ESTIMATION OF HARDNESS

Aim:

To determine the total, permanent and temporary hardness of given water by

complexometric titration using standard 0.01M EDTA solution.

Principle:
Hard water is due to metal ions (minerals) that are dissolved in the ground water.
Generally water contaminated with Ca or Mg salts is called hard water. When impurities
are in form of bi carbonate salts, they are easily removed by boiling as boiling
decomposes bi carbonates to insoluble carbonates. It is said to be temporary hardness.
When they are in in form of chlorides or nitrates etc. it is called permanent hardness.
A complex is a molecule or ion formed by the reaction of two or more ions or molecules
capable of independent existence. A metal atom can usually form a bond with one or
more donor atoms which have at least one unshared pair of electrons. The number of
donor atoms which bond with a given atom depends on the number of electron pairs
that the metal ion can accept, in other words, the coordination number of the metal ion.
Complexing agents, or ligands, which can provide more than one pair of electrons
(multidentate ligands), are also called chelating agents.
Many metals forms complexes with such reagents as contain appropriate ligands. The
most important chelating agent in analytical chemistry is ethelyene diamine tetra acetic
acid (EDTA). The tetra basic form of this acid forms complexes with virtually all metal
ions. EDTA is a hexadentate ligand; each of the acid oxygen and each of the amine
nitrogen can donate one electron pair. The metal ion is usually held in a one-to-one
complex with EDTA. The complexes have four or five 5-membered rings, contributing
significantly to their stability. Dissociation constant values indicate that EDTA behaves
like a dicarboxylic acid. That is two of its carboxyl groups are strongly acidic and other
two hydrogen are released during formation of complex. In forms of its disodium salt, it
is used to estimate Ca++ and Mg++ ions.
It is important to realize that the electron pairs of the carboxylic acid groups of EDTA are
only available to the metal ion when the acid is dissociated. This means that the
effectiveness of the complexing agent is strongly affected by pH. At low pH EDTA will
be in the acid form and will not be an effective complexing agent. Additionally, many
metal ions form complexes with hydroxide ions. Hydroxide ions compete with the
chelating agent for coordination sites in the metal ion. Therefore, the effectiveness of
the complexing agent will also be reduced at high pH. For a given chelating agent and
metal ion, there will be an optimum pH for the titration which will depend on the pKa
values for the chelating agent and the formation constants for the metal-hydroxide

complexes. Therefore suitable buffer solution is added to keep pH of the solution nearly
constant and pH sensitive indicators are used. In the estimation of hardness with EDTA,
an azo dye called Eriochrome Black-T is used as an indicator. This forms a metal
indicator complex, the stability of which is lower than that of the metal EDTA complex.
The solution is initially red due to metal ion indicator complex. As the titration proceeds,
the metal ions forms more stable complex with EDTA, hence the indicator anion goes in
to solution. As the indicator accumulates the colour changes from red to blue at the end
point.

Reagents:
Given sample of hard water, standard EDTA solution, buffer solution (pH=10), solution
of Eriochrome Black-T

Apparatus:
Pipettes, burette, conical flasks, hot plate.

Procedure:
Total hardness:
Clean the burette and fill with standard EDTA solution and note the initial reading.
Pipette out 25 ml of given hard water in a clean conical flask.
Add 5 ml of buffer solution (pH=10) and 4-5 drops of indicator.
Titrate it against standard EDTA solution.
At the end point colour changes from red to blue.
Repeat it for two concordant readings.
Permanent hardness:
Take another 25 ml sample of same water and boil it for aout 15-20 minutes. This will
make temparory hardness to precipitate.
Filter it off and titrate the filtrate as described above.

Observation:
Burette: standard EDTA solution

Pipette: 25 ml of given water sample + 5 ml of buffer solution (pH=10)

Indicator: Eriochrome Black-T
Colour change: red to blue

Observation table:
Total hardness:
S. No.

Volume of water Burette reading (ml)

sample taken
Initial
final

Vol. Of
solution
(ml)

1.

25 ml

.........ml

2.

25 ml

.........ml

3.

25 ml

.........ml

EDTA
used

V2=.........ml

Permanent hardness:
S. No.

Volume of water Burette reading (ml)

sample taken
Initial
final

Vol. Of
solution
(ml)

1.

25 ml

.........ml

2.

25 ml

.........ml

3.

25 ml

.........ml

EDTA
used

V2=.........ml

Calculation:
Total hardness:
Total hardness (mg/L as CaCO3) = Burette reading X M EDTA X MW of CaCO3 X1000
Volume of sample

Permanent hardness (mg/L as CaCO3) = Burette reading X M EDTA X MW of CaCO3

X1000
Volume of sample

Subtract value of permanent hardness from total harness to get value of temporary
hardness

Result:
Total hardness (mg/L as CaCO3) =
Permanent hardness (mg/L as CaCO3) =..
Temporary hardness (mg/L as CaCO3) =