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Principle:
Hardness of water is due to the presence of calcium and magnesium salts in water. Ehtylene
diamine tetraacetic acid (EDTA) forms complexes with a large number of cations including
Ca2+ and Mg2+ ions depending upon pH of the solution. Hence, it is possible to determine the
total hardness of water using EDTA solution. EDTA in the form of its sodium salt (H 2Y2-) is
more often used in place of EDTA in complexometric titration for estimation of metal ions
because pure EDTA (H4Y) is sparingly soluble in water. EDTA has six binding sites (the
four carboxylate groups and the two amino groups) providing six pairs of electrons. The
resulting metal-ligand complex, in which EDTA forms a cage-like structure around the
metal ion, is very stable at specific pH. All metal-EDTA complexes have a 1:1
stoichiometry. The H2Y2- form complexes with metal ions as follows.
M + H2Y2- MY2- + 2H+ (1)
where, M is Ca2+ and Mg2+ present in water. Reaction (1) can be carried out quantitatively at
pH of 10 using Eriochrome Black T (EBT) indicator. EBT forms a wine-red complex with
M2+ ions which is relatively less stable than the metal-EDTA complex. On titration EDTA
first reacts with free M2+ ions and then with the metal-EBT indicator complex. The end point
of the reaction is change of colour from wine red to steel blue.
Requirements
Reagents and solutions: Standard hard water (0.001M), EDTA solution (0.001M), EBT
indicator, hard water sample and NH3-NH4Cl buffer solution.
Apparatus: Burette, pipette, conical flask, standard flask and burette stand
Procedure
Titration I - Standardization of EDTA
Pipette out 20 mL of the standard calcium ion solution (0.01N) into a clean 250 mL conical flask.
Add one full test tube of ammonia buffer (NH 4OH NH4Cl) solution to maintain the pH around
10. Add three drops of Eriochrome Black T (EBT) indicator and titrate the solution against
EDTA solution taken in the burette. The end point is change of color from wine red to steel blue.
Repeat the titration for concordant titre values. Let V1 be the volume of EDTA consumed.
V2 X 20 X 1000
1000mL of given hard = mg of CaCO3eqvt
V1 X 20
V2 X 1000
= mg / L
V1
Conical Flask: 20 mL of boiled and cooled sample water + one test tube buffer solution + 2 drops
of EBT
V3 X 20 X 1000
1000 mL of given boiled hard water = mg of CaCO3eqvt.
V1 X 20
= V3 X 1000 mg / L or ppm
V1
= (4.5*1000)/19.8 ppm
= V2 V3 X 1000 ppm.
V1 V1
V2 V3
= V1 X 1000 ppm.
= 136.36 ppm Result:
Evaluation of result