PROBLEMS ON CALCULATION

OF HARDNESS

Why Hardness is
objectionable
Excess of soap is required.
Form scale in boilers
Hydrogen produced may lead to
violent explosion
Fe3O4 + 4H2
4H2O + 3Fe(hot)

Calculation of Hardness

Reported in terms of equivalents of calcium

carbonate.
Equivalents of calcium carbonate =

Mass of hardness producing substance Chemical equivalent of CaCO3

Chemical equivalent of hardness producing substance

Equivalents of calcium carbonate =

Mass of hardness producing substance50

Chemical equivalent of hardness producing substance

chemical equivalent The weight (in grams) of a substance that

combines with or displaces 1 g of hydrogen. It is found by
dividing the formula weight by its valence.

Units of Hardness
Parts per million (ppm)
1ppm = 1 part of CaCO3 equivalent in 106
parts of water
Milligrams per liter (mg/litre)
1 mg/liter = 1ppm
Degree Clarke (Cl)
Number of grains (1/7000lb) of CaCO3
equivalent per gallon (=10lb) of water
part of CaCO3 equivalent hardness in
70000 parts of water

Units of Hardness
Degree French ( Fr)
Parts of CaCO3 equivalent hardness per 105
parts of water
Various units:
1ppm = 1mg/lit = 0.1 Fr = 0.07 Cl
1 Cl = 1.43 Fr = 14.3ppm = 14.3mg/lit
1 Fr = 10ppm = 10mg/lit = 0.7 Cl

Problem # 1
A sample of water on analysis gave the following
results:
CaCO3 = 10gr/gallon,
MgSO4 = 4gr/gallon,
CaSO4 = 2 gr /gallon,
MgCl2 = 1 gr/gallon
Fe2O3 = 0.04gr/gallon,
SiO2 = 1 gr/gallon
Calculate the total hardness in degrees clarke.

Problem # 1

Calculation of CaCO3 Equivalents.

Hardness

Amount

CaCO3

10gr/gallon

MgSO4

Multiplication Eq. of CaCO3

factor
100/100

10x100/100=10

4gr/gallon

100/120

4x100/120=3.33

CaSO4

2 gr /gallon

100/136

2x100/136=1.47

MgCl2

1 gr/gallon

100/95

1x 100/95= 1.05

Total hardness = 15.85gr/gallon = 15.85Cl

Exercise
Calculate the temporary hardness and permanent
hardness of water in ppm and degrees clarke from
the following results
Mg(HCO3)2=16.8mg/lit
MgCl2 = 19 mg/lit
Mg(NO3)2 = 29.6mg/lit
CaCO3 = 20mg/lit
MgSO4 = 20mg/lit
KCl = 74.5mg/lit
At. Mass of
H=1,C=12,O=16, N=14, Mg = 24, K = 39, Cl=35.3, Ca=
40,S=32

Exercise
What is the temporary hardness and
total hardness in ppm of sample of
water containing
Ca(HCO3)2 = 16.2mg/lit
Mg(HCO3)2 = 7.3 mg/lit
MgCl2 = 9.5mg/lit
CaSO4 = 13.6mg/lit
Ans. 15ppm, 35ppm

At. Mass of
H=1,C=12,O=16, N=14, Mg = 24, K = 39, Cl=35.3, Ca=
40,S=32

Exercise
What is the temporary hardness and total
hardness in ppm of sample of boiler feed
water containing
Ca(HCO3)2=18mg/lit
CaSO4=8.2 mg/lit
Mg(HCO3)2=5mg/lit
MgSO4=7.1 mg/lit
MgCl2 = 6.5mg/lit
At. Mass of
H=1,C=12,O=16, N=14, Mg = 24, K = 39, Cl=35.3, Ca=
40,S=32

Chemical Analysis of water

Problem
250ml of a sample of unfiltered and
filtered water gave a solid residue of
0.255g and 0.250g respectively.
Calculate the total solids dissolved as
well as suspended in ppm

Soln:
250 ml of unfiltered water = 0.255g solids
1000ml of unfiltered water = 0.255x1000g
solids
250
= 1.02g/1000ml

= 1020mg/lit

= 1020ppm

Soln:
250 ml of filtered water = 0.250g solids
1000ml of filtered water = 0.250x1000g
solids
250
= 1.0g/1000ml

= 1000mg/lit

= 1000ppm

Soln:
Suspended solids content
= 1020-1000
= 20ppm

Calculation of Lime and

Soda Requirement
Lime is required for Ca(HCO3), Mg(HCO3)2 ,
MgCl2 ,MgSO4 ,Al salts, Iron salts, CO2 , HCl, H2SO4
and HCO3
If masses of different substances are converted
in to equivalents of CaCO3 then 100 parts of CaCO3
are equivalent to 74 parts of Ca(OH)2
Lime Requirement =74/100{ Temp Ca+2 + 2(Temp
Mg+2)+ Perm (Mg+2 +Fe+2 +Al+3)+HCl + H2SO4+HCO3- all
in terms of CaCO3 equivalents}

Calculation of Lime and

Soda Requirement
Similarly
Soda is required for permanent Ca2+
hardness, Permanent Mg hardness,Al salts,
Fe salts HCl, H2SO4 and HCO3
Soda requirement = 106/100 {Perm. Ca2+
+Perm. (Mg2+ + Al3+ + Fe2+) +HCl + H2SO4 +
HCO3- all in terms of CaCO3 equivalents

Lime-Soda Process

Ca(HCO3)2 + Ca(OH)2
2CaCO3 +2H2O
Mg(HCO3)2 +2 Ca(OH)2
2CaCO3 +Mg(OH)2 +2H2O
MgCl2 + Ca(OH)2
Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2
Mg(OH)2 + CaSO4
FeSO4 + Ca(OH)2
Fe(OH)2 + CaSO4
2Fe(OH)2 + H2O + 0.5O2 2Fe(OH)3
Co2 + Ca(OH)2
CaCO3 +H2O
2HCl + Ca(OH)2
CaCl2 + H2O
H2SO4 + Ca(OH)2 CaSO4 + H2O
CaCl2 + Na2CO3
CaCO3 + 2NaCl
CaSO4 + Na2CO3
CaCO3 + Na2SO4
2HCO3- + Ca(OH)2 CaCO3 +H2O +CO32-

Calculation of Lime and

Soda Requirement
Calculate the amounts of Lime and Soda per
month of 30 days to soften 32000 liters of water
daily. It contains
CaCO3 = 1.7ppm
CaSO4 = 0.84ppm
MgCO3 = 0.72ppm
MgCl2=0.78ppm
MgSO4 = 0.68ppm
NaCl=0.83ppm
Fe2O3 = 3.41ppm
SiO2=3.64ppm
Purity of lime is 88.4% and Soda purity is 99.2%

 Soln:
Note:
NaCl, SiO2, Fe2O3 dont require soda and
lime

Salt

Amount

Hardness

CaCO3

1.7ppm

1.78100/100=1.7ppm

CaSO4

0.84ppm

0.84100/136=0.617

MgCO3

0.72ppm

0.72100/84=0.857

MgCl2

0.78ppm

0.78100/95=0.82

MgSO4

0.68ppm

0.68100/120 =1.41

 Lime Requirement =74/100{ Temp Ca+2 + 2(Temp Mg+2)+ Perm

(Mg+2 +Fe+2 +Al+3)

Lime required =74/100 {1.7 +

2(0.857)+0.82+1.41}
=4.17 mg/lit
Soda requirement = 106/100 {Perm. Ca2+
+Perm. (Mg2+ + Al3+ + Fe2+)
Soda requirement =
106/100{0.617+0.82+1.41}
= 3.01 mg/lit
Amount of water to be required =
32000lit/day x 30 days/month =
960000litres water

 1 Lit water require lime = 4.17mg

960000 = 4.17x 960000
=4003200mg

=4.00kg lime (100%)

88.4% Purity lime needed =4.00x 100/88.4

=4.52kg/month

 1 Lit water require Soda = 3.01mg

960000 = 3.01 x 960000
=2897107.2mg

=2.89kg lime (100%)

99.2% Purity soda needed=2.89 x 100/99.2

=2.91 kg/month

Exercise
Calculate the amount of lime and soda needed for
softening of 10000 lit of hard water which on
analysis gives
CO2 = 30ppm
Mg(HCO3)2 =87.6ppm
MgCl2=95ppm
Mg(NO3)2 = 29.6ppm
MgSO4 = 48ppm
H2SO4 = 19.6ppm
Mg=24,C=12, Cl=35.3,Na=23, O=16,S=32,H=1
Ans= 2.803kg,2.014kg

Exercise
Calculate the cost of Lime and Soda
required for softening of one million liters
of water having the following composition:
Free CO2 = 40ppm
Carbonate hardness = 205ppm,(CaCO3)
Free HCl = 36ppm
Rate of Lime is Rs.15 / 40kg and that of
soda is Rs 16/kg