Chemistry 213

Experiment 7
Determining Water Hardness by EDTA Titration

LEARNING OBJECTIVES

The objectives of this experiment are to . . .

 Determine the total hardness (total calcium and magnesium ion concentration).

 Learn how to titrate with EDTA solution.

 Determine permanent hardness and the temporary hardness.

BACKGROUND

Do you know if you have hard or soft water at home? Water containing high concentrations of
Ca2+, Mg2+, Fe2+, or Fe3+ ion is called hard water. Ca2+ and Mg2+ are the most common sources of
hardness in water. The source of drinking water in the Southeast Minnesota is the bedrock
aquifers consist of limestone and dolomite. Limestone contains calcium carbonate and dolomite
contains calcium magnesium carbonate. When dissolved in water, the ions from the stones
increase the hardness of water.

Ca2+ and Mg2+ ions react with soap to form a precipitate (a soap scum or a “bathtub ring”) which
sticks to sinks, bathtubs, and fabrics. They can form large amounts of insoluble calcium
carbonate, magnesium carbonate, and iron(III) carbonate when heated and form scale inside
pipes, teakettles, and water heaters. Scale buildup can impede water flow. Water softening
using ion exchangers can remove the hard water ions to produce soft water. Soft water
produced by ion exchangers contains sodium ions (Na+) instead.

Total hardness refers to the total concentration of Ca2+ and Mg2+ ions in the water. The
temporary hardness refers to the amount of Ca2+ and Mg2+ ions that can be removed as insoluble
carbonates by boiling the water.

Ca2+ (aq) + 2HCO3-(aq) -> CaCO3 (s) + H2O (l) + CO2 (g)
Mg2+ (aq) + 2HCO3-(aq) -> MgCO3 (s) + H2O (l) + CO2 (g)
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Permanent hardness refers to the amount of Ca2+ and Mg2+ ions remaining in the water after
removal of temporary hardness. Total hardness is the sum of permanent hardness and temporary
hardness.

We can determine the total amount of Ca2+ and Mg2+ ions in water by titrating a water sample
with a standardized EDTA solution. EDTA forms strong 1:1 metal-EDTA complex with Ca2+
and Mg2+ ions. The indicator used in the titration is Calmagite indicator which is red/magenta in
the presence of free Ca2+ and Mg2+ ions and blue in their absence.

Structure of EDTA (ethylene diamine tetraacetate)

Structure of Metal-EDTA complex

We commonly report water hardness as milligrams of CaCO3 per liter of water or ppm.
Therefore, we calculate the number of millimoles of EDTA used in titration and convert
it to the number of millimoles of Ca2+ and Mg2+ ions (it is a 1:1 reaction). Then it is
converted to milligrams of CaCO3. Following table shows the classification of hard/soft
water. Calculations: Hardness is also expressed in grains per gallon (gpg) or, simply,
grains. One grain is equal to 0.0648 g. The hardness value in grains represents the
number of grains of CaCO3 per gallon of water. The conversion factor of: 1 gram/liter =
58.41783 grains/gallon or 1 grain/gallon = 17.1 ppm can be used to find the grain
hardness value for your water samples. We will use milligrams of CaCO3 per liter (ppm)
in today’s lab.

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Table I. Classification of water hardness (hardness as calcium carbonate).
Classification mg/L or ppm grains/gal
Soft 0 - 17.1 0-1
Slightly hard 17.1 - 60 1 - 3.5
Moderately hard 60 - 120 3.5 - 7.0
Hard 120 - 180 7.0 - 10.5
Very Hard 180 & over 10.5 & over

Example: A student used 11.35 mL of 0.0100 M EDTA solution to titrate 25.00 mL of the
sample water. Report the hardness in milligrams of CaCO3 per liter of the sample (or ppm).
What is the classification of the water sample (soft, slightly hard, moderately hard, etc.)?

millimoles of EDTA required = 0.0100 M  0.01135 L  1000 mmol/mol = 0.1135 mmol

millimoles of Ca2+ in 25 mL = millimoles of EDTA required = 0.1135 mmol
milligrams of CaCO3 in 25 mL= mmol of Ca2+  molar mass of CaCO3 = 0.1135 mmol  100
mg/mmol = 11.35 mg
1000mL
mg of CaCO3 in 1 L = 11.35 mg  = 454 mg CaCO3/L
25 mL
According to the classification of water, this sample is very hard (over 180 ppm).

SAFETY PRECAUTIONS

The fumes from the NH3/NH4Cl buffer at pH 10 are toxic, corrosive, and irritating. Dispense
under a fume hood. Wash hands thoroughly before leaving the lab.

EXPERIMENTAL PROCEDURE

Total Hardness of the Water Sample

1. Pipet 25 mL of the water sample into a 125 mL Erlenmeyer flask. Add 1 mL of pH

10 buffer and 5 drops of calmagite indicator.

2. Titrate the water sample with EDTA solution until the color changes from magenta to
blue. Near the end point, add EDTA dropwise. Record the volume.

3. Repeat this two more times.

4. Prepare a control sample and titrate as shown above. Use a 25 mL sample of distilled
water as your control. Repeat two more times.

Permanent Hardness

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 1. Transfer a 100 mL water sample into a 250 mL beaker. Gently boil the water for 15
minutes. Allow the boiled water to cool to room temperature.

2. Filter the water directly into a clean 100 mL volumetric flask. Rinse the inside wall
of the beaker twice with 1 mL portions of distilled water each time. Filter the rinses
into the volumetric flask. Fill the volumetric flask to the mark with distilled water.
Mix the sample by inverting the flask several times while holding the stopper firmly
in place.

5. Pipet 25 mL of the filtered sample into a flask and add 1 mL of pH 10 buffer and 5
drops of calmagite indicator.

6. Titrate the water sample with EDTA solution until the color changes from magenta to
blue. Near the end point, add EDTA drop-wise. Record the volume.

7. Repeat this two more times.

Data Analysis

1. For each analysis, calculate the millimoles of EDTA required for titration and
average the results.

2. For the determination of the total hardness, report the milligrams of CaCO3 per liter
of the water sample.

3. For the determination of the permanent hardness, report the milligrams of CaCO3 per
liter of the water sample.

4. The temporary hardness is the total hardness minus the permanent hardness.

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 Determining Water Hardness by EDTA Titration

Names ____________________ Date __________________

Data Sheet
Source of water sample __________________
Concentration of EDTA, M __________________

Total Hardness of the Water Sample

Volume of water sample titrated, mL __________________

Trial# 1 2 3
Volume of EDTA required, mL ________ ________ ________
Number of mmol of EDTA, mmol ________ ________ ________
Number of mmol of Ca2+, mmol ________ ________ ________
Total hardness, mg CaCO3 in L sample ________ ________ ________

Average Total Hardness, mg CaCO3/L ________

Classification of your water sample _______________

Total Hardness of Distilled Water (Control)

Volume of distilled water sample titrated, mL__________________

Trial# 1 2 3
Volume of EDTA required, mL ________ ________ ________
Number of mmol of EDTA, mmol ________ ________ ________
Number of mmol of Ca2+, mmol ________ ________ ________
Total hardness, mg CaCO3 in L sample ________ ________ ________

Average Total Hardness, mg CaCO3/L ________

Classification of distilled water _______________

Permanent Hardness of the Water Sample

Volume of water sample titrated, mL __________________

Trial# 1 2 3
Volume of EDTA required, mL ________ ________ ________
Number of mmol of EDTA, mmol ________ ________ ________
Number of mmol of Ca2+, mmol ________ ________ ________
Permanent hardness, mg CaCO3 /L ________ ________ ________

Average Permanent Hardness, mg CaCO3/L ________

Temporary Hardness of the Water Sample

Temporary Hardness, mg CaCO3 /L= Total – Permanent Hardness ______________

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Determining Water Hardness by EDTA Titration

Name ____________________
Section___________________
Date_____________________
Pre Laboratory Assignment

1. What is the purpose of this experiment?

2. Distinguish between permanent and temporary water hardness.

3. A student used 6.05 mL of 0.0100 M EDTA solution to titrate 25 mL of the sample

water. Report the hardness in milligrams of CaCO3 per liter of the sample. What is the
classification of the water sample (soft, slightly hard, moderately hard, etc.)?