HARDNESS OF WATER

 Hardness of water is that characteristic

prope y which prevents lathering of soap
easily.
 This is due to presence of ce ain salts of
calcium, magnesium and other heavy
metals dissolved in water.
 SOFT WATER
 Water that gives lather with soap easily and
readily is known as So water.
 No Ca and Mg salts.
 Cleansing quality of soap not depressed.
 Less fuel and time required in cooking
 HARD WATER
 Hard water forms scum when it comes into
contact with soap.
Presence of Ca and Mg salts.

Cleansing quality of soap depressed.

More fuel and time required in cooking, as

hardness causing salts elevated water boiling

Reaction of Soap (sodium stearate) with CaCl2 and MgSO4

2C17H35COONa + CaCl2 → (C17H35COO)2Ca↓ +2NaCl

Calcium Stearate

2C17H35COONa + MgSO4→(C17H35COO)2Mg↓ +Na2SO4

Magnesium Stearate
 TYPES OF HARDNESS
1. Temporary hardness:
 It is caused by the presence of dissolved bicarbonates of
calcium, magnesium and other heavy metals.
 Temporary hardness is easily removed by boiling.

 On boiling bicarbonates are decomposed into insoluble

carbonates or hydroxides.
 Also known as carbonate hardness or alkaline hardness
2. Permanent hardness
 It is due to the presence of chlorides and sulphates of
calcium, magnesium and other heavy metals.
 Unlike temporary hardness, permanent hardness is not
removed on boiling
 Also known as non-carbonate hardness or non alkaline
hardness
 Total hardness = Temporary hardness + permanent
hardness
 DEGREE OF HARDNESS
• Expressing hardness of water in equivalents of
CaCO3
• The choice of CaCO3 is due to its molecular
weight 100 (M) (equivalent weight M/2 = 50)
and it is the most insoluble salt that can be
precipitated in water treatment.
 DEGREE OF HARDNESS
• Equivalents of CaCO3 =
Mass of hardness causing substance (mg/l) x multiplication factor
multiplication factor
= 100/ (molecular weight of hardness causing substance)
OR
= 50/ (equivalent weight of hardness causing substance)
Eg: Ca(HCO3)2
Chemical equivalets of Ca(HCO3)2 = 81, Molecular weight = 162
 UNITS OF HARDNESS
 1 ppm = 1 pa of CaCO3 present in 106 pa s of water
 1 mg/lit = 1 mg of CaCO3 present in 1 lit of water

 oCl = pa s of CaCO equivalent hardness per

3
70000 pa s of water
 oFr = pa s of CaCO3 equivalent hardness per

105pa s of water
Relationship between units:
 PROBLEMS ON HARDNESS
Example 1: A sample of water contains 33.3 mg of CaCl2 per liter.
Calculate the hardness of water sample in terms of CaCO3 equivalent.
Solution: 1 liter of water contains = 33.3 mg of CaCl2
= 33.3 × (100 /111) mg of CaCO3 eq.
= 30 mg of CaCO3 eq.
Hence, hardness of water sample = 30 mg /l CaCO3 eq.
• A sample of water on analysis is found to contain the following
impurities.
Impurity Ca(HCO3)2 Mg(HCO3)2 CaSO4 MgSO4
Quantity mg/L 4 6 8 10

M.wt 162 146 136 120

Calculate the temporary, permanent and total hardness of

water in ppm, oFr and oCl.
Solution:
Constituent mg/L 100/M.wt CaCO3 equivalent
Ca(HCO3)2 4 100/162 0.617 X 4 = 2.47 mg/L
Mg(HCO3)2 6 100/146 0.684 X 6 = 4.11 mg/L
CaSO4 8 100/136 0.735 X 8 = 5.58 mg/L
MgSO4 10 100/120 0.833 X 10 = 8.33 mg/L
Determination of temporary Hardness:-
THS is due to presence of bicarbonates of Ca and Mg
THS = 2.47+ 4.11 =6.58 mg/L (or) ppm
As 1mg/L = 1ppm = 0.1 oFr = 0.07 oCl
Temporary hardness = 6.58 mg/L (or) ppm
= 6.58 x 0.1 =0.658 oFr
= 6.58 x0.07= 0.46 oCl
Determination of permanent hardness:-
PHS is due to presence of CaSO4 and MgSO4
Total hardness = Temporary Hardness + permanent
Hardness
=6.58 + 14.21 = 20.79 mg/L
= 20.79 ppm
= 20.79 x 0.1 = 2.079 oFr
= 20.79 x 0.07 = 1.4553 oCl
DETERMINATION OF HARDNESS - EDTA METHOD
Why hardness to be determined?
 Drinkable or not drinkable - (ISO- 200 mg/l)

 Applicable in industry or not

Boiler feed water hardness - (ASME - 0.3ppm

depend on pressure)
 Applicable in irrigation or not
Chemicals required:-
 EDTA

 Standard hard water

 Buffer solution of pH=10

 Unknown solution

 Eriochrome black-T
Glasswares required:-  Bure e, Measuring jar,
Conical flask, Pipe e
Role of EDTA ?
Ethylene diammine tetraacetic acid
 Complexing agent – form complexes with
metals like Ca2+, Mg2+
 Hexadentate ligand – six donor sites (Two
nitrogen lone pairs and four acetyl group)
 Disodium salt of EDTA using for lab purpose –
because of high purity and solubility
 Role of Eriochrome black-T (EBT) ?
Metal ion indicator – to determine end point
 The most common way to detect the end point in
EDTA titration is with a metal ion indicator.
 Metal ion indicators are compounds that change
colour when they bind to a metal ion to form complex.
 Eriochrome black-T is a metal ion indicator used in
EDTA titrations. Free state and combined state both
have different colours (pH dependent)
Role of Buffer solution (pH=10) ?
 Buffer solution is resistant to pH change
 Stabilize the system
 Buffer solution of pH 9-10 is using in EDTA
titration (at pH = 10, EBT colour is blue)
 16.9 g NH4Cl in 143 ml NH4OH
DETERMINATION OF HARDNESS - EDTA METHOD
Procedure:
Preparation of standard hard water
1g CaCO3 in 1L of H2O
OR
Preparation of standard solution
0.3g ZnSO4 in 100 ml
DETERMINATION OF HARDNESS - EDTA METHOD
Pa : 2: Standardization of EDTA
 Pipe e out 20ml of Standard hard

water (or ZnSO4 solution), into a

conical flask.
 Add 5ml (approx) of buffer
20 ml SHW +
solution and a few drops of 5 ml Buffer solution +
2-3 drops of Eriochrome
black-T = wine red colour
Eriochrome black-T indicator. The
solution a ains wine-red colour.
DETERMINATION OF HARDNESS - EDTA METHOD
Pa : 2: Standardization of EDTA:
 Titrate the contents of the conical
flask against the solution of EDTA
solution.
 Stop the addition of solution from
the bure e when the colour of the
solution in the conical flask
changes from wine-red to blue.
DETERMINATION OF HARDNESS - EDTA METHOD
 Note the bure e reading and repeat the
titration to get concurrent results. Let the
volume of EDTA as V2.
 M1V1 = M2V2
 M1 = (molarity of standard hard water) or
standard ZnSO4 solution
 V1 = volume of standard hard water or standard
 M2 = molarity of EDTA solution =?
 V2 = volume of EDTA solution (Bure e reading)
DETERMINATION OF HARDNESS - EDTA METHOD
Pa 3: Determination of Total Hardness of Test Sample of
Water
 Pipe e out 20ml of unknown
sample of water in the conical
flask.
 Add 5ml (approx) of buffer and 3
20 ml test sample +
to 4 drops of Eriochrome black-T 2-3 drops of eriochrome
5 ml Buffer sol u tio n +
black-T = wine red colour
indicator. The solution a ains
wine-red colour..
DETERMINATION OF HARDNESS - EDTA METHOD
Pa 3: Determination of Total Hardness of Test Sample of
Water
 Titrate the contents of the conical flask
against the solution of EDTA solution.
 Stop the addition of solution from the
bure e when the colour of the solution
in the conical flask changes from wine-
red to blue. Let the volume of EDTA as
V2
M2V2 = M3V3
M2 = molarity of EDTA solution
 V2 = volume of EDTA solution (Bure e reading in this

titration)
 M3 = molarity of unknown water

 V3 = volume of unknown water (20 ml)

Total Hardness = M3 x 100 x 1000 ppm

IV. Determination of Permanent Hardness of
Unknown Water Sample:
 20ml of boiled water in conical flask + 5ml buffer

+ few drops Eriochrome black-T indicator. The

solution a ains wine-red colour.
 Titrate the contents against EDTA solution. Stop

the addition, when the colour changes from

wine-red to blue. Let volume of EDTA consumed
M2V2 = M4V4
M2 = molarity of EDTA solution
V2 = volume of EDTA solution (Bure e reading)
M4 = molarity of boiled water
V4 = volume of boiled water (20 ml)
Permanent hardness = M4 x 100 x 1000 ppm

Total hardness = Temporary hardness + permanent

hardness.
Temporary hardness = Total Hardness – permanent
DETERMINATION OF HARDNESS - EDTA METHOD
Principle:-
20 ml of SHW or EB-T forms unstable wine red
ZnSO4 + 5 ml Buffer complex with Ca+2 and Mg+2 ions
solution + 2-3 drops
M+2 + EBT → [ M-EBT ]
of eriochrome wine red complex
black-T = wine red (unstable)
colour M = Ca+2 and Mg+2 ions of hard
water
Principle:-
The stability of a metal indicator complex is less
than that of metal EDTA complex. During titration
EDTA combines with Ca+2 or Mg+2 ions of M-EBT
complex and forms stable colourless [M-EDTA]
complex. Blue colour of the solution is due to free
EBT. EBT at pH~10 will give blue colour
[M-EBT]compl
Wine red ex + EDTA → [M-EDTA] compl
Colourlexess
+ EBT
blue colour
M = Ca+2 and Mg+2 ions of hard water
Potable/Domestic/Municipal Water and its specifications
The water supplied by municipality should be fit for human
consumption. It should satisfy the following requirements:
 It should be colourless, odourless, and pleasant to taste.

 Turbidity should not exceed 10 ppm. TDS should not exceed 500
ppm.
 Hardness nearly 120 ppm

 It should not be very alkaline (pH 8.0).

 It should be free from dissolved gases.(H2S,CO2)

 It should be free from objectionable minerals such as Pb, As, Cs, Mn

 MUNICIPAL WATER TREATMENT
Stages:
1. Screening
2. Sedimentation
3. Coagulation
4. Filtration
5. Disinfection(chlorination & ozonization)
As required, other steps wil be added, depending on the
chemistry of the treated water.
 1. Screening: Water is allowed to pass through the mesh
screens whereby large floating ma ers are removed
 2. Sedimentation:
Water is allowed to stand undisturbed for 2−5 h in big se ing tanks.
Suspended pa icles se le down due to gravity and clear water raises
which can be drawn out with the help of the pumps.
Disadvantages
• It requires long big tanks.
• It takes a long time.
• It removes only 70−75% suspended ma er.
•If water contains clay and colloidal impurities, coagulants
are added before sedimentation.
 3. Coagulation:
Colloidal pa icles from the water are removed by adding
coagulants such as alum, Al2(SO4)3, NaAlO2, etc., which
produces flocs. Smaller pa icles gather together to form
bigger flocs. They can be easily removed by filtration. Some
bacteria and colour are also removed.
NaAlO2 + 2 H2O → Al(OH)3↓ + NaOH
Coagulation
4. Filtration:
Colloidal ma er, bacteria, micro-organism are removed.
Water is passed through a large area sand bed. The filter
may be pressure filter or gravity filter.
5. Sterilization/disinfection:
Water a er passing through sedimentation, coagulation, and
filtration still contains a small percentage of pathogenic micro-
organisms such as bacteria. Its removal can be achieved by
sterilization
The chemicals used for killing bacteria are called disinfectants.
Water can be sterilized by the following methods:
(a)Boiling: Water is boiled for 10−15 min, where most of the
pathogenic bacteria are killed.
(b)By adding bleaching powder. Bleaching powder (calcium
hypochlorite) in calculated amount is added to water and allowed to
 Cl2 + H2O → HCl + HOCl
HOCl + Germs → germs are killed

(c) By chlorination
Cl2 + H2O → HCl + HOCl
HOCl + Germs → germs are killed
The quantity of chlorine to be added is impo ant.
Break-point Chlorination (Free residual chlorination):
Significance: The disinfection wil not complete if chlorine is
insufficient. If excess chlorine is added, it causes irritation, bad taste,
and odour. In order to understand the amount of sufficient
chlorine to be added to untreated water break point chlorination is
calculating
It involves in addition of sufficient amount of chlorine to oxidize
a)Organic ma er b) Reducing substances
c) Free ammonia
The dosage of applied chlorine and the free Chlorine can be
 Break point chlorination

Free chlorine residual = Cl2, HOCl, Ocl-

Combined chlorine residual = chloramines, chloro-organic compounds
Total chlorine residuals = Free chlorine + Combined chlorine
 Stage I: The water reacts with reducing compounds in the water. These
compounds use up the chlorine, producing no chlorine residual.
 Stage II: The chlorine reacts with organic ma er and ammonia
naturally found in the water. Some combined chlorine residual is
formed – chloro organic compounds and chloramines. In this stage it
doesn’t undergo oxidation. NH3 + Cl2 NH2Cl
 Stage III: If again chlorin dosage is increased, oxidation of chloro
organic compound and chloramines occurs.
NH2Cl NHCl2 NCl3 N2
Therefore amount of free residual chlorine also decreases. When the
oxidative destruction is complete, it reaches a minima. This is the break
 Stage IV: A er minima, the added chlorine is not used in any
reaction. Thus residual chlorine increasing in direct propo ion to
added chlorine.
The breakpoint is the point at which the chlorine demand has
been totally satisfied - the chlorine has reacted with all reducing
agents, organics, and ammonia in the water.
When more chlorine is added a er the breakpoint, the chlorine
reacts with water and forms hypochlorous acid (free residual
chlorine) in direct propo ion to the amount of chlorine added.
This process is known as breakpoint chlorination.
(e) Disinfection by ozone:
O3 is prepared by passing silent electric discharge through
cold, dry O2. It is highly unstable.
O3→ O2 + (o)
O3 is an excellent, harmless disinfectant. It is highly unstable
and decomposes to give nascent oxygen (o). (o) is a powe ul
oxidizing agent. It oxidizes organic ma er in water and also kil s
bacteria.
Determination of Fluoride ion by ion selective electrode method
Significance:
1.Fluoride ions are essential for the formation of tooth enamel.
2.But excess amount of fluorine intake leads to fluorosis. In order to
understand the fluorine level in water is within permissible limit or
not, fluoride ion selective electrode method is using.
3.According to World Health Organization, standard rate of fluoride
of drinking water is 0.5–1 ppm
A fluoride selective electrode is a type of ion selective electrode
sensitive to the concentration of the fluoride ion. A common
example is the lanthanum fluoride electrode.
Apparatus
Potentiometer, Reference electrode, Fluoride ion selective electrode
Procedure
1.Prepare different standard solutions of fluoride ions (0.5mg/l, 1mg/l etc.
).
2.Inse both electrodes (Reference electrode, Fluoride ion selective
electrode) of potentiometer in each solution and find out the emf
(potential difference (mV)).
3.Plot a graph with log of concentration on x axis and emf on the y
axis.
4.We can find out the concentration of unknown by drawing a line
Fluoride ion selective electrode-Principle
1.Membrane: The lower end of the tube is closed by ion-selective
membrane consists of a single crystal of lanthanum fluoride LaF3
doped with europium to improve its electrical conductivity.
2.Electrode is made of silver
3.Electrolyte is a solution with low concentration of fluoride ions.
4.When the electrode is immersed in the sample solution, fluoride
ions can effectively diffuse through membrane channels in the LAF3
crystal. Because of this a pd is created across the ion-selective
membrane. This emf (pd) measured relative to standard reference
electrode
Fluoride ion selective electrode
 Defluoridation of water-Nalgonda Technique
Removal of excess fluorides from water can be done by Nalgonda
Technique. Sodium aluminate or lime is added first into the water while
stirring. The addition of bleaching powder (disinfection) and alum
follows. The flocs formed are allowed to se le down and filtered.
Steps
1.Mixing: Add sufficient amount of lime and alum or sodium aluminate
to the sample water
2.Flocculation- This is the precipitation step. In this step added lime
(CaO) and sodium aluminate reacts with fluorine and forms
corresponding calcium fluoride (CaF2) and aluminium fluoride (AlF3) as
3. Sedimentation: Formed precipitate allowed to se le down
4. Filtration: Filtrate the solution and separate the precipitate
5. Disinfection and distribution: To the filtered solution add bleaching
powder as disinfectant and a er treatment water ready for the
distribution. CaOCl2 + H2O → Ca(OH)2 + Cl2
Cl 2
MIXING
+ H 2O → HCl + HOCl
FLOCCULATION
, HOCl + Germs → germs are kil ed
SEDIMENTATION

DISTRIBUTION DISINFECTION FILTRATION