EXPERIMENT NO.

1
Object:

To determine the total, permanent and temporary hardness of water in ppm by Versenate
Method.

Theory:

Hardness of water is defined as soap consuming power. Any salt which precipitates soap is
responsible for hardness. As soaps are sodium or potassium salts of higher fatty acids, sodium
and potassium don’t cause any hardness. The divalent soluble salts e.g. Ca(HCO3)2, Mg(HCO3)2,
CaSO4, MgSO4, CaCl2 and MgCl2 etc. are generally found in appreciable amounts and are thus
considered responsible for hardness in ground water. The presence of FeSO4, Al2(SO4)3 also
cause hardness in water although their presence are not very common. The determination of
hardness of water is essential for the quality control of the water used in machines etc.

The following units represent the degree of hardness:-

Milligrams per litre ( mg/l) is the number of mg of hardness causing impurities expressed in terms of
calcium carbonate present in 1 litre of water.
Parts per million (ppm) is the number of parts by weight of hardness causing impurities expressed in
terms of calcium carbonate present in one million parts by weight of water.
Grains per gallon (gr/gal) is the number of grains of hardness causing impurities expressed in terms of
calcium carbonate present in one gallon of water.
Degree Clark ( 0Cl) is the number of parts by weight of hardness causing impurities expressed in
terms of calcium carbonate present in 70,000 parts by weight of water.
Degree French ( 0 Fr) is the number of parts by weight of hardness causing impurities expressed in
terms of calcium carbonate present in 105 parts by weight of water.
Equivalents per million (epm) is the number of equivalents of calcium carbonate corresponding to the
weight of hardness causing impurities expressed in terms of calcium carbonate per million parts by
weight of water.
The units of degree of hardness are related as follows :-

100 mg/l = 100 ppm = 2 epm = 100 Fr = 70 Cl = 7 gr/gal.

The versenate, commercial name of disodium salt of ethylene diamine tetra acetic acid (EDTA)
forms stable and soluble complex with a large number of metal ions responsible for hardness.
Versenate method is the best method available for the estimation of hardness as it is simple
inexpensive and gives accurate results. The determination is based upon the fact that when a
water sample is titrated with a solution of versenate, calcium and magnesium ions present in
water react with the compound to form soluble and un-ionizable complex at about pH 10 thus
rendering Ca2+ and Mg2+ inactive. The end point is detected by Eriochrome Black T indicator
which gives red colour of the presence of Ca2+ and Mg2+ (ions) due to the formation of red
metal-indicator complexes at pH 10. The addition of versenate solution results in the formation
of more stable metal-EDTA complexes as compared to metal-indicator complexes. The
versenate first reacts with hardness producing metal ions present in water and when they are
consumed it reacts with metal ions released from the less stable metal indicator which gives rise
to its original blue colour at the end point. The formula of the versenate is:

Ethylenediaminetetraacetic acid disodium salt (EDTA)

The above equation can be written as:

The metal ions get attached in place of H-atoms of the carboxylic acid groups, present in the
versenate, forming stable complexes and not through the carboxylate ions created by the
ionization of Na+ in solution.
Eriochrome Black T is a monosodium salt of an organic dye (NaH2D−). In solution it can be
represented by the formula H2D−. Initially, when it is added to hard water along with buffer
solution of pH 10, the reaction is:

On addition of versenate, the red colour diminishes and ultimately at the end point changes from
red to sky blue.

Apparatus and Chemicals Required:

Burette, pipette, conical flask, 250 ml standard flask, funnel, watch glass, Buffer solution (pH
10), Eriochrome Black T. Versenate solution, dil. HCl (1:1), ammonia (1:1), CaCO3 and litmus
paper.

Method:

Preparation of Standard Calcium Chloride Solution:

Weigh out accurately about 0.0500 g (w) of pure CaCO3 on a watch glass transfer it into a well
cleaned conical flask rinsed with distilled water. Add 3 ml of dil. Hydrochloric acid (1:1) to
dissolve all the CaCO3, add distilled water, heat for 5 minutes to remove CO2. Cool and
neutralize the excess of acid with pure dil. Ammonia (1:1) using litmus paper as indicator which
changes from red to blue.

Transfer the solution into a cleaned 250 ml standard flask rinsed with distilled water 2 or 3 times.
Wash the conical flask 2-3 times with small portions of distilled water and transfer the washings
to the standard flask and finally make the volume upto the mark by adding distilled water. Shake
this standard solution vigorously to make it homogeneous.
Standardization of Versenate Solution:

Take 50 ml of standard CaCl2 solution is a conical flask, Add 8-10 drops of indicator and 10 ml
of buffer solution containing NH4Cl + NH4OH ) to hold the pH around 10. Titrate with versenate
solution till the colour first changes from red to blue. Note down the burette reading.
Determination of Total Hardness:
Take 50 ml of the hard water sample in the conical flask. Add 8-10 drops of the indicator and 10
ml of buffer solution to hold the pH around 10. The colour of the solution will be red if any
hardness is present. Now add the reagent (versenate solution) from the burette until the red
colour just changes to pure blue. Note down the burette readings.
Determination of Permanent Hardness:

Take 50 ml of the hard water sample in a beaker rinsed with distilled water. Boil it to reduce its
volume to approximately less than half (to ensure that the temporary hardness is completely
removed). Cool and filter it into a conical flask rinsed with distilled water, Wash the flask with
distilled water 2-3 times and filter the washings also into the same flask to ensure that no
permanent hardness producing salts are left in the flask. Titrate the filtrate with the versenate
solution as above note down the end point when the colour changes from red to pure blue.

Observations:

Weight of the watch glass + CaCO = ag

Weight of the watch glass alone = bg

Weight of CaCO3 = (a-b ) g = c g

Standardization of Versenate Solution:

S.No. Volume of Standard Burette Readings Volume of versenate
Hard Water (CaCO3) solution consumed
Solution Initial Final

1 50 ml 0.0

V1 ml
2 50 ml 0.0

3 50 ml 0.0
Determination of Total Hardness:

S.No. Volume of Hard Burette Readings Volume of versenate

Water sample (Total solution consumed
Hardness) Initial Final

1 50 ml 0.0 -
V2 ml
2 50 ml 0.0 -

3 50 ml 0.0 -

Determination of Permanent Hardness:

S.No. Volume of Hard Burette Readings Volume of versenate

Water Sample solution consumed
(Permanent) Initial Final

1 50 ml 0.0

V3 ml
2 50 ml 0.0

3 50 ml 0.0

Calculations:

250 ml standard CaCl2 solution contains c mg of CaCO3

1000 ml standard hard water (CaCO3) solution will contain = x c = 4c mg

Hardness of hard water (CaCO3) solution will be = 4c mg/L or 4c ppm

Volume of standard hard water solution taken for titration = 50 ml

Amount of Hardness in 50 ml satandard hard water =

(1) V1 ml of versenate solution is consumed by 50 ml of standard hard water.

 Hence V1 ml of versenate solution is equivalent to CaCO3

1 ml of versenate solution will be equivalent to of CaCO3

= of CaCO3 = FACOR

(2) Volume of versenate solution consumed by 50 ml of hard water sample = V2 ml

Hardness in 50 ml of hard water sample will be = V2 x FACTOR

OR

= V2 x

Hardness in 1000 ml of hard water sample = / or ppm

(3) Permanent hardness can be calculated as:

Temporary hardness = [Total hardness - Permanent]

Results:

The total hardness of the given sample of water = …. ppm

The permanent hardness of the given sample of water = …. ppm

The temporary hardness of the given sample of water = ….ppm

Significance:

The use of hard water in the boilers leads to several boiler defects like scale and sludge
formation, corrosion, caustic embrittlement and priming and foaming. The use of hard water in
washing etc. also leads to unnecessary wastage of soap. So the hard water should be softened
before feeding it to boiler.

However, the presence of soluble salts in drinking water is essential for normal maintenance of
health but the total dissolved solids should not be more than 1000 ppm and the hardness should
not be more than 500 ppm.