Hardness and Water Softening

Dr. Akepati S. Reddy

Associate Professor
School of Energy and Environment
Thapar University, Patiala
Hardness
Hardness: multivalent metal ions (di or multivalent cations) that
form precipitates with soaps
Based on the hardness waters are classified as
Soft water (0-70 mg/L),
Moderately hard water (70-150 mg/L),
Hard water (>150 mg/L) water with hardness >300 is often known as
very hard water
Cations causing hardness: Ca
2+
, Mg
2+
, Sr
2+
, Fe
2+
, Mn
2+
, Al
Hardness is associated with: HCO
3
-
, SO
4
2-
, Cl
-
, NO
3
-
, SiO
3
2-
, PO
4
3-
Hardness categories
Calcium Hardness (Ca
2+
H), Magnesium Hardness (Mg
2+
) and Total
Hardness (TH) based on the responsible cations
Mg
2+
H = T H - Ca
2+
H
Carbonate Hardness (CH) and Non-carbonate Hardness (NCH) based
on the associated anions
CH is also known as temporary hardness (bicarbonates) and it can
be removed by boiling and by lime (CaO or Ca(OH)
2
)
NCH (also known as permanent hardness) is associated with SO
4
2-

and Cl-- can be removed by soda ash &lime unaffected by boiling
Hardness
If Alkalinity < TH, then CH = Alkalinity
If Alkalinity TH, then CH = TH
NCH = TH Total Alkalinity
Sodium Alkalinity = Total Alkalinity Total Hardness (TH)
Method used for hardness measurement: EDTA (Ethylene-diamine-
tetra-acetic acid) method
Eriochrome Black T is indicator forms complex with free EDTA and
change colour from red to blue
Boiling off and filtering removes temporary hardness and permanent
hardness can be used
Calcium hardness is also measured by EDTA method but after
precipitating the Mg at 13 pH and using different indicator (calcon)
Hardness is expressed in mg/L as CaCO
3
and at times in meq/L
Concentrations in mg/L can be converted into meq/L by dividing
with equivalent weight of the species
X mg/L of Ca
2+
= X/20 meq/L of Ca
2+
(20 is equi. wgt. of Ca
2+
)
X mg/L of Mg
2+
= X/12.2 meq/L of Mg
2+
(12.2 is equi. wgt. of Mg
2+
)
X mg/L of TH as CaCO
3
= X/50 meq/L of TH (50 is equi. wgt. of CaCO
3
)
X mg/L of CO
2
= X/22 meq of CO
2
(22 is equi. wgt. of CO
2
)
At >8.3 pH carbon dioxide does not exisit
At >11.3 even biocarbonate disappears
Measurement of Calcium hardness
Samples pH is raised to ~13 for precipitating magnesium as
hydroxide and not allowing its reaction with EDTA - in the titration
with EDTA, calcon (Hydroxy naphthol) is used as an indicator
Preliminary titration to find approximate volume of EDTA needed
To the sample, add a few drops of polyvinyl alcohol and 1-2 ml of 50%
NaOH, and heat to 60-70
o

Add 2 shots of hydroxy naphthol powder indicator and titrate rapidly
with EDTA to clear blue colour
Final titration to find accurate volume of EDTA needed
To the sample, add a few drops of polyvinyl alcohol, 2 shots of hydroxy
naphthol powder indicator and accurately measured ~95% of the EDTA
volume used in the preliminary titration
Heat to 60-70
o
, add 1-2 ml of 50% NaOH, mix and titrate with EDTA to
a clear blue end point
Note:
Addition of 95% of the EDTA (prior to precipitating magnesium as Mg(OH)
2
)
reduces the calcium ion level to a very low value
Precipitated Mg(OH)2 obscures the end point, and the ppt. formed adsorbs
and coprecipitates calcium ions
Polyvinyl alcohol and heating to 70
o
reduces adsorption of calcium ions
Eriochrome Black T does not give satisfactory color change at high pH -
hydroxy naphthol functions at a high pH but in the same manner
Why to soften water and by what methods?
Hard water forms scales in water heating systems like boilers
Forms foam/leather with soap and increase the soap consumption
Water softening processes
Ion-exchange process
Lime-soda ash process
Advantages (and disadvantages) of the lime soda ash process
The lime added to water in the process is totally removed.
TDS (total dissolved solids) of the water is significantly reduced
Lime also precipitates the soluble Fe and Mn
Excess lime treatment can provide disinfection (through raising
the water pH!) and aid in the coagulation process
Removal of non-carbonate hardness requires soda ash and
when soda ash is applied, Na+ remains in the finished water
Schemes of water softening by lime-soda ash process
Excess lime treatment
Selective calcium removal
Split treatment
Indices
(describing behavior of CaCO
3
in water)
Langelier Saturation Index (LSI) and Ryznar Stability Index (RSI)
Langelier Saturation Index (LSI)
A calculated number developed by Wilfred Langelier (1936)
It predicts the CaCO
3
stability of water (whether the carbonate will
precipitate, dissolve, or remain in equilibrium) and stated as
LSI = pH - pHs
pHs (the pH at which water is saturated in CaCO
3
) is calculated by
pHs = (9.3 + A + B) - (C + D)
A = (Log
10
[TDS] - 1)/10
B = -13.12 x Log10(
o
C + 273) + 34.55 (2.09 at 25C)
C = Log10[Ca
2+
as CaCO
3
] - 0.4 - - (2.5(Ca
2+
)
D = Log
10
[alkalinity as CaCO
3
]
LSI is temp. sensitive (increasing temp. increases the LSI value)
Indices
(describing behavior of CaCO
3
in water)
Water with an LSI between -0.5 and +0.5 will not display any
mineral dissolving or scale forming properties
LSI > 0 indicates super-saturation of water with CaCO
3
and tendency of
precipitation of CaCO
3
scale layer - LSI < 0 indicates under-saturated
and dissolution of solid CaCO
3

Ryznar Stability Index (RSI)
Developed from empirical observations of corrosion rates and film
formation in steel mains
Defines as RSI = 2 pHs pH (measured)
RSI between 6.5 and 7.0 indicates that the water is at saturation
equilibrium with calcium carbonate
RSI > 8 indicates water is under saturated and tends to dissolve any
existing solid CaCO
3
RSI < 6.5 indicates super-saturation of water with CaCO
3
and tendency
to form CaCO
3
scale
Example: find LSI and RSI for the water with pH = 7.5; TDS = 320
mg/L; Calcium = 150 mg/L (or ppm) as CaCO
3
; Alkalinity = 34
mg/L (or ppm) as CaCO
3
Lime-Soda ash process: Chemistry
A chemical precipitation method - uses lime (CaO/Ca(OH)
2
)
and soda ash (Na
2
CO
3
)
Lime removes carbonate hardness (CH), and Soda ash removes
non-carbonate hardness (NCH) from water
Hardness is removed as Calcium Carbonate (CaCO
3
) and
Magnesium Hydroxide (Mg(OH)
2
) precipitates
The lime added first reacts with CO
2
to form carbonate
precipitate and then with carbonate hardness
Mg
2+
CH hardness reacts with lime to form MgCO
3
& CaCO
3
ppt.
MgCO
3
in turn reacts with lime added to form Mg(OH)
2
ppt.
One mole of Ca
2+
CH requires one mole of lime
One mole of Mg
2+
CH requires two moles of lime
Lime added converts Mg
2+
NCH into Ca
2+
NCH and forms
CaCO
3
ppt.
Soda ash added converts Ca
2+
NCH into CaCO
3
precipitate
Removal of 1 mole of Ca
2+
NCH requires 1 mole of soda ash
Removal of 1 mole of Mg
2+
NCH requires 1 mole each of lime
and soda ash

Lime-Soda ash process: Chemistry
CaCO
3
and Mg(OH)
2
are slightly soluble in water
0.6 meq/L (30 mg/L as CaCO
3
) of CaCO
3
and 0.2 meq/L (10 mg/L as
CaCO
3
) of Mg(OH)
2
do not be removed through coagulation-
flocculation-settling/filtration
Theoretical solubility of CaCO
3
is 17 mg/L and of Mg(OH)
2
is 9 mg/L
Practical minimum TH for the softened water is taken as 50-80 mg/L
Minimum practical limit of softening is 40 mg/L Goal set for
the softening is 75-120 mg/L as CaCO
3
Limited completion of the chemical reactions, inadequate mixing and
not complete removal of the ppt. affect the limits the softening
Residual hardness in the form of CaCO
3
and Mg(OH)
2
can
result in easy scaling recarbonation involving conversion of
the hardness into Ca
2+
and Mg
2+
bicarbonate is practiced
In the 1
st
stage of recarbonation the OH- is neutralized to <10.5 (?)
Ca(OH)
2
added in excess and residual MG(OH)
2
are converted into Ca
2+

and Mg
2+
carbonate
In the 2
nd
stage of recarbonation, carbonate is converted into
bicarbonate through brining down pH to ~8.5
Both Ca
2+
and Mg
2+
are converted into Ca
2+
and Mg
2+
bicarbonates
Lime-Soda ash process: Chemistry
Water with high magnesium hardness requires excess lime
treatment (to increase of pH to >11.0 for softening) and two
stage recarbonation
Softened water has both calcium and magnesium hydroxides and 1
st

stage recarbonation converts these hydroxides into carbonates
The 2
nd
stage recarbonation reduces the pH to 8.4-8.6 and converts
the carbonate into bicarbonate
CO2 is totally neutralized by 8.3 pH, bicarbonate is totally converted to
carbonate by 11.3 pH, and above 11.3 pH all the alkalinity will be
carbonate and hydroxide
Split treatment is preferred when magnesium hardness is high
the softening process is bypassed by part of the water and
added with the softened water
Overall lime requirement and carbon dioxide requirement for
recarbonation can be reduced here
When the magnesium hardness is low, addition of excess lime
is not needed and a single stage recarbonation is sufficient
Softened water is finally filtered after the recarbonation for
removing if any suspended particles left in water

Lime Addition
Lime and soda ash addition
( )
( )
( )
2 3 2 2 3
2 3 2 2 3
2 3 2 2
HCO Ca O H CO CaCO
HCO Mg O H CO MgCO
O H MgCO CO OH Mg
+ +
+ +
+ +
Recarbonation
Bar diagram
showing ion composition of water
Used in
dose calculations of lime, soda ash and carbon dioxide for softening
presenting the ionic composition of water before, after and after
recarbonation steps of softening
Has two rows, a top row showing cations (CO
2
, Ca
2+
, Mg
2+
, Na
+
, and
K
+
) concentrations and a bottom row showing anion (OH
-
, CO
3
2-
,
HCO
3
-
, SO
4
2-
, Cl
-
, NO
3
-
) concentrations in meq/L
X mg/L of Ca
2+
= X/20 meq/L of Ca2+ (20 is eq. weight of Ca
2+
)
X mg/L of Mg
2+
= X/12.2 meq/L of Mg2+ (12.2 is eq. weight of Mg
2+
)
X mg/L of TH as CaCO
3
= X/50 meq/L of TH (50 is eq. weight of CaCO
3
)
X mg/L of CO
2
= X/22 meq of CO
2
(22 is eq. weight of CO
2
)
Ion balance is used as the basis for deciding the acceptability of
results presented in the bar diagram


Ion balance should be <5% for results acceptability
| | | | ( )
| | | | ( )
100
+

=


anions cations
anions cations
balance Ion
Hypothetical combination of positive and negative ions in the water sample
A water softening case
A water softening case
(Chemical requirements calculation)
A water softening case
(ion composition after addition of softening chemicals
A water softening case
(ion composition after addition of softening chemicals
Excess lime treatment
Treatment is done in 2 stages (each stage includes a recarbonation
step), and the final effluent is filtered
In the 1
st
stage excess lime (more than stoichiometrically required)
upto 1.25 meq/L is added to raise the pH to 11.0 and removing the
carbonate harness, and then recarbonation to reduce pH to 10.3 for
converting the excess OH- into CO
3
2-
Second stage involves dosing of soda ash for removing the non-
carbonate hardness and recarbonation to convert OH- and CO
3
2-
into
bicarbonate
Selective calcium hardness removal system
Water having Mg
2+
hardness <40 mg/L as CaCO
3
is subjected to this
scheme of water softening
Mg
2+
hardness is not removed here
Both carbonate and non-carbonate hardness of Ca
2+
are removed
through dosing both lime and soda ash
Excess lime is not added
The process is carried out in a single stage
Split treatment
Part of the raw water is bypassed the first stage softening and the rest
is softened by excess lime (for CH removal)
Fraction bypassed is decided on the requirement of satisfying 40 mg
Mg
+2
/L as CaCO
3
in the finished water
Excess lime, added in the 1
st
, is neutralized by the bypass flow, and the
1
st
stage recarbonation is eliminated (lowers CO
2
needs)
Since all the raw water is not passing through the 1
st
stage of soften,
lime requirements of the softening process are lower
Sludge recycling is believed to further reduce the chemical
requirements