Determination of Hardness of water

Muhammad Hazim Tarar

Department of Chemistry and Chemical Engineering, Syed Babar Ali School of Science and
Engineering, Lahore University of Management Sciences (LUMS), Sector U, DHA Lahore 54792
Email: 22100053@lums.edu.pk

Abstract: In this experiment, the hardness of water samples will be determined. The
calcium/magnesium molarity in the water will be measured by performing a titration
with EDTA. Eriochrome-Black T will be used as the indicator. Firstly, standardization of
EDTA will be performed and then the determination of calcium/magnesium
concentration. After standardizing the EDTA, the average molarity was found to be
0.00334 M. The calcium concentration was found to be 25.384 ppm

INTRODUCTION
Water ‘hardness’ is a measure of the amount of hard water cations in water. These hard water
cations include calcium, magnesium, iron, zinc and the other polyvalent metal ions. In most
water samples, calcium and magnesium are the chief contributors to water hardness. Hardness
in water causes problems both at domestic as well as at the industrial level. Both Ca2+ and
Mg2+ ions react with soap to form water-insoluble salts. As a result, the soap loses some of its
cleaning power and the insoluble Ca2+ and Mg2+ salts of fatty acids form a scum that sticks to
sinks, bathtubs, and fabrics. There are two types of hard water; temporary hard water and
permanent hard water. Water that contains bicarbonates of calcium or magnesium (or of both)
is called Temporary Hard Water. These bicarbonates are soluble in water and produce
corresponding ions. Temporary hardness in water can be easily removed by boiling. Upon
boiling, calcium/magnesium bicarbonates decompose to give calcium/magnesium carbonates,
which are insoluble in water. Therefore, they precipitate out. Water that contains chlorides or
sulfates of calcium or magnesium (or of both) is called Permanent Hard Water. This type of
hardness cannot be removed by boiling.

Calcium and magnesium are easily measured by titration with the complexing agent standard
ethylenediaminetetraacetic acid (EDTA) solution. The EDTA complexes the Ca2+ or Mg2+ metal
ion.

Fig 1.1 formation of EDTA- Metal complex

Fig 1.2 EDTA-Metal complex
The Y4- ion that forms a 1:1 complex with the metal ion( Ca or Mg) is the completely
deprotonated anion of ethylenediaminetetraacetic acid (“H4Y”). At pH=10, the EDTA is present
in solution primarily as its monoprotonated form, HY3-. The endpoint of an EDTA titration is
determined with a metallochromic indicator. The aforementioned indicators are technically
complexing agents themselves, since they change color as they combine with a metal ion,
either Mg or Ca. Two popular indicators for titrating Ca2+ or Mg2+ are Eriochrome black T and
Calmagite. Although, in this experiment, Eriochrome black T was used as the indicator. The
latter indicator changes from blue to red color when it combines with a metal ion to form a
complex ion.
In a titration, EDTA, which is a relatively stronger complexing agent, compared to Eriochrome-
black T, inevitably displaces the indicator form the metal ion allowing the indicator to return to
a sky-blue color, indicating the end of the reaction.

Fig 1.3 (above) Titration reaction & Fig 1.4 (below) Endpoint reaction
In this experiment, an EDTA solution is prepared and standardized with a standard calcium
solution. The standardized EDTA is then used to analyze the hardness of samples of water.
EXPERIMENTAL SECTION
Chemicals. Disodium salt of EDTA, Ammonium hydroxide, Eriochrome black-T, Ammonium chloride,
HCl (conc), Calcium carbonate, Ethanol, Deionized water, Distilled water

Glassware/Equipment. Volumetric Flask 1000 mL (2), 250mL Erlenmeyer flask (2), Volumetric Flask
100 mL (2), Cylinder 50 mL, Pasteur pipette, Funnel, Pipette 2 mL, Burette, Cylinder 25 mL

Procedure:
Solution preparation
Buffer solution: 3.5 g ammonium chloride (NH4Cl) was dissolved in 28.5 mL concentrated
ammonium hydroxide and dilute to 100 mL with distilled water.
Standard calcium solution: 0.25 g of anhydrous calcium carbonate was added into a 150 mL
Erlenmeyer flask and 50 mL of deionized water was added. A few drops of 6 M HCl were added
until all CaCO3 had dissolved. 50 mL of distilled water was added and boiled for a few minutes
to expel CO2. The solution was transferred quantitatively to a 1000 mL volumetric flask and
diluted to the mark with distilled water.
EDTA disodium salt solution: Dissolve 3.723 g disodium EDTA in distilled water and dilute to 1
L.

Figure 1.5 EDTA

Eriochrome black-T 0.5% solution: Dissolve 0.5 g in 100 mL of ethanol-water (80 + 20, v/v).

Figure 1.6 Eriochrome black-T

Standardization of the EDTA Solution

Before using the EDTA to titrate water samples, we must know its exact concentration. We will
use the solution of calcium carbonate (1.00 g CaCO3/ L) as the primary standard. Measure
exactly 15.0 mL of the CaCO3 solution into a 250 mL flask. Approximately 30 mL of deionized
water is added to the flask. 2.0 mL of the buffer solution is added. The remainder of the
titration must be completed within 15 minutes of the time when the buffer is added. 4 drops of
Eriochrome Black-T indicator solution are added. Titration is done using the EDTA titrant. At the
endpoint the color should change from wine red to a pale blue. The concentration of EDTA is
calculated by using formula M1V1 = M2V2. This procedure is repeated twice more and the
EDTA Titre values are recorded.
Water samples hardness analysis
We will analyze a hard water sample by the following procedure. Exactly 25.0 mL of the hard
water sample is measured into a 250 mL flask. Approximately 25 mL of deionized water is
added to the flask. 2.0 mL of the buffer solution is then added. The remainder of the titration
must be completed within 15 minutes of the time when the buffer is added. Add 4 drops of
Eriochrome Black T indicator solution. Titration was done using the EDTA titrant. At the
endpoint, the color changed from red to blue. The volume mmoles of EDTA required for
titration were determined. This procedure was repeated twice more. This data and the data
from parts A and B to calculate the hardness of your water sample in mg CaCO3/L H20 (ppm).

Results and discussion

Molarity of standard calcium solution = 0.002498 M Ca +2 ions

Table 1.1 Data for the standardization of EDTA solution with standard CaCO3 solution (15
mL).
EDTA 1st 2nd 3rd

Initial 31 31 26.5
volume
(mL)
Final 42.5 42.0 37.7
volume
(mL)
Titre 11.5 11.0 11.2
(mL)

MW value for CaCO3 = 100.09

Average Molarity of EDTA solution (calculated using average value of EDTA titres) = 0.00334
M EDTA

Table 1.2 Titration of water sample (25 mL) with standard EDTA solution

EDTA 1st 2nd 3rd

Initial 41.3 43.2 45.2

volume
(mL)
Final 43.2 45.1 47.1
volume
(mL)
Titre 1.9 1.9 1.9
(mL)

Table 1.3 Total no. mmoles of Ca/Mg and hardness in ppm units

number. Volume of EDTA [Ca+2 / Mg+2 ¿ Hardness (ppm)

Titrant (ml) (mmoles)
1 1.9 0.00635 25.384

2 1.9 0.00635 25.384

3 1.9 0.00635 25.384

The purpose of this lab was to determine the water hardness in water samples with EDTA.
Calcium and magnesium are the most common ions that are able to dissolve in water thus,
contributing to water hardness. EDTA was standardized Eriochrome Black T was used as the
indicator. The most basic form of EDTA is Y4- which primarily reacts with most metal ions, such
as Ca +2 ions forming a 1:1 ratio. Therefore, we used the molarity of EDTA, along with the Titre
values of EDTA to calculate the moles of Ca+2 and Mg +2 ions, in the water samples, which we
will then use to calculate the molarity of the water samples and, hence, the hardness of the
water samples. Three samples of water were run; these three samples started as a winered
color when the indicator was added. Once the titration was done, the three samples turned
into a fade blue indicating equivalence point had reached. In the presence of Mg2+ ions, this
indicator forms a wine-red metal−indicator complex MgIn−, the stability of which is lower than
that of metal−EDTA complex. The solution is initially red. As EDTA is added, it will complex free
Ca2+ and Mg2+ ions, leaving the metal−indicator complex alone until essentially all of the free
calcium and magnesium have reacted. At this point EDTA will displace the indicator from the
metal−indicator complex; the indicator reverts to its uncombined form, which is sky blue,
establishing the endpoint of the titration. Possible sources of errors in this lab may have
resulted from two known systematic errors and random errors. The systematic errors could’ve
come from weighing the calcium carbonate, due to the scale not being properly balanced or
from a measurement error of the titrant, because of too much titrant being added.

Conclusion
Since the water sample, has a hardness of 25.384 ppm, its hardness designation is “soft”. The
hypothesis for this experiment was to determine if EDTA titration can identify the total
“hardness” of water through mathematical means. The outcome of this hypothesis is confirmed
by the data in the results and discussion section of this lab report. This lab experiment
demonstrated the successful implementation of titration to test the “hardness” of water
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