Experiment No.

Aim: To determine the hardness of a given water sample.

Brief Theory:
Water hardness is caused by multivalent metallic cations, primarily the divalent Ca2+ and Mg2+
ions. Equations 1 and 2 represent the respective hardness. Anions and monovalent cations such
as Na+ and K+ do not contribute to hardness.
Ca2+ (aq) + 2HCO3- CaCO3 (s) + H2O+CO2 Eq. (1)
Mg2+ (aq) + 2OH-(aq) Mg(OH)2 (s) Eq. (2)

Hard water adversely affects the suitability of water for uses in domestic and industrial
purposes. The excessive hardness of water results in the scaling of boilers and water heaters.
Therefore, it is necessary to control the hardness. Depending on the hardness value, water may
be described as:
Degree of Hardness Hardness (mg/l as CaCO3)
Soft <50
Moderately hard 50-150
Hard 150-300
Very hard >300

Although hardness is caused by cations, it may also be discussed in terms of carbonate

(temporary) and non-carbonate (permanent) hardness. Carbonate hardness refers to the amount
of carbonates and bicarbonates present in water that can be removed or precipitated by boiling.
This type of hardness is responsible for the deposition of scale in hot water pipes and kettles.
When total hardness is numerically greater than that of total alkalinity (expressed as CaCO3),
the amount of hardness equivalent to alkalinity is called carbonate hardness. When the hardness
is numerically equal to less than the total alkalinity, all hardness is carbonate hardness. The
amount of hardness in excess of total alkalinity expressed as CaCO3 is non-carbonate hardness.
Non-carbonate hardness is caused by the association of the hardness-causing cations with
sulphate, chloride or nitrate and is referred to as “permanent hardness”. This type of hardness
cannot be removed by boiling. Hardness is determined by the EDTA method in alkaline
conditions. EDTA and its sodium salts form a soluble chelated complex with certain metal ions
as shown in equation 3.

M2++ EDTA [M.EDTA] complex Eq. (3)

The reaction between calcium ions and EDTA only occurs at a high pH; therefore, a solution
that has a constant pH of 10 (called a buffer) is added to the water sample. Eriochrome Black
T, a metal ion indicator, is used to visualize the endpoint. Eriochrome Black T (EBT) (blue
colour solution) serves as an excellent indicator to show when all hardness ions are consumed.
When a small amount of EBT is added to the hard water with pH>10, it combines with Ca2+
and Mg2+ ions to form weak complex ions (wine-red colour solution). A small amount of
indicator is added to the solution containing the Ca2+ that forms a wine-red complex.

M2++ EBT [M.EBT] complex Eq. (4)

The endpoint is indicated when the original red solution turns to blue which ensures the EDTA
has reacted with all the calcium ions present in the water sample.

1
Apparatus:
Burette, Pipette, Spatula, Dropper

Reagents:
 Standard Ethylenediaminetetraacetic acid (EDTA): Weigh approximately 3.72 g of
disodium ethylenediaminetetraacetate dihydrate (Na2EDTA·2H2O). Dissolve the
weighed EDTA in deionized water and make up the volume to 1 litre in a volumetric
flask. Mix thoroughly to prepare a 0.01 M standard EDTA solution.
 Buffer solution of pH 10.
 Eriochrome Black T indicator: Dissolve 0.4 g of Eriochrome Black T powder and 4.5
g of hydroxylamine hydrochloride in 100 ml of 95 % ethanol.

Experimental Procedure:
Total hardness
i. Take 100 mL of the sample in a conical flask.
ii. Add a few drops (~1 ml) of the pH 10 buffer solution to the conical flask.
iii. Add 5 - 6 drops of Eriochrome Black T indicator. The colour of the solution will
become dark red.
iv. Clean and fill the burette with the EDTA solution and record the initial volume.
v. Titrate the solution with EDTA till the colour of the solution changes from red to blue.
vi. Record the final volume of the burette and calculate the total hardness by using the
given formula.

Permanent hardness
i. Take 100 ml of the sample in a beaker and put it on a hot plate.
ii. Boil the sample for 15 minutes after the temperature reaches the boiling point. During
the process of boiling, the temporary hardness will be removed. Also, some water will
be lost as a result of evaporation.
iii. Make the sample equivalent to 100 ml by adding distilled water.
iv. Add a few drops (~1 ml) of the pH 10 buffer solution to the conical flask.
v. Add 5 - 6 drops of Eriochrome Black T indicator. The colour of the solution will
become dark red.
vi. Clean and fill the burette with the EDTA solution and record the initial volume.
vii. Titrate the solution with EDTA till the colour of the solution changes from red to blue.
viii. Record the final volume of the burette and calculate the permanent hardness by using
the given formula.
Calculations:
mL of EDTA used in titration (unboiled sample)
Total Hardness as CaCO3 (mg/L) = × 1000 mg/L
mL of Water sample
mL of EDTA used in titration (boiled sample)
Permanent Hardness as CaCO3 (mg/L) = × 1000 mg/L
mL of Water sample
Temporary hardness as CaCO3 (mg/L) = Total Hardness - Permanent Hardness

Observation Table:

2
For un-boiled sample

Sample No Volume (ml) Burette Reading Volume

of Sample (ml) of
EDTA
Initial Final

For boiled sample

Sample No Volume (ml) Burette Reading Volume
of Sample (ml) of
EDTA
Initial Final

Results:

Home Work
Q1. Write down the environmental significance of measuring the hardness of water samples.
Q2. Why is Eriochrome Black T used as an indicator in the hardness measurement experiment?
Q3. What is the role of a pH buffer in the hardness measurement procedure?
Q4. How might the presence of other metal ions in the water sample impact the accuracy of the
hardness measurement?

You tube Video Link:

https://www.youtube.com/watch?v=Sa0WfA9UGG0