J. A. Ines/Chemistry 26.

1 (2018) P a g e |1

Quantitative Determination of Total Hardness in Drinking Water by

Complexometric EDTA Titration
J.A. Ines1
1National Institute of Geological Sciences, College of Science, University of the Philippines, Diliman, Quezon City, 1101

Performed: March 14, 2018 Submitted: March 21, 2018

ABSTRACT

Drinking water is a necessity in a person’s daily life. One of the sources of drinking water is the mineralized
water which contains dissolved ions that are necessary to meet the required mineral intake of a person however
when in excess, they can cause health problems. This experiment aims to determine the amount of dissolve
minerals, called water hardness of mineralized water to predict its safeness for human consumption. In this
experiment, the amount of Mg2+ and Ca2+ of a commercialized drinking water was determined using
complexometric titration. The water sample was titrated with 0.0087 M ethylenediaminetetraacetic (EDTA)
acid, a stable chelating agent which was standardized against 0.00500 M Ca 2+ solution and Erichrome black-T as
indicator. The endpoint of titration was signaled by color change of the solution from wine red to clear blue. It
was determined from three trials that the sample contains an average of 151 ± 3 ppm CaCO3 (95 % confidence)
with a relative standard deviation of 6.69 ppt which is smaller compared to the labeled value which is 176.1 ppm
CaCO3. The water sample falls at the “hard” range of the water hardness scale which implies tha it contains
significant amount of Mg2+ and Ca2+ which can be a good source of calcium and magnesium nutrients although
moderation is needed.

Introduction human especially for those with deficiency problems

Water contains dissolved ions that came from natural
sources it passes by such as sedimentary rocks as it
flows from one place to another. Although several
types of ions are present in a water sample, calcium
and magnesium are the two predominant ions that
can be traced since these are the elements that
composed most of the sedimentary rocks. [1]. The
amount of dissolved calcium and magnesium ions in a
water sample is known as water hardness. Most of the
chemical analysis do not differentiate calcium and
magnesium ions from each other instead, it is
expressed collectively in terms of parts per million of
calcium carbonate since most of the ions that
contribute to the hardness of water came from
carbonate minerals [2].
Determining hardness of water is vital since it
measures the quality of water and its impact and
safeness for industrial and household use [7]. For
households using hard water, soaps are hard to
dissolve and they form insoluble salts of carbonates
called “scum” that leaves traces on washed utensils
and on drains. In industries, heated hard water
produces precipitates of insoluble CaCO3 and MgCO3
which clogs water pipes when they accumulate [3].
However on fish culturing, hard water is desired for
its high calcium content since it contributes to the
bone formation and blood clotting of different aquatic
species such as catfish [4].
For drinking water, hardness is determined to know
its possible effects on a person’s health. The dissolved
ions in the water can serve as a supplement in
reaching the required dietary mineral intake for
associated with the said ions [5]. However, excessive
amount of these dissolved minerals which are above
the prescribed level can cause health problems [6].
Commercially available mineralized drinking water
contains dissolved ions that are stated on its
packaging, specifically on the “Nutrition Facts”.
Checking the hardness of a mineral water is needed
since there is a variation in the actual concentration
of the ions in contrast with the labeled values since
these products are prepared in different batches [5].
Water hardness is measured through complexometric
titration. This type of titration involves the reaction
between a metal ion and a ligand, an electron donor
that has lone pairs that will interact with the metal
ion to form a complex and the equivalence point is
determined by an indicator. [7][8]. There are two
types of ligands namely; monodentate ligand, which
binds in a metal ion using only one atom, and
multidentate ligand, which attached itself to the metal
ion using more than one atom. Multidentate ligand is
also called as chelating ligand which form more stable
complex than the monodentate ligand [8].
For complexometric titration, the ligand is usually the
titrant while the solution containing the metal ion is
the analyte [8]. For this experiment the titrant to be
used is the multidentate ligand
ethylenediamenetetraacetic (EDTA) acid while the
analyte is the Ca2+ and Mg2+ ions in a water sample of
Viva! mineralized water. The reaction between the
metal ions and EDTA is described by the following
equation.
 J. A. Ines/Chemistry 26.1 (2018)
M2+(aq) + H4Y (aq) ↔ MH2Y (aq) + 2H+(aq)
where M2+ is Ca2+ and Mg2+ ions and Y is EDTA. A NH3-
NH4+ buffer solution was added in the analyte to
maintain the pH of the solution at 10. The basic buffer
solution will resist the change in pH of the solution
hence, counteracting the H+ that is being formed in
Equation 1. Applying Le Chatelier’s Principle the
reaction will proceed in forming the complexes.
Ca2+(aq) + Y4-(aq) ↔ [Ca(Y)]2-(aq) Kf = 5.0 x 1010
Mg2+(aq) + Y4-(aq) ↔ [Mg(Y)]2-(aq) Kf = 4.9 x 108
The indicator used is the Erichrome black-T (EBT).
The hardness of the water sample is reported in parts
per million (ppm) of CaCO3.
This experiment aims to apply the concepts of
complexometric titration in order to determine the
total hardness of a commercialized drinking water
specifically Viva! mineralized water and to classify it
under the water hardness scale. The experiment also
aims to compare and contrast the calcium and
magnesium ion contents of the mineralized water as
stated in the labeled value and its respective
experimental value resulting from the titration.
Methodology
The following solutions needed for the experiment
were prepared from compounds and stock solutions.
The 500.0 mL 0.1000 M EDTA stock solution was
prepared by dissolving Na2H2EDTA·2H2O solids into
distilled water. One gram of MgCl2·6H2O was also
added in the solution. NaOH pellets were added and
the solution was heated up in order to speed up the
dissolution of EDTA solids. The prepared solution was
then diluted to mark and transferred into a clean
reagent bottle.
A 100.0 mL 0.0500 M Ca2+ solution was prepared from
CaCO3 solids. The solids were dissolved using
concentrated HCl and the solution was heated up in
order to fasten the rate of dissolution of CaCO3 solids.
The solution was then diluted to mark and
transferred into a clean plastic bottle.
A
250.0 mL 1.0 M NH3-NH4+ buffer solution was also
prepared from 2.059 g NH4Cl solids and 14.3 mL NH3
stock solution. A pH meter was used in order to check
that the pH of the solution is 10.
A 250.0 mL 0.0100 M working EDTA solution was
prepared from 0.1000 M EDTA stock solution while
50.0 mL 0.0050 M Ca2+ solution was prepared from
0.0500 M Ca2+ stock solution.
In order to determine the exact concentration of the
titrant EDTA, it was standardized with 0.0050 M Ca 2+
solution as the primary standard. The Ca2+ solution
was prepared from 99.9% pure CaCO3. Three flasks
P a g e |2
(1) were prepared and 10.0 mL of the Ca2+ solution and
75.0 mL distilled water was transferred into the
flasks. 3 mL of the buffer solution and 2-3 drops of the
EBT indicator was also added. Adding too much
indicator is avoided in order to observe a sharp
endpoint. Initial volume of the titrant was recorded
and the titration was done in one of the flasks until
the wine red color of the solution changes to clear
blue. The final volume of the titrant is recorded.
Same procedure was done with the two remaining
(2) flasks.
(3)
For the analysis of water sample, 50 mL water sample
was transferred into a 250 mL Erlenmeyer flask. The
sample was prepared and titrated with the same
methods used in standardization. Three trials were
performed.
The obtained values from the titration were used in
calculating the ppm CaCO3 of the water sample. It was
then classified using the water hardness scale
(Appendix A). The obtained values was also compared
to the labeled values in the packaging of the bottle
(Appendix A).
Result and Discussion
For this experiment, complexation titration was
applied to determine the total hardness of Viva!
mineralized water. Complexation titration is used to
determine the amount of metal ions in a sample,
particularly Ca2+ and Mg2+ for this experiment.
Comparable to acid-base titration, it uses an indicator
to signal the endpoint of the titration. The color
change for complexometric titration however
indicates formation of complex resulting from the
reaction of the ligand titrant and the analyte while the
color change in an acid-base titration signifies
neutralization of the solution.
EDTA was used as the titrant since as a multidentate
specifically a hexadentate, it forms stable complexes.
EDTA is also useful to detect metal ions in analyte
since it reacts with metal ions to form complexes in a
1:1 ratio regardless of the charge of the metal ion.
Exceptions to these ions are the alkali metals.
The Ca2+ solution was prepared by dissolving CaCO3
in HCl. The reaction is as follows
CaCO3(s) + 2H+(aq) → Ca2+(aq) + H2CO3(aq) (4)
↔ H2O(l) + CO2(g)
Calcium carbonate was dissolved in hydrochloric acid
in order isolate Ca2+. Calcium carbonate was
converted into H2CO3 and further breakdown into
H2O(l) and CO2(g) which produces effervescence during
the dissolution. The concentration of the stock
solution prepared was computed to be 0.0500 M
while the concentration of the working Ca2+ solution
is 0.0050 M
 J. A. Ines/Chemistry 26.1 (2018)
NaOH pellets were added to convert EDTA into a
more soluble salt which speeds up the rate of
dissolution [9]. As the pH of a solution rises, the
carboxyls (COO-) and H+ of the EDTA dissociates,
hence, EDTA becomes ionic and soluble in water. The
four carboxyls of EDTA dissociates at different pKa,
with the last one dissociates at a pKa of approximately
10.3 [10]. MgCl2·6H2O crystals were added in
preparing the EDTA solution to provide a sharper
endpoint for the titration.
Calcium ions bind with EDTA in a very slow rate. The
addition of MgCl2 in the EDTA solution will form Mg-
EDTA complex. Titrating the water sample containing
Ca2+ with the EDTA solution with Mg-EDTA complex,
will form Ca-EDTA complex by the displacement of
Mg2+ by the Ca2+ in the sample since Ca-EDTA complex
is more stable than Mg-EDTA complex. The displaced
Mg2+ will react to the Erichrome Black-T indicator,
forming wine red complex. After all the EDTA reacts
with Ca2+, it will eventually react with the Mg2+ in the
Mg-EBT, displacing the indicator. When all of the EBT
are displaced, the solution will turn to clear blue,
indicating the presence of free EBT molecules. This
method of titration is also known as displacement
method [7]. The reaction is as follows.
Mg2+ + H2Y2-  MgH2Y (5)
Ca2+ +
MgH2Y  CaH2Y + Mg2+ (6)
Mg + CaHIn  MgHIn + Ca2+
2+ (7)
The analyte was maintained at pH 10 with the NH3-
NH4Cl buffer, given that having a pH greater than 10
would cause the precipitation of the Mg2+ and Ca2+
ions, The NH3-NH4Cl buffer was chosen considering
that it forms ammine complexes with the metals and
prevents the formation of soluble Mg(OH)2 and
Ca(OH)2 to ensure complete reaction with the EDTA
titrant. A pH10 solution allows some EDTA to remain
protonated and with deprotonated EDTA complexing,
keeping the endpoint sharp.
The indicator used for this experiment is the
Erichrome Black-T. It is a metal ion that behaves like a
weak acid [7].
H2O + H2In- ↔ H2In2- + H3O+ (8)
(red) (blue)
Generally, the color of the metal-EBT complex is wine
red. Adjusting the pH of the solution to 7 and above
will allow the blue species (H2In2-) to predominate in
the absence of a metal ion, indicating that all metal
ions are chelated by EDTA [7].
Table 1. Summary of standardization of EDTA
solution
Trial 1 2 3
Volume of working
10.0 mL 10.0 mL 10.0 mL
Ca(II) standard,
Net volume of EDTA 5.5 mL 5.6 mL 6.1 mL
P a g e |3
Molarity of Edta 0.0091 M 0.0089 M 0.0082 M
Average Molarity 0.0087 M
The prepared EDTA solution was standardized
against the primary standard Ca2+ solution which has
a molarity of 0.0050 M. It was determined from three
trials that the prepared EDTA solution has an average
molarity of 0.0087 M, smaller compared to target
concentration which is 0.0100 M.
The titer of the solution was computed by multiplying
the average molarity of EDTA solution with the molar
mass of working standard, CaCO3. The titer is
computed to be 0.875 mg CaCO3/mL EDTA.
The theoretical hardness of Viva! mineralized water
was based on the Ca2+ and Mg2+ concentration written
on its packaging. Using the 1:1 stoichiometry
relationship of Ca2+ and Mg2+ with CaCO3, the
concentration of Ca2+ and Mg2+ was then related to
CaCO3. The theoretical water hardness was computed
using the following equation:
WHTheo = ppm CaCO3 (Mg) + ppm CaCO3 (Ca) (9)
where WHTheo is the theoretical water hardness and
ppm CaCO3 (Mg) and ppm CaCO3 (Ca) are the
concentration of CaCO3 related Mg2+ and Ca2+
respectively, expressed in parts per million. It was
determined that Viva! mineralized water contains
176.1 ppm CaCO3 as based on the labeled values.
The water hardness is expressed in terms of CaCO3
since most of the hardness are caused by carbonate
minerals [2]. Also, its molar mass, which is
approximately equal to 100 g/mol is convenient to
use to express concentrations in parts per million
(ppm).
Table 2. Summary of sample analysis
Trial 1 2 3
Volume of working
50.0 mL 50.0 mL 50.0 mL
Ca(II) standard
Net volume of EDTA 8.6 mL 8.7 mL 8.6 mL
Total Hardness,ppm 150 ppm 152 ppm 150 ppm
Average Hardness 151 ppm
After analyzing the water sample with standardized
EDTA solution, it was found out that the sample only
contains 151 ppm CaCO3, 14.25 % smaller compared
to the theoretical value which is 176.1 ppm CaCO3.
Classifying the obtained value in the water hardness
scale (Appendix A), it was determined that the water
sample falls at the “hard” range.
The three trials performed has a relative standard
deviation of 6.69 ppt. The confidence interval (95%)
is [149 ppm, 154 ppm]. The low relative standard
deviation infers that the measurements are precise.
There is a 95% probability that the true mean of the
samples lies from 149ppm to 154 ppm.
 J. A. Ines/Chemistry 26.1 (2018)
The low concentration of EDTA solution may be due
to solution preparation. Using more glassware in
solution preparation will result to a lower
concentration. When transferring, some particles are
not are being transferred hence the more transferring
is done, the larger the error and the lower the
concentration. This may be reduced by minimizing
the glassware that will be used in solution
preparation.
Similar to EDTA solution, the low concentration of
CaCO3 may be caused by wet glassware in which the
sample is contained. This will cause the solution to be
more dilute, thus the concentration is lower than
expected. It should be also noted that these bottled
mineral waters are prepared in different batches
hence; variation in concentration should be expected
[5].
For both standardization and analysis of water
sample, overtitrating the solution will lead to a lower
concentration than the actual concentration. Not
swirling the solution may lead to overtitration since
there is a possibility that the endpoint is already
reached but since the color change from wine red to
clear blue takes some time, the student may titrate
the solution beyond the endpoint. This error may be
reduced by swirling the solution for every drop of the
titrant to fasten the change in color of the solution.
Other sources of error are subjectivity of color
perception of an observer, especially if the person is
color blind. The error may be reduced by limiting the
number of people who will perform the trials for
titration to reduce personal bias. Not washing the
burette with titrant will also lead to a lower
concentration. Overall, to avoid errors, the
procedures should be followed accordingly.
Conclusion
Determining the hardness of a commercialized
drinking water like Viva! mineralized water is useful
in predicting its safeness and effect for human
consumption. Complexometric titration is the
appropriate method to be performed in this kind of
chemical analysis. Choosing EDTA as the titrant forms
stable complexes and EBT as the indicator provides a
sharp endpoint for titration.
The resulting water hardness from three trials of
titration is 151 ± 3 ppm (95% confidence) which is
smaller than the labeled value which is 176.1 ppm.
The sample obtained is not as hard as stated in the
packaging but it still falls at the “Hard” range of water
hardness scale. This is expected since the product is
P a g e |4
advertised as a mineralized water which contains
ions that supplements body’s required mineral intake
especially those with ion deficiencies.
The experiment is a success since the obtained
hardness from three trials is precise in which they
have a relative standard deviation of 6.69 ppt. The
measurements also have a high accuracy considering
the confidence interval is narrow. The experimental
hardness is 14.25% away from the hardness stated in
the packaging.
It is recommended that the solutions be prepared
properly to avoid erroneous data especially the Ca 2+
solution since the titrant will be standardized against
it. It is also recommended that swirling should be
observed when titrating. It is recommended that only
one person will observe the color change of solution
to reduce personal bias.
References
[1] World Health Organization. (2011). Hardness in
Drinking-water [PDF]. Geneva, Switzerland:
World Health Organization.
[2] Jircitano, A. J. (n.d.). Determination of the
Hardness of Water [PDF]. Erie, Pennsylvania:
Pennsylvania State University- Behrend College.
[3] Perlman, H. (2016, December 15). Water
Hardness. Retrieved March 18, 2018, from
https://water.usgs.gov/edu/hardness.html
[4] Wurts, W. A. (1993). Understanding Water
Hardness. World Aquaculture, 24(1), 18.
[5] Azoulay, A.; Garzon, P.; Eisenberg, M. J. (2001)
Journal of General Internal Medicine. 16 (3),
168–175.
[6] Rylander, R. (2014) Journal of Water and
Health. 12 (1), 34.
[7] Skoog, D., West, D., Holler, F. J. & Crouch, S.
(2004). Fundamentals of Analytical Chemistry
(8th edition). California: Brooks/Cole. Thomson
Learning.
[8] Harris, D. (2010) Quantitative Chemical Analysis
8th ed. Madison Avenue, NY: W.H. Freeman and
Company.
[9] Petrucci, R., Harwood, W., Herring, F., General
Chemistry, Eight Edition. Upper Saddle River,
New Jersey: Prentice Hall, Inc.
[10] Hájek, T. (2014). Why EDTA needs basic
condition for dissolving? Retrieved from
https://www.researchgate.net/post/Can_
somene_explain_why_EDTA_needs_basic_
condition_for_dissolving
 J. A. Ines/Chemistry 26.1 (2018) P a g e |5

APPENDIX

A. TABLE AND FIGURES

Table 1. Mineral Contents of Viva! Mineralized Water

Mineral Formula Content

Bicarbonates HCO3 135.00 mg/L
Calcium Ca 54.00 mg/L
Chloride Cl 80.00 mg/L
Magnesium Mg 10.00 mg/L
Sodium Na 65.00 mg/L
Sulfate SO4 35.00 mg/L
Total Dissolved Solids - 280.00 mg/L
pH = 8.00
Source: Nutrition Facts of Viva! Mineralized Water

Table 2. Water Hardness Scale

Water Hardness ppm CaCO3

Soft 0 – 20
Moderately Soft 20 – 60
Moderately Hard 61 – 120
Hard 121 – 180
Very Hard ppm > 180
Source: Hardness in Drinking-water. World Health Organization. 2011

Table 3. Standardization of EDTA Solution

Trial 1 2 3
Volume of working Ca(II) standard, mL 10.0 mL 10.0 mL 10.0 mL
Final volume of EDTA, mL 5,5 mL 11.1 mL 25.8 mL
Initial volume of EDTA, mL 0.0 mL 5.5 mL 19.7 mL
Net volume of EDTA, mL 5.5 mL 5.6 mL 6.1 mL
Molarity 0.0091 M 0.0089 M 0.0082 M
Average Molarity 0.0087 M

B. SAMPLE CALCULATIONS

1. Concentration of the standard of EDTA solution, in molarity

Ca2+ Stock Solution Concentration:

MCa2+ =

MCa2+ =
MCa2+ = 0.0500 M

Working Ca2+ Solution Concentration:

M1V1 = M2V2

MCa2+ = 0.0500 (
MCa2+ = 0.0050 M
 J. A. Ines/Chemistry 26.1 (2018) P a g e |6

EDTA Solution Standardization:

MEDTA =

Trial 1

MEDTA =
= 0.0091 M

Trial 2

MEDTA =
= 0.0089 M

Trial 3

MEDTA =
= 0.0082 M

Average MEDTA = 0.0087 M

2. Titer of the solution as mg CaCO3 per mL of standardized EDTA Solution

Titer = MEDTA x FW CaCO3

= 0.00874 M x 100.09 g /mol
= 0.875
= 0.875

3. Total hardness of the water sample as ppm CaCO3

mass (g) CaCO3 = MEDTA x VEDTA x x M.W. CaCO3

ppm CaCO3: =

Trial 1
mass (g) CaCO3 = x 0.0086 L x x
= 7.52 x 10-3 g CaCO3

ppm CaCO3 =
= 150 ppm CaCO3

Trial 2
mass (g) CaCO3 = x 0.0087 L x x
= 7.61 x 10 g CaCO3
-3

ppm CaCO3 =
= 152 ppm CaCO3

Trial 3
mass (g) CaCO3 = x 0.0086 L x x
= 7.52 x 10-3 g CaCO3
 J. A. Ines/Chemistry 26.1 (2018) P a g e |7

ppm CaCO3 =
= 150 ppm CaCO3

Average ppm CaCO3 = 151 ppm CaCO3

4. Total cation content based on the concentration of Ca and Mg on the bottle label.

ppm CaCO3 Ca2+ = x x x

= 134.9 ppm CaCO3
ppm CaCO3 Mg2+ = x x x
= 41.18 ppm CaCO3
Total Water Hardness (theoretical):
Total ppm CaCO3 = ppm CaCO3 Ca2+ + ppm CaCO3 Mg2+
= 134.9 ppm CaCO3 + 41.18 ppm CaCO3
= 176.1 ppm CaCO3

5. Relative standard deviation (in ppt) and confidence limits (95% confidence level)

Relative Standard Deviation =

̅
=
= 6.69 ppt

Confidence Interval =̅
√
= √
= 151 ppm
= [149 ppm, 154 ppm]

6. Relative Error
% Error = (Theoretical – Experimental) / Theoretical x 100%
= (176.1 ppm – 151 ppm)/ 176.1 ppm x 100%
= 14.25 %