HARDNESS OF WATER ∆

Mg(HCO3)2 → MgCO3 ↓ + H2O + CO2 ↑

First Year B.Tech. (Insoluble)
Engineering Chemistry, Subject Code: NCY-101/102
Unit/Module V: Water Analysis (2) Noncarbonate hardness or Permanent: caused by the presence chlorides and
sulphates of Ca, Mg, Fe and other heavy metals. Unlike the temporary hardness,
Dr. C.L. Gehlot, Professor
permanent hardness cannot be removed by boiling water. It needs some treatments.
INTRODUCTION
EQUIVALENCE OF CaCO3
HARDNESS OF WATER: Hardness of water is the soap consuming power of water and The concentration of hardness as well as non-hardness constituting ions are usually
hardness is the characteristics of water, which prevents the lathering of soap. Hardness in expressed in terms of equivalent amount of CaCO3, since this mode permits the
water is due to the presence of certain salt of calcium, magnesium and other heavy metals multiplication and division of concentration, when required. The choice of CaCO 3 in
dissolved in water. particular is due to its molecular weight i.e.,100, equivalent weight i.e.,50, it is most

When hard water is treated with soap (i.e., sodium or potassium salt of higher fatty acids insoluble salt that can be precipitated in water treatment.

like oleic, palmitic or stearic etc.) It does not produce lather but on other hand forms a Calculation of equivalents of calcium carbonate

white scum or precipitate. The precipitate is formed due to the formation of insoluble soaps Dissolved Molar Mass Chemical Multiplication factor for
Salt/Ion Equivalent converting in to equivalents of
of Ca and Mg. A typical reaction of soap (sodium stearate) with CaCl2 and MgCl2 may be CaCO3
expressed as: Ca (HCO3)2 162 81 100/162

2C17H35COONa + CaCl2 → (C17H35COO)2 Ca ↓ + 2 NaCl Mg (HCO3)2 146 73 100/146

(Sodium stearate, soap) (Hardness) (Calcium stearate, Insoluble) CaSO4 136 68 100/136

CaCl2 111 55.5 100/111

2C17H35COONa + MgSO4 → (C17H35COO)2 Mg ↓ + Na2SO4 MgSO4 120 60 100/120

(Magnesium stearate, Insoluble) MgCl2 95 47.5 100/95
Thus, water which does not produce lather with soap readily but forms a white CaCO3 100 50 100/100
curd/precipitate is called hard water. On other hand, water which forms lather easily on
MgCO3 84 42 100/84
shaking with soap is called soft water, such water consequently does not contain dissolved
CO2 44 22 100/44
Ca and Mg salts.
Ca (NO3)2 164 82 100/164
TYPES OF HARDNESS: Hardness of water may be classified in to two types namely:
Mg (NO3)2 148 74 100/148
(1) Carbonate hardness or Temporary: is caused by the presence of dissolved
HCO3- 61 61 100/122
carbonates, bicarbonates and hydroxides of Ca, Mg and other heavy metals.
OH- 17 17 100/34
It can be removed by water boiling. CO32- 60 30 100/60

∆ NaAlO2 82 82 100/164
Ca(HCO3)2 → CaCO3 ↓ + H2O + CO2 ↑
(Insoluble) Al2(SO4)3 342 57 100/114
 FeSO4.7H20 278 139 100/278 C17H35COONa + H2O ↔ C17H35COOH +NaOH
Sodium stearate (Soap) Stearic acid
H+ 1 1 100/2
C17H35COOH + C17H35COONa → Leather
HCl 36.5 1 100/73 Stearic acid Soap

This causes wastage of lot of soap being used. Moreover, sticky precipitate adheres on
Equivalence of CaCO3 fabric /cloth gives spots and streaks.

= mass of hardness producing substance x Chemical equivalent of CaCO3 (ii) Bathing: Hard water produces sticky scum on bath tub and body. Thus, cleansing quality
-------------------------------------------------------------------------------------------------------------------------------------------------- of soap is depressed and lot of soap wasted.
Chemical equivalent of hardness producing substance
(iii) Cooking: Due to hardness producing salt boiling point of water is elevated, consequently
= Mass of hardness producing substance x50 more fuel and time required for cooking.
--------------------------------------------------------------
Chemical equivalent of hardness producing substance (iv) Drinking: Hard water causes bad effect on digestive system. Possibility of forming
calcium oxalate in urinary tract is increased.
UNITS OF HARDNESS:
(2) Industrial use:
(i) Parts per million(ppm): is the parts of calcium carbonate equivalent hardness per 106
(i) Textile industry: precipitate of Ca and Mg soaps adhere to the fabric. When fabric dyed
parts of water. i. e. 1 ppm =1 part of CaCO3 eq. hardness in 106 parts of water. 1ppm=1 mg
do not produce exact shades of color and spoil the beauty of fabric.
per litre.
(ii) Sugar industry: Causes difficulty in crystallization of sugar during sugar refining.
(ii) Degree Clarke(◦Cl):is the no. of grains of CaCO3 equivalent hardness per gallon of water
or parts of CaCO3 equivalent hardness per 70,000 parts of water. (iii) Dyeing industry: Dissolved Ca, Mg and Fe salts in hard water may react with dyes
forming undesirable precipitate. Which yields impure shades and spot-on fabric.
1◦Clarke=1 grain of CaCO3 equivalent hardness per gallon of water or 1◦Cl =1 part of CaCO3
equivalent hardness per 70,000 parts of water (iv) Paper industry: Ca, Mg salts react with chemicals and materials used for smooth and
glossy finish to paper and color of paper affected.
(iii) Degree French(◦Fr): is the parts of CaCO3 equivalent hardness per 105 parts of water.
1◦Fr=1 part of CaCO3 hardness equivalent per 105 parts of water (v) Laundry: hard water causes wastage of water and may even causes coloration of cloths.

(iv) Milliequivalent per litre (meq/L): is the no. of milli equivalent of hardness present per (vi) Concrete making: Hard water used for concrete affects hydration of cement and
litre . strength of the hardened concrete.

Thus 1 meq/L=1 meq. of CaCO3 per litre of water (vii) Steam generation in boiler: Causes scale and sludge formation, boiler corrosion,
RELATIONSHIP BETWEEN VARIOUS UNITS OF HARDNESS: priming and foaming, caustic embrittlement. Sludge is a soft, loose and slimy precipitate
formed with in the boiler. Sludges are formed by the substances having greater solubilities in
1ppm =1 mg/L = 0.1◦Fr = 0.07◦Cl= 0.02meq. /L
hot water than in cold water e.g. MgCO3, MgCl2, CaCl2 and MgSO4 etc.
1mg/L= 1ppm = 0.1◦Fr = 0.07◦Cl =0.02meq. /L
Boiler corrosion: is decay process of boiler material by a chemical or electrochemical attack
1◦Cl= 1.433◦Fr =14.3 ppm =14.3 mg/L= 0.286 meq. /L by its environment.
1 ◦ Fr= 10 ppm = 10 mg/L= 0.7◦Cl= 0.2 meq. /L
Caustic embrittlement: is a type of boiler corrosion caused by using highly alkaline water in
1 meq. /L =50 mg/L = 50 ppm= 5◦ Fr = 0.35◦Cl the boiler.

DISADVANTAGES OF HARD WATER:

(1) Domestic use
(i) Washing:
(viii) Pharmaceutical Industry: May produce certain undesirable pharmaceutical products. HCO3- 2HCO3- + Ca(OH)2→CaCO3+H2O+CO32- L-S
(eg. NaHCO3)
SOFTENING OF HARD WATER:

The process of removing hardness producing salts from water is known as softening of Ca(HCO3)2 Ca(HCO3)2+Ca(OH)2→2CaCO3+2H2O L
water. In industry, main three methods employed for softening of water. (Temp.Ca)

(1) LIME SODA PROCESS: In this method, the soluble calcium and magnesium salts in Mg(HCO3)2+2Ca(OH)2→2CaCO3+Mg(OH)2+ 2H2O 2L
Mg(HCO3)2
water are chemically converted in to insoluble compounds by adding calculated (Temp.Mg)
amount of lime [Ca (OH)2] and soda [Na2CO3], CaCO3 and Mg(OH)2 so precipitated
CO2+Ca(OH)2→CaCO3+ H2O L
may be filtered off. CO2

Notes: 2H+ +Ca(OH)2→Ca2+ +2H2O

L+S
H+(Free acids, Ca2+ + Na2CO3→CaCO3+2Na+
(i) If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca2+ +2HCO3-) and (Mg2+ HCl, H2SO4 etc.)

+2HCO3-) respectively then calculation results will be same.

Fe2+ +Ca(OH)2→Fe(OH)2 +Ca2+
Coagulants
(ii) Equivalent weight of NaAlO2 is equal to its molar mass. FeSO4 2Fe(OH)2 +H2O+O2→2Fe (OH)3
L+S
Ca2+ +Na2CO3→CaCO3+2Na+
(iii) If treated water contains OH- and CO32- ions, then these are formed from
excess eq. each of Ca(OH)2 plus Na2CO3 and Na2CO3 respectively .So these 2Al3+ +3Ca(OH)2→2Al(OH)3 +3Ca2+
Al2(SO4)3 L+S
3Ca2+ +2Na2CO3→3CaCO3+ 6Na+
excess amounts should be added to the calculations.

(iv) When impurities are given as CaCO3 and /or MgCO3, these should be -L
NaAlO2 NaAlO2+2H2O→Al(OH)3 +NaOH
considered due to bicarbonates of Ca and /or Mg respectively.
2NaOH is equivalent to Ca(OH)2
(v) Substance like NaCl, KCl, Na2SO4 , SiO2, Fe2O3 etc. do not impart any hardness
and therefore, these do not consume any lime or soda. These should not be
taken in to consideration for calculating the lime and soda requirements.

Calculation of lime soda requirement

Now 100 parts by mass of CaCO3 are equivalent to (i) 74 parts of Ca(OH)2 and (ii)
Constituent Reactions Need 106 parts of Na2CO3

Ca2+ Ca2+ +Na2CO3→CaCO3 +2Na+ S Hence, Lime requirement for softening

(perm. Ca)
=74/100 [Temp.Ca2+ +2xTemp.Mg2+ + Perm.(Mg2+ +Fe2+ +Al3+) +CO2+H+ (HCl or
H2SO4) +HCO3- –NaAlO2 : All in terms of CaCO3 eq.]
Mg2+ Mg2+ + Ca(OH)2→Mg(OH)2 +Ca2+
(perm. Mg) Soda requirement for softening
Ca2+ +Na2CO3→CaCO3 +2Na+ L+S
=106/100[Perm. (Ca2+ +Mg2+ +Al3+ +Fe2+)x H+ (HCl or H2SO4) –HCO3- : All in terms of
CaCO3 eq.]
TYPES OF LS PROCESS: which sludge settle down (iii) sand filter-which ensures complete removal of sludge
(i) Cold lime soda process: Calculated amount of lime and soda are mixed with water
from the softened water.
at room temp. At room temp.the precipitates formed are finely divided so they do
not settle down easily and cannot be filtered easily. Hence, small amount of
coagulants such as alum, aluminium sulphate, sodium aluminate etc) added which
hydrolyse to flocculent, gelatinous precipitate of aluminium hydroxide and entraps
the fine precipitate. Use of sodium aluminate as coagulant also helps in removal of
silica as well as oil if present in water. Cold LS process provides water containing a
residual hardness of 50 to 60 ppm.
NaAlO2 +2H2O →NaOH + Al (OH)3↓

Al2(SO4)3 +3Ca (HCO3)2→2Al (OH)3↓ +3CaSO4+6CO2↑

Coagulant Hard water

Fig. Hot lime-soda softener

Advantages of L-S process: (i) It is very economical (ii) if this process is combined
with sedimentation with coagulation, lesser amounts of coagulants shall be required.
(iii) the process increases the pH value of treated water, thereby corrosion of
distribution pipes is reduced. (iv) Besides, the removal of hardness, the quantity of
minerals in water are reduced. (v) To certain extent, Fe and Mn are also removed
from the water. (vi) Due to alkaline nature of treated water, amount of pathogenic
bacteria in water is considerably reduced.
Disadvantages of L-S process: (i) For efficient and economical softening, careful
Fig. Cold lime-soda softener
operation and skilled supervision is required. (ii) Disposal of large amount of sludge
(ii) Hot lime soda process: It is operated at a temp. of 80 to 150°C.Since hot process (insoluble precipitate) poses a problem. However, the sludge may be disposed off in
is operated at a temp. close to the boiling point of the solution. Hence, (a) the raising low –lying areas of the city. (iii) This can remove hardness only upto 15 ppm,
reaction proceeds faster (b) the softening capacity of hot process is increased to which is not good for boilers.
many folds(c) the precipitate and sludge formed settle down rapidly and no
coagulants required (d) much of dissolved gases such as CO2 and air driven out of the (2) ZEOLITE OR PERMUTIT PROCESS: Chemical structure of sodium zeolite may be

water (e) viscosity of softened water is lower, so filtration of water becomes much represented as Na2O.Al2O3.XSio2.Y,H2O Where X=2-10, Y=2-6, expressed as Na2Ze.

easier. This in turn increases the filtering capacity of filters (f) hot lime soda process Zeolite is hydrated sodium alumino silicate, capable of exchanging reversibly its

produces water of comparatively low residual hardness of 15 to 30 ppm. Hot lime sodium ions with hardness producing ions in water. Zeolite are also known as

soda plant consists of three parts namely (i) a reaction tank-in which raw water, permutits. Zeolites can be classified in to two types (i) Natural zeolites: are non

chemicals and steam are thoroughly mixed (ii) conical sedimentation vessel –in porous. For e.g. natrolite, Na2O.Al2O3.4SiO2.2H2O (ii) Synthetic zeolites: are porous
 and possess gel structure. They are prepared by heating together china clay, faldspar The washing containing CaCl2 and MgCl2 are led to drain and the regenerated zeolite bed
and soda ash. Such zeolites possess higher exchange capacity per unit weight than thus obtained is used for softening purpose.
natural zeolites. Limitations of Zeolite Process:
Zeolite Process: In this process hard water is percolated at a specified rate through a (1) If water is turbid, the suspended matter must be removed by coagulation or
bed of zeolite, kept in a cylinder. The hardness causing ions (Ca2+, Mg2+ etc.) are filtration before the water is admitted to zeolite bed, otherwise the turbidity will
retained by zeolite as CaZe and MgZe: while outgoing water contains sodium salts. clog the pores of zeolite bed, thereby making it inactive.
Reaction taking place during zeolitec process are: (2) If water contains large quantities of colored ions such as Mn2+ and Fe2+, they must be
Na2Ze +Ca(HCO3)2→CaZe+2NaHCO3 removed first because these ions produce Mn and Fe zeolite, which cannot be easily
Na2Ze+ Mg(HCO3)2 →MgZe+ 2NaHCO3 regenerated.
Na2Ze+CaCl2 (or CaSO4) →CaZe +2NaCl or Na2SO4 (3) Mineral acids if present in water, destroy the zeolite bed. Therefore, they must be
Na2Ze+MgCl2 (or MgSO4) →MgZe +2NaCl or Na2SO4 neutralized with soda before admitting the water to zeolite softening bed.
(Zeolite) (Hardness) Advantages of zeolite process:
(1) It removes the hardness almost completely and water of about 10 ppm hardness is
produced.
(2) The equipment used is compact occupying a small space.
(3) No impurities are precipitated so there is no danger of sludge formation in the
treated water at a later stage.
(4) The process automatically adjusts itself for variation in hardness of incoming water.
(5) It is quite clean
(6) It requires less time for softening.
(7) It requires less skill for maintenance as well as operation.
Disadvantages of zeolite process:
(1) The treated water contains more sodium salts than in L-S process.
(2) The process only replaces Ca2+ and Mg2+ ions by Na+ ions but leaves all the acidic
ions (like HCO3- and CO32-) as such in the softened water. When such softened water

FIG. Zeolite water softener (containing NaHCO3 and Na2CO3) is used in boilers for steam generation, NaHCO3
decomposes producing CO2, which causes corrosion and Na2CO3 hydrolyses to
Regeneration of zeolite: When zeolite is completely converted in to CaZe and MgZe and it
NaOH, which causes caustic embrittlement.
ceases to soften water i.e.it gets exhausted. At this stage the supply of hard water is
Caustic Embrittlement is a type of boiler corrosion, caused by using highly alkaline
stopped and exhausted zeolite is reclaimed by treatment of zeolite bed with a Conc. 10%
water in the boiler. Caustic soda attacks the surrounding area, thereby dissolving iron
brine (NaCl) solution.
of boiler as sodium ferroate. This causes embrittlement of boiler parts, particularly
CaZe or MgZe + NaCl → Na2Ze + CaCl2 or MgCl2
stressed parts like bends, joints, rivets etc . ,causing even failure of boiler.
(Exhausted Zeolite) (Brine) (Reclaimed Zeolite) (Washing)
 (3) High turbidity water cannot be treated efficiently by this method because fine
impurities get deposited on the zeolite bed, thereby creating problem for its
working.
(3) ION EXCHANGE OR DE-IONIZATION OR DEMINERALIZATION PROCESS:
Ion exchange resins are insoluble, crossed linked, long chain organic polymers with a
micropores structure and the “functional groups” attached to the chain are
responsible for the ion exchanging properties. Resins containing acidic functional
groups (-COOH, -SO3H) are capable of exchanging their H+ ions with other hard water
cations. While basic functional groups (-NH2=NH as hydrochloride) are capable of
exchanging their anions (OH-) with other hard water anions. Ion exchange resins may
be classified as:

(i) Cation exchange resins (RH+) : are mainly styrene divinyl benzene copolymers, which
on sulphonation or carboxylation become capable of exchange their H+ ions with
the cations in the water.
FIG: Basic or anion exchange resin (Hydroxide form)
Process: The hard water is passed first through cation exchange column which removes all
cations like Ca2+ and Mg2+ 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,
which removes all the anions like SO42- , Cl- etc. present in water and equivalent amount of
OH- ions are released from this column to water. Thus:

R’OH- + Cl- → R’Cl- + OH-

2R’OH- +SO42- → R’2SO42- +2OH-

FIG: Acidic or Cation exchange resin (Sulphonate Form) 2R’OH- +CO32- → R’2CO32- +2OH-

H+ and OH- ions (released from cation exchange and anion exchange column respectively)
(ii) Anion exchange resins (R’OH): are styrene divinyl benzene or aniline formaldehyde
copolymers, which contain amino or quaternary ammonium or quaternary get combined to produce water molecule.
phosphonium or tertiary sulphonium group as an integral part of the resin matrix.
These, after treatment with Dil. NaOH solution, become capable to exchange their H+ +OH- → H2O
OH- ions with anions in water.
Thus, the water coming out from the exchanger is free from cations as well as anions. Ion
free water is known as deionized or dematerialized water.
Regeneration: When capacities of cation and anion exchangers to exchange H+ and OH- ions
respectively are lost, they are then said to be exhausted.

The exhausted 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+ (washing)

The column is washed with deionized water and washing (which contains Ca 2+,Mg2+ etc. and
Cl- or SO42- ) is passed to sink or drain.

The exhausted anion exchange column is regenerated by passing a solution of dil.

NaOH.The regeneration can be represented as:

R’SO42- + 2 OH - →2R’OH- + SO42-(washing) FIG: Demineralization of water

The column is washed with deionized water and washing (which contains Na + and SO42- or Cl-
ions) is passed to sink or drain. CHEMICAL ANALYSIS OF WATER

The regenerated ion exchange resins are then used again. (1) ESTIMATION OF FREE CHLORINE:

Advantages: (1) The process can be used to soften highly acidic or basic waters (2) It free chlorine in water ,if present beyond a certain limit (250 ppm ),makes the muncipal

produces water of very low hardness (say 2 ppm) so it is very good for treating water for use water unfit for drinking purpose,because chlorine gas is injurious to human

in high pressure boilers. metabolism.The estimation of free cholorine in water is based on the oxidation of KI by free
chlorine.Thus,when the water sample is treated with an excess of KI solution ,the free
Disadvantages: (1) The equipment is costly and more expensive chemicals are required. (2)
chlorine present in water oxidizes KI and liberates an equivalent amount of Iodine,which
If water contains turbidity, then the output of the process is reduced. The turbidity must be
dissolves in excess KI forming a deep violet colored complex.
below 10 ppm. If it is more, it has to be removed first by coagulation and filtration.
Cl2 + 2KI →2KCl + I2
(Water) Excess
KI + I2 → KI3
(violet colored complex)

The amount of liberated iodine can be estimated by titrating thev resulting solution against
standard sodium thiosulphate solution (Hypo) using starch as an indicator.

I2 + 2Na2S2O3→2NaI +Na2S4O6

(Sod.Tetrathionate)

I2+ Starch→ Deep blue complex.

Procedure: Take 10 ml of 10% KI solution in a stoppered 250 ml conical flask + 50 ml of The possible combinations of ions causing alkalinity in water are: (i) OH- only or (ii) CO32-
water sample → Put on the stopper and shake the flask vigorously→ Remove the stopper only or (iii) HCO3- only or (iv) OH- and CO32- together or (V) CO32- and HCO3- together. The
and wash the adhering solution in to flask, with about 5-10 ml of distilled water→Then possibility of OH- and HCO3- ions together is ruled out, because they combine to form CO32-
titrate the solution against N/50 sodium thiosulphate solution from burette using starch as
OH-+ HCO3- → CO32- + H2O
indicator drop by drop. At the end point deep blue colored contents turn to colorless.
NaOH+ NaHCO3→Na2CO3 + H2O
Calculation:
Thus, OH- and HCO3- ions cannot exist together in water. On the basis of same reasoning, all
Let 50 ml of water sample = V ml of N/50 Na2S2O3 solution
three (OH-, CO32- and HCO3- ) cannot exist together.
50x Normality of free chlorine = Vx(N/50)
(i) Determination of strength of alkali mixture (NaOH and Na2CO3)
Reactions:
Normality of free chlorine= V/2500
(i) NaOH + HCl →NaCl + H2O
and strength of free chlorine = Vx35.5/2500 g/L = V x35.5x106/2500x1000 ppm
(ii) Na2CO3 +HCl →NaHCO3 +NaCl P or V1
= 14.2 V ppm (iii) NaHCO3+ HCl →NaCl + CO2 +H2O M or V2

(2) ESTIMATION OF ALKALINITY: Reaction (i) corresponds to full neutralization of NaOH and reaction (ii) and (iii) correspond
to half neutralization of Na2CO3
The alkalinity of water is attributed to the presence of the (i) caustic alkalinity (due to OH- Procedure:
and CO32- ions) and (ii) temporary hardness (due to HCO-3). These can be estimated
10 ml of alkali mixture in a conical flask + 1-2 drops of Phenolphthalein indicator → pink
separately by titration against standard acid using phenolphthalein and methyl orange as
color appears → titrate the contents against N/50 HCl drop by drop until pink color
indicator. The determination is based on the following reactions:
disappears → This is first end point ( i.e. Phenolphthalein end point) (P) → To the same
(i) [OH-] + [H+] → H2O mixture add 1-2 drops of methyl orange indicator → light yellow color appears →continue

(ii) [CO32-] + [H+]→ [HCO3-] P or V1 M or V2 the titration with N/50 HCl until the light yellow color changes to orange red color → This is

(iii) [HCO3-] + [H+]→ H2O +CO2 the second end point( i.e. methyl orange end point) (M)

Reaction (i) corresponds to full neutralization of NaOH and reaction (ii) and (iii) correspond Calculation:
to half neutralization of Na2CO3
P or V1 = Vol.of HCl corresponds to full neutralization of NaOH plus half of Na2CO3
The titration of water sample against standard acid up to phenolphthalein end point [P]
marks the completion of reactions (i) and (ii) only. This amount of acid corresponds to full M or V2= Vol.of HCl corresponds half neutralization of Na2CO3
hydroxide plus one half the normal carbonate present. On other hand, titration of water
Therefore, Vol. of HCl for complete neutralization of NaOH = V1-V2=Xml. (P-M)
sample against a standard acid to methyl orange end point marks the completion of
reactions (i), (ii) and (iii). Hence, the amount of acid used after phenolphthalein end point Vol. of HCl for complete neutralization of Na2CO3 = 2XV2=Yml. (2M)

corresponds to one half of normal carbonate plus all the bicarbonates, while the total For NaOH N1V1=N2V2
amount of acid used represents the total alkalinity (due to hydroxide, bicarbonate and
N1X10= 1/50 X (V1-V2)
carbonate ions)
Hence, strength of NaOH = N1X Eq. Wt. (40) = g/lit
For Na2CO3 N1X10= 1/50 X 2V2
Strength of Na2CO3 = N1X Eq.Wt.(53) = g/lit

(ii) Determination of strength of alkali mixture (Na2CO3 and NaHCO3)

(3) ESTIMATION OF HARDNESS OF WATER:
Reactions:
(i) Na2CO3 +HCl →NaHCO3 +NaCl] P or V1 The estimation of water hardness as applied to boiler water and other water is of great

(ii) NaHCO3+ HCl →NaCl + CO2 + H2O interest for the chemical industry in general. Determination of hardness of water can be

(iii) NaHCO3+ HCl →NaCl + CO2 + H2O M or V2 done using the following method:

Reaction (i) and (ii) correspond to half neutralization of Na2CO3 and (iii) correspond to full (i) EDTA Titration method: This is a complexometric method using ethylene diamine
neutralization of NaHCO3 tetraacetic acid (EDTA) as titrant.

Procedure: Theory: Water generally contains Ca and Mg salts, which are responsible for hardness of

10 ml of alkali mixture in a conical flask + 1-2 drops of Phenolphthalein indicator → pink water. When EBT (Eriochrome Black T) is added hard water then Ca and Mg salts react with

color appears → titrate the contents against N/50 HCl drop by drop until pink color EBT at 10 pH to give rise an unstable complex having wine red color. When we add EDTA

disappears → This is first end point ( i.e. Phenolphthalein end point) (P) → To the same solution to complex then unstable complex converted in to a stable complex having sky blue

mixture add 1-2 drops of methyl orange indicator → light yellow color appears →continue color.

the titration with N/50 HCl until the light yellow color changes to orange red color → This is
the second end point( i.e. methyl orange end point) (M)

Calculation:

P or V1 = Vol.of HCl corresponds to half neutralization of Na2CO3

In the form of its sodium salt yields the anion:
M or V2= Vol.of HCl corresponds half neutralization of Na2CO3 plus complete neutralization
of NaHCO3

Therefore, Vol. of HCl for complete neutralization of Na2CO3 = 2XV1=Xml. (2P)

Vol. of HCl for complete neutralization of NaHCO3 = V2-V1=Yml.(M-2P)

Which forms complex with Ca2+ and Mg2+
For Na2CO3 N1V1=N2V2

N1X10= 1/50 X 2V1

Hence, strength of Na2CO3 = N1X Eq.Wt.(53) = g/lit.

For NaHCO3 N1X10= 1/50 X(V2-V1)

Strength of NaHCO3 = N1X Eq.Wt.(84) = g/lit.

Where M=Ca or Mg. It may be pointed that the EDTA is used as its disodium salt.
 pH=10 CO32- 60 30 100/60
M2+ +EBT → [M-EBT] complex
NaAlO2 82 82 100/164
(Ca2+ or Mg2+ of hard water) Wine red
Titration Al2(SO4)3 342 57 100/114
[M-EBT] complex +EDTA → [M-EDTA] complex + EBT FeSO4.7H20 278 139 100/278
Wine red (Blue)
When all Ca2+ or Mg2+ ions have formed [M-EDTA] complex then next drop of EDTA added H+ 1 1 100/2
displaces the EBT indicator form [M-EBT] and the wine-red color changes to sky blue (due to HCl 36.5 1 100/73
EBT). Thus, at end point,
[M-EBT] complex +EDTA → [M-EDTA] complex + EBT (Blue)
Mg(HCO3)2 Mg(HCO3)2+2Ca(OH)2→2CaCO3+Mg(OH)2+ 2H2O =2L
Procedure:
(Temp.Mg)
10 ml. Hard water sample (unknown) +5 ml. Buffer solution (NH4Cl-NH4OH) + 1-2 drops of
EBT→wine red color appears→ titrate with EDTA drop by drop until the color changes to sky HCO3- 2HCO3- + Ca(OH)2→CaCO3+H2O+CO32- =L-S
(e.g.NaHCO3)
blue. Perform the titrate to get concordant reading.
NaAlO2 NaAlO2+2H2O→Al(OH)3 +NaOH =-L
Hardness of water
= Vol. of EDTA used for unknown (given) hard water/ Note: Substance like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc.do not impart any hardness and
Vol. of EDTA used for known (standard) hard water X 1000 therefore, these do not consume any lime or soda. These should not be taken in to
= ppm in terms of CaCO3 equivalents consideration for calculating the lime and soda requirements.

Advantages of EDTA method: This method is preferred over other methods because of Lime requirement for softening
(i) greater accuracy (ii) convenience (iii) more rapid method =74/100 [Temp.Ca2+ +2xTemp.Mg2+ + Perm.(Mg2+ +Fe2+ +Al3+) +CO2+H+ (HCl or
SOLVED NUMERICAL PROBLEMS: H2SO4) +HCO3- -NaAlO2 : All in terms of CaCO3 eq.]
Calculation of equivalents of calcium carbonate
Soda requirement for softening
Dissolved Molar Mass Chemical Equivalent Multiplication factor for converting in
Salt/Ion to equivalents of CaCO3 =106/100[Perm. (Ca2+ +Mg2+ +Al3+ +Fe2+)x H+ (HCl or H2SO4) –HCO3- : All in terms of
CaCO3 eq.]
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146 Q.1 How many grams of FeSO4 dissolved per litre gives 210.5 ppm of hardness?
Solution: FeSO4 = CaCO3
CaSO4 136 68 100/136 56+16+64=136 gm=152 gm = 100gm
CaCl2 111 55.5 100/111 ∴ 100 ppm of hardness = 152 ppm of FeSO4
210.5 ppm of hardness = 152x210.5/100= 319.96 ppm of FeSO4
MgSO4 120 60 100/120
=319.96 mg/L or ppm or 0.31996 gm /L of FeSO4
MgCl2 95 47.5 100/95 Q.2.Calculate the temporary and permanent hardness of a sample of water containing:
CaCO3 100 50 100/100 Mg(HCO3)2= 7.3mg/L ,Ca(HCO3)2=16.2 mg/L , MgCl2= 9.5mg/L ,CaSO4= 13.6 mg/L
(Atomic weight of Mg and Ca are 24 and 40 respectively.)
MgCO3 84 42 100/84 Solution: Conversion in to CaCO3 equivalents:
CO2 44 22 100/44 Constituents Multiplication factor CaCO3 equivalents
Ca(NO3)2 164 82 100/164
Mg(HCO3)2= 7.3mg/L 100/146 7.3x100/146= 5mg/L
Mg(NO3)2 148 74 100/148 Ca(HCO3)2=16.2 mg/L 100/162 16.2X100/162=10 mg/L
HCO3- 61 61 100/122 MgCl2= 9.5mg/L 100/95 9.5X100/95=10 mg/L
CaSO4= 13.6 mg/L 100/136 13.6X100/136=10 mg/L
OH- 17 17 100/34
 = 9,06830 mg x 10-6 kg =1.171 kg
Temporary hardness, due to Mg (HCO3)2 and Ca (HCO3)2
=(5+10) mg/L=15 mg/L or 15 ppm
Q.5. A water sample on analysis gave the following data:
Permanent hardness due to MgCl2 and CaSO4 Ca2+=30 mg/L, Mg2+=24 mg/L, CO2=24mg/L, HCl=50 mg/L, K+=10mg/L
=(10+10 mg/L=20 mg/L or 20 ppm Calculate the quantities of lime (90% pure) and soda (94% pure) required to softened one
million litres of water sample.
Solution: Conversion in to CaCO3 equivalents:
Q.3.Calculate the temporary and total hardness of a sample of water containing:
Mg(HCO3)2= 73mg/L ,Ca(HCO3)2=162 mg/L , MgCl2= 95mg/L ,CaSO4= 136 mg/L
Constituents Multiplication factor CaCO3 equivalent
(Atomic weight of Mg and Ca are 24 and 40 respectively.)
Ca2+ = 30 mg/L 100/40 30x100/40=75.0 mg/L
Solution: Conversion in to CaCO3 equivalents:
Mg2+ =24 mg/L 100/24 24x100/24=100.0 mg/L
CO2 =24mg/L 100/44 24x100/44=54.5 mg/L
Constituents Multiplication factor CaCO3 equivalent
HCl=50 mg/L 100/73 50x100/73=68.5 mg/L
Mg(HCO3)2= 73mg/L 100/146 73x100/146= 50mg/L
Ca(HCO3)2=162 mg/L 100/162 162X100/162=100 mg/L
MgCl2= 95mg/L 100/95 95X100/95=100 mg/L Lime requirement:
CaSO4= 136 mg/ L 100/136 136X100/136=100 mg/L =74/100[Mg2++CO2 +HCl as CaCO3 eq.] x Vol.of water x (100% purity)
=74/100[(100+54.5+68.5) mg/L]x 106Lx(100/90)
Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2
=74/100[223mg/L]x 106 Lx(100/90)=(74x223x106)/90 mg
=(50+100) mg/L=150 mg/L or 150 ppm
=1.834x108 mg =1.834x102kg=183.4 kg
Total hardness =Temporary + permanent
Soda requirement:
=(150) mg/L+(200) mg/L =350 mg/L or 350 ppm
=106/100[Ca2++Mg2++ HCl as CaCO3 eq.]x Vol.of water x(100% purity)
Q.4.Calculate the quantity of lime and soda required for softening 50,000 litres of water =106/100[(75+100+68.5) mg/L] x106 Lx (100/94)
containing following salts per litre: Ca(HCO3)2=8.1 mg/L ,Mg(HCO3)2= 7.5mg/L , CaSO4= 13.6 =106/100[243.5mg/L]x 106 Lx (100/94)=(106x243.5x106)/94 mg
mg/L ,MgSO4= 12.0 mg/L , MgCl2= 2.0 mg/L and NaCl=4.7 mg/L. =2.946x108mg=2.946x102kg=294.6 kg

Solution: Conversion in to CaCO3 equivalents: Q.6. A water sample on analysis gave the following data:
Constituents Multiplication factor CaCO3 equivalent Ca2+=30 mg/L, Mg2+=18mg/L, K+= 19.5 mg/L, CO2=11mg/L, HCO3-= 122 mg/L, Cl-=35.5 mg/L,
SO42-=48mg/L
Ca(HCO3)2=8.1 mg/L 100/162 8.1X100/162=5.0 mg/L (i) Calculate the total hardness and alkalinity of water sample
Mg(HCO3)2= 7.5mg/L 100/146 7.5X100/146=5.14 mg/L (ii) Calculate lime-soda required for softening one litre of this sample of hard water
CaSO4= 13.6 mg/L 100/136 13.6X100/136=10.0 mg/L Solution: Conversion in to CaCO3 equivalents:
MgSO4= 12.0 mg/L 100/120 12.0X100/120=10.0 mg/L
Constituents Multiplication factor CaCO3 equivalent
MgCl2= 2.0 mg/L 100/95 2.0X100/95=2.11 mg/L
Ca2+=30 mg/L 100/40 30x100/40=75 mg /L
Mg2+=18mg/L 100/24 18x 100/24=75 mg /L
Lime requirement for 50,000 L water: CO2=11mg/L 100/44 11x 100/44=25 mg/L
=74/100[ Ca(HCO3)2+2xMg(HCO3)2+ MgSO4+ MgCl2 as CaCO3 equivalent]x vol. of water HCO3-= 122 mg/L 100/122 122x 100/122 = 100 mg /L
=74/100[5.0+2x5.14+10.0+2.11] mg/Lx50,000 L
(i) Total hardness= (75+75) mg/L=150 mg/L or 150 ppm
=74/100[27.39 mg/L]x50,000L=10,13,430 mg
Alkalinity present = (HCO3- -CO2 ) = (100-25) mg/L = 75 mg/L or 75 ppm
=10,13,430 mgx10-6 kg=1.0134 kg
(ii) Lime requirement =74 /100[ Mg2+ + CO2 +HCO3- as CaCO3 eq.]
Soda requirement for 50,000 L water:
= 74/100[75+25+100] mg /L = 148 mg/L
=106/100[CaSO4+ MgSO4+ MgCl2 as CaCO3 equivalent]x vol. of water
Soda requirement = 106/100[Ca2+ + Mg2+ - HCO3- as CaCO3 eq.]
=106/100[10.0+10.0+2.11] mg/L x50,000 L = 106/100[ 75+75-100] mg /L= 53 mg/L
=106/100[17.11mg/L]x50,000 L=9,06830 mg
 Q.10. A water sample contains the following impurities: Ca2+=20 ppm, Mg2+=18 ppm, HCO3-
=183ppm and SO42-=24ppm. Calculate the amount of lime and soda needed for softening.
Q.7. 100 ml of water sample has a hardness equivalent to 12.5 ml of 0.08N MgSO 4. What is (Atomic weight of Mg and Ca are 24 and 40 respectively.)
its hardness in ppm? Solution: Conversion in to CaCO3 equivalents:
Solution: 100 ml of water sample=12.5 ml of 0.08N MgSO4
=12.5X0.08ml of 1N MgSO4 Constituents Multiplication factor CaCO3 equivalent
= 1ml of 1N MgSO4=1 ml of 1N CaCO3 eq.
= 0.001 L of 1N CaCO3 eq. Ca2+ = 20 ppm 100/40 20x100/40=50 ppm
=0.001x50 g CaCO3 eq. =0.05 g CaCO3 eq. (or 50 mg CaCO3) Mg2+ =18 ppm 100/24 18x100/24=75 ppm
Therefore, 1000 ml (or /L) of water sample=50 mg CaCO3 eq.x1000 ml/100 ml HCO3- =183ppm 100/122 183x100/122=150 ppm
=500 mg CaCO3 eq.
Hence, the hardness of water sample is 500 mg CaCO3 eq. Per litre or 500 ppm.
Lime requirement:
Q.8. 100 ml of a sample of hard water neutralizes exactly 12 ml of 0.12 N HCl using methyl =74/100[perm. Mg2+ +HCO3- as CaCO3 equivalent]
orange as indicator. What kind of hardness is present? express the same in terms of CaCO 3 =74/100[75+150] ppm=166.5 ppm or mg/L
equivalent. Soda requirement:
Solution: Hardness is temporary, since methyl orange does not give the value for =106/100[perm. Ca2+ + Mg2+-HCO3- as CaCO3 equivalent]
permanent hardness. =106/100[50+75-150] ppm=Negative or Nil
100 ml of sample = 12 ml of 0.12 N HCl
= 12x0.12 ml of 1N HCl
=1.44 ml of 1 N HCl or 1N CaCO3 eq.
=1.44x10-3 L x 50 g CaCO3 eq. L-1
= 0.072 g CaCO3 eq.or 72 mg CaCO3 eq.
Hence,1000 ml (or 1 L) of water =72 mg CaCO3 eq. x 1000 ml /100 ml=720 mg CaCO3 eq.
Temporary hardness of water is 720 ppm

Q.9. 0.5 g of CaCO3 was dissolved in HCl and the solution made upto 500 ml with distilled
water. 50 ml of the solution required 48 ml of EDTA solution for titration. 50 ml of hard
water sample required 15 ml of EDTA and after boiling and filtering required 10 ml of EDTA
solution. Calculate the hardness.
Solution: 500 ml of SHW =0.5 g or 500mg CaCO3 eq.
Hence, 1 ml SHW = 1mg CaCO3
Now 48 ml of EDTA = 50 ml SHW =50 mg CaCO3 eq.
Therefore, 1 ml of EDTA = 50/48 mg CaCO3 eq.
(i) Calculation of the total hardness of water:
50 ml hard water =15 ml EDTA = 15x (50/48) mg CaCO3 eq.
= 15.625 mg CaCO3 eq.
Hence, 1000 ml of hard water = 15.625 x 1000/50 mg CaCO3 eq.
= 312.5 mg /L CaCO3 eq.
Therefore, total hardness =312.5 mg /L or 312.5 ppm
(ii) Calculation of non-carbonate hardness:
50 ml boiled hard water = 10 ml EDTA
= 10 x (50/48) mg CaCO3 eq.
= 10.417 mg CaCO3 eq.
Hence, 1000 ml boiled hard water = 10.417 x 1000 /50 mg CaCO3 eq.
= 208.3 mg CaCO3 eq.
Therefore, non-carbonate hardness = 208.3 mg/L or 208.3 ppm
Hence, carbonate hardness = (312.5-208.3) = 104.2 ppm