QUANTITATIVE

DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA
TITRATION
N. CASTOR
1INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES DILIMAN, QUEZON CITY 1101, PHILIPPINES

DATE SUBMITTED: APRIL 6, 2015
DATE PERFORMED: MARCH 4, 2015
______________________________________________________________________________________________________________________________

ABSTRACT
Total hardness of water is deHined as the sum of the ions in water, mainly Ca2+ and Mg2+, which can be disruptive
in daily life as they precipitate with hydroxides and therefore cause blockages of different apparatus. Drinking
hard water, however, is recommended as these ions are vital to the body. Both these reasons call on the
quantitative determination of the total hardness of the water. In this experiment, the total hardness of the water
was measured through the use of complexometric EDTA titration. EDTA, a multi dentate ligand, was used as the
titrant, while the analyte was composed of an NH3-NH4Cl buffer, the metal ions, and the EBT indicator that binds
to them. The EBT indicator causes a wine red solution to appear which, as the EDTA is introduced into the
analyte, slowly turns into a light blue solution. This is considered the endpoint. The titration was done with the
buffer at pH 10, to allow maximum complexation of the metals and the EDTA ligand. Standardization of the EDTA
solution was done to determine the molarity of the EDTA solution. After this, the analysis of the water sample, a
mineral water brand, Hidden Spring, proceeded. At the end of the experiment, it was discovered that the total
hardness of the mineral water sample chosen had 250.77 ppm CaCO3. Despite the difference from the theoretical
value of 206.53 ppm CaCO3, the results were precise.
______________________________________________________________________________________________________________________________

INTRODUCTION
Hardness is deAined as the presence of different
ions, mainly Ca2+ and Mg2+, in a water sample. These
ions are usually acquired as the rain water dissolves
organic salts while passing through rock and soil [1]
[8]. Total hardness is deAined as the sum of all the
ions in a water sample [1]. The higher the total
hardness, the higher the number of these ions are in
the sample. The detection and measurement of
these ions in water is important as the presence of
these ions can cause several problems both
industrially and in the household. One of these
examples is the precipitation, called scum, of these
ions with soaps to form Ca(OH)2 and Mg(OH)2 (1).
This precipitation would reduce the effectiveness of
the soaps as suds would be less likely to form [1].
These precipitates may also clog the pipes of sinks,
bathtubs, etc., constricting the Alow of water.
Another instance when ions can be a problem is
during the heating of hard water. When hard water

containing large amounts of HCO3- is boiled, the

Ca2+ and Mg2+ ions precipitate into CaCO3 and
MgCO3 (2). These CaCO3 and MgCO3 precipitates in
turn clog the pipes and vessels of water heaters,
teakettles, and commercial boilers [1][2].

Ca2+ + 2OH Ca(OH)

2

(1)
Mg 2+ + 2OH Mg(OH)2

Ca2+ + HCO3 CaCO3 + H+

2+

Mg + HCO3 MgCO3 + H+

(2)

However, despite the problems they give rise to, the

presence of these ions are not regarded as health
concerns. In fact, drinking hard water is advised
because they contain vital minerals such as Ca2+ and
Mg2+ ions. Thus, it is common to Aind high
concentrations of these ions in drinking water.

The measurement of the hardness of water is done

through a process called complexometric titration.
Complexometric titration makes use of molecules
called ligands. These molecules donate one or more
electron pairs to a metal ion in order to form a
complex with that ion [3]. In complexometric
titration, it is used as the titrant while the metal ion
is used as the analyte [3]. EDTA is an example of such
a ligand. EDTA, or ethylenediaminetetraacetic acid,
whose structure is found in Aigure 2, is also the most
commonly used ligand in complexometric titrations.
This is due to the fact that it is a multi dentate
ligand which allows it to have a 1:1 ratio with metal
ions. Multi dentate ligands bond to the metal ion at
more than one site due to them having more than
one electron pair which they use to bond with the
metal ion. This property can be explained by the
chelate effect. While at one site, the bonding may be
weak, having more than one bonding site per
molecule would allow the multiplication of these
formation constants as seen in Aigure 1. This allows
the multi dentate ligand to have a very high
formation constant, thus allowing the metal ion to
form a complex with it instead of the indicator, due
to the lower formation constant of the metal-
indicator complex [2]. Figure 2 shows EDTAs
structure and the hydroxide and amine sites where
it donates electron pairs. Figure 3 shows the
octahedral shape the Metal ion-EDTA complex that
forms.

M+ Ligandsite1 K1 = 100
M+ Ligandsite2 K 2 = 100

M+ Ligandsite n K n = 100
M+ Ligandall sites K1x K 2x...x K n = 100n
Figure 1. The chelate effect of a hypothetical M and
a multi dentate Ligand. Note that the Ainal formation
constant Kf is a very large number.

Figure 2.
Structure
of EDTA [4]. Its bonding sites are at the hydroxides
and amine groups.

Figure 3. Complexation of a deprotonated EDTA

and a Metal ion, M [5].

Complexometric EDTA titrations work by having the
metal ions bond to an indicator, such as EBT, or
eriochrome black T, Airst. This bond is then broken
as the EDTA is introduced into the analyte, and
replaces the indicator as it bonds to the metal ion.
As more and more EDTA is made to react with the
analyte, more metal-EDTA complexes occur than
metal-indicator complexes. This is because the
indicator chosen has a formation factor that is less
than the formation factor of EDTA, meaning the
Metal ion-EDTA complex is favored over the Metal
ion-Indicator complex. The arrangement of their
formation constants and order of complexation can
be seen in Aigure 4. The corresponding reaction of
the titrant (Y4-) to the analyte with the indicator
(In3-), and the observable color the indicator
exhibits in this experiment can be seen in (3)[2].
This process continues until endpoint, or when
almost no more metal-indicator complexes exist in
the solution. In this experiment, the Calcium-
Indicator complex forms Airst, followed by the
M a g n e s i u m - I n d i c a t o r c o m p l e x , t h e n t h e
Magnesium-EDTA complex, while the Calcium-EDTA
complex forms last.

H+ + Y4 + MgIn MgY2 + HIn

wine red

blue

(3)

Ca2+ + In3 CaIn

K f = 2.5 x 105

Mg 2+ + In3 MgIn

K f = 1.0 x 107

Mg 2+ + Y4 MgY2

K f = 4.9 x 108

Ca2+ + Y4 CaY2

K f = 5.0 x 1010

Figure 4. The metal-ligand and metal-indicator

complexes and their corresponding formation
constants. The order in which they form is arranged
from top to bottom.
Total Hardness is measured in ppm CaCO3 or mg
CaCO3 per liter of water sample [8]. The Ca2+ and
Mg2+ is assumed to originate from CaCO3. This is
done to simplify the solution. The mass of this
hypothetical CaCO3 is then solved for by relating the
ppm through dimensional analysis [3]. Then the
amount of the Ca2+ and Mg2+ in terms of CaCO3 is
added and the sum is said to be the total hardness
of the water sample. The water sample is then
deAined as soft, moderately soft, hard, etc. through
relating its ppm CaCO3 to its corresponding water
hardness found in table 1. The calculations and the
formulas used for this experiment can be found in
the appendix.
Table 1. The water hardness scale. [2]
Water Hardness

ppm CaCO3

Soft

0-20

Moderately Soft

20-60

Moderately Hard

61-120

Hard

121-180

Very Hard

>180

In this experiment, the following solutions were

prepared: 250.0 mL of 0.0100 M working EDTA
solution from 0.1 M EDTA stock solution, 50.0 mL of
0.0050 M working standard Ca2+ solution for
standardization from 0.0500M Ca2+ stock solution,
250.0 mL 1.0 M NH3-NH4+ pH 10 buffer solution
from NH4Cl and NH3, and EBT indicator solution.
T h e A i r s t p a r t o f t h e e x p e r i m e n t w a s
standardization of the EDTA solution. The working
standard Ca2+ was divided into three Alasks. The
buffer solution and the indicator were then added

into the three Alasks. Immediately after the addition

of buffer and indicator, the solution was then
titrated with the EDTA solution. Next, the volume
required to reach the blue endpoint was noted. The
volume required to reach the endpoint was then
used to calculate the molarity of the EDTA solutions.
The next part of the experiment was the analysis of
the water sample. 150.0 mL of the selected water
sample was divided equally into three erlenmeyer
Alasks. Buffer solution and indicator was then
added, and after mixing, the solution was
immediately titrated with the EDTA solution. The
volume of the EDTA solution required to reach the
blue endpoint was then noted down and used, along
with the calculated molarity of the EDTA solution
taken in the Airst part of the experiment, to calculate
for the concentration of the Ca2+ and Mg2+ ions.

RESULTS AND DISCUSSION

This experiment started out with the preparation of
the solutions. 500.0 mL of 0.1000 M EDTA solution
was prepared by dissolving 18.612 g of Na2H2EDTA.
2H2O in 200 mL dissolved H2O and then adding 1.0
g MgCL2.6H2O into a beaker. The solution was then
transferred and diluted to mark into a 500 mL
volumetric Alask. The MgCL2.6H2O was added to
provide a sharper endpoint and to increase the
formers solubility [6]. NaOH was also added to aid in
the dissolution of EDTA as it raises the pH level of
the solution. The higher the pH level, the more
deprotonated EDTA-4 (Y-4) exists [6] allowing more
[Mn+-EDTA]4-n complexes to form. If the pH is lower
than 10, the metals will still possibly bind, but not
as well, as some sites of the EDTA solution would
then be protonated. However, a pH that would be
too high would result in the precipitation of
Mg(OH)2 and CaCO3 [8]. 100 mL of 0.0500 M stock
Ca2+ solution was then prepared by adding 0.50045
g of CaCO3 solids and mixing it to concentrated HCl
solution into a beaker while being heated. The
addition of HCl triggered the breakdown of the CO3
anions through the formation of H2O and CO2(g).
Next, 250.0 mL of 1.0 M NH3-NH4+ pH 10 buffer was
made from NH4Cl and NH3. This was done by
dissolving 2.056 g of NH4Cl in 14.3 mL of 14.8 M
NH3 and diluting to 250.0 mL. A buffer is important
in EDTA titrations as it allows the reaction to have a
sharper endpoint and to keep the pH at a constant
10. 25 mL was then taken from the 0.1 M stock
EDTA solution to make 250 mL 0.01 M working
EDTA solution that will be used in the titration.

Finally, 5 mL was taken from the 0.0500 M Ca2+ to

make 50.0 mL of 0.0050 M working standard Ca2+
solution that will also be used in the titration.

The next part is the standardization of the EDTA

solution. 10.00 mL of the 0.0050 M working
standard CaCO3 solution was pipetted into three
250 mL Erlenmeyer Alasks. 75 mL of distilled H2O
was then added to each Alask. 3 mL of the prepared
buffer solution, and 2-3 drops of EBT indicator was
added and mixed to one of the solutions and was
titrated right away. It is crucial that EBT was not
added more than the prescribed amount as this may
cause the endpoint to not be as sharp [2]. It is also a
must that the samples be titrated right away as the
EBT indicator can undergo air oxidation [7] thus
reducing its effectiveness as an indicator and
producing erroneous data. The volume of the EDTA
required to reach the blue endpoint from the wine
red starting point was then noted down. This was
repeated two more times for the two other Alasks.
The average molarity and the titer was then
calculated for and presented along with the other
values in table 2. The change is color is explained by
the order of complexation of the different
complexes seen in Aigure 4 and the color change is
explained by (3). Basically, as the EDTA is
introduced to the analyte and forms complexes with
both the Mg2+ and Ca2+ ions, more and more HIn-
forms. This Hydrogen-Indicator complex exhibits
the light blue color that is considered to be the
endpoint of the titration.
Table 2. Standardization of prepared 0.01 EDTA
solution
Trial

Volume of
working
Ca(II)
standard,
mL

10

10

10

Net
Volume of
EDTA, mL

8.25

7.95

7.9

M EDTA

0.00958

0.00994

0.01000

Average M
EDTA

0.00984

Titer

0.985

It can be seen in table 2 that the molarity of the

prepared EDTA solution was off by 0.00016 M.
However, this is a very small difference and may be
negligible. In fact, the third trial shows the
calculated molarity of the EDTA solution to be
exactly 0.01. The titer indicated in table 2 can be
deAined to how concentrated the solution is and
how well it can reach the endpoint.
The Ainal part of the experiment was the analysis of
the water sample. In this experiment, the chosen
commercial mineral water brand was Hidden
Spring. 50.0 mL of the water sample was placed into
each of the three 250 mL erlenmeyer Alasks. Similar
to the standardization, 3 mL of the buffer solution
followed by 2-3 drops of the EBT indicator was
added, taking care again not to add too much of the
indicator. Immediately after the addition of the
indicator, the samples were titrated to prevent air
oxidation of EBT. The volumes of the EDTA solutions
required to reach the endpoint were then used to
calculate for the total hardness of the water sample.
These values are shown in table 3.
Table 3. Analysis of the water sample.
Trial

Volume of
water
sample,
mL

50

50

50

Net
Volume of
EDTA, mL

12.7

12.7

12.8

250.12

250.12

252.09

Total
Hardness,
ppm
Average

250.77

RSD

4.5342 ppt

ConAidenc
e Interval,
ppm

250.77 2.8228

It can be seen in table 3 that the average total

hardness calculated was 250.77 ppm CaCO3.
However, the theoretical total water hardness
calculated from the given data on the back of the
packaging of the water bottle was 206.53 ppm
CaCO3. This gives us an absolute error of 21.42%. It

can also be seen in table 3 that the relative standard

deviation is 4.5342 parts per thousand of the water
sample. This means that the measurements were
precise. Furthermore, the conAidence interval was
only 2.8228 ppm, which also exhibits the high
precision of the data.

SUMMARY AND CONCLUSIONS

The total hardness of the mineral water sample was
calculated to be at 250.77 ppm CaCO3 using a
0.0984 M EDTA solution as the titrant. The results
gathered were precise, but inaccurate, yielding an
absolute error of 21.42% as the theoretical total
water hardness was at 206.53 ppm CaCO3. This
value was calculated from the manufacturer given
data at the back of the bottle (refer to appendix).
This inaccuracy may be inAluenced by the presence
of other ions in the water sample that the EDTA
ligand formed a complex with. This experiment only
took into consideration the presence of [Ca-EDTA]2-
and [Mg-EDTA]2- complexes failing to take into
consideration the possible presence of other ions.
Therefore, it is recommended that the theoretical
total hardness of water include all possible ions that
may bond with the titrant at the endpoint. However,
despite this failure to take into consideration other
factors affecting total hardness, the experiment was
a success in being able to identify the total hardness
of the water including unknown ions. An evidence
of this is the high degree of precision that the
results exhibited.

[3] Skoog, D., & West, D. (1996). Fundamentals of

analytical chemistry (7th ed.). Fort Worth: Saunders
College Pub.
[4]http://cnx.org/resources/
0418e3a849c5083ecc35ba9e8c9249b4/
graphics9.jpg
[5] http://openwetware.org/images/thumb/e/e8/
E D T A _ w i t h _ l i g a n d . p n g / 2 0 0 p x -
EDTA_with_ligand.png
[6] COMPLEXOMETRIC DETERMINATION OF Mg2
and Ca2. (n.d.). Retrieved April 4, 2015, from http://
www.ux1.eiu.edu/~cAjpb/teaching/quant/labs/
experiment8.pdf
[7] Titration of Zinc with EDTA. (n.d.). Retrieved
April 4, 2015, from http://www.chem.uky.edu/
courses/che226/labs/complexometric_zinc.html
[8] Yappert, M., & DuPre, D. (n.d.). Complexometric
Titrations: Competition Of Complexing Agents In
The Determination Of Water Hardness With EDTA.
Journal of Chemical Education, 1422-1422.

Another possible source of error would be the

indicator, Eriochrome Black T. It was mentioned
that it undergoes air oxidation and that may have
affected the results of the experiment. It may have
caused a decrease in the accuracy of the titration by
showing a delayed endpoint. This would have
caused an increase in the volume of EDTA required.
A possible recommendation to this is the use of a
different indicator such as Calmagite, which does
not undergo air oxidation.

REFERENCES
[1] Suffredini, C. (1994). Determining Water
Hardness by EDTA Titration. Chemical Education
Resources, Incorporated.
[2] Analaytical Chemistry Academic Group, 2012.
Analytical Chemistry Laboratory Manual. Quezon
City: UP Diliman.

Appendix
Required Calculations

Formula

Weight of measured CaCo3, g

0.791

FM CaCO3, g/mole

100.09

% purity

0.9997

Standardization of 0.01 M
EDTA
Trial

Formula

First Dilution Ca2+ Molarity

= Weight of CaCO3 FM CaCO3 %

purity 0.1 L

0.0790051653511839
0.0790051653511839
0.0790051653511839

Second Dilution Ca2+ Molarity

=First Dilution Ca2+ Molarity 0.005 0.00790051653511839

0.00790051653511839
0.0079005165351183
L 0.05 L

moles Ca2+ in 10 mL aliquot

= Second Dilution Ca2+ Molarity

0.01 L

0.0000790051653511839
0.0000790051653511839
0.0000790051653511

moles EDTA

= moles Ca2+

0.0000790051653511839
0.0000790051653511839
0.0000790051653511

volume used of EDTA solution, mL

Taken from data

8.25

M EDTA

= moles EDTA volume used of

EDTA solution, mL

0.00957638367893138
0.00993775664794766
0.010000653841922

Average M EDTA

=AVERAGE(M EDTA)

0.00983826472293369

Titer, mg CaCO3/mL sample

= Average M EDTA x FM CaCO3 x

1000 mg 1000 mL

0.984711916118433

Trial

Formula

Volume of water sample, L

Taken from data

0.05

0.05

0.05

Net volume of EDTA, L

Taken from data

0.0127

0.0127

0.0128

Total hardness, ppm

= Average M EDTA x Net volume of

EDTA x FM CaCO3 x 1000 mg
Volume of water sample

250.116826694082
250.116826694082
252.086250526319

Average Hardness, ppm CaCO3

= AVERAGE(Total Hardness, ppm)

250.773301304828

RSD, ppt

=STDEV(Total Hardness, ppm)

AVERAGE(Total Hardness, ppm)
1000 ppt

4.53416441771968

Con^idence Interval, ppm CaCO3

= Average(Total Hardness, ppm)

250.773301304828 +/-
4.3 x STDEV(Total Hardness, ppm)
SQRT(3)

Theoretical Total Water Hardness,

ppm

62.431ppm CaCO3=(25mgCa/L)
(1moleCa/40.078gCa)
(1moleCaCO3/1moleCa)(100.09CaCO3g/
CaCO3moles)

7.95

7.90

Analysis of Water Sample

2.82284082620624

144.10ppm CaCO3=(35mgMg/L)(1moleCa/
24.305gMg)(1moleCaCO3/1moleMg)
(100.09CaCO3g/CaCO3moles)

Preparation of solutions
Required weight EDTA sol, g

= 0.1000 M EDTA 0.500 L 372.24 18.612

g/m

Required weight stock Ca2+ solution,

g

= 0.05 M 0.1 L 100.09 g/m

0.50045

Required volume for working EDTA

solution, L

= 0.250 L x 0.01 M 0.1 M

0.025

Required volume for working

standard Ca2+ solution, L

= 0.05 L x 0.005 M 0.05 M

0.005

Calculations for Buffer

Preparation
step 1

0.250 L x 1.0 M = 0.250 total moles

step 2

pH = pKa + log ([base]/[acid])

step 3

10.0 = 9.26 + log ([base]/[acid])

step 4

0.74 = log([base]/[acid])

step 5

[base] or moles base = 5.495 x [acid]

or moles acid

step 6

moles acid + moles base = 0.250

NH4Cl required

5.495 x moles acid + moles acid =

0.250

moles acid x
FM NH4Cl
(53.419) =
2.056 g

NH3 required

5.495 x moles acid conc. NH3 M

(14.8 M) = volume taken from NH3
conc

volume taken
from NH3 conc
= 0.0143 L