteria not removed through chlorination + sand filtration

Quite thin liquid flow is fairly rapid

Reasonably strong
Can be cleaned and reused
High cost + easily clogged (especially when filtering insoluble materials)
Too slow for mass water supply

e.g. Giarda and Cryptosporidium

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Gather, process and present information on the range and chemistry of the tests used to:

- Identify heavy metal pollution of water

- Monitor possible eutrophication of waterways
Heavy Metal Pollution
Heavy Metals: Transition metals + lead (some contexts Arsenic is also included)
Relatively high atomic mass
Most concern: Mercury, lead, cadmium, chromium, arsenic
Lesser extent: Silver, zinc and copper
Toxic: Bioaccumulate in the body + biomagnify along each step of the food chain neurological damage and death

- Bioaccumulation: High buildup in body of organism, not excreted

- Biomagnification: Increase of concentration as it moves up food chain

Sources of Heavy Metal Pollution:

- Mercury:
Certain industrial processes

- Lead:
Petrol contamination of soil (washed with rain water)
Discarded car batteries

- Cadmium:
Zinc smelting
Paints
Sewage treatment
Testing Procedures:
Qualitative - precipitation reaction
Heavy metals generally have low solubility (esp. in presence of halide or sulfate ions)

- Precipitation will reveal presence but not necessarily the type of ion

Water sample acidified and drops of Na2S added:

- Precipitate: Pb2+, Ag+, Hg2+, Cu2+, Cd2+, As3+
Hg2+(aq) + S2-(aq) HgS (s)
Water sample made slightly alkaline and drops of Na2S added:
- Precipitate: Cr3+, Zn2+, Fe2+
Quantitative: - Atomic Absorption Spectroscopy (AAS)
Most effective method
Water sample is vaporised in a flame
Ground state atoms of element irradiated by light of particular wavelength from hollow cathode lamp and absorbed
only by those atoms

- Measurement: Fraction of absorbed light = concentration of element in water

Samples of absorbance related using calibration curve

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Eutrophication
Define: Process whereby lakes, rivers + slow-moving water bodies effectively become lifeless due to excess nutrients
- Water is enriched with nutrients (e.g. Nitrate: NO - and Phosphate: PO 3- ions), leading* to algal blooms
3

Algal Bloom: excessive growth of algae & other aquatic organisms

Alternative*: To such an extent that algal blooms becomes highly likely

Process of Eutrophication:
1. Excess nutrients enter the waterway (Nitrate: NO3-, Ammonium: NH4+, Phosphate: H2PO4-)

- Supplied by surrounding rocks and soils + natural decay of organic matter

2. Algal and aquatic plant growth increase (algal bloom)

- Algae grow and multiply rapidly, releasing toxins

- Algae grow on surface of the water, blocking sunlight and atmospheric oxygen
3. Reduced light penetration and increased oxygen demand (respiration)
4. Lower-level and plants die and begin to decompose
5. B.O.D increases (decomposition of organic material by bacteria)
6. D.O decreases
7. Aquatic organisms (e.g. fish) and algae die (insufficient nutrients) decompose and use remaining D.O

- Algae decay anaerobically: Putrid mess which results in death of remaining life forms
Sources contributing to nutrient level:
- Sewage
- Plant and animal waste (farms)
- Fertiliser run-off + phosphate-based detergents
- Industrial waste
Testing Procedures:
Quantitative Test: - colorimetric method for phosphate
Phosphorous generally the growth-limiting nutrient in algal blooms phosphate has greatest control on growth rate
Water treated with strong oxidant (e.g. Nitric Acid) to ensure phosphorous present as PO43-)
Ammonium molybdate (NH4)2MoO4 solution added with catalyst
Forms pale-yellow phosphomolybdate complex (NH4)2PO412MoO3
Measured amount of solid ascorbic acid (Vitamin C) added to solution blue colour produced from complex
Absorbance of blue colour compared to absorbance of standard phosphate solution treated identically (colorimeter)
colorimetric method for nitrate
Nitrate is reduced to nitrite (sample flowed through tube of granulated cadmium)
NO3

-+

2H+

Cd Cd2+ + 2e+ 2e- NO2- + H2O

Solutions of two organic compounds added successively to nitrite solution reddish-purple colour
Absorbance of solution compared to standard nitrate solution treated identically (colorimeter)

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1Gather,

BOS: 28218087

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
Chemical additives in the water and the reasons for the presence of these additives

Catchment Area:
Define: Geographic area from which all streams and rainfall drain into a citys water storage dam
Warragamba Dam is Sydneys main storage dam, Catchment area: 9000+ km2, accounts for 80% of Sydneys water
- Contains:
Small rural settlements
Residential development areas
Major cities

- Characteristics of Area:

Grazing and Dairy farming

Tourism and Recreation
Mining + extractive industries

Possible sources of Contamination:

Agricultural activities:

- Crop growth and livestock (e.g. cattle grazing + poultry) leads to run off of animal manure directly entering water system
Nitrate (NO3- ) and Phosphate (PO43-) nutrients lead to eutrophication

- Animal waste (faeces) promotes bacterial growth e.g. E. Coli, Giarda and Cryptosporidium
High B.O.D and increased acidity

Effluent:

- 9 sewage plants in area may release poorly treated waste into water supply during rainfall
Nitrate (NO3- ) and Phosphate (PO43-) nutrients lead to eutrophication
Bacterial growth and faecal coliform e.g. E. Coli, Giarda and Cryptosporidium

Stormwater Runoff:

- Sediment and toxic material on roads can flow into water supply
- Soil leaches out minerals e.g. Fe3+ and Mn2+ ions
Coloured tinge + metallic taste in water

Human Activity

- Active or abandoned mines e.g. copper and zinc can leach out heavy metal pollutants
Increase acidity of water

- Logging and land-clearing affect water in dam

Increased turbidity + TDS

Note: Refer back to previous sections (Revision)

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2. The Chemistry of Art - Section 1

Identify the sources of the pigments used in early history as readily available minerals
Pigments: Natural colouring matter of plant or animal tissue; fine coloured particles which are insoluble
Paint has an extensive history:

- Oldest known paintings: - Australian Aboriginal rock art (17 000 years ago)
- French Lascaux cave paintings (15 000 years ago)

Pigments in early history were derived from natural sources

E.g. minerals in coloured earths + soft rocks:

- Readily available in environment

- Did not require complex extraction processes

Same basic colours (red, yellow, black, white) used by Aboriginals:

- Earth colours, particular red

- Desert culture + value
Ochre: Natural earth of silica + clay owing its colour to presence of Iron(III) oxide in anhydrous or hydrated form

- Red: Contains anhydrous Iron (III) oxide (Fe2O3)

- Obtained by burning/drying yellow ochre (laterites) in sun to remove water
- Brown: Nearly pure limonite [FeO(OH)]
- Yellow: Contains hydrated Iron oxides, main: mineral goethite (Fe2O3H2O)
- Black: Contained in naturally occurring manganese (IV) oxide [MnO2]
- Charcoal: Mainly graphite, an allotrope of carbon (sources: burnt wood, animals bones + soot from lamps)
- White:
- Kaolin: White clay hydrated aluminium silicate (Al2O3 2SiO2 2H2O)
- Chalk: Calcium carbonate (CaCO3)
- Gypsum: Calcium sulfate dihydrate (CaSO4 2H2O)
Mineral

Colour

Chemical Formula

gypsum

white, grey

CaSO4 2H2O

cerussite

white, grey

PbCO3

stibnite

lead-grey, blackish

Sb2S3

galena

lead-grey

PbS

graphite

black

cinnabar

red, brownish red

HgS

haematite

earthy to bright red

Fe2O3

malachite

bright green

Cu2(CO3)(OH)2

azurite

azure blue to dark blue

Cu3(CO3)2(OH)2

orpiment

lemon yellow - brownish yellow

As2S3

turquiose

bluish green

CuAl6(PO4)4(OH)8 4H2O

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Explain why pigments used needed to be insoluble in most substances

Pigments are coloured solids suspended in a medium (usually colourless)
Need for insolubility:

When medium dries up, colour remains

Preservation used for longer periods of time
Hot climates: Cosmetics would not dissolve in perspiration
Chemical stability
Intense colours with high opacity + reflectance

If pigments were soluble:

- Rain + groundwater would easily wash colour of paint away
destroys painting

Outline the early uses of pigments for:

- Cave drawings
- Self-decoration including cosmetics
- Preparation of the dead for burial
Cave Drawings:
Primary use of pigments in early history were for cave painting:
Australian Aboriginal Rock Art (17 000 BC):

- Found near Aboriginal ceremonial sites or corroboree grounds (coming of age)

- Paint used to depict mythological culture
- Paint mixed in mouth, consisting of grounded rocks (gypsum and ochre) + saliva
Spluttered (sprayed by mouth) onto walls

Lascaux Cave Paintings in France (15 000 BC):

- Depicted images of hunting animals and rituals
- Pigments mixed with cave water (high calcium content good adhesion + durability)
- Applied with crushed twig tips and bundles of animal hair e.g. bison
Pigments used were derived from natural sources:
Black:

Red, Brown, Yellow: Ochre

- Burning fine grasses

- Crushing charcoal
White:

- Lime
- Pipe clay
- Ashes and Emu dung
Pigments ground to powder and mixed with fixatives/binders

- Fixatives: Liquid used to preserve or stabilise pigment

e.g. Blood, raw egg, animal fat, water

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Self-decoration including Cosmetics:

Cosmetics had two major functions:
- Surface coatings designed to enhance or protect skin
- Cleansers
E.g. Face paint, eye-shadow, face whitener and eyeliner
Aboriginals:
Ochre + Kaolin applied with fingers or brushes

- Body painting for traditional ceremonies e.g. coming of age

Egyptians;
Used better quality earth colours (Extraction techniques improved pigments finely grounded + fewer impurities)
Eyeshadow:
- Orpiment sulfide used as green-yellow eyeshadow
- Green: Verdigris + resin or powdered sand mixed with malachite
Eyeliner:
- Egyptians lined their eyes heavily with kohl
Kohl: Black/grey powder made with powdered stibnite (Sb2S3); manganese (IV) oxide (MnO2) + CuO

- Moistened with saliva, then drawn around eyes

Lipstick:
- Cinnabar, naturally occurring form of red mercury (II) sulfide, HgS, crushed + ground as a rouge in lipstick
Skin Paint:
- Elemental gold essential to Egyptian culture
Covered the nipples

- Azurite (2CuCO3) was naturally blue highlighted blue veins of breast

- Malachite, Cu2(CO3)(OH)2 prepared by careful selection, grinding and sieving of ore
Bright green eye paint

Greeks and Romans:

White lead (basic lead carbonate, 2PbCO3 Pb(OH)2) was one of the first artificially prepared pigments

- Popular as face powders

- No longer used (toxicity)
- Mixed with vermillion + red lead pink colours
Vermillion: Synthesised mercury (II) sulfide, made by heating mercury and suffer together in flask
Red Lead: Minium, PbO2 2PbO, produced from oxidation of molten lead

Preparation of the Dead for Burial:

Ancient Egyptians:
Had tomb painted for decoration + ceremonial purposes (reverence for passage of the dead)
- Body was decorated same as living; tomb painted

- e.g. pharaoh Tutankhamen had paint box containing powdered gypsum, orpiment, haematite and malachite gifts

- Internal organs replaced with mixture of resins, oils + beeswax; treated with natron (salt) to dry and preserve
Ancient Mayans:
Colour red was associated with blood represented death and rebirth
- Bodies soaked in red ochre to preserve and ensure safe passage to afterlife

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Explain that colour can be obtained through pigments spread on a surface layer (e.g. paints) or mixed with
the bulk of material (e.g. glass colours)
Wood panels and canvas are unsuitable for direct painting:
- Too rough and adsorbent
Adsorbent: Substance which attracts other particles to its surface

- Traditionally prepared with layers of ground/priming with gesso

Gesso: Mixture of gypsum or chalk + animal glue, applied as thick warm liquid and set to a brittle, creamy white layer

Paints are used so that colour is obtained by spreading pigments over surface layer:

- Pigments suspended in medium thinly spread as protective coating/decorative layer

- Medium disperses pigments on surface then dries to form adherent film which preserves + protects pigments
Spreads:
Egg Tempera:
- Used in panel panel painting
- Medium egg yolk mixed with water; pigments added to tempera and used straight away
Gilded:
- Process of coating painting in gold
- Area is coated with mixture of Iron (III) oxide + egg white, then burnished after being set hard
- Gold leaf added using glue (e.g. egg white), then burnished again
Lake Pigments:
- Organic pigment precipitated with inert binder and dried can cover large areas
Structure and Stages of Painting:
Support layers: Backing of painting (e.g. canvas or wood)
Ground Layer: Brittle white layer of gesso, scraped + polished until surface smooth for painting
Paint layers: Pigments mixed with binder + medium and spread onto layer. Colours superimposed to achieve complex
effect (each paint layer one pigment colour)
Varnish Layer: Provides depth of saturation, added to protect paint layers
Mixing with Bulk of Material:
Until 19th Century, paint layer consisted of several superimposed layers
- Modern painting mixing pigments together e.g. glass colour
Metal Oxide pigments are finely powdered and added
- Addition allows formation of coloured glass when cooled

Intensity and shade of glass not always desirable:

- Flashing: Coating clear glass with thin layer of coloured glass during molten stage lighter colour e.g. ruby
- Staining: Alters tone of colour
Glass painted with silver nitrate (AgNO3) then fired in oven.
Process repeated different shades e.g. yellow (pale lemon to deep orange)

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Describe paints as consisting of:

- the pigment
- A liquid to carry the pigment
Paint: Substance composed of solid colouring matter suspended in liquid medium/vehicle

- Uses: Applied as protective or decorative coating to various surfaces e.g. canvas

Three components: Pigment, Binder, Medium
Pigment:
Granular solids composed of very fine particles which gives paint its colour
Absorb and reflect different wavelengths of light colour
Insoluble and chemical stable
Retains colour after medium dries up
Derived from natural sources in early times
Binder:
The glue which keeps pigments together; carries pigment to be spread over surface
Controls flow properties of coating and forms protective coating improves hardness and resistance to wear
Medium:
Liquid suspending the pigment
Allows paint to be spread evenly over surface

- Must be viscous enough to prevent paint from running

- Not too thick (restricts artists work + hard to apply)
Helps bind pigment together + achieve better adhesion to surface
e.g. Water, oil, egg yolk, wax, sap urine

Describe an historical example to illustrate the relationship between the discovery of new mineral deposits
and the increasing range of pigments
Availability of pigments increase due to:
- Discovery of new mineral deposits
- Improved extraction methods (useful minerals)
- Increased trading (distant communities)

Generally,
Greater number of minerals = more pigments

E.g. Sienna (Yellow-brown coloured pigment): Fe2O3 H2O (Hydrated iron (III) oxide)
- One of the first used in Italy
- Named after Siena, city located in Tuscany
- Mined from Renaissance WWII

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Analyse the relationship between the chemical composition of selected pigments and the position of the
metallic component(s) of each pigment in the Periodic Table
Many chemical compositions of pigments used in the 21st century have within them a metallic element:
- Metallic components mainly found in transition metal section (d- block)
Often related to certain colour/colour range

Iron: Usually associated with colours in red-orange range

Copper: Blue-green range
Cobalt: Yellow-purple range
Chromium: Red-yellow range
Electron configuration contributes to colour produced by transition metals:
- Colour of metal depends on energy gap between d-orbitals
Different metals have different d-orbital energies (different electrostatic attraction, shielding + configuration)

- Colour produced when electron absorbs proton of quantised energy moves up and back down
- Elements e.g. zinc are colourless (d-orbital full no available electron transitions)

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Process information from secondary sources to identify the chemical composition of identified cosmetics
used in an ancient culture such as early Egyptian or Roman and use available evidence to assess the
potential health risk associated with their use
Various health risks associated with use of pigments as cosmetics:
Cosmetics: Enhanced features of people who wore them [Greek/Roman]

- No concern with ill effects resulting from long term use + ingestion (in particular when saliva medium)
E.g. White lead, vermillion
Cosmetic

Element

Pigments containing Element

Health Risk

Face Powder

Lead

White Lead:

Toxic by Ingestion + Inhalation:

(PbCO3)2 Pb(OH)2

- Lead is heavy metal bioaccumulates

- Skin, eye and respiratory irritant
- Effects: Brain damage, mental retardation,
death

Eye Shadow

Arsenic

Orpiment:

Highly toxic by Ingestion + Absorption:

As2S2

- Carcinogenic
- Effects: Reproductive disorders

Realgar:
As4S4

Body Paint

Copper

Green Malachite:

Harmful through Ingestion:

Cu2(CO3)(OH)2

- Eye irritant
- Effects: Gastrointestinal discomfort,

Blue Azurite:

respiratory damage

Cu3(CO3)2(OH)2

Eyeliner

Sulfur

Ultramarine

Not Poisonous low potential health risk

Antimony

Kohl (Stibnite):

Harmful by Ingestion + Inhalation:

Sb2S2

- Skin, eye and respiratory irritant

- Chronic exposure liver + kidney damage

Pyrolusite:

Harmful by Ingestion + Inhalation:

MnO2

- Reduced fertility in men

Mercury:

Highly toxic by Ingestion, Inhalation + Absorption:

HgS

- Heavy Metal bioaccumulates

- Harmful in small quantities
- Damages CNS + kidneys (causes disease)

Mascara
Manganese

Lipstick

Cinnabar
Vermillion

- Overexposure death

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Identify data, gather and process information from secondary sources to identify and analyse the chemical
composition of an identified range of pigments
Australian Aboriginals:
Pigment/Mineral

Colour

Chemical Composition

Formula

Red Ochre (Haematite)

Red

Anhydrous Iron (III) Oxide

Fe2O3

Yellow Ochre (Limonite)

Yellow

Hydrated Iron (III) Oxides

Fe2O3 H2O

Brown Ochre (Goethite)

Brown

Nearly pure limonite

FeO(OH)

Manganese (IV) Oxide

Black

Manganese (IV) Oxide

Mn2O

Charcoal

Black

Mainly graphite

Kaolinite

White

Hydrated Aluminium Silicates

Al2O3 2SiO2 2H2O

Chalk (Calcite)

White

Calcium Carbonate

CaCO3

Gypsum

White

Calcium Sulfate Dihydrate

CaSO4 2H2O

(Pyrolusite)

Egyptians and Romans:

Pigment/Mineral

Colour

Chemical Composition

Formula

Vermillion/Cinnabar

Red

Mercury (II) Sulfide

HgS

Minium/Red Lead

Red

Lead Tetroxide

PbO2 2PbO

Realgar

Orange-scarlet

Tetra-arsenic Tetrasulfide

As4S4

Orpiment

Yellow

Arsenic Trisulfide

As2S3

Massicot

Yellow

Lead (II) Oxide

PbO

Malachite

Green

Basic Copper Carbonate

CuCO3 Cu(OH)2

Verdigris

Blue-Green

Basic Copper (II) Acetate

Cu(CH3COO)2 2Cu(OH)2

Azurite

Blue

Basic Copper Carbonate

2CuCO3 Cu(OH)2

Egyptian Blue/Blue Frit

Blue

Calcium Copper Silicate

CaO CuO 4SiO2

White Lead

White

Basic Lead Carbonate

(PbCO3)2 Pb(OH)2

Pigment/Mineral

Colour

Chemical Composition

Formula

Natural Ultramarine

Blue

Complex Sodium
Aluminosilicate + sulfur

Na8-10Al6Si6O24S2-4

Naples Yellow

Yellow

Lead (II) Antimonate

Pb3(SbO4)2

Lead Tin Yellow

Tin Yellow

Lead Tin Oxide

Pb2SnO4

Italian Ochres

Sienna, Umbers, Green Earths

Italian:

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Post 18th Century:

Pigments/Minerals

Colour

Chemical Composition

Formulae

Chrome Yellow

Yellow

Lead (II) Chromate

PbCrO4

Chrome Red

Red

Basic Lead (II) Chromate

PbCrO4 Pb(OH)2

Cadmium Yellow

Yellow-Orange

Cadmium Sulfide

CdS

Cadmium Red

Red

Cadmium Sulfide Selenide

CdS CdSe

Titanium White

White

Titanium Oxide

TiO2

Zinc White

White

Zinc Oxide

ZnO

Bibliography
Chemical Monitoring and Management:
Textbooks:
Irwin, D et al. (2005) Chemistry Contexts 2. Second Edition. Pearson Place, Sydney. Pages Used: (262-281). Date
Accessed: 1/11/2015

- Chemistry Contexts 2 contained a lot of valuable information and was used as a guide to address each dot point with
supporting diagrams, equations and formulae. It was the reference point for initial study

Smith, Roland. (2005) Conquering Chemistry HSC. Fourth Edition. Sydney, McGraw-Hill. Pages Used: (262-294)
Date Accessed: 1/11/2015

- This book contained detailed information regarding water quality, treatment and environment factors affecting water quality.
It helped a lot with the first dot point and included in-depth chemical equations, formulae, diagrams and explanations. The
diagrams were clear, labelled and annotated, and it also helped the filtering + monitoring section of my notes.

The Chemistry of Art:

Textbooks:
Irwin, D et al. (2005) Chemistry Contexts 2. Second Edition. Pearson Place, Sydney. Pages Used: (48-65). Date
Accessed: 1/11/2015

- The textbook had very detailed information that addressed each dot point. There was a great deal of information on
pigments, and hence, for chemistry of art in particular, it was the most used source of information for researched. I found
however that the provision of information was sometimes very jumbled in order, not following the order of the syllabus,
thought it was not a great hindrance as one could simply cross reference and reassemble the pages to maintain validity.

Internet sites:
NSW HSC Online. Chemistry -9.8 The chemistry of Art. Charles Stuart University. Date Accessed: 1/11/2015

- This particular website had summaries of all the relevant information followed under each specific syllabus dot point, and
also led to further trusted websites describing the colour with graphical interpretation of each pigment and its uses. As a
result, I colour coded my pigment notes based upon these results.