TLK-209 LABORATORIUM LINGKUNGAN I
HARDNESS anda ALKALINITY
(Basic water treatment)
This short section touches on some aspects of water
softening and water stabilization, and no more than
a very simplified introduction to water softening. In
this section only calcium and magnesium are
considered which in reasonable for most waters.
The soluble salt of calcium and magnesium
commonly found in water cause hardness.
Hardness forms insoluble precipitates with soap
and requires more soap to be used to obtain lather.
Soap normally the sodium salt of a fatty acid. When
soap added to water containing polyvalent metal
ions the salt formed by the polyvalent metal ions
and the fatty acid precipitates, forming a scum.
Only when all the polyvalent metal ions have
precipitated will a lather form.
Thus, hardness is caused by dissolved polyvalent
metal ions. In practice it is only bivalent metal
ions that occur to significant extent in normal water,
notably calcium and magnesium.
Waters that are high in bivalent ions can also
cause scaling problems in hot-water systems. It also
causes boiler scale. In the past, it was common to
soften hard water. However, there is a view that soft
waters are associated with heart disease and thus
softening is less common now.
Hardness is defined by the total concentration of
bivalent metals ions present-but expressed as mg
CaCO3/liter.
This is the equivalent calcium carbonate
concentration that would have the same effect as the
bivalent metal ions actually present. Calcium
carbonate has an equivalent weight of 50, and thus
the equivalent hardness due to a concentration M of
a bivalent metal ions is:
Hardness as CaCO3 = M (mg/l) x 50
Equivalent Wt of M
The total hardness:
Is calculated by summing the result of the above
calculation for all bivalent metal ions present. It can
also be measures directly by titration.
Classification of hardness:
1. carbonate hardness
2. non carbonate hardness
Where the metal ions are associated with
bicarbonate, boiling will result the bicarbonate
being converted to carbonate and precipitating as
calcium and magnesium carbonate.
NOTE:
Magnesium carbonate is
- soluble in cold water but
- less soluble in boiling water and thus is largely
removed by boiling
Where the metal ions are associated with chloride,
sulfate, or other anions, with no carbonate present,
boiling will not precipitate the bivalent metal.
For this reason carbonate hardness is also referred to
as temporary hardness, an non carbonate hardness
as permanent hardness.
The most common cause of carbonate hardness is
water passing through chalk or limestone aquifer,
with non carbonate hardness often associate with
water passing through clay soils containing sulfates.
There are no hard and fast standards for hardness but
water with more than 200 mg CaCO3/l is normally
considered to be hard.
Water softening involves the removal of bivalent
metal ions. It is popular with consumers because it
reduces scum formation and scaling of kettles, and it
is needed for hot water heaters and boilers to
reduces or eliminate scale formation. For industrial
scale boilers and for power stations it is essential to
soften the water used.
There are two main ways to soften water:
1. removal of the bivalent ion by precipitation
Chemical precipitation is the process normally used in
potable water treatment.
2. replacement of the bivalent ions by sodium ions
using an ion exchange process.
3. Other less common options are:
- electrodalysis reversal (EDR)
- reverse osmosis optimised for softening.
The only circumstances where ion exchange or other
process might be used are where water contains a
high proportion of non-carbonate hardness, or the
hardness continually varies.
In industrial water treatment ion exchange is more
common on boiler feed waters.
Chemical Precipitation of hardness
If OH (as either lime or sodium hydroxide) added to
water containing carbonate hardness, the bivalent
metals will precipitate as either calcium carbonate
or magnesium hydroxide.
Where non-carbonate hardness is present, adding
lime and carbonate to the water also results in
precipitation of calcium carbonate or magnesium
hydroxide.
It is normal to use:
- calcium hydroxide (lime) as the source of
hydroxide, and
- sodium carbonate (soda or soda ash) as the source
of carbonate.
Thus the process used to remove both carbonate
and non-carbonate hardness is commonly referred
to as the lime-soda method. The proportion of lime
and soda requires depend on the composition of the
hardness.
Lime-soda method
I. Removal of carbonate hardness.
The first part of the lime-soda method considered
is the addition of the lime to precipitate carbonate
hardness.
Carbonate hardness is associated with carbonate
and calcium and magnesium ion present in water.
The initial reaction on adding lime is a reaction
between dissolved CO2 and the lime.
Assuming that the CO2 is dissolved as carbonic
acid, this is represent as:
This reaction does not affect the hardness but does
represent a lime demand that needs to be satisfied
before there is any softening.
Adding additional lime results in the precipitation
of calcium and magnesium.
Calcium is precipitated in a single-stage reaction:
Thus 1 mole of lime removes 1 mole of calcium
carbonate.
Magnesium is precipitated in a two stages reaction:
Notes:
In the 1st stage the bicarbonate is essentially
neutralized by the lime, with calcium bicarbonate
precipitating. Magnesium carbonate is soluble in cold
water (but is less soluble in hot water and thus is
largely removed by boiling).
In the 2nd stage addition of additional lime results in
the formation of insoluble magnesium hydroxide.
Thus 2 moles of lime are requires to remove 1 mol of
magnesium carbonate.
II. Removal of non carbonate hardness.
The 2nd part of the lime-soda method considered is the
addition of lime and sodium carbonate to
precipitate non-carbonate hardness.
Calcium non-carbonate hardness is removed by
adding sodium carbonate:
The calcium is precipitated as calcium carbonate,
with 1 mole of sodium bicarbonate of lime removing
1 mol of calcium non-carbonate.
Magnesium non-carbonate hardness is removed by
adding sodium carbonate and lime:
The magnesium is precipitated as a hydroxide,
with the hydroxide supplied by lime, and the sodium
carbonate required to remove the calcium added as
lime.
Thus one mole of lime and one and 1 mole of sodium
carbonate are required to remove 1 mole of
magnesium non-carbonate hardness.