Chemistry 232

Water Hardness: EDTA Titrimetric Method

Purpose: This experiment is designed to demonstrate a method to determine the hardness of water
samples. It also serves as an example of a method using complex ion formation to do quantitative analysis.

Introduction: The total concentration of alkaline earth metal ions, such as calcium and magnesium, in water
determine the hardness of water. The term hard water comes from the fact that these metal ions precipitate
soap molecules from water making it "hard" to get things clean. The calcium in hard water precipitates as
calcium carbonate (lime scale), if the water is boiled.
Water hardness is usually determined by measuring the total amount of calcium and magnesium present, since
the concentrations of these ions far exceed those of other alkaline earth metals. The accepted practice for
reporting hardness is as mg CaCO3/L, as if all of the hardness were from calcium carbonate. Table 1 gives a
classification of the hardness of water. Further information about water hardness is given on p. 277 of Harris.

Table 1. Water Hardness Classification

Hardness, mg CaCO3/L Hardness
< 15 very soft
15-50 soft
50-100 medium hard
100-200 hard
> 200 very hard

There are several methods used for measuring hardness. We will titrate using ethylenediamine-N,N,N',N'
tetraacetic acid (EDTA). EDTA is a chelating agent that can donate electrons (Lewis base) thereby forming a
complex with metal ions (Lewis acid). The EDTA will complex first with the Ca2+ and then with the Mg2+.
As with any titration we will need an indicator to determine when all of the Ca2+ and Mg2+ have complexed
with the EDTA (i.e. the endpoint). The indicator used in this experiment is Eriochrome
Black T. At pH 10 the indicator will be in the form HInd2- (Ind stands for indicator), which is blue. The
indicator, reacts with Mg2+ (colorless) to give a red complex.
The general procedure for this experiment starts with a sample of hard water that contains calcium and
magnesium. To insure that all cations stay in solution and that the indicator works properly, a buffer is used to
adjust the pH to 9.9 - 10.1. After the pH is adjusted and the indicator is added, the EDTA titrant is added via
a burette.

First the EDTA (H2Y2-) will complex with the calcium ions, forming a red solution:

1) H2In- + Ca2+ → CaIn- + 2H+

At the endpoint, the EDTA will complex with the calcium and the indicator becomes unbound, which is
indicated by the red → blue color change:
 (2) EDTA + CaIn- + 2 H+ → H2In- + CaEDTA
(red) (blue)

Experimental:
A. Solution preparation

(1) Buffer solution: Dissolve 17.5 g ammonium chloride (NH4Cl) in 142 mL concentrated ammonium
hydroxide and dilute to 250 mL with distilled water.
(2) Standard calcium solution: Place ~ 1.5 g anhydrous calcium carbonate (in oven) into a beaker, and
place in a dessicator for 10 minutes. Weigh exactly 1.000g anhydrous calcium carbonate into a clean 600 mL
Erlenmeyer flask and add 200 mL deionized water. Add a few drops of 6 M HCl until all CaCO3 has
dissolved. Add 200 mL distilled water and boil for a few minutes to expel CO2. Transfer quantitatively to a
1000 mL volumetric flask and dilute to the mark with distilled water.
(3) Dissolve 3.723 g disodium EDTA in distilled water and dilute to 1 L.

B. Standardization of the EDTA Solution

1.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.
2. Measure exactly 15.0 mL of the CaCO3 solution into a 250 mL flask. Add approximately 30 mL of
deionized water to the flask.
3. Add 2.0 mL of the buffer solution. The remainder of the titration must be completed within 15 minutes of
the time when the buffer is added.
4. Add 4 drops of Eriochrome Black T indicator solution.
5. Titrate using the EDTA titrant. At the end point the color should change from red to a pale blue.
6. Repeat this procedure at least twice.

C. Water Samples

You will analyze Four Paper Plant water samples and a hard water unknown (provided by the instructor). You
may need to filter the Paper Plant Water samples.
1. Measure exactly 25.0 mL of the hard water sample into a 250 mL flask. Add approximately 25 mL of
deionized water to the flask.
2. Add 2.0 mL of the buffer solution. The remainder of the titration must be completed within 15 minutes of
the time when the buffer is added. 3. Add 4 drops of Eriochrome Black T indicator solution.
4. Titrate using the EDTA titrant. At the end point the color should change from red to blue.
5. Repeat this procedure at least twice.
6. Use this data and the data from parts A and B to calculate the hardness of your water sample in
mg CaCO3/L.
7. Repeat the procedure for the Paper Plant water samples (you may have to adjust the procedure in order
to see the color change!)

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Data Analysis:
1. Tabulate the data for the EDTA standardization and calculate the mean and standard deviation for the
EDTA concentration. Include each mass of CaCO3 used (your numbers should be written out to 2 decimal
places), each volume of EDTA used (1 decimal place) and each calculated concentration of EDTA
2. Tabulate the data for the sample analyses and calculate the mean and standard deviation for the hardness
of the samples. Classify the hardness of your water. Include each volume of EDTA used.

Additional Problems:
1. (a) An EDTA solution was prepared by dissolving approximately 4 g of the tetra-sodium salt in
approximately 1 L of water. An average of 42.35 mL of this EDTA solution was required to titrate 50.00 mL
aliquots of a standard that contained 0.7682 g of MgCO3/L. Determine the concentration of the EDTA
solution.
(b) Titration of a 25.00 mL sample of mineral water at pH 10 required 18.81 mL of the EDTA solution
from (a). A 25.00 mL aliquot of the mineral water was rendered strongly alkaline to precipitate the magnesium
as Mg(OH)2. Titration with a calcium-specific indicator required 15.77 mL of the EDTA solution. Calculate (i)
the ppm of CaCO3 in the mineral water, and (ii) the ppm of MgCO3 in the mineral water. Hint: the first EDTA
titration measures the moles of Mg2+ and Ca2+. By precipitating Mg2+ as Mg(OH)2, one can perform a
titration where only the moles of Ca2+ are determined.
2. A 50.00 mL aliquot of a solution containing iron(II) and iron(III) required 13.73 mL of 0.01200 M
EDTA when titrated at pH 2.0 (when only iron(III) is titrated). A second 50.00 mL aliquot of the solution
required 29.62 mL of EDTA when titrated at pH 6.0 (when both iron(II) and iron(III) are titrated). Determine
the concentration of iron (II) and iron (III) in ppm in the solution.
3. A 24-hour urine specimen was diluted to 2.000 L. After the solution was buffered to pH 10, a 10.00 mL
aliquot was titrated with 26.81 mL of 0.003474 M EDTA. The calcium in a second 10.00 mL aliquot was
isolated as CaC2O4 (s), redissolved in acid, and titrated with 11.63 mL of EDTA solution. Assuming that 15 to
300 mg of magnesium and 50 to 400 mg of calcium are normal, did this specimen fall within these ranges? Hint:
the EDTA titration measures the moles of Mg2+ and Ca2+ while the CaC2O4 isolation and titration measures the
moles of Ca2+ only.

Report: This is a long report and should contain the following:

1) Introduction and background
2) Discussion of experimental results (including calculations)
3) Conclusions (about the experiment and the results you obtained)
4) References
5) Answers to questions
6) Signed pledge

PLEDGE: My signature at the end of this report is my pledge that this work is my own. I have neither given
nor received help from other students.

Signature ________________________________________

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Date _____________