Hardness

 Hardness in water is that characteristic , “Which

prevents the lathering of soap”

 Originally , it was defined as the soap consuming

capacity of water sample.

 This is due to presence in water of certain salts of Ca,

Mg, and other heavy metal ions like Al ,Fe and Mn.
Difference between Hard water and soft water
 Types of Hardness
It is of following types
1. Temporary Hardness
 It is caused by the presence of dissolved bicarbonates of Ca ,Mg
and other heavy metals.
 Thus ,the salts responsible for temporary hardness are Ca(HCO3)2
and Mg(HCO3)2
 Temporary hardness can be largely removed by boiling of water,
when bicarbonates are decomposed ,yielding insoluble carbonates
or hydroxides, which are deposited as bottom of vessel.
 Types of Hardness
2. Permanent Hardness
 It is due to presence of dissolved chlorides and sulphates of calcium ,
magnesium, iron and other heavy metals.
 Hence the salts responsible for permanent hardness are: CaCl2, MgCl2,
CaSO4, MgSO4,Al2(SO4)3 etc.
 Unlike temporary hardness,permanent hardness is not destroyed on boiling.
But it can be removed by like Lime soda process, Zeolite Process,Ion-
exchange process.
Units of Hardness
Units of Hardness and their inter relationship
 Degree of Hardness
 Although hardness of water is never present in the form of calcium carbonate
because it is insoluble in water , hardness is conveniently express in the terms of
equivalent amount (equivalents) of CaCO3.
 The reason for choosing CaCO3 as the standard for reporting hardness of water is
the ease in calculations as its molecular weight is exactly 100.
 Moreover, it is the most insoluble salt that can be precipitated in water treatment.
Multiplication factors of different salts
Numerical related to determination of Hardness
Q 1. A water sample contains 410 mg of CaSO4 per liter. Calculate the
hardness in terms of CaCO3 equivalents

Q 2. How many grams of MgCO3 dissolved per litre gives 84 ppm of

hardness?
EDTA
 Ethylene diamminetetra acetic acid is a tetra protic acid.
 Because of its limited solubility, it is not used directly. It is usually employed as the
soluble disodium salt dihydrate because it can be obtained in high state of purity
and is primary standard.

EBT
 Eriochrome Black T .
 It is typically metal-ion indicator.
 Sodium 1-(1-hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulphonate.
 Estimation of Hardness
Determination of hardness is important for industrial purpose
mainly, because it forms scale and sludge inside the boilers and
pipelines which reduces the capacity and efficiency of the boiler.

In present experiment hardness of water sample is determined by

EDTA-titration method. In this method different soluble complex
such as M-EBT and M-EDTA are formed hence it is also called as
complexometric titration method.

Disodium salt of EDTA is used during solution preparation as its

solubility is better than pure EDTA. pH of the reaction mixture is
maintain at 8-10 using ammonical buffer solution.

When indicator is added in water sample at pH 8-10, it reacts with

Ca and Mg ions present in water and forms M-indicator complex of
wine red colour. During titration EDTA first reacts with remaining Ca
and Mg ions in water and forms M-EDTA complex which is
colourless. When EDTA reacts with all the Ca and Mg ions it attacks
on the M-indicator complex and set the indicator free. This appears
as blue colour at end point.
•
 PROCEDURE
[A] Standardization of EDTA solution:

1. Wash, rinse and fill the burette with EDTA solution.

2. Take 20 mL of standard hard water sample into a conical flask.
3. Then, add 10 mL or half test tube buffer solution (ammonical buffer) and 2-3
drops of EBT indicator. Shake well, the solution turns in wine red colour.
4. Titrate the above solution with EDTA solution drop-wise from burette, until the
colour of the solution changes from wine red to blue.
5. Record the volume of EDTA consumed. Let it be X.
6. Repeat the titration till getting concordant reading.

[B] Titration between unknown hard water (UHW) sample and standardized EDTA
Repeat all the steps mentioned above for unknown hard water sample. Let
the volume of EDTA consumed for unknown hard water sample. Let it be Y.

[C] Titration between boiled hard water (BHW) sample and standardized EDTA
Repeat all the steps mentioned above for boiled hard water sample also. Let
the volume of EDTA consumed for boiled hard water sample. Let it be Z.
 OBSERVATION TABLE

[A] Titration between standard hard water (SHW) and EDTA

S. No. Volume of standard hard Burette Reading (ml) Concordant Reading (X)
water (SHW) (mL)
(mL) Initial Final
1 20 0.0
2 20 0.0 -----
3 20 0.0

[B]Titration between unknown hard water (UHW) and standardized EDTA solution
S. No. Volume of unknown hard Burette Reading (mL) Concordant Reading (Y)
water (UHW) (mL)
(mL) Initial Final
1 20 0.0
2 20 0.0 -----
3 20 0.0

[C] Titration between boiled hard water (BHW) and standardized EDTA solution

S. No. Volume of boiled Burette Reading Concordant Reading (Z)

water (BHW) (mL) (mL)
(mL) Initial Final
1 20 0.0
2 20 0.0 -----
3 20 0.0
A] Standardization of EDTA
CALCULATION
Hardness of standard hard water (SHW) = 1000 ppm
So, 1000 mL of SHW contains = 1000 mg CaCO3
Thus, 1 mL of SHW contains = 1000/1000 mg CaCO3 = 1mg CaCO3
X mL EDTA consume = 20 mL SHW = 20 mg CaCO3
Hence, 1 mL EDTA is equivalent to = 20/X mg CaCO3

[B] Hardness of unknown hard water (UHW) sample

20 mL UHW consumes = Y mL EDTA
= Y x 20/X mg CaCO3
Thus, 1 mL UHW = Y/20 x 20/X mg CaCO3 = Y/X mg CaCO3
Hence, 1000 mL of UHW = Y/X x 1000 mg/L CaCO3
Total hardness = …………..ppm

[C] Hardness of boiled hard water (BHW) sample

20 mL BHW consumes = Z mL EDTA
= Z x 20/X mg CaCO3
Thus, 1 mL BHW = Z/20 x 20/X mg CaCO3 = Z/X mg CaCO3
Hence, 1000 mL of BHW = Z/X x 1000 mg/L CaCO3

Permanent hardness = …………..ppm