J.

B. Naval / Chemistry 26.1 (2019) P a g e | 1

Quantitative Determination of Total Hardness in Drinking Water by Complexometric

EDTA Titration.
Joshua B. Navala,*, Joone Xyron V. Creencia b
aInstitute of Biology - University of the Philippines Diliman
bCollege of Arts and Letters - University of the Philippines Diliman

Performed 13 March 2019; Submitted 22 March 2019

A B S T R A C T
In this experiment, complexometric EDTA Titration was performed to determine the total hardness of Viva!
Mineralized Water. The titration was done under an alkaline environment in pH 10 which is achieved by adding
NH3-NH4+ buffer solution. EDTA titrant was standardized then was used to titrate the water sample containing a
few drops of Eriochrome Black T indicator which turned the solution into purple. The endpoint of titration was
marked by the color change of the solution from purple to sky blue. The students were able to obtain an average
of 144.7 ppm CaCO3 which was the value for the total hardness of the water sample and was considered “hard”
according to the scale of water hardness. This conclusion obtained agrees with the theoretical water hardness
of the Viva! Mineralized Water. The students were successful in achieving the objectives of the experiment.

Introduction
Figure 1. Chemical structure of EDTA.
One of the factors that determines the quality
of a water sample is its total hardness. Minerals found It can be seen that in the structure of EDTA
in groundwater produces metal ions such as calcium, that it is hexadentate. It can form four to six bonds
magnesium, manganese and iron [1] which is essential with a metal ion. This shows that EDTA is a very
for the human body. The higher the concentration of versatile chelating agent [5], meaning it can capture
these ions in the water, the “harder” the water sample metals present in water more effectively in
is. Specifically, the total hardness of mineral water is comparison to the bidentate or tetradentate complex
defined by the sum of its calcium and magnesium ions. A chelate is produced when a metal ion
content. Calcium is considered to be the most coordinates with two or more donor groups of a
abundant in water in comparison to the other single ligand to form a heterocyclic ring [4].
minerals [2]. Water hardness is determined by the
mass in milligrams of CaCO3 per liter of water which The four oxygen atoms and two nitrogen
is also equivalent to ppm (parts per million). atoms has unshared electron pairs that bonds to a
metal ion forming a more stable complex ion [5]. The
In the experiment performed, the water conditions for this ion to form can be controlled so
hardness of Viva! Drinking water was analyzed that a specific metal ion would bond to it. In this
through complexometric EDTA titration. A experiment, calcium and magnesium bonds with
complexometric reaction is involved in this type of these ligands forming a more stable complex ion.
titration. This requires the reaction between complex
ions in a solution. A critical factor in this is the
extreme ability of the complex ion to be dissolved or
its solubility [3]. The electron-pair donors of the
complex ion reacts with the metal ions present in
water. These donors are also considered as the
complex ion’s ligands which have at least one pair of
electrons that are available for the formation of
covalent bonds [4].

Figure 2. Chelate formed by the EDTA’s ligands and

one calcium ion

Through this reaction, metal is “harvested” by

the EDTA through chelation. Since EDTA and the

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph
 J. B. Naval / Chemistry 26.1 (2019) P a g e | 2

calcium ion are both colorless, it was essential that a buffer was added to each solution then followed by 2
specific indicator to detect the end point of titration. drops of EBT indicator. Initially, the solution was wine
For this experiment, Eriochrome Black T was used red to purple in color. This was titrated slowly using
which reacted with magnesium forming MgIn-, a EDTA solution as the titrant until the endpoint is
wine-red complex. As EDTA was being added to the reached which is the color change from wine red/
water sample solution, it forms chelates first with the purple to clear blue. This was done in three trials to
free calcium ions then with the magnesium ions. As obtain a more accurate result.
the process reaches its endpoint, EDTA will displace
the magnesium ion from the MgIn- complex, changing Through standardization, the students were
the color of the solution from wine-red to the able to determine the exact concentration of the EDTA
uncombined form of the indicator which is sky blue solution. Analysis of water sample was done after
[5]. this. 50.0 mL of the commercial mineral water sample
was pipetted to was 250-mL Erlenmeyer flask using a
Titration reaction: 50-mL volumetric pipette. Same procedure in
titrating of the standardization was done in this part
of the experiment. 3 mL of the buffer was added
followed by the addition of EBT indicator. The
endpoint was reached when the color of the solution
End point reaction: changed from wine red/purple to clear blue. Three
trials was done to ensure the accuracy of the values
obtained.

Results and Discussion

In this experiment, results from the analysis In the standardization, the students were able
was compared to what the Viva! Mineral Water claims to determine the exact concentration of EDTA
wherein it states that it is 54 ppm Ca which is solution prepared which resulted to 8.6728 x 10-3 M,
equivalent to 134.85 ppm CaCO3 and 10 ppm Mg which was the calculated average of three trials
which is equivalent to 41.18 ppm of CaCO3. Both of performed. This was then used for the calculations for
these values was obtained through stoichiometric the concentration of calcium carbonate present in the
calculations. Adding the two values of the water sample. Standardization is necessary in every
concentration of CaCO3 yields to 176.03 ppm CaCO3 titration experiment to ensure the accuracy of the
which is considered as “hard” in the water hardness values that will be obtained in the process.
scale.
After the three trials of titration of the Viva!
Materials and Methods water sample, the CaCO3 content of it was obtained in
ppm. The value computed was 144.7 ppm of CaCO3.
The students prepared two stock solutions Theoretically Viva! water mineral is assumed to have
specifically 500.0 mL 0.1000 M EDTA solution and 176.03 ppm CaCO3. This may be relatively different to
100.0 mL 0.0500 M Ca2+ solution. EDTA solution was the experimental value but according to the water
prepared by Ca2+ solution was prepared by dissolving hardness scale, the students were able to confirm that
0.5005 g CaCO3 (100% purity) with 40 mL distilled the commercial mineral water is “hard”. The RSD
water. HCl was then added to dissolve CaCO3 while obtained from the three trials was 84.255 ppt with a
stirring and heating the solution. The solution is then confidence interval of 144.7 +/- 30.3 ppm at 95%
transferred to a 100-mL volumetric flask and was confidence level.
diluted to the mark. Working solutions was obtained
from these stock solutions, specifically, 250.0 mL
0.0100 M EDTA solution and 50.0 mL 0.0050 M
working standard Ca2+. Buffer solutions was also
prepared by the students specifically 250.0 mL 1.0 M
NH3-NH4+ pH 10 buffer solution from NH4Cl and NH3.

This was followed by the standardization of

the EDTA titrant. The students pipetted 10.00 mL of
the working standard CaCO3 solution into each of
three 250-mL Erlenmeyer flasks then 75 mL of
distilled water was added to each flask resulting to a
total of 85 mL solution per flask. After this, 3 mL of Table 1. The water hardness scale.

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph
 J. B. Naval / Chemistry 26.1 (2019) P a g e | 3

Complexometric titration was appropriate for The possible reasons for the deviation of the
this type of analysis since this involves a reaction experimental value of water hardness to the
wherein metal ions is being “captured” during the theoretical are the errors committed in the
titration and the quantitative value obtained from this experiment. Some of these errors might include
is necessary for computing for the water hardness. errors in solution preparation, over-titrating, and the
The solution was also buffered at pH 10 using the use of excessive EBT indicator which would prevent
NH3/NH4+ buffer which kept the EDTA (H4Y) in the the students from achieving a sharper endpoint.
form HY-3, where it forms a complex with the alkaline Another possible reason is the preparation of the
earth metals (e.g, calcium, magnesium) efficiently but mineral water by the company itself, it may not have
does not form chelates with other cations that might contained the exact amount as to what it assumed to
have been present in the water sample [5]. contain in the label.

Hard water samples can be essential to the
human body specifically those containing calcium and
magnesium since these serve as nutrients that are
essential to various body process that happens in the
organ systems. However, hard water is not beneficial
in every situation. When soap is added to the calcium
ions in hard water, bubbles cannot form since calcium
breaks the surface tension present to form these
bubbles [6]. On the other hand, soft water cannot
break the surface tension because it lacks CaCO3.

Conclusion and Recommendations

Through the experiment, the students were

able to observe and confirm the effectiveness of
complexometric titration by being able to obtain a
Figure 3. Forms of EDTA in different pH levels relatively similar value of water hardness of the Viva!
Mineralized Water to its theoretical value.
The use of EDTA as titrant was also effective
since EDTA is hexadentate complex ion which In the experimental value obtained we were
contains multiple ligands making it a good chelating able to observe that the use of EDTA as titrant and
agent [5]. EDTA is also highly soluble thus the chelates EBT indicator was effective in calculating the water
formed are more stable than the EDTA ions itself hardness of the Viva! Mineralized Water. The
favoring this complexation reaction to proceed. students were able to understand the essence of
buffer solutions, which was responsible for making a
s e t - u p t h a t w o u l d l e a d t o t h e d e s i r e d
complexometric reaction to happen.

In this experiment the students were able to

obtain the experimental total hardness of the
commercial mineral drinking water by applying
complexometric titration. This objective was
The use of EBT indicator was also effective in successfully attained by the students after
this experiment since it reacts with the magnesium performing the experiment.
ions, forming the wine red/purple complex, which is
the last to react with EDTA, ensuring that all the It is recommended that in the next students
calcium ions was consumed by EDTA before the may be more careful in preparing the solutions and
endpoint of the titration. in the process of titration to prevent over-titrating
and to obtain more accurate results. Less EBT
indicator can be also recommended since this would
lead to a sharper endpoint in titration. Water sample
must be fresh and free from possible sources of
contamination.

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph
 J. B. Naval / Chemistry 26.1 (2019) P a g e | 4

References

[1] Waterfilters.net. “Understanding Hard Water and

Water Softening” (accessed March 20, 2018)

[2] Determination of Water Hardness By

Complexometric Titration Class Notes.html (accessed
March 20, 2018)

[3] Khopkar, S. M. Basic Concepts of Analytical

Chemistry. New Age Internationals, 2004; pp. 63-76

[4] Skoog, D. A.; West, D. M.; Holler, F. J.; Crouch, S.

R. Fundamentals of Analytical Chemistry, 8th ed.; :
David Harris, 2004; pp. 563-565

[5] Jircitano, A. J. Determination of the Hardness of

Water. http://chemistry.bd.psu.edu/jircitano/Water05.pdf
(accessed Mar 21, 2019).

[6] Perlman, H.; Usgs. Water Hardness. https://

water.usgs.gov/edu/hardness.html (accessed Mar 21,
2019).

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph
 J. B. Naval / Chemistry 26.1 (2019) P a g e | 5

Appendix

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph
 J. B. Naval / Chemistry 26.1 (2019) P a g e | 6

*Corresponding author. Mobile: 09054262915

E-mail address: jbnaval1@up.edu.ph