QUANTITATIVE DETERMINATION OF TOTAL HARDNESS IN DRINKING

WATER BY COMPLEXOMETRIC EDTA TITRATION

DARLENE M. ROXAS
1
and JULLIE ANNE B. SALGADOS
2

1,2
NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 31 JANUARY 2014
DATE PERFORMED: 23 JANUARY 2014



ABSTRACT

The determination of water hardness is a useful test that provides a measure of quality of water for households and industrial uses. The
hardness of water is defined in terms of its content of calcium and magnesium ions. The objective of this experiment is to apply the
concept of complexometric titration in the determination of total hardness in drinking water. The working standard CaCO3 solution was
added with buffer solution and EBT indicator for the standardization of the EDTA titrant solution. The analysis of water sample involved
the titration of a measured volume of mineralized water of the brand Viva! (plus buffer solution and EBT indicator) with the EDTA
solution.A color change from wine red to clear blue indicates the titration endpoint. The computed total hardness as CaCO3 ppm was
12.23 ppm which is classified as hard water, while the total cation content is 192.57 ppm.. Relative standard deviation was computed
and it resulted to 41.68 ppm and confidence interval at 95% confidence level is[112.27 ppm, 138.19 ppm]. The total hardness proves
the feasibility of the information about the quality of Viva! as a reliable source of water The tap water was also analyzed and the
obtained total hardness is 62.15 ppm which is classified as moderately hard water.Certain errors during the experiment may have
caused by the intrinsic error of the method and typical random errors including human error.



INTRODUCTION

One of the factors that establish the quality of a water
supply is its degree of hardness. The hardness of
water is defined in terms of its content of calcium and
magnesium ions.

Hardness in water is caused by the presence of a
variety of certain dissolved polyvalent metallic ions in
solution in water predominantly calcium and
magnesium, although other ions for example,
aluminum, barium, iron, manganese, strontium, and
zinc, also contribute. The source of the metallic ions
are typically sedimentary rocks, and the most
common are limestone (CaCO3) and dolomite
(CaMg(CO3)2).[1]

The determination of water hardness is a useful test
that provides a measure of quality of water for
households and industrial uses. Hardness is of
concern in domestic water consumption because hard
water increases soap consumption, leaves a soapy
scum in the sink or tub, can cause water heater
electrodes to burn out quickly, can cause
discoloration of plumbing fixtures and utensils, and is
perceived as less desirable water. In industrial water
use, hardness is a concern because it can cause
boiler scale and damage to industrial equipment.[2]

The total amount of hardness in water is expressed
as the sum of its calcium carbonate (CaCO3) and its
magnesium hardness. However, for practical
purposes, total hardness is expressed as parts per
million of calcium carbonate. This means that
regardless of the amount of the various components
that make up hardness, they can be related to a
specific amount of calcium carbonate. That is,
hardness is expressed in mg/L or ppm of CaCO3. The
mg/L of Ca and Mg must be converted into mg/L as
CaCO3 before they can be added. The hardness of
water can be classified based on the table below.


Table 1. The water hardness scale.
Water Hardness ppm CaCO3
Soft 0-20
Moderately soft 20-60
Moderately hard 61-120
Hard 121-180
Very hard >180

In this experiment, total hardness in drinking water is
quantitatively determined by complexometric titration
using EDTA as titrant. IUPAC has defined
'complexometric titration' as a titration based on
reaction of a metal ion with a ligand to form a soluble
complex and in which one of the two reactants is
used a titrant.[3]

Since this type of titration depends upon the
combination of ions (other than H
+
and OH
-
) to form a
soluble and involved treatment of complex ions such
as magnesium, calcium, iron, lead and zinc, some of
its application includes determination of ion content in
a living cell and introduce these ions into cell in case
of deficiencies. Currently, this type of titration is
widely used in the medical industry because of the
micro liter size sample involved [4].

Water hardness can also be determined using
different instruments. A colorimeter is a device that
measures the absorbance of particular wavelengths
of light by a specific solution. The rate of absorbance
is directly proportional to the concentration of the
solution given by the Beer-Lambert Law. The
concentration of specific ions can be determined
using this. Another method is the use of test strips.
This chemically impregnated pads change to different
color when reacted to a specific ion. There is a color
chart that represents color and their various
concentrations. [5]

The objective of the experiment is for the student to
be able to apply the concept of complexometric
titration in the determination of total hardness in
drinking water.

For the standardization of the 0.01 M EDTA solution,
10 mL of the 0.0050 M working standard CaCO3
solution was measured and placed into each of three
250-mL Erlenmeyer flasks, then added with 75 mL
distilled water. Three mL of the NH3-NH4+ buffer
solution was put into the solution, followed by 2-3
drops of the EBT indicator. Titration of the solution
with the standard EDTA solution followed immediately
after, which must be done until a color change from
wine red to clear blue is observed.

In the analysis of the Viva! Mineralized water sample
and tap water sample, 50 mL of the both water
sample was measured into each of three 250 mL
Erlenmeyer flasks. The same procedure from the
standardization process was followed. Note that the
type of sample water used is mineralized or spring
water, since natural minerals (e.g., calcium,
magnesium, iron) are still present. Purified water and
distilled water cannot be titrated since contaminants,
including minerals all undergone different stages of
filtration process, so using this kind of water would not
form any complex ions when titrated with EDTA.

RESULTS AND DISCUSSION

Upon preparation of stock EDTA solution, MgCl26H2O
crystals were added to the dissolved salt EDTA. The
fact that Mg-EDTA has a higher formation constant
hence a higher tendency to form complexes than Ca-
EDTA, Mg
2+
from EDTA solution can easily displace
Ca
2+
ions and form Mg-EDTA complex.




Since Ca-EDTA has a lower Kf, formation constant,
Ca-EDTA is less stable because there is a greater
energy for the complex to form, so adding more Mg
2+

ions will make the endpoint sharper. On the other
hand, EDTA is essentially insoluble in water, and will
only dissolve when pH is neutralized to 8. Addition of
base, in this experiment NaOH pellets, facilitates
dissolution of acid form of EDTA.

Carbonate error can cause discrepancy in pH reading
so adding HCl while dissolving CaCO3 during the
solution preparation is important for all reactions
between metal ions and EDTA are pH dependent,
and for divalent ions, solutions must be kept basic
(and buffered) for the reaction to go to completion [6].
Most ligands are basic and bind to H
+
ions throughout
a wide range of pH. Some of these H
+
ions are
frequently displaced from the ligands (chelating
agents) by the metal during chelate formation,so
buffer was used to hold the pH constant. In this
experiment, NH3-NH4Cl buffer was used since EBT
2 4 2 10
Ca + EDTA CaEDTA 5.0 10
f
K x
+
=
2 4 2 8
Mg + EDTA MgEDTA 4.9 10
f
K x
+
=

indicator only works when the pH is at 8 to 10,
whereas the buffer has a pH equal to 10 [7].

The concentration of the two most common hard
water ions, Ca
2+
and Mg
2+
was determined by titrating
the water sample with a known chelating agent,
ethylenediaminetetraacetic acid (EDTA). It was
standardized with CaCO3 thrice and the resulting
average concentration of EDTA is 0.0069 M. During
standardization, purple color appeared upon addition
of EBT indicator compared to the expected wine red
color of the solution. This may happen since there are
no Mg
2+
ions in the solution, and the indicator only
exists as wine-red complex due to the magnesium
ions.


Viva! Mineralized water was titrated with the
standardized EDTA. The starting color sample upon
addition of EBT indicator was wine red due to the
existence of Mg
2+
ions (3), and upon titrating with
EDTA, the color gradually changes from wine red to
clear blue, indication that the endpoint is reached,
which occurs when Ca
2+
ions complexes with EDTA
(1), the same time the Mg
2+
complexes with it (2)
sequentially and the Mg-EBT complex breaks as
illustrated in the equation.



Table 2 below shows the titration data of Viva!
Mineralized water with standardized EDTA. The
computed average hardness from three trials is
125.23 ppm (see Appendix B for calculations) which
can be classified as hard based from water hardness
scale. Q-test was first conducted and all values are
accepted. The standard deviation computed is 5.22
ppm while the relative standard deviation is 41. 68
ppt. The confidence limit was also computed with
confidence level at 95% and the resulting interval is
[112.27 ppm, 138.19 ppm].

Table 2. Viva! Mineralized Water Analysis Titration
Data
Trial 1 2 3
Water
sample
50 mL 50 mL 50 mL
Final vol of
EDTA
8.9 mL 18.4 mL 27.2 mL
Initial vol of
EDTA
0 mL 8.9 mL 18.4 mL
Net vol
EDTA
8.9 mL 9.5 mL 8.8 mL
Total
Hardness
122.93
ppm
131.21
ppm
121.55
ppm

The total cation content of the water sample based
from labels given Ca
2+
and Mg
2+
content was also
computed by adding the total CaCO3 ppm and total
CaCO3 ppm from MgCO3 is 192.57 ppm, which can
be classified as very hard water. Comparing this with
respect to the data obtained from EDTA titration, it
claims to have a higher Ca
2+
and Mg
2+
content when
the computed total hardness from complexometric
titration appears to be less.

The large difference of the total hardness of the two
may due to different errors arose during the titration
or preparation of the solution. The discrepancy may
be caused by several factors. Overtitration of the
sample analysis is the common source of error since
the detection of blue endpoint is not distinguishable to
purple color. The delayed change of color of the
solution can also be the cause of overtitration. It is
also important to note that the indicator used must be
suitable for the type of titration, which in this
experiment we used EBT since it selectively binds
with the Mg
2+
ions. Neglect to add buffer can also
cause error in the concentration of the standardized
EDTA since it is very sensitive to pH change, so it is
also important to note that proper selection of kind of
buffer based on each pH range, in which in this
experiment, is at 10.

Another titration was done to determine the hardness
of tap water. Table 3 below shows the titration data of
the tap water titrated with standardized EDTA and the
computed average total hardness as CaCO3 ppm is
62.15 ppm which is classified as moderately hard
based from table 1.

Table 3. Tap Water Analysis Titration Data
Trial 1 2
Water sample 50 mL 50 mL
Final vol of EDTA 4.5 mL 9.0 mL
Initial vol of
EDTA
0 mL 4.5 mL
Net vol EDTA 4.5 mL 4.5 mL
Total Hardness 62. 15 ppm 62.15 ppm

- 4- + 2- 2-
3 2
MgIn +Y +H O MgY +HIn +H O
( - ) ( ) red wine clear blue

2+ 2-
Mg + HIn MgIn +H
+

Compared to the commercial mineral waters total
hardness, it is as half as much of it. But daily
consumption of this kind of water is not advisable
because it may contain chloride (to kill germs) that
can easily react with other organic materials, and
other alkaline substance (to maintain pH and prevents
corrosion of pipes).

SUMMARY AND CONCLUSIONS

The standardized EDTA resulted to a 0.0069 M after
titrating it thrice with primary standard CaCO3. Viva!
Mineralized water was used as sample and has an
initial Ca
2+
content of 54 ppm and Mg
2+
content with
14 ppm. The water sample was titrated with
standardized EDTA using EBT indicator. The
selection of the indicator was based on the range of
its pH which is 8 to 10. NH3-NH4Cl buffer with pH at
10 was used to maintain the pH of the solution since
EDTA is pH dependent. After three trials of titration,
the computed hardness of water are 122.93 ppm,
131.21 ppm, 121.55 ppm and has an average of
125.23 ppm. The values are checked using Q-test to
eliminate outliers, and in this set, suspected outliers
are accepted. The computed relative standard
deviation is 41.68 ppm. The calculated confidence
interval at 95% confidence level is [112.27 ppm,
138.19 ppm]. The total cation content based from the
label of the sample water was also computed for
comparison, and it resulted to 192.57 ppm, much way
larger than the data obtained from the titration. The
large difference in the value may be caused by
overtitration or inaccurate solution preparation that
may have affected some parameters including the
concentration of the standardized EDTA and the total
hardness based from the titration data. Moreover, the
two calculated hardness have showed the level of
hardness of Viva! Mineral water which ranges from
hard to very hard. The hardness of water only shows
that pertinent ions, like Ca
2+
and Mg
2+
, are present
and are good for daily consumption.

On the other hand, another titration was done to test
the hardness of the tap water. It resulted to a total ion
content of 62.15 ppm as CaCO3 ppm. It was classified
as moderately hard water, which means few minerals
or ions are present in the water, which in only true
since this running water are all treated to filter off
contaminants, in which some of the minerals may
have been filtered off during the process.

REFERENCES

[1] Selinus, O. Essentials of Medical Geology:
Revised Edition. 2013. New York City: Springer.

[2] Spellman, F. The Science of Water: Concepts and
Applications, Second Edition. 2000. Boca Raton,
Florida: CRC Press. 302.

[3] Iqbal, S., Setii, M. An Introduction to Analytical
Chemistry. 1994. Delhi: Discovery Publishing House.
143-144.

[4] . N.p.. Web. 29 Jan 2014.
<http://amrita.vlab.co.in/?sub=2&brch=193&sim=352
&cnt=1>.

[5] "Measuring Water Hardness." www.lamotte.com.
LaMotte Company. Web. 29 Jan 2014.
<http://www.lamotte.com/en/blog/test-factors/75-
measuring-water-hardness>.

[6] . N.p.. Web. 29 Jan 2014.
<http://www.titrations.info/EDTA-titration-water-
hardness>.

[7] Andersen, Robert Arthur. Algal Culturing
Techniques. 2005. Burlington, USA:Elsevier
Academic Press. 53-54

APPENDIX A Tables

Table 1. The water hardness scale.

Table 2. Viva! Mineralized Water Analysis Titration Data

Table 3. Tap Water Analysis Titration Data

Table 4. Standardization of EDTA solution Titration Data
Trial 1 2 3
Working Ca(II) standard 10 mL 10 mL 10 mL
Final volume of EDTA 7.5 mL 14.6 mL 22.0 mL
Initial Vol of EDTA 0 mL 7.5 mL 14.6 mL
Net Vol of EDTA 7.5 mL 7.1 mL 7.4 mL
M of EDTA 0.0068 M 0.0071 M 0.0068 M


APPENDIX B CALCULATIONS

Calculations
A. Standardization of EDTA Solution
















( )( )
3
Titer 0.0069 M EDTA 99.97 / CaCO
0.6906 /
g mol
g L
=
=
2
2
3
2
2
2
2
(1)
1 1 Ca
Ca 0.5041
99.97 1 CaCO
0.005041 Ca
0.005041 Ca 1000 mL 1
M of Ca
100 mL L 10
= 0.005041 M Ca
0.005
M of EDTA
mol mol
mol g
g mol
mol
mol
+
+
+
+
+
+
| | | |
=
| |
\ .\ .
=
| || |
=
| |
\ .\ .
=
( )
( )
( )
2
2
(2)
2
(3)
041 M Ca 10 mL
0.0068 M
7.5 mL
0.005041 M Ca 10 mL
M of EDTA 0.0071 M
7.1 mL
0.005041 M Ca 10 mL
M of EDTA 0.0068 M
7.4mL
+
+
+
=
= =
= =

B. Analysis of Viva! Water Sample


























( )
( )( )
(1)
T x EDTA
ppm CaCO3 =
V
0.6906 g/L 8.9
1000
=
50 1
= 122.93
sample
mL
mL
mg
x
mL g
ppm
| |
|
\ .
( )
( )( )
(2)
T x EDTA
ppm CaCO3 =
V
0.6906 g/L 9.5
1000
=
50 1
= 131.21
sample
mL
mL
mg
x
mL g
ppm
| |
|
\ .
( )
( )( )
(3)
T x EDTA
ppm CaCO3 =
V
0.6906 g/L 8.8
1000
=
50 1
= 121.55
sample
mL
mL
mg
x
mL g
ppm
| |
|
\ .
( )
3
3
1 1 99.97
54.00
39.99 1
= 134.99
molCaCO mol mg
ppmCaCO ppm
g molCa mol
ppm
| |
| || |
=
| | |
\ . \ .
\ .
( )
3 3
3 3
3
1 1 1 99.97
14.00
24.305 1 1
= 57.58
molMgCO mmolCaCO mol mg
ppmCaCO ppm CaCO
g molMg mmolCO mmol
ppm
| | | || |
| |
=
| | | |
\ .
\ .\ .\ .
3 3 3
CaCO + CaCO from MgCO
=134.99 57.58
= 192.57
total ion content ppm ppm
ppm ppm
ppm
=
+
( )
( ) ( ) ( )
2
1
2 2 2
X X
SD
1
122.93 125.23 131.21 125.23 121.55 125.23

3 1
= 5.22
n
i
n
ppm
=

=

+ +
=

C. Tap Water Analysis
RSD 1000
X
5.22
1000
125.23
41.68
SD
x ppt
x ppt
ppt
=
=
=
( )( )
tSD
Confidence Limit X
4.30 5.22
=125.23
3
125.23 12.96
Confidence Limit: 112.27 138.19
n
ppm ppm
=

( )
( )( )
(1)
T x EDTA
ppm CaCO3 =
V
0.6906 g/L 4.5
1000
=
50 1
= 62.15
sample
mL
mL
mg
x
mL g
ppm
| |
|
\ .