Water Quality

Hardness of Water
 Hardness
• The term hardness is used to characterize a water
that does not lather well, cause a scum in the
bath tub, and leaves hard, white crusty deposits
(scale) on coffee pots, tea kettles, and hot water
heaters.
• The failure to lather well and the formation of
scum on bath tubs is the result of the reaction of
calcium and magnesium with soap.
– Ca2+ + (soap)- Ca(soap)2(s)
• Therefore soap cannot interact with the dirt on
clothing
• Hardness is defined as the sum of polyvalent
cations in consistent units.
• The common units are mg/L as CaCO3 or
meq/L.
• The predominant polyvalennt contributors to
hardness are calcium and magnesium
The natural process by which water
becomes hard
 Type of Hardness
• As calcium and magnesium predominate,
therefore the total hardness (TH) of water is
considered as sum of these elements:
– TH = Ca2+ + Mg2+
• Total hardness is also broken down into two
components
– That associated with the HCO3- anion called the
carbonate hardness
– That associated with other anions called non
carbonate hardness
– Therefore: TH = CH + NCH
 Carbonate Hardness
• CH is defined as the amount of hardness equal to
the total hardness or the total alkalinity,
whichever is less.
• It is also called as the temporary hardness
because it can be removed by heating the water.
• When pH is less then 8.3, HCO3- is the dominant
form of alkalinity, so the total alkalinity is taken as
equal to the amount of HCO3-.
 Noncarbonate Hardness
• It is defined as the total hardness in excess of
alkalinity.
• If the alkalinity is greater or equal to the total
hardness, then there is no noncarbonate
hardness.
• NCH is called as the permanent hardness
because it is not removed when water is
heated.
 Bar Chart of Water Composition
• To understand the process of softening bar chart
of water composition is used.
• By convention, bar chart is constructed with
cations in the upper bar and anions in the lower
bar.
• In the upper bar calcium is placed first and
magnesium second, other cations follow them
without any specified order
• In the lower bar bicarbonates are placed first and
other anions are placed without any specific
order.
 Example
• Given the following analysis of a groundwater,
construct a bar chart of the constituents,
expressed as CaCO3.
Ion mg/L as ion
Ca2+ 110
Mg2+ 6
Na+ 20
HCO3- 280
SO42- 52
Cl- 42
 Solution
• Convert the concentrations of ions into CaCO3
equivalent by the formula:
– mg/L as CaCO3 = mg/L ion x (EW CaCO3 / EW ion)
Ion mg/L as ion EW CaCO3 / mg/L as
EW ion CaCO3
Ca2+ 103 2.5 258
Mg2+ 5.5 4.12 23
Na+ 16 2.18 35
HCO3- 255 0.82 209
SO42- 49 1.04 51
Cl- 37 1.41 52
• Total cations = 316 mg/L as CaCO3, of which
281 mg/L as CaCO3 is hardness
• Total anions = 312 mg/L as CaCO3 of which the
carbonate hardness is 209 mg/L as CaCO3
• The discrepancy between the cations and
anions show that there were some other ions
which were not analyzed.
• Construct the bar graph according to scale.
Relationship among TH, CH and NCH
by bar chart
 Example
• A water has an alkalinity of 200 mg/L as
CaCO3. The Ca2+ concentration is 160mg/L as
the ion, and the Mg2+ concentration is 40mg/L
as the ion. The pH is 8.1. Find the total,
carbonate, and noncarbonate hardness?
 Softening Process
• Softening of water sample can be
accomplished by either
– The lime-soda process
• or by
– The ion exchange method.
 Lime-Soda Softening
• In lime-soda softening it is possible to
calculate the chemical doses necessary to
remove hardness.
• The chemical processes used to soften water
are a direct application of law of mass action.
• We increase the concentrations of CO32-
and/or OH- by the addition of chemicals and
derive the reactions given in next slide to the
right.
• In Lime-Soda softening method the Ca and Mg
ions are precipitated on the basis of the
following two solubility reactions:

OR
• In order to precipitate CaCO3, the pH of the
water must be raised to 10.3
• To precipitate magnesium, the pH must be
raised to about 11.
• If there is not sufficient naturally occuring
bicarbonate alkalinity then we must add CO32-
to 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 NCH than CH
because we must add another chemical to
provide CO32-, therefore we leave as much
NCH in the water as possible.
• Bicarbonate alkalinity is converted to
carbonate by the addition of hydroxyl ions.
• The common source of hydroxyl ion is
Ca(OH)2, which is obtained by the slaking of
quick lime (CaO).
• When carbonate ions must be supplied, the
most common chemical chosen is sodium
carbonate (Na2CO3), commonly referred as
soda ash or soda.
 Softening Reactions
• Softening reactions are regulated by
controlling the pH.
– First raised to precipitate CaCO3
– Then if necessary, is raised to precipitate Mg(OH)2
• Finally if necessary CO32- is added to
precipitate the NCH.
• Six important softening reactions are
discussed further in next slide.
Neutralization of Carbonic Acid

– In order to raise pH, first any free acid which may be

present in water is neutralized.
– CO2 is the principal acid present in unpolluted,
naturally occurring water.
– No hardness is removed in this step.
Precipitation of CH due to Calcium

• In order to precipitate calcium carbonate, pH

must be raised to 10.3.
• To achieve this pH all bicarbonate ions are
converted to carbonate ions.
Precipitation of CH due to Magnesium
• In order to remove the carbonate hardness that
results from the presence of magnesium, lime
must be added to achieve a pH of 11.
• The reaction may be considered to occur in two
stages:
i. All of the bicarbonate ions are converted, but
MgCO3 is soluble in water.

ii. With the addition of more lime hardness due to Mg

is removed.
 Removal of NCH due to Calcium

• For this any increase in pH is not required,

but additional carbonates are provided in the
form of soda ash
Removal of NCH due to Magnesium

• If it is required to remove the noncarbonate

hardness due to magnesium, both lime and soda
ash must be added.

• Although the Mg is removed but there will be no

change in hardness because the calcium is still in
solution, therefore the last step will be again the
removal of Ca.
 Removal of Calcium

• To remove Ca soda must be added.

• This is the same reaction as the one to remove

NCH due to Ca.
 Reactions in summarized form
Neutralization of Carbonic Acid

Precipitation of Carbonate Hardness

Precipitation of Noncarbonate Hardness due to Calcium

Precipitation of Noncarbonate Hardness due to Magnesium