Discipline of Environmental and Food Chemistry

LABORATORY CLASS
- waters hardness Determination of waters hardness (using the complexometric method)
Waters hardness is represented by the total metallic cations, with the exception of
those of the alkaline metals and of the hydrogen ions present in water.
Calcium and magnesium ions are found in higher concentrations than the other
cations, this is why the hardness of water can be defined as the total soluble calcium and
magnesium salts which are contained in water.
Calcium and magnesium bicarbonates form the waters temporary hardness (Ht) and
calcium and magnesium nitrates, chlorides and sulfates form the waters permanent hardness
(Hp). Their sum form the waters total hardness (Htotal).
Through boiling, the calcium and magnesium bicarbonates are transformed into the
corresponding carbonates (which are insoluble), with the emission of the corresponding
carbon dioxide; in this way, the temporary hardness disappears through boiling.
Waters hardness is expressed in degrees of hardness, which can be: German
degrees (1 German degree = 10 mg CaO) or French degrees (1 French degree = 10 mg
CaCO3).
Principle of the method
Total hardness is determined by titration with a solution of complexon III 0,01 M
solution (the sodium salt of ethylenediaminetetraacetic acid), in the presence of the
Eriochrome Black T indicator, at pH = 10, with a color change from red to blue.
The reactions which take place:
- When the indicator (Eriochrome Black T) is added in the titration flask, in the water sample,
Eriochrome Black T forms a red colored chelate complex with the bivalent ions, which is
only slightly stable:

- During the titration, sodium ethylenediaminetetraacetate reacts with the bivalent metal ions,
forming calcium and magnesium ethylenediaminetetraacetate:

Discipline of Environmental and Food Chemistry

- At equivalence, the metal from the labile chelate formed with Eriochrome Black T is
unbound by complexon III, with the formation of the more stable complexonate and with the
reformation of the blue colored indicator:

Reagents
- complexon III 0,01 M solution;
- calcium chloride standard solution;
- ammonia buffer solution;
- sodium hydroxide, 2N solution;
- indicator I (Eriochrome Black T);
- indicator II (murexide);
- hydrochloric acid 10 % solution;
Establishing the factor of the complexon III solution
10 ml of calcium chloride standard solution, 1 ml of sodium hydroxide solution 2N,
0,1 g of indicator (II) and 10 ml of distilled water are introduced in a 100 ml Erlenmeyer
flask. The mixture is titrated with complexon III solution until the color changes from red to
intense violet.
Operating mode
A. Total hardness (Htotal):
- For the samples of water which do not contain alkaline carbonates (sample which is
negative towards phenolphthaleine): 25 ml of the sample, 10 ml of ammonia buffer, 0,1 g of
indicator (I) and 25 ml of distilled water are added. The mixture is titrated with complexon III
0,01 M solution until the color changes from red to blue.
Calculation
Total hardness (Htotal) = ( 0,561 * V1*F / V * 10 ) * 1000 German degrees
- 1 ml of complexon III 0,01 M solution titrates 0,561 mg CaO;
- V1 = the volume of complexon III solution used for titration (ml);
2

Discipline of Environmental and Food Chemistry

- V = the volume of the sample (ml);

- F = the factor of the complexon solution;
- 10 = the quantity of CaO corresponding to 1 German degree of hardness;
If the volume of titrated complexon III solution exceeds 5 ml, the determination can be done
on a sample dilluted with distilled water in a proportion of 1:1.
B. Temporary hardness (Ht) :
- Is calculated from the alkalinity of the water, determined by titration with HCl 0,1 N of 100
ml of water, in the presence of methyl-orange.
Calculation
1 ml of HCl 0,1 N titrates 2,8 mg CaO;
German degrees of hardness/L = 2,8*V*F, in which:
- V = the volume of hydrochloric acid used for titration;
- F = the factor of the hydrochloric acid solution;
The permanent hardness (H p) is calculated by difference between the total hardness
and the temporary hardness; Hp = Htotal - Ht;
If after these determinations the values obtained for the temporary hardness are higher
or equal to the total hardness (the sample contains alkaline carbonates), the operating mode is
modified as follows:
- the total hardness is determined by the complexonometric method, after the sample
is boiled for 1-2 minutes in the presence of 2 ml of HCl 10 %;
- the permanent hardness is determined by the same method, operating as follows: a
volume of 200-300 ml of the sample is introduced in a Berzelius beaker and the water is
boiled for 30 minutes; after cooling, the volume is brought again to the initial volume; the
sample is filtered; the total hardness is determined by the complexonometric method, using
25 ml of the filtrate; temporary hardness is determined by difference: H t = Htotal - Hp;
Interpretation of results
For drinkable water, the total hardness (German degrees): minimum 5;