Titration - I

Standardization of EDTA
Standard hard water Vs EDTA

Burette Reading (ml) Volume of

No Volume of Std hard EDTA (ml) Indicator
water (ml) (V1) Initial Final (V2)

1 20 0
Eriochrome
Black – T
(EBT)
2 20 0

CALCULATION:
Volume of standard hard water (V1) = ---------------- ml
Normality of standard hard water (N1) = ---------------- N
Volume of EDTA solution (V2) = ---------------- ml
Normality of EDTA solution (N2) = ?
V1 × N1
N2 =
V2

N2 =

= N

Normality of EDTA solution (N2) = ----------------------- N

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EXP. NO: DATE:

DETERMINATION OF HARDNESS OF WATER

(EDTA – METHOD)

AIM:
To estimate the amount of (i) Total (ii) Temporary and (iii) Permanent hardness in the
given sample of water. You are provided with a standard hard water containing known
CaCO3 amounting exactly to 0.01N and approximately same normal EDTA solution.

PRINCIPLE:
A hard water is one which does not readily give lather with soap solution. Instead, it will
form fine turbid precipitate as indicated follow.
2C17H35COONa + CaCO3 → (C17H35COO) 2 Ca↓ + Na2CO3
(Sodium stearate) (Present in water)
Hardness is mainly due to the presence of bi- carbonates, chlorides and sulphates of
Ca , Mg2+ ions. Among these bicarbonates cause temporary hardness and other salts cause
2+

permanent hardness. Temporary hardness is removed simply by boiling.

Hardness can be estimated by titration with the reagent EDTA (Ethylene Diamine
Tetra Acetic Acid). It is available as its disodium salt. For the titration the indicator namely
Eriochrome Black – T is used. This indicator forms wine red colour complex with the cation
presents in water but this complex is unstable.
AT THE BEGINNING: (on the addition of Indicator)
Ca2+ + EBT → (Ca – EBT) Wine Red Colour Complex
DURING TITRATION:
Ca2++ EDTA → (Ca – EDTA) – Colourless
(Present free in water)

AT THE END POINT:

(Ca – EBT) + EDTA → (Ca – EDTA) + EBT
(Wine red) (Free Indicator, steel blue)
Free indicator has steel blue colour. Hence the end point is the change of Wine red
into steel blue colour. Metal – EDTA complexes are stable only at the pH range of 8.5 to 10;
For this purpose, an ammoniacal buffer (NH4OH + NH4Cl) is used. Hardness of water is
expressed in terms of CaCO3 equivalents and the equivalent weight of CaCO3 is 50.

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 Titration -II
Estimation of Total hardness
Hard water Vs Standard EDTA

Burette Reading (ml) Volume of

No Volume of Tap water EDTA (ml) Indicator
(ml) (V2) Initial Final (V1)

1 20 0
Eriochrome
Black – T
2 20 0 (EBT)

CALCULATION:
Volume of EDTA solution (V1) = ------------------ ml
Normality of EDTA solution (N1) = -------------------N
Volume of Tap water (V2) = ------------------ml
Normality of Tap water (N2) = ?
V1 × N1
N2 =
V2

N2 =

= N

Normality of Tap water (N2) =----------------------- N.

Total hardness of Tap water in terms of CaCO3 equivalent

= Normality of tap water × 50 × 1000
= × 50 × 1000
= mg/l

Total hardness of Tap water = ------------------------- mg/l.

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Procedure:
Titration I STANDARDISATION OF EDTA
The burette is filled with the given EDTA solution after proper washing and rinsing.
20ml of standard hard water is pipette out into a conical flask. About 5 ml of ammoniacal
buffer solution is added which is followed by a few crystals of Eriochrome Black – T (EBT)
indicator. Wine red coloration is obtained. This solution is titrated against EDTA solution.
The end point is the change of wine red into steel blue colour. The titre value is noted. From
the titre value normality of EDTA is calculated.
Titration II ESTIMATION OF TOTAL HARDNESS
Exactly 20 ml of tap water is transferred into a conical flask. About 5 ml of the
ammoniacal buffer and a few crystals of indicator (EBT) are added. It is then titrated against
the same EDTA kept in the burette. The end point is the change of wine red into steel blue
colour. The titre value is noted. From the titre value, the hardness strength (normality) of tap
water is calculated. From the strength the hardness is evaluated.
Titration III ESTIMATION OF PERMANENT HARDNESS
A fresh sample of 20 ml of the same tap water is taken in a conical flask. It is kept for
boiling over Bunsen burner for about 20 minutes. The bicarbonates are decomposed into
carbonates and settle down as precipitate.
Ca (HCO3)2 → CaCO3 ↓ + H2O + CO2
It is cooled and then filtered. The filtrate is titrated against EDTA after the addition of
about 5 ml of ammoniacal buffer and few crystals of EBT indicator. The same end point is
observed. From the titre value, the hardness is calculated which corresponds to permanent
hardness alone.

IV. TEMPORARY HARDNESS = TOTAL HARDNESS – PERMANENT HARDNESS

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 Titration - III
Estimation of Permanent hardness
Boiled hard water Vs Standard EDTA

Burette Reading (ml) Volume of

No Volume of Boiled EDTA (ml) Indicator
water (ml) (V2) Initial Final (V1)

1 20 0
Eriochrome
Black – T
2 20 0 (EBT)

CALCULATION:
Volume of EDTA (Titre value) (V1) = ---------------- ml
Normality of EDTA (N1) = ------------------- N
Volume of Boiled water (V2) = ----------------- ml
Normality of Boiled water (N2) = ?

V1 × N1
N2 =
V2

N2 =

Normality of Boiled water N2 = ----------------------N.

Permanent hardness of Boiled water in terms of CaCO3 equivalent
= Normality of Boiled hard water × 50 × 1000
= × 50 × 1000
= mg/l
Temporary hardness = Total hardness – Permanent hardness
= -
= mg/l

Temporary hardness = ------------------------ mg/l. (or) ppm

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RESULT:
1. Total hardness of water = ------------------------ mg/l (or) ppm.

2. Permanent hardness of water = -------------------------mg/l (or) ppm.

3. Temporary hardness of water = ----------------------- mg/l (or) ppm.

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 ESTIMATION OF HARDNESS OF WATER
(EDTA – METHOD)

No. Content Titration – I Titration - II Titration - III

1 Burette Solution EDTA Std. EDTA Std. EDTA

2 Pipette Solution 20ml of Std. 20ml of Tap 20ml of boiled

Hard water water water

3 Reagents to be added 5ml of ammonia 5ml of ammonia 5ml of ammonia

buffer buffer buffer
(NH4OH + (NH4OH + (NH4OH +
NH4Cl) NH4Cl) NH4Cl)

4 Indicator EBT EBT EBT

(Erichrome (Erichrome (Erichrome
Black – T) Black – T) Black – T)

5 End point Wine red to Wine red to Wine red to

Steel blue Steel blue Steel blue

Equivalent weight of CaCO3: 50

Hardness in Water = Normality X 50X 1000 ppm

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 DETERMINATION OF HARDNESS OF WATER SAMPLE

1. What is temporary hardness?

Hardness of water due to presence of carbonates and bicarbonates of
Calcium and magnesium is called temporary hardness.
2. What is permanent hardness?
Hardness of water due to presence of chlorides and sulphates of calcium
and magnesium is called permanent hardness.
3. What is the other name for temporary and permanent hardness?
Carbonate and non – carbonate hardness.
4. What is the unit of hardness?
ppm and mg/l
5. Give the structure of EDTA
HOOCH2C CH2COOH
N ─ CH2 ─ CH2 ─ N
HOOCH2C CH2COOH
6. What is the role of buffer solution?
To maintain pH 9 – 10.
7. What is the name of the buffer used in EDTA titration?
Mixture of Ammonium chloride (NH4Cl) &Ammonium hydroxide (NH4OH)
8. Why hardness is expressed in equivalents of calcium carbonate?
Calcium carbonate is most insoluble salt and its molecular weight and
equivalent weights are 100 and 50 respectively.
9. What is hard water and soft water?
Water which readily lathers with soap is called soft water and which
does not produce lather is known as hard water.

10. What is the indicator used in this titration?

Eriochrome Black – T