Water Softening (Hardness Removal)

Water softening is a process used to remove calcium, magnesium, and

certain other metal cations from hard water.

•In a softening plant the chemical doses are much higher, and the
corresponding sludge production is greater.
Hardness
•Hardness is defined as the sum of all polyvalent cations, primarily
calcium and magnesium ions (Ca+2 and Mg+2).
•The term hardness is used to characterize a water that does not lather
well, causes a scum in the bathtub, and leaves hard, white, crusty
deposits/scales on tea kettles, and hot water heaters etc.
•The failure to lather well and the formation of scum on bathtubs is
the result of the reactions of calcium and magnesium with the soap.
Cont.….
The common units of expression are mg/L as CaCO3, or meq/L.
•A common water treatment goal is to provide water with a hardness in
the range of 75 to 120 mg/L as CaCO3.
•As water with hardness levels exceeding 150 mg/L as CaCO 3 is
considered objectionable.
•Although all polyvalent cations contribute to hardness, the predominant
contributors are calcium and magnesium.
Reference: Introduction to Environmental Engineering (Mackenzie…)
Reference: Introduction to Environmental Engineering (Mackenzie…)
Natural Process responsible for water hardness
As rainwater enters the topsoil, the respiration of microorganisms increases the
CO2 content of the water.
The CO2 reacts with the water to form H2CO3.
Limestone, which is made up of solid CaCO3 and MgCO3 reacts with the
carbonic acid to form calcium bicarbonate [Ca(HCO3)2] and magnesium
bicarbonate [Mg(HCO3)2].
While CaCO3 and MgCO3 are both insoluble in water, the bicarbonates are quite
soluble.
 Gypsum (CaSO4) and MgSO4 may also go into solution to contribute to the
hardness.
•Calcium and magnesium are the dominant elements, so it's common to simplify
softening calculations by considering the total hardness (TH) as the combined
concentration of these ions.

where the concentrations of each element are in consistent units (mg/L as CaCO 3
or meq/L).
Total hardness is often broken down into two components:
1) Hardness associated with the HCO3- anion (called carbonate hardness and
abbreviated CH), and
2) Hardness associated with other anions (called noncarbonate hardness and
abbreviated NCH). Can also called permanent hardness.
Total hardness, then, may also be defined as:
Methods of Softening Process
Softening can be accomplished by:
1) The lime-soda process or
2) By ion exchange..
Soda Lime Softening Process
Hardness precipitation is based on the two solubility reactions:
Ca2+ + CO32- CaCO3 (s)
Mg2+ + 2OH- Mg(OH)2 (s)
The objective is to precipitate the calcium as CaCO3 and the magnesium as
Mg(OH)2.
•To precipitate CaCO3, the pH of the water must be raised to about 10.3.
•To precipitate magnesium, the pH must be raised to about 11.
Softening Chemistry
•Water softening employs chemical processes based on the law of mass action.
•It involves increasing the concentration of carbonate ions (CO 32-) and/or hydroxide
ions (OH-) through chemical additives and drive the reaction to the right.
•The most common source of hydroxyl ions is calcium hydroxide (Ca(OH) 2 and
the moat common source of carbonate ions is sodium carbonate (Na 2CO3).
•It is economical to buy quick lime (CaO) instead of hydrated lime.
•The quick lime is converted to hydrated lime at the water treatment plant by mixing
CaO and water to produce slurry of Ca(OH) 2, which is fed to the water for
softening,
Lime-soda Softening (Softening Reactions)
1. Neutralization of carbonic acid (H2CO3).
•To raise the pH, we must first neutralize any free acids that may be present in the
water.
•CO2 is the principal acid present in unpolluted, naturally occurring water. No
hardness is removed in this step
……………………(1)
2. Carbonate hardness removal
………….(2)
Mg…………(3)
3. Noncarbonate hardness removal.
………(4)

Ca………(5)

lime will remove CO2 (Equation1) and carbonate hardness (Equations 2 and 3) and
replace magnesium with calcium in solution (Equation 4). Equation 5 shows that
soda ash (Na2CO3) is then used to remove calcium noncarbonated hardness, which
may be present in the untreated water or may be the result of the precipitation of
magnesium noncarbonated hardness (Equation 4).
Solve Example 8.3
Numerical Problems from 8.1-8.14 from Environmental Engineering Fundamentals,
Sustainability and Design by James and Zimmerman book
Ion-Exchange Softening
•Ion exchange can be defined as the reversible interchange of ions between a
solid and a liquid phase in which there is no permanent change in the
structure of the solid.
•In water softening by ion exchange, the water containing the hardness is passed
through a column containing the ion-exchange material.
•The hardness in the water exchanges with an ion from the ion-exchange material.

where R represents the solid ion-exchange material.

•By the above reaction, calcium (or magnesium) has been removed from the water
and replaced by an equivalent amount of sodium, that is, two sodium ions for each
cation.
•The alkalinity remains unchanged.
•The exchange results in essentially 100 percent removal of the hardness from the
water until the exchange capacity of the ion-exchange material is reached.
 Regeneration
•When the ion-exchange material becomes saturated, no hardness will be
removed.
•At this point, breakthrough is said to have occurred because the hardness passes
through the bed.
• At this point, the column is taken out of service, and the ion-exchange material
is regenerated.
•That is, the hardness is removed from the material by passing water containing a
large amount of NaCl through the column.
•The mass action of having so much NaCl in the water causes the hardness of the
ion exchange material to enter the water and exchange with the sodium:

The ion-exchange material can now be used to remove more

hardness. The CaCl2 is a waste stream that must be disposed of.
Zeolites
Zeolites are crystalline solids structures
made of silicon, aluminum and
oxygen that form a framework with
cavities and channels inside where
cations, water and/or small
molecules may reside. They are
often also referred to as molecular sieves
Ion exchange resins
•Ion exchange resins are used to soften water by replacing the cations with sodium ions (and
possibly the anions with chloride ions) of sodium chloride.
•They may also be used to demineralize water where the cations are replaced by H+ ions
and the anions are replaced by OH− ions
Resins/Zeolites
There are some large water treatment plants that utilize ion-exchange
softening, but the most common application is for residential water
softeners.
The ion-exchange material can either be naturally occurring clays, called
zeolites, or synthetically made resins.
 There are several manufacturers of synthetic resins.
The resins or zeolites are characterized by the amount of hardness
that they will remove per volume of resin material and by the amount
of salt required to regenerate the resin.
The synthetically produced resins have a much higher exchange capacity
and require less salt for regeneration. However, they also cost much more.

Measurements used to express water hardness in ion-exchange differ from units

used in lime-soda softening. Hardness is expressed as grains per gallon rather than
mg/l of calcium carbonate.

People who work in the water softening industry often work in units of
grains of hardness per gallon of water (gr/gal)(unit of water hardness).
It is useful to remember that 1 gr/gal equals 17.1 mg/L.
Since the resin removes virtually 100 percent of the hardness, it is necessary
to bypass a portion of the water and then blend in order to obtain the desired
final hardness.
 %Bypass= (100)
These reactions represent cation exchange, the exchange of positive
ions. To replenish the sodium ions used, units need to be regenerated
with material containing high amounts of sodium, normally salt brine.
This allows the resin to be reused many times.
Ion-exchange does not alter the water’s pH or alkalinity.
However, the stability of the water is altered due to the removal of
calcium and magnesium and an increase in dissolved solids.
Example 6.10
A home water softener has 0.1 m3 of ion exchange resin with
an exchange capacity of 57 kg/m 3. The occupants use 2,000
L of water per day. If the water contains 280.0 mg/L of
hardness as CaCO3 and it is desired to soften it to 85 mg/L
as CaCO3, how much should be by passed?