QUANTITATIVE DETERMINATION OF TOTAL HARDNESS IN

DRINKING WATER BY COMPLEXOMETRIC EDTA TITRATION

J. FERNANDEZ1 and J. LIM2
1

INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE

INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE PERFORMED: 24 JANUARY 2014
2

ABSTRACT
The objective of this experiment is to apply the concept complexometric titration in the determination of total
hardness in drinking water. Water hardness can be defined as a measure of the calcium and magnesium ions in ppm
of calcium carbonate. Ethylenediaminetetraacetic acid (EDTA), an organic hexadentate ligand, was used as the
titrant because of its 1:1 combination ratio with metal cations. Eriochrome Black T (EBT), a magnesium ion indicator,
was used due to its behavior as a weak acid and its ability to be both an acid-base and a metal ion indicator. 0.01 M
EDTA solution was standardized with 0.0050 M CaCO3 solution. The standardized EDTA solution was then used to
titrate 50.00 mL of the drinking water sample. The calculated ppm CaCO3 from the titration data was 0.2491 ppm
CaCO3 with 0.1221 ppm CaCO3 confidence interval. The total water hardness of the drinking sample was
estimated to be at 0 ppm CaCO3. A percent error of % was observed. It can be concluded that the sample is about as
soft, in terms of water hardness, as the company claims it to be. More information on the mineral content of the
product will be needed to reduce error.

INTRODUCTION
Water hardness is defined in terms of the
concentration of calcium carbonate that is equivalent
to the total concentration of all the multivalent cations
in a sample of water. [1] The determination of water
hardness is important because it provides a measure
of the quality of water for household and industrial
uses. The ions in hard water precipitate with soaps,
which lessen the cleansing action of soap.
Furthermore, hard water, upon being heated,
precipitates calcium carbonate, which clogs pipes [1].
Table 1. The Water Hardness Scale
Water Hardness
ppm CaCO3
Soft
0-20
Moderately soft
20-60
Moderately hard
61-120
Hard
121-180
Very hard
> 180
Complexometric titrations with EDTA have been used
to determine every metal cation with the exception of

alkali metal ions or the Group 1-A metals [1]. In the

experiment, the experimenters apply the concept of
complexometric titration in the determination of total
hardness in drinking water.
Water hardness is usually determined by an EDTA
titration after the sample has been buffered to pH 10.
Magnesium forms the least stable EDTA complex and
is therefore not titrated until enough reagent has been
added to complex the other cations in the water
sample. Calmagite or Eriochrome Black T, both
magnesium-ion indicators, can be used as indicators
in water-hardness titrations [1]. The wine-red color of
the Magnesium-Indicator complex (MgIn-) breaks up
into at the equivalence point (blue complex HIn2-) as
shown in the reaction as shown:
H+ + Y4- + MgIn- MgY2- +HIn2In the initial stages of the titration, magnesium ions
are displaced from the EDTA complex by calcium ions
and are free to combine with the Eriochrome Black T,
therefore imparting a red color to the solution.

RESULTS AND DISCUSSION

Water hardness is the total concentration of alkaline
earth ions, which are mainly Ca 2+ and Mg2+, in water.
Hardness is commonly expressed as the equivalent
number of milligrams of CaCO3 per liter. Thus, if [Ca2+]
+ [Mg2+] = 1mM, we would say that the hardness is
100 mg per liter because 100 mg CaCO 3 = 1 mmol of
CaCO3. Water whose hardness is less than 60 mg per
liter is considered to be soft. If the hardness is
above 270 mg/L, the water is considered to be hard.
[2]
In a complexometric titration, analyte and titrant form
a complex ion, and the equilibrium constant is called
the formation constant, Kf. Chelating (multidentate)
ligands form more stable complexes than do
monodentate ligands, because the entropy of
complex formation favors the binding of one large
ligand rather than many small ligands. [3]
Ethylenediaminetetraacetic acid, or EDTA, is widely
used in titrations of metal cations because it forms 1:1
complexes with the cations. It is an aminocarboxylic
acid which has 6 binding sites (the four carboxylate
groups and the two amino groups), providing six pairs
of electrons. In the experiment, EDTA was used to
measure water hardness. Basically, EDTA captures
the metal cations in the water by tightly bonding to
them, thus making the water soft. [4] The structure of
EDTA is shown in figure 1 below.

Figure 1. Structure of ethylenediaminetetraacetic acid,

commonly known as EDTA

To start, 18.6 g of Na2H2EDTA2H2O were dissolved in 200

mL of distilled water. NaOH pellets and 1.0 g of MgCl26H2O
were then added. Addition of metal, like magnesium, in the form of
salt causes the metal-EDTA complex to form faster. It also
ensures that Mg2+ will be initially present in the titrant and that there
will be a sharper endpoint. NaOH causes an increase in the
dissociation of ions and also serves as a neutralizer of the H + from
the EDTA.

The standard CaCO3 solution was then prepared by dissolving

1.2515 g of pure CaCO3 with 40 mL of distilled water. HCl was
added in the solution to ensure fast dissolution of the solids. The
buffer solution with pH 10 was prepared by mixing 2.0 g of NH 4Cl
and 14.3 mL of NH3. The indicator used was eriochrome black-T
which binds with the excess ions to form the wine-red complexes.
Once the EDTA has displaced all the EBT bounded to metal
cations, the solution reaches its endpoint, a clear blue solution.
Since EDTA is a weak acid, the pH used was basic at pH 10.
Calculating the EDTA and metal cation concentrations is pH
dependent so it is important to keep the pH constant. For this
purpose, a buffer solution was used. In the experiment a pH of 8
or higher is needed in order for the blue color to be visible so the
NH3-NH4Cl was used.
Fifty milliliters of 0.0050 M working standard Ca2+
solution and 250 mL 0.0100 M working EDTA solution
were prepared from 0.0500 M Ca2+ and 0.1000 M
EDTA respectively through dilution.
In the standardization of 0.0100 M EDTA, 10 mL of
0.0050 M working standard CaCO3 solution was
pipetted into each of the 3 250-mL Erlenmeyer flask
which was then diluted with 75 mL of distilled water.
Three mL of buffer solution and 2 drops of EBT
indicator were also added to each flask. The solutions
were titrated with the 0.0100 M standard EDTA
solution. Table 2 below shows a summary of the net
volume of EDTA used for each trial.
Table 2. Net volume of EDTA used for standardization
Trial

Net volume of EDTA, mL

14.5

14.3

14.1

Note that the values obtained are quite close to each

other and can be labelled precise. The errors in
titration were kept at low by titrating very slowly.
In the titration process, the solutions were first
observed to be wine red because of the reaction of
EBT with the ions. As EBT is added to the solution,
[Mg-In] - will form based on the reaction below.
Mg2+ + HIn2- (blue) + H2O MgIn- (wine red) + H3O+

(1)

After the solution was titrated with EDTA, the color

gradually changed until it turned into clear blue
solution which marked the endpoint. At this point, the

reaction between the indicator-metal complex and

EDTA is as follows:
MgIn- (wine red) + Y4- + H3O+ MgY2- + HIn2- (blue) + H2O

(2)

Equations 1 and 2 show the reactions that take place

and tell why there is a wine red solution in the start of
the experiment and a clear blue solution after the
whole titration process. [5]
In the analysis of water sample, 50.0 mL of the
commercial mineral water (Absolute) was transferred
to a 250-mL Erlenmeyer flask. Three mL of buffer and
2 drops of EBT were added to the flask and the
solution was titrated with EDTA. This was repeated for
two more trials. Table 2 shows a summary of the data
obtained.
Table 3. Net volume of EDTA for water sample
analysis
Trial

Net volume of EDTA, mL

0.05

0.05

0.05

Like the data from the standardization, the obtained

values were very precise. In fact they are all the
same. With just a drop of EDTA, the slightly purple
solutions became clear blue.
Molarity of EDTA and total water hardness were then
calculated from the data. The obtained water
hardness was greater than the brands claimed
hardness which is 0 ppm. Nevertheless, the water is
still considered soft because its total water hardness
does not exceed 20 ppm.
Possible sources of errors include titration errors,
weighing errors and other human errors which could
have affected the pH and volume of titrant.
SUMMARY AND CONCLUSIONS
Complexometric titration was performed for the
determination of the total hardness in drinking water.
Complexometric titration includes and integrates the
complexation reactions of metal cations with
particular ligands. Ethylenediaminetetraactic acid
(EDTA) is an organic, hexadentate ligand that was
used as the titrant and the drinking water sample as
the analyte. EDTA was used because of its 1:1

combination ratio with metal cations, regardless of the

charge. The indicator used is Eriochrome Black T
(EBT). EBT behaves as a weak acid, and is a good
acid-base indicator and at the same time, a metal ion
indicator. The red color would predominate in the
presence of a metal cation and would turn to its blue
counterpart with the absence of the said cation at pH
equal to 7 or higher. The addition of MgCl 22H2O prior
to the preparation of EDTA solution would form MgEDTA complexes, which would hasten the formation
of Ca-EBT complex through the displacement of
magnesium ions to and from complexes of EDTA and
EBT. The displaced H+ would be neutralized by the
added NaOH pellets, and would ensure the complete
dissolution of Na2H2EDTA 2H2O crystals. The
addition of HCl to CaCO3 prior to the preparation of
the Ca2+ solution would separate the ion more
effectively than with water, since the reaction of the
two would produce carbon dioxide, water, and
chlorine and calcium ions. Several complexation
reactions are happening all throughout the titration
process. These reactions include the formation of
metal-EDTA (Ca-EDTA and Mg-EDTA) and metal-EBT
(Ca-EBT and Mg-EBT) complexes as well as the
displacement reactions of the metal-EBT complexes
with the excess EDTA and the gradual displacement
of calcium ions with the Mg-EDTA complex. Obtaining
a sharper endpoint after the titration process would
require a constant pH, which for this experiment is at
pH equal to 10. A buffer is required to maintain the
solution at this constant pH to ensure a sharper
endpoint. The buffer will also hasten the complexation
process by forming a stable complex of NH3 ligands
and metal cations. The NH3 ligands would then be
replaced by stronger EDTA ligands, which form much
more stable complexes. Several possible sources of
error can be found throughout the experiment. These
may include, but are not limited to, not washing of the
burette with the titrant EDTA solution, rapid addition of
EDTA to the solution, failure to maintain buffer pH at
10, addition of too much buffer, and the presence of
other interfering ions in the sample.
The total water hardness of the drinking water sample
based from the concentrations of calcium and
magnesium indicated is 0 ppm CaCO3. The average
ppm CaCO3, based on the titration data, is calculated
to be at 0.2491 ppm CaCO3 with 0.1221 ppm
CaCO3 confidence interval. It can be concluded that
the sample is about as soft, in terms of water
hardness, as the company claims it to be. This may

be due to the original assumption that the hardness

was at 0 ppm a perfectly pure sample. More

information on the mineral content of the product will

be needed to reduce error in the experiment.

REFERENCES
[1] Whitten, Kenneth W.. Chemistry. 8th ed. Belmont,
CA: Thomson Brooks/Cole, 2004
[2] Harris, Daniel C.. Quantitative chemical analysis.
7th ed. New York: W.H. Freeman, 2006
[3] Harvey, David. Modern analytical chemistry.
Boston: McGraw-Hill, 2000

[4] Skoog, Douglas A.. Fundamentals of analytical

chemistry, 9th ed., [International ed. Belmont, CA.:
Brooks/Cole, Cengage Learning, 2014
[5] Silberberg, Martin S.. Principles of general
chemistry. Boston: McGraw-Hill Higher Education,
2007.

APPENDIX
A. Calculations
M working standard

g CaCO3
5.00 mL stock CaCO3
1000 mL 1

0.995
Mworking standard = mL CaCO3 1 L
MW CaCO3
50.00 mL diluted CaCO3
1.2515 g 1000 mL 1 mol
5.00 mL

0.995
100 mL
1L
100.1 g
50.00 mL

= 0.012441 M
M EDTA
Trial 1

M working standard V working standard

MEDTA = V EDTA
=

Trial 2
MEDTA =

Trial 3
MEDTA =

(0.012441 M)(10.0 mL)

(14.5 mL)

M working standard V working standard

V EDTA
(0.012441 M)(10.0 mL)
(14.3 mL)

= 0.0087 M

M working standard V working standard

V EDTA
(0.012441 M)(10.0 mL)
(14.1 mL)

Average M EDTA
=

= 0.00858 M

= 0.00882 M

0.00858 M +0.00882 M + 0.0087 M

3

= 0.0087

0.0087 mmol EDTA 1 mmol CaCO3 100.1 mg CaCO3

Titer = Ave. MEDTA x MW CaCO3 = mL EDTA

1 mmol EDTA 1 mmol CaCO3
mg CaCO3

0.87087 Titer ( mL EDTA

ppm CaCO3
Trial 1

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.5 mL EDTA)
mL
EDTA
=
50.0 mL sample
( 0.87087

= 0.2526

ppm CaCO3
Trial 2

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.3 mL EDTA)
mL EDTA
=
50.0 mL sample
( 0.87087

= 0.2491

ppm CaCO3
Trial 3

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.1 mL EDTA)
mL EDTA
=
50.0 mL sample
( 0.87087

= 0.2456

ppm CaCO3
Average ppm CaCO3
=

RSD =

0.2526 ppm +0.2491 ppm+0.2456 ppm

= 0.2491 ppm CaCO3
3

s
1000 ppt =
x

0.00001225
1000 ppt = 0.04916 ppt
0.2491

ts
4.30 0.04916
X
0.2491
95% Confidence Interval =
n =
3

= 0.2491 0.1221 ppm CaCO3

0.0087 mmol EDTA 1 mmol CaCO3 100.1 mg CaCO3

Titer = Ave. MEDTA x MW CaCO3 = mL EDTA

1 mmol EDTA 1 mmol CaCO3
mg CaCO3

0.87087 Titer ( mL EDTA

ppm CaCO3
Trial 1

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.5 mL EDTA)
mL EDTA
=
50.0 mL sample
( 0.87087

= 0.2526

ppm CaCO3
Trial 2

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.3 mL EDTA)
mL
EDTA
=
50.0 mL sample
( 0.87087

= 0.2491

ppm CaCO3
Trial 3

Titer V EDTA
ppm CaCO3 = V sample

mg CaCO3
)(14.1 mL EDTA)
mL EDTA
=
50.0 mL sample
( 0.87087

= 0.2456

ppm CaCO3
Average ppm CaCO3
=

RSD =

0.2526 ppm +0.2491 ppm+0.2456 ppm

= 0.2491 ppm CaCO3
3

s
1000 ppt =
x

95% Confidence Interval =

0.00001225
1000 ppt = 0.04916 ppt
0.2491
ts
4.30 0.04916
X
0.2491
=
n
3

= 0.2491 0.1221 ppm CaCO3