Water Technology

Introduction:
Composed of hydrogen and oxygen
Occupies a unique position in industries.
Most important use is in the steam generation.
Water is also used as coolant in power and chemical plants.
In addition it is widely used in other fields such as
production of steel, rayon, paper, atomic energy, textiles etc.

CHARACTERISTICS IMPARTED BY IMPURITIES IN WATER:

The natural water is usually contaminated by different types of

impurities.
Physical impurities
Color
Turbidity and sediment
Taste and odour
Bacterial impurities
Microorganisms (algae, pathogenic bacteria, fungi,
viruses, pathogens, parasites worms etc.)
Suspended impurities
Dust particles, clay and sand
Organic suspended impurities
Silica aluminium hydroxide, ferric hydroxide colouring
matter
Radioactive Substances

Chemical impurities in water:

Inorganic and organic chemicals released from dyes, paints,
drugs, pesticides, textiles, tanneries etc .
Acidity from industrial wastage like acid, mine, drainage, etc.
Usually acidity is caused by the presence of free CO2, mineral
acid and weakly dissociated acids.
Dissolved gases (O2, CO2, NH3)

Mineral matters have origin from rocks and industrial effluents.

These include mineral acids, Ca2+, Mg2+, Na+, K+, Fe2+, Cl-,
NO3-, F-, SiO2 etc.

Contaminant

Potential Health Effects

from Ingestion of Water

Sources of Contaminant in
Drinking Water

Antimony

Increase in blood cholesterol;

decrease in blood sugar

Discharge from petroleum

refineries; fire retardants;
ceramics; electronics; solder

Arsenic

Skin damage or problems

with circulatory systems, and
may have increased risk of
getting cancer

Erosion of natural deposits;

runoff from orchards, runoff
from glass & electronics
production wastes

Asbestos
(fiber >10 micrometers)

Increased risk of developing

benign intestinal polyps

Decay of asbestos cement in

water mains; erosion of
natural deposits

Barium

Increase in blood pressure

Discharge of drilling wastes;

discharge from metal
refineries; erosion of natural
deposits

Beryllium

Intestinal lesions

Discharge from metal

refineries and coal-burning
factories; discharge from
electrical, aerospace, and
defense industries

Cadmium

Kidney damage

Chromium (total)

Allergic dermatitis

Copper

Short term exposure:

Gastrointestinal distress
Long term exposure: Liver
or kidney damage
People with Wilson's
Disease should consult
their personal doctor if the
amount of copper in their
water exceeds the action
level

Cyanide (as free cyanide)

Nerve damage or thyroid

problems

Corrosion of galvanized
pipes; erosion of natural
deposits; discharge from
metal refineries; runoff
from waste batteries and
paints
Discharge from steel and
pulp mills; erosion of
natural deposits
Corrosion of household
plumbing systems; erosion
of natural deposits

Discharge from steel/metal

factories; discharge from
plastic and fertilizer
factories

Drinking water standards comparative table

Parameters

Units

WHO
standard

BIS
Standard

6.5-9.2

6.5-8.5

mg/l

500

500

Sulphate

mg/l

200

200

Chloride

mg/l

250

200

Cyanides

mg/l

0.05

0.05

Fluride

mg/l

1.5

0.6-1.2

Aluminium

mg/l

0.2

Arsenic

mg/l

0.01

pH
TDS (Total
dissolved salts)

0.01

Drinking water standards comparative table

Parameters

Units

WHO
standard

BIS
Standard

Cadmium

mg/l

0.003

0.01

Lead

mg/l

0.01

0.05

Mercury

mg/l

0.001

0.001

Sodium

mg/l

200

Zinc

mg/l

WHO- World Health Organization

BIS - Bureau of Indian standards

Hard water
Has high mineral content (in contrast with soft water).
Hardness in water is defined as the presence of multivalent cations.
It can cause water to form scales and a resistance to soap.
It can also be defined as water that does not produce lather with
soap solutions, but produces white precipitate (scum).
Hard water minerals primarily consist of calcium (Ca2+), and
magnesium (Mg2+) metal cations, and sometimes other dissolved
compounds such as bicarbonates and sulfates.
Types of hardness:
i) Temporary hardness

ii) Permanent hardness

Temporary hardness:
Combination of calcium ions and bicarbonate ions in the water. It
can be removed by boiling the water or by the addition of lime
(calcium hydroxide).
Boiling promotes the formation of carbonate from the
bicarbonate.

The following is the equilibrium reaction when calcium carbonate

(CaCO3) is dissolved in water:
CaCO3(s) + CO2(aq) + H2O Ca2+(aq) + 2HCO3-(aq)

Permanent hardness:
Usually caused by the presence in the water of calcium and
magnesium sulfates and/or chlorides which become more
soluble as the temperature rises.
Permanent hardness can be removed using a water softener or

ion exchange column, where the calcium and magnesium ions

are exchanged with the sodium ions in the column.

In industrial settings, water hardness must be constantly

monitored to avoid costly breakdowns in boilers, cooling towers
and other equipment that comes in contact with water.
Hardness is controlled by the addition of chemicals and by
large- scale softening with zeolite (Na2Al2Si2O8.xH2O) and ion
exchange resins.
Unit of hardness:

Hardness is expressed in terms of equivalent of calcium

carbonate.
[It is the most insoluble salt that can be precipitated in water
treatment.]

Hardness in Terms of Calcium Carbonate Equivalents:

It is customary to express hardness in terms of equivalents of CaCO3. The
reason for choosing CaCO3 as the standard for calculating hardness of
water is due to:
1. Its molecular weight is exactly 100, which makes mathematical
calculations easier.
2. It is the most insoluble salt, thus can be easily precipitated in water
treatment processes. The CaCO3 equivalents for various salts are as
follows:
100g of CaCO3 111g of CaCl2 136 g of CaSO4 95 g of MgCl2 120 g of
MgSO4 162g of Ca(HCO3)2 146 g of Mg(HCO3)2 164 g of Ca(NO3)2 44
g of CO2 148 g of Mg(NO3)2
If x g of CaCl2 s present in a water sample, then amount of CaCl2 present on
terms of its equivalent will be:
1 g mole of CaCl2 1 g mole of CaCO3
111 g of CaCl2 100 g of CaCO3
55.5 g of CaCl2 50 g of CaCO3
x g of CaCl2=50/55.5*x g of CaCO3

In general calcium carbonate equivalent of hardness is given by

Wt. of the substance producing hardness X Eq.wt. of CaCO3
= ---------------------------------------------------------------------------Eq.wt.of substance

Various units used to express hardness of water are as under

Parts per million (ppm): calcium carbonate equivalent per 106 parts of water
Milligrams per liter (mg/L): number of calcium carbonate equivalent
present per liter of water

hardness

Degree French (oFr): 1 part of calcium carbonate equivalent hardness per 70,000
parts
Clarkes Degree(oCl):1 part of calcium carbonate equivalent hardness per 105 parts
of water
1ppm=1mg/L=0.1 oFr=0.07oCl

Very Soft water

0-70

ppm of CaCO3

Soft water

70-140

ppm of CaCO3

Slightly hard water

140-210 ppm of CaCO3

Moderately hard

210-320 ppm of CaCO3

Hard water

320-530 ppm of CaCO3

Very hard water

530

ppm of CaCO3

Determination of total hardness of water:

EDTA method
EDTA is a weak acid and has a structure as shown below.
CH 2COOH

HOOCH 2C
N

CH2

CH2

1.a. The structure of EDTA

CH 2COOH

HOOCH 2C

1.a
-

CH 2COO

O OCH2C
N

CH2

CH2

N
CH 2COO

O OCH2C

1.b

1.b.
The
structure
of
tetracarboxylate [EDTA]4- ion
formed by the dissociation of
EDTA

Tetracarboxylate ion(1.b) is electron rich having six bonding sites.

The four carboxylate groups and the two nitrogen atoms. Each site has
an electron pair available for bonding.

The [EDTA]4- anion wraps itself around a Ca2+ or Mg2+ ion so that all
six electrons pairs are shared with the metal ion as shown in the
figure. In this manner [EDTA]4- forms strong 1:1 complexes known as
chelates with metal ions like Ca2+ and Mg 2+.

Structure of [Mg-EDTA]2- chelate

Structure of [Ca-EDTA]2- chelate

In an aqueous solution buffered at pH 10,

Erio T also dissociate forming [H-Erio T ]2- ion a blue ion that bonds
with either Mg2+ or Ca

2+

ion to form a wine red complex. The

reaction of [H-Erio T]2- ion with Ca2+ and Mg2+ ions are reversible.

Mg 2+(aq)+ [ H-Erio T]2-(aq,blue)+ H2O

Ca 2+(aq) + [ H-Erio T]2-(aq,blue) + H2O

[Mg-Erio T]-(aq,wine red)+ H3O (aq)

[Ca-Erio T]-(aq,wine red) + H3O (aq)

When the end point is reached [EDTA]4- anion breaks

up the wine red [Mg-Erio T]- and [Ca-Erio T]complexes releasing the [ H-Erio T]2- ion and hence
the solution changes from wine red to permanent blue
color.
[Ca-Erio T]-(aq,wine red) +H3O(aq)+[EDTA]4T]2(aq,blue)+ H2O

[Ca-EDTA] aq +[ H-Erio

[Mg-Erio T]-(aq,wine red)+H3O(aq) +[EDTA]4(aq,blue) + H2O

[Mg-EDTA] aq+[ H-Erio T]2-

Procedure:
Total hardness:
Pipette out 50 ml of the sample of water into a clean titration flask, add 1 ml
of NH3-NH4Cl buffer solution and 3-4 drops of indicator.
Titrate against standard EDTA till the color changes from wine red to clear
blue without any reddish tinge. Let the volume of EDTA required be v1 ml.
Permanent hardness:
Transfer 50 ml of the sample of water into a clean 500 ml beaker and boil
gently for 20-30minutes.
Cool and filter it directly into a 250 ml conical flask.
Add 1 ml of buffer solution followed by 3-4 drops of indicator.
Titrate against standard EDTA as described above. Let the volume of EDTA
required be v2 ml.

Calculation :
1000ml of 1 M EDTA = 100g CaCO3
1ml of Z M EDTA = 100/ 1000 g of CaCO3

V1 ml of 0.01 M EDTA =

V1 X Z X 100
-------------------------- g of CaCO3
1000

50 ml of water sample contains =

V1 X Z X 100
-------------------------- g of CaCO3
1000

106 ( 1 million ) ml of water sample contains =

Similarly
Permanent hardness =

( Mol.weight of CaCO3 =100g)

V2 X Z X 100 X 106
----------------------------1000 X 50

V1 X Z X 100 X 106
----------------------- g of CaCO3
1000 X 50

g of CaCO3

Softening of water:
Ion exchange or deionization or demineralization process
Ion-exchange resins are widely used in different separation,
purification, and decontamination processes. The most
common examples are water softening and water purification.
An ion-exchange resin or ion-exchange polymer is an
insoluble matrix (or support structure) normally in the form of
small (12 mm diameter) beads.
Insoluble cross linked long chain organic polymer and the
functional groups attached to the chains are responsible for the
ion exchange properties.

 Material has highly developed structure of pores on the

surface of which is sites with easily trapped and released ions.
The trapping of ions takes place only with simultaneous
releasing of other ions; thus the process is called ion-exchange
Resins containing acidic functional groups are capable of
exchanging their H+ ions with other cations
Resins containing basic functional groups are capable of
exchanging their anions with other anions.
The ion exchange resin may be classified as

Acidic or cationic exchange resin

Basic or anion exchange resin

Cation exchange resins(RH+)

They are mainly styrene-divinyl benzne copolymers which on
sulphonation or carboxylation become capable to exchange
their hydrogen ions with the cations in the water.
Acidic or cationic exchange resin (Sulphonate form)

Anion exchange resins:

They are styrene divinyl benzene or amine-formaldehyde
copolymerization which contains quaternary ammonium or quaternary
phosphonium or tertiary tertiary sulphonium groups as an integral part of
the resin matrix. These after treated with dil NaOH becomes capable of
exchanging their OH- ions with anions of water.
Basic or anion exchange resin (hydroxide form)

Ion exchange or deionization or demineralization process

The hard water is passed first through cation exchange column:

2RH+ + Ca2+
2RH+ + Mg2+

R2Ca2+ + 2H+
R2Mg2+ + 2H+

After cation exchange column the hard water is passed through

anion exchange resin column :
ROH- + ClRCl+ OH2ROH- + SO42R2SO42- + 2OH-

H + + OHH2O
Thus water coming out from the exchange is free from cations
as well as anions.
Ion free water is known as deionized or demineralised water.
Regeneration:
Cation exchange column is regenerated by passing a solution
of dil HCl or dil H2SO4. The regeneration can be represented as
R2Ca2+ + 2H+
2RH + Ca2+
Exhausted anion exchange column is regenerated by passing a
solution of dil. NaOH. The regeneration can be represented as
R2SO42- + 2OH-

2ROH + SO42-

Advantages:

Can be used to soften highly acidic or alkaline

waters.

It produces water of very low hardness.

Disadvantages:

The equipment is costly

Expensive chemicals are needed.

Output of the process is reduced if water

contains turbidity.(turbidity must be below10ppm)

Mixed bed deionizer:

Consists of a single cylinder containing an intimate mixture of
hydrogen exchanger and strongly basic anion exchanger.
Water passed through this bed comes in contact with two kind of the
resin alternatively.
The net effect of this exchanger is equivalent to passing water
through a series of several cation and anion exchangers.
The outgoing water from this mixed bed exchanger contains less than
1ppm of dissolved salts.

Regeneration :
The mixed bed is back washed
Lighter anion exchanger gets displaced
Forms an upper layer above the heavier cation exchanger.
Regeneration of Anion exchanger - Passing caustic soda from the
top and then rinsed.
Regeneration of Cation exchanger Passing H2SO4 solution.
PP

 Boiler feed Water (Scales and Sludges)

In boilers,
water evaporates continuously
concentrations of the dissolved salts increases
when concentrations of dissolved salts reach saturation point,
they form precipitates on the inner walls of the boiler.
Sludge

Scale

Loose slimy precipitate

A hard, adhering
crust/coating on the inner
walls of the boiler,

Scale and sludge in Boilers

Disadvantages of sludge formation

Sludges are poor conductor of heat.

Tend to waste a portion of heat generated.
Sludges get entrapped in the scale and both get deposited as scales.
Disturbs the working of the boiler.

Prevention of sludge formation:

By using well softened water
By frequently blow-down operation, i.e., drawing off a portion
of the concentrated water.

Formation of scales may be due to

(1) Decomposition of calcium bicarbonate:

Ca (HCO3)2 CaCO3 + H2O + CO2
(In low-pressure boilers)

CaCO3 + H2O Ca (OH) 2 (soluble) + CO2

(In high-pressure boilers)

(2) Deposition of Calcium Sulphate:

Solubility of calcium sulphate in water decrease with rise of
temperature.
Hence CaSO4 gets precipitated as hard scale on the heated
portions of the boiler.

(3) Hydrolysis of magnesium salts:

Dissolved Mg salts undergo hydrolysis forming magnesium
precipitate, which forms a soft type of scale

hydroxide

MgCl2 +2H2O Mg(OH)2 + 2HCl

(Scale)

(4) Presence of silica:

SiO2,present deposits as calcium silicate (CaSiO3) and / or
magnesium silicate (MgSiO3).
These deposits stick on the inner side of the boiler surface.
Difficult to remove.

Disadvantages of scale formation

Wastage of fuel
Scales have a low thermal conductivity
Rate of heat transfer from boiler to inside water is greatly decreased.
Lowering of boiler safety
Due to scale formation, over heating of boiler is done.
Causes distortion of boiler tube.
High pressure boiler is unsafe to bear the pressure of the steam.

Decrease in efficiency
Scales may deposit in the valve and condensers of the boiler
and choke them partially.
Danger of explosion
When thick scales crack, the water comes suddenly in contact with
over-heated iron plates.

 Removal of scales
With the help of scraper or piece of wood or wire brush.
By giving thermal shocks, if they are brittle.
By dissolving them by adding chemicals, (5-10% HCl, EDTA) if they
are adherent and hard.
By frequent blow -down operation, if the scales are loosely adhering.

Prevention of scales formation

(1) External Treatment: Includes efficient softening of water
(i.e., removing hardness-producing constituents of water)

(2) Internal Treatment: Accomplished by adding a proper

chemical to the boiler water either:
(a) to precipitate the scale forming impurities in the form of
sludges,which can be removed by blow-down operation, or
(b) to convert them into compounds, which will stay in dissolved
form in water and thus do not cause any harm.

Priming and Foaming:

Priming:
When a boiler is steaming some particles of the liquid water are

carried along-with steam.

Priming is caused by:

the presence of large amount of dissolved solids

high steam velocities

sudden boiling

improper boiler design and

sudden increase in steam- production rate.

Foaming
Production of persistent foam or bubbles in boilers.
Is due to presence of substances (oils) which reduce the
surface
tension of water.

Priming and foaming usually occur together.

They are objectionable because
(i) Efficiency reduces as dissolved salts in boiler water get
deposited on super-heater and turbine blades, as water
evaporates.
(ii) Life of the machinery may decrease as dissolved salts may
enter the parts of other machinery.
(iii) Maintenance of the boiler pressure becomes difficult, as
actual height of the water column cannot be judged properly.

Priming can be avoided by

Fitting mechanical steam purifiers.

Avoiding rapid change in steaming rate.
Maintaining low water levels in boilers.
Efficient softening and filtration of the boiler-feed water.

Foaming can be avoided by

Adding anti-foaming chemicals like castor oil.
Removing oil from boiler water by adding compounds like sodium
aluminate.