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English definition

The soap consuming capacity of water. It is


traditional measure of the ability of water to
react with soap to produce lather or foam.
Technical definition
The presence of high mineral content of
divalent cations mostly calcium, magnesium
and iron ions.
 Calcium usually enters the water as either Calcium Carbonate
(CaCO3), in the form of limestone and chalk, or Calcium
Sulphate (CaSO4), in the form of other mineral deposits.
 The predominant source of Magnesium is Dolomite
(CaMg(CO3)2).
 Calcium is dissolved in water as it passes over and through
limestone deposits. Magnesium is dissolved as water passes
over and through dolomite and other magnesium bearing
formations. Because groundwater is in contact with these
geologic formations for a longer period of time than surface
water, groundwater is usually harder than surface water.
 Industries also discharge their effluent waters which may
have high concentrations of Ca2+ and Mg2+ into surface waters
like rivers and lakes and this increases the hardness of the
water.
 There are two types of hardness:
 Temporary hardness
 Permanent Hardness
 Temporary hardness is caused by a combination of
calcium ions and bicarbonate ions in the water. It can
be removed by boiling the water or by the addition of
lime water (calcium hydroxide). Boiling promotes the
formation of carbonate from the bicarbonate and
precipitates solid calcium carbonate, leaving water that
is softer upon cooling.
 Temporary hardness its due to certain conditions of
temperature and Carbon dioxide, by manipulating
these conditions we can remove temporary hardness.
 The following is the equilibrium reaction when calcium
carbonate (CaCO3) is dissolved in water:
 CaCO3(s) + CO2(aq) + H2O → Ca2+(aq) + 2HCO3-(aq)

 Upon heating, less CO2 is able to dissolve into the
water. Since there is a deficiency of CO2, the
reaction cannot proceed from left to right. Instead
the reaction is forced to the left (that is products to
reactants) to re-establish equilibrium, and solid
CaCO3 forms. Boiling the water will remove the
hardness as long as the precipitated CaCO3 is
removed e.g. by decantation. After cooling, if
enough time passes, the water will re-absorb CO2
from the atmosphere and the reaction will again
proceed from left to right, allowing the CaCO3 to
re-dissolve.
 Permanent hardness is hardness (mineral
content) that is cannot be removed by boiling.
It is usually caused by the presence of calcium
and magnesium sulphates and/ or chlorides
Condition range
Soft 0-60mg/l
Moderately hard 61-120mg/l
Hard 121-180mg/l
Very hard >180mg/l
Basically it is the precise mixture of minerals
dissolved in water, together with the water’s pH
and temperature that determines the behavior of
hardness.
 These have been categorised into problems in
the domestic setting and problems in the
industrial setting.
 Hard water causes scaling, which is the left-over mineral
deposits that are formed after the hard water has
evaporated. This is also known as lime scale. The scale can
clog pipes , ruin water heaters , coat the insides of tea and
coffee pots, and decrease the life of toilet flushing units
 Hardness reduces the life of fabrics (clothes, blankets etc.).
Even with soft water, washing fabrics causes the fibers in
clothing to break down, eventually leading to weak and
easily torn clothing with repeated washings. Thus, more
washing generally equals less longevity with clothing.
Having hard water speeds up this effect and further reduces
the overall lifespan of the clothes.
 More water is required for laundry as the soap solutions
form a white precipitate (scum)

 Insoluble salt residues that remain in hair after
shampooing with hard water tend to leave hair
rougher and harder to untangle.
 Bathing with soap in hard water leaves a film
of sticky curd on the skin.
 Soap curds deposit on dishes, bathtubs and
showers, and all water fixtures.
 Cooking-boiling point of water is increased
because of the presence of salts hence more
energy and time wasted.
 Hard water causes scaling. The scale can clog pipes
and ruin water heaters.
 Industries like soft drink manufacturers, paper
manufacturers and pharmaceuticals need a certain
level of hardness and so if the water is hard
beyond their required level they have to treat.
 In sugar processing industries water containing
sulphates, nitrates, alkali carbonates cause
difficulties in crystallisation of sugar. Moreover the
sugar so produced may be deliquescent.

 Originally water hardness was understood to be
measurement of the capacity of water to
precipitate soap, chiefly by the Calcium and
Magnesium ions present. Total hardness is defined
as the sum of the Calcium and Magnesium
concentrations, both expressed as Calcium
Carbonate, in mg/l. It may range from zero to
hundreds of mg/l, in terms of Calcium Carbonate,
depending on the source and treatment to which
the water has been subjected. It is an important
parameter to consumers, both domestic and
industrial.
Laboratory procedure
 Equipment required: Standard glassware including burettes and
conical flasks

Method A, Calcium Ca2+


 Pipette 50ml into a 100ml conical flask.
 Add 2ml of NaOH solution using a tilt measure or dispenser.
 Add approximately 0.1-0.2g of MUREXIDE/NaCl indicator using
a clean micro spatula
 Titrate immediately with 0.01M EDTA mixing continuously until
the colour changes from pink to purple.
 Note the initial and final burette readings on your result sheet and
calculate the EDTA used.
 Calculate the Calcium concentration and calcium hardness using
the following formulae:
 1 mole EDTA = 1 mole Ca2+ (40.08g)
 1 litre of 0.01M EDTA = 0.01 mole Ca2+(0.4008g)
 V2 ml of EDTA = (V2 / 1000) x 0.4008g Ca2+

 Ca2+ + EDTA4- = Ca(EDTA) 2-

 Calculating moles of EDTA
 M=mol/vol
 mol = MxV
 but M=0.01mol/l
 Volume of EDTA = 6.4ml obtained from titration
 n= 6.4/1000 x 0.01 identical to Ca2+
 =64X10-6mol
 m=n x MR = 64x10-6 mol x (40 g/mol) =0.00256g
 M(mg) = 0.00256g x 1000 (mg/g)
 = 2.56mg
 Conc = 2.56mg/50ml = 0.0512mg/ml

 Concentration in 1000ml
 Conc = 0.0512mg/ml x 1000

 =51.2mg/l
 Mass of CaCO3 =n x MR =64x10-6mol x 100.1g/mol
 =0.0064g
 Mass of CaCO3 (mg) = mass (g) x1000mg/g=0.064g x1000=6.4mg
 Conc= 0.128mg/ml x 1000ml/l =128mg/l

 1. Pipette 50ml sample into a 100ml conical flask
 2. Add 2ml ammonia/ ammonium chloride buffed
using a tilt measure dispenser
 3. Add 0.1-0.2g mix of ERIOCHROME BLACK
T/NaCl indicator using micro spatula.
 4. Titrate immediately with 0.01M EDTA mixing
continuously until the colour changes from pink to
purple.
 5. Note the initial and final burette readings on
your result sheet and calculate the EDTA used
(V2).
 6. Calculate the total hardness and the magnesium
concentration using the following formulae:
 To calculate the concentration of magnesium it
is necessary to find the titration value of EDTA
for Calcium in the same volume of sample
hardness value of EDTA as determined by the
following method.
 Magnesium as Mg2+= [(V2-V1) x 1000 x 0.01 x
24.3]/ x

 e.g for V2 =10.5ml, V1= 6.4ml and x=50


 Concentration of Mg2+Calculation

 0.01mol (EDTA)/L x (V2 - V1) ml/(1000ml/l) x (1mol Mg2+
/1mol EDTA) x (24.3g/mol) x (1000mg/g) x (1000ml/50ml)

 [Mg2+]=19.93mg/l
 =20mg/l as Mg2+
 Total Hardness in Calcium Carbonate terms =2.5[Ca2+] +
4.117[Mg2+]

 To express Mg2+ concentration as CaCO3, the following
equation can be used
 Mg2+ as mg/l x 4.117=mg/l Mg as CaCO3
 Eg 20 mg/l Mg as Mg2+ =82mg/l as CaCO3
There are three main types of softening processes
 Chemical precipitation

 Ion exchange

 Boiling
• Temporary hardness is the one which can be removed by
boiling mainly because it is made up of a combination of
calcium and bicarbonate ions in the water.
• Boiling promotes the formation of carbonate from the
bicarbonate and precipitates solid calcium carbonate,
leaving water that is softer upon cooling.
Ca2+(aq) + 2HCO3-(aq) ↔ CaCO3(s) + CO2(aq) + H2O
• Upon heating, less CO2 is able to dissolve into the water.
Since there is a deficiency of CO2, the reaction cannot
proceed from right to left.
• Boiling the water will remove the hardness as long as the
precipitated CaCO3 is removed e.g. by decantation. After
cooling, if enough time passes, the water will re-absorb CO2
from the atmosphere and the reaction will again proceed
from right to left, allowing the CaCO3 to re-dissolve.
• The basic principle that works in ion exchange is
exchange of ions responsible for hardness mainly Ca2+
and Mg2+ for sodium or potassium, thereby effectively
reducing the concentration of hardness minerals to
tolerable levels and thus making the water softer.
• An ion exchange water softener unit with beads uses
sodium chloride (table salt) for ion exchange process.
• As the hard water passes through and around the
beads, the hardness mineral ions are preferentially
adsorbed, displacing the sodium ions.
Ca2+ - {Cat(s)}2 + 2Na+ + 2Cl- → 2Na+ - {Cat(s)} + Ca2+ +
2Cl-
• The beauty of ion exchange is that the softening of
water does not require the removal of all ionic solutes,
just those cations responsible for water hardness.
• Sodium ion at low concentrations is harmless in water
to be used for most purposes, and sodium chloride is a
cheap and convenient substance with which to
recharge the cation exchangers.
• When the bead or sodium zeolite has a low
concentration of sodium ions left, it is exhausted, and
can no longer soften water. The resin is recharged by
flushing (often back flushing) with salt water.
• Sodium chloride is not the only compound with ion-
exchange properties there are zeolites or aluminum
silicate minerals , potassium chloride and synthetic ion
exchange resins.
 This process involves the addition of slaked
lime(Calcium Hydroxide –Ca(OH)2) to a hard
water supply to convert the hydrogen
carbonate hardness to carbonate which
precipitates and can be removed by filtration:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 +2H2O.
 The addition of sodium carbonate also
permanently softens hard water containing
Calcium Sulphate, as the Calcium ions form
Calcium Carbonate which precipitates out and
potassium sulphate is formed which is soluble.
The calcium carbonate that is formed sinks to
the bottom. Sodium sulphate has no effect on
the hardness of water.
 CaSO4 + Na2CO3 → CaCO3 + Na2SO4
Calcium sulphate + → Calcium carbonate +sodium
sulphate
 Mg(HCO3)2 + Ca(OH)2 → MgCO3 +2H2O
Magnesium bicarbonate + lime → Calcium carbonate
+ water
 MgSO4 +Ca(OH)2 →CaSO4 + Mg(OH)2
Magnesium sulphate + Calcium Hydroxide→Calcium
sulphate+Magnesium hyroxide
 CO2 + Ca(OH)2 → CaCO3 + H2O
Carbon dioxide + Calcium hydroxide → Calcium
Carbonate+water
 Assuming the influent water sample contains
200mg/l of Total hardness as (Calcium carbonate)
and the effluent water contains a total hardness of
100mg/l as Calcium Carbonate. The water
treatment plant recieves 10Ml/d

 Ca(HCO3) + Ca(OH)2 2 CaCO3+2H2O

 m(CaCO3) = 100mg/L x 100x106L/d


 = 100 x 108 mg/d
 = 100 x 105 g/d
𝑚
 𝑛=
𝑀𝑟
 n= 10 x 108/100.1
 = 9.99 x 103 mol (CaCO3)/d x 1mol (
Ca(OH)2)/2 mol CaCO3
 = 4.995 x 103 mol ( Ca(OH)2/d
 Mass of Lime required per day
 m= n x MR(Ca(OH)2)
 = (4.995 x 103) x 74.1
 =370.13 x 103 g(Ca(OH)2)/d
 = 370.13 Kg(Ca(OH)2)/d