EXPT.

6 DETERMINATION OF THE HARDNESS

OF A GIVEN WATER SAMPLE BY
COMPLEXOMETRIC TITRATION
Structure
6.1 Introduction
Objectives
6.2 Principle
6.3 Requirements
6.4 Solutions Provided
6.5 Procedure
6.6 Observations and Calculations
6.7 Result

6.1 INTRODUCTION
As you are aware, natural water contains wide variety of organic and inorganic
dissolved impurities as well as suspended solids and gases. The dissolved inorganic
impurities present in water are mainly chlorides, sulphates, carbonates, and
bicarbonates of sodium, potassium, calcium and magnesium. The chemical nature and
physical behaviour of the impurities present in water determine the quality of water
and also forms the basis for the procedures used in the analysis of water. Water
containing carbonate, chloride and sulphate salts of heavy metals, mainly calcium and
magnesium is called hard water. When some simple soap (not a synthetic detergent)
is added to a sample of hard water, an insoluble substance commonly known as "soap
scum" is produced. This is due to the formation of insoluble salts which decrease the
cleaning efficiency of the soap. As the soap scum can deposit itself and remain on the
object being cleaned it poses problems in the general uses of the soap like, washing
hair, cleaning clothes, washing dishes etc.

The hardness of water due to the presence of bicarbonates of calcium and magnesium
is termed temporary hardness. Such hardness can be removed simply by boiling the
water; the soluble bicarbonates decompose on heating to give insoluble carbonates that
separate out. On the other hand the hardness due to the presence of chlorides and
sulphates of calcium and magnesium cannot be removed by boiling and is therefore
called permanent hardness. Though calcium and magnesium present in hard water
are nutrients that are needed for good human health, hard water is not desirable for use
at home or in industry. In industry when hard water is used for making steam, the
dissolved solids precipitate on heating and clog boiler pipes and deposit on boiler
plate. You may have noticed a similar hard white deposit called "scale" in the kettle
used for boiling water for making tea.

It is not necessary to separately determine the amount of each ion contributing to the
hardness of water. Instead, all ions contributing to hardness are determined
collectively. A uniform standard has been adopted to express hardness of water. It is
reported as parts per million (ppm) of CaCO3. It is equivalent to the number of
milligrams of CaCO3 per kg of water. The hardness of water may range from zero to
hundreds of ppm, depending on the source. An excellent way to determine hardness of
water is to perform a complexometric titration using a standard solution of
ethylenediaminetetraacetic acid (EDTA) solution.

In this experiment you would learn about and perform a complexometric titration to
determine the hardness, of a given water sample, expressed in terms of ppm of CaCO3.

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 In the next experiment you would learn about the determination of ascorbic acid in a
vitamin C tablet.

Objectives
After studying and performing this experiment you should be able to:
• define total, temporary and permanent hardness of water,
• explain the principle of complexometric determination of hardness of water,
• describe the formation of a complex of metal ions with ethylenediamine-
tetraacetic acid (EDTA),
• explain the role of the buffer in complexometric titrations with EDTA,
• explain the principle of metallochromic indicator used in the titration with
EDTA, and
• determine total, temporary and permanent hardness of a given sample of water
by complexometric titration.

6.2 PRINCIPLE
Hardness is an expression for
The determination of the total hardness of water is based on complexometric titration
the sum of the concentrations
of the calcium and of calcium and magnesium present in it with an aqueous solution of the disodium salt
magnesium ions present in a of ethylenediaminetetraacetic acid at pH value of 10. EDTA is a well-known
water sample. complexing agent, which is extensively used in analytical work on account of its
powerful complexing action and commercial availability. Its chemical formula can be
represented as follows.
HOOC-H2C CH2-COOH

:N CH2 CH2 N:

HOOC-H2C CH2-COOH

Structure of ethylenediamminetetraacetic acid (EDTA)

EDTA is capable of forming stable 1:1 complexes with most of the metal ions. For
example, the reaction of its disodium salt with calcium ions can be represented as:
2+
Ca (aq.) + Na2EDTA (aq.) Ca.EDTA2- (aq.) + 2Na2+

The general structure of the metal-EDTA complex is given below.

Structure of metal-EDTA complex

The equivalence point of a complexation titration occurs when stoichiometrically
equivalent amounts of analyte and titrant have reacted. It means that the solution
concentrations of the metal ion and EDTA are equal. As the concentration of metal ion

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decreases abruptly at the end point, in principle, any method, which can determine this
disappearance of free metal ions, can be used to detect equivalence point in
complexometric titrations. The end point of a complexometric titration is usually
detected with the help of a metallochromic indicator. Metallochromic indicators or As the indicator is added in
metal ion indicators are the compounds that are capable of forming a complex with the very small amount generally
metal ion being determined. The metal-indicator complex has an intense color, which no titration error is observed.
is distinctly different from the uncomplexed indicator. The second requirement is that
the metal-indicator complex should be weaker than the metal-EDTA complex. The
end point is manifested by change in the colour of the metal ion indicator. Let us learn
about the way a metallochromic indicator helps in the determination of the end point
of complexometric titrations.

In the beginning of the titration, the added indicator binds to an equivalent amount of
the metal ion and the colour of the solution is due to the metal-indicator complex. On
adding the titrant the free metal ions get complexed with EDTA. Once all the free
metal ions get complexed i.e., just before the equivalence point, the added EDTA
displaces the indicator from the metal-indicator complex. This is due to the fact that
the metal-EDTA complex is stronger than the metal-indicator complex. Since the
colour of the free indicator is different from that of the metal-indicator complex, the
colour of the solution changes. This marks the end point of the titration. The accuracy of the end point
depends on the relative
strength of the metal–indicator
M.In(n-3)+ (aq.) + H2EDTA2- M.EDTA4+ (aq.) + HIn2+(aq.) + H+ (aq.) and metal–titrant complex. If
the metal–indicator complex
In the complexometric determination of the hardness of water we use eriochrome is too strong, the color change
occurs after the equivalence
black T (EBT) or solochrome black as metal ion indicator. Eriochrome black T is point. If is too weak, the end
sodium 1-(1-hydroxy-2-napthylazo)-6-nitro-2-napthol-4-sulphonate. Its structure is point is observed before
as shown below. reaching the equivalence
point.
OH OH

Na + O3S N N

O2N

Structure of eriochrome black –T

Eriochrome black –T (EBT) forms a wine red complex with the metal ions. At the end The indicator however, cannot
point the indicator is set free and the solution becomes blue in colour, marking the end be used to indicate the end
point. point of the titration if the
solution contains only Ca+2.
M.In + H2Y2- M.Y2- (aq.) + HIn2- This is so because the calcium
ions form too weak a complex
(Wine red) (Blue) with the indicator and does
not give a sharp endpoint.
Therefore a very small
Here, H2Y2- represents disodium salt of EDTA and HIn2- represents eriochrome black
amount of Mg+2 is added
T in a buffer solution of pH 10. (as Mg-EDTA) in the
titration mixture for a sharper
In the titration you are going to perform, the indicator used, EBT, can form complexes endpoint. This small amount
with the Ca+2 and Mg+2 ions. However, the magnesium indicator complex is more has an insignificant effect on
the final result.
stable than the calcium – indicator complex but less stable than the magnesium-EDTA
complex. Consequently, during the titration of solution containing magnesium and
calcium ions with EDTA in the presence of eriochrome black, the indicator binds with
Mg2+ ions initially. The added EDTA reacts first with the free calcium ions, then with
the free magnesium ions, and finally with the magnesium-indicator complex. The
magnesium-indicator complex is wine red in colour and the free indicator is blue
between pH 7 and 11, the colour of the solution changes to blue at the end point.

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 If magnesium ions are not present in the solution containing calcium ions they must be
added. These are required for the colour change of the indicator. As the Ca – indicator
complex is not very stable it may dissociate well before the end point and may
introduce large error in the determination. Generally a small amount of magnesium
chloride is added to the EDTA solution before it is standardized. Another procedure, is
At present, several different
indicators are available for
to incorporate a little magnesium-EDTA complex (MgY2) (1-10%) in the buffer
each metal ion. It is possible solution or to add a little 0.005 M magnesium-EDTA (Na2MgY) to the calcium ion
to choose a metallochromic solution. This method is better because in such a case the EDTA can be used for other
indicator purely on the basis titrations also.
of ease in observing a color
change. MgY2 + Ca2+ ⇌ CaY2- + Mg2+
The titration with EDTA, using eriochrome black as indicator, yields the combined
calcium and magnesium content in the sample. In order to determine the individual
amounts of Ca++ and Mg++ ions, the Ca++ ions are determined separately by using a
specific indicator, e.g, calcon. The difference between the two titrations is a measure
of the magnesium content.

You must be wondering why we have been consistently mentioning about the pH of
the titrating mixture should be 10. It must be borne in mind that while using the
metallochromic indicators one must be careful about the pH of the reaction solution.
This is so because most of the metallochromic indicators, in addition to being
complexing agents, are also acid-base indicators. In other words, they are capable of
undergoing a color change with a corresponding change in pH of the solution. Thus if
the pH is not maintained we may obtain the colour change even when the end point
has not been reached. Further, if the pH is too high, the metal ions present in hard
water may precipitate as hydroxide(s) causing the reaction with EDTA to be slow.
You are advised to have a relook at sub section 11.3.3 of the unit 11 of MCH 001
course.

6.3 REQUIREMENTS
Apparatus Chemicals
Volumetric flasks (100 cm3, 250 cm3) 1each Calcium carbonate
Beaker (600 cm3 and 400 cm3) 1each Disodium EDTA
Burette (50 cm3) 1 Magnesium chloride
Pipettes (10 cm3) 1 Eriochrome black-T indicator
Weighing bottle 1 Ammonium hydroxide
Burette stand with clamp 1 Ammonium chloride
Conical flasks (100 cm3) 2 Methyl red
Conical flasks (250 cm3) 1
Funnel 1

6.4 SOLUTIONS PROVIDED

NH4OH-NH4CI Buffer solution, (pH= 10) : It is prepared by dissolving 64g of solid
NH4Cl in about 100 cm3 of distilled water taken in a one litre volumetric flask and
adding 570 cm3 of ammonia solution (sp.gr. 0.88) to it. The solution is then diluted to
the mark with distilled water.
Mordant black 11 (Eriochrome black T) (C.I. 14645), 0.5% solution: It is prepared
by dissolving 0.50g of eriochrome black-T indicator in 100 cm3 of ethanol-water (80
% v/v).
0.01M Na2EDTA: It is prepared by dissolving about 3.73 g of disodium dihydrogen-
ethylenediaminetetraacetate in about 200 cm3 of metal ion free distilled water taken in
a 1 dm3 volumetric flask and making up the volume with distilled water.

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Mg-EDTA complex (0.005 M) solution: It is prepared by adding equal volumes of
the solutions of 0.01M disodium salt of EDTA and 0.01M MgCl2. A portion of Mg-
EDTA solution, when treated with a few drops of eriochrome black-T at pH 10
should change to a wine red colour, which should change to pure blue on the addition
of one drop of 0.01 M EDTA solution and wine red on addition of a single drop of
0.01 M MgCl2 solution.

6.5 PROCEDURE
The determination of the total hardness of a water sample by complexometric titration
consists of the following steps:
a) Preparation of standard solution of calcium carbonate
b) Standardisation of EDTA solution
c) Titration of given water solution with standardised solution of disodium EDTA
using eriochrome black-T indicator to determine the total hardness of water
d) Boiling water and filtering to remove temporary hardness followed by the
determination of permanent hardness

a) Preparation of standard solution of calcium carbonate (1000 ppm)

Follow the instructions given below in sequential manner to prepare the standard
solution.
• Weigh about 1.0 g of dried calcium carbonate on a rough balance and
transfer it to a clean dry weighing bottle and accurately weigh the
weighing bottle with calcium carbonate and record the mass.

• Transfer the calcium carbonate to a clean conical flask of 250 cm3

capacity through a glass funnel.

• Slowly add (drop by drop in the beginning), about 5 cm3 of 1 M

hydrochloric acid solution. Swirl the contents of the flask until all the
carbonate is dissolved.

• Add a few drops of methyl red indicator solution and adjust to an

intermediate orange colour with 2 M ammonium hydroxide solution or
1 M hydrochloric acid solution, as required. Transfer, quantitatively, to a
1dm3 volumetric flask and make the volume upto the mark.

b) Standardization of EDTA solution

• Pipette out 20.0 cm3 of the standard solution of calcium ions into a
250 cm3 conical flask and dilute to about 100 cm3, with deionized water.

• Add 4 cm3of the buffer solution, 6 drops of the eriochrome black T

indicator solution and 0.1 cm3 (2drops) magnesium-EDTA solution (0.005
M).

• Titrate with the EDTA solution, quickly initially and slowly towards the
end of the titration. Continue addition of the EDTA solution till you get a
distinct blue endpoint. Record your observation in Observation Table 6.1.

• Repeat the standardization procedure at least three times and record your
observations in Observation Table 6.1.

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 c) Determination of total hardness of water
• Take 50 cm3 of the given sample of water in a 250 cm3 conical flask. Add
10 cm3 of the buffer solution and 0.1 cm3 (2drops) magnesium-EDTA
solution (0.005 M).
• Add 3-4 drops of indicator solution and titrate with standard EDTA
solution (0.01 M) until the colour changes from red to pure blue.
• Record your observations in Observation Table 6.2 and calculate the total
hardness of water expressed in ppm of CaCO3.

d) Determination of permanent hardness

• Place 250 cm3 of the given sample of water in a 600 cm3 beaker and boil
gently for 20-30 min.
• Cool and filter it directly into a 250 cm3 volumetric flask; do not wash the
filter paper, dilute the filtrate to the mark with deionised water and mix
well.
• Titrate 50.0 cm3 of the filtrate by the same procedure as was used for the
total hardness. Record your observation in Observation Table 6.3.
• Calculate the permanent hardness as parts per million of CaCO3.
• Calculate the temporary hardness of the water by subtracting the
permanent hardness from the total hardness.

6.6 OBSERVATIONS AND CALCULATIONS

a) Preparation of standard solution of calcium carbonate
Mass of weighing bottle + calcium carbonate = m1 g = ..............g
Mass of weighing bottle (after transferring calcium carbonate)
= m2 g = .............. g
Amount of calcium carbonate transferred = m1 – m2 = m g = ............. g
Molar mass (Mm) of calcium carbonate = 100 g mol−1
Volume of calcium carbonate prepared = 1000 cm3
m × 1000 m
Molarity of calcium carbonate solution = M Ca CO3 = = = ...........M
100 × 1000 100
= 1000 m ppm

b) Standardisation of ethylenediamminetetraacetic acid

Volume of standard CaCO3 solution taken in conical flask, VCa = …cm3
Solution in the burette: EDTA
Indicator used: Eriochrome black- T

Observation Table 6.1: Standardisation of ethylenediamminetetraacetic acid

S.No. Volume of calcium Burette reading Titre value (in cm3)
Carbonate (in cm3) Initial Final (Final-initial reading)
1
2
3
Concordant reading

The concentration of the given EDTA solution can be determined as follows.

The reaction involved:

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 Ca2+ + EDTA CaEDTA + 2H+

Molarity equation: MCaVCa = MEVE

M Ca VCa
ME =
VE

Substituting the values, the molarity of EDTA=

The molarity of given EDTA solution is = ……….M

c) Determination of total hardness of water in ppm of CaCO3

Volume of water sample taken in conical flask, VW = …cm3
Solution in the burette: EDTA
Indicator used: Eriochrome black -T

Observation Table 6.2: Determination of total hardness of water

S.No. Volume of water Burette reading Titre value (in cm3)
sample (in cm3) Initial Final (Final-initial reading)
1
2
3
Concordant reading

The total hardness of water can be determined as follows.

The reaction involved:
Ca2+ + EDTA CaEDTA + 2H+

Molarity equation: MCaVCa = MEVE

M EV E
M Ca =
VCa

M EV E
As the volume of water sample taken was VW cm3, we get: M Ca =
Vw
Substituting the values, the molarity of CaCO3 = ……M
The concentration of CaCO3 (in g dm-3) = …….M x 100
The concentration of CaCO3 (in ppm or mg dm-3) = …….M x 100 x 1000
Thus the total hardness of the given sample of water = M EVE ×10 5 ppm
Vw

d) Determination of permanent hardness of water in ppm of CaCO3

Volume of boiled water sample taken in conical flask, VW = …cm3
Solution in the burette: EDTA
Indicator used: Eriochrome black-T

Observation Table 6.3: Determination of permanent hardness of water

S.No. Volume of boiled Burette reading Titre value (in cm3)
water sample Initial Final (Final-initial reading)
(in cm3)
1
2
3
Concordant reading

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 The permanent hardness of water can be determined as follows.

The reaction involved:

Ca2+ + EDTA CaEDTA + 2H+

Molarity equation: MCaVCa = MEVE

M EV E
M Ca =
VCa
M EV E
As the volume of water sample taken was VW cm3, we get: M Ca =
Vw

Substituting the values, the molarity of CaCO3 = ……M

The concentration of CaCO3 (in g dm-3) = …….M x 100
-3
The concentration of CaCO3 (in ppm or mg dm ) = …….M x 100 x 1000
M EV E
Thus the permanent hardness of the given sample of water = ×10 5 ppm
Vw

e) Determination of Temporary Hardness of Water

The temporary hardness of water can be determined as follows:
Temporary hardness = Total hardness – permanent hardness

6.7 RESULT
• The total hardness of given sample of water was found to be: ……ppm of
CaCO3
• The permanent hardness of given sample of water is found to be: …ppm of
CaCO3
• The temporary hardness of given sample of water is found to be: … ppm of
CaCO3

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