QUANTITATIVE DETERMINATION OF TOTAL HARDNESS
IN DRINKING WATER BY COMPLEXOMETRIC EDTA
TITRATION
A. ARNOCO1, J. REYES2
1
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
2
DEPARTMENT OF MINING, METTALURGICAL, AND MATERIALS ENGINEERING, COLLEGE OF
ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 28, 2016
INSTRUCTOR: INGUITO, J.N.
1. What is the significance of determining the
hardness of water?
Mineral drinking water contains minerals
such as calcium and magnesium which are good
for the body. These minerals make the water
‘hard’. Hardness of water is easier described in
relation to soap. When water forms soap scum
when used with soap, then the water is
relatively high. Other than that, hardness of
water is also related to several environmental
issues like algal bloom and destruction of
marine habitats [1].
2. Why do we express water hardness as ppm
CaCO3?
Water hardness is expressed as ppm CaCO 3
since the molecular weight of CaCO 3 is
100g/mol which makes calculations easier.
Water hardness does not only come from Ca
but also with other minerals like Mg. These
minerals are treated as if they were Ca in
calculations since calculations are based from
amount of CaCO3 in the water [2].
3. Discuss the use of EDTA as a complexing
agent and titrant.
To determine the CaCO3 content of the
water sample, EDTA was used as a titrant.
EDTA is a multidentate ligand and is a
chelating agent. It complexes almost to all
metal ions which is one of the reasons why this
was used in this experiment.
EDTA was used as a complexing agent until
all calcium ions complexated completely. The
endpoint of this EDTA titration is the production
of Calgamite, a weaker complexing agent which
changes color upon decomplexation [3].
4. Discuss the use of EBT as indicator. Why do
we add MgCl2∙6H2O crystals to the titrant?
EBT was used as indicator in the titration.
Initially, when put into the analyte, the color
became wine purple. Perhaps, this color was
attained since EBT is blue in a buffered solution
at pH 10 and red when Ca 2+ ions are added.
Since the analyte contains both buffer and Ca 2+,
the color of the analyte became wine purple.
At the endpoint of the titration, when
enough EDTA reacted in the analyte, all Ca2+
have been bounded by the EDTA ligands and
then the blue colored endpoint was reached
since virtually, it is only the buffer that is in the
analyte that the EBT can indicate [4].
5. Why do we add NaOH to the EDTA solution
if the disodium EDTA crystals do not
dissolve?
 Disodium EDTA crystals do not dissolve
unless in a basic environment. Addition of
NaOH is necessary to adjust the pH of the
solution to be able to dissolve the disodium
EDTA. However, the addition of NaOH must be
slow so that the pH does not escalate too
quickly [5].
6. Outline and explain the pertinent chemical
equations involved in the titration.
In this experiment, the hardness of water
was determined thru the amount of Ca and Mg
minerals in the water in terms of ppm CaCO 3.
Ca2+ + H2EDTA2- → CaEDTA2- + 2H+
The chemical equation above shows the
reaction between Ca ion and EDTA. This
reaction has a formation constant of 5.0 × 1010.
Mg2+ + H2EDTA2- → MgEDTA2- + 2H+
The chemical equation above shows the
reaction between Mg ion and EDTA. This
reaction has a formation constant of 5.01 x 10 8.
To get the total hardness of the water,
we treat Ca and Mg together as in one complex
as shown below.
M2+ = Ca2+ + Mg2+
then
M2+ + H2EDTA2- → MEDTA2- + 2H+
[6]
. complexing agents? What reagent, if any,
7. Discuss the relationship of pH and
feasibility of titration of cations using
EDTA.
Buffer was used in this titration since the
reactions involved must occur at constant pH.
EDTA and EBT have polyprotic properties which
is why at differing pH, they can be protonated
differently. EDTA can be protonated six times
while EBT, three [7].
8. Enumerate some other applications of
EDTA complexation (besides
complexometric titration)
Aside from complexometric titration, EDTA
is also used as sequestering agent in many
industries. In the food industry for example,
EDTA is used as a preservative to prevent
catalytic oxidative decolorization. In soft drinks,
EDTA is used to prevent the formation of
benzene, a carcinogen, from sodium benzoate
and ascorbic acid. Other applications of EDTA
are for the anti-coagulation in blood and is used
as an absorbent to harmful nitric oxides [8].
9. Why do we perform the analysis of Ca and
Mg at pH 10?
The analysis of Ca and Mg are performed at
pH 10 because their reactions with the titrant
occur at pH 10. The pH by which the Ca
complexates with EDTA is 7.3 while Mg, 10.
Therefore, the minimum pH by which both
reactions occur is pH 10 [9].
10. What is the effect, if any, of using too
much buffer in the analysis?
Using too much buffer in the analysis may
cause difficulties in detecting the endpoint of
the titration. The system will be very resistant
to pH change that is why the endpoint may be
difficult to observe, or worse it cannot be
observed [9].
11. What is the purpose of auxiliary
served as auxiliary complexing agent in
this titration? Discuss.
Auxiliary complexing agents bind to a metal
strongly to prevent metal hydroxides from
precipitating but weak enough to give up the
metal when EDTA is added [10]. No auxiliary
complexing agents were used in this
experiment.
12. Correlate the stability of the Mg-EDTA, Ca-
EDTA, Mg-EBT, and Ca-EBT complexes with
the values of the formation constants.
EDTA and EBT complexes are generally
stable complexes. Comparing Ca-EBT with a
formation constant of 2.5x10 5 is lower/ less
stable than Mg-EBT with 1.0x10 7 which
displaces Ca. When EDTA is added in the
system, Ca-EDTA with a formation constant of
5.0 × 1010 is higher than that of Mg-EBT with
formation constant 1.0x107, therefore, Ca-EDTA
is formed instead [11].
13. Discuss the difference between the
experimental value of water hardness and
the stated value of water hardness on the
label of your water sample.
From the calculated values, the
experimental value of water hardness is
ppm while the stated value of water hardness
on the label of the water sample is ppm.
The % deviation of the experimental from the
stated value is %. Deviations may have been
caused by several errors which may include
over titration or perhaps, the dishonesty of the
manufacturer in labeling the water bottle.
14. Enumerate and discuss some possible
sources of error. Determine their effect on
your calculated parameters.
Some errors may have occurred during the
weighing of the disodium EDTA, solution
preparations, buffer preparations and titration.
Instrumental errors may have occurred in
the weighing of the solid since the equipment
used are old and could have not displayed the
accurate weight of the sample. Solution
preparations can be also be sources of errors
due to parallax reading of volumes. For the
titration, the color change, whether it was
faintly or overly titrated is also subjective to the
experimenter. Another cause of error may be
from excess or deficiency of buffer in the
analyte changing the pH of the system [3].
REFERENCES
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http://water.usgs.gov/edu/hardness.html
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terms of CACO3? https://www.quora.com/why-
is-water-hardness-measured-in-terms-of-caco3
(accessed Oct 5, 2016).
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James Holler. "Fundamentals of Analytical
Chemistry 8th ed." Harcourt Brace College
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(accessed Oct 4, 2016).
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Water by Complexometric Titration
http://www.ausetute.com.au/camgedta.html
(accessed Oct 4, 2016).
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http://www.chm.bris.ac.uk/motm/edta/edtah.h
tm
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Administration: Center for Food Safety and
Applied Nutrition
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II
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[10] D.C. Harris, Quantitative Chemical Analysis
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[11] COORDINATION CHEMISTRY
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