WWE 2020 11 UnitOperations Softenning

Water and Wastewater Treatment
(CE F342)
Unit Operations - Softenning
BITS Pilani Module 3 - 6
Hyderabad Campus
Softening
• The removal of ions that cause hardness is called

softening.
• Majority of treatment systems that employ softening are

those using a groundwater source.
• a number of surface water sources with a groundwater

component that is hard employ softening as part of their
treatment process.
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BITS Pilani, Hyderabad Campus
Hardness
• Hardness is defined as the sum of all polyvalent cations (in consistent units) including
calcium, magnesium, iron, manganese, strontium, and aluminum. The common units of
expression are mg/L as CaCO3 or milliequivalents per liter (meq/L).
• Although all polyvalent cations contribute to hardness, the predominant contributors are
calcium and magnesium.
• Hardness in natural waters comes from the dissolution of

minerals from geologic formations that contain calcium and
magnesium. Two common minerals are calcite (CaCO3 )
and dolomite [CaMg(CO3)2].
• Calcite and dolomite react with the carbonic acid to form

calcium bicarbonate [Ca(HCO3)2] and magnesium
bicarbonate [Mg(HCO3)2] . While CaCO3 and CaMg(CO3)2
are not very soluble in water, the bicarbonates are quite
soluble.
• Calcium chloride (CaCl2 ), gypsum (CaSO4 ), magnesium chloride (MgCl2) , and
magnesium sulphate (MgSO4) may also dissolve to contribute to the hardness.
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Total Hardness
Since calcium and magnesium predominate, total hardness (TH) of a
water is defined as the sum of these elements (Cations)
++ +
𝐓𝐇 = 𝐂𝐚 𝟐 𝐌𝐠𝟐
The concentrations of each element are in consistent units (mg/L as CaCO3 or meq/L).
Two components of total hardness may also be termed in terms of

anions:
• Those associated with HCO3- anion (called carbonate hardness, CH)

• Those with other anions (called non-carbonate hardness NCH).
𝐓𝐇 = 𝐂𝐇 + 𝐍𝐂𝐇
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Alkalinity
• Found by experimentally determining how much acid it takes to

lower the pH of water to 4.5.
• In most waters the only significant contributions to alkalinity are the
carbonate species and any free H+ or OH- .
• The total H+ that can be taken up by a water containing primarily
carbonate species is
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Titration curve for OH-CO3
mixture
• Below pH of 4.5, essentially all of the
carbonate species are present as
H2CO3, and the alkalinity is negative
(due to the H+).
• At a pH of 8.3 most of the carbonate

species are present as HCO3- and the
alkalinity equals HCO3-.
• Above a pH of 12.3, essentially all of the

carbonate species are present as [CO32]
and the alkalinity equals [CO32-]+[OH- ].
The [OH-] may not be insignificant at this
pH.
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Carbonate buffer system
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Constituent species of of
Alkalinity vs pH
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Concept of equivalent Weight
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Molarity to mg/L
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Conversions from mg/l of any ion
to mg/l as CaCO3
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Often, the concentrations are measured in terms of
equivalents, or in
mg/L as , in which case the 2 is already accounted for in
the conversions, so
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Carbonate Hardness
• Carbonate hardness is defined as

the amount of hardness equal to
the total hardness or the total
alkalinity, whichever is less.
• Carbonate hardness is often

called temporary hardness
because boiling the water
removes it.
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Non Carbonate hardenss
• Non-carbonate hardness is
defined as the total hardness in
excess of the alkalinity.
• If the alkalinity is equal to or

greater than the total hardness,
then there is no noncarbonate
hardness.
• Noncarbonate hardness is
called permanent hardness
because it is not removed when
water is heated.
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Ex.1
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Example
• A water has an alkalinity of 200 mg/L as CaCO3 . The

Ca2+ concentration is 160 mg/L as the ion, and the Mg2+
concentration is 40 mg/L as the ion. The pH is 8.1. Find
the total, carbonate, and noncarbonate hardness.
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Temporary and Permanent
Harness
• Carbonate hardness is often called temporary hardness
because boiling the water removes it.
• Noncarbonate hardness is called permanent hardness

because it is not removed when water is heated.
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Softening
• Softening is accomplished by lime-soda process, ion exchange, Nano
filtration, or reverse osmosis.
• Primary purpose of lime-soda softening by municipal water treatment

systems was to satisfy domestic consumer desire to reduce the
aesthetic and economic impact of soap precipitation.
• But now reduced with the introduction of synthetic detergents and

home water softeners.
• Other substantial benefits include removal of heavy metals,

NOM, turbidity, and pathogens as well as improving the water quality
that reduces costs for distribution system corrosion, boiler and cooling
water feed, and home water heater systems.
• Also removes arsenic, chromium, iron, lead, manganese, and mercury

during removal of hardness
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Softening
• To soften the water, an ion in Equilibrium of solid and dissolved species of

common ions:
Source: Adapted from Loewenthal and Marais
common in the solubility [1982]
equilibrium is selected to Mineral Solubility, mg/L as at 00C

react with calcium or Calcium carbonate 15
magnesium so the reaction Calcium chloride 336000

Calcium sulphate 1290
forms more precipitate. Calcium hydroxide 2390
Magnesium bicarbonate 37100
Magnesium carbonate 101
Magnesium chloride 362000
• In the case of calcium, the Magnesium hydroxide 17
precipitate is CaCO3. In the Magnesium sulphate

Sodium bicarbonate
170000
38700
case of magnesium, the Sodium carbonate 61400
Sodium chloride 225000
precipitate is Mg(OH)2 . Sodium hydroxide 370000
Sodium sulphate 33600
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The objective of Softening
• To precipitate the calcium as CaCO3 and the magnesium as Mg(OH)2
• To precipitate CaCO3, the pH must be raised to about 10.
• To precipitate Mg2+, the pH must be raised to about 11.
• If there is not sufficient naturally occurring bicarbonate
alkalinity (HCO3)- for the CaCO3(s) precipitate to form (that
is, there is non-carbonate hardness), we must add CO32- to
the water.
• Magnesium is more expensive to remove than calcium, so
we leave as much Mg2+ in the water as possible.
• It is more expensive to remove noncarbonated hardness
than carbonate hardness because we must add another
chemical to provide the CO32- . Therefore, we leave as
much non-carbonate hardness in the water as possible 27
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Softening
• Temporary hardness
– By boiling. Heating drives the CO2 out of solution and the pH

increases as shown
• Has practical limitations in large sale implementation
– Adding lime (only CH or temporary hardness is removed)
𝐶𝑎(𝐻𝐶𝑂3)2 + 𝑪𝒂(𝑶𝑯)𝟐 → 2𝐶𝑎𝐶𝑂3 ↓ +2𝐻2𝑂
𝑀𝑔 𝐻𝐶𝑂3 2 + 𝑪𝒂 𝑶𝑯 𝟐 → 𝐶𝑎𝐶𝑂3 ↓ + 𝑀𝑔𝐶𝑂3 + 2𝐻2𝑂

𝑀𝑔𝐶𝑂3 + 𝑪𝒂 𝑶𝑯 𝟐 → 𝐶𝑎𝐶𝑂3 ↓ + 𝑀𝑔 𝑂𝐻 2 ↓ +2𝐻2𝑂
• Precipitates (insoluble) removed by sedimentation

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Softening – Lime Soda process
• Lime – CaO (Quick lime) – Slaked to form Ca(OH)2
• Soda – Na2CO3 – called Soda Ash
• Adding lime only removes carbonate Hardness, Soda ash is added to

provided to remove non carbonate harness
• In the lime-soda ash process, hydrated (slaked) lime is added to the

water, raising the pH to about 10.3.
• At this pH, calcium carbonate and magnesium hydroxide are

relatively insoluble, and precipitate out as solids.
• Soda ash is further added to remove permanent hardness.
“dependence of CaCO3 and Mg(OH)2 solubility on pH, lime-soda ash softening is able to
achieve the seemingly odd feat of reducing the calcium ion concentration in water by adding
calcium (as lime) to the water”
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Reactions in Lime soda Process
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Softening Limits
• Lime-soda softening cannot produce a water completely

free of hardness because of the solubility of CaCO3 and
Mg(OH)2, the physical limitations of mixing and contact,
and the lack of sufficient time for the reactions to go to
completion.
• Minimum calcium hardness that can be achieved is about

30 mg/L as CaCO3, and the minimum magnesium
hardness is about 10 mg/L as CaCO3
• Many utilities will operate at total hardness goals of up to

140 to I50 mg/L as CaCO3 .
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Process Limitations and
Empirical Considerations
• In order to achieve reasonable removal of hardness in a
reasonable time period, an excess of Ca(OH)2 beyond the
stoichiometric amount usually is provided.
• This excess varies between 20 and 40 mg/L as (0.4 – 0.8

meq/L) depending on the magnesium removal required,
but usually 20 mg/L (0.4 meq/L).
• Although the reactions shown above use lime and soda

ash as sources of hydroxyl ion and carbonate ion, other
sources like sodium hydroxide (NaOH) can be substituted
for Ca(OH)2
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Magnesium removal
• Magnesium in excess of about 40 mg/L as CaCO3 forms

scales on heat exchange elements in hot water heaters.
• Because of the expense of removing magnesium, we normally

remove only that magnesium which is in excess of 40 mg/L as
CaCO3.
• For magnesium removals less than 20 mg/L as CaC03, the basic excess
of lime mentioned above is sufficient to ensure good results.
• For magnesium removals between 20 and 40 mg/L as CaC03, we must

add an excess of lime equal to the magnesium to be removed.
• For magnesium removals greater than 40 mg/L as CaC03, the excess

lime we need to add is 40 mg/L as CaC03
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Ex3
Prepare a bar chart for Sweetwater’s water analysis given below and determine
the chemical dosage required for selective calcium removal. Estimate the dosage of
quicklime (CaO) that needs to be added if the purity of lime is 90%.
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Ex 4
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• The amount of Lime to be added is 277.51mg/L as CaCO3
• Determine if any NCH need be removed. The amount of NCH that

can be left (NCHf) is equal to the final hardness desired (80.0 mg/L)
minus the CH left due to solubility and other factors (40.0 mg/L)
The amount of soda to be added is 55.37 mg/L as CaCO3
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EX 5.
• From the water analysis presented below, determnine

the amount of lime and soda (in mg/L as CaCO3)
necessary to soften the water to 90.00 mg/L as CaCO3 )
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• Given the following water, determine the amount (mg/L)
of 90 percent purity CaO and 97 percent purity Na2C03
that must be purchased to treat the water to a final
hardness of 85 mg/L; 120 mg/L.
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Typical process flow of softening
treatment
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Recarbonation
• the pH must be reduced to stop the precipitation reaction

that will deposit CaCO3 in the filters and distribution
system piping because this will cement them closed.
.
• pH is adjusted back to normal by recarbonation, where is

CO2 bubbled into the water. This decreases the pH but
also adds carbonate to the water, which may cause some
residual calcium hardness to precipitate as calcium
carbonate.
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Ion Exchange
• involves replacement of the unwanted ions in solution

with ions of a different species that are attached to an
insoluble resin.
• can be used to remove nitrate ions, metal ions, and other
contaminant ions as well as the ions responsible for
hardness.
• Laboratory quality deionized water is obtained in this way,
but too expensive to use in municipal treatment plants.
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Ion Exchange
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Regeneration of resin
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BITS Pilani
Hyderabad Campus
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Water and Wastewater Treatment

• The removal of ions that cause hardness is called

• Majority of treatment systems that employ softening are

• a number of surface water sources with a groundwater

• Hardness in natural waters comes from the dissolution of

• Calcite and dolomite react with the carbonic acid to form

Two components of total hardness may also be termed in terms of

• Those associated with HCO3- anion (called carbonate hardness, CH)

• Found by experimentally determining how much acid it takes to

• At a pH of 8.3 most of the carbonate

• Above a pH of 12.3, essentially all of the

• Carbonate hardness is defined as

• Carbonate hardness is often

• If the alkalinity is equal to or

• A water has an alkalinity of 200 mg/L as CaCO3 . The

• Noncarbonate hardness is called permanent hardness

• Primary purpose of lime-soda softening by municipal water treatment

• But now reduced with the introduction of synthetic detergents and

• Other substantial benefits include removal of heavy metals,

• Also removes arsenic, chromium, iron, lead, manganese, and mercury

• To soften the water, an ion in Equilibrium of solid and dissolved species of

equilibrium is selected to Mineral Solubility, mg/L as at 00C

magnesium so the reaction Calcium chloride 336000

precipitate is CaCO3. In the Magnesium sulphate

– By boiling. Heating drives the CO2 out of solution and the pH

• Has practical limitations in large sale implementation

– Adding lime (only CH or temporary hardness is removed)

𝐶𝑎(𝐻𝐶𝑂3)2 + 𝑪𝒂(𝑶𝑯)𝟐 → 2𝐶𝑎𝐶𝑂3 ↓ +2𝐻2𝑂

𝑀𝑔 𝐻𝐶𝑂3 2 + 𝑪𝒂 𝑶𝑯 𝟐 → 𝐶𝑎𝐶𝑂3 ↓ + 𝑀𝑔𝐶𝑂3 + 2𝐻2𝑂

• Precipitates (insoluble) removed by sedimentation

• Adding lime only removes carbonate Hardness, Soda ash is added to

• In the lime-soda ash process, hydrated (slaked) lime is added to the

• At this pH, calcium carbonate and magnesium hydroxide are

• Soda ash is further added to remove permanent hardness.

• Lime-soda softening cannot produce a water completely

• Minimum calcium hardness that can be achieved is about

• Many utilities will operate at total hardness goals of up to

• This excess varies between 20 and 40 mg/L as (0.4 – 0.8

• Although the reactions shown above use lime and soda

• Magnesium in excess of about 40 mg/L as CaCO3 forms

• Because of the expense of removing magnesium, we normally

• For magnesium removals between 20 and 40 mg/L as CaC03, we must

• For magnesium removals greater than 40 mg/L as CaC03, the excess

• Determine if any NCH need be removed. The amount of NCH that

The amount of soda to be added is 55.37 mg/L as CaCO3

• From the water analysis presented below, determnine

• the pH must be reduced to stop the precipitation reaction

• pH is adjusted back to normal by recarbonation, where is

• involves replacement of the unwanted ions in solution

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