WATER SOFTENING

removal of hardness
Hardness is?...
primarily Ca, Mg, plus Fe, Mn, St, Al

How is Softening done?...

Precipitation of Ca and Mg, or
Ion exchange of Ca / Mg with ion such as Na

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 Why bother?

Hardness in 300-500 mg/l as CaCO3

range considered excessive
high soap consumption
scaling in heating vessels and pipes
Even > 150 mg/l may result in
consumer objection
60-120 mg/l as CaCO3 is considered a
moderate amount

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 Formation of Hardness

Precipitation

Topsoil

Subsoil
CO2 + H2O H2CO3

Limestone CaCO3(s) + H2CO3 Ca(HCO3)2

MgCO3(s) + H2CO3 Mg(HCO3)2

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 Hardness
Carbonate Hardness
Often called "temporary hardness" because
heating the water will remove it. When the
water is heated, the insoluble carbonates will
precipitate and tend to form bottom deposits
in water heaters.
Ca2+, Mg2+ associated with HCO3-, CO32-
CH = TH or Total alkalinity, whichever is less

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 Hardness
Non-Carbonate Hardness
Called permanent hardness because it is not
removed when the water is heated. It is much
more expensive to remove non-carbonate
hardness than carbonate hardness.
Ca2+, Mg2+ associated with other ions, Cl-,
NO3-, SO42-
NCH = TH - CH
If Alkalinity Total hardness, then NCH = 0

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 Hardness Units
milligrams per liter (mg/L) as calcium
carbonate (most common)
parts per million (ppm) as calcium carbonate
grains per gallon of hardness (to convert from
grains per gallon to mg/L, multiply by 17.1)
equivalents/liter (eq/L)

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 LIME - SODA ASH SOFTENING

Addition of lime, Ca(OH)2, & soda ash,

Na2CO3 causes precipitation of Ca, Mg
Lime often added as CaO, quick lime
CaO + H20 --> Ca(OH)2
Three basic processes
Excess lime treatment
Selective calcium removal
Split treatment

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 Stoichiometry
CO2 + Ca(OH)2 --> CaCO3 + H2O

Ca(HCO3)2 + Ca(OH)2 --> 2 CaCO3 + 2 H20

Mg(HCO3)2 + Ca(OH)2 --> CaCO3 + MgCO3 + 2H20
Mg(CO3) + Ca(OH)2 --> Mg(OH)2 + CaCO3
MgS04 + Ca(OH)2 --> Mg(OH)2 + CaS04

MgCl2 + Ca(OH)2 --> Mg(OH)2 + CaCl2

CaS04 + Na2CO3 --> CaC03 + Na2SO4
CaCl2 + Na2CO3 --> CaC03 + 2NaCl

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 Solubilities

Ca(OH)2 is very soluble, Mg(OH)2 is not

MgCO3 is very soluble, CaCO3 is not
CaCO3 and Mg(OH)2 are relatively insoluble
CaCO3: ~ 30 mg/l as CaCO3
0.6 meq/l
Mg(OH)2: ~ 10 mg/l as CaCO3
0.2 meq/l
MW is ?... 58 mg/mmol
EW is?... 29 mg/meq
mg/l is ?... 5.8 mg/l as Mg(OH)2

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 Removal by precipitation
Is complete removal possible?...
No, lime-soda ash softening
cannot remove all hardness

What about CO2?

CO2 + Ca(OH)2 --> CaCO3 + H2O
CO2 must be considered because it
consumes lime

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 Effectiveness

80-100 mg/l as CaCO3 is usually

considered acceptable result of lime-
soda ash softening,

as long as Mg is < 40 mg/l as CaCO3

any more causes scaling in heating vessels

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 Stoichiometry Table

meq of lime and soda ash to remove a

meq of X initially present
X Lime Soda Ash
CO2 1 0
Ca(HCO3)2 1 0
Mg(HCO3)2 2 0
MgCO3 1 0
MgSO4 1 1
CaSO4 0 1
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