___ Date: ___

EXPERIMENT 1. ESTIMATION OF Ca2+, Mg2+ (TOTAL HARDNESS) IN

WATER SAMPLE
OBJECTIVE
To determine the total hardness of water sample by EDTA (Ethylene Diaamine Tetra
Acetic acid) method. You are provided with EDTA solution and standard hard water.

APPARATUS
Burette, Pipette , Conical Flask, Standard Flask, Funnel

PRINCIPLE
SOFTWATER: Water that produces lather with soap easily is called soft water. Soft water does
not affect cleaning action of soap.
HARD WATER: Water that produces curd with soap and produces very little lather
is called hard water. Hard water affects cleaning ability of soap. Hard water contains
bicarbonate, chlorides and sulphates (any one or all) of calcium and magnesium. There are two
types of hardness in water. 1. Temporary hardness 2. Permanent hardness. The total hardness
is the sum of temporary and permanent hardness. The standard way to express water hardness is
in ppm CaCO3 which has the formula weight of 100.1 g/mole.
TEMPORARY HARD WATER: Water that contains bicarbonate of calcium and magnesium
or of both is called temporary hard water.
PERMANENT HARD WATER: Water that contains chlorides or sulphates of calcium or
magnesium or of both is called Permanent water.
An excellent way to determine water hardness is to perform a complexometric titration
using a standard ethylenediaminetetraacetic acid (EDTA) solution. EDTA will complex with
calcium and magnesium in a one-to-one molar ratio.EDTA is a
complexing agent and it has 6 lone pairs of electrons. It can
act as a quadridentate, pentadentate or hexadentate ligand.
Eriochrome black-T is used as indicator. The
indicator forms a weak complex with the metal ions present in the hard water and gives wine red
colour at a pH of 10 ± 0.1.
 1. When Eriochrome Black T (EBT) indicator is added to the hard water at pH range 9 – 10 it
gives wine red coloured unstable complex with Ca2+ and Mg2+ ions of the sample water.
Ca2+ Ca2+
⃗
EBT / pH 9−10 EBT complex
2+ 2+
Mg Mg

Hard water (Unstable complex)

(Wine Red Colour)

2. Now when this wine red-coloured complex is titrated against EDTA solution (of known
strength), EDTA gradually forms a stable complex with the hard water containing Ca 2+ and Mg2+
ions and replaces EBT in the unstable complex. At the end point Eriochrome Black T (EBT) is
left free in the alkaline medium which shows the steel blue colour.
Ca2+ Ca2+
EBT complex + EDTA ⃗
pH 9−10 EDTA complex + EBT
2+
Mg Mg2+ (Steel Blue
colour)
Hard water (stable colourless complex)

PROCEDURE
Titration I Standardisation of EDTA
Wash the burette with distilled water, rinse it with the EDTA and fill it upto the zero
mark. Pipette out 20 ml of standard hard water into a clean conical flask and add 10 – 15 ml of
ammonia buffer solution followed by the addition of few drops of Eriochrome Black T (EBT)
indicator. The solution turns wine-red in colour. Titrate the wine red solution against EDTA
taken in the burette till the wine red colour changes to steel blue colour. Let the volume of EDTA
consumed be V1 ml.

Titration II Estimation of Ca2+, Mg2+ (total hardness)

Pipette out 20 ml of sample hard water into a clean conical flask and add 10 – 15 ml of
ammonia buffer solution followed by the addition of few drops of Eriochrome Black T (EBT)
indicator. The solution turns wine-red in colour. Titrate this solution against EDTA taken in the
burette till the wine red colour changes to steel blue colour. Let the volume of EDTA consumed
be V2 ml.

RESULT
Ca2+, Mg2+ (Total hardness) present in sample hard water = ___________ ppm

Titrarion I Standardisation of EDTA

Standard hard water Vs EDTA

Burette reading
Volume of
Volume of Concordant
standard hard Indicator
Sl. No. EDTA (V1) value
water used
Initial Final (ml) (ml)
(ml)
(ml) (ml)

1. 20 0 21.5 21.5 21.5

Eriochrome
2. 20 Black – T
(EBT)
3. 20

Calculation

Standardisation of EDTA solution

1 ml of standard hard water = 1 mg of CaCO3 eq. hardness

Volume of standard hard water taken = 20 ml
Therefore, 20 ml standard hard water = 20 mg of CaCO3 eq. hardness
Volume of EDTA consumed = ____ ml [V1 ml (from Titration I)]
i.e., V1 ml of EDTA solution = 20 mg of CaCO3 eq. Hardness

20
Therefore, 1 ml of EDTA will be = ---- mg CaCO3 eq. hardness
V1
= ______ mg CaCO3 eq. hardness
Titration II
Estimation of total hardness

Sample hard water Vs EDTA

Burette reading
Volume of
Volume of Concordant
sample hard Indicator
Sl. No. EDTA (V2) value
water used
Initial Final (ml) (ml)
(ml)
(ml) (ml)

1. 20 0 11.9 11.9 11.9

Eriochrome
2. 20
Black - T
3. 20

Estimation of total hardness

Volume of EDTA consumed = V2 ml (from Titation II)

20
1 ml of EDTA = ---- mg CaCO3 eq hardness
V1

20
V2 ml of EDTA = ---- x V2 mg CaCO3 eq. hardness
V1

20
20 ml of sample hard water contains = ---- x V2 mg CaCO3 eq. hardness
V1

20
---- x V2
V1
Then, 1000 ml of sample hard water will contain = ----------- x 1000 mg CaCO3 eq. hardness
20

V2
= ---- x 1000 mg CaCO3 eq. hardness
V1
Ca2+, Mg2+ (Total hardness) = _________ mg/lit. or ppm.
 Experiment 1
TITLE:_____________________________________________________________________

SHORT PROCEDURE

Experiment Title
Titration I Titration II
Title

Burette Solution

Pipette Solution

Indicator

Endpoint

Additional condition

Formula

PRINCIPLE OF THE EXPERIMENT

NOTES & CALCULATION

QUESTIONS

1. What is hard water and soft water?

2. What is meant by permanent hardness?

3. What is meant by temporary hardness?

4. What is the other name for temporary and permanent hardness?

5. What is the unit of hardness?

6. Why is hardness expressed in equivalents of calcium carbonate?

7. How can temporary hardness be removed?

8. What is Complexometric titration?

9. Give the structure of EDTA and EDTA-Metal Complex

10. In titration, why does the colour of the solution change from winered to blue?

11. What is the name of the buffer used in EDTA titration?

12. What is the role of buffer solution?