Experiments

EXPERIMENT 13 DETERMINATION OF
HARDNESS IN A WATER
SAMPLE
Structure
13.1 Introduction
Objectives
13.2 Principle
13.3 Requirements
13.4 Solutions Provided
13.5 Procedure
13.6 Observations
13.7 Calculations
13.8 Results
13.9 Precautions

13.1 INTRODUCTION
In Sec. 5.3 of this course, we have explained hardness as one of the chemical
characteristics of water. You may recall that hardness is the capacity of water for
reducing and destroying the lather of a soap. The principal hardness causing ions are
Mg2+. and Ca 2+.. The cations of iron, aluminium, manganese, strontium and zinc also
cause hardness but to a negligible extent. In conformity with the current practice, total
hardness is defined as the sum of calcium and magnesium concentration both
expressed as ppm of CaCO 3. The degree of hardness of drinking water has been
classified in terms of the equivalent CaCO3 concentration as follows.
Soft: 0-75 ppm
Moderately hard: 75-150 ppm
Very hard: >150 ppm

Hardness may also be expressed in terms of carbonate (temporary) and non-carbonate

(permanent) hardness. Carbonate hardness is due to bicarbonates of Ca2+ and Mg 2+ and
it can be removed or precipitated by boiling. This type of hardness is responsible for
the deposition of scale in hot water pipes and kettles. Non-carbonate hardness is
caused by the association of the hardness causing cations with sulphate, chloride or
nitrate. It cannot be removed by boiling. Total hardness includes both carbonate and
non-carbonate hardness types.

Objectives
After studying the details of this part and performing the experiment, you should be
able to
• define the terms, total hardness, carbonate hardness, and non-carbonate hardness
and
• estimate total hardness and hardness due to Ca2+ and Mg 2+ ions.

13.2 PRINCIPLE
As mentioned in experiment 9 of CHE-3(L) course, total hardness of water can be
estimated by titrating a sample of water with EDTA salt (disodium salt of ethylene
diamine tetraacetic acid) solution in presence of NH4Cl – NH4OH buffer. Eriochrome
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black T is used as the indicator. The solution changes from wine red colour to blue Determination of
colour at the endpoint of the titration. Hardness in a Water
Sample
The hardness due to calcium ion can be estimated by titrating the water sample with
EDTA using murexide as indicator at pH 12, when Mg2+ ion is made inactive due to
precipitation. With murexide indicator, EDTA titration results in change of colour
from pink to purple at the endpoint.

The hardness due to Mg2 + ion can be calculated by subtracting hardness due to Ca 2+
ion from total hardness. The metal ions, Fe3+, Cd2+, Al3 + etc., if pres ent, could interfere
with EDTA titration. Methods are available for inhibiting the action of these ions
during EDTA titration. In this experiment, assume that hardness in the water sample
arises only due to Ca2+ and Mg2+ as cations.

In Experiments 9 and 10 of CHE-3(L) course, the method of determining total

hardness is discussed in detail; you are advised to study these details to understand
• the principle of complexometric titration using EDTA
• use of eriochrome black T as indicator
• the reason for using NH 4Cl - NH4OH buffer to maintain pH10 explained in terms
of stability of EDTA complexes with Ca2+ and Mg2+ ions
• the reason for adding Mg-EDTA complex as part of the NH 4Cl – NH4OH system
explained in terms of requirement of sufficient inactive Mg 2+ ions to provide a
sharp colour change at the endpoint.
Let us explain the principle behind calculation of hardness. The calcium and
magnesium ions (represented as M2 + in Eq. 13.1) react with EDTA in the molar
ratio 1:1.
,

M2+ + EDTA → [M(EDTA)]2+ ….. (13.1)

i.e., MaVa = MbVb ….. (13.2)

where Ma and Va are the molarity and volume of EDTA; Mb is the molarity of
hardness (due to Ca2+ and Mg 2+ ions) of the water sample in terms of CaCO3 and Vb is
the volume of the water sample. We use Eq.13.2 to calculate total hardness and,
hardness due to Ca 2+ and Mg2+ ions individually.

M aVa
Mb = ….. (13.3)
Vb

Eq. 13.3 provides concentration of CaCO3 in terms of molarity. You can calculate
hardness in ppm unit using Eq. 5.1. of Unit 5 of this course. The molar mass of CaCO3
is 100 gram mole −1.

Hardness in ppm unit = Mb ×100 × 1000 = 105Mb ….. (13.4)

For determining total hardness, the titration is carried out between water sample and
EDTA in presence of NH4Cl – NH4OH buffer and eriochrome black T indicator.
Using Eqs. 13.3 and 13.4,
5  molarity   volume of EDTA to 
10    
Total hardness in ppm  of EDTA  eriochrome black T endpoint 
= .. (13.5)
unit as CaCO 3  Volume of the water sample

For determining hardness due to calcium ion, the water sample is titrated against
EDTA at pH 12 using murexide indicator. At pH 12, Mg 2+ becomes inactive due to
precipitation.
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Experiments
 molarity   volume of EDTAto 
10    
5

Hardness due to Ca ion

2+
 of EDTA  murexide endpoint 
 = .. (13.6)
in ppm unit as CaCO3  Volume of the water sample

Hardness due to Mg ion   Total 

2+
=   − hardness due to Ca ion
2+
... (13.7)
in ppm unit as CaCO3   hardness 

FOR YOUR ATTENTION

While applying Eqs. 13.5 and 13.6 , you have to use molarity (M) unit for
concentration and, cm 3 unit for volume. The result is to be expressed in ppm
CaCO3 unit in the case of all the three equations, Eqs. 13.5 to 13.7.

13.3 REQUIREMENTS
Apparatus Chemicals
3
Burette (50 cm ) –1 Calcium carbonate (AR)
Pipette (20 cm3) –1
Pipette (5 cm 3) –1
Pipette (50 cm3) –1
Conical flasks (250 cm3) –2
Weighing bottle
Standard flask (250 cm3) –1
Standard flask (100 cm3) –1
Funnel –1
Burette stand with clamp –1

13.4 SOLUTIONS PROVIDED

Buffer solution
It is prepared by dissolving 64 g of NH4Cl in 570 cm3 of ammonia solution (sp. gr.
0.88) and, adding a solution of 4.716 g of disodium salt of EDTA (molar mass =
372.31 g mol−1) and 3.120 g of MgSO 4.7H2O or 2.576 g of MgCl2. 6H2O in 200 cm3 of
distilled water and diluting to 1 dm 3 with distilled water.

Sodium hydroxide 2 M
80 g NaOH is dissolved in distilled water and diluted to 1 dm3.

EDTA solution (0.01 M)

3.723 g EDTA disodium salt is dissolved in distilled water and diluted to 1dm3.
Eriochrome black T indicator
0.05 g indicator is weighed and mixed with 100 g NaCl to prepare dry powder.
Murexide indicator
A ground mixture of 0.2 g of murexide (ammonium purpurate) is prepared with 100 g
of solid sodium chloride.

13.5 PROCEDURE
I. Preparation of standard calcium solution

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Weigh accurately about 1.0 g AR grade CaCO 3 and transfer to 250 cm3 conical flask. Determination of
Place a funnel in the neck of a flask and add 1 : 1 HCl till CaCO3 dissolves Hardness in a Water
Sample
completely. Add 100 cm3 distilled water and boil for 20-30 minutes to expel CO2.
Cool and add methyl red indicator. Add 3 M, NH4OH or 1 : 1 HCl dropwise till
intermediate orange colour develops. Transfer carefully the contents of the flask to a
250 cm3 standard flask and make up to mark. Shake the solution till it is
homogeneous. Pipette out 25 cm 3 of the solution into a 100 cm3 standard flask and
make up to mark and again, shake the contents thoroughly. If the weight of CaCO 3
taken is 1g exactly, then,

1 cm3 of the calcium solution

in 100 cm3 standard flask = 1 mg CaCO3.

Also it has a molarity of 0.01 M. You must use calcium solution kept in
100 cm3 standard flask for standardising EDTA solution. A white crystalline
precipitate of calcium
II. Standardisation of edta solution carbonate may appear after
the buffer is added, if the
Fill up the burette with the EDTA salt solution after rinsing it with the solution. water is very hard. This
Pipette out 20 cm3 of the calcium solution (kept in 100 cm3 standard flask) into a should dissolve during the
250 cm3 conical flask, add 5 cm3 of the buffer solution and a pinch of eriochrome course of the titration. The
precipitate may dissolve
black T. Titrate with EDTA salt solution till wine red colour changes to blue. The slowly; however, it must
solution should be stirred thoroughly and the titrant added slowly near the endpoint. dissolve before the endpoint
Conduct the titrations till you get concordant titre values. Enter the values in Table is reached.
13.1.
In some cases, where the
III. Estimation of total hardness alkalinity of the water
sample is very high, it is
Pipette out 100 cm3 of the water sample into 250 cm 3 conical flask, add 2 cm 3 of the recommended to boil a
buffer solution and a pinch of eriochrome black T. Titrate with EDTA salt solution as known volume of the water
mentioned above till the wine red colour changes to blue colour. Enter the titre values sample with a few drops of
in Table 13.2. HCl to remove CO 2. Cool,
and add a few drops of
methyl red and neutralise
IV. Estimation of calcium hardness with NaOH solution till the
red colour is discharged.
Take 100 cm3 sample in a 250 cm3 conical flask. Add 1 cm3 NaOH (to raise pH to 12),
and, a pinch of murexide indicator. Titrate with EDTA till pink colour changes to
purple. Enter the titre values in Table 13.3.

For titrations conducted for estimating total hardness and calcium hardness, the titre
value of EDTA salt solution must not be less than 10 cm3. Adjust the volume of the
water sample accordingly.

13.6 OBSERVATIONS
Approximate mass of the weighing bottle = m1 = ………..g

Mass of the weighing bottle + CaCO3

= m2 = ………..g
(before transferring the substance)

Mass of the weighing bottle

(after transferring the substance) = m3 = ………..g

Amount of CaCO3 transferred = m2 – m3 = m = ………g

Molar mass (M m ) of CaCO 3 = 100 g mol−1

Volume of calcium solution prepared = 250 cm3

83
Experiments m 1000 −3
Molarity of calcium solution in = M1 = × mol dm
3
250 cm standard flask 100 250
Since the solution in 100 cm3 standard flask is prepared from that in 250 cm3
standard flask by diluting four times,
M1
= M2 =
Molarity of calcium solution in 4
3
100 cm standard flask m −3
= mol dm
100
−3
= ................... mol dm
Table 13.1: Calcium solution vs. EDTA salt solution.
S. Volume of calcium Burette reading Volume of EDTA
no. solution/cm 3 Initial Final salt solution/cm 3
(Final – initial)
1 20

2 20

3 20

Table 13.2: Water sample containing NH4Cl - NH 4OH buffer vs. EDTA salt
solution (for estimation of total hardness using eriochrome black-T indicator).
S. Volume of water Burette reading Volume of EDTA
no. sample/cm 3 Initial Final salt solution/cm 3
(Final – initial)
1 100

2 100

3 100

Table 13.3: Water sample containing NaOH solution vs. EDTA salt solution (for
estimation of calcium hardness using murexide indicator).

S. Volume of water Burette reading Volume of EDTA

no. sample/cm 3 Initial Final salt solution/cm 3
(Final – initial)
1 100

2 100

3 100

13.7 CALCULATIONS
I. Determination of molarity of EDTA solution

Volume of calcium solution = V1 = 20 cm 3

Molarity of calcium solution

(calculated above) = M2 = …………….. mol dm−3

Volume of EDTA solution

84 = V2 = ………cm3
 (as per Table 13.1) Determination of
Hardness in a Water
Sample
20 M 2
Molarity of EDTA solution = M3 = (Using Eq.13.1)
V2
= ……………………. mol dm −3
II. Estimation of total hardness of water
Molarity of EDTA solution
(calculated in Step I) = M3 = …………. mol dm−3

Volume of EDTA solution = V3

(as per Table 13.2)
= ………… cm3
Volume of water sample = 100 cm3
Using Eq. 13.5,

10 5 M 3 V3
total hardness of the water sample (x) = ppm CaCO3
100
= ...........................ppm CaCO3
III. Estimation of calcium and magnesium hardness
Molarity of EDTA solution
(calculated in Step 1) = M3
= ………………..…. mol dm −3

Volume of EDTA solution = V4

(as per Table 13.3)

= ………………….….…. cm 3
Volume of water sample = 100 cm3

Using Eq. 13.6,

calcium hardness in
the sample of water (y) 5
10 M 3V4
= ppm CaCO3
100
Magnesium hardness in the = ........................... ppm CaCO3
sample of water
= Total hardness
− calcium hardness

= (x – y)

= …………… ..ppm CaCO3

13.8 RESULTS
i) Total hardness of the = ………….……ppm CaCO3
water sample

ii) Calcium hardness of

the water sample = ……….…….. ppm CaCO3
85
= ………….……ppm CaCO3
Experiments iii) Magnesium hardness of
the water sample
13.9 PRECAUTIONS
1. Carry out the titration within 5 minutes to minimise the tendency towards CaCO3
precipitation.
2. Use reagent blank for colour comparison.
3. The final volume of sample and blank should be kept constant (usually 100 cm3).
4. Use deionized or double distilled water for dilutions.
5. Add same quantity of indicator for sample and blank.
6. Adjust volume of sample such that hardness is in the range 5 to 20 mg.

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