Sulphates

Def: Salts or esters of sulphuric acid, Sulphates can be found

in water as the oxidised forms of sulphites, sulphides and
thiosulphates or as organically bound sulphates.

Sources: any industry which uses or produces sulphuric

acid such as Mining and heavy chemical industry
effluents

Effects: Sulphates exhibit a therapeutic effect in high

concentrations

Max Allowable Conc: 250 mgL-1.

 Turbidimetric Method using Barium Chloride

The method works by reacting barium chloride with the

sulphate,
O O
2+ 2-
Ba + S O Ba S O
O O O O
….the barium forms a precipitate with the sulphate ions present
in solution

The precipitation affects the turbidity of the sample. Turbidity is

the measure of the fine suspended matter in water The
turbidity of the solution at 450nm is directly proportional to
the concentration of sulphate initially present in the sample.
 Total Phosphorous
Phosphates are the most common form in which
phosphorus occurs
These water soluble salts of phosphoric acid
commonly appear in a mineral form, they are
primarily used in detergents and as a
component of fertilizers
• Excess phosphates can cause eutrophication of a water body
producing algal blooms.

• The algae present in the contaminated water body grow rapidly in

the presence of excess nutrients.

• When they are growing they produce oxygen by photosynthesis

during day light hours and when it is dark, they change to a
different metabolic process that utilizes available oxygen in the
water.

• When the algae die, oxygen production ceases and bacterial

decomposition, which uses up the dissolved oxygen in the water,
occurs. This results in red tides recognised by a reddish tint in the
water of affected areas.
phosphorus occurs in a wide variety of inorganic
and organic forms

While these may exist in either the dissolved,

colloidal, or particulate forms, the
predominant species is orthophosphate in
either the mono- or diprotonated forms
(HPO42-,H2PO4-)
 Analysis
The only form of phosphate determined directly is
orthophosphate other forms of phosphates
including condensed phosphate and organically
bound phosphates have to be converted to
orthophosphates by acid- persulphate reaction

The term total phosphates is the total phosphate

concentration after it has all been converted to
orthophosphate reactive phosphates is another
measurement which indicates the orthophosphates
present initially.
 Ascorbic Acid Method
Pre-treatment …………………
converts all the phosphate compounds in a sample to orthophosphate by
reacting them with potassium persulphate in the presence of acid (R and
R! represent different organic fragments)
O
O O 2-
R P R' K2S2O8 H2SO4 H3PO4 (K+) (SO4)
+ + + 2
+ 3
OH

The above is the reaction of an organically bound phosphate with potassium

persulphate (K2S2O8) and sulphuric acid.
…………this produces the orthophosphate (H3PO4), Potassium ions and
sulphate ions.
In order to speed up the rate of reaction the reaction is carried out at high
heat (150°C)
The next stage in the reaction is the formation of a complex with
the orthophosphates by reacting the orthophosphate with
molybdate, [a molybdate is a compound containing an
oxoanion with molybdenum]

12MoO3 + H2PO4- (H2PMo12O40)-

This forms a yellow phosphomolybdate complex

The phosphomolybdate complex then reacts
with ascorbic acid

• It is reduced to a molybdenum (Various structures for the

molybdenum blue species have been suggested in the
literature) blue complex the concentration of which is
proportional at 880nm to the amount of phosphates
present in the sample
 Nitrogen Ammonia
• Ammonia is a product of the microbiological decay of
animal and plant protein. It can be directly reused by
plants to produce protein. Ammonia and ammonia
compounds are applied directly as fertilizers.

• The presence of ammonia nitrogen in surface water

usually indicates domestic pollution.
• Ammonia in ground water is normal and is due to
microbiological processes.
 Analysis using the Salicylate method

This method involves multiple reactions before a

final green color is developed, all reagents
however, are contained in convenient powder
pillows (Salicylate Reagent Powder Pillows and
Alkaline Cyanurate Powder Pillows) for the
HACH Salicylate Method
• Ammonia compounds are initially combined
with hypochlorite to form monochloramine
(1), which then reacts with salicylate to form
5-aminosalicylate (2).
• Oxidation of 5-aminosalicylate is carried out in the presence of a
catalyst, nitroprusside or Fe(CN)5NO2– (also called
nitroferricyanide), which results in the formation of indosalicylate, a
blue-colored compound.

• The blue color is masked by the yellow color (from excess

nitroprusside) causing a green-colored solution.
The intensity of the color is directly proportional to the ammonia
concentration in the sample.
Copper by the Bicinchoninate method
• Copper can be determined by the reaction of copper with 2,
2’-biquinoline-4,4’-dicarboxylic acid (bicinchoninic acid).

• Bicinchoninate reacts with Cu1+ to produce a purple-colored

complex.

• Bicinchoninate does not react readily with Cu2+.

 Determination of Cu2+
• ..... begins by reducing it to Cu1+.

• The CuVer 1 Reagent combines the bicinchoninate reagent

with a buffer and reducing agent, allowing determination of
Cu1+ and Cu2+.

• Total recoverable copper can be determined with this method

if the sample is first digested to convert all of the copper
present (including insoluble forms and complexed forms) to
free copper.
Write out the chemical reactions involved and
using these explain in your own words how
the following can be analysed using a Portable
UV Spectrometer:

1. Total Phosphorous
2. Nitrogen Ammonia
3. Sulphates
4. Copper
5. Iron
 Background on Oxygen Demand Testing
• Oxygen demand is an important parameter for determining the
amount of organic pollution in water.

• Applications of the Test: measuring waste loadings of treatment

plants and in evaluating the efficiency of treatment processes,
testing lake and stream water samples for organic pollution.

• Oxygen demand testing does not determine the concentration of a

specific substance; rather, it measures the effect of a combination
of substances and conditions.

• Because oxygen demand is not a pollutant, it poses no direct threat

to fish or other life. It can, however, pose an indirect threat to living
organisms by reducing the level of dissolved oxygen.
Methods of measuring oxygen
demand:
Two measure oxygen demand
directly:
1. Biochemical Oxygen Demand (BOD) and
2. Chemical Oxygen Demand (COD).
3. A third method— Total Organic Carbon
(TOC)—measures oxygen demand
indirectly.
 TOC
• Total Organic Carbon (TOC) testing is important in
drinking water treatment as an indicator of potential
disinfection by-product formation.

• In wastewater, TOC is valuable as a surrogate for COD

testing and has applications in domestic wastewater
pre-treatment standards, effluent discharge
limitations, and industrial process waters.

• The colorimetric TOC test measures the total amount

of non-volatile organic carbon in a sample.
• The method is based on controlled
digestion/diffusion in a sealed glass assembly.

• Sample carbon is oxidized to carbon dioxide by

persulfate oxidation.

• The carbon dioxide diffuses into a colored pH

indicator solution where it is converted into carbonic
acid.

• The resulting color change is proportional to the

concentration of carbon present in the sample
 Chemical reactions
• Inorganic carbon is removed from the sample by
adjusting the sample to pH 2 with a buffer, and
stirring vigorously for 10 minutes:
TOC = Total Carbon – Inorganic Carbon

• A suitable volume of treated sample and potassium

persulfate is added to a 16-mm screw top digestion
vial containing Acid Digestion Solution Reagent.
• A 9-mm sealed glass ampule containing the TOC
Indicator Solution is opened and placed inside the
digestion vial.
• The whole assembly is then sealed with a screw cap
and digested at 103–105° C (217–221 °F) for 2 hours.

• In the presence of acidic persulfate and with

increased pressure and elevated temperature, the
sample’s organic carbon is oxidized to carbon
dioxide.
• For example, in the persulfate digestion of a sample
that contains formate, the chemical reaction is:
S2O82– + HCOO– → HSO4– + SO42– + CO2
• The evolved CO2 then diffuses and is trapped
in an aqueous solution containing a pH
indicator.

• The absorbed CO2 forms carbonic acid

according to:
CO2 + H2O → 2H+ + CO32–

• The pH indicator (prior to CO2 absorption) is in

its deprotonated, or basic, form (D–).
• As the absorbed CO2 level increases, the hydrogen
ion level will also increase, resulting in an increase of
the protonated form of the indicator:
D– (Color A) + H+ → DH (Color B)

• The concentration of the carbon in the sample is

proportional to the color change, either the change
in Color A (ΔD–), or the change Color B (ΔDH) or the
sum (ΔD– + ΔDH).