ESTIMATION OF HARDNESS BY EDTA

Aim

To determine the hardness in an unknown water sample

Scope This determination is help full in calculating various types of hardness causing substances present in water It also gives an idea about the quantity of chemicals required to treat water hardness

Principle / Theory

Water hardness is an indication of the sum of the calcium and magnesium ion concentration. These cations form insoluble salts with soap, decreasing its cleansing property (effectiveness). They also form hard deposits in hot water heaters. The standard way to express water hardness is in ppm as CaCO3 which has the formula weight of 100.1 g/mole. An excellent way to determine water hardness is to perform a complexometric titration using a standard di sodium salt of ethylenediaminetetraacetic acid (EDTA) solution. Due to steric hindrances, EDTA will complex with calcium and magnesium in a one-to-one molar ratio. The endpoint in this experiment is determined using EBT indicator. The indicator imparts a wine red color to the solution while there are calcium and magnesium ions that have not complexed with EDTA. Once the endpoint has been reached and there is no more uncomplexed Ca or Mg, the indicator will give a steel blue color. No hint of red color will be left.
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Reaction pH10 i. Ca 2+/Mg2+ (in H2O) + 2 Na-EBT Colourless Steel Blue (EBT)2Ca + 2Na+ (H2O) Wine red

pH10 ii. (EBT)2Ca + EDTA diNa Ca-EDTA + Wine red Meta stable colourless Stable 2 Na-EBT Steel Blue

Structures

: EBT , EDTA , M-EDTA complex

Figure 1: Structure of EBT

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Figure 2: Structure of di-Sodium EDTA

Figure 3: Octahedral Metal-EDTA complex

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Reagents required and their Preparation

1. Standard Hard water (SHW): 1 gram of CaCO3 is dissolved in minimum amount of dil.HCl and the clear solution is made up to 1 litre in a standard volumetric flask.

2. EDTA: 3.9 grams of di sodium salt of EDTA is dissolved in 1litre of de ionised water.

3. EBT indicator: 500mg of EBT is dissolved in 100ml of absolute alcohol.

4. Ammonia buffer: 67.5 grams of ammonium chloride is dissolved in water. 570 ml of ammonia is added and the solution is made up to 1 litre.

Procedure Titration 1: Standardisation of EDTA / Determination of EDTA equivalence

50ml of standard hard water is taken in a clean conical flask. To this 10ml of ammonia buffer and 5 drops of EBT indicator are added. A wine red colouration appears.

The above solution is titrated against EDTA solution taken in a burette till the wine red colour changes to Steel blue colour. The titration is repeated for concordance and the readings are tabulated . From the concordant value the EDTA equivalence is calculated.

Let the volume of EDTA consumed be T1 ml (concordant titer value)

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Titration 2: Estimation of Total Hardness

50ml of sample hard water is taken in a clean conical flask. To this 10ml of ammonia buffer and 5 drops of EBT indicator are added. A wine red colouration appears. The above solution is titrated against EDTA solution taken in a burette till the wine red colour changes to Steel blue colour. The titration is repeated for concordance and the readings are tabulated. From the concordant value the total hardness is calculated.

Let the volume of EDTA consumed be T2 ml (concordant titer value)

Titration 3: Estimation of Permanent Hardness

50ml of sample hard water is taken in a clean conical flask and heated to dryness. All the temporary hardness causing ions, being thermally unstable forms insoluble precipitates (CaCO3 and Mg (OH)2. The residue is redissolved in minimum water and filtered. The permanent hardness causing substances, being soluble goes into the filtrate while the temporary hardness causing substances remains in the residue. The filtrate is made up to 50 ml. To this 10ml of ammonia buffer and 5 drops of EBT indicator are added. A wine red colouration appears. The above solution is titrated against EDTA solution taken in a burette till the wine red colour changes to Steel blue colour. The titration is repeated for concordance and the readings are tabulated. From the concordant value the permanent hardness is calculated.

Let the volume of EDTA consumed be T3 ml (concordant titer value)

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Calculations: i. From titration 1 : EDTA Equivalence

1 gram of CaCO3 is dissolved in 1 litre of water 1000mg of CaCO3 is present in 1000ml of water 1ml of water contains 1mg of CaCO3 Hence 50ml of Standard HW = 50mg of CaCO3 50ml of SHW consumes T1 ml of EDTA 50mg of CaCO3 T1 ml of EDTA 1ml of EDTA 50 mg of CaCO3 T1

ii.

From titration 2 : Total Hardness

50ml of Sample H W consumes T2 ml of EDTA EDTA equivalence = 50/T1 Amount of CaCO3 in 50ml of sample hard water = T2 X 50/T1 Therefore Total Hardness (ie mg / L ) = [T2 X 50 ] X 1000 T1 50

= 1000 [T2 /T1] ppm.

iii.

From titration 3 : Permanent Hardness

50ml of Boiled sample HW consumes T3 ml of EDTA EDTA equivalence = 50/T1 Amount of CaCO3 in 50ml of Boiled sample hard water = T3 X 50/T1 Therefore Permanent Hardness (ie mg / L ) = [T3 X 50 ] X 1000 T1 = 1000 [T3 /T1] ppm.
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iv.

Calculation of Temporary hardness

Temporary hardness = Total hardness Permanent Hardness =1000 [T2 /T1] 1000 [T3 /T1] = 1000 [T2 T3] ppm T1

REFER CLASS NOTES FOR PROBLEMS BASED ON EDTA METHOD

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