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HARDNESS REMOVAL
LIME-SODA ASH SOFTENING PROCESS

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WATER HARDNESS

Hardness
defined as the sum of all polyvalent
cations (in consistent units)
HARDNESS
 The calcium and magnesium ions
predominate and the convention in
performing softening calculations is to
define the total hardness (TH) of water
as a sum of these elements in mg/L
as CaCO3 or meq/L

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Carbonate Hardness, CH
 temporary hardness
 carbonate ions is the ‘final form’ from
dissolved CO2

 Magnesium noncarbonate hardness (MgNCH) can also be defined as

equal to the equivalents of magnesium present if there are fewer
equivalents of carbonate species than of calcium, or,
NON-CARBONATE HARDNESS
 the MgNCH is equal to the total NCH if the carbonates exceed calcium
 in order to complete the treatment, some form of carbonate must be equivalents
added; Soda ash, Na2(CO3), provides this.  if there is magnesium noncarbonate hardness, soda ash must be added
 the reaction involving soda ash is: to precipitate the calcium from the lime used

 this reaction removes the calcium noncarbonate hardness (CaNCH),

which in equivalents is equal to the equivalents of calcium minus the
equivalents of carbonate species

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Alkalinity and pH
BAR CHART
 pH simply expresses the degree of
hydrogen ion concentration
 Alkalinity is the true measure of acid-
neutralizing capacity (buffering)

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Process Limitations & Empirical

Considerations
Minimum calcium hardness that can be achieved is
about 30 mg/L as CaC03 and the minimum
magnesium hardness is about 10 mg/L CaC03.
Based on empirical experience, the minimum extra
amount is 20 mg/L of Ca(OH)2 expressed as CaC03 but
amounts greater than 40 mg/L as CaC03 does not
appreciably improve the addition kinetics
Only the magnesium in excess of 40 mg/L as CaC03 is
removed as these form scales on heat exchangers
Because excess lime adds hardness in the form of SOFTENING
Ca2+, it is removed in a subsequent re-carbonation
process

1. the precipitation is carried out in a single stage in which

the lime and soda ash are added together. This may be
followed by pH adjustment either by the addition of a strong
acid such as sulfuric acid, or by recarbonation in one or two
stages.

2. the lime is added in a first stage, followed by recarbonation,

then the soda ash is dosed in a second stage, also followed by
recarbonation for pH adjustment.
LIME-SODA SOFTENING

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Recarbonation
aims to replace the carbon dioxide gas removed
by the addition of lime
Re-carbonation is often necessary to prevent
after precipitation on the filters or in the
distribution piping because the retention time in
settling basins is usually inadequate to permit
complete formation of the insoluble compounds

Recarbonation
 =[ ][ ] = 5 10 SOFTENING REACTIONS
 ( ) =[ ][ ] = 9 10
TH = Ca2+ + Mg2+
TH=CH+NCH
CO2 + Ca2+ + 2OH- ↔ CaCO3 + H2O  CH=associated with the HCO3- anion
 equal to total hardness or the total alkalinity, whichever is less
CO2 + Mg(OH)2 ↔ Mg2+ + CO32- + H2O  called temporary hardness because boiling water removes it
 heating drives CO2 out of solution and the pH increases
 NCH= associated with other anions
CO2 + CaCO3 + H2O ↔ Ca2+ + 2HCO3-  total hardness in excess of the alkalinity
 called permanent hardness because it is not removed by heating
CO2 + Mg2+ + CO32- + H2O ↔ Mg2+ +
2HCO3-

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SOFTENING REACTIONS
3.Precipitation of carbonate hardness due to magnesium
1.Neutralization of carbonic acid (H2CO3) 1)Bicarbonate converts to carbonate

CO  Ca ( OH ) 2   CaCO  H 2O 
2 3(s) Mg 2
 2 HCO 3  Ca ( OH ) 2   MgCO 3  CaCO 3(s)  2 H 2O
2.Precipitation of carbonate hardness due to calcium
2)MgCO3 is soluble (hardness does not change), add more lime to remove hardness due
 to magnesium
Ca 2
 2 HCO 3  Ca ( OH ) 2   2 CaCO 3( s )  2 H 2O
2
Mg 2
 CO 3  Ca ( OH ) 2   Mg ( OH ) 2 ( s )  CaCO 3( s )

4.Removal of noncarbonate hardness due to calcium

Process limitations and empirical considerations

Ca 2
 Na 2 CO 3   CaCO 3(s)  2 Na
 Lime-soda softening cannot produce a water completely free
5.Removal of noncarbonate hardness due to magnesium of hardness
2
Mg 2
 Ca ( OH ) 2   Mg ( OH ) 2 ( s )  Ca Thus, the minimum calcium hardness that can be achieved is
about 30 mg/L as CaC03 and the minimum magnesium
Ca 2
 Na 2 CO 3   CaCO 3(s)  2 Na  hardness is about 10 mg/L CaC03.

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Process limitations and empirical considerations Process limitations and empirical considerations
historically the goal for final total hardness has been set between 75 an extra amount of Ca(OH)2 beyond the stoichiometric amount usually is
and 120 mg/L as CaC03. provided.
 In recent years, many utilities have raised the target hardness to 120 to  Based on empirical experience, the minimum extra amount is 20 mg/L
150 mg/L as CaC03 to reduce chemical cost and residuals production of Ca(OH)2 expressed as CaC03 (or 0.40 meq).
(Horsley et al., 2005)  Magnesium in excess of about 40 mg/L as CaC03 (0.80 meq) forms
scales on heat exchange elements in hot water heaters.

Process limitations and empirical considerations

Softening processes
normally only the magnesium in excess of 40 mg/L as CaC03 is
removed.
 The selection of chemicals and their dosages depends on the
 For magnesium removals less than 20 mg/L as CaC03, the basic extra raw water composition, the desired final water composition,
amount of lime mentioned above is sufficient to ensure good results. operation conveniences, sludge production and cost.
 For magnesium removals between 20 to 40 mg/L as CaC03, an extra
amount of lime equal to magnesium to be removed is added.

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Removal of CO2 Lime Softening

It may be neutralized by the addition of lime
 When the concentration exceeds 10 mg/L as CO2 (227 mg/L as CaCO3  It is also called selective calcium removal or partial lime
or 0.45 meq/L), the economics of removal by aeration (stripping) are softening.
favored over removal by lime neutralization.
 Only lime is added.
 Air stripping is a separate process.
The desired control pH is 10.3.
 No hardness is removed in this process.


Excess lime softening

Lime-soda softening

 Only lime is added.  Both lime and soda ash are added.
 The desired controlled pH is 11.3.  The desired control pH is 11.3.

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CHEMICAL DOSAGES
ESTIMATING CO2 CONCENTRATION
 The equilibrium expressions for carbonic acid are:  For water temperatures other than 25oC, the dissociation constants may be estimated as

where T absolute temperature, K.

 With this assumption, the procedure to solve the problem is:

a. Calculate the [H+] from the pH.
b. Correct the K a value for temperature. What is the estimated CO2 concentration of a water with a pH of
c. Calculate the [HCO3-] from the alkalinity. 7.65 and a total alkalinity of 310 mg/L as CaCO3? Assume the
d. Solve the first equilibrium expression of the carbonic acid dissociation water temperature is 25C.
for [H2CO3 ].
e. Use the assumption that [CO2]=[H2CO3] to estimate the CO2
concentration.

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Solution: The [HCO3-] concentration is 6.20x10-3 moles/L

With pKa1, solve for carbonic acid concentration
*The [H+] concentration=[H+]=10-7.65= 2.24x10-8 moles/L CO2=H2CO3

Problem 1
25.0 mL of 0.0020M potassium
chromate are mixed with 75.0 mL
of 0.000125M lead(II) nitrate. Will
a precipitate of lead(II) chromate
form? Ksp of lead(II) chromate is
1.8 x 10-14.

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