Department of Chemistry, TCE, Madurai

Module I

Water Chemistry

Water Chemistry: Water- sources-Hardness of water-types-Estimation of hardness of water by

EDTA method. Disadvantages of hard water -Boiler troubles- scale & sludge. Internal treatment
methods. External treatment methods - zeolite, ion exchange.Desalination process - reverse
osmosis, electro-dialysis, multi stage flash distillation. Waste water treatment processes.

1.1 Importance of Water

Water is the most important creation of nature and it is absolutely essential for all life on the
earth. Water has been called both ‘the matrix of life’ and ‘the universal solvent’. There is no substitute
or alternate for water. Water makes up more than two thirds of human body weight. The human
brain is made up of 95% water; blood is 82% and lungs 90%. Water is important to the mechanics
of the human body. In fact, all the cell and organ functions that make up our entire anatomy and
physiology depend on water for their functioning.
Although water is plenty on the world, 97% is in the form of sea water, 2% in the form of
polar ice cubes and only 1% water fresh water is available for all our usage. This limited amount of
water is further polluted to a great extent by manmade activities. For drinking and industrial
purpose, we need water free from impurities and pollutants.
1.2 Unique Properties of Water
1.2.1Physical Properties of Water

Water has some very important uses in our world. It is the universal liquid and will find a use in
99% of life’s functions. This unique ability of water to be so versatile and ubiquitous is due to some of its
very impressive properties. These properties of water are often overlooked, but are the main reason for
what makes water such a valuable compound,

 Water is colorless, odorless and tasteless liquid in its natural state.

 Water conducts heat more easily than any liquid except mercury.

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 Water has a high specific heat

 Water has a boiling point of 100 0C.

 The freezing point of water is 0 0C

 One unique property of water is that in the solid state, it is less dense. Up to 4°C water’s density
does increase on cooling. But after that point water becomes less dense. This is why ice floats in
water.

 Water has high viscosity due to very strong intermolecular interactions

 Water has a high surface tension. It allows for the formation of water droplets and waves,
allows plants to move water (and dissolved nutrients) from their roots to their leaves, and the
movement of blood through tiny vessels in the bodies of some animals.

 Water is an excellent solvent. In fact, it is known as a Universal Solvent. Due to a water

molecule’s polarity, it can dissolve almost any substance.

1.2.2 Chemical Properties of Water

 Amphoteric Nature: One of the unique qualities of Water is its amphoteric nature. An amphoteric
substance is one which can act as an acid or a base. These two following reactions show this
amphoteric nature.

H2O (l) + HCl (aq) ⇌ H3O++ Cl–

H2O (l) + NH3 (aq) ⇌ NH4+ + OH–

 Hydrolysis Reaction: Water has a very high dielectric constant. This results in it having a strong
hydrating tendency. Water has strong reactions with ions of salts and creates hydrating shells
around them.

SiCl4 + 2H2O → SiO2 + 4HCl

 Redox Reactions: Water is a great source to obtain dihydrogen since it can be reduced by reacting
it with highly electropositive metals such as Sodium.

H2O + Na → 2NaOH + H2

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1.3 Structure of Water

1.4 Sources of Water

There are various sources of water. About 97% of the water on the Earth’s surface is covered
with water. The two main sources of water are:

 Groundwater – This includes water bodies like Wells and Springs.

 Surface water – This includes different water bodies like Sea, Oceans, Reservoirs, Rivers,
Streams, Ponds, Lakes and Tanks.

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1.5 Standards for drinking water

Water quality refers to the physical, chemical and biological characteristics of water. It is a
measure of the condition of water relative to the requirements of one or more biotic species and or to
any human need or industrial purpose. Drinking water quality standards describes the quality
parameters set for drinking water. They are Physical, Chemical and Biological Parameters.

Physical quality parameters Chemical parameters Biological parameters

Colour pH BOD
Odour Acidity DO
Taste Hardness Standard plate count test
Conductivity Alkalinity Most Probable Number
Turbidity Chloride/Sulphate/Fluoride
Total Dissolved Solids Metals-Iron etc.,
(TDS)
Total Suspended Solids Nitrate
(TSS)
Total Solids (TS) COD

There are few agencies for fixing quality of drinking for they are
 WHO (World Health Organization)
 BIS (Bureau of Indian Standard)
 ICMR (Indian Council for Medical Research)

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1.5.1 Colour
Pure water is colourless but water in nature is often coloured by foreign substances.

The tanning, humic acid etc. present in the organic debris (leaves, wood, weeds etc.) impart
a yellowish brown colour to water as it comes in contact with them. Iron oxide cause
reddish water and manganese oxides cause brown or blackish water. Industrial wastes
from textile and dyeing operations, food processing, pulp and paper production, chemical
production, and mining, refining and slaughter house operations may add substantial
colouration to water in receiving streams.

1.5.2 Odour and Taste

Many substances with which water comes into contact in nature or during human
use may impart perceptible taste and odour. These include minerals, metals and salts from
the soil, and products from biological reactions and constituents of waste water.
Water tastes bitter when contaminated with alkaline impurities and salty when the
impurities are metallic salts. Biological decomposition of organic debris imparts a
characteristic taste and odour of rotten eggs which is mainly due to hydrogen sulphide.
Growth of algae, micro-organisms, hydrogen sulphide and ammonia give an obnoxious
odour to water making it unfit for use.

1.5.3 Total Dissolved Solids (TDS)

These are a measure of the combined content of all inorganic and organic substances
contained in a liquid in molecular, ionized or micro-granular (colloidal sol) suspended
form. Generally the operational definition is that the solids must be small enough to
survive filtration through a filter with two-micrometer (nominal size or smaller)
pores.TDS measurement is used as an indication of aesthetic characteristics of drinking
water and as an aggregate indicator of the presence of a broad array of chemical
contaminants.

The United States has established a secondary water quality standard of 500 mg/l
to provide for palatability of drinking water. The two principal methods of measuring total
dissolved solids are gravimetric analysis and conductivity.

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1.5.4 Total Suspended Solids (TSS), in that the latter cannot pass through a sieve
of two micrometres and yet are indefinitely suspended in solution.

1.5.5 Total solids (TS) are a measure of the suspended and dissolved solids in water.

1.5.6 Electrical conductivity of water is directly related to the concentration of

dissolved ionized solids in the water. Ions from the dissolved solids in water create the
ability for that water to conduct an electric current, which can be measured using a
conventional conductivity meteror TDS meter.

1.5.7 Turbidity is the measure of relative clarity of a liquid. It is an optical characteristic

of water and is an expression of the amount of light that is scattered by material in the
water when a light is shined through the water sample. The higher the intensity of
scattered light, the higher the turbidity. Material that causes water to be turbid include clay,
silt, finely divided inorganic and organic matter, algae, soluble colored organic
compounds, and plankton and other microscopic organisms.The most widely used
measurement unit for turbidity is the Formazin Turbidity Unit (FTU). ISO refers to its
units as FNU (FormazinNephelometric Units).

1.5.8 Biochemical Oxygen Demand (BOD) is the amount of dissolved oxygen

needed (i. e., demanded) by aerobic biological organisms to break down organic material
present in a given water sample at certain temperature over a specific time period. The
BOD value is most commonly expressed in milligrams of oxygen consumed per litre of
sample during 5 days of incubation at 20 °C and is often used as a surrogate of the degree
of organic pollution of water.

Microorganisms such as bacteria are responsible for decomposing organic

waste. When organic matter such as dead plants, leaves, grass clippings, manure, sewage,
or even food waste is present in a water supply, the bacteria will begin the process of
breaking down this waste. When this happens, much of the available dissolved oxygen is
consumed by aerobic bacteria, robbing other aquatic organisms of the oxygen they need to
live.

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Biological Oxygen Demand (BOD) is a measure of the oxygen used by

microorganisms to decompose this waste. If there is a large quantity of
organic waste in the water supply, there will also be a lot of bacteria present
working to decompose this waste. In this case, the demand for oxygen will be
high (due to all the bacteria) so the BOD level will be high. As the waste is
consumed or dispersed through the water, BOD levels will begin to decline.

Nitrates and phosphates in a body of water can contribute to high

BOD levels. Nitrates and phosphates are plant nutrients and can cause
plant life and algae to grow quickly. When plants grow quickly, they also
die quickly. This contributes to the organic waste in the water, which is
then decomposed by bacteria. This results in a high BOD level.

When BOD levels are high, dissolved oxygen (DO) levels decrease
because the oxygen that is available in the water is being consumed by the
bacteria. Since less dissolved oxygen is available in the water, fish and other
aquatic organisms may not survive.

1.5.9 Chemical Oxygen Demand (COD) is a measure of the total quantity of

oxygen required to oxidize all organic material & inorganic material into carbon dioxide
and water. COD is the total measurement of all chemicals (organics & in-organics) in the
water / waste water.COD includes both biodegradable and non-biodegradable substances
whereas BOD contains only bio-degradable. Hence COD is always greater than BOD
1.6 Characteristics of potable water
 The following are the important characteristics of potable water
 It should be clear, colorless and odorless
 It should be pleasant to taste
 It should be free from harmful microorganisms and suspended impurities
 The pH of the water should be 6.5 - 7.5
 It should be free from dissolved gases viz,CO2, H2S, etc and Pb, Cd, Mg, Arsenic, etc
 It should have hardness less than 500 ppm, chloride 250 ppm, fluoride 1.5 ppm and TDS 500
ppm
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1.7 Alkalinity

Alkalinity is the acid neutralizing capacity of solutes in a water sample.

Alkalinity consists of the sum of titratable carbonate (CO32-), bicarbonate (HCO3-) and
hydroxyl ions (OH-) in the water sample. It can be determined by titration using
methyl orange and phenolphthalein indicator. Reactions involved during estimation
using HCl are given below.

Phenolpthalein alkalinity: OH¯ + H+→ H2O

CO32- + H+→ HCO3-

Methyl Orange alkalinity: HCO3- + H+→ CO2

1.8 Hardness

The character of water that

Prevents the lathering of soap

Produces white precipitate (scum) with soap solution is called Hardness.

Generally salts like chloride, bicarbonates and sulfates of Ca2+, Mg2+ and Fe2+
make hardness to water. Hardness of water or hard water can be detected by treatment with
soap solution. This hard water on treatment with soap which is stearic or palmitic acid salt
of sodium causes white precipitate formation of calcium or magnesium stearate or
palmitate.

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1.9 Soft water

Water, which produces lather readily with soap solution is called soft water.

1.10 Types of hardness

Depending on the types of dissolved salts present in the water, hardness of water can be
classified in to two types.

1. Temporary hardness

2. Permanent hardness

1.10.1 Temporary hardness – (Carbonate hardness (CH) /Alkaline hardness)

This is due to the presence of bicarbonate ions of calcium and magnesium and
carbonate of Fe2+ dissolved in water. The hardness due to the bicarbonate ions can be
easily removed by boiling the water or by adding lime to the water.

1.10.2 Permanent hardness- (Non carbonate hardness)

This is due to the presence of chlorides and sulphates of calcium and magnesium
salts dissolved in water. It cannot be removed easily on boiling. It requires some treatment
methods like zeolite process, soda addition etc,.

1.10.3 Total hardness - The sum of the temporary hardness and permanent hardness.

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1.11 Disadvantage of Hardness

The hard water cannot be used for many domestic and industrial applications.
1.11.1 . Domestic uses:
a) Bathing
When hard water is used for bathing, soap does not lather with it so it forms white and sticky
precipitate. It makes loss of soap and also more amount of water.
b) Drinking
When hard water is used for drinking, it leads to the formation of urinary stone and other health
problems due the hardness producing calcium ions. So it not advisable to drink hard water
c) Cooking
When hard water is used for cooking, certain food items like rice, pulses, grams, and vegetables
etc, takes more time to cook. So it causes waste of time and fuel.
1.11.2 Industrial uses:
a) Cement Industries
When hard water is used in cement industries, the process of setting of cement is affected and it
takes long time to setting.
b) Sugar Industries
When hard water is used in sugar industries, the process of crystallization of sugar will be
affected. So preparation of sugar will be affected.
c) Dyeing Industries
When hard water is used in dyeing industries, the fabric materials will not get the exact colour
produced by the dye, there will be different colour due the hardness producing ions. So it cannot be
used.
d) Pharmaceutical Industries
When hard water is used in pharmaceutical industries, the hardness causing ions will form
unwanted by products. So there will be loss in formation of products.

1.12 Expression of hardness in CaCO3 equivalence

Hardness is expressed in CaCO3 equivalence. Because,

i) It is the most insoluble and easily precipitatable salt.

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ii) Its molecular weight is 100 and equivalent weight is 50.

As these are whole numbers, it is very easy to use them in calculations.

1.13 Units of hardness:

The hardness of water is expressed in the following units

i) ppm ii) mg/L iii) degree Clarkes iv) Degree French

1 ppm - 1 part by weight of CaCO3 equivalent hardness/106 parts of

water 1 mg/L - 1mg of CaCO3 / 1 Lr of water
O
Clarke’s Degree ( Cl) - 1 part of CaCO3 equivalent hardness / 70,000 parts of water
O
French degree( Fr) - 1 part of CaCO3 equivalent hardness / 105 parts of water
Therefore ,1ppm = 1mg/L = 0.07 O Cl = 0.1 O Fr

Table of Hardness

Nature of water ppm in CaCO 3

equiv.,
Soft 0-50
Moderately soft 50-100
Slightly hard 100-150
Moderately hard 150-200
Hard 200-300
Very hard Above 300

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1.14 Determination of Hardness by EDTA method-Complexometric titration

method

The estimation of water hardness as applied to boiler water and other water is of
great interest for the chemical industry in general. Determination of hardness of water can
be done by (i) O.Hehner's method (ii) Soap titration method (iii) complexometric
titration method with EDTA.

EDTA-Ethylenediaminetetraacetic acid act as a chelating/sequestering agent which

chelate metal ions present in water.
a) Theory

Ethylenediaminetetraacetatic acid (EDTA) forms colorless, stable complexes

with Ca2+ and Mg2+ ions present in water at pH 9-10. To maintain the pH of the
solution at 9-10, NH4Cl, NH4OH is used. Eriochrome Black-T(EBT) is the metal ion
indicator used at this pH level in the determination of hardness by complexometric
titration with EDTA. EBT is a complex organic compound (sodium – 1 – (1-hydroxy 2-
naphthylazo)-6-nitro-2-naphthol-4- sulphonate). It has two ionisable phenolic
hydrogen atoms.

HO

HOOCH2C CH2COONa N N SO 3-

N CH2 CH2 N OH
NaOOCH2C CH2COOH NO2

b) Mechanism:

When Eriochrome Black T (an alcoholic solution of blue dye) is added to the hard
water at pH around 9-10 it gives wine red coloured unstable complex with Ca2+ and
Mg2+ ions of the sample water. Now when this wine red-coloured complex is titrated
against EDTA solution (of known strength) the colour of the complex changes wine red to
original blue colour showing the endpoint. EDTA extracts the metal ions from the metal
ion EBT complex and forms stable colorless complex by releasing the free
indicator,Whereby the end point of the titration is the color change from wine red to blue.

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c) Chemicals required:

1. 0.01 M = 0.02 N CaCO3 solution = 1gms CaCO3 dissolved in 1 litre deionized

water

2. 0.01 M EDTA solution = prepared by dissolving 4 gms EDTA crystals

in 1 Litre of water deionized water

3. Buffer solution (pH = 10) = prepared by adding 67.5 gms NH4Cl to 570

ml NH3 solution dilute to 1 litre

with deionized water

4. EBT indicator = prepared by dissolving 1 gm EBT in 200

ml ethanol/ methanol.

d) Procedure

Titration-I

Standardization of EDTA: Std Hard water Vs. EDTA

(i) 20 ml of standard hard water solution is pipeted out into a conical flask.

(ii) 5 ml of buffer solution and few drops of Eriochrome Black-T solution

are added. The indicator, which is originally blue color, would acquire a
wine- red color.
(iii) The solution will be titrated with EDTA solution taken in the burette, till the
wine red color changes to blue which is the end point. Let the burette reading
of EDTA be V2 ml.

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Titration-II
Determination of Total hardness :Standardised EDTA Vs. Sample water
Repeated the above titration method for sample hard water instead of standard hard
water. Let the burette reading of EDTA be V3 ml.
Titration-III

Determination of Permanent hardness: Standardised EDTA Vs. Sample water

100 ml of sample hard water is taken in 250 ml beaker. It is boiled to remove

temporary hardness to about half of this volume and cool to room temperature.
Filtered through filter paper to remove insoluble CaCO 3 and MgCO3. Now 20 ml of
this solution is piped out into a clean conical flask. Let the burette reading of EDTA
be V5 ml.

e) Calculations

I. Standardization of EDTA
Normality of standard hard water = N1(0.01N
)
Volume of standard hard water in conical = V1(20 ml)
flask
Volume of EDTA consumed (burette reading) = V2
Normality of EDTA = N2
V 1N 1 = V 2N 2
N2 = V2N2/V1
II. Determination of Total hardness
= N2
Normality of ETDA solution
Volume of EDTA consumed (burette reading) = V3

Volume of sample hard water in conical flask = V4

Normality of sample water = N4
V3 = V 4N 4
N2
N4 = V3
N2/V4

Total hardness = N4 X 50 X 1000 ppm in CaCO3 equiv.,

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III. Determination of Permanent hardness

Normality of ETDA solution = N2
Volume of EDTA consumed (burette = V5
reading)
Volume of sample hard water in conical flask = V6
Normality of sample water = N6
V5 N 2 = V 6N 6
N6 = V5 N 2/V 6
Permanent = N6 X 50 X 1000 ppm in CaCO3
hardness equiv.,
Temporary hardness =Total hardness - Permanent
Solved Problems hardness
1.Calculate the temporary hardness and permanent hardness of a sample of water which contains
16.2 mg of calcium bicarbonate, 29.2 mg of magnesium bicarbonate, 33.3 mg of calcium chloride,
18 mg of magnesium sulfate and 55 mg of sodium chloride per litre of water.
Solution
Calcium carbonate equivalent of 16.2 mg of Ca(HCO3)2 = (100/162) x 16.2= 10 mg
Calcium carbonate equivalent of 29.2 mg of Mg(HCO3)2 = (100/146) x 29.2= 20 mg
Calcium carbonate equivalent of 33.3 mg of CaCl2 = (100/111) x 33.3= 30 mg
Calcium carbonate equivalent of 18 mg of Mg SO4 = (100/120) x 18 = 15 mg
Temporary hardness [due to Ca(HCO3)2+ Mg(HCO3)2 = 10+20 = 30 mg/ lire = 30 ppm
Permanent hardness [due to CaCl2 + MgSO4 ] = 30+15 = 45 mg/ lire = 45 ppm

2.Standard hard water contains 15g of CaCO3 per litre. 20 ml of this solution required 25 ml of
EDTA solution. 100 ml of sample of water required 18 ml EDTA solution. The sample after
boiling required 12 ml of EDTA solution. Calculate the temporary and permanent hardness of the
given sample of water in terms of ppm
Solution:
Given
1liter of standard hard water: 15 g of CaCO3 eq = 15,000mg of CaCO3 eq
Therefore 1 ml of standard hard water (SHW) = 15,000/1,000 mg of CaCO3 eq
Now 25 ml of EDTA solution = 20 ml of SHW = 20x 15 mg of CaCO3 eq
= 300 mg of CaCO3 eq
Therefore 1 ml of EDTA solution = 300/25 mg of CaCO3 eq

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= 12 mg of CaCO3 eq
Calculation of total hardness of water
100 ml of hard water = 18 ml of EDTA solution
= 18x12 mg of CaCO3 eq
= 216 mg of CaCO3 eq
Therefore for 1000 ml of hard water = 216 x (1000/100) mg of CaCO3
eq
Hence total hardness of water = 2160 mg of CaCO3 eq
Calculation of permanent hardness of water
100 ml of boiled water = 12 ml of EDTA solution
= 12x12 mg of CaCO3 eq
= 144 mg of CaCO3 eq
Therefore for 1000 ml of hard water = 144x (1000/100) mg of CaCO3 eq
Hence the permanent hardness of water = 1,440 mg of CaCO3 eq
Calculation of temporary hardness of water
Temporary hardness = Total hardness – Permanent hardness
2,160 - 1,440 = 720 ppm

1.15 Softening of water

Water used for industrial purpose (such as steam generation) should be free from
hardness producing substances. The process of removing hardness producing ions like
Ca2+, Mg2+other cations and anionsetc., in water is called softening of water.
It can be done in two ways.

1. External Treatment methods

2. Internal Treatment methods

1.15.1 External Treatment Methods

It involves the removal of hardness producing salts from the water before feeding into
the boiler.
a) Zeolite Process
The word zeolite is derived from Greek words (Zein + lithos) which mean boiling
stones, The chemical structure of Sodium Zeolite is represented as Na 2O, Al2O3, X SiO22-

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10, Y 2-6 H2O.as they regarded as hydrated sodium alumino silicate which are capable of
exchanging their sodium ions for other divalent ions in water. Hence Zeolites find more
applications in softening of water for domestic and industrial purpose. Zeolites are known
as permutits. There are two types of zeolites are
Natural Zeolites (Non porous structure) eg. Natrolite

Synthetic Zeolites (Porous structure)

Natural zeolites are derived from green sands by washing, heating and
treatment with NaOH. But the synthetic zeolites are prepared from solutions of sodium
silicate and aluminium hydroxide. They may also prepared by heating china clay,
feldspar and soda ash and granulating the resultant mass after cooling. It has more
exchange capacity per unit weight than the natural zeolites.

Simple structure cage structure

Structure of Zeolite
The various reactions taking place during softening process are

Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3

Mg(HCO3)2 + Na2Ze CaZe + 2NaHCO3

CaSO4 + Na2Ze CaZe + 2Na2SO4

MgSO4 + Na2Ze CaZe + 2Na2SO4

CaCl2 + Na2Ze CaZe + 2NaCl

MgCl2 + Na2Ze CaZe 2NaCl

+

The softened water is enriched with large amount of sodium salts, which do not cause any
hardness, but cannot be used in boiler.

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Regeneration

After some time zeolite gets exhausted. The exhaustedzeolite is again regenerated by
treating with 100% solution of NaCl.

CaZe + 2NaCl Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze + MgCl2

Advantages of zeolite

 Removes hardness completely.

 No formation of scale and sludge in treated water

 Takes less time for softening

 The equipment used is compact and occupies a small space.

 This method is cheap, because the exhausted zeolite can be used again.

Disadvantages of zeolite

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 Treated water contains more sodium

 Acidity of treated water increases

 Highly turbid water cannot be treated. Since it blocks the pores of the zeolite bed.

 Acidic water cannot be used, because regeneration is very difficult.

 Water containing Fe, Mn cannot be treated, because regeneration is very difficult.

 The process cannot be used for brackish water, since it contains Na+ions. So the
ion exchange reaction will not occur.
b) Lime-soda process
Basic principle:

 Lime [Ca(OH)2] and soda [Na2CO3 ] are the reagents used to precipitate the
dissolved salts of Ca2+ and Mg2+ as CaCO3 and Mg(OH)2.
 The precipitated CaCO3 and Mg(OH)2 are filtered off.

 Lime reacts with temporary hardness, CO2, acids, bicarbonates and alums.

 Lime cannot remove the calcium permanent hardness which should be removed by
soda.
 The precipitation reactions with lime and soda are very slow.

 Only calculated amounts of lime and soda are to be added. Excess amount of lime
& soda causes boiler troubles like caustic embrittlement
 Calculation of lime & soda required for the process:

1. LIME REMOVES THE TEMPORARY HARDNESS

Ca(HCO 3)2 + Ca(OH)2→2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2→Mg(OH)2 + 2CaCO3 +H2O

2. LIME REMOVES THE PERMANENT MAGNESIUM HARDNESS

MgCl2 + Ca(OH)2→Mg(OH)2 +CaCl2
MgSO4 + Ca(OH)2→ Mg(OH)2 + Ca SO4

3. SODA REMOVES ALL THE SOLUBLE CALCIUM PERMANENT HARDNESS

CaCl2+ Na 2CO 3→ CaCO3 + NaCl

CaSO4 + Na 2CO3→ CaCO3 + Na 2 SO4

Water softened by this process contains appreciable concentrations of soluble salts namely

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sodium sulpate which cannot be used in high pressure boiler installations.

c) Ion exchange method or Demineralisation process.

Here all the cations and anions are completely removed. The soft water, produced by
lime- soda and zeolite processes, does not contain hardness producing Ca2+ and Mg2+
ions, but it will contain other ions like Na+, K+, SO42-, Cl- etc., On the other hand,
Demineralised water does not contain both anions and cations.
Thus soft water is not demineralised water whereas demineralised water is soft water.
Demineralised process uses ion exchange resin, which are long chain, insoluble, cross
linked, organic polymers. There are 2 types.
i) Cation exchange resins (RH+ or RSO3H) containing acidic functional groups (-
SO3H, -COOH) are capable of exchanging their H+ ions with other cations of
hard water.(e.g) Sulphonated coals , sulphonated polyester, styrene-divinyl
copolymers.
ii) Anion exchange resins (R’OH, R-NH2) containing basic functional groups
(OH-, NH2)are capable of exchanging their anions with other anions of hard
water.(e.g) Ureaformaldehyde, cross-linked quaternary ammonium salts.

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Process:

The hard water is passed first through cation exchange column, which removes all the
cations (like Ca2+, Mg2+ etc ) from it, and equivalent amount of H+ ions are released from
this column to water. Thus
2RH+ + Ca2+ R2Ca2+ + 2H+

2RH+ + Mg2+ R2Mg2+ + 2H+

After cation exchange column, the hard water is passed through anion exchange column,
2
which removes all the anions like SO4 -Cl- etc., present in the water and equivalent

2R'OH - + SO 4 2- R2'SO 42- + 2OH-

2R'OH - + Cl - R2'Cl- + 2OH-

amount of OH- ions are released from this column to water. Thus

Thus the water coming out from the exchanger is free from cations and anions. Ion-free, is
known as deionized or demineralized water.

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Regeneration:
On prolonged use, as all the resins are exhausted, there will be no H+ or OH –
ions to exchange the unwanted ions. So, they have to be regenerated. Cation resins are
regenerated by HCl and anion resins by NaOH.

Advantages of Ion exchange method:

i. Can be used for high pressure boilers also.

ii. It canbe treated for highly acidic or alkaline water.

iii. We can get pure water as hardness as low of 2 ppm.

Drawbacks of Ion exchange method:

i. Expensive

ii. Fe, Mn cannot be removed as they form complexes with resins.

iii. Cannot be used for turbid water as they clog the resins.

1.16 Desalination of brackish water

a) Hyper filtration/ Super filtration of brackish water treatment
The process of removing of common salt (NaCl) from salt water is called
‘Desalination’. Water containing dissolved salts (contains > 1000 but < 35, 000 ppm of
dissolved salts) with a peculiar salty taste is called brackish water. Various methods are
available for desalination process like Reverse Osmosis, Distillation, Electro dialysis,
Freezing, Solar distillation, etc.
Desalination techniques are mainly classified into two types:

(1) Processes using a membrane that employ the concept of filtration

(2) Distillate through evaporation (thermal process)
Based on installed capacity, the leader in the membrane desalination process is reverse
osmosis (RO) and in evaporation process is multi-stage flash distillation process (MSF).

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a) Reverse Osmosis method

Osmosis: When two different concentrated solutions are separated by a semi-permeable
membrane, due to osmotic pressure, low concentrated solvent flows to higher one. This is
known as osmosis. But when we apply an excess and opposite hydrostatic pressure (15-
40kg/cm2) to overcome the osmotic pressure, then higher concentrated solvent will flow to
the lower one. This is known as reverse osmosis. During this RO process, only the water
flows across the membrane and it prevents the salt migration. So, this method is also called
as ‘Super filtration’. The membrane is made up of cellulose acetate, cellulose butyrate,
polymethacrylate.

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Advantages of Reverse Osmosis:

 Life time of membrane is high. The membrane can be replaced within a few
minutes, thereby providing uninterrupted water supply.
 Removes ionic, non-ionic and colloidal silica impurities, which cannot be
removed by demineralization method.

 Low capital cost.

 Simple operational procedure.
Disadvantages
 Cost of the membrane and maintenance is difficult
 Skilled operator is required

b) Electro dialysis
Electrodialysis is the process of separating ions of the salt from the salt water
through ion-selective membranes by passing direct current.
An electrodialysis cell consists of alternate Cation Exchange Membrane(CEM)
and Anion Exchange Membrane (AEM). An ion selective membrane has permeability
for only one kind of ions with specific charge. Therefore cation selective membrane is
permeable to cations only and anion selective membrane permeable to anions only. The
cathode is placed near the cation exchange membrane and anode is placed near the anion
exchange membrane.
ED is very useful for water treatment: removal of mineral salts, sulfate, nitrate, etc.
from brackish water and sea water. ED is also useful for waste water reduction or recovery.
Examples for ion selective membrane
Cation selective membrane – poly styrene containing sulphonic acid group.
Anionselective membrane –poly styrene containing tetra ammonium chloride

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When saline water is fed into the electrodialysis cell and direct current is applied
through the electrode’s perpendicular to the direction of water flow. As the current passes
through the electrodes, from the compartment 2 and 4 cations move towards the cathode
through cation exchange membrane and anions move towards the anode through anion
exchange membrane. The net result is the decrease of ions (salt) from 2 and 4
compartment while the concentration of ions (salts) in the adjacent compartment 1,3 and 5
is increased. Now the compartment 2 and 4 are filled with pure water and the
compartments 1,3 and 5 are filled with concentrated brine water. Thus salinity is removed
from salt water.
c) Nano filtration
Filtration is a process of removing particulate matter from water by forcing the water
through a porous media. This porous media can be natural, in the case of sand, gravel and
clay, or it can be a membrane wall made of various materials. The size of materials that
can be removed during filtration depends upon the size of the pores of the filter. The chart
below summarizes the types of particles that are removed from the water with each type of
membrane filter. The green arrow indicates that the particle is small enough to pass through
the filter, whereas the deflected orange arrow indicates that the filter blocks the particle
from passing through the filter.

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A nanofiltration filter has a pore size around 0.001 micron. Nanofiltration removes most
organic molecules, nearly all viruses, most of the natural organic matter and a range of salts.
Nanofiltration removes divalent ions, which make water hard, so nanofiltration is often used
to soften hard water. The technique is mainly applied for the removal of organic substances,
such as micro pollutants and multivalent ions.

d) Desalination with renewable energy systems

Solar distillation (Basin still or multiply tray tilted still solar distillation)
Distillation processes mimic the natural water cycle as saline water is heated, producing
water vapour, which in turn is condensed to form fresh water. These processes include: multi-
stage flash distillation (MSF), multi-effect distillation (MED), and vapour-compression
distillation (VC).

Solar distillation is a relatively simple treatment of brackish (i.e. contain dissolved salts)
water supplies. Solar energy is a low tech option.

In this process, water is evaporated using solar energy,then the vapour condenses as pure
water. This process removes salts and other impurities in water.The solar radiation is
transmitted through the glass or plastic cover and captured by a black surface at the bottom of the
still. A shallow layer of water absorbs the heat which then produces vapour within the chamber of

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the still. This layer should be 20mm deep for best performance.

a) Multistage flash distillation process

Multistage stage flash distillation for desalination is carried out in a pressure vessel that is
divided into numerous sections that have decreasing pressures and temperatures. The sections each
have a set of coils that have seawater pumped through them. These coils serve two purposes:
condensing the steam produced by the flash evaporation and preheating the seawater to almost the
required temperature for distillation.

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The seawater then passes through an inline steam heater, taking it up to a temperature
between 70 oC and 100 oC; the seawater now being considered to be brine. Multi-flash distillation
plant engineers will sometimes reduce this temperature to decrease the formation of scale.

The brine now passes into the different stages and, as it is at a higher temperature than the
sections, some of it flashes to steam. This is condensed by the seawater coils at the top of the sections,
with the condensate dropping down onto the collection trays under the coils.

This continues to the final stage when the brine is pumped to waste and the collected distilled
water is delivered to storage tanks. There is a salinometer on the discharge line to the storage tanks
that operates a tank isolating valve/dump valve in the event of a high ppm alarm.

1.17 Water for Boiler Purpose

1.17.1 Boiler feed water
One of the major industrial applications of water is generation of steam for chemical
processing and for power generation. The feed water must be specially treated to avoid problems in
the boiler. If hard water obtained from natural resources is feed directly to the boilers, the following
troubles may arise.
1.17.2 Boiler Troubles
 Scales and Sludge formation
 Priming and Foaming
 Caustic Embrittlement
 Boiler corrosion

Requirement of boiler feed water Type of Boilers used in industries

pH Low pressure boilers

Hardness Intermediate boilers
Alkalinity High pressure boilers
Total Dissolved solids Very high pressure boilers
Total Suspended solids Uper critical boilers
Corrosive substances

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1.17.3 Boiler Scale

When water containing dissolved impurities is used for steam generation, its dissolved-
solid content increases continuously and is eventually thrown out of solution in the form of
deposits. On the basis of their physical characteristics, the deposits are differentiated into scales and
sludges.

Sludge is soft, friable, loose and muddy deposit resulting from settling and thickening, and
accumulates in places of poor water circulation such as header, joints, bends, etc.
a) Removable of sludge materials
1.Sludges are poor conductors of heat and may lead to chocking of feed lines (clogging of tube
openings and valves.) They are, however, less troublesome than scales because, being loose,
they can be easily removed with a wire brush or can even be flushed out with water.
2.Blow down operation-It involves removal of a portion of concentrated boiler-water
(containing suspensions and sludges) from a suitable opening near the bottom of the boiler
and its replacement by fresh feed-water

A deposit is termed as scale when it is sufficiently dense, hard, coherent and adherent, i.e., it
sticks firmly to the boiler surface from which it is very difficult and uneconomical to remove and
being a good insulator results in disruption of normal functioning of the boiler unit.

Scales have been classified on the basis of their chemical composition. Scales constituted
chiefly by the salts of Calcium and Magnesium (CaSO4, CaCO3, Ca3(PO4)2,Mg3(PO4)2, Mg(OH)2,
etc.) are called alkaline earth scales. Depending on which of these salts predominates, alkaline

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earth scales are further differentiated into carbonate scales (CaCO3), sulphate scales (CaSO4), etc.
b) Formations of scales are due to
1. Decomposition of calcium bicarbonate :
1) Ca(HCO3)2 → CaCO 3 ↓ + CO2 ↑ + H2O

2) Mg(HCO 3)2 → Mg(OH)2 ↓ + 2CO2↑

CaCO3 is the major constituent of the scales formed in low pressure boilers. In high
pressure boilers, CaCO3 is hydrolysed to give more soluble Ca(OH)2.

3) CaCO3+ H 2O → Ca(OH)2↓ + CO2↑

Carbonate scale is not very hard and can be removed with wire brush.

2. Decomposition of calcium sulphate:

The solubility of calcium sulphate in water decreases with rise of temperature. Thus,
solubility of CaSO4 is 3200 ppm at 15 OC and it reduces to 55 ppm at 230 OC and 27 ppm at
320 OC.
3. Hydrolysis Magnesium salts:
Dissolved magnesium salts undergo hydrolysis forming magnesium hydroxide
precipitate, which forms a soft type of scales.
MgCl2+ H2O → Mg(OH)2↓ + 2HCl
4. Silicate scales consist chiefly of silica deposits or silicates of varying composition. Silicate
scales are very hard and stick very firmly to the metal surface. Being porous, they have a
very low thermal conductivity. They are the most troublesome scales formed in the boiler.
5. Iron-oxide scales consist predominantly of Fe2O3and Fe3O4. Small amounts of other iron
salts such as phosphates and silicates are also sometimes present.

c) Disadvantages of Scale Formation

 Poor water circulation and decrease in efficiency.

 Increase in fuel consumption.
 Boiler shut-down while over-heating
d) Removal of scales can be done by:
 Wooden scraper or wire brush, suitable for removing loose scales.
 Blow down operations for loose scales.

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 Giving thermal shocks, which involve alternate heating and cooling to make the scales brittle.
 Chemical treatment with 5-10% HCl for carbonates and EDTA treatment for Ca/Mg
salts forming complexes.
These are methods for the removal of the scales, when they are formed. There are also some methods
for the prevention of scale formation by internal or external treatment.

Differences between sludge and scale

Sludg Scale
e
Loose, slim , non-adherent Hard, thick , strong adherent precipitate
precipitate
Due to salts like MgSO4 MgCl2 Due to salts like CaSO 4
Demerits Demerits
Poor conductance, Poor conductance
decrease the boiler efficiency to lesser Decrease the boiler efficiency to maximum
extent and causing chocking in the extent
pipelines Cause reduced fuel
economy Improper boiling
Boiler explosion etc.,
It can be prevented by periodical It can be prevented by special methods like
replacement of concentrated hard external treatment of ion exchange Internal
water by fresh water. This process carbonate, phosphate, Calgon conditioning
is known as “blow down” method. Mechanical hard scrubbing methods.

e) Priming and Foaming:

Due to rapid boiling, the steam may carry some water droplets along with it. This is called wet
steam. The process of wet steam production is called Priming. It can reduce the heat of the steam and
cause corrosion in the pipelines.
1. Priming is due to
 Improper design of boiler
 High water level
 High velocity of steam
 Uneven boiling


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2. Priming can be controlled by

 Proper boiler design
 Maintaining proper water level
 Proper boiling
Foaming
If oils and greases are present, they produce stable bubbles on the water surface. This will
increase the wet steam production. This is known as “Foaming”.
Foaming is prevented by adding
 Anti foaming agents (e.g.) synthetic poly amides, castor oil
 Coagulants (e.g.) Aluminum hydroxide
 Foaming and priming are collectively known as ‘ Carry over”.
1.17.4 Boiler Corrosion
It may be due to three major reasons:
 Dissolved Oxygen
 Dissolved CO2
 Dissolved salts like MgCl2
i) Corrosion Due to dissolved oxygen:
Dissolved oxygen in presence of water, causes corrosion.
4Fe + 6H2O + 3O2 4Fe (OH)3
Prevention of corrosion by
a) Chemical method
 Adding Sodium Sulphite : 2Na2SO3 + O2 2Na2SO4
 This method results in other precipitates which can have some side effects. So this method is
less preferred.
 Adding Hydrazine: N2H4 + O2 N2 + 2 H2O
 This method results in inert gas and pure water, and has no side effects. So it is preferred.
b) Mechanical de-aeration method:
 This is based on the principle that at high temperature, low pressure and high exposed area, the
solubility of gases in water is decreased. So, the gases can be expelled easily.
 Here, the water is fed into the mechanical de aerator which is provided with vacuum pump,
heaters and perforated plates.
 The out coming water will be free from dissolved gases.

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ii) Corrosion due to CO2

Salts like Calcium bicarbonate on heating produces CO 2. CO2 dissolves in water to form
carbonic acid which corrodes the boiler metal.
Δ
Ca(HCO3)2 CaCO3 + H2O + CO2
H2O + CO2 H2CO3
Prevention from CO2 corrosion
1. Chemical method: By adding calculated amount of ammonium hydroxide
2NH4OH + CO2 (NH4)2CO3 + H2O
2. Mechanical de aeration method (similar to oxygen method)

iii) Corrosion due to Dissolved salts like MgCl2

Dissolved salts like MgCl2 cause acid formation. This will be prevented by alkali neutralization.
MgCl2 + 2 H2O Mg(OH)2 + 2 HCl (Corrosive acid)
Neutralization:
Excess acidic nature is neutralized by adding alkalis and vice versa.
HCl + NaOH NaCl + H2O

1.18 Internal treatment method:

Internal treatment involves addition of chemical to the boiler water either to (i) precipitate the
scale forming impurities in the form of sludge’s, which can be easily removed or (ii) convert the
impurities to soluble compounds, so that scale formation can be avoided. Important internal
treatments involve

(a) Colloidal Conditioning:

In low pressure boilers, scale formation can be avoided by adding certain organic substances
such as linseed extract, tannins, lignins, glues, agar-agar, etc., which can act as protective colloids.
These substances get coated over the scale forming particles of CaCO 3, CaSO4 etc., as and when
formed, and thus prevent there aggregation. These particles therefore remain suspended in boiler-
water and are easily removed by blow-down.

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(b) Phosphate Conditioning:

A suitable orthophosphate is added to precipitate calcium as Ca3 (PO4 )2 sludge which is

subsequently removed by blow-down and thus the scale formation is prevented.

3CaCl2 + 2Na3PO4 → Ca3(PO4)2 + 6NaCl

The three sodium orthrophosphates viz., Na3PO4; Na2HPO4 and NaH2PO4 have been used for
phosphate conditioning as also sodium pyrophosphate (Na4P2O7) and sodium metaphosphate
(NaPO3). The typical reactions of the various phosphates with the hardness represented as CaCO 3
may be as follows:
2Na3PO4 + 3CaCO3→ Ca3(PO4)2 + 3 Na2CO3
2Na2HPO4 + 3CaCO3 → Ca3(PO4)2 + 2Na2CO3 +CO2 +H2O
2NaH2PO4 + 3CaCO3→ Ca3(PO4)2 + Na2CO3 + 2CO2 + 2H2O

The quality of feed water dictates the choice of a particular phosphate to be used.

Phosphate conditioning is suitable for scale prevention at all operation pressures without any
risk of caustic embrittlement. However phosphates being costlier, phosphate conditioning is
economical only when residual harness of boiler-feed water is not more than 4-5 ppm. Another
drawback is the deposition of Fe3(PO4)2 scale at higher phosphate concentrations or at lower pH
values. Moreover the orthophosphate solutions have to be pumped directly into the boiler in order to
prevent the deposition of highly insoluble Ca3(PO4)2 in the feed-lines.

(c) Carbonate Conditioning:

Sodium carbonate is added to the boiler-water to precipitate calcium as CaCO3 for

subsequent removal by blow-down. Carbonate conditioning is used only in low pressure boilers.

CaSO4 + Na2CO3→ CaCO3

(d) Calgon conditioning

It involves in adding calgon (sodium hexameta phosphate) to boiler water. It prevents the
scale and sludge by forming soluble complex with CaSO4
Na2[Na4(PO3)6] ---------> 2Na+ + [Na4 P6O18 ]2-
2CaSO4 + [Na4P6O18]2- ---------> [Ca2P6O18]2- + 2 Na2 SO4

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(e) Sodium aluminate conditioning

Sodium aluminate is hydrolysed yielding NaOH and gelatinous Al(OH)3. The NaOH
formed reacts with magnesium salts to precipitate Mg(OH)2. This Mg(OH)2 and Al(OH)3 are
flocculent and entraps the colloidal as well as the finely divided impurities like silica in the boiler
water and the loose precipitate is finally removed by blow down operation.

NaAlO2 + 2H2O → NaOH + Al(OH)3↓

MgCl2 + 2NaOH →Mg(OH)2 ↓ + 2NaCl

(f) Electrical conditioning:

Rotating mercury bulbs on heating by the boiling water emit electrical discharges that
prevent scale formation by the particles.
(g) Radioactive conditioning:
Tablets of radioactive salts placed inside a boiler emit radiations, which prevent scale
formation.
1.19 Caustic Embrittlement
Embrittlement is the name that has been given to boiler failures due to development of certain
types of crack resulting from excessive stress and chemical attack. In steam boiler operation, the
chemicals that are believed to be responsible are NaOH and silica. During softening processes,
Na2CO3 are added and it gives rise to NaOH at elevated temperature according to the following
reaction.
Na2CO3 + H2O → 2NaOH + CO2

Steam boilers are made by rivetting constructions rather than welding and are particularly
liable to damage by caustic alkali solutions. This cracking is not due to corrosion and the cracks
appear like brittle fracture and hence called caustic embrittlement. NaOH attacks and dissolves out
iron of boiler forming sodium ferroate. This finally causes the stressed parts like bends, joints, rivets
to lead to the boiler failure.

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Concentration cell develops between the boiler and the NaOH of different concentrations as

+ Fe Concentrated Dilute Fe –

rivets, joints NaOH NaOH plane

etc. Solution Solution Surfaces

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Prevention of Caustic Embrittlement

 Addition of sodium phosphate as softening agent instead of Na2CO3.

 Addition of sodium sulfate to ensure a weight ratio Na2SO4/NaOH > 2.5, whereby the
deposition of Na2SO4 prevents the penetration of NaOH into the cracks and stops caustic
embrittlement in high pressure boilers.
 Addition of organic agents like tannin, lignin, querbracho etc. also prevents cracking similar
to sodium sulfate in low pressure boilers.
 Use of crack-resisting steels: Certain steels containing Al added during manufacture appear
to be resistant against caustic cracking.

1.20 Waste water treatment

Waste water is generated from various sources viz., domestic, industrial, commercial or
agricultural activities and any sewer inflow or sewer infiltration. Wastewater contains physical,
chemical and biological pollutants and when it is discharged to the environment without suitable
treatment, causes water pollution and affects the environment badly. The flow chart of the waste water
treatment processes are given in Figure.

Fig. The flow chart of a conventional sewage treatment plant

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a) Chemical pollutants

I. Washing water (personal, clothes, floors, dishes, cars, etc.), also known as grey water
II. Surplus manufactured liquids from domestic sources (drinks, cooking oil, pesticides, lubricating
oil, paint, cleaning liquids, etc.)
III. Heavy metals, including mercury, lead, and chromium
IV. Organic particles such as feces, hairs, food, vomit, paper fibers, plant material, humus, etc.;
V. Soluble organic material such as urea, fruit sugars, soluble proteins, drugs, pharmaceuticals, etc.;
VI. Inorganic particles such as sand, grit, metal particles, ceramic powders , etc.;
VII. Gases such as hydrogen sulfide, carbon dioxide, methane, etc.;
VIII. Emulsions such as paints, adhesives, mayonnaise, hair colorants, emulsified oils, etc.;
IX. Toxins such as pesticides, poisons, herbicides, etc.
X. Pharmaceuticals and hormones and other hazardous substances

b) Biological pollutants

If the wastewater contains human wastes, as is the case for sewage, then it may also
contain pathogens of one of the four types:

I. Bacteria (for example Salmonella, Shigella, Campylobacter, Vibrio cholerae),

II. Viruses (for example hepatitis A, rotavirus, enteroviruses),
III. Protozoa (for example Entamoeba histolytica, Giardia lamblia, Cryptosporidium parvum) and
Parasites such as helminths and their eggs
(e.g. Ascaris (roundworm), Ancylostoma (hookworm), Trichuris (whipworm));

Disadvantages of Waste water

Since waste water contains lot of organic and inorganic chemicals, solid particles and
microorganism, it initiates biochemical reactions. Those biochemical reactions create biochemical
oxygen demand (BOD). Organic chemicals are also liable to be broken down using strong oxidizing
agents and these chemical reactions create chemical oxygen demand (COD). Both the BOD and COD
tests are a measure of the relative oxygen-depletion effect of a waste contaminant. The BOD test
measures the oxygen demand of biodegradable pollutants whereas the COD test measures the oxygen
demand of oxidizable pollutants.

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1.20.1 Waste water treatment process

In order to purify the waste water, four processes are generally used.
1. Preliminary Treatment.
2. Primary Treatment
3. Secondary or Biological Treatment and
4. . Tertiary or Advanced Treatment
1. Preliminary Treatment
Preliminary treatment involves the removal of floating materials (leaves, papers, rags) and
settleable inorganic solids (sand, grit), besides oily substances (fats, oils, greases). The three major
types of equipment-screeners, grit chambers, and skimming tanks are employed in preliminary
screening.

2. Primary Treatment
Primary treatment is aimed at the removal of fine suspended organic solids that cannot be
removed in the preliminary treatment. It is sometimes necessary to use chemical coagulants to facilitate
or aid sedimentation, and this process is referred to as chemical precipitation or coagulation-aided
sedimentation

a) Principle of Sedimentation:
The solid particle of the sewage tends to settle down due to gravity. However, most of the solid
particles of organic compounds remain in a suspended state in a flowing sewage. If the flow of the
sewage is stopped and if it is stored in a tank referred to as sedimentation tank, the solid particles can
settle down at the bottom. The process of sedimentation is influenced by several factors. These include
the size, shape and specific gravity of particles, besides viscosity and flow velocity of sewage.

b) Chemical-aided Sedimentation:
It is not always possible to remove the colloidal wastes in sewage by plain sedimentation.
However, addition of certain chemicals aids sedimentation, a process referred to as chemical
precipitation or chemical-aided sedimentation. By this technique, about 60-80% of the suspended
particles can be removed. Chemical precipitation involves three stages—coagulation, flocculation and
sedimentation. The most commonly used coagulants in sewage treatment are alum (alluminium sulfate),

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iron salts (ferric sulfate, ferrous sulfate, ferric chloride), lime and soda ash (sodium carbonate), sodium
silicate and sodium aluminates. When alum is added, it forms alumininium hydroxide, which helps in
the easy settlement of the finely suspended particles through flock sedimentation.

Al2(SO4)3 + 6H2O 2Al(OH)3 + 3H2SO4

Fine particle settlement by flock sedimentation

3. Secondary or Biological Treatment

Biological treatment of sewage is required for the removal of dissolved and fine colloidal
organic matter. This process involves the use of microorganisms (bacteria, algae, fungi, protozoa,
rotifers, nematodes) that decompose the unstable organic matter to stable inorganic forms. The carbon
based compounds are converted to CO2 and nitrogen based compounds are converted to ammonia and
finally nitrates. The biological treatment processes of sewage are broadly classified as aerobic,
anaerobic and pond processes.

4. Tertiary Treatment

The aim of tertiary treatment is further purifications of waste water as well as recycling. Tertiary
treatment or advanced treatment is sometimes needed for the removal of suspended and dissolved
substances, after the conventional primary and secondary treatments. Tertiary treatment process broadly
involves the removal of suspended and dissolved solids, nutrients (nitrogen, phosphorus) and
pathogenic organisms.

There are four major processes under the tertiary treatment:

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1. Solids removal. 2. Nitrogen removal. 3. Phosphorus removal. 4. Disinfection

Disinfection with chlorine:
Chlorine is a very widely used disinfectant, as it satisfies the criteria of an ideal disinfectant. The
most commonly used chlorine compounds are — chlorine gas (Cl2), calcium hypochloride
[Ca(COCI2)], sodium hypochlorite (NaOCI) and chlorine dioxide (CIO 2). The disinfection efficiency of
chlorine depends on the number of microorganisms in the water being treated, pH and temperature.
Among many disinfectants, chlorine is cheap and effective. Chlorine produces hypo chlorous acid
which is a germicide and attacks the cells of bacteria and virus and kills them.
Cl2 + H2O HCl + HOCl (hypochlorous acid)
Germs + HOCl Germs are killed
The final composition of tertiary treated waste water is
BOD ‹1 ppm, NH4+ ‹1 ppm, PO43- ‹1 ppm
The treated water is has high clarity, free from odour, low BOD and it is nearly equivalent to potable
water and can be recycled.
Disinfection by Ozone
Ozone is an excellent disinfectant, which is produced by passing silent discharge through cold
and dry oxygen
3O2 2O3
2O3 O2 + [O]
Nascent Oxygen
The nascent oxygen is a very powerful oxidizing agent and kills the bacteria and also oxidizes
the organic matter in the water.
Sludge Disposal
Sludge, which is collected from sewage treatment processes are disposed off by the following
methods
a) Burial at sea
b) Land spreading - as a fertilizer
c) Sludge digestion - Anaerobic decomposition of sludge produces CH4 and can be used as fuel for
power generation.

********

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Municipal water treatment (Not for examination)

Municipalities have to supply potable water or drinking water fit for human consumption. It
should follow the essential requirements
1. It should be clear and odourless
2. It should be pleasant in taste.
3. It should be cool and less turbidity.
4. It should be free from dissolved gases like H2S
5. It should be free from metals like lead, arsenic, chromium etc
6. It should not be high alkalinity and pH around 6.5-8.0
7. It should be free from harm full micro organisms

Purification of water for domestic use

A) Removal of suspended impurities
1. Screening: The raw water is passed through screens, having large numbers of holes, where
floating materials are retained by them.
2. Aeration The process of mixing water with ait is known as aeration. The main purpose of
aeration is
(i) To remove gases like CO2 ,H2S and other volatile impurities causing bad taste and odour
to water.
(ii) To remove ferrous and manganous salts as insoluble ferric and manganic salts.
3. Sedimentation: It is a process of allowing water to stand undisturbed in big tanks, about 5
M deep, when most of the suspended particles settle down at the bottom due to the force
of gravity. The clear water is then drawn from tank with the help of pumps. The retention
period in a sedimentation tank ranges from 2-6 hours. When water contains fine clay
particles and colloidal matter, it becomes necessary to apply sedimentation with
coagulation for removing such impurities.
4. Sedimentation with coagulation is the process of removing fine suspended and colloidal
impurities by the addition of required amount of chemicals to water before sedimentation.
Coagulant, when added to water, forms an insoluble gelatinous, flocculent precipitate which
5. descent through water, adsorbs and entangles very fine suspended impurities forming bigger
flocks, which settle down easily. Coagulatants like alum, ferrous sulphate etc which
neutralize the negative charge on the colloidal clay particles. After losing their charge the
particles which settle down due to the force of gravity. Thus coagulants are generally added

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in solution form for proper mixing and sedimentation.

(i) Alum [K2SO4. Al2(SO4)3. 24 H2O is the most widely used in water treatment plants.
Al2(SO4)3 + Ca (HCO3)2 2Al(OH)3 + 3 CaSO4 + 6 CO2
(ii) Sodium aluminate (NaAlO2 )
NaAlO2 + 2H2O → NaOH + Al(OH)3↓

MgCl2 + 2NaOH →Mg(OH)2↓ + 22NaCl

Aluminum hydroxide is also used for floc sedimentation

(iii) Copperas or ferrous sulphate [FeSO4 .7H2O] is also commonly used for coagulation
purposes. It gives results above pH values of 8.5.
FeSO4 + Mg (HCO3)2 Fe (OH)2 ↓+ MgCO3 + H2O + CO2
4 Fe(OH)2+ O2 + 2H2O 4 Fe (OH)3 ↓
(dissolved oxygen) ferric hydroxide -heavy flock
6. Filtration
It is a process of removing colloidal matter and most of the bacteria, micro-organisms, etc by
passing water through a bed of fine sand and other proper sized granular materials is carried out by
using sand filter.
Operation of sand filter

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 Department of Chemistry, TCE, Madurai

A sand filter consists of a thick top layer of fine sand placed over coarse sand layer and
gravels. It is provided with an inlet of water and an under drain channel at the bottom for exit of
filtered water. Sedimented water entering the sand filter is uniformly distributed over the entire fine
sand bed. During filtration, the sand pores get clogged, due to retention of impurities in the pores.
When the rate of filtration becomes slow, the working of filter is stopped and about 2-3 cm of the
top fine sand layer is scrapped off and replaced with clean sand and the filter is put back into the
use again. The scrapped sand is washed with water, dried and stored for reuse at the time of
next scrapping operation.
B) Removal of micro-organisms
Water after passing through sedimentation, coagulation and filtration operations still contains
a small percentage of pathogenic bacteria. Consequently water used for drinking purpose should be
free from disease producing bacteria’s, micro-organisms. The process of destroying the disease
causing bacteria’s, micro-organisms etc from the water and making it safe is called Disinfection.
The disinfection of water can be carried out by following ways

1. By boiling
By boiling water for 10-15 minutes, all the diseases causing bacteria’s, micro-organisms are
killed and water becomes safe to use.
2. Disinfection by Ozone
Ozone is an excellent disinfectant, which is produced by passing silent discharge through
cold and dry oxygen
3O2 2 O3
2 O3 O2 + [O] Nascent Oxygen
The nascent oxygen is a very powerful oxidizing agent and kills the bacteria and also oxidizes the
organic matter in the water. But this process is costly and cannot be used in large scale. Ozone is
unstable and cannot be stored for long time.
3. By using ultraviolet radiations
UV rays are produced by passing electric current through mercury lamp. This is particularly
useful for sterilizing water in swimming pool. It is costly. Turbid water cannot be used.
4. By Chlorination
(i) Adding Bleaching powder
In small water works about 1 kg of bleaching powder per 1,000 kilolitres of water is
mixed with water and allowed to stand undisturbed for several hours. The chemical action

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 Department of Chemistry, TCE, Madurai

produces hypochlorous acid which is a germicide.

CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HCl + HOCl (hypochlorous acid)
Germs + HOCl Germs are killed
Drawbacks:
 Bleaching powder introduces calcium in water, thereby making more hard.
 Bleaching powder is deteriorates, due to continuous decomposition during storage.
(ii) By Chlorine gas
Chlorine produces either gas or in concentrated solution form) hypochlorous acid which is a
germicide.
Cl2 + H2O HCl + HOCl (hypochlorous acid)
Germs + HOCl Germs are killed
(iii) By using chloramines
When chlorine and ammonia are mixed in the ratio 2:1 by volume, a compound called
chloramines is formed. Chloramine is much more lasting than chlorine and more effective than
chlorine alone. Moreover, it imparts a good taste to be treated –water.
Cl2 + NH3 ClNH2 + HCl
ClNH2 + H2O HOCl + HCl

Break point chlorination (or free-residual chlorination)

It involves in addition of sufficient amount of chlorine to oxidize the organic matter,
reducing substances and free ammonia in raw water; leaving behind free chlorine, which possess
disinfecting action against diseases producing bacteria.

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 Department of Chemistry, TCE, Madurai

Chlorine may be added to water directly as a gas or in the form of bleaching powder. When
chlorine is applied to water, the results obtained can be depicted graphically in the above graph. The
graph shows the relationship between the amount of chlorine added to water and the residual
chlorine.
It is seen from the graph that initially the applied chlorine is used to kill the bacteria and
oxidises all the reducing substances present in the water and there is no free residual chlorine. As the
amount of applied chlorine increases, the amount of combined residual chlorine increases. This is
due to the formation of chloramine and other compounds. At one point, on further chlorination, the
oxidation chloramines and other impurities starts and there is a fall in the combined chlorine content.
Thus the combined residual chlorine decreases to a minimum point at which oxidation of
chloramines and other impurities and free residual chlorine begins to appear this minimum point is
known as break point chlorination. Thus, the break point chlorination eliminated bacteria’s,
reducing substances, and organic substances responsible for the bad taste and odour, from the water.
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Department of Chemistry, TCE, Madurai