Analytical Chemistry

MALAYAN COLLEGES LAGUNA

Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

I. OBJECTIVES

Upon completion of the experiment, the student should be able to:

 standardize the EDTA solution

 determine the hardness of some natural water samples and tap water; and
 apply the techniques involved in the preparation of solutions, standardization of solutions,
and analysis of unknown solutions for acid-base titrations.

II. A. LABORATORY EQUIPMENT / INSTRUMENTS

Equipment/ Accessories Quantity

50-mL beaker 2
50-mL buret 1
25-mL transfer pipet 1
250-mL Erlenmeyer flasks 2
125-mL Erlenmeyer flasks 2
aspirator 1

B. CHEMICALS AND REAGENTS

Chemical/ Reagent
0.0100M CaCO3 standard solution
0.0100M Mg-EDTA standard solution
Ammonia-ammonium chloride buffer, pH 10
Eriochrome Black T, 0.5% wt/vol in Ethanol
Unknown water sample
Distilled Water

III. DISCUSSION OF FUNDAMENTALS

Introduction

Under the law of infinite probability, it implies that everything might happen or can happen,
even at the lowest of chances. What is interesting is that the things that you don’t know would
happen, is already happening without further analysis of proof. Chemistry and its world always bring
that shock and awe to the people that deepen their knowledge unto it. A good example would be
the formation of complexes, or the bonding of metals to ligands, which are defined as complex

Experiment 8: Complexometric Titration Page | 1

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

forming nonmetal species. They bond without having to transfer an electron pair, but they donate
electrons, like what the principle of covalent bonding follows, instead of ionic bonding. These
complex formations have been regarded into a number of useful applications. One of them would
be determining the hardness of water (The hardness of water comes from the dissolved impurities
that are found on tap water, usually alkaline earth metals precipitated in carbonates) through
complexometric titration. By titrating the ligand into the water sample (usually tap), it will form a
complex on the metal ions around it (the water should be buffered on a correct pH setting, and one
must use an indicator), and by calculation, the hardness of water is determined.

IV. METHODOLOGY

A. Standardization of EDTA solution (2 trials)

25-mL of standard CaCO3 solution was transferred into an

Erlenmeyer flask using the buret

2-3-mL of NH3-NH4Cl buffer of pH 10 was then added to the

solution.

The six drops of the prescribed indicator, Eriochrome black T

(EBT) was then added.

The solution was titrated with the EDTA solution to the sky
blue endpoint.

The molarity of the standard EDTA solution was calculated.

Experiment 8: Complexometric Titration Page | 2

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

The average molarity and average deviation were taken and

were used for the rest of the calculations for the
experiment.

B. Determination of hardness of unknown water (2 trials)

The 25-mL pipet used was rinsed with a small amount of the
water sample.

Exactly 25-mL of the unknown sample was transferred to a

clean Erlenmeyer flask.

20 drops of the NH3-NH4Cl buffer and 4-5 drops of EBT were

added to the sample, and were then swirled to uniformity.

The solution was titrated with the standardized EDTA

solution to the sky blue endpoint.

The hardness of the unknown water sample was calculated

and was reported as ppm CaCO3.

Experiment 8: Complexometric Titration Page | 3

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

V. DESCRIPTION OF THE APPARATUS / SET – UP

VI. DATA SHEET

Table 1. Standardization of EDTA
Trial 1 Trial 2
Vol CaCO3 (mL) 25.0 25.0
Vol EDTA (mL) 25.4 24.8
Molarity of EDTA (M) 9.84×10-3 0.010081
Average M 9.962×10-3

Table 2. Determining the hardness of water

MW CaCO3 = 100.1 g/mol

Trial 1 Trial 2
Vol H2O (mL) 25.0 25.0
Vol EDTA (mL) 1.9 1.8
ppm CaCO3 75.772 71.784
Average ppm 73.778

Experiment 8: Complexometric Titration Page | 4

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

VII. SAMPLE COMPUTATIONS

A. Table 1
1-25.4
2-24.8
.
MEDTA =

B. Table 2
1-1.9
2-1.8

Trial 1:
= 75.772 ppm (mg/L)
Trial 2:
= 71.784 ppm (mg/L)

VIII. RESULTS AND DISCUSSIONS

The earth’s surface is covered, 7 % with water, and its inhabitants need water to survive their
everyday lives. There are different types of water, though, and some are non-potable. We humans
decide what to drink and sometimes treat water for it to be safe for drinking. Our regular tap water
contains metal ions, like Ca2+, Mg2+, Fe3+, SO42-, and HCO3-, being the reason for it being called hard
water. The Ca2+ ion has the highest concentration of metal, and thus hardness is measured in terms
of CaCO3 concentration, parts per million.

There are two types of water hardness, temporary and permanent. Temporary is when the
metal ions in the water are removable through boiling and permanent is when they can’t be.
Temporary hard water contains only bicarbonate ions and permanent hard water contains Ca2+,
Mg2+, Fe3+ and SO4-. Bicarbonate dissolves from water, as shown in the equation:
HCO3- ⇆ H2O + CO2
thus removing the CO2, while the remaining ions, Ca2+, Mg2+, Fe3+ and SO42- can’t be eliminated, thus
being permanently hard.

Experiment 8: Complexometric Titration Page | 5

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

Hard water does not pose threats to our health—rather, it supplies our calcium and magnesium
requirements, considering that we take supplements for those. It becomes important in the
industrial field because hard water is unsuitable for many uses because it makes the ions leave
insoluble precipitates. This is then where the method of water softening comes in. Industries usually
soften their hard water to improve efficiency. Hard water requires more detergent for washing and
contributes to equipment scaling.

Water hardness can be compared depending on its calcium carbonate content. The table below
shows its rating:

Hardness rating CaCO3 concentration (mg/L)

Soft 0 to <75
Medium 75 to <150
Hard 150 to <300
Very hard 300 and greater

One method of knowing the hardness of water is by making the unknown water sample undergo
complexometric titration. This is usually done with ethylenediaminetetracetic acid (EDTA). EDTA is a
common chelating agent that can make 6 bonds with metal ions, thus forming complexes. The two
nitrogen atoms have two lone pairs each and can
still form two bonds and the four OH- groups can
form four more bonds to the metal.

The experiment required the use of Eriochrome

black T, an azo dye that turns red when it forms a
complex and blue when in its protonated form. Its
blue endpoint is reached when the metal ions are
chelated after sufficient EDTA is used. This is
because EDTA reacts with the divalent metal ions
complexed with the EBT indicator, thus leaving the EBT alone.

In the experiment, we tried to determine the hardness of the unknown water sample given to
us. First of was the standardization of the EDTA solution to be used for the titration. When the
molarity of the EDTA was determined, the unknown water sample was treated with NH3-NH4Cl
buffer of pH 10.00 and the Eriochrome black T indicator. The initial color of the solution was red,
indicating its basicity. It was then titrated with the standardized EDTA solution. When enough EDTA
was added to the solution to chelate the divalent ions, the solution turned light blue. The hardness

Experiment 8: Complexometric Titration Page | 6

Analytical Chemistry
MALAYAN COLLEGES LAGUNA
Laboratory

CHM130L

EXPERIMENT NO. 8
COMPLEXOMETRIC TITRATION

of the water was then determined by knowing first the concentration of Ca2+ ions in the unknown
water sample, and it was reported as ppm (parts per million).

IX. SUMMARY AND CONCLUSIONS

This experiment confirmed the underlying facts and figures behind complex formation and one
of its applications: determining the hardness of water by using complexometric titration. The EDTA
solution, which is needed for complex formation, is standardized to know the exact concentration of
it for future calculations. By getting a tap water sample, it was assessed with the Eriochrome Black T
indicator (wine red) and was put in an ammonia solution that is buffered with ammonium (in the
form of ammonium chloride) to know the endpoint. By using the standardized EDTA solution, the
analyte is titrated complexometrically. After getting all values, by computation the hardness of
water is determined as ppm calcium carbonate. Only the calcium carbonate is considered to be in
the tap water sample, since majority of it is the reason why there are hard deposits on water pipes
(or as referred to as calcium deposits), and since EDTA is in the form MgEDTA, the magnesium
carbonate can be disregarded. Also, calcium carbonate is the majority of the alkaline earth
carbonates present in the solution.

X. REFERENCES

Christian, Gary D. 2004. Analytical chemistry (6th ed.). John Wiley and Sons Inc.

Hage, David S. and James D. Carr. 2011. Analytical chemistry and quantitative analysis. New
Jersey: Pearson Prentice Hall.

Harris, Daniel C. 2003. Quantitative chemical analysis. (6th ed). New York: W. H. Freeman and
Company.

Madamba, Lilia S.P. 1995. Chemistry 32 Laboratory Instruction Manual (3rd rev). Los Baños:
Analytical and Environmental Chemistry Division, Institute of Chemistry, University of the Philippines
Los Baños.

Skoog, Douglas et. al. 2004. Fundamentals of Analytical Chemistry (8th ed.). Singapore:
Thomson Learning.

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