Engineering Chemistry

Dr. Payal Joshi

Water Technology
Contents: Hardness of water. Determination of hardness of water by EDTA titration. Numericals based on
hardness of water and EDTA method.
Softening Methods: Hot and Cold Lime-Soda Method, Zeolite Method and Ion-Exchange Method. Numerical
based on lime-soda and zeolite method.
Drinking water purification: Removal of microorganisms, by adding bleaching powder, chlorination (no
breakpoint chlorination), Ozonization, Desalination by Reverse Osmosis, Ultrafiltration.

Hardness of Water: Natural waters containing large quantities of dissolved salts of Calcium
(Ca) & Magnesium (Mg) is called hard water. It is a characteristic of preventing lather formation
of water with soap. Ca2+ & Mg2+ ions react with soaps which are salts of fatty acids (stearic or
palmitic acid) to give insoluble scums or precipitates of calcium or magnesium stearate or
palmitate.
2C17H35COO- + Ca2+ (C17H35COO)2 Ca (scum)
2C17H35COO- + Mg2+ (C17H35COO)2 Mg(scum)
This property or tendency is called hardness of water. The cause of hardness is the precipitation
of soap and hence prevents lathering.
Hardness of water is of two types:
1. Temporary/Alkaline/Carbonate hardness is due to dissolved bicarbonates of Ca2+ & Mg2+
in water. It is so called since it can be easily removed simply by boiling with bicarbonates readily
getting precipitated.
Ca(HCO3)2 CaCO3 + H2O + CO2
Mg(HCO3)2 MgCO3 + H2O + CO2
Ca(HCO3)2 /Mg(HCO3)2 + 2C17H35COONa (C17H35COO)2 Ca/Mg + 2 NaHCO3
CaCl2/MgCl2 + 2C17H35COONa (C17H35COO)2Ca/Mg + 2NaCl
CaSO4/MgSO4 + 2C17H35COONa (C17H35COO)2 Ca/Mg + Na2SO4
2. Permanent Hardness/Non-alkaline/Non-carbonate is due to the presence of dissolved
sulfates & chlorides of Ca, Mg, Fe, etc in water. Permanent hardness cannot be removed easily
on boiling, but requires special chemical treatment. Temporary & Permanent hardness added
together gives Total hardness.
Determination of Hardness of water by EDTA Titration: It is for determining total amount of
Ca2+ & Mg2+ ions in water. The procedure involves titrating sample with standard EDTA solution
using an organic dye indicator EBT (Eriochrome Black T). EDTA is a weak acid with the
structure given below:

Engineering Chemistry

Dr. Payal Joshi

(a) Structure of ethylenediaminetetraacetic acid,

EDTA. (b) Structure of tetracarboxylate ion, [EDTA]4, formed by dissociation of EDTA.
In an aqueous solution buffered at pH 10, EDTA dissociates to form a maximum amount of
tetracarboxylate ion, [EDTA]4-. This ion is electron-rich, having six bonding sites: four
carboxylate groups and two nitrogen atoms. Each site has an electron pair available for
bonding. [EDTA]4 anion wraps itself around Ca2+ or Mg2+ ions and all six electron pairs are
shared with the metal ions.
The reactions occurring in EDTA titration is shown as below:
Mg2+ + EBT (blue) ------------> [Mg2+ ---EBT]
[Mg2+ ---EBT] (wine red unstable complex) ---> [Mg2+ --- EDTA]
(stable)+ EBT (blue)

Structure of [MgEDTA]2 chelate (1:1 complex) [Complexation Reaction]

Experimental Procedure:
Preparation of Reagents: Standard Hard Water: 1 gm pure dry CaCO3 dissolved in minimum
quantity of dilute HCl. Solution evaporated to dryness on water bath & residue left is dissolved
in distilled water & solution is diluted to 1 litre. The hardness of solution is 1 mg of CaCO3
equivalent/ml.
EDTA solution, EBT indicator => prepared
Buffer solution : NH4Cl + conc. NH3.
Standardization of EDTA solution: Pipette 50 ml of standard hard water in conical flask. Add
10-15 ml buffer solution (pH=10), 4-5 drops of EBT indicator. Solution is titrated against EDTA
till colour changes from wine red to deep blue (V1 ml).
Total hardness of water sample: Titrate known volume of the water with standard EDTA
solution, using Eriochrome Black T indicator. From molarity & volume of EDTA solution used
& volume of water titrated, one can calculate total Ca2+ and Mg2+ ion concentration in water
sample. Report this total hardness in ppm of equivalent CaCO3.

Engineering Chemistry

Dr. Payal Joshi

Permanent hardness & temporary hardness of water sample: Boil known volume of water,
filter any precipitated CaCO3 & MgCO3. Analyze the filtrate for permanent hardness by titrating
with EDTA solution. Further calculate temporary hardness in water sample. Finally, determine
individual Ca2+ & Mg2+ ion concentration in water sample using titration data
For total hardness : 50 ml hard water sample titrated against EDTA (V2 ml)
Permanent hardness : 50 ml hard water sample is boiled for 10-15 min, filtered, diluted with
D/W to make up to 50 ml & titrated against EDTA (V3 ml)
Temporary Hardness = Total hardness Permanent hardness
Units of Hardness: In terms of dissolved Ca & Mg salts calculated as CaCO3 equivalent
Reason of expressing hardness as CaCO3 equivalents is due to the fact that its Molecular mass
(M) = 40+12+48=100 (Equivalent weight = 50) makes calculations simple & quick. Also, it is
the most insoluble salt that can be precipitated in water treatment.
Equivalent of CaCO3 = Mass of hardness producing material x chemical equivalent of
CaCO3/Chemical equivalent of hardness producing substance
Eq CaCO3 = Mass of hardness producing material x 50/ Chemical equivalent of hardness
producing substance
Molecular mass of Ca(HCO3)2 = 162; Molecular mass of CaCO3 = 100; Thus, CaCO3:
Ca(HCO3)2 = 100:162. Chemical equivalent of Ca(HCO3)2 = 162/2 = 81
Thus, 162 parts by mass of Ca(HCO3)2 or 2 equivalents would react with same amount of soap as
100 parts by mass of CaCO3 (or 2 eq). Ca(HCO3)2 expressed as CaCO3 eq can be written as,
162 x 100/162 = 100 equivalents of CaCO3
Effects of Hard water: There are numerous disadvantages of using hard water in domestic and
industrial purposes.
In domestic use: Domestic use: i. Washing : no lather formation ,wastage of soap
ii. Bathing: no lather formation. Also the resulting precipitates stick on body
iii. Cooking: due to dissolved salts boiling point of water is elevated, causing unnecessarily
wastage of time & fuel.
iv: Drinking: bad effect on metabolic system. Calcium oxalate stones may develop in urinary
tracts, if used regularly. Also it causes deposition of Ca in the bone joints.
In industrial use: i: Textiles: loss of soaps during washing of yarn, & fabrics. Ppt sticks on
fabric & when it is colored. Also Fe, Mn etc salts leave colored spots on fabrics
ii. Sugar: crystallization of sugar is affected due to presence of sulfate ions.
iii. Dyeing: Dissolved Ca, Mg, Fe salts react with dye forming undesirable ppts giving poor
shades of color on the fabric.
iv: Paper: Ca and Mg salts tend to react with chemicals to provide smooth and glossy finish to
paper. Iron salts affect the colour of the paper.
v.Pharmaceutical industry: If hard water is used in drug, injections, ointments preparations, it
results in undesirable products in them causing ill health.
Softening of water: Softening techniques involve removal of Ca, Mg, Fe salts and other similar
metallic ions that form insoluble metallic soaps.
Three important industrial methods employed for softening of water are: 1. Cold and hot lime
soda process, 2. Permutit or zeolite process, 3. Ion-exchange or demineralization process.

Engineering Chemistry

Dr. Payal Joshi

Clarks Process: Calculated amount of slaked lime [Ca(OH)2] added to hard water.
Bicarbonates are converted into insoluble carbonates & removed by settling & filtration.
Lime-Soda Process: In this method hard water is treated with calculated amounts of lime
[Ca(OH)2] and soda ash [Na2CO3] in reaction tanks, so as to convert hardness producing
chemicals into insoluble compounds which are then removed by settling & filtration. About 10%
excess of chemicals are added in the reaction of tanks to complete the reaction quickly. The
following reactions take place:
Reactions with Lime:
i)
To neutralize any free acid present
2HCl + Ca(OH)2

CaCl2 + 2H2O
H2SO4 + Ca(OH)2

CaSO4 + 2H2O
ii)
To precipitate aluminum & iron salts as hydroxide
Al2(SO4)3 + 3 Ca(OH)2 2Al(OH)3 + 3CaSO4
FeSO4 + Ca(OH)2
Fe((OH)2 + CaSO4
iii)
To precipitate dissolved CO2
CO2 + Ca(OH)2
CaCO3 + H2O
iv)
To ppt Ca and Mg bicarbonates as carbonates
Ca(HCO3)2 + Ca(OH)2
2CaCO3 + 2H2O
Mg(HCO3)2 + 2Ca(OH)2
Mg(OH)2 + CaCO3 + 2H2O
(v)
To ppt all permanent magnesium hardness as hydroxide
MgCl2 + Ca(OH)2
Mg(OH)2 + CaCl2
(vi) To convert HCO3- ions (like NaHCO3 and KHCO3) in to carbonates
2NaHCO3 + Ca(OH)2
CaCO3 + 2H2O + Na2CO3
Reaction with Soda: Soda removes all the soluble permanent hardness due to calcium
salts.(ie that which is present originally as well as that which is introduced during removal of
Mg2+ , Fe2+ , Al3+ , HCl, H2SO4, CO2 etc by lime )
CaCl2 + Na2CO3
CaCO3 + 2NaCl
CaSO4 + Na2CO3
CaCO3 + Na2SO4
Points to be remembered while solving numerical:
(1) One equivalent of Mg(HCO3)2 consume two equivalents of lime
(2) CaCO3 & MgCO3 impurities should be considered as bicarbonate hardness. i.e, amount of
MgCO3 first convert into CaCO3 equivalent, then twice of it should be added in lime, as
in case of Mg(HCO3)2.
(3) NaCl, KCl, SiO2, Fe2O3 etc do not consume lime or soda.
(4) If there are extra bicarbonate ions, they consume one equivalent of lime &
simultaneously produce one equivalent of CO32- . So add it in lime & subtract from soda.
2 HCO3- + Ca(OH)2 CaCO3 + CO32- + 2H2O
(5) If NaAlO2 is added as coagulant, it produces one equivalent of OH- ions which is
equivalent to one equivalent of lime. Thus this amount must be subtracted from lime.
NaAlO2 + 2H2O NaOH + Al(OH)3
Amount of Lime required = 74/100 [Temp Ca2+ + (2 Temp Mg2+ ) + perm Mg2+ + Fe2+ ,
Al3+ + H+ (HCl/H2SO4) + HCO3- - NaAlO2] Vol of water x 100/%pure . In kg
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Engineering Chemistry

Dr. Payal Joshi

Amount of Soda = 106/100 [perm Ca hardness + perm Mg hardness + Salts like Fe, Al +
Acids - HCO3-] Vol of water x 100/%pure . In kg
106
Chemical reactions taking place during lime soda treatment are slow & ppt of CaCO3 &
Mg(OH)2 are fine & produce super-saturated solution. As a result, after deposition occurs in
pipes, boiler tubes etc clog the valves & lead to corrosion. To avoid this;
i)
Thorough mixing of chemicals & hard water.
ii)
Sufficient time allowed to complete reactions
iii)
Accelerators ie. Substances that bring down the fine particles of precipitates eg.
Activated charcoal
iv)
Coagulants ie. Substances which help in the formation of coarse precipitates are
added eg alum
v)
Proper sedimentation chamber for precipitation to settle, before filtration being
carried out.
Cold Lime-Soda Process: When the chemicals (lime & soda) are added for softening water at
room temperature, it is called cold lime soda process. At this temperature the precipitates are
finely divided & do not settle easily, nor they can be filtered. It is necessary therefore to add
coagulants like alum, sodium aluminate etc.
NaAlO2 + 2H2O
NaOH + Al(OH)3
This process provides water containing a residual hardness of 50-to 60 ppm.
Tank is fitted with a stirrer and vigorous stirring is carried out for thorough mixing process. After
softening, soft water rises upwards and heavy sludge settles down. Softened water passes
through filtering media ensuring complete removal of sludge and finally filtered water flows out
through the top.

Hot lime soda method: This process is similar to cold lime soda process. Here, the chemicals
along with the water are heated near about the boiling point of water by exhaust steam. As the
reaction takes place at high temperature, there are the following advantages:
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Engineering Chemistry

Dr. Payal Joshi

1. Precipitation reaction becomes almost complete.

2. Reaction takes place faster.
3. Sludge settles rapidly & hence no coagulant is needed.
4. Dissolved gases (which may cause corrosion) are removed.
5. Viscosity of soft water is lower, hence filtered easily.
6. Residual hardness is low compared to the cold process.
Hot lime-soda process consists of three parts:
1. Reaction tank in which complete mixing of the ingredients take place
2. Conical sedimentation vessel where sludge settles down and,
3. Sand filter where sludge is completely removed.
Soft water from this process is used for feeding boilers.
Advantages: Lime-soda process is economical, process involves corrosion resistance of the
water, mineral content of water is reduced, pH of the water rises, which reduces the content of
pathogenic bacteria.

Disadvantages: i) Huge amount of sludge is formed and disposal is difficult, ii) Due to residual
hardness, water is not suitable for high pressure boilers.
Zeolite/Permutit Softener: Hydrated sodium alumino silicate, Na2O.Al2O3.x SiO2.yH2O
Zeolites are capable of exchanging reversibly their sodium ions for hardness producing ions in
water. They are of two types
Natural Zeolites: are non-porous more durable & are derived from green sands by washing,
heating & treating with NaOH.
Synthetic Zeolites: porous & possess gel structure. Synthetic Zeolites have higher exchange
capacity per unit weight.
Theory: When hard water is passed over a bed of sodium zeolite, Ca2+ , Mg2+ ions are taken up
by the zeolite simultaneously releasing equivalent Na+ ions in exchange for them.
CaCl2 + Na2Z

CaZe + 2NaCl
MgSO4 + Na2Z

MgZe + Na2SO4
Regeneration: When Zeolite is completely converted into calcium & magnesium Zeolites, it
ceases to soften water i.e, it gets exhausted. It is generated by treating with 10% brine solution.
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Engineering Chemistry

Dr. Payal Joshi

CaZe + 2NaCl
Na2Ze
+ CaCl2
MgZe + 2NaCl
Na2Ze + MgCl2
Process: Hard water enters from top at a specified rate & passes over a bed of sodium zeolite
kept in a cylinder. Softened water is collected at the bottom of cylinder & is taken out from time
to time.

Limitations:
(i)
Turbid water should not be employed as it will block the pores of zeolite & make
them inactive.
(ii)
Any colored Fe ions must be removed earlier since it is difficult to regenerate it from
iron zeolite.
(iii) Mineral acid present in water must be neutralized earlier with soda otherwise that
may destroy zeolite bed.
Advantages:
i)
Water of about 10 ppm hardness is produced.
ii)
Process automatically adjusts itself for different hardness of incoming water.
iii)
Requires less skill in maintenance as well as operation.
iv)
Compact equipment, occupy less space.
v)
No impurities are formed, so no formation of sludge and hence it is a cleaner process.
Disadvantages:
i)
Treated water contains more sodium salts
ii)
The method only replaces Ca2+ & Mg2+ ions by Na+ ions, but leaves all acidic ions
(HCO3 - & CO3 --) in soft water. Such soft water containing NaHCO3, Na2CO3 etc
when used in boilers, NaHCO3 decomposes to give CO2 which cause boiler corrosion
& Na2CO3 hydrolyses to NaOH causing caustic embrittlement.
Ion-Exchange Process: It is reversible exchange of ions of same charge between mobile liquid
phase & an insoluble solid (stationary phase). Ion-exchanger is an insoluble material liberating
counter ions by electrolytic dissociation.
Cation exchanger: High molecular weight, cross-linked polymer containing sulphonic (-SO3H),
carboxylic (-COOH), or phenolic (-OH) as a part of resin and equivalent amount of cations.
H-R (resin) + Na+
Na-R (resin) + H+
2NaR (resin) + Ca2+
CaR2 (resin) + 2Na+ (resin)
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Engineering Chemistry

Dr. Payal Joshi

Anion exchanger : Is a polymer containing quaternary ammonium groups (-N+R2 ) containing

equivalent amount of anions, Cl-, OH-, etc
2RCl + SO42R2(SO4) + 2Cl(resin) (solution)
(resin)
(solution)
Water from which all the cations & anions are removed is called demineralized or deionized
water.

Demineralisation of water
Water is first passed to cation exchanger in acid form. All cations will be exchanged for H+ ions.
Next, water coming from cation exchanger is passed into anion exchanger in basic form and
anions are exchanged for OH-. Let us consider water contains a major impurity as calcium
sulphate. Hence the reactions are as follows:
2RCOOH (Na+) + Ca2+ (RCOO)2Ca + 2H+ + 2Na+ (Cation exchange)
2ROH + SO42- R2SO4 + 2OH- (Anion exchange)
H+ + OH- H2O (demineralized water)
After some time, resin requires regeneration, as they become ineffective. Adding a strong acid
regenerates cation resin and the anion resin is regenerated by adding strong base.
(RCOO)2Ca + H2SO4 2RCOOH + Ca2+
R2SO4 + NaOH ROH + SO42Justify the statement: During demineralization using ion-exchange, water is first passed
through cation exchanger and next into anion exchanger.
Cation exchangers are easily attacked by alkalies, whereas all types of ion-exchangers are not
attacked by acids. When water is passed through cation exchanger, salts present in water are
converted into corresponding acids, which on passing anion exchanger do not harm it and finally
get converted into pure water. If reverse sequence is used, then alkalies produced on passing
water through anion exchanger will harm the cation exchanger in the subsequent step.
Drinking Water or Municipal Water
Removal of microorganisms: Water after passing through sedimentation, coagulation and
filtration operations still contain a small percentage of pathogenic bacteria. The process of
destroying or killing disease-producing bacteria, microorganisms, etc from water and making it
safer for use is called disinfection. Chemicals or substances added to water for killing bacteria,
etc are known as disinfectants.
Chlorination: Chlorine (gas or in concentrated solution form) produces hypochlorous acid
which is a powerful germicide.
Cl2 + H2O HOCl + HCl
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Engineering Chemistry

Dr. Payal Joshi

Bacteria + HOCl Bacteria killed

HOCl H+ + OClHypochlorite ion (OCl-) cause inactivation of enzymes of microorganisms that is necessary for
metabolism thereby leading to death of microorganisms. Hence chlorine is found to be the most
effective disinfectant.

Chlorine is the most widely used disinfectant. Liquid chlorine is more effective when applied to
filtered water at such a point, where adequate mixing is done. The apparatus in which
chlorination is carried out is known as chlorinator. It is a high tower with number of baffle
plates. Water and proper quantity of concentrated chlorine solution (0.3-0.5 ppm) are introduced
at its top. During their passage through the tower, they get thoroughly mixed. Treated water is
taken out from the bottom.
Advantages of chlorine: Effective and economic, requires little space for storage, stable & does
not deteriorate on keeping, does not introduce salt impurities in water & hence is an ideal
disinfectant.
Disadvantages of chlorine: Excess of chlorine, if added, produces a characterisitic unpleasant
taste & odour causing irritation to mucuos membrane. Quantity of free chlorine in treated water
should not exceed 0.1-0.2 ppm.
Bleaching powder treatment: It is used for the disinfection of drinking water or swimming
pool water. 1kg of bleaching powder (Calcium hypochlorite, Ca(ClO)2 per 1000 kilolitres of
water is mixed and water is allowed to stand undisturbed for several hours. Chemical action
produces hypochlorous acid (powerful germicide). Disinfecting action of bleaching powder is
due to chlorine made available by it.
CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HCl + HOCl (hypochlorous acid)
Germs + HOCl Germs killed
Drawbacks: Bleaching powder introduces calcium in water, thereby making it harder. Bleaching
powder gets deteriorated due to its continuous decomposition while storage. Only calculated
quantity of bleaching powder should be used, since an excess of it gives bad taste and smell to
treated water.
Disinfection by Ozone: Ozone is an excellent disinfectant which is produced by passing silent
electric discharge through cold and dry oxygen.
3O2 2O3
Ozone is highly unstable and breaks down liberating nascent oxygen,
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Engineering Chemistry

Dr. Payal Joshi

O3 O2 + [O]
Nascent oxygen is very powerful oxidizing agent and kills all bacteria and also oxidizes the
organic matter present in water. For carrying out disinfection by ozone, ozone is released or
injected (2-3ppm) in water and the two are allowed to come in contact for 10-15 min in
sterilizing tank (shown below). Disinfected water is removed from the top.

Advantages: Though the method is costlier than chlorination, it simultaneously removes colour,
odour and taste without leaving any residue. Its excess is not harmful as it is unstable and
decomposes in oxygen.
Disadvantages: It is an expensive method and cannot be employed for disinfection of municipal
water supply.
Reverse Osmosis: Osmosis describes the flow of solvent from dilute to concentrated solution
through a semipermeable membrane. Reverse osmosis
describes the flow of solvent in the opposite direction, i.e, from
concentrated solution to dilute solution across a semipermeable
membrane by applying hydrostatic pressure in excess of
osmotic pressure. The diagram of a reverse osmosis cell is
shown here, where desalination of brackish water is carried out.
This method is largely used for purification of sea water for
domestic use. Reverse osmosis has many advantages like; i)
removal of ionic, non-ionic, colloidal and high molecular
weight solutes from water; ii) regeneration of process involves
easy replacement of semipermeable membrane; iii) easy
maintenance and economical; iv) uninterrupted supply of large
volume of water for industrial or domestic purpose.
Ultrafiltration: Ultrafiltration (UF) is a pressure-driven separation process, governed by a
screening principle and dependent on particle size. UF membranes have a pore size between 1
nm and 100 nm, thus allowing retention of
compounds with a molecular weight of 300 to
5,00,000 Dalton.
It is suitable for retaining biomolecules, bacteria,
viruses, polymers, colloidal particles and sugar
molecules. UF membranes have the ability to purify,
separate, and concentrate target macromolecules.
UF does this by pressurizing the solution flow.
Solvent and other dissolved components that pass
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Engineering Chemistry

Dr. Payal Joshi

through the membrane are known as permeate. Components that do not pass through are known
as retentate. Ultrafiltration removes bacteria, protozoa and some viruses from the water.
Applications: a) Pretreatment in sea water desalination plants in combination with reverse
osmosis
b) Sterile filtration of drinking and beverage water
c) Wastewater treatment and re-use
d) Removal of metal hydroxides in wastewater treatment.
Distinguish between:
Temporary Hardness
It is caused due to the presence of bicarbonates and
carbonates of Ca2+, Mg2+, Fe2+ etc. Salts like
Ca(HCO3)2, CaCO3, Mg(HCO3)2, MgCO3, etc.
It can be removed by boiling.
It is also known as carbonate or alkaline hardness.
Temporary hardness leads to formation of loose
deposits (sludge) of carbonates and hydroxides of
Ca2+, Mg2+, if used in boilers

Permanent Hardness
It is caused due to the presence of Cl-, SO42-, nitrates of
Ca2+, Mg2+, Fe2+, etc other than carbonates and
bicarbonates. Salts like CaCl2, CaSO4, Ca(NO3)2,
MgCl2, MgSO4, Mg(NO3)2.
It cannot be removed by boiling, but needs chemical
treatment.
It is also known as non-carbonate or non-alkaline
hardness.
Permanent hardness leads to formation of hard deposits
(scales) if used in the boilers

Cold Lime soda method

Process requires several hours to complete.
Coagulants are required, like sodium aluminate
NaAlO2+H2O NaOH + Al(OH)3

Hot lime soda method

Process requires 15 minutes.
Coagulants are not required, precipitate settles
rapidly.

Dissolved gases like oxygen, CO2 are not removed.

Dissolved gases like oxygen, CO2 are removed.

Filtration takes place very slowly.

Filtration takes place rapidly as viscosity of water

decreases.
This process gives water with residual hardness of 1530 ppm.

This process gives water with residual hardness of 5060 ppm.

Zeolite Process
Produces water with hardness of almost zero
hardness.
Capital cost is higher
Exhausted zeolite bed can be regenerated with brine,
hence operating cost is low.
Salts causing temporary hardness are converted to
NaHCO3 which is present in soft water creating
problems to feed such waters in boilers.
No problems of after-precipitation.

Lime soda Method

This process produces water having hardness of 15-60
ppm depending on whether it is a cold or hot process.
Capital cost is lower.
Chemicals like lime, soda, coagulants are consumed
making operation cost higher.
Temporary hardness is completely removed.

Problems of after-precipitation.

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