CHEMISTRY OF SOFTENING

- Excess Lime Treatment -

1. Dissolved CO2 reacts with lime

a. H 2CO3 * + Ca(OH)2 CaCO3 (s) + 2 H 2O

2. Carbonate hardness

b. Ca + + + 2 HCO3− + Ca(OH)2 2 CaCO3 (s) + 2 H 2O

Mg + + + 2HCO3− + Ca(OH)2 + CO3− − 2 H 2O

++
c. CaCO3 (s) + Mg
d. Mg + + + CO3− − + Ca(OH)2 CaCO3 (s) + Mg(OH)2 (s)

Net of c and d:
e. Mg + + + 2HCO3− + 2 Ca(OH)2 2 CaCO3 (s) + Mg(OH)2 (s) + 2 H 2O

Comment: Equation c: Addition of 1 meq/L of Ca(OH)2 per meq/L of Mg + + raises

the pH to 9. Because MgCO3 is very soluble under those conditions, the pH must
be raised to pH = 10.8 or higher such that Mg + + is precipitated as the hydroxide,
Mg(OH)2 , which is relatively insoluble. This requires addition of an additional 0.6 –
1.0 meq/L of Ca(OH)2 and is referred to as excess lime.

3. Non-carbonate hardness
f. Ca + + + SO −4 − + Na 2CO3 CaCO3 (s) + 2Na+ + SO −4 −
g. Mg + + + SO −4 − + Na 2CO3 + Ca(OH)2 CaCO3 (s) + Mg(OH)2 (s) + SO −4 −

4. Tabulation of stoichiometric quantities of lime and soda ash required for hardness
removal can be accomplished using the equations above
LIME
• 1 meq lime per meq CO2. (primarily exists as CO2(aq) = H2CO3* in water).
• 1 meq lime per meq alkalinity associated with hardness.
• 1 meq lime per meq Mg++ to be removed.

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SODA ASH

• 1 meq soda ash per meq non-carbonate hardness.

Softening Limitations

The solubility of Mg(OH)2 at pH 10.5 yields approximately 9 to 10 mg/L Mg++

(as CaCO3) and the solubility of CaCO3 yields approximately 17 mg/L Ca++
(as CaCO3). Thus it is theoretically impossible to produce a water with less
than about 25 mg/L of total hardness (mg/L as CaCO3). In addition, both
Mg(OH)2 and CaCO3 tend to form supersaturated solutions that do not
approach saturation rapidly even in the presence of precipitated material. In
practice it is impractical to provide for detention times that permit complete
precipitation; consequently waters softened by the lime or soda-ash
processes usually contain from 50 mg/L to 150 mg/L (70 – 100 is achievable
and desired range) as CaCO3 of residual hardness.

Forms of lime:

CaO + H2O Ca(OH)2

MW = 56 MW = 74
(free lime) (slaked lime)

74
Ca(OH)2 equivalent = CaO reqd. x
56

Less CaO is required: therefore, the transportation costs are less for it than
for the hydrated lime, Ca(OH)2.

5. Softening Example:

a. Given: A river water is to be softened to a hardness of about 80 mg/L by the

lime-soda ash process. Analysis of the water shows the following
composition:

Free CO 2 (H2CO3*) = 12 mg/L as CO 2

Ca + + = 65 mg/L as Ca + +
Mg + + = 26 mg/L as Mg + +
Alkalinity = 244 mg/L as HCO3−

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 SO −4 − = 57.5 mg/L as SO −4 −

Cl- = 90 mg/L as Cl-

pH = 7.8

b. Find:

1) Carbonate and non-carbonate hardness

2) Determine the lime and soda-ash requirements if the lime supply is

quick or free lime (CaO) at 90% purity and the soda ash is 98%
Na 2CO3 . Use an excess of 1 me/l of CaO.

3) Compute these requirements in pounds per million gallons.

4) If the quick lime costs $40/ton and the soda ash $50/ton, calculate the
cost of chemicals per million gallons of water softened.

5) Compute the volume of sludge produced per million gallons of water

treated.

c. Solution:

1) Convert to reacting units (meq/L)

Cations Anions

 65 mg/l  −  244 mg/l 

Ca + +   HCO 3  
 20 mg/meq  = 3.25 meq/L  61 mg/meq  = 4.0 meq/L

 26 mg/l   57.5 mg/l 

Mg++   SO4  
 12.2 mg/meq  = 2.13 meq/L  48 mg/meq  = 1.2 meq/L

 90 mg/l 
Cl-  
 35.5 mg/meq  = 2.54 meq/L

Total = 5.38 meq/L = 7.74 meq/L

Recall, electroneutrality requires that the concentration of cations in meq/L

must equal the concentrations of anions in meq/L. Because Na+ is seldom
determined directly, it is calculated by difference.

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 Therefore, Na+ = 7.74 - 5.38 = 2.36 meq/L

CO2: (12 mg/L) / (22 mg/meq) = 0.545 meq/L

Decreasing reactivity w/
lime

Ca + + = 3.25 meq/L Mg + + = 2.13 Na+ = 2.36 meq/L

meq/L

CO2 HCO3− = 4.0 meq/L SO −4 − = 1.2 Cl- = 2.54 meq/L

.545 meq/L
meq/L

1) Carbonate hardness = 4.0 meq/L

Non-carbonate hardness = total hardness - carbonate hardness

NCH = 5.38 meq/L - 4.0 meq/L = 1.38 meq/L

2) Lime and Soda Ash Requirements

CO 2 : 0.545 meq/L

HCO3− : 4.0 meq/L

Mg++: 2.13 meq/L

Excess: 1.0 meq/L

________
Total = 7.675 meq/L CaO @ 100% purity

grams 1
∴ CaO (reqd) = 7.675 meq/L x 28 x
equivalent .90

CaO (read) = 238 mg/L (90% CaO)

Soda Ash Requirements

NCH: 1.38 meq/L (total)

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 grams 1
∴ Na 2CO3 (reqd) = 1.38 meq/L x 53 x
equivalent . 98

Na 2CO3 (reqd) = 74.6 mg/L (98% Na 2CO3 )

3) Use in pounds per million gallons:

1 gallon - 8.34 pounds

∴ 106 gallons = 8.34 x 106 pounds

CaO (reqd) = 238 mg/L (ppm) x 8.34

∴ CaO (reqd) = 1985 pounds/MG

NOTE: mg/L = ppm = pounds per million pounds

Na 2CO3 (reqd) = 74.6 mg/L (ppm) x 8.34

Na 2CO3 (reqd) = 622 pounds/MG

5) Volume of sludge produced per million gallons. (Refer to equations a-

g on page 1.)

Appropriate meq/L CaCO3 meq/L Mg(OH)2

Equation produced produced
a 0.545 0
b 6.50 0
c 0.75 0
d 0.75 0.75
f 0 0
g 1.38 1.38

Total 9.925 2.13

CaCO3 produced = 9.925 meq/L x 50 g/eq. = 496 mg/L

CaCO3 produced = 496 mg/L x 8.34 = 4140 #/MG

Mg(OH)2, produced = 2.13 meq/L x 29.2 g/eq. = 62.3 mg/L

Mg(OH)2, produced = 62.3 mg/L x 8.34 = 519 #/MG

Total = 4140 #/mg + 519 #/MG = 4659 #/MG

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Because softening sludge contain between 90 and 95% moisture, the
approximate total wet weight of sludge produced is:

gal . sludge
or 46590 #/MG/(8.34#/gal) = 5590
MG treated

gal . sludge
or 23.29 tons/MG x 2000#/ton x 1/(8.34#/gal) = 5590
MG treated

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