HARDNESS OF WATER

First Year B.Tech.

Engineering Chemistry, Subject Code: BCY-101/102
Unit/Module V: Water Analysis
Dr. C.L. Gehlot, Associate Professor

INTRODUCTION:

HARDNESS OF WATER: Hardness of water is the soap consuming power of water and
hardness is the characteristics of water, which prevents the lathering of soap. Hardness in
water is due to the presence of certain salt of calcium, magnesium and other heavy metals
dissolved in water.

When hard water is treated with soap (i.e., sodium or potassium salt of higher fatty acids like
oleic, palmitic or stearic etc.) does not produce lather but on other hand forms a white scum
or precipitate. The precipitate is formed due to the formation of insoluble soaps of Ca and
Mg. A typical reaction of soap (sodium stearate) with CaCl2 and MgCl2 may be expressed as:
2C17H35COONa + CaCl2 → (C17H35COO)2 Ca ↓ + 2NaCl
(Sodium stearate, soap) (Hardness) (Calcium stearate, Insoluble)
2C17H35COONa + MgSO4 → (C17H35COO)2 Mg ↓ + Na2SO4
(Magnesium stearate, Insoluble)
Thus, water which does not produce lather with soap readily but forms a white
curd/precipitate is called hard water. On other hand, water which forms lather easily on
shaking with soap is called soft water, such water consequently does not contain dissolved
Ca and Mg salts.
TYPES OF HARDNESS: Hardness of water may be classified in to two types namely:
(1) Carbonate hardness or Temporary: is caused by the presence of dissolved carbonates,
bicarbonates and hydroxides of Ca, Mg and other heavy metals.
It can be removed by water boiling.

∆
Ca(HCO3)2 → CaCO3 ↓ + H2O + CO2 ↑
(Insoluble)
∆
Mg(HCO3)2 → MgCO3 ↓ + 2CO2 ↑
(Insoluble)
(2) Non-carbonate hardness or Permanent: caused by the presence chlorides and sulphates
of Ca, Mg, Fe and other heavy metals. Unlike the temporary hardness, permanent hardness
cannot be removed by boiling water. It needs some treatments.
EQUIVALENCE OF CaCO3
The concentration of hardness as well as non-hardness constituting ions are usually expressed
in terms of equivalent amount of CaCO3, since this mode permits the multiplication and
division of concentration, when required. The choice of CaCO3 in particular is due to its
molecular weight i.e.,100, equivalent weight i.e.,50, it is most insoluble salt that can be
precipitated in water treatment.
Calculation of equivalents of calcium carbonate

Dissolved Molar Chemical Multiplication factor for

Salt/Ion Mass Equivalent converting in to equivalents of
CaCO3
Ca (HCO3)2 162 81 100/162
Mg (HCO3)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
CaCO3 100 50 100/100
MgCO3 84 42 100/84
CO2 44 22 100/44
Ca (NO3)2 164 82 100/164
Mg (NO3)2 148 74 100/148
HCO3- 61 61 100/122
OH- 17 17 100/34
CO32- 60 30 100/60
NaAlO2 82 82 100/164
Al2(SO4)3 342 57 100/114
FeSO4.7H20 278 139 100/278
H+ 1 1 100/2
HCl 36.5 1 100/73
Equivalence of CaCO3
= Mass of hardness producing substance x Chemical equivalent of CaCO3
-------------------------------------------------------------------------------------------------
Chemical equivalent of hardness producing substance

= Mass of hardness producing substance x 50

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Chemical equivalent of hardness producing substance

UNITS OF HARDNESS:
(i) Parts per million(ppm): is the parts of calcium carbonate equivalent hardness per 106 parts
of water. i. e. 1 ppm =1 part of CaCO3 eq. hardness in 106 parts of water. 1ppm=1 mg per litre.
(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.

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
(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

(iv) Milliequivalent per litre (meq/L): is the no. of milli equivalent of hardness present per
litre .
Thus 1 meq/L=1 meq. of CaCO3 per litre of water
RELATIONSHIP BETWEEN VARIOUS UNITS OF HARDNESS:
1ppm =1 mg/L = 0.1◦Fr = 0.07◦Cl= 0.02meq./L
1mg/L= 1ppm = 0.1◦Fr = 0.07◦Cl =0.02meq. /L
1◦Cl= 1.433◦Fr =14.3 ppm =14.3 mg/L= 0.286 meq. /L
1◦Fr= 10 ppm = 10 mg/L= 0.7◦Cl= 0.2 meq. /L
1 meq. /L =50 mg/L = 50 ppm= 5◦ Fr = 0.35◦Cl
DISADVANTAGES OF HARD WATER:
(1) Domestic use
(i) Washing:
C17H35COONa + H2O ↔ C17H35COOH +NaOH
Sodium stearate (Soap) Stearic acid
C17H35COOH + C17H35COONa → Leather
Stearic acid Soap
This causes wastage of lot of soap being used. Moreover, sticky precipitate adheres on fabric
/cloth gives spots and streaks.
(ii) Bathing: Hard water produces sticky scum on bath tub and body. Thus, cleansing quality
of soap is depressed and lot of soap wasted.
(iii) Cooking: Due to hardness producing salt boiling point of water is elevated, consequently
more fuel and time required for cooking.
(iv) Drinking: Hard water causes bad effect on digestive system. Possibility of forming calcium
oxalate in urinary tract is increased.
(2) Industrial use:
(i) Textile industry: precipitate of Ca and Mg soaps adhere to the fabric. When fabric dyed do
not produce exact shades of colour and spoil the beauty of fabric.
(ii) Sugar industry: Causes difficulty in crystallization of sugar during sugar refining.
(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.

(iv) Paper industry: Ca, Mg salts react with chemicals and materials used for smooth and
glossy finish to paper and colour of paper affected.
(v) Laundry: hard water causes wastage of water and may even causes coloration of cloths.
(vi) Concrete making: Hard water used for concrete affects hydration of cement and strength
of the hardened concrete.
(vii) Steam generation in boiler: Causes scale and sludge formation, boiler Corrosion, 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 hot water
than in cold water e.g. MgCO3, MgCl2, CaCl2 and MgSO4 etc.

Boiler corrosion: is decay process of boiler material by a chemical or electrochemical attack

by its environment
Caustic embrittlement: is a type of boiler corrosion caused by using highly alkaline water in
the boiler.
(viii) Pharmaceutical Industry: May produce certain undesirable pharmaceutical products.
SOFTENING OF HARD WATER:
The process of removing hardness producing salts from water is known as softening of water.
In industry, main three methods employed for softening of water.
(1) LIME SODA PROCESS: In this method, the soluble calcium and magnesium salts in water
are chemically converted in to insoluble compounds by adding calculated amount of lime
[Ca(OH)2] and soda [Na2CO3], CaCO3 and Mg(OH)2 so precipitated may be filtered off.
Notes:
(i)If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca2+ +2HCO3-) and (Mg2+ +2HCO3-)
respectively then calculation results will be same.
(ii)Equivalent weight of NaAlO2 is equal to its molar mass.
(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 excess amounts should be added
to the calculations.

(iv)When impurities are given as CaCO3 and /or MgCO3, these should be considered due to
bicarbonates of Ca and /or Mg respectively.
(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

Constituent Reactions Need

Ca2+ Ca2+ +Na2CO3→CaCO3 +2Na+ S

(perm. Ca)

Mg2+ Mg2+ + Ca(OH)2→Mg(OH)2 +Ca2+ L+S

(perm. Mg) Ca2+ +Na2CO3→CaCO3 +2Na+

HCO3- 2HCO3- + Ca(OH)2→CaCO3+H2O+CO32- L-S

(eg. NaHCO3)

Ca(HCO3)2 Ca(HCO3)2+Ca(OH)2→2CaCO3+2H2O L
(Temp.Ca)

Mg(HCO3)2 Mg(HCO3)2+2Ca(OH)2→2CaCO3+Mg(OH)2+ 2L
(Temp.Mg) 2H2O

CO2 CO2+Ca(OH)2→CaCO3+ H2O L

H+(Free acids, 2H+ +Ca(OH)2→Ca2+ +2H2O L+S

HCl, H2SO4 etc.) Ca2+ + Na2CO3→CaCO3+2Na+
 Coagulants Fe2+ +Ca(OH)2→Fe(OH)2 +Ca2+ L+S
FeSO4 2Fe(OH)2 +H2O+O2→2Fe(OH)3
Ca2+ +Na2CO3→CaCO3+2Na+

Al2(SO4)3 2Al3+ +3Ca(OH)2→2Al(OH)3 +3Ca2+ L+S

3Ca2+ +2Na2CO3→3CaCO3+ 6Na+

NaAlO2 NaAlO2+2H2O→Al(OH)3 +NaOH -L

2NaOH is equivalent to Ca(OH)2

Now 100 parts by mass of CaCO3 are equivalent to (i) 74 parts of CaCO3 and (ii) 106 parts
of Na2CO3
Hence, Lime requirement for softening

=74/100 [Temp.Ca2+ +2xTemp.Mg2+ + Perm. (Mg2+ +Fe2+ +Al3+) +CO2+H+ (HCl or H2SO4) +HCO3-
-NaAlO2 : All in terms of CaCO3 eq.]
Soda requirement for softening
=106/100[Perm. (Ca2+ +Mg2+ +Al3+ +Fe2+) H+ (HCl or H2SO4) –HCO3- : All in terms of CaCO3 eq.]
TYPES OF LS PROCESS:
(i) Cold lime soda process: Calculated amount of lime and soda are mixed with 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↓
Sodium Aluminate
Al2(SO4)3 +3Ca(HCO3)2→2Al(OH)3↓+3CaSO4+6CO2↑
Coagulant Hard water

Fig. Cold lime-soda softener