Experiment No.

1. Object

To determine the hardness of water by EDTA method.

2. Apparatus & Reagents:
Burette (50ml), pipette (10ml), conical flask (250ml), glass funnel, beaker (250ml),
volumetric flask (100ml), standard hard water sample, standard M/100 EDTA solution,
buffer solution (pH=10), Eriochrome Black-T as indicator

3. Theory:
Hard water is water which does not produce lather with soap solution.
A reaction of soap(sodium stearate) with MCl2 and MSO4 is shown below:
2C17H35COONa+MCl2/SO4 → (C17H35COO)2M↓ + 2NaCl/Na2SO4
Sodium Stearate Metal Stearate (insoluble)
Where M=
Ca+2/Mg+2
There are two types of water hardness:
1. Temporary (carbonate hardness) 2. Permanent hardness.
Temporary hardness is due to the presence of calcium hydrogen carbonate Ca(HCO3)2(aq) and
magnesium hydrogen carbonate Mg(HCO3)2(aq).
Both calcium hydrogen carbonate and magnesium hydrogen carbonate decompose when heated.
The original insoluble carbonate is reformed. This happens when water is boiled. The
precipitation reactions are as follows:
Ca(HCO3)2 → CO2(g) + H2O + CaCO3(s)
Mg(HCO3)2→ CO2(g) + H2O + MgCO3(s)
Boiling the water causes the precipitation of solid calcium /magnesium carbonate. This removes
the calcium ions or magnesium ions from the water, and so removes the hardness. Therefore,
hardness due to hydrogen carbonates is said to be temporary.
Generally an increase in water temperature causes an increase in the solubility of most salts. But
as you may have understood from above there are exceptions like CaCO3, CaSO4, MgCO3, Mg
(OH)2 all of which become less soluble as the temperature increases.
Permanent hardness is hardness (mineral content) that cannot be removed by boiling. It is usually
caused by the presence of calcium sulphate/calcium chloride and/or magnesium
sulphate/magnesium chloride in the water, which do not precipitate out as the temperature increases.
 Ions causing permanent hardness of water can be removed using a water softener, or ion exchange
column.
Total Permanent Hardness = Calcium Hardness + Magnesium Hardness
The calcium and magnesium hardness is the concentration of calcium and magnesium ions
expressed as equivalent of calcium carbonate.
Principle of EDTA Titration:

EDTA (Ethylene diamine tetra acetic acid) is a commonly used complexing agent,
which is very much used in analytical purposes on account of its powerful complex making
characteristic and commercial availability. It can be represented as:

(HOOCH2C) 2N-CH2-CH2-N(CH2COOH)2

The ability of EDTA to potentially donate its six lone pairs of electrons for the formation of
coordinate covalent bonds to metal cations makes EDTA a hexadentate ligand. Disodium EDTA
is commonly used to standardize aqueous solutions of transition metal cations because of its
excellent solubility. EDTA forms complexes with Ca+2 and Mg+2, as well as with other metal
cations in solution. Such complexes have the general formula: MZ-2.
Where, M=Ca+2, Mg+2etc.
The reaction with M+2ions (Ca+2Mg+2) may be represented as:

M+2 + H2Z-2 ↔ MZ-2 + 2H+

EDTA (Ethylene diamine tetra acetic acid):

 EDTA-metal ion complex

EBT (Eriochrome Black T):

Eriochrome Black –T ( Unionized=blue; ionized= wine red)

IUPAC name: Sodium 1-[1-Hydroxynaphthylazo]-6-nitro-2-naphthol-4-sulfonate

EBT is a metal ion indicator used in determination of hardness by complexometric method with
EDTA. At pH 10, indicator EBT reacts with M+2 and gives wine red coloured unstable complex.
When EDTA is added to this solution, M+2 preferentially complexes with EDTA, because the
metal-EDTA complex is more stable than the metal indicator complex and liberates the free
indicator at the end point, thereby producing a sharp colour change from wine red to blue.
M+2 + EBT → [M-EBT]+2

[M-EBT]+2 + EDTA→ [M-EDTA]+2 + EBT

(i) Preparation of standard hard water:
1 gm of dry CaCO3 is dissolved in dilute HCL then evaporated to dryness on water bath. The

residue which is left is dissolved in distilled water to make one lit of solution. Each ml of this

solution contain 1 mg of CaCO3

(ii) Preparation of EDTA sol.:

0.01M EDTA solution is prepared by dissolving 3.7 g of its disodium salt (Molecular Wt. =372.25) in 1 lit.
of distilled water.

(iii) Preparation of EBT sol.:

It is prepared by dissolving 0.5g of EBT in 100 ml. of alcohol.

(iv) Preparation of buffer sol.:

70g of NH4Cl is dissolved in 570ml. of NH3 and solution is diluted to one liter using distilled water.

4. Procedure: It involves following steps:

Standardization of EDTA soln.

1.Pipette out 10 ml of the standard hard water sample into a conical flask.
2.Add 2ml of buffer solution (pH≈10) and 2-3 drops of EBT indicator.
3.Titrate the solution against EDTA solution (filled in burette) until the colour changes from
wine red to clear blue. This is the end point. Note the volume of titrant(V1ml.)

Total Hardness:

4. Repeat the above procedure with hard water sample. Note the volume of titrant (V2ml.)

Permanent Hardness:

5 Take 100ml of hard water sample and boil it gently in 250ml beaker for an hour.
6 Filter the solution into a 100ml volumetric flask. Make the solution 100ml with distilled
water and shake thoroughly.
7 Pipette out 10 ml of water sample into a conical flask.
8 Add 2ml of buffer solution and 2-3 drops of EBT indicator.
9 Titrate it against EDTA solution until the wine red colour changes to clear blue at the end
point & note the burette reading (V3).
5 Observation Table : For standard Hard water
Volume of Volume of EDTA (ml) Concordant reading
S.No. standard hard
water (ml) Initial (ml) Final (ml) Difference (ml) (V1ml)

1.

2.

3.

For hard water sample (Total Hardness):

Volume of EDTA Concordant reading
Volume of
S.No. water Initial (ml) Final (ml) Difference (ml) (V2ml)
sample (ml)

1.

2.

3.

For boiled water sample (Permanent Hardness):

Volume of EDTA
Volume of Difference Concordant reading
S. No. boiled water Initial (ml) Final (ml)
sample (ml) (ml) (V3ml)

1.

2.

3.
6. Calculations:

7. Result:
The hardness of a given water sample:

1. Total hardness = _______________ ppm

2. Permanent hardness= _______________ ppm

3. Temporary hardness= _______________ ppm

8. Precautions:
(i) Use 1-2 drops of indicator.

(ii) Wash all the apparatus with distilled water.

(iii) All solutions should be freshly prepared.

9. Industrial Applications:
i) All types of hardness viz. temporary, permanent, and total hardness can be determined by
using this method.
ii) Various methods can be employed to soften the water before its supply for domestic or
industrial purposes.
iii) Quality of water can be assessed by knowing its hardness.
iv) To minimize the precipitation of soap.

v) To avoid the redeposit ion of insoluble soap on the yarn or fabric being washed.

vi) To avoide ppt of some dyes as calcium and magnesium salts.

vii) To avoid the sludge and scales formation on equipment and in boilers .

PO a b c d e f g h i j k L

Mapping √ √ √
 VIVA QUESTIONS
Q.1 What are the difference between hard water & soft water

Q.2 What is complexometric titrations?

Q.3 Draw the structures of EDTA and EBT.

Q.4 Draw the structure of EDTA metal complex.

Q.5 What is buffer solutions?

Q.6 Why disodium salt of EDTA is used?

Q.7 What colour changes is observed at the end point?

Q.8 Write principle & chemical reactions involved in this titration.

Q.9 Why hardness is expressed in terms of CaCO3 equivalent?

Q.10 Which salts are responsible for permanent hardness