1 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF

WATER

COMPLEX-FORMATION TITRATION

Determination of the Total Hardness of Tap Water

Submitted by:

Czaika Kate ĺrica V. Cervantes

Performed with:

Keziah Borja

Gezelle Tadifa

Author Note

This paper was prepared for Analytical Chemistry 23 Laboratory, Section 2, taught by Sir

Arnold C. Gaje

December 05, 2014

2 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

Abstract

Water hardness can be defined as a measure of the amount of calcium and

magnesium salts present in water. A titration technique, complex-formation titration, was

used in this study. An indicator was added to a sample, that was tested, which turned red

signifying that magnesium is present in the sample and blue indicating that calcium ions are

present. The overall aim of this study is to improve adeptness with quantitative titrimetric

determinations and to be familiar with a method for determination of total hardness of water

and metal ions using (ethylenediamminetetraacetic acid)EDTA, a chelating agent. And also

to determine the total hardness the tap water obtained from College of Arts and Sciences

(CAS) building, University of the Philippines, Miagao, Iloilo City, which is predicted to be

extremely high compared to commercial mineral water. As for the procedure, in the

preparation of the EDTA solution, 2g of Na 2H2Y·2H2O was added with 10mL MgCl·6H 2O

solution and diluted with 100mL distilled water in a 500mL volumetric flask. For the

standardization and analysis, a 0.2g of 1° saturated CaCO3was added with 50mL distilled

water in a 250mL volumetric flask and added with 1:1 HCl, drop wise. Then it was diluted to

the mark and mixed thoroughly. With 50mL CaCO3 solution, 5mL of NH4++NH4Cl buffer

and 5 drops of EBT indicator was added and then titrated with EDTA until the endpoint.

These were performed in triplicate to obtain three samples. It was found that the total

hardness of the water sample obtained met with the hypothesized outcome in which a high

amount of hardness wasobserved.

3 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

I. Introduction

Hard water is due to metal ions(minerals) that are dissolved in the ground water. The

primary contributors to “hardness” of water areCalcium and Magnesium ions. Calcium is

also of biological importance. The determination of these two elements by usual procedures

(i.e. by non-instrumentalprocedures) usually requires gravimetric analysis because ordinary

titrationmethods (acid-base, redox) are not appropriate since neither ion has useful acid-base

or oxidation-reductionproperties.

There are two types of water hardness:

Temporary Hardness,which is due to the presence of bicarbonate ion, HCO 3-in the water.

However, by boiling the water to expel the CO2the hardness of the water may be eliminated,

as how the following equation directs:

HCO3-⇌ H2O + CO2 (g)

While, permanent hardness is due to the presence of the ions Ca 2+, Mg+2, Fe3+ and

SO4-.Unlike temporary hardness, this type of hardness cannot be removed and water with this

type of hardness is thought to be permanently hard.

The water that will be analyzed in this experiment, which is tap water instead of mineral

water, possesses the latter. Therefore, to determine the total hardness of the water that will be

tested, it will be titrated with a standard solution of ethylenediamminetetraacetic acid,

(EDTA). EDTA will serve as a chelating agent which purpose is to capture the metal ions.

Despite of its role, EDTA simply binds the metal ions to itself very tightly which causes the

water to become softened, however the metal ions are not eliminated from the water.
4 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

The analytical study conductedwill involvethe determination of both the "total hardness" and

the relative concentrations of Mg and Ca in a certain sample. The titration shall be conducted

under circumstances where both ions will react with the EDTA until the end point is detected

after both are titrated. A subsequent titration of the solution determines only the remaining

Ca ion, which remains soluble.

The following are the objectives of this study:

(1) to improve adeptness with quantitative titrimetric determinations

(2) to be familiar with complex-formation titrations for determinations of total

hardnessof water and metal ions usingEDTA

Ho: There is difference between the expected and the true value of the total hardness of tap

water and mineral water

H1: There is no difference between the total hardness of tap water and mineral water

In the titration, two solutions are mixed which contains reactants for specific chemical

reactions under conditions that:

a.) the end point can be detected though occurrence of color change

b.) the concentration of the reactant in a standard solution shall be used to calculate

the amount of the other reactant

With Eriochrome Black T (EBT), indicator, calcium ion alone gives no sharp end point

because in the pH region of the titration (pH 11), the EBT acts as an acid-base indicator (i.e.

sensitive to H+ ion concentration).The Mg+ ions which usually remain present with calcium

also form somewhat lesser stable complex than calcium complex with EDTA solution, as
5 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

shown:

Mg++ + H2Y- = MgY- + 2H+

The Mg-EBT complex is more stable than the Ca-EBT complex but less stable than the Mg-

EDTA complex. Hence, during the titration of a solution containing Mg 2+ and Ca+ ions with

EDTA in the presence of EBT, the EDTA reacts first with the free Ca + ions, then with the

free Mg2+ and finally with the magnesium indicator complex. Since the Mg-EBT complex is

wine red in color and the free indicator is blue between pH 7 and 11, the color of the solution

changes from red to blue at the end point as:

Mg E-(red) + H2Y-- MgY-- + HE--(blue) + H

Mg2+ ions are required for the color change of the indicator to detect the correct end point.

Concentration is also an important concept in this experiment. Two units of concentration:

moles of solute
Molatiry = (1)
liter solution

moles Ca2+ion ( molarity EDTA ) (mL EDTA added)

=
1L 50.00 mLof water sample titrated

mass of solute
%w/v = ×100 % (2)
volme of solution

For the calculation of the total hardness, the following equation shall be used:

Ppm CaCO3= ¿ ¿

II. Materials and Methods

6 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

For the preparation of the EDTA solution, Na2H2Y·2H2O weighing 2g was added with 10mL

MgCl·6H2O solution and diluted with 100mL distilled water. Next, the solution made was

transferred to a volumetric flask which holds a capacity of 500mL. It was diluted to the mark

after and then mixed thoroughly and labeled properly.

As for the standardization and analysis, a 1° saturated CaCO 3 was weighed accurately to 0.2g

and added with 50mL distilled water in a volumetric flask with a 250mL capacity. Next, a

drop wise addition of 1:1 HCl onto the solution was done then it was diluted to the mark and

mixed thoroughly. With a 50mL of the prepared Calcium solution, a 5mL of NH 4++NH4Cl

buffer and 5 drops of EBT indicator was added. The mixture was then titrated with EDTA

until the endpoint, in which a color change from red to blue was observed. These were done

three times to obtain three replicates.

The previous steps were done again in triplicate using tap water instead of Calcium solution.

III. Results

It was found that there is a difference between the expected and true value of total hardness

of tap water with the following calculation results as basis of conclusion.

A. Standardization of EDTA Solution

Weight of pure CaCO3: 0.2720g

% Purity of CaCO3: 99.5%

Total volume of standard CaCO3 solution: 250mL

Trials 1 2 3
7 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

Volume of standard CaCO3 50.00 50.00 50.00

solution: (ml)

Final Reading EDTA 35.60 32.40 31.20

(ml)

Initial Reading EDTA 0.01 0.01 0.01

(ml)

Net Volume of EDTA 35.59 32.39 31.19

(ml)

Molarity of EDTA (M) 0.0762 0.0837 0.0869

Average Molarity of 0.0823

EDTA

Titer(mg CaCO3/mL 7.6426×10−6 8.3977×10−6 8.7207×10−6

EDTA)

B. Sample Analysis

Brand of mineral water used: tapwater

Ca content as CaCO3: __________________

Mg Content as MgCO3: __________________

8 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
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Trials I II III

Vol. of water sample (ml) 100.00 100.00 100.00

Volume of EDTA (mL)

Final volume (ml) 22.60 22.40 22.50

Initial volume (ml) 0.01 0.01 0.01

Net Volume (ml) 22.59 22.39 22.49

Trials n Ca2+

1 0.0186

2 0.0184

3 0.0185

Average 0.0185

C. Total Hardness

Trials Total Hardnes

(mg CaCO3/L)

1 1861.6

2 1841.6
9 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

3 1851.6

Average 1851.6

Corrected weight of CaCo3: wt. CaCO3× % purity

0.2720g ×.995 % = 0.27064

W corr CaCO3
Molarity of EDTA:
V corr EDTA × FW CaCO 3

0.27064 g
Trial 1: 35.60−.10 × 1 L × 100.087 g = 0.0762M
1000 mL mol

0.27064 g
Trial 2: 1L g = 0.0837M
32.40−.10 × × 100.087
1000 mL mol

0.27064 g
Trial 3: 1L g = 0.0869M
31.20−.10 × × 100.087
1000 mL mol

M EDTA × mL of EDTA added

n Ca2+:
100.00 mLwater sample titrated

0.0823 M ×22.60 mL
Trial 1: = 0.0186
100.00 mL

0.0823 M ×22.40 mL
Trial 2: = 0.0184
100.00 mL

0.0823 M ×22.50 mL
Trial 1: = 0.0185
100.00 mL
10 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

1 mol CaCO3
×
ppm CaCO3: n Ca2+ 100.087 g CaCO3 1000 mg
1 mol ca2 +¿ × × ¿
1 mol CaCO3 1g

Ca2 +¿ 1mol CaCO 3

0.0186 × ¿
Trial 1: 1L 2+¿ 100.087 gCaCO 3 1000 mg = 1861.6 ppm
1 mol ca × × ¿
1 mol CaCO3 1g

Ca2+¿ 1 mol CaCO3

0.0184 × ¿
Trial 2: 1L 2+¿ 100.087 g CaCO3 1000 mg = 1861.4 ppm
1mol ca × × ¿
1 mol CaCO3 1g

Ca 2 +¿ 1mol CaCO 3
0.0185 × ¿
Trial 2: 1L 2+¿ 100.087 g CaCO 3 1000mg = 1861.5 ppm
1 mol ca × × ¿
1 mol CaCO3 1g

IV. Discussion

The analysis of the water hardness provided results that we had expected for all three

samples. All the samples analyzed were expected to be extremely hard because the water

obtained was only tap water and not commercial water which did not undergo any

purification process.Therefore, the calcium and magnesium ions absorbed into the water

from sources such as limestone are able to remain in the water.

Each method performed resulted in different results. EDTA titration is measured by

observing how much EDTA is required to result in the solution turning blue. There is no

occurrence of error in this method of determining the amount of solid in a solution

wheremore EDTA is used than is actually required to turn the solution blue. EBT was also

used in order to measure the amount of calcium and magnesium ions that reside in the water,

but other solids are not taken into account. Various number of human may exist as well such
11 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
WATER

as adding different drop sizes during the EDTA titration or making a mathematical error

when calculating the concentration using certain measurements.

Tap water sources in CAS building, University of the Philippines Visayas, Miagao, Iloilo

city tend to have high concentrations of Mg2+ and Ca2+ ions, therefore, being hard.

V. Conclusion

Water hardness is defined as a measure of the amount of calcium and magnesium salts

dissolved in water. Hard water is water that contains large amounts of dissolved calcium and

magnesium ions, and soft water is water that little or none of the ions. Water samples with a

moderately high hardness rating shows an extremely high amount of concentrations and less

amount of EDTA is added to reach end point. The results that were expected to be found,

such as water from a faucet to be hard, held true and the hypothesis was proven correct.

VI. Contribution of Partners

During the experiment, we titrated two samples each, one which used 50mL of CaCO 3

solution sample and one with tap water sample. I provided the mineral water that was

supposed to be used, but because of the late notice about using tap water I drank the bought

mineral water instead. Ms. Borja prepared the CaCo 3 solution with the help of Ms. Tadifa

while I prepared the set up and prepared the EDTA solution.

VIII. References
12 COMPLEX-FORMATION TITRATION: DETERMINATION OF TOTAL HARDNESS OF
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Literature cited:

1. Complexometric Titration with EDTA, Source:http://cd1.edb.hkedcity.netRetrieved from:

http://chemy.biz/A2_Chemistry/edta.htm

2. D. Spurlock, (1999-2014), Determination of Water Hardness By Complexometric

Titration Class NotesRetrieved from

http://homepages.ius.edu/DSPURLOC/c121/week13.htm

3. Experiment 5, Chem 23 (lab): Complex-Formation Titration: Determination of the total

hardness of the commercial mineral water, Department of Chemistry, University of the

Philippines Visayas.

4. Skoog,West,Holler and Crouch.(2003) Fundamentals of Analytical Chemistry, 8th

ed.,Brooks Cole

5. Day and Underwood., (1991) Quantitative Analysis

6. Prof. J. Martizano, Analytical chemistry 23 (lec): Complex Formartion Equilibria notes