Determination of Hardness The following of any given water

sample may be determined by the following methods.

 (i) O. Hehner's method
 (ii) Soap titration method
 (iii) EDTA method

Of these EDTA method is preferable due to its

▪ Greater accuracy
▪ Convenience and
▪ More rapid procedure
It is a complexometric titration method.

Principle: Ethylene diamine tetra acetic acid is the titrant used in

this method. The lone pairs of electrons present on nitrogen and
oxygen help in the complex formation with the metal ions present
in hard water.
To make EDTA more soluble in water disodium salt is used.

Disodium Salt of EDTA

 EBT-Eriochrome black-T is the indicator used.

 EBT forms complexes with the metal ions in hard water at a pH

10. To maintain the pH at 10, NH4OH−NH4Cl buffer solution is
used.
 Both EDTA and EBT form complexes with the metal ions(M2+),
but they differ in their nature.
 The complex formed by EDTA is strong and colourless whereas that by EBT
is weak and wine red coloured.
 Initially when EBT is added to hard water, it turns wine red due to the
formation of M-EBT complex.
M2+ + EBT → M-EBT
weak, wine red coloured

 When EDTA is added, the free metal ions remaining get complexed as
M-EDTA.
M2+ + EDTA → M-EDTA
strong, colourless
 A point reaches where no more free M2+ are present, the
displacement of EBT from the complex will take place letting
EBT free. As free EBT is blue in colour, this marks the end
point.
M-EBT+ EDTA → EBT + M-EDTA
blue
 The volume of EDTA consumed till the end point corresponds
to the hardness present in the water sample.

After adding EBT to At the end point

hard water
 Procedure and calculations
 1.Prepration of Standard Hard Water
• 1g pure dry CaCO3 is weighed and evaporated to dryness in a china dish with min.
qty of dil.HCl. Residue is dissolved in distilled water and made upto 1000 mL in a Std
Flask.
• 1g CaCO3 in 1 L, or1000 mg CaCO3 in 1000 mL or 1mg CaCO3 in 1mL

 2.Standardisation of EDTA solution:

• Burette filled with EDTA

• 50 mL hard water (pippetted) + 10-15 mL Buffer + 4-5 Drops EBT.

• It is then titrated against EDTA soln till wine red colour changes to blue.

• Let the volume of EDTA Consumed be V mL.

 V mL of EDTA = 50 mL of standard hard water

= 50 mg of CaCO3
∴ 1 mL of EDTA = 50/V1 mg of CaCO3
 3. Determination of total hardness
• 50 mL of unknown hard water sample is titrated with EDTA as above.
• Let the volume of EDTA consumed be V1 mL
 50 mL of unknown hardwater = V1 mL of EDTA
= V1 X 50/V mg of CaCO3
 1L (1000mL) of unknown hard water = 50/V X V1 /50 X 1000 mg of CaCO3
equivalent

 ∴ total hardness of water = V1 /V X 1000 mg/L or ppm

 4. Determination of permanent hardness
• 250 mL of unknown water sample is boiled in a beaker till its volume is reduced to 50 mL,
so that all the bicarbonates present get decomposed.Then the water is filtered and the
filtrate is made upto 250 mL with distilled water. 50 mL of this water is titrated against
EDTA. Let the volume of EDTA consumed be V2mL.
 50 mL of boiled water =V2 mL of EDTA = V2 X 50/ V mg of CaCO3
∴ permanent hardness of water= 50/V X V2 /50 X1000
= V2 /V X 1000 mg/L or ppm
➢ 5. Calculation of temporary hardness
• Difference between total and permanent hardness will give temporary hardness.
 Temporary hardness = Total Hardness – Permanent hardness
= 1000(V1 – V2)/V mg/L or ppm
 Questions:

 Write the structure of EDTA

 What is the principle involved in EDTA method of estimation of
hardness?
 Describe the estimation of hardness of water by EDTA method.