2.

3 Total Water Hardness

Objective:
To determine the total hardness of the given samples by EDTA titrimetric method.

Principle:
Originally, the hardness of water was understood to be a measure of the capacity of water for
precipitating soap. Soap is precipitated chiefly by the calcium and magnesium ions commonly
present in water, but may also be precipitated by ions of other polyvalent metals, such as
aluminium, iron, manganese, strontium and zinc, and by hydrogen ions. Because, all but the first
two are usually present in insignificant concentrations in natural waters, hardness is defined as a
characteristic of water, which represents the total concentration of just the calcium and the
magnesium ions expressed as calcium carbonate. However, if present in significant amounts, other
hardness producing metallic ions should be included.
When the hardness is numerically greater than the sum of the carbonate alkalinity and the
bicarbonate alkalinity, the amount of hardness, which is equivalent to the total alkalinity, is called
carbonate hardness; the amount of hardness in excess of this is called non-carbonate hardness.
When the hardness is numerically equal to or less than the sum of carbonate and bicarbonate
alkalinity all of the hardness is carbonate hardness and there is no noncarbonate hardness. The
hardness may range from zero to hundreds of milligrams per litre in terms of calcium carbonate,
depending on the source and treatment to which the water has been subjected.
Ethylenediamine tetra-acetic acid and its sodium salts (EDTA) form a chelated soluble complex
when added to a solution of certain metal cations. If a small amount of a dye such as Eriochrome
black T is added to an aqueous solution containing calcium and magnesium ions at a pH of 10 ±
0.1, the solution will become wine red. If EDTA is then added as a titrant, the calcium and
magnesium will be complexed. After sufficient EDTA has been added to complex all the
magnesium and calcium, the solution will turn from wine red to blue. This is the end point of the
titration.
Experimental Sequence
1. Measure the pH of the sample with a pH meter or pH indicator paper. Fill the microburet
with the concentrated EDTA solution, and adjust to a known volume.
2. In order to measure the total hardness value (i.e., the Ca2+ + Mg2+ concentration), place
a 2-rnL, solids-free water sample (measured with a volumetric pipet) in an Erlenmeyer
flask. Add 23 mL of the pH 10 buffer, swirl and add one or two crystals (or a small amount
of powder) of the Eriochrome black solid indicator. Swirl until total dissolution. The
mixture should now appear with ared wine color. Titrate this with the EDTA solution to
adark-blueendpoint. If the amount of titrant needed to reach the endpoint is too small to be
measured, repeat the titration with another sample using a more dilute titrant (e.g., 0.001
M EDTA). Note: If the blue color appears from the start, this means there is no measurable
hardness in the sample.
2.3 Total Water Hardness
3. With a volumetric pipet, put 2 mL of the sample (free of solids) in a25-mL Erlenmeyer
flask. Add 1 mL of 2 M NaOH to ensure that the pH is frankly basic (pH rv 11); add one
or two crystals of solid murexide indicator (or a small amount of its powder), and swirl
softly until they dissolve. Titrate with 0.01 M EDTA to a violet endpoint. If the amount of
titrant needed to reach the endpoint is too small to measure, repeat the titration with another
sample using a more dilute titrant (e.g., 0.001 M EDTA). This value will let us know the
calcium ion concentration in the sample. Repeat this method with each water sample.
4. One mole of EDTA is consumed for each mole of Ca2+ or Mg2+. Because the MW of
calcium carbonate is virtually equal to 100, then the concentration of Ca or Mg (expressed
as mg/L of calcium carbonate) can be calculated with the following equation:

Total or Ca^2+ Hardness, mg/L as CaCO3 =

𝑔
(𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑇𝑖𝑡𝑟𝑎𝑛𝑡)𝑥 (𝐸𝐷𝑇𝐴 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦)𝑥 100 𝑥 1000 𝑚𝑔/𝑔
𝑚𝑜𝑙
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑎𝑚𝑝𝑙𝑒

Scenario: 100 mL of water sample was given, the titration volume is 10 mL