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UFAZ-L1-Chemistry 1st Semester

PRACTICAL WORK

DETERMINATION OF THE HARDNESS OF WATER

OBJECTIVES

i) Learn to accurately dose cations H +, Ca+2, Mg+2 and anions NO3−, SO42− in water to evaluate the
quality of the water.

ii) Learn different analysis techniques: complexometric titration, colorimetry.

INTRODUCTION

The hardness of water is defined in terms of its content of calcium and magnesium ions, and it’s due to
the presence in the water of calcium and magnesium carbonates (CaCO3, MgCO3). These cations form insoluble
salts with a reagent in soap, decreasing it’s cleaning effectiveness. Hard water is high in dissolved minerals,
both calcium and magnesium. You may have felt the effects of hard water, literally, the last time you washed
your hands. Depending on the hardness of your water, after using soap to wash you may have felt like there was
a film of residue left on your hands. In hard water, soap reacts with the calcium (which is relatively high in hard
water) to form "soap scum". When using hard water, more soap or detergent is needed to get things clean, be it
your hands, hair, or your laundry.
Total hardness is defined as the sum of calcium and magnesium hardness. It corresponds to the sum of the
Ca+2 and Mg+2 concentrations in a non-boiled water.

Total hardness is expressed in :

1. mg/L of CaCO3 ([MgCO3] can be calculated in equivalents of CaCO3)
2. Hydrotimetric ( oH) or French Degrees (of) : water with 10 mg/L of CaCO3 corresponds to 1oH.
3. Milliequivalents / L : concentration of the positive charges due to Ca +2 and Mg+2 ions.

Classification Hardness in mg/L Hardness in mmol/L Hardness in oH

Soft 0-60 0-0,60 0-6
Moderate Hard 61-120 0,61-1,20 6,1-12
Hard 121-180 1,21-1,80 12,1-18
Very Hard ≥181 ≥1,81 ≥18,1

The sum of Ca+2 and Mg+2 ions can be determined by Complexometry, which is a titration with a
chelating agent. Chelating agents (from greek χηλη’ = chel`e meaning claw), are chemical compounds whose
structures permit the attachment of their two or more donor atoms (or sites) to the same metal ion simultaneously
and produce one or more rings. These molecules are also called ”chelates” or chelating groups, and the formation
of rings is called ”chelation”.
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The chelating agent used is EDTA: ethylenediaminetetraacetic acid. This reagent is a weak acid that can lose
four protons on complete neutralization; its structural formula is:

For EDTA to be able to bind to the hard ions, it is important that it remains deprotonated. To do this,
a buffer solution is added to keep the pH at a high level. This allows EDTA to bind freely with hard ions like Ca2+.
The four acid sites and the two nitrogen atoms all contain unshared electron pairs, so that a single EDTA
ion can form up to six bondings to a given metal to form a complex ion or coordination compound. The complex
is typically quite stable, and the conditions of its formation can ordinarily be controlled so that it contains EDTA
and the metal ion in a 1 : 1 mole ratio.
The formation of the complex can also be controlled to be selective for a particular metal ion.

In a titration to establish the concentration of a metal ion, the EDTA which is added combines
quantitatively with the cation to form the complex. The end point occurs when essentially all of the cation has
reacted.
In this experiment, we will use EDTA solution to determine the hardness of an unknown water sample.
Since both EDTA and Ca+2 are colorless, it is necessary to use a rather special indicator to detect the end point of
the titration. The indicator most often used is called Eriochrome Black T, which forms a rather stable wine-red
complex, MgIn−, with the magnesium ion.

As EDTA is added, it will complex free Ca+2 and Mg+2 ions, leaving the MgIn− complex alone until
essentially all of the calcium and magnesium have been converted to chelates. At this point ”free” EDTA
concentration will increase sufficiently to displace Mg+2 from the indicator complex ; the indicator reverts to an
acid (uncombined) form, which is sky blue, and this establishes the end point of the titration.
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When a ligand (EDTA in this case) forms complexes with two metal ions at equal concentration in a
solution, the ligand will form complexes preferentially with the metal ion that produces the complex with the
larger stability constant:

Ca+2 + EDTA-4  (EDTA-Ca)2- k = 1010,7

Mg+2 + EDTA-4  (EDTA-Mg)2- k = 108,7

Since the stability constant of the calcium complex is significantly larger than the Mg complex, the reaction
with calcium proceeds to completion before any reaction with magnesium. When a ligand that forms a very stable
complex with a metal ion is added to a solution of the metal ion complexed with another ligand in a less stable
complex, the stronger complexing agent (ligand) will tend to decompose the existing complex and withdraw the
metal ion into a complex with itself.
EBT-Mg complex is less stable (k=107) than the EDTA-Mg complex (k=108,7). In our case, Mg+2 is
complexed with EBT, but when all Ca+2 will be complexed with EDTA, the ”free” EDTA will displace the EBT
from the EBT-Mg complex and form a EDTA-Mg complex, leaving the EBT uncomplexed again.
The color of the EBT-Mg complex is red, and the color of uncomplexedd EBT is blue. A solution with
excess EBT is therefore purple. Adding EDTA, the color of the solution will change from purple to pure blue
as the red EBT-Mg complex is consumed.
The titration is carried out at a pH of 10, in an NH3-NH4+ buffer, which keeps the EDTA (H4Y)
mainly in the form, H3Y−, where it complexes the Group 2 ions very well but does not tend to react as readily
with other cations such as Fe+3 that might be present as impurities in the water. Taking H4Y and H3In as the
formulas for EDTA and EBT, respectively, the equations for the reactions which occur during the titration are :

Main Reaction : H3Y−(aq) + Ca+2(aq) → CaY2−(aq) + H+(aq) (same for Mg+2)

End Point : HY3−(aq) + MgIn−(aq) → HIn2−(aq)

CHEMICALS AND MATERIALS

- 250-mL Erlenmeyer flask

- pipette
- burette
- distilled water
- commercial sample of bottled mineral water
- pH 10 buffer solution
- Eriochrome Black T colored indicator
- 10−2M EDTA solution.

SAFETY CONSIDERATIONS

Always wear protective goggles, gloves and a lab coat. The fumes from the NH3/NH4Cl buffer at pH 10 are toxic,
corrosive, and irritating. Dispense under a fume hood. Eriochrome Black T will stain skin and closes. Wash hands
thoroughly before leaving the lab.
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UFAZ-L1-Chemistry 1st Semester

PRACTICAL WORK

DETERMINATION OF THE HARDNESS OF WATER

EXPERIMENTAL PROCEDURE
Titration

You will carry out experimental procedures with 2 different water samples.
Titration for each water sample should be carried out 3 times.

- Transfer 50-mL of the water sample for hardness analysis into a 250-mL Erlenmeyer
flask.
- Complete until 100 mL volume with distilled water.
- Add 10 mL of pH 10 buffer solution and 5 drops of the colored indicator (Eriochrome
Black T).
- Fill the burette with a 10−2M EDTA solution.
- Titrate the solution in the flask until the color changes from red to blue (to ensure a
correct titration, compare with a reference solution).

pH Determination of mineral water

- Measure the pH of a bottled water sample.

- Compare the pH of the bottled water sample with the help of the bottle label.

DISPOSAL OF REACTION PRODUCTS

The chemical waste from this experiment may be diluted with water and poured down the sink.
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UFAZ-L1-Chemistry 1st Semester

DETERMINATION OF THE HARDNESS OF WATER

Name: Group: Date:

Partner(s):
Laboratory Report

Purpose:

Apparatus and materials:

Toxicity and safety of chemicals:

Experimental Procedure: differentiate and explain the steps of the procedure and the controlled parameters.

Reactions:

Calculations: Show your calculations in detail. Remember to include measurement units with each numerical
value. The number of significant numbers in your answers must be correct.

Analysis, interpretation of results, comments. Error Analysis - what might have affected the accuracy of this
investigation?

Instructor’s Signature: Date: