Experiment No.

1
Aim

Determination of hardness of water by EDTA method

Apparatus

Burette, Pipette, Conical flask, Beakers, etc.

Chemicals

Standard hard water, hard water sample, boiled water sample,

EDTA solution, Eriochrome black-T indicator,
Ammonia buffer solution.

Theory
The presence of calcium and magnesium ions is the main cause of
hardness of water. The chlorides, sulphates and biocarbonates of calcium and
magnesium react with the sodium salt of long chain fatty acids (soap) and form
insoluble scum of calcium and magnesium which have no detergent value.

2C17H35COONa

CaCl2

(C17H35COO)2Ca + 2NaCl

Sodium stearate

Calcium stearate

(soluble)

(insoluble)

Hardness of water is that characteristics which prevents lathering of soap. The

water which does not form lather but form white scum or precipitate is called had
water.

The hardness of water is of two types,

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Temporary hardness: This type of hardness is due to the presence of dissolved

salts of Ca and Mg ions and other heavy metals. This hardness can be easily
eliminated by simple boiling process.
Ca(HCO3)2

CaCO3 + H2O + CO2

Mg(HCO3)2

MgCO3 + H2O + CO2

Permanent hardness: The hardness which is due to presence of chloride and

sulphate of Ca and Mg and other heavy metals. Such type of hardness cannot
removed by boiling but it required a special treatment such as soda-lime, ion
exchange and zeolite. The hardness of a given water sample can be determined
by complexometric titration using EDTA solution.

Structure of EDTA
EDTA forms complexes with Ca2+ and Mg2+ ions in aqueous solutions. This
complex has general formula

Where, M- Ca2+, Mg2+ etc.

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The solubility of the metal-EDTA complex is governed by the pH of the

solution. Lowering the pH may decrease the stability of the complex. The
divalent metal ion-EDTA complexes are stable at around pH 8 to 10. Therefore
pH is maintained by using ammonia buffer solution.
Eriochrome black-T is used as an indicator in the determination. When
EBT is added to hard water, the Ca and Mg ions form a wine red complex with
the indicator.
M2+ + EBT

[ M2+ - EBT ] complex

(Wine red / unstable)

When EDTA is added to this solution, wine red color changes to blue, this
is due to the formation of the metal ion - EDTA complex.
[ M2+ - EBT ] complex + EDTA
Wine red (unstable)

[ M2+ -EDTA ] complex + EBT

blue (stable)

Procedure
1. Titration between standard hard water and EDTA.
Pipette out 10 ml of std. hard water sample in a conical flask and add 2 ml of
buffer solution to it. Then add 2-3 drops of Eriochrome Black-T indicator. Wine
red colour is obtained. Titrate against EDTA solution until colour changes from
wine red to deep blue. Note down the end point (R1). Repeat this procedure till
constant reading is obtained.

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2. Determination of total hardness of water sample:

Pipette out 10 ml of hard water sample in a conical flask and add 2 ml of buffer
solution to it. Then add 2-3 drops of Eriochrome Black-T indicator. Wine red
colour is obtained. Titrate against EDTA solution until colour changes from wine
red to deep blue. Note down the end point (R 2). Repeat this procedure till
constant reading is obtained.
3. Determination of permanent hardness of water sample:
Take 50 ml of water sample in a beaker. Gently boil this for about half an hour.
Pipette out 10 ml of this sample in a conical flask and add 2 ml of ammonia buffer
solution and add 2-3 drops of EBT indicator, wine red colour is obtained. Titrate
this solution with EDTA from burette till colour changes from wine red to deep
blue. Note down the end point (R3). Repeat this procedure till constant reading is
obtained.

Observations
1. Titration between standard hard water and EDTA
Sr.No.

Volume of CaCl2

Volume of
EDTA

Constant
reading
(R1)

1
2
3

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2. Titration between hard water and EDTA

Sr.No.

Volume of hard
water

Volume of
EDTA

Constant
reading
(R2)

Volume of
EDTA

Constant
reading
(R3)

1
2
3

3. Titration between boiled water and EDTA

Sr.No.

Volume of boiled
water

1
2
3
Calculations
Std. hard water is prepared by dissolving ________ gm of CaCl 2 in 1 liter of
distilled water.
Hence, 10 ml of std. hard water = __________ (X) mg of CaCl2.
From observation table no. 1
__________ (R1) ml of EDTA is required for 10 ml of CaCl2.
__________ (R1) ml of EDTA = __________ (X) mg of CaCl2.
(X) x 1
1 ml of EDTA = = ___________ mg of CaCl2.
R1

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I.

Total hardness
1 ml of EDTA = ____________ mg of CaCl2.

So, ________ (R2) ml of EDTA =

(X) x R 2/R1 = _________ mg of CaCl2.

But _________ (R2) ml of EDTA is required for 10 ml of hard water sample.

Therefore, 10 ml of hard water contains . (X) x R 2/R1 mg of
CaCl2.
1000 ml of hard water sample = _________ (X) x R 2/R1 x 1000/10 mg of CaCl2.
Total hardness

II.

= .. mg/lit or ppm

(1)

Permanent hardness
1 ml of EDTA = ____________ mg of CaCl2.

So, ________ (R3) ml of EDTA =

(X) x R 3/R1 = _________ mg of CaCl2.

But _________ (R3) ml of EDTA is required for 10 ml of boiled water.

Therefore, 10 ml of hard water contains . (X) x R 2/R1 mg of CaCl2.
1000 ml of boiled water = _________ (X) x R3/R1 x 1000/10 mg of CaCl2 (2)

III.

Temporary hardness
Now, Temporary hardness = Total hardness - Permanent hardness
= ____________
= ____________ mg/lit or ppm.

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Result

The given water sample contains,

1.

Total hardness

= mg/lit or (ppm)

2.

Permanent hardness

= mg/lit or (ppm)

3.

Temporary hardness

= mg/lit or (ppm)

Precautions
1.

Titration should be performed slowly near the end point.

2.

No tinge of reddish blue should remain at the end point. The

solution should be clear blue.

3.

pH of buffer solution must be maintained between 8-10.

Viva voce questions.

1. What is EDTA? Write the structure of EDTA.
2. What is EBT?
3. What is pH? Write the formula for it. What is its range?
4. Write the relationship between pH and pOH?
5. What is a buffer solution? Give examples.
6. Why the pH range is to be maintained around 10 in EDTA titration?
7. On what principle the colour changes from wine red to steel blue?

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8. What is the molecular and equivalent weight of CaCO3?

9. EDTA as such can be used for preparing the solution? Why?
10.Why ammonia buffer is used?
11. Define hardness. Name the types of hardness?
12. Why CaCO3
is used as a standard for calculating hardness?
13. What is hard water and soft water?
14. What is the formula to calculate Total, permanent and Temporary hardness?

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