24PCBSX11 - Chemistry Laboratory

Exp. No.: 2
DETERMINATION OF TOTAL, TEMPORARY AND PERMANENT
Date : HARDNESS OF WATER - BY EDTA METHOD

2.1 AIM
To estimate the total, permanent and temporary hardness of the given water sample.

2. 2 PRINCIPLE
One of the important reagents used in the estimation of metal ion complexometric
titration is EDTA, which is Ethylene Di amine Tetra Acetic acid. The EDTA is insoluble in water
and hence its disodium salt is used.

Structure of EDTA

Here using disodium salt of EDTA due to water solubility. It is a very reactive reagent
because it has the tendency to complex with bivalent, trivalent and tetravalent cations easily.
This property of EDTA is very conveniently exploited in the estimation of hardness of water
since Ca2+, Mg2+ ions are present in it. Since it is a hexadentate ligand, it forms an octahedral
and ionic complex. The reaction is

[Ca2+ (EDTA)] is thermodynamically more stable than [Mg (EDTA)]2+. The Ca2+ ion is
larger in size than Mg2+ ions and hence it complexes with EDTA with minimum inter
coordinating sites repulsion. The equilibrium is highly sensitive to pH changes as illustrated in
the above equation. Hence in order to favorably shift the equilibrium towards the right, a
buffer (NH4Cl / NH4OH) is employed. It maintains the pH between 9 and 10, which is actually
essential in this estimation. To detect the completion (i.e.) the end point, an indicator,
Eriochrome Black-T is used. The free indicator in the pH range 9 – 10 is steel blue. But, it is
capable of forming wine red coloured complex with Mg2+ of water.

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TITRATION – I : STANDARDIZATION OF EDTA

1. Burette solution : EDTA
2. Pipette solution : Standard hard water
3. Buffer : 10 ml of ammonia buffer
4. Indicator : Eriochrome Black – T (EBT)
5. End point : Wine red colour to steel blue

TABLE 2.1
Standard Hard Water Vs EDTA
Volume of Burette reading (ml) Volume of
Sl. Concordant
standard hard EDTA used
No. Initial Final value (ml)
water (ml) V1 (ml)
1 20 0

2 20 0

3 20 0

CALCULATION - I:
Volume of standard hard water = 20 ml

Volume of EDTA solution consumed (V1) = …………. ml

1 ml of standard hard water contains 1 mg of calcium carbonate

20 ml of standard hard water contains 20 mg of calcium carbonate

20 ml of standard hard water consumes V1 ml of EDTA

V1 ml of EDTA solution = 20 mg of CaCO3

20
 1 ml of EDTA solution = mg of CaCO3 equivalent hardness
V1

20
=
……….

= ………….. mg of CaCO3 equivalent hardness

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 24PCBSX11 - Chemistry Laboratory
Hence, when the buffer and indicator are added to a water sample, the whole solution
would thus appear as wine red colour. In this solution there might be free Ca 2+, free Mg2+ and
(Mg-Indicator) complex. When EDTA is added to it slowly, it complexes first with Ca 2+and then
with free Mg2+. Hence at the end point there is no more wine red coloured (Mg-Indicator)
complex, and so the whole solution appears steel blue. From the volume of EDTA consumed,
the hardness of water can be calculated.
EDTA is not a primary standard because its molecular weight is not exactly known, due to
uncertainty with respect to number of water molecules in it. Hence it requires standardization,
and it is done using standard hard water containing 1mg CaCO3 / 1 ml.

2.3 APPARATUS REQUIRED

S.No Apparatus / Equipment Range Quantity
1 Burette 50 ml 1
2 Pipette 20 ml 1
3 Conical flask 250 ml 1
4 Beaker 250 ml 1
5 Funnel 5 cm 1
6 Polyethylene wash bottle 500 ml 1
7 Standard measuring flask 100 ml 1

2.4 REAGENTS REQUIRED

1. EDTA
2. Standard hard water (containing 1 mg of CaCO3 / ml)
3. Ammonia buffer (NH4Cl / NH4OH)
4. EBT (Eriochrome Black-T) indicator

2.5 PROCEDURE

2.5.1 TITRATION – I : STANDARDIZATION OF EDTA

Step – I : The burette, pipette and the conical flask were washed thoroughly with tap water and
distilled water. The burette was rinsed with small quantity of EDTA solution and filled. Then
the pipette was rinsed with standard hard water solution.
Step – II : Exactly 20 ml of standard hard water was pipette out and transferred in to a clean
conical flask. 10 ml of buffer solution and 3 drops of EBT indicator were added. After shaking, a
wine red colour was observed.
Step – III : The solution in the conical flask was titrated against EDTA solution taken in the
burette. The end point was the colour change from wine red to steel blue. The burette reading
was noted in Table 2.1 and repeated for concordant value. Let the volume of EDTA consumed
be V1 ml.

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TITRATION – II : ESTIMATION OF TOTAL HARDNESS

1. Burette solution : EDTA
2. Pipette solution : Given sample water
3. Buffer : 10 ml of ammonia buffer
4. Indicator : Eriochrome Black – T (EBT)
5. End point : Wine red colour to steel blue colour

TABLE 2.2
Water Sample vs EDTA
Volume of Burette reading (ml) Volume of
Sl. Concordant
water sample EDTA used
No. Initial Final value (ml)
(ml) V2 (ml)
1 40 0

2 40 0

3 40 0

CALCULATION - II:
Volume of the hard water = 40 ml
Volume of EDTA consumed (V2) = ..…….... ml

20
40 ml of the given water sample contains X V2 mg of CaCO3 equivalent hardness
V1

20 1000
1000 ml of given water sample contains X V2 X mg of CaCO3 equivalent hardness
V1 40

……… X ….…. X 1000

= PPM
40

Total hardness of the given sample of hard water = ………….. PPM

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2.5.2 TITRATION II ESTIMATION OF TOTAL HARDNESS OF WATER SAMPLE

Step – I : The burette was filled with EDTA solution. 40 ml of the given water sample was
transferred into a clean conical flask and 10 ml of ammonia buffer and 3 drops of EBT indicator
were added.

Step – II : A wine red colour was developed and the whole mixture was titrated against EDTA
solution taken in the burette.

Step – III : At the end point the colour was changed from wine red to steel blue. The burette
reading was noted in Table 2.2. The titration was repeated for concordant value. Let the
volume of EDTA consumed be V2 ml.

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TITRATION – III ESTIMATION OF PERMANENT HARDNESS

Burette solution : EDTA
Pipette solution : Sample water after boiling and cooling
Buffer : 10 ml of ammonia buffer
Indicator : Eriochrome Black – T (EBT)
End point : Wine red colour to steel blue colour

TABLE 2.3
Water Sample (After Boiling and Cooling) Vs EDTA

Volume of water Burette reading (ml) Volume of

S. Concordant
sample after boiling EDTA used
No. Initial Final value (ml)
and cooling (ml) V3 (ml)
1 40 0

2 40 0

3 40 0

CALCULATION – III :
Volume of the sample (after boiling and cooling) = 40 ml
Volume of EDTA consumed (V3) = ………… ml
40 ml of water sample consumes V3 ml of EDTA
40 ml of water sample contains 20
X V3 mg of CaCO3 equivalent hardness
V1

1000 ml of water sample contains 20

X V3 X
1000
mg of CaCO3 equivalent hardness
V1 40

……… X ….…. X 1000

= PPM
40

Permanent hardness = ………………. PPM

CALCULATION – IV: ESTIMATION OF TEMPORARY HARDNESS:

Temporary hardness of water = Total hardness – Permanent hardness

= ………….. – ………..… = ……………..PPM.

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2.5.3 TITRATION III: ESTIMATION OF PERMANENT HARDNESS OF THE WATER SAMPLE

Step – I : The burette was filled with EDTA solution. 100 ml of the water sample was taken in a
beaker and heated to boiling for 30 minutes on a hot plate.

Step – II : The solution was cooled and filtered through filter paper and the filtrate was
collected in a 100 ml standard measuring flask. The filter paper was also washed with distilled
water and the washings were collected in the same SMF. The solution was diluted with distilled
water to the mark.

Step – III : From that 40 ml of the water sample was pipette out and transferred into a clean
conical flask along with 10 ml of ammonia buffer and 3 drops of EBT indicator. The wine red
coloured solution was titrated against EDTA solution.

Step – IV : The end point observed was the colour change from wine red to steel blue and the
burette reading was noted in Table 2.3. The titration was repeated for concordant value. Let
the volume of EDTA consumed be V3 ml.

2.5.4 Estimation of temporary hardness

Temporary hardness of water sample is calculated by subtracting permanent hardness

from total hardness.

Temporary hardness of water = Total hardness – Permanent hardness

2.6 RESULT

1. Total hardness of water = …………… PPM.

2. Permanent hardness of water = …………… PPM.

3. Temporary hardness of water = …………… PPM.

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