WATER TECHNOLOGY

Soft and hard water, Estimation of hardness of water by EDTA Method,

Numerical Problems on Temporary and Permanent Hardness -
Disadvantages of Hard Water, Boiler troubles –Priming, foaming, scale and
sludge, Caustic embrittlement, Industrial water treatment –Ion-exchange
processes, Desalination of brackish water- Reverse osmosis (RO) and
electrodialysis. Wastewater treatment-Block diagram (primary, secondary,
tertiary).

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 UNIT-I: WATER TECHNOLOGY
Hardness of Water:
Water is classified into two categories depending upon its behaviour towards soap solution.
a) Soft water: Water which produces lather with soap solution readily is called soft water.
Examples: Distilled water and rain water.
b) Hard water: Water which does not produce lather with soap solution easily is called hard
water. Examples: River water and sea water.
Hardness of water is due to the dissolved impurities of the salts like bicarbonates, chlorides and
sulphates of calcium and magnesium.
Hard water does not produce lather with soap solution readily because the cations (Ca 2+
and Mg2+) present in hard water react with soap to form precipitate of calcium and magnesium
salts of fatty acids.
M2+ + 2C17H35COONa (C17H35COO)2 M + 2 Na+
From Hard water sodium stearate Metal stearate
Where M = Mg or Ca
TEMPORARY AND PERMANENT HARDNESS:
Hardness of water is of two types. Temporary hardness and Permanent hardness:
i) Temporary hardness: It is due to the presence of soluble bicarbonates of calcium and
magnesium. Such water is also said to possess carbonate hardness. The term temporary
indicates that most of the hardness can be removed by simply boiling the water.
The methods employed for removing temporary hardness are the following.
1. By boiling: Temporary hard water contains calcium and magnesium bi-carbonates. These
salts are decomposed on boiling the water, forming insoluble calcium and magnesium carbonates
which can easily be removed by filtration.
Ca(HCO3)2 CaCO3 + H2O + CO2
Calcium bicarbonate Calcium Carbonate
(Soluble) (Insoluble)
Mg(HCO3)2 Mg(OH)2 + 2CO2
Magnesium bicarbonate Magnesium Hydroxide
(Soluble) (Insoluble)
2. Clark’s Method: This is the cheapest method for removing temporary hardness of water and
is therefore widely used. In this method sufficient amount of lime (Calcium hydroxide) is added
to the water which converts all the soluble bicarbonates into insoluble carbonates as shows
below:
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
 (Soluble) (Lime) (Insoluble)
Mg(HCO3)2 + Ca(OH)2 CaCO3 + MgCO3 + 2H2O
(Soluble) (Lime) (Insoluble) (Insoluble)
ii) Permanent Hardness: It is due to the presence of chlorides and sulphates of calcium and
magnesium. Such water is said to possess “Non-Carbonate Hardness”. The term permanent
indicates that such type of hardness cannot by removed by simple boiling of water.
The permanent hardness can be removed by addition of calculated quantity of sodium
carbonate (washing soda) by which calcium and magnesium carbonates are precipitated as shows
below:
CaSO4 + Na2CO3 CaCO3 + Na2SO4
(Soluble) washing soda (insoluble)
MgSO4 + Na2CO3 MgCO3 + Na2 SO4
(Soluble) washing soda (insoluble)
CaCl2 + Na2CO3 CaCO3 + 2NaCl
(Soluble) washing soda (insoluble)
MgCl2 + Na2CO3 MgCO3 + 2NaCl
(Soluble) washing soda (insoluble)
Units of Hardness And its Inter conversion:
The hardness causing ions are usually expressed in terms of an equivalent amount of CaCO 3.
Units of Expression of Hardness:
1) Parts per million (ppm)
2) Milligram per litre
3) Degree French (0Fr)
4) Clarke’s degree ( 0Cl)
1) Parts per million (ppm): It is defined as the number of parts of hardness causing
substance in CaCO 3 equivalent hardness per 10 6 parts (one million) of water.
2) Milligram per litre (mg/litre): The number of milligrams of hardness causing substance
in CaCO3 equivalent hardness present per litre of water.
3) Degree Clark (0Cl): The number of parts of hardness causing substance in CaCO 3
quivalent hardness per 70,000 parts of water.
4) Degree French (0Fr): The number of parts of hardness causing substance in CaCO 3
equivalent hardness per 10 5 parts of water.
The hardness of water can be converted into all the four units by making use of the
following inter conversion formula.
1ppm = 1mg / litre = 0.07 0Cl = 0.1 0Fr
10Cl = 1.43 0Fr = 14.3 ppm = 14.3 mg/litre
1 0Fr = 0.7 0Cl = 10ppm = 10 mg/litre
For finding the hardness of water in ppm or mg/lt or any unit, it is necessary the all the
hard salts should be represented as equivalents of calcium carbonate salt. The choice of calcium
carbonate in particular is due to its molecular weight being 100 and equivalent weight 50 which
is found to be a convenient number an also it is most insoluble salt. Calcium carbonate
equivalent can be achieved by using the following formula.

Table gives the multiplication factor for converting into CaCO 3 equivaletns.
Hard salt Molecular weight Equivalent weight Multiplication factor
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaSO4 136 68 100/136
MgSO4 120 55.5 100/120
CaCl2 111 60 100/111
MgCl2 95 47.5 100/95
CaCO3 100 50 100/100
MgCO3 84 42 100/84
Mg(NO3)2 148 74 100/148
Problems:
1. Calculate the carbonate hardness and non carbonate hardness of sample water containing the
dissolved salts in one litre of hard water as given below. Also calculate total hardness.
Ca(HCO3)2 =32.4mg; Mg(HCO3)2 = 14.6mg; CaSO4 = 13.6mg; MgSO4 =11.1mg; CaCl2 =
12.0mg; MgCl2 = 9.5mg.
Solution:
Hardness producing salt Amount Multiplication factor Equivalents of CaCO3

Ca(HCO3)2 32.4 100/162 20

Mg(HCO3)2 14.6 100/146 10

CaSO4 13.6 100/136 10

MgSO4 22.2 100/120 20

CaCl2 12.0 100/111 10

MgCl2 9.5 100/95 10

Temparary hardness due to Ca(HCO 3)2 and Mg(HCO3)2 = 20 + 10 = 30ppm

Permanent hardness due to CaSO4, MgSO4,CaCl2 and MgCl2 =10+20+10+10= 50ppm
Total hardness = 30ppm + 50ppm = 80ppm or mg/l
2. A sample of water gives on analysis 13.6 mg/l of CaSO 4, 7.3 mg/l of Mg(HCO3)2. Calculate
the total hardness and permanent hardness.
3. Calculae the total hardness of 1000 litre of a sample of water containing the following
impurities 16.2 mg/l of Ca(HCO3)2, 11.1 mg/l of CaCl2, 60 mg/l of MgSO 4 and 19 mg/l of
MgCl2.
4. A sample of hardwater contains the following dissolved salts per litre. CaCl2 = 111 mgs,
CaSO4 = 1.36 mgs, Ca (HCO 3)2 = 16.2 mgs, Mg(HCO 3)2 = 14.6 mgs, Silica = 40 mgs,
Turbidity = 10 mgs. Calculate the temporary, permanent and total hardness of water in ppm,
degree Clark and degree French.
5. Calculate the temporary and permanent hardness of water in 0Cl, containing the following
dissolved salts. CaCO3 = 50 mg/l, MgCl2 = 9.5 mg/l, CaCl2 = 22.2 mg/l and MgSO4 = 12
mg/l.
6. A sample of water contains 100 ppm of total hardness and 25 ppm of temporary hardness.
Calculate the permanent hardness of water in degree Clark and degree French.
Estimation of Hardness by EDTA Method:
Disodium salt of Ethylene Diamine Tetra Acetic acid is used as the permanent complexing agent
with Ca2+ and Mg2+ ions of hard water in the EDTA method.
The structure of EDTA is given below.

Before starting the titration, to the hard water ammonium buffer (to maintain pH 10) and EBT
indicator are added which form an unstable complex of wine red color.

After the titration, the sodium salt of EDTA form Stable complex with water containing Ca 2+ and
Mg2+ ions replacing the unstable complex. The completion of the complex formation is indicated
by EBT indicator giving a sky blue color. + EDTA

Procedure:
1. Preparation of standard hard water: 1g of pure dry CaCO3 should be dissolved in small
quantity of dilute HCl and then evaporated to dryness on a water bath. The residue is
dissolved in distilled water and make up to 1L. 1 ml of this solution contains 1 mg of
CaCO3 equivalent hardness.
2. Preparation of EDTA solution: 3.72 grams of pure sodium salt of EDTA crystals should
be dissolved in 1L of water (0.01 M).
3. Preparation of Indicator: 0.5g of EBT should be dissolved in 100mL of alcohol.
4. Preparation of buffer solution: It can be prepared by mixing 67.5g of NH 4Cl in 570mL
of liquid ammonia and then diluted to 1L with water.
5. Standardization of EDTA solution: The burette is filled with the EDTA solution. 50 ml
standard hard water pipette out into a clean conical flask. Add 10-15 ml of buffer solution
and few drops of Erichrome black – T indicator. The wine red solution in the conical
flask is titrated against the burette EDTA solution till the wine red color changes to sky
blue color. Let the volume of EDTA consumed be V 1 ml.
6. Titration of unknown hard water or Estimation of total hardness: 50 ml sample hard
water pipette out into a clean conical flask. Add 10-15 ml of buffer solution and few
drops of Erichrome black – T indicator. The wine red solution in the conical flask is
titrated against the burette EDTA solution till the wine red color changes to sky blue
color. Let the volume of EDTA consumed be V2 ml.
7. Estimation of Permanent hardness: Take 250ml of water sample in a large beaker, boil
it till volume is reduced to about 50ml [when all bicarbonates are decomposed to
insoluble CaCO3 + Mg(OH)2]. The temporary salts settle down. Filter and wash
thoroughly and make up solution again to 250 ml. pipette out 50 ml 0f made up solution
into clean conical flask and titrate it against EDTA solution in the burette to get the end
point. Let the volume of EDTA consumed be V3 ml
Calculations:
V1 ml of EDTA = 50 ml of standard hard water
 V1 ml of EDTA = 50 mg of CaCO3
 1ml of EDTA = 50/V1 mg of CaCO 3 equivalent
Now 50ml of given hard water = V2 ml of EDTA
= V2 X50/V1 mg of CaCO3 equivalent
 1L (1000ml) of given hard water = 1000 V2/V1 mg of CaCO3 equivalent
 Total hardness of water = 1000V2/V1 mg/L=1000V2/V1 ppm
Now 50ml of boiled water = V3 ml of EDTA
= V3 X 50/V1 mg of CaCO3 equivalent
 1000 (mL) = (1L) of boiled water
Permanent hardness = 1000 V3/V1 mg of CaCO3 equivalent
 Permanent hardness = 1000 V3/V1 ppm
And Temporary hardness = Total hardness – Permanent hardness
V V 
= 1000  2  3  ppm
 V1 V1 
1000(V2  V3 )
= ppm
V1
Advantages of EDTA method:
This method is definitely preferable over the other methods, because of the (i) greater accuracy
(ii) convenience and (iii) more rapid procedure.
DISADVANTAGES OF HARDWATER:
1. In the domestic use, hardwater is not suitable for washing as it will not give lather with
soap. So no cleaning takes place. It causes wastage of lot of soap.
2. Hardwater is not suitable for bathing also. Because cleaning is not proper.
3. Due to the impurities in water, the boiling point is elevated. So more fuel and time are
required when hard water is used for cooking. The food will have unpleasant taste. It
may also injurious to health.
4. Drinking hardwater disturbs the digestive system and also calcium oxide crystals may
accumulate in urinary tract. Hence excretion becomes difficult.
5. Even in industries also, use of hardwater is not recommended.
i) In the textile industry, cleaning of raw textile becomes difficult.
There may be fading of colour of the textile. Colours may not be fixed properly.
ii) In sugar industry, the crystallization of sugar will be difficult. Quality of sugar
will be poor.
iii) In paper industry, the dissolved salts in water may react with constituents of
paper and may decrease the quality.
iv) In the Pharmaceutical industry hard water should not be used at all as it can
change the composition of drugs. Consumption of such drugs leads to further
problems.
v) In boilers if hard water is used scales and sludges may be formed. This leads to
several complications.
vi) Water containing chlorides and sulphates, if used for concrete making, affects the
hydration of cement and the final strength of the hardened concrete.
SOFTENING MEHODS OF WATER

1. ION-EXCHANGE PROCESS:
Ion-exchange resins are insoluble, cross linked, long chain organic polymers with a micro
porous structure and the functional groups attached to the chains are responsible for the ion
exchange properties. Process includes the exchange of the cations and anions of the dissolved
salts with H+ and OH- ions respectively. For this two types of ion-exchangers are used i.e.
Cation exchangers and Anion exchangers.
Thus all the cations and anions present in the dissolved salts are exchanged with cation
exchanger and anion exchanger.
Process: This process involves the following steps.
Step-1: The hard water is passed through a bed of cation-exchange resin (RCOOH or R-SO3H)
of tank ‘A’. The Ca2+ and Mg2+ ions are exchanged with H + ions of the resin.
2RCOOH + Ca2+ (RCOO)2Ca + 2H+
2RCOOH + Mg2+ (RCOO)2 Mg + 2H+
Thus, hardness producing cations (Ca2+ & Mg2+) are removed. The water coming out contains
H+, Cl-, SO 42- and HCO3 - ions.
Step-2: The hardwater is then passed through a bed of anion exchange resin (R-OH or R-NH2) of
tank ‘B’. The Cl-, SO 42- and HCO3 - ions are exchanged with OH - ions of the resin.
R-OH + Cl - RCl + OH -
2R-OH + SO42- R2SO4 + 2OH-
R-OH + HCO3 - RHCO3 + OH -
Thus, hardness producing anions (Cl-, SO4 2-& HCO3-) are removed.
Step-3: The H + ions produced in tank ‘A’ combine with OH - ions produced in tank ‘B’ to form
water.
H+ + OH - H 2O
Thus, this process removes all types of hardness producing cations and anions present in water.
The resulting water is known as demineralized or deionized water.
Regeneration of Resins: With constant use, the resins get exhausted. This can be
regenerated as follows:
i) The exhausted cation-exchange resin can be regenerated by passing dilute HCl.
(RCOO)2Ca + 2HCl 2RCOOH + CaCl2
(RCOO)2 Mg + 2HCl 2RCOOH + MgCl2
CaCl2 and MgCl2 are removed as wash.
ii) The exhausted anion-exchange resin can be regenerated by passing dilute NaOH.
RCl + NaOH R-OH + NaCl
R2SO4 + 2NaOH 2R-OH + Na2 SO4
RHCO3 + NaOH R-OH + NaHCO3
NaCl, Na2 SO4 and NaHCO3 are removed as wash.
Advantages:
1. It produces very pure water of hardness nearly 2 ppm.
2. Highly acidic and alkaline water can be treated by this process.
3. It is very good fit for use as boiler feed water.
Disadvantages:
1. The equipment is costly and more expensive.
2. Highly turbidity water cannot be treated by this process.
3. The turbidity must below 10 ppm. If it is more, it has to be removed first by coagulation and
filtration.
Desalination of brackishwater
The process of removing common salt(NaCl) from the water is known as
desalination. Water containing high concentration of dissolved salts with
apeculiar salty taste is called brackishwater. Sea water is an example containing
3.5% of dissolved salts. The common methods for the desalination of brackish
 water are
i) Electrodialysis
ii) Reverseosmosis

Eletctrodialysis: It is a method in which the ions are pulled out of the salt water
by passing direct current, using electrodes and thin rigid plastic membrane pair.

Principle:
 When direct current is passed through saline water using electrodes, salt ions
present in saline water migrates towards their respective electrodes through ion
selective membrane, under the influence of applied emf.
Construction:
The electro dialysis unit consists of a chamber, two electrodes a cathode and an anode.
The chamber is divided into three compartments with the help of thin, ion selective
membranes which are permeable to either cation or anion
Process:
 When direct electric current is passed through saline water, the Na + ions moves towards
cathode (-ve pole) and the chloride ions moves towards anode (+ve pole) through
membrane.
 The concentration of brine decreases in the central compartment, where as the
concentration in outer compartments increases.
 Desalinated brine (pure water) is removed from time to time, while concentrated one is
replaced by fresh brine.
 Ionselective membranes are employed for more efficient separation, which has
permeability for one kind of ions.
 Cation selective membrane (which possesses functional groups such as RSO3 -) is
permeable to cations only.
  Anion selective membrane (possess functional groups such as R4 N+Cl-) is permeable to
anions only
Advantages:
 It is a compact unit, economical.
 Best suited if electricity is easily available.

Reverse osmosis:

Principle:
This reverses the natural process of osmosis, where water moves from a low concentration of solutes to
a high concentration. By applying external pressure greater than the natural osmotic pressure, water is
forced from the impure side (high concentration) to the pure side (low concentration).

Construction:
The electro dialysis unit consists of a chamber, two electrodes a cathode and an anode. The
chamber is divided into two compartments with the help of thin semi permeable
membranes which are allows to solvent particles. The membraneconsists of very thin film
of cellulose acetate, affixed to either side of a perforated tube. However,more recently
superior membranes made of poly methacrylate and polyamide polymers have come in to
use.
Process : Reverse osmosis is one of the membrane filtration process. The process is used to
remove salts and Organic micro pollutants from water. When two solutions of unequal
concentrations are separated by a semi permeable membrane, flow of solvent takes place from
dilute to concentrate side due to osmosis. If, however a hydrostatic pressure in excess to
osmotic pressure is applied on the concentrated side, the solvent flow is reversed, i.e, solvent is
forced to move from concentrated side to dilute side across the membrane. Thus in reverse
osmosis method, pure solvent is separated from its contaminants, rather than removing
contaminants from the water. The membrane filtration is sometimes also called super-filtration
or hyper-filtration.
Advantages:
1. Reverse osmosis possesses distinct advantages of removing ionic as well
as non-ionic, colloidal and high molecular weight organic matter.
2. It removes colloidalsilica,which is not removed by demineralization.
3. The maintenance cost is almost entirely on there placement of the semi permeable
membrane.
4. The life time of membrane is quitehigh,about2years,

Boiler Troubles:
Water is mainly used in boilers for the generation of steam for industries and power houses. A
boiler is an instrument in which water under pressure is converted into steam by the application
of heat and this steam is utilized for various purposes like electricity generation.
For boiler feed water all the impurities are not necessarily eliminated, and only those impurities
which lead to operational troubles in boilers are eliminated.
Boiler-feed water should correspond with the following composition:
• Its hardness should be below 0.2 ppm.
• Its caustic alkalinity (due to OH-) should be between 0.15 and 0.45 ppm.
• Its soda alkalinity (due to Na2CO3) should be 0.45 – 1 ppm.
The following are the boiler troubles that arise due to the presence of dissolved salts
I) Scale and sludge formation
II) Boiler Corrosion
III) priming and foaming
IV) caustic embrittlement.
I. Sludge and Scale Formation in Boilers:
Sludge : 
 Soft,loose, slimy and nonsticky precipitate formed with in the boiler.
 Formed at comparatively colder portions of the boiler and are collected at the bends,
joints. 
 Easilyremoved withwirebrush
Scale :
 Hard and sticky deposites formed on the inner walls of the boiler.
 Difficult to remove, even with the help of hammer &Chisel. 

Reason for scale and sludge
 Decomposition of Temporary Hardness
Mg(HCO3)2 → Mg(OH)2+2CO2
Ca(HCO3)2→ CaCO3 + H2O + CO2
 Deposition of calcium sulphate:- Solubility of CaSO4 decreases with
increase in temperature. It is completely insoluble in super heated
[Link] scale formation takesplace in highpressure boilers
 Hydrolysis of magnesium salts:-
 MgCl2 + 2H2O→Mg(OH)2 + 2HCl
 Presence of silica : formation of calcium and magnesium silicates
Disadvantages /effects of scale and sludge:-
 Wastage of fuel
 Lowering of boiler safety
 Decrease in efficiency
 Danger of explosion
 Excessive sludge formation disturbs the working of the boiler.
 It settles in the regions of poor water circulation such as pipe connection, plug opening,
gauge-glass connection, thereby causing even choking of the pipes.
Prevention/Removal of scale and sludge :-
• By using softened water.
 Mechanical/chemical method
 Loosely adhering scales are removed with the help Scraper/wire brush
 Brittle scales are removed by giving Thermal shocks
 Loosely adhering scales are removed by frequent blow downoperation (frequently
removing precipitates)
 Scale is removed by washing with 5-10% HCl.


II. Priming and Foaming:

Priming: Priming in boilers is the carryover of water particles with the steam.
Foaming: Foaming in a boiler is the formation of stable bubbles on the water's surface.
Cause / Reason for priming and foaming
 Large amount of dissolved solids like alkali sulfates and chlorides present
 Sudden boiling operation
 Inadequate amount of steam space
 Improper design of steam boiler
 Sudden acceleration in steam-production rate
 High concentrations of solids
 High water levels
 Excessive load
Effects/disadvantages of Priming and foaming
  Reduction in boiler efficiency
 Increase in maintenance costs
 Lowers the lifespan of the machinery parts
 The actual height of the water column cannot be accurately estimated, which makes the
maintenance of the pressure part challenging.
 The dissolved salts in the water passed by the wet steam damages the turbine blades and
superheaters, resultantly reducing their efficiency
 The dissolved salts in the water may impact the other machinery parts that decrease the
overall lifespan of the steam boiler.
 Effieciency of the boiler is lowered
 Difficult to keep up steam pressure
 Wastage of heat
 Dissolved salts deposited on the machinery which cause corrosion
Prevention/Removal of priming and foaming

 Improved steam boiler design

 Introducing mechanical steam purifiers in boiler systems
 Maintaining low water levels in the boiler
 Utilization of soft water
 Reducing the amount of dissolved salts in the feedwater
 The addition of anti-foaming agents like castor oil which spreads on the surface of water
and therefore neutralizes the surface tension reduction
 The removal of foaming agent like oil from boiler water by using coagulants which
entrap oil drops.
 Blow down of the boiler can prevent foaming

CAUSTICEMBRITTELMENT

Caustic embrittlement is a type of boiler corrosion where boiler metal becomes brittle and cracks
due to the accumulation of concentrated caustic substances, mainly sodium hydroxide

Reason:
 It is a type of boiler corrosion, caused by highly alkaline water in the boiler.
 In limesoda process, it is likely that, some residual Na2CO3 is still present in the
softened water
 This Na2CO3 decomposes to give NaOH and CO2 due to which the boiler water
becomes “Caustic”.
Na2CO3+ H2O →2NaOH +CO2↑
 This very dilute caustic water flows into the minute hair cracks in the boiler, by
 capillary action.
 This concentrated alkali dissolves iron of boiler as sodium ferroate.
 It causes embrittlement of boiler parts such as bends joints, rivets etc,due towhich the
boilergets fail.
Fe + NaOH → Na2FeO2+H2
Insoluble soluble
Effects:
 Cracking and failure
 Boiler explosion risk
 Intergranular cracking:
 Material embrittlement
 Decreased efficiency

Prevention

 Use sodium phosphate instead of sodium carbonate

 Control alkalinity
 Perform regular blowdown
 Add corrosion inhibitors
 Use organic inhibitors

waste water treatment:

QUESTIONS
1. Explain how can you determine the total hardness of water by EDTAmethod?
2. What are the different units in which the hardness of water is expressed? How are they
related to each other?
3. Discuss the various boiler troubles , their causes and prevention.
4. Problems on hardness.
5. Write a brief account on a) Caustic embrittlement b) Prmimg and foaming..
6. Explain how the water is softened by Ion-Exchange method? Explain with neat
diagram and relevant equations.
7. Explain the Reverse osmosis with neat sketch.
8. Explain the Electrodialysis with neat sketch.
9. Explain waste water treatment methods.