QUANTITATIVE DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA

TITRATION

JOHN JOSEPH CHUA

DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 26 MARCH 2015
DATE PERFORMED: 6 APRIL 2015

ABSTRACT
Complexometric Ethylenediaminetetraacetic Acid (EDTA) Titration is used to quantitatively
determine the total hardness of Hidden Spring Drinking Water. Total Water Hardness, which is
measured in ppm CaCO3, is the intensity of the presence of calcium and magnesium ions in water
that is detected by formation of complexes. Through the application of knowledge regarding
complex formation and complex stability, the methodology of the titration for the determination of
calcium and magnesium ion concentration is concisely discussed. EDTA, in the form of H2Y2- at pH
10, is used as the complexing agent of titration. Through three trials of the complexometric
titration, the computed total water hardness for the experiment is 215.1450363 ppm CaCO3,
whereas the total water hardness indicated on the bottle label is 206.5834385 ppm CaCO3. With
respect to the total water hardness on the bottle label, the experimental value deviates by 4.144%.
Overall, the experiment is a success due to its relative closeness to the value indicated on the bottle
label.

INTRODUCTION

Water hardness is the traditional measure

of the capacity of water to react with soap;
hard water requiring considerably more
soap to produce lather [1]. Predominance of
metallic ions such as Calcium and
Magnesium cations in hard water allows
formation of insoluble mineral deposits
which may reduce efficiency in industrial
processes such as heating and in the
cleansing action of soaps [2].

Table 1. Water Hardness Scale (3)

Water Hardness
Soft
Moderately Soft
Moderately Hard
Hard
Very Hard

ppm CaCO3
0-20
20-60
61-120
121-180
>180

Water hardness is assigned with levels of

ppm CaCO3, which are tabulated in table 1.
Amount of CaCO3 in milligrams per liter is a

general term that indicates the total

quantity of divalent salts present in a water
sample. It does not specifically identify
whether calcium, magnesium, or other
divalent salt is the main cause of the
hardness of water but it simplifies
calculations due to the ~100 g/mol formula
mass of CaCO3 [4]. Since hard water hinders
efficiency in industrial processes, soft water
is preferred. On the other hand, hard water
is inclined to human consumption. Presence
of the metallic ions Ca2+ and Mg2+ can aid in
the human bodys calcium and magnesium
needs [3]. Although there are no convincing
evidences that relate hardness of water to
adverse effects, more research are needed
to establish direct effects and relations
regarding human consumption [1].

Complexometric titrations involve the
application of complexation reactions. In
this method of titration, a metal ion reacts
with a suitable ligand to form a complex,
and the equivalence point is determined by
1

an indicator or an appropriate instrumental

method [5]. Through the addition of the
titrant, identification of the amount of metal
ions in the analyte can be quantitatively
determined. It is already mentioned that
total water hardness is characterized by
presence of calcium and magnesium ions;
therefore, complexometric titration is used
to determine total hardness in drinking
water.

To determine the amount calcium and

magnesium, which determines the total
water hardness in the drinking water
sample, Ethylenediaminetetraacetic acid or
EDTA is used as the complexing agent or the
titrant in the solution.

EDTA is a widely used complexometric

titrant. It also has six potential sites for
bonding a metal ion: four carboxyl groups
and two amino groups, wherein the latter
has an unshared pair of electrons. With
these potential sites, EDTA is said to be a
hexadentate ligand, which also makes it a
chelating agent. [4]

formation of the complex studied is very

probable.

EDTA is used in the determination of total

water hardness as a titrant because the
Formation Constants (Kf) of EDTA with the
discussed metal cations are relatively high.

Formation Constants for EDTA

Complexes
Cation
KMY
log KMY
Ag+
2.1 x 107
7.32
Mg2+
4.9 x 108
8.69
2+
Ca
5.0 x 1010
10.70
Sr2+
4.3 x 108
8.63
2+
7
Ba
5.8 x 10
7.76
Mn2+
6.2 x 1013
13.79
Table 2. Formation Constants for EDTA
Complexes

As tabulated in table 2, the Kf of Mg2+ with
EDTA is 4.9x108 and 5.0x1010 for Ca2+. It has
been previously stated that the species
required for complexation of the said metal
ions is H2Y2-, which is present at pH 10.
Therefore, for the complexation to be
favored, the system should be maintained at
pH 10.

Figure 1. EDTA Structure [6]

The metal cations to be given a quantitative

analysis have a charge of 2+, which
indicates that to maximize the complexation
of these metal cations, EDTA must be kept
in its form as H2Y2-, which is its halfneutralized form. To maintain this form of
EDTA, a pH of at least 10 is required.

Complex formation constant, denoted as Kf,

is an equilibrium constant which is the ratio
of the concentration of products versus the
concentration of the reactants raised to
their appropriate stoichiometric factors. A
large value for the Kf indicates that the

Complexometric titration also deals with

visible indicators that mark the end point of
the titration. CaH2Y and MgH2Y are colorless
complexes, but with the addition of
Eriochrome Black T as an indicator, physical
observations in the titration endpoint can
be seen. Eriochrome Black T is used to
generate an unambiguous color change
from wine red to sky blue.[4] To observe this
color change, complexometric titration
involving EDTA develops a series of
displacement reactions, which lie on which
has higher formation constants.

Mg2+ + ErioT ErioT-Mg (1)

According to (1), addition of Eriochrome

Black T to the analyte forms a wine red
complex, which confirms the presence of
Mg2+.

Ca2+ + H2Y2- CaH2Y (2)

Mg2+ + H2Y2- MgH2Y (3)
Ca2+ + MgH2Y2- CaH2Y + Mg2+ (4)

Addition of the titrant EDTA, which is in the

form H2Y2-, will react with Ca2+ to form
CaH2Y complex (2) which has a Kf value of
5.0x1010; Mg2+ in the drinking water sample
that did not complex with Eriochrome Black
T will now complex with EDTA to form
MgH2Y (3) which has a Kf value of 4.9x108.

ErioT-Mg + H2Y2- MgH2Y + ErioT (5)

forming CaH2Y, while excess Ca2+ will

displace Mg2+ in the MgH2Y complex, as
seen in equation (4). The displacement is
due to the higher Kf value of CaH2Y than
MgH2Y, so the production of CaH2Y is more
probable to happen. Because of the
hastened formation of CaH2Y complex,
excess EDTA will be met faster, thus a
sharper endpoint.

At (5), the initial excess of EDTA after

complexation with all the Ca2+ and Mg2+ in
the analyte will displace Eriochrome Black
T in its complexation with Mg2+ during (1).
The displacement reaction results in the
free Eriochrome Black T, which produces
the sky blue color. The presence of the said
color marks the end point of titration,
where no metal cations are to form
complexes with EDTA.

In preparation of 0.0500 M Ca2+

equation (6) is involved.

Therefore, the total water hardness, which

is expressed in ppm CaCO3, can be
calculated from the volume of titrant
(EDTA) used and the molarity of the titrant
acquired from standardization. To acquire
quantitative data of the aforementioned
variables, the solutions in table 3 are
prepared.

Solution
EDTA
Ca2+(aq)
NH3-NH4+ Buffer
Drinking Water
Sample
Eriochrome
Black T

Volume
500 mL
100.0 mL
250.0 mL

Molarity
0.100 M
0.0500 M
1.0 M

150 mL
X mL

Table 3. Solution Preparation

In the preparation of 0.100 M of EDTA, 1 g

of MgCl26H20 and NaOH pellets are added.
Addition of the said species increases the
solubility of NA2H2EDTA because of the
diverse ion effect. The addition of MgCl2
allows the complexation of EDTA with Mg2+
which ensures a sharp endpoint of titration.

In equation (3), Mg2+ formed a complex

with EDTA, resulting in the presence of
MgH2Y complex in the titrant. Therefore,
there are free EDTA and Magnesiumbound EDTA. Calcium ions in the drinking
water sample react with the free EDTA

(aq),

the

CaCO3 + CO2 + H2O Ca2+ + 2HCO3- (6)

Since equation (6) is endothermic, heating

allows dissolution of the solid reactant
CaCO3, forming Ca2+ completely. If CaCO3
produced insoluble solids in the solution,
addition of HCl will dissolve the precipitate
in the reaction (7).

CaCO3 + 2HCl CaCl2 + H2O + CO2 (7)

Addition of the NH3-NH4+ buffer ensures
that upon the addition of the titrant there is
minimal change in pH. Computed amounts
of each reactant compose the buffer which
maintains the pH of the system at pH 10.

After preparation of the required solutions,

a 10 mL of diluted aliquot of the Ca2+(aq)
solution is used for standardization of the
EDTA titrant. 3 mL of the NH3-NH4+ buffer is
added, along with the addition of
Eriochrome Black T Indicator. The same
procedure has been done with the water
sample. 50 mL of the drinking water is used
for the complexometric titration. All of the
titrations are done three times.

RESULTS AND DISCUSSION

Complexometric EDTA Titration has been

done to show the amount of Ca2+ and Mg2+
in the drinking water sample, which is
referred to as total water hardness once
expressed in ppm CaCO3.

In an overview, the complexometric

titration involved solution preparation,
EDTA Solution Standardization, and
titration of the drinking water sample. The

following data presented are the computed

results from the methodologies.

Trial
mL EDTA
used
M EDTA
Average M
EDTA

5.9

5.8

6.2

0.0084 0.00852 0.007976

0.008294425 M

Table 4. Standardization of EDTA Solution

Three trials of the standardization of the

EDTA solution correspond to the three
computed molarities indicated on table 4.
The mean value is used as the molarity of
EDTA solution for further calculations. All
the data underwent and passed the Grubbs
Test. Theoretically, the molarity of the
EDTA solution is 0.01 M. The computed
value of 0.008294425 M deviated from the
theoretical value by 17.05575%. The
deviation may be caused by inaccurate
weighing of the reagents, fast addition of
titrant so endpoint was observed more
immediately and the percent purity of the
analytical reagent is taken to account.

The titer of the solution is computed to

make the calculations for ppm CaCO3 easier.
Using the average molarity of the
standardized EDTA solution, the titer is
computed and is expressed as mg CaCO3 per
mL of standardized solution. The computed
titer is 0.829608109 mg CaCO3/mL
Standardized EDTA Solution.

Trial
Net
Volume of
EDTA
Average
Volume
Standard
Deviation
Relative
S.D
Confidence
Limits

EDTA used during the titration has a

standard deviation of approximately
0.057735, which is relatively small. Using
the computed titer, the total hardness of
water can be known.

The amount of CaCO3 computed from the
titer is 10.75725181 mg. Therefore, the
experimental ppm of CaCO3 is 215.1450363
ppm. The drinking water sample is very
hard, according to the boundaries given on
table 1.

Ions
Ca2+
Mg2+
Total Water
Hardness

ppm
25
35

ppm CaCO3
62.40648379
144.1769547

206.5834385 ppm CaCO3

Table 6. Ions and Total Water Hardness

Indicated on Bottle Label

The experimental value deviates from the

theoretical value by 4.144%. The small
deviation is possibly brought about by
instrumental error, impurity of reagents
and solvents used and imprecise color
comparing.

Instrumental errors include wrong usage of

glassware and wrong weighing of reagents.
Presence of calcium and magnesium ions in
water that was used in dilution of all
solutions will result in an increased
computed total hardness. The same result
will happen if there are varying degrees of
sky blue that is used in determining the
endpoint of the titration.

12.9

13

13

12.966666666667
0.057735027
4.45257277

If the pH of the system changes by a greater

extent, the species of EDTA will change to a
more protonated or more deprotonated
form which will reduce the complexation of
EDTA with the metal ions calcium and
magnesium. Drastic changes in pH may be
brought about by wrong preparation of the
buffer.

12.823333

13.11

Table 5. Volume of Titrant Used and Some

Statistical Measures

The data on table 5 indicate the volumes of

titrant used during the titration involving
the drinking water sample. The volume of

SUMMARY AND CONCLUSIONS

Through the complexometric EDTA titration

of drinking water, the total hardness of
Hidden Spring Drinking water is identified.
The experimental total water hardness is
215.15 ppm CaCO3 while the total water
4

hardness indicated on the label in 206.58

ppmCaCO3. The percent error with respect
to the indicated total water hardness is
4.144%.

Generally, the drinking water is found to be

very hard, which is ideal for drinking.
Because of this fact, the experiment can be
considered a success because of relatively
low standard deviations and closeness to the
ideal water hardness of the computed ones.

REFERENCES

[1] WHO. (n.d). Hardness in Drinking-water:

Background document for development of
WHO Guidelines for Drinking-water Quality.
Health criteria and other supporting
information.
Geneva:
http://www.who.int/water_sanitation_heal
th/dwq/chemicals/en/hardness.pdf

[2] Casiday, C., Frey, R. (n.d). Water
Hardness: Inorganic Reactions Experiment.
Department of Chemistry, Washington
University St. Louis. St Louis, MO:
http://www.chemistry.wustl.edu/~edudev
/LabTutorials/Water/FreshWater/hardnes
s.html

[3]Oram, B. (n.d). Hard Water Hardness
Calcium Magnesium Water Corrosion
Mineral
Scale.
Dallas,
PA:
http://www.waterresearch.net/index.php/watertreatment/tools/hard-water-hardness

[4] University of Canterbury. (n.d).
Determination of Total Calcium and
Magnesium ion Concentration. College of
Science, University of Canterbury.

[5] Skoog, D., et.al., (2004). Fundamentals of
Analytical Chemistry. Belmont, CA:
Brooks/Cole-Thomson Learning.


[6] OpenStar CNX. (n.d). U.S Students in
Open-Source
Book
Program.
http://cnx.org/resources/60c9ece3d13106
99f7311bf16087ff7e/graphics4.jpg


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