J. E. Birdwell / Chemistry 26.

1 (2019) P a g e |1

Quantitative Determination of Total Hardness in Drinking Water by Complexometric

EDTA Titration
Department of Food Science and Nutrition, College of Home Economics
University of the Philippines-Diliman, Quezon City, Philippines
Performed 13 March 2019; Submitted 22 March 2019

ABSTRACT
Water is an essential component used for a number of life sustaining processes. It is used for biological
processes as well as for industries and manufacturing. Water hardness is the amount of calcium and magnesium
dissolved in water. This experiment aims to determine the total water hardness of a water sample by
complexometric titration. It involves the formation of a complex through the reaction of the EDTA titrant and
the analyte. The reaction forms a complex with the indicator, Eriochrome Black T, which forms a wine red
complex while the reaction between the metal cation and the EDTA forms a clear blue complex. Endpoint is
indicated with a color change from wine red to clear blue. Through experimentation, the calculated average
total hardness of the mineral water sample was 12.14 ppm with a percent error of 79.09% based from the
theoretical value of the total water hardness that is 58.05 ppm. Its relative standard deviation is zero due to a
consistent net volume of titrant. The calculated total hardness states that the water sample falls under the soft
water category.
Introduction

Water a vital component for all living things in
the planet. Water is used for a number of life-
sustaining processes in the world such as
photosynthesis and cellular respiration. It can be
graded according to its mineral content. Water
hardness is the amount of dissolved calcium and
magnesium in the water. The higher the mineral
content, the “harder” the water. Because of its cation
capacity, hard water replaces the potassium and
sodium ions in water to form “soap scum” or the soap
film experienced during washing making hard water
inefficient for cleaning [1].
However, due to its high mineral content it is better
for human consumption as it contributes to a small
but significant amount of calcium (Ca2+) and
magnesium (Mg2+) to a person’s dietary needs.
Although hard water is regarded to be a better option
when it comes to drinking water, it can also bring
problems to the water transportation equipment of
residential areas as it can form mineral build up on the
pipes and damage heating devices [2]. In this
experiment, water hardness is expressed in parts per
million (ppm) of calcium carbonate. Ca2+ in the water
sample outweighs the other multivalent ions present,
making it an acceptable representation of the total
amount of minerals found in the water sample. [1]
Water hardness is ofted tested by
complexometric EDTA Titration. Complexometric
titration is a form of volumetric analysis in which a
formation of a complex is used to indicate the end
point of titration [3]. In complexometric titrations, a
metal ion reacts with a suitable ligand to form a
complex, and the equivalence point is determined by
an indicator or an appropriate instrumental method.
Complexometric titrations with EDTA have been
applied to the determination of virtually every metal
cation with the exception of the alkali metal ions.
Ethyldiaminetetraacetic acide (EDTA), a hexadentate
ligand, is among the most important and widely used
reagents in titrimetry. It has six potential sites for
bonding a metal ion: four carboxyl groups and two
amino groups, each of the latter with an unshared pair
of electrons [1].
Figure 1. Structure of EDTA molecule

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 J. E. Birdwell / Chemistry 26.1 (2019) P a g e |2

Materials and Methods the ions of Ca2+. The more reactants added, the more
Solution Preparation it pushes the reaction forward and indicator easily
forms complexes with metal ions [1]. Also, NaOH
The solutions that were needed for the lowers the pH in which EDTA is being dissolved in.
experiment were prepared, namely 500.0 mL of 0.1000
M stock EDTA solution, 100.0 mL of 0.0500 M stock Ca2+ The pH of the analyte needs to be maintained at pH 10.
solution, and 250.0 mL of 1.0 M NH3-NH4+ with pH 10 In order for EDTA to react with metal ions, the
buffer solution obtained from NH4Cl solids and NH3 hydrogens that are attached to the carboxylate group
stock solution. Then, 250.0 mL of 0.0100 M working in the molecule must be removed. So this means that
EDTA solution was prepared from the stock EDTA the solution must be basic in order for the metal ions
solution and 50.0 mL of 0.0050 M working standard to bond with EDTA [4]. This also explains the need for
Ca2+ solution from 0.0500 M stock solution.
a NH3-NH4+ with pH 10 buffer solution to be added to
Standardization the analyte.
For the standardization of the EDTA solution,
10.0 mL of the working calcium solution was pipetted
into each of three 250-mL Erlenmeyer flasks and 75 mL
of distilled water was added to each flasks. 3 mL of
buffer solution was added, which was followed with 2
drops of EBT indicator. The flask was swirled and was
titrated until endpoint was reached, which was a color
change from light purple to clear blue. The initial and
final volume were recorded and the procedure was
triplicated.
Sample Analysis
For the drinking water analysis, a 50.0 mL
sample of commercial drinking water (Summit Natural
Drinking Water) was pipetted into three 250-mL
Erlenmeyer flasks. Three (3) mL of buffer solution was
again added, which was followed with 2 drops of EBT
indicator. The flask was swirled and was titrated until
endpoint was reached, which was a color change from
light purple to clear blue. The initial and final volume Figure 2. EDTA Titration Curve 50.0 mL of 0.00500 M
were recorded and the procedure was triplicated. Ca2+(K'CaY = 1.75 x1010) and Mg2+(K'MgY = 1.72 x108) at pH
10.0. *The shaded area shows the transition range for EBT. [1]

Results and Discussion

EDTA is the most widely used complexometric
titrant. It is a valuable titrant because EDTA combines
with metal ions in a 1:1 ratio regardless of the charge
on the cation. Moreover, it not only forms chelates
with all cations but also these chelates are stable for
titration [1].
The stock EDTA solution was prepared by
dissolving an appropriate amount of salt by distilled
water. The MgCl2•6H2O and NaOH pellets added to the
solution steepen the curve of its titration because
MgCl2*6H2O it produces Mg2+ which will account for
During the preparation of the Ca2+ stock
solution, a small amount of concentrated HCl was
used to dissolve CaCO3. HCl increases the dissociation
of CaCO3 as it HCl reacts to CaCO3 to form H2CO3 and
CaCl2, which are water soluble. Because CaCO3’s
dissociation in water is low, this step is crucial along
with the addition of MgCl2•6H2O to ensure that there is
an ideal amount of Ca2+ to react with EDTA so that the
values in the standardization will be accurate.
The indicator used in the titration of the analyte
was Eriochrome Black T (EBT). It is widely used
determination of the water hardness in a water
 J. E. Birdwell / Chemistry 26.1 (2019)
sample, since it bonds with magnesium and calcium,
which then produces a vividly colored wine red
solution [5].
The chemical equations involved are:
Ca2+ + HIn- → CaIn- + H+ (1)
Ca2+ + Y4- → CaY2- (2)
CaIn- + Y4- + H3O → CaY2- + HIn- + H2O (3)
*Where EDTA is denoted by Y and In denotes EBT
The first reaction occurs upon the addition of
EBT to the analyte. Because the primary standard only
contains Ca2+, it will form a wine red complex with the
calcium ions. The second reaction occurs because not
all calcium ions will form a complex with EBT. The free
calcium ions with then form a complex with EDTA
during titration. When all free Ca2+ are consumed, Ca2+
from Ca-EBT complex will then form a clear blue
complex with EDTA as shown in the third equation.
During the analysis of the water sample, Mg-
EBT and Mg-EDTA will form instead of Ca-EBT and Ca-
EDTA because it has a higher formation constant. A
similar reaction occurs as shown by these equations:
Mg2+ + HIn- → MgIn- + H+ (1)
Mg2+ + Y4- → MgY2- (2)
MgIn- + Y4- + H3O → MgY2- + HIn- + H2O (3)
The average molarity of the standardized EDTA
solution was found out to be 0.0087 M and a titer of
0.8674 mg CaCO3 per mL of EDTA. Using these values,
the experimental value of ppm CaCO3 of the water
sample can be calculated.
The theoretical ppm of CaCO3 or the total cation
content was obtained from the given values on the label
of the commercial drinking water. It was found out that
the theoretical value was 58.05 ppm CaCO3, which was
classified under soft water.
The concentration of CaCO3 obtained from the
titration of the sample was found out to be 12. 14 ppm
and because all the trials had the same net volume of
EDTA, the relative standard deviation is 0 ppt and the
confidence interval is 12.14 ± 0 ppm at any confidence
level. This was also classified as soft water.
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The percent error of the experimental value was
found out to be 79.09%.
Conclusion and Recommendations
The values obtained from the experiment are
significantly different than the values posted on the
label of the drinking water. This means that if the values
are accurate, the water contains much less minerals
than advertized. The water although vastly different
from the theoretical total hardness, is still classified
under soft water.
Possible sources of error could be overtitration
of the analyte due to a fast titration, however the
calculated percent error seems to be too high for that
alone. It is possible that the actual concentration of the
EDTA titrant may be higher than calculated or that the
analyte solution was not in the proper pH where all of
the Mg2+ was able to form a complex with the indicator.
The other ions that may have also bonded with EDTA are
also not accounted in the experiment and calculations,
which may be a source of error.
Determing the water’s hardness is important to
avoid premature equipment damage in industrial and
residential settings. It also propagates awareness on the
substances that are present in the food items we ingest.
Water quality should be observed and maintained not
only in the urban areas but also and most importantly in
the agricultural sector.
References
[1] Skoog, D. A.; West, D. M.; Holler, F. J.; Crouch, S. R.
Fundamentals of Analytical Chemistry, 8th ed.; : David
Harris, 2004; pp. 563-565
[2] Perlman, H. Hardness in water, USGS Water Science
School https://water.usgs.gov/edu/hardness.html
(accessed Mar 21, 2019).
[3]Schwarzenbach, G.; Flaschka, H. Complexometric
titrations; Methuen: London, 1969.
[4]De la Camp, U.; Seely, O. Complexometric Ca
Determination
http://www5.csudh.edu/oliver/che230/labmanual/cal
cium.htm (accessed Mar 21, 2019).
[5]Young, A.; Sweet, T. Analytical Chemistry 1955, 27,
418-420.
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Appendix