Experiment#05: Determination of Hardness of Water Using EDTA

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Experiment#05

Determination of Hardness of Water using EDTA

Principle:
Hardness in water is due to the presence of dissolved salts of calcium and
magnesium. It is unfit for drinking, bathing, washing and it also forms scales in
boilers. Hence it is necessary to estimate the amount of hardness producing
substances present in the water sample. Once it is estimated, the amount of
chemicals required for the treatment of water can be calculated. The estimation of
hardness is based on complexometric titration. Hardness of water is determined by
titrating with a standard solution of ethylene diamine tetra acetic acid (EDTA)
which is a complexing agent. Since EDTA is insoluble in water, the disodium salt
of EDTA is taken for this experiment. EDTA can form four or six coordination
bonds with a metal ion.
Total hardness:
Total hardness is due to the presence of bicarbonates, chlorides and sulphates of
calcium and magnesium ions. The total hardness of water is estimated by titrating
the water sample against EDTA using Eriochrome Black-T (EBT) indicator.
Initially EBT forms a weak EBTCa2+/Mg2+ wine red colored complex with
Ca2+/Mg2+ ions present in the hard water. On addition of EDTA solution,
Ca2+/Mg2+ ions preferably form a stable EDTACa2+/Mg2+ complex with EDTA
leaving the free EBT indicator in solution which is steel blue in color in the
presence of ammonia buffer (mixture of ammonium chloride and ammonium
hydroxide, pH 10).
Eriochrome Black-T + Ca2+/Mg2+ Eriochrome Black-T-Ca2+/Mg2+
(Wine red)
Eriochrome Black-T-Ca2+/Mg2+ + EDTA EDTA-Ca2+/Mg2+ + Eriochrome Black-T
(Wine red) (Steel blue)
Temporary hardness:
Temporary hardness is due to the presence of bicarbonates of calcium and
magnesium ions. It can be easily removed by boiling. When water is boiled,
temporary hardness producing substances (bicarbonates) are precipitated as
insoluble carbonates or hydroxides. This precipitate can be removed by filtration.
(The filtrate is used in the next step).
Eriochrome Black-T + Ca2+/Mg2+ Eriochrome Black-T-Ca2+/Mg2+
(Wine red)
Eriochrome Black-T-Ca2+/Mg2+ + EDTA EDTA-Ca2+/Mg2+ + Eriochrome Black-T
(Wine red) (Steel blue)

Permanent hardness:
Permanent hardness is due to the presence of chlorides and sulphates of calcium
and magnesium ions. This type of hardness cannot be removed by boiling. The
filtrate obtained from the above step contains permanent hardness producing
substances and is estimated against EDTA using EBT indicator.

Materials and Apparatus:


 Eriochrome Black T indicator
 pH 10 NH3-NH4Cl buffer,
 0.01M EDTA (disodium salt)
 Commercial sample of bottled mineral water
 Apparatus required for titration
Procedure:
The burette is filled with standard EDTA solution to the zero level, following
usual precautions.
1. Estimation of Total Hardness
50 ml of the given water sample is pipetted out into a clean conical flask. 5 ml
ammonia buffer and 2 drops of EBT indicator are added and titrated against EDTA
from the burette. The end point is the change of color from wine red to steel blue.
The titration is repeated to get concordant value.
2. Estimation of Permanent Hardness:
100 ml of the given sample of water is pipetted out into a clean beaker and boiled
for 20 minutes. It is then filtered to remove the precipitate formed due to the
decomposition of temporary hardness producing salts. The filtrate is made up to
100 ml in standard measuring flask (SMF) using distilled water. 50 ml of the
made-up solution is pipetted out into a conical flask, 5 ml ammonia buffer and 2
drops of EBT indicator are added and titrated against the EDTA. The end point is
the change of color from wine red to steel blue. The titration is repeated to get
concordant value.
3. Temporary Hardness:
The temporary hardness is calculated from the total and permanent hardness.
Temporary Hardness = Total Hardness - Permanent Hardness
Observations:
Titration-1 Estimation of Total Hardness
Standard EDTA VS Water Sample
Volume of hard Burette reading Volume of EDTA Indicator
water sample solution
(ml) Initial final (ml)

50 0 15.0 15.0 EBT


50 0 15.1 15.1 EBT
50 0 15.0 15.0 EBT
50 0 15.0 15.0 EBT
50 0 15.1 15.1 EBT

Titration-2 Estimation of Permanent Hardness


Standard EDTA X Boiled water sample
Volume of hard Burette reading Volume of EDTA Indicator
water sample solution
(ml) Initial final (ml)

50 0 5.0 5.0 EBT


50 0 5.1 5.1 EBT
50 0 5.0 5.0 EBT
50 0 5.0 5.0 EBT
50 0 5.1 5.1 EBT
Calculations:
1 ml of 0.01 M EDTA = 1 mg of CaCO3
V1 ml of EDTA = V1 mg of CaCO3
Calculation of total hardness:
Volume of EDTA solution consumed = 15.0ml
Volume of hard water taken = 50ml

Total hardness = Volume of EDTA solution consumed X 1000 ppm


Volume of Hard water taken

= 300ppm
Calculation of permanent hardness:
Volume of EDTA solution consumed = 5 ml
Volume of boiled water taken = 50ml

Permanent Hardness = Volume of EDTA solution consumed X1000 ppm


Volume of the boiled water taken

= 100ppm
Calculation of temporary hardness:
Temporary hardness of water = Total hardness - Permanent hardness
= 200 ppm
Result:
The collected water sample contains
Total hardness = 300 ppm
Permanent hardness = 100 ppm
Temporary hardness = 200 ppm

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