4/2/2012

Hard water
• Hard water is the type of water that has high
mineral content (in contrast with soft water).
Hard and Soft Water • Hard water minerals primarily consist of calcium
(Ca2+), and magnesium (Mg2+) metal cations, and
sometimes other dissolved compounds such as
bicarbonates (HCO3-) and sulfates (SO42-).
• Calcium usually enters the water as either
calcium carbonate (CaCO3), in the form of
limestone and chalk, or calcium sulfate (CaSO4),
in the form of other mineral deposits.
1 2

Hard water Hard water

• The predominant source of magnesium is • Although water hardness usually only measures
dolomite [CaMg(CO3)2]. the total concentrations of calcium and
magnesium (the two most prevalent, divalent
• Hard water is generally not harmful. metal ions), iron, aluminium, and manganese
• The total water 'hardness' (including both Ca2+ may also be present at elevated levels in some
geographical locations.
and Mg2+ ions) is read as parts per million (ppm)
• Hardness in water can cause water to form scales
or weight/volume (mg/L) of calcium carbonate and a resistance to soap.
(CaCO3) in the water. • It is also water that doesn’t produce lather with
• Ppm (Ca) is usually defined as one milligram of soap solutions, but produces white precipitate
calcium carbonate (CaCO3) per litre of water (scum).

3 4

1
 4/2/2012

Temporary hardness Temporary hardness

• Temporary hardness is caused by a • The following is the equilibrium reaction when
combination of calcium ions and bicarbonate calcium carbonate (CaCO3) is dissolved in water:
ions in the water. • CaCO3(s) + H2CO3(aq) ⇋ Ca2+(aq) + 2HCO3-(aq)
• It can be removed by boiling the water or by • Boiling the water will remove hardness as long as
the addition of lime (calcium hydroxide). the solid CaCO3 that precipitates out is removed.
• Boiling promotes the formation of carbonate • After cooling, if enough time passes the water
from the bicarbonate and precipitates calcium
will pick up CO2 from the air and the reaction will
carbonate out of solution, leaving water that
again proceed from left to right, allowing the
is softer upon cooling.
CaCO3 to "re-dissolve" into the water.
5 6

Permanent hardness Permanent hardness

• Permanent hardness is hardness (mineral • Hard water causes scaling, which is the left
content) that cannot be removed by boiling. over mineral deposits that are formed after
• It is usually caused by the presence of calcium the hard water had evaporated.
and magnesium sulfates and/or chlorides in the
water, which become more soluble as the • This is also known as limescale.
temperature rises. • The scale can clog pipes, ruin water heaters,
• Permanent hardness can be removed using a coat the insides of tea and coffee pots, and
water softener or ion exchange column, where decrease the life of toilet flushing units
the calcium and magnesium ions are exchanged
with the sodium ions in the column.
7 8

2
 4/2/2012

Water Softening Water Softening

• A water softener reduces the dissolved calcium, • The most economical way to soften household
magnesium, and to some degree manganese and water is with an ion exchange water softener.
ferrous iron ion concentration in hard water
• A water softener works on the principle of cation • This unit uses sodium chloride (table salt) to
or ion exchange in which ions of the hardness recharge beads made of the ion exchange
minerals are exchanged for sodium or potassium resins that exchange hardness mineral ions for
ions, effectively reducing the concentration of sodium ions.
hardness minerals to tolerable levels and thus
making the water softer and giving it a smoother
feeling

9 10

Water Softening Water Softening

• As the hard water passes through and around • Temporary hardness, caused by hydrogen
carbonate (or bicarbonate) ions, can be removed
the beads, the hardness mineral ions are by boiling.
preferentially absorbed, displacing the sodium • Calcium bicarbonate, often present in temporary
ions. hard water, may be boiled in a kettle to remove
the hardness.
• This process is called ion exchange.
• In the process, a scale forms on the inside of the
kettle in a process known as "furring".
• This scale is composed of calcium carbonate.
• Ca(HCO3)2 → CaCO3 + CO2 + H2O

11 12

3
 4/2/2012

Water Softening Water Softening

• Hardness can also be reduced with a lime- • The addition of sodium carbonate also
soda ash treatment. permanently softens hard water containing
calcium sulfate, as the calcium ions form calcium
• This process involves the addition of slaked carbonate which precipitates out and sodium
lime (calcium hydroxide Ca(OH)2) to a hard sulfate is formed which is soluble.
water supply to convert the hydrogen • The calcium carbonate that is formed sinks to the
carbonate hardness to carbonate, which bottom.
precipitates and can be removed by filtration: • Sodium sulfate has no effect on the hardness of
water.
• Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Na2CO3 + CaSO4 → Na2SO4 + CaCO3
13 14

Ion-exchange resin Ion-exchange resin

• The water to be treated passes through a bed • As the water passes through the resin column,
of the resin. the hardness ions replace the hydrogen,
• Negatively-charged resins absorb and bind sodium or potassium ions which are released
metal ions, which are positively charged. into the water.
• The resins initially contain univalent hydrogen, • The "harder" the water, the more hydrogen,
sodium or potassium ions, which exchange sodium or potassium ions are released from
with divalent calcium and magnesium ions in the resin and into the water.
the water.

15 16

4
 4/2/2012

Ion-exchange resin Disadvantages of Hard Water

• Resins are also available to remove carbonate, • These "hardness ions" cause three major kinds
bi-carbonate and sulphate ions which are of undesired effects.
absorbed and hydroxyl ions released from the (1) metal ions react with soaps and calcium-
resin. sensitive detergents, hindering their ability to
lather and forming a precipitate
• Both types of resin may be provided in a single
water softener 2C17H35COONa + Ca2+ → (C17H35COO)2Ca + 2Na+

• Presence of "hardness ions" also inhibits the

cleaning effect of detergent formulations
17 18

Disadvantages of Hard Water Disadvantages of Hard Water

(2) calcium and magnesium carbonates tend to (3) Presence of ions in an electrolyte, in this
precipitate out as hard deposits to the surfaces of
pipes and heat exchanger surfaces. case, hard water, can also lead to galvanic
• The resulting build-up of scale can restrict water corrosion, in which one metal will
flow in pipes. preferentially corrode when in contact with
• In boilers, the deposits act as an insulation that another type of metal, when both are in
impairs the flow of heat into water, reducing the contact with an electrolyte
heating efficiency and allowing the metal boiler
components to overheat.
• In a pressurized system, this can lead to failure of
the boiler
19 20