Experiment 5

Determining the Total Hardness of Water

by the EDTA Method

Aim of the Experiment: To determine the total hardness of water by the EDTA method.
Apparatus Required: Pipette, burette, conical flask, beaker, measuring flask, etc.
Chemicals Required: Given sample of water, standard Eriochrome Black T indicator, standard EDTA
solution, and ammonical buffer solution (NH4OH + NH4Cl).
Theory: Water containing Ca+2 and Mg+2 ions as carbonates, bicarbonates, chlorides and sulphates is
known as hard water. The hardness of water plays a very important role in domestic activities, sugar
industry, pharmaceuticals, textile industry, food processing industry, etc. So measuring the hardness of
water and removing the same is very important.
A sample of water is called hard water if it is hard to make lather in it with soap. Soap is a sodium
or potassium salt of higher fatty acids like stearic acid, oleic acid, palmatic acid, etc. When soap is dis-
solved in hard water, the Ca++ and Mg++ ions present in it react with fatty acid ions forming insoluble
salts which are precipitated out.
2C17H35COONa + Ca++ → (C17H35COO)2Ca + 2Na+
(Sodium Stearate, Soap) (or Mg+2) (ppt.)
The total hardness of water is the sum of: (i) temporary hardness, and (ii) permanent hardness.
(i) Temporary Hardness: Temporary hardness is caused by the presence of bicarbonates of Ca++
and Mg++ ions, but these can be removed simply by boiling. Hence the condition is called temporary
hardness.
Ca(HCO3)2 → CaCO3 + CO2 + H2O
heat (ppt.)
Mg(HCO3)2 → MgCO3 + CO2 + H2O
(ppt.)
The precipitate is removed by filtration.

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(ii) Permanent Hardness: This condition is caused by the presence of chlorides, sulphates, and car-
bonates of Ca++ and Mg++ ions. These can be removed only by chemical methods.
The hardness of water is usually determined by the EDTA method which is a complexometric method
that gives more accuracy, convenience and rapidity.
The EDTA method is a complexometric method for determining the hardness of water. EDTA is
the disodium salt of ethylene diamine tetra acetate.
NaOOC− CH2 CH2−COOH
N −CH2−CH2−N
HOOC− CH2 CH2−COONa

In an aqueous solution, EDTA ionizes to give EDTA−2 and 2Na+ ions. EDTA−2 ion is a strong chelating
group.
Eriochrome Black T is a typical metal ion indicator which forms an unstable complex with Ca++
and Mg++ ions when added to hard water at pH around 10 and gets a wine red colouration. When this
unstable complex solution is titrated against the standard EDTA solution, the colour of the solution
changes from wine red to blue, showing the end point. The structure of the indicator is given below:
NO
2
O
N
N

O
S

−
Na
OH

+
O
HO

Since this indicator contains two phenolic ionisable hydrogen atoms, the Eriochrome Black T indicator
can be represented as Na+ H2In−; its full name is [Sodium−1−(1−hydroxy−2−napthylazo)−6−nitro−2−
naphthol−4−sulphonate]. When hard water containing Ca++ and Mg++ ions is treated with the indicator,
it forms an unstable complex with these ions.

Ca+2 + Na+H2In− → [Ca+2 Na+H2In−]

or Mg+2
(indicator) or Mg+2 (unstable complex having
wine red colour)
This solution, when titrated with the standard EDTA solution, turns blue in colour at the end point.
The Ca+2 and Mg+2 ions have greater attraction towards EDTA than towards Na+H2In− , and thus they
form a more stable complex with EDTA while the indicator molecule is released at the end.
[Ca+2 Na+H2In−] + EDTA → [Ca++ EDTA] + Na+H2In−
or Mg+2 or Mg+2
(unstable complex) (stable complex) (indicator)
The optimim pH for determining the total hardness of water by the EDTA method is 10.0 ± 0.1. This
is maintained by adding an ammoniacal buffer solution.

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 EXPERIMENT 5 | 23

Total hardness is the sum of the temporary hardness and the permanent hardness of water. Tempo-
rary hardness is removed by boiling hard water and removing the precipitate by filtration. Permanent
hardness is determined by complexometric titration with EDTA.

Procedure
Preparation and standardisation of hard water
1. Weigh 1 gm of pure and dry CaCO3 accurately and transfer it into a 250 cc beaker.
2. Dissolve it with a minimum quantity of dilute HCl.
3. Boil it to dryness, cool, and dissolve the residue with a little amount of water.
4. Transfer the entire content along with washings into a 1L measuring flask and dilute it up to the
mark with distilled water. This solution contains 1 mg/ml of CaCO3 and it can be standardised
(however, standard hard water is also available and can be used directly.)

Determining the total hardness of water

1. Clean the burette with water and then rinse and fill it with the supplied standard EDTA
solution.
2. Pipette out 10 ml of standard hard water (1 ppm.) into a 250 cc clean conical flask.
3. Add 2 cc of buffer solution (NH4OH + NH4Cl buffer) and put in it 2 drops of Eriochrome Black
T indicator. The colour of the solution changes to wine red.
4. Titrate the solution slowly against the EDTA solution taken in the burette till the end point
where the colour changes from wine red to blue.
5. Repeat the titration with fresh solution till three concordant readings are obtained. Assume the
volume of EDTA used is V1 cc.
6. Repeat the titration process with the supplied sample water and find out the volume of EDTA
used. Assume it is V2 cc.

Determining the permanent hardness of water

1. Take 100 cc of supplied hard water in a 250 cc beaker and heat gently so that it boils slowly for
about an hour.
2. Cool and filter it into a 100 cc measuring flask and increase the volume up to the mark with
distilled water.
3. Pipette out 10 cc of this water into a 250 cc clean conical flask. Add 2 cc of ammoniacal buffer
solution. Then add 2 drops of Eriochrome Black T indicator so that the colour changes to wine
red.
4. Titrate this solution against the standard EDTA solution till the end point where the colour
changes to blue.
5. Repeat the titration process with fresh solutions till 3 concordant readings are obtained.
Assume the volume of EDTA used is V3 cc.

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Observation and Tabulation

(i) Tabulation for total hardness (with standard hard water)

No. of Volume of Standard IBR FBR Difference Remarks

Observations Hard Water (in cc) (in cc) (in cc) (in cc)
1. 10
2. 10
3. 10 V1 cc

(ii) Tabulation for total hardness (with sample hard water)

No. of Volume of Sample IBR FBR Difference Remarks

Observations Hard Water (in cc) (in cc) (in cc) (in cc)
1. 10
2. 10
3. 10 V2 cc

(iii) Tabulation for permanent hardness (with sample hard water)

No. of Volume of Sample IBR FBR Difference Remarks

Observations Hard Water (in cc) (in cc) (in cc) (in cc)
1. 10
2. 10
3. 10 V3 cc

Calculation
1 cc of standard hard water ≡ 1 mg of CaCO3
From table, i) V1 cc of EDTA solution ≡ 10 cc of standard hard water.
or, 1 cc of EDTA solution ≡ 10/V1 cc of standard hard water (1)
Again, for sample hard water (Table ii), 10 cc of sample hard water
≡ V2 cc of EDTA solution
≡ V2 × 10/V1 cc of standard hard water
≡ V2 × 10/V1 mg of CaCO3.
Hence, 1 cc of sample hard water = V2 × 10/ V1 × 10 = V2/V1 mg CaCO3.

So, 1000 cc of sample hard water ≡ 1000 × V2/V1 mg CaCO3 = 1000 × V2/V1 ppm
= The total hardness of water (A).

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 EXPERIMENT 5 | 25

Again, according to Table (iii), the permanent hardness of water is as follows:

10 cc of boiled sample hard water ≡ V3 cc of EDTA solution.
or, 1000 cc of boiled sample hard water ≡ 100 × V3 cc of EDTA solution.
But from eq. (1),
1 cc of EDTA solution ≡ 10/V1 mg of CaCO3.
So,
1000 cc of boiled sample of hard water ≡ 100 × V3 cc of EDTA solution
= 10/V1 × 100 × V3 mg CaCO3
= 1000 × V3/V1 mg CaCO3
= 1000 × V3/V1 ppm
= Permanent hardness of water (B).
The temporary hardness of water = A − B = 1000 V2/V1 − 1000 V3/V1
= 1000/V1 (V2 – V3) mg CaCO3
= 1000/V1 (V2 – V3) ppm.

Sample Calculation
(i) Standardisation of hard water:
10 cc of standard hard water ≡ 1.5 cc of EDTA solution.
Given the above, 1 cc of standard hard water ≡ 1 mg of CaCO3.
so, 10 cc of standard hard water ≡ 1.5 cc of EDTA solution
≡ 10 mg of CaCO3.
or, 1 cc of EDTA solution ≡ 10/1.5 = 6.6667 mg of CaCO3 (1)
(ii) Total hardness of water:
10 cc of unknown hard water ≡ 2.6 cc of EDTA solution
≡ 2.6 × 6.6667 = 17.333 mg of CaCO3.
1000 cc of unknown hard water ≡ 100 × 17.333 = 1733.3 mg of CaCO3
= 1733.33 ppm (2a)
(iii) Permanent hardness of water:
10 cc of boiled hard water ≡ 0.8 cc of EDTA solution.
1000 cc of boiled hard water ≡ 0.8 × 100 = 80 cc of EDTA solution
≡ 80 × 6.6667 = 533.333 mg of CaCO3 (3b)

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Hence,
temporary hardness of water = total hardness of water
− permanent hardness of water
= A − B = 1733.33 − 533.33
= 1200.0 mg of CaCO3
= 1200.0 ppm. of CaCO3.

Conclusion
In the given sample of water, the temporary and permanent hardness is 1200.0 and 533.33 ppm.
respectively.

Precautions
1. All the glassware like pipette, burette, beaker, etc. should be cleaned and rinsed properly with
water.
2. Freshly prepared solutions/reagents should be used in the experiment.
3. Required amount of buffer solution should be added in order to maintain pH at 10 during
titration.
4. The end point should be noted correctly.
5. The same amount of indicator should be added each time.
6. The hard water should be boiled till a white turbidity appears.

Short Questions for Viva Voce

1. What do you understand by hard water?

Ans. The water in which it is hard to get lather with soap is hard water.
2. Why does hardness arise in water?
Ans. The hardness of water is due to the presence of Ca++ and Mg++ ions as carbonates, bicarbonates,
chlorides, and sulphates.
3. What are the types of hardness of water?
Ans. Hardness of water is of two types, namely (i) temporary hardness and (ii) permanent hardness.
4. What do you mean by temporary hardness of water?
Ans. Water containing bicarbonates of Ca++ and Mg++ ions is called temporary hard water.
5. How can temporary hardness of water be removed?
Ans. Temporary hardness of water can be removed by simply boiling it so that the bicarbonates are
converted into insoluble carbonates and can be removed by filtration.
Ca(HCO3)2 → CaCO3 + H2O + CO2
(ppt.)
Mg(HCO3)2 → MgCO3 + H2O + CO2
(ppt.)

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 EXPERIMENT 5 | 27

6. What do you mean by permanent hardness of water?

Ans. Water containing carbonates, sulphates, and chlorides of calcium and magnesium is called
permanent hard water. It cannot be removed by simple methods.
7. How can permanent hardness of water be removed?
Ans. This is done by chemical methods like: (i) lime−soda process, (ii) zeolite or permutit process,
and (iii) ion−exchange method.
8. Which buffer solution is used in this experiment?
Ans. Ammoniacal buffer consisting of a mixture of NH4Cl and NH4OH.
9. What do you mean by a buffer solution?
Ans. A buffer solution is a solution which resists the change in pH upon addition of a little acid or
alkali to it.
10. Why is ammoniacal buffer used in this experiment?
Ans. It has pH = 10.0. The optimum pH for determining the total hardness of water by the EDTA
method is 10.0 ± 0.1.
11. Give one example of an acidic buffer.
Ans. Mixture of acetic acid and sodium acetate.
12. What are the reasons for measuring hardness of water?
Ans. The knowledge of hardness of water is very essential for domestic purposes and for use in the
sugar industry, pharmaceuticals, food processing industry, leather industry, textile industry,
adhesives industry, etc.
13. What is the full name of EDTA?
Ans. Ethylene diamine tetra acetate.
14. Why is the EDTA method preferred over other methods for determination of hardness of water?
Ans. This method gives better accuracy, convenience and more rapidity.
15. What is the formula of EDTA?
Ans.

NaOOC−CH2 CH2−COOH
N− CH2− CH2−N
HOOC−CH2 CH2−COONa

16. Why is this method called ‘determination of total hardness of water’?

Ans. Total hardness = temporary hardness + permanent hardness of water is determined by this
method.
17. Why does hard water not produce lather with soap?
Ans. The hard water containing Ca+2 and Mg+2 ions reacts with fatty acid ions of soap and precipi-
tates out instead of forming lather.

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18. Why should hard water not be used for industrial purposes?
Ans. This is because:
(i) the calcium and magnesium salts form scales in the boilers, and
(ii) MgCl2 hydrolyses in water to form HCl which causes corrosion to metal parts.
19. Why does the colour change from wine red to blue at the end point?
Ans. The wine red colour appears due to the formation of an unstable complex with Ca+2 and Mg+2
ions when indicator is added. By titration with EDTA, it forms a stable complex with Ca+2 and
Mg+2 ions, and the colour changes from wine red to blue.

20. Why and how is the pH maintained at 10 during titration?

Ans. By adding ammoniacal buffer solution having pH 10 at which the formation of complexes with
Ca+2 and Mg+2 ions takes place.
21. What are the units of hardness of water?
Ans. (i) ppm. (parts per million), i.e. 1CaCO3/MgCO3 equivalent hardness per 106 parts of water.
(ii) mg/L i.e. no. of milligrams of CaCO3 equivalent hardness per litre of water
22. Why is sodium salt of EDTA used?
Ans. Because it is highly soluble in water.
23. Why is the titration not carried out in an acid medium?
Ans. In an acid medium, the indicator Eriochrome Black−T tends to polymerise and form a red
brown colour. Hence it cannot be used in an acid medium.
24. Write the formula of Eriochrome Black−T.
Ans.
NO2
O
N
N

O
S

−
Na
OH

+
O

OH

Q.25 Name an indicator used in complexometric titration.

Ans Eriochrome Black−T.

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