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WATER TECHNOLOGY
INTRODUCTION
Water is the most important compound for the existence of human beings, animals & plants.
Among the various sources of water surface & underground water are normally used for
domestic & industrial purposes. Such water must be free from undesirable impurities. The
process of removing all types of impurities from water & making it fit for domestic or industrial
purpose is called water treatment.
HARD WATER
Water which does not produce lather freely with soap is called hard water. This is due to the
formation of insoluble soaps of calcium & magnesium.
2C17H35COONa + CaCl2
2C17H35COONa +MgSO4
SOFT WATER
Water which produce lather freely with so soft water. Hardness is the property of water which
does not produce lather with soap.
TYPES OF HARDNESS
Depending on the type of dissolved salts present in water, hardness can be classified in two types
1) Temporary hardness
2) Permanent hardness
TEMPORARY HARDNESS
The hardness which is removed by boiling of water is called temporary hardness. This is due to
the presence of bicarbonates of calcium & magnesium.
Ca (HCO3)2
Mg (HCO3)2
Mg (OH) 2 +2 CO2
PERMANENT HARDNESS
The hardness which is not removed even after boiling of water is called permanent hardness.
This is due to the presence of chlorides and sulphates of Ca & Mg.
MgSO4 = 120
MgCl2 = 95
Mg (HCO3)2 = 146
CaCl2 = 111
CaSO4 = 136
Amount in mg/lt.
Molecular weights
Mg (HCO3)2
14.6
146
14.6 x 100
_________ =10
146
MgCl2
9.5
95
9.5 x 100
_________ =10
95
6.0
120
6.0 x 100
_________ =5
120
16.2
162
16.2 x 100
_________ =10
162
MgSO4
Ca (HCO3)2
Amount equivalent
to
CaCO3
PROBLEM 2:
A sample of water is found to contain the following analytical data in mg/lt. Mg (HCO3)2 = 16.8;
MgCl2 = 12; MgSO4 = 29.6; NaCl=5 . Calculate the temporary & permanent hardness of the
sample of water & express it in ppm. (Atomic weight of Mg =24; H = 1 ; C =12 ; O =16; Cl =
35.5; Na = 23; S = 32)
SOLUTION:
Name of the
hardness producing
salt
Amount in mg/lt.
Molecular weights
Amount equivalent
to
CaCO3
Mg (HCO3)2
16.8
146
16.8 x 100
_________ =11.5
146
MgCl2
12
95
12x 100
_________ =12.63
95
29.6
120
29.6 x 100
_________ =24.66
120
MgSO4
NaCl does not contribute any hardness to water & hence it is ignored
.
ALKALINITY
Alkalinity is due to presence of soluble hydroxide (OH-), carbonate (CO32-) & bicarbonate
(HCO3-) ions. These can be determined by titrimetry using standard acid, phenolphthalein &
methyl orange as indicators. The determination is based on the following reactions
(i) (OH-) + (H+)
H2O
(HCO3-)
H2O + CO2
P
M
Alkalinity is classified into three types based upon the anion present in the water
(i) Hydroxide alkalinity _ due to ( OH-)
(ii) Carbonate alkalinity _ due to (CO32-)
(iii) Bicarbonate alkalinity _ due to (HCO3-)
DETERMINATION OF VARIOUS TYPES OF ALKALINITY
Steps involved in the determination of various types of alkalinity ere as follows,
EXPERIMENTAL PROCEDURE
TITRATION 1: Determination of phenolphthalein alkalinity
Pipette out 100 ml of the given water sample a clean conical flask. Add 2 to 3 drops of a
phenolphthalein indicator & titrate it against N/50 H2SO4 taken in the burette. The end point is
the disappearance of pink colour.Let the volume of acid consumed be V1.
TITRATION II: Determination of methyl orange alkalinity
To the same solution add 2 to 3 drops of methyl orange indicator and continue the titration
against the N/50 H2SO4 .The end point is appearance reddish orange. Let the volume of acid
consumed be V2.
CALCULATION
(i) Calculation of Phenolphthalein alkalinity
Volume of acid used to phenolphthalein end point V1 = V1 ml
N1 = N/50
V2 =100 ml
N2=?
N1 = N/50
V2 =100 ml
N2=?
CONCLUSION
(i) When P=O, both OH- & CO32- are absent & alkalinity is due to HCO3- only.
(ii) When P = M, only is CO32- present, half of carbonate neutralization reaction takes place
with phenolphthalein indicator. Complete carbonate neutralization reaction occurs when methyl
orange indicator is used.
Alkalinity due to CO32- = 2P
(iii) When P = M, only OH- is present, alkalinity due to OH- = P = M.
(iv) When P > M, besides CO32- , OH- ions are also present.
Alkalinity due to complete CO32- = 2(M P)
Alkalinity due to OH- = (2P M)
(v) When P < M, besides CO32- , HCO3- ions are also present.
Alkalinity due to CO32-= 2P
Alkalinity due to HCO3- = (M 2P)
CALCULATION OF ALKALINITY OF WATER
Results of P &
M end point
OHppm
CO32ppm
HCO3ppm
Nature of
alkalinity
P=0
Only bicarbonate
P = 1/2 M
2P
Only carbonate
P < 1/2 M
2P
M 2P
Bicarbonate &
carbonate
P > 1/2 M
(2P M)
2(M P)
Hydroxide &
carbonate
P=M
P=M
Only hydroxide
= 100 ml
V1 = 16.7 ml
N1 = N/50
V2 =100 ml
N2=?
PROBLEM 2:
100 ml of a water sample on titration with N/50 HCl gave a titre value of 6.8 ml to
phenolphthalein end point & 13.6 ml to methyl orange end point. Calculate the alkalinity of the
water sample & comment on the type alkalinity present.
SOLUTION:
Volume of water sample
= 100 ml
V1 = 2P = 2 X 6.8 = 13.6 ml
N1 = N/50
V2 =100 ml
N2=?
=136 PPM
CH2COOH
N--CH2CH2N
HOOCH2C
CH2COOH
PRINCIPLE
The amount of hardness causing ions can be estimated by titrating the water sample against
EDTA using Erichrome Black- T indicator at a PH of 8 to 10. In order to maintain the PH buffer
solution is added.
When the EBT indicator is added to the water sample it forms wine red coloured weak complex
with Ca2+ & Mg2+ ions.
Ca2+
PH 8 10
Ca
+ EBT
EBT
Mg2+
complex
Mg
Wine red coloured weak complex
When this solution is titrated against EDTA, it replaces the indicator from tee weak complex &
form stable EDTA complex. The colour of the free indicator is steel blue.
Ca
PH 8 10
EBT
Ca
+ EDTA
Mg
EDTA
Mg
Preparation of solutions
EDTA: 4 gm of EDTA is dissolved in 1000 ml of distilled water.
EBT: 0.5 gm EBT in 100 ml alcohol
complex + EBT
steel blue
Standard hard water: 1 gm of calcium carbonate is dissolved in minimum amount of dil. HCl
& then made up to 1000 ml using distilled water.
Buffer: 67.5 gms of ammonium chloride & 570 ml of ammonia are dissolved & the solution is
made up to 1000 ml using distilled water.
Experimental procedure
(i) Standardisation of EDTA
Pipette out 20 ml of standard hard water into a clean conical flask. Add 10 ml of buffer solution
& 5 drops of EBT indicator & titrate it against EDTA.The end point is the change of colour from
wine red to steel blue.
Let the volume of EDTA consumed be V1 ml.
(ii) Estimation of total hardness of water sample
Pipette out 20 ml of the given hard water sample into a clean conical flask & titrate it against as
before.
Let the volume of EDTA consumed be V2 ml.
(iii) Estimation of permanent hardness of water sample
Take 100 ml of the same hard water sample in a 250 ml beaker.Boil it for 15 minutes.Cool &
filter the solution and make upto 100 ml in a standard flask by adding distilled water. Pipette out
20 ml of the made up solution into a clean conical flask & titrate it against EDTA as before.
Let the volume of EDTA consumed be V3 ml.
Calculations
(i) Standardisation of EDTA
1 ml of standard hard water =1 mg of CaCO3
20 ml of standard hard water =20 mg of CaCO3
20 ml of standard hard water consumes V1 ml of EDTA
1ml of EDTA = 20/V1 mgs of CaCO3 equivalent hardness
(ii) Estimation of total hardness of water sample
20 ml of given hard water consumes V2 ml of EDTA
=V2 X 20/V1 mgs of CaCO3 equivalent hardness
1 ml of EDTA
= 1 mgs of CaCO3
= 33 ml of EDTA
= 33 X 1000/100
Total hardness
(ii)Permanent Hardness
100 ml of the hard water after boiling cooling & filtering = 10 ml of EDTA
=10 mgs of CaCO3
1000 ml of the hard water
Permanent hardness
= 10 X 1000/100
= 100 mgs/lt (or) PPM
CHARACTERISTICS OF WATER
As per the suggestion given by World Health Organization (WHO) & by Indian Council of
Medical Research (ICMR), the following are the important characteristics of potable water.
1. It should be clear, colourless & odourless.
2. It should be cool & pleasant to taste.
3. It should be free from harmful bacteria & suspended impurities.
4. It should be free from dissolved gases like CO2, H2S etc & poisonous minerals like lead,
arsenic, manganese etc.
5. Hardness should be less than 500 ppm.
6. Chloride content should be less than 250 ppm.
7. Fluoride content should be less than 1.5 ppm.
8. Total dissolved solid content should be less than 500 ppm.
Finely divided clay, silica etc. do not settle down & cannot be removed by sedimentation. Such
impurities are removed by coagulation method. Al2 (SO4)3 is added to water. It gets hydrolyzed
to form a gelatinous precipitate of Al (OH)3 which entraps the finely divided & colloidal
impurities ,settles to the bottom & can be removed easily.
FILTERATION
It is the process of removing bacteria, colour, taste, odour & suspended particles by passing
through filter beds containing fine sand, coarse sand & gravel. When the rate of filtration
becomes very slow, the filtration is stopped & the thick top layer is scrapped off & replaced with
clean sand.
STERILIZATION
The process of destroying the harmful bacterias is known as sterilization.
The process can be carried out by
1. Boiling
2. by ozonation
3. By using ultraviolet radiations.
4. by chlorination
Chlorination can be done by
a)by adding chlorine gas
b) By adding chloramines
c) By adding bleaching powder.
When bleaching powder is added to water, it produces HOCl which is a powerful germicide.
CaCOCl2 + H2O
Ca (OH) 2 + Cl2
Bleaching powder
Cl2 + H2O
HCl + HOCl
(Hypochlorous acid)
HOCl + Bacterias
Prevention
1. Sludge formation can be prevented by using soft water.
2. They can also be removed by blow down operation .It is a process of removing a portion of
concentrated water by fresh water from the boiler during steam production.
Scale
If the precipitate forms hard & adherent coating on the inner walls of the boiler, it is called
sacle.Scales area farmed by Ca (HCO3)2, CaSO4 & Mg (OH) 2
Disadvantages
1. Scales act as thermal insulators.
2. Any crack leads to explosion.
Prevention
1. Scale formation can be removed by external & internal treatment.
2. They can be removed by applying shocks, scrapers, wire brush etc.
Priming & Foaming
During production of steam in the boiler, due to rapid boiling, liquid droplets are carried along
with steam.Steam containing liquid droplets is called wet steam. These droplets carry with them
some dissolved salts & suspended impurities. This is called carry over.
Priming
Priming is the process of production of wet steam.Priming is caused by
1. High steam velocity
2. High water level in the boiler.
3. Sudden boiling water.
4. Poor boiler design.
Prevention
Priming can be controlled by
1. Controlling the velocity of steam
2. Good boiler design
Foaming
The formation of stable bubbles above the surface of water is called foaming.
Foaming is caused by
1. Presence of oil & grease
2. Presence of finely divided particles.
Prevention
1. Adding coagulants like sodium aluminate, aluminium hydroxide.
2. Adding antifoaming agents like synthetic polyamides.
Caustic embrittlement
Caustic embrittlement means intercrystalline cracking of boiler metal.
In high pressure boilers Na2CO3 undergoes decomposition to give NaOH.
Na2CO3 + H2O
2NaOH + CO2
This NaOH flows into minute hair cracks by capillary action & dissolves the surrounding area of
iron as sodium ferroate.
Fe + 2NaOH
Na2FeO2 +H2
This causes brittlement of boiler parts causing even failure of the boiler.
Prevention
This can be prevented by
1. Using sodium phosphate as softening agent instead of sodium carbonate.
2. By adding tannin, lignin to the water which blocks the hair cracks.
Boiler corrosion
4Fe (OH) 3
Removal
Dissolved oxygen can be removed by chemical or mechanical methods.
a)Chemical method
Sodium sulphite, hydrazine are used for removing oxygen.
2Na2SO3 + O2
N2H4 +O2
2Na2SO4
N2 + 2H2O
b) Mechanical method
Water is allowed to fall slowly on the perforated plates fitted inside the tower.
The high temp. & low pressure produced inside the tower reduces the dissolved oxygen content
of the water.
Dissolved CO2
Dissolved CO2 in water produces carbonic acid which is acidic & corrosive in nature.
CO2 + H2O
H2CO3
Removal
CO2 can be removed by adding NH4OH.
2NH4OH + CO2
Dissolved MgCl2
Salts like MgCl2, CaCl2 undergo hydrolysis at higher temperature to give HCl which corrodes the
boiler.
MgCl2 + 2H2O
Mg (OH) 2 + 2HCl
Fe + 2HCl
FeCl2 + H2
FeCl2 + 2H2O
Fe (OH)2 + 2HCl
Removal of acids
Corrosion by acids can be avoided by the addition of alkali to the boiler water.
HCl + NaOH
NaCl + H2O
SOFTENING METHODS
The process of hardness producing salts from water is known as softening or conditioning of
water.
Softening can be done in two methods
1. External conditioning
2. Internal conditioning
EXTERNAL CONDITIONING
It involves the removal of hardness producing salts from water before feeding into boiler. The
external treatment can be done by Ion exchange process.
ION EXCHANGE OR DEMINERALISATION PROCESS
This process removes almost all ions present in the hard water. The process is carried out by
using ion exchange resins, which are long chain, cross linked, insoluble organic polymers with a
micro porous structure. The functional groups attached to the chains are responsible for the ion
exchanging properties.
Cation exchanger
Resins containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their H+
ions with other cations of hard water. It is represented as RH2
Ex: sulphonated coals, sulphonated polystyrene.
Anion exchanger
Resins containing basic functional groups (-NH2, -OH) are capable of exchanging their anions
with other anions of hard water. It is represented as R (OH) 2
PROCESS
The hard water first passed through a cation exchanger column which absorbs all the cations like
Ca2+, Mg2+, Na+ & K+ present in the hard water.
RH2 + CaCl2
RH2 + MgSO4
RCa + 2HCl
RMg + H2SO4
The cation free water is then passed through a anion exchange column which absorbs all the
anions like Cl-, SO42- present in the water.
R (OH) 2 + 2HCl
R (OH) 2 + H2SO4
RCl2 + 2H2O
RSO4+ 2H2O
The water coming out of the anion exchange is completely free from cations & anions.
Regeneration
When the cation exchange resin is exhausted it can be regenerated by passing dil. HCl.
RCa + 2HCl
RH2 + CaCl2
R (OH) 2 + 2NaCl
Advantages
1. Highly acidic or alkaline water can be treated
2. The water will have very low hardness (nearly 2 ppm)
Disadvantages
1. Water containing turbidity, Fe and Mn cannot be treated.
2. The equipment is costly & more expensive chemicals are needed.
It involves the removal of scale forming substance, which were not removed in the external
treatment, by adding chemicals directly into the boiler.
1. Carbonate conditioning
Scale formation can be avoided by adding Na2CO3 to the boiler water. CaSO4 is converted into
CaCO3 which can be removed easily.
CaSO4 + Na2CO3
CaCO3 +Na2SO4
2. Phosphate conditioning
Scale formation can be avoided by adding sodium phosphate. The phosphate reacts with Ca2+ &
Mg2+ salts to give soft sludges of Ca & Mg phosphates.
3CaSO4 + 2Na3PO4
3. Calgon conditioning
Calgon is sodium hexa Meta phosphate Na2 (Na4 (PO3)6). This salt interacts with Ca ions forming
a highly soluble complex & prevents the precipitation of scale forming salt.
2CaSO4 + Na2 (Na4 (PO3)6)
DESALINATION
The process of removing common salt from water is known as desalination. Depending upon the
quantity of dissolved solids, water is graded as
(i)Fresh water _ contains < 1000 ppm of dissolved solids
(ii)Brackish water _ contains > 1000 but < 35000 ppm of dissolved solids
(iii)Sea water _ contains >35000 ppm of dissolved solids
Desalination can be carried out either by reverse osmosis or electro dialysis.
REVERSE OSMOSIS
When two solutions of different concentrations are separated by a semi permeable membrane,
solvent flows from a region of lower concentration to higher concentration. This process is called
osmosis & the driving force is called osmotic pressure.
If hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration side,
the solvent flows from higher concentration to lower concentration. Thus in the process of
reverse osmosis pure water is separated from salt water. The membranes used are cellulose
acetate, cellulose butyrate etc.
Advantages
(i)The life time of the membrane is high, & it can be replaced within few minutes.
(ii)It removes ionic as well as non- ionic, colloidal impurities.
(iii)Due to low capital cost, simplicity, low operating, this process is used for converting sea
water into drinking water.