QUANTITATIVE DETERMINATION OF TOTAL

HARDNESS IN DRINKING WATER BY

COMPLEXOMETRIC EDTA TITRATION
J. OLIVEROS1
1

INSTITUE OF BIOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 27 FEBRUARY 2015
DATE PERFORMED: FEBRUARY 2015

ABSTRACT
The purpose of the study was to determine the total hardness of a specific brand of
drinking water using the concepts learned about the complexometric EDTA titration.
The hardness of water is defined in terms of its content of calcium and magnesium
ions, and by the complexometric EDTA titration, which is the process of metal ion
titration until an end product of complexes is obtained, hardness can be
determined. There total hardness of water was identified to categorize the use a
specific type of water whether it is used domestically or industrially. The
determination of water hardness is also a useful test that provides a measure of
quality of water for households, particularly for water potability. The working
standard CaCO3 solution was added with buffer solution and Eirochrome Black T
(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 Hidden Spring (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 was 248.7 ppm (average of the three trials), which is
classified as very hard water. This proves that Hidden Spring is a reliable source of
mineral water. However, possible errors during the experiment may have caused by
the intrinsic error of the method and typical random errors including human errors.
INTRODUCTION
Water hardness is important to fish
culture and is a commonly reported
aspect of water quality. It is a measure
of the quantity of divalent ions such as
calcium, magnesium and/or iron in
water. There are many different divalent
salts; however, calcium and magnesium
are the most common sources of water
hardness [1].
Hardness is traditionally measured by
chemical titration. The hardness of a
water sample is reported in milligrams
per liter (same as parts per million, ppm)

as calcium carbonate (mg/l CaCO3).

Calcium carbonate hardness is a general
term that indicates the total quantity of
divalent salts present and does not
specifically identify whether calcium,
magnesium and/or some other divalent
salt is causing water hardness. Hardness
can be a mixture of divalent salts. In
theory, it is possible to have water with
high hardness that contains no calcium
[1].
The determination of water hardness is a
useful test that provides a measure of
quality of water for households and

industrial
uses.
Originally,
water
hardness was defined as the measure of
the capacity of the water to precipitate
soap. Hard water is not a health hazard.
People
regularly
take
calcium
supplements.
Drinking
hard
water
contributes a small amount of calcium
and magnesium toward the total human
dietary
needs
of
calcium
and
magnesium. The National Academy of
Science states that consuming extremely
hard water could be a major contributor
of calcium and magnesium to the diet
[2].
Table 1. Water Hardness Scale
Water Hardness
Soft

ppm CaCO3
0 20

Moderately Soft

20 60

Moderately
Hard

61 120

Hard

121 180

Very Hard

> 180

The ions involved in water hardness, i.e.

Ca2+(aq) and Mg2+(aq), can be
determined by titration with a chelating
agent, ethylenediaminetetraacetic acid
(EDTA), usually in the form of disodium
salt (H2Y2-). The titration reaction is:

Eriochrome Black T is commonly used as

indicator for the above titration. At pH
10, Ca2+(aq) ion first complexes with the
indicator as CaIn+(aq), which is wine red.
As the stronger ligand EDTA is added, the
CaIn+(aq) complex is replaced by the
CaY2-(aq) complex which is blue. The
end point of titration is indicated by a
sharp color change from wine red to
blue.
Titration using Eriochrome Black T as
indicator determines total hardness due
to Ca2+(aq) and Mg2+(aq) ions.
Hardness due to Ca2+(aq) ion is
determined by a separate titration at a
higher pH, by adding NaOH solution to
precipitate
Mg(OH)2(s),
using
hydroxynaphthol blue as indicator [3].
EDTA also forms a 1:1 molar ratio with
metal ions in a complex. This results in
increased stability for the metal-ion
complex formed. For this reason, EDTA is
primarily used as the titrant when
performing complexometric titrations [8].
Figure 1 below shows the chemical
structure of EDTA.

Figure 1. Chemical Structure of EDTA

[9]

METHODOLOGY
The experiment started by preparing all
the needed solutions for the study. The
solutions prepared were 500 mL 0.1000
M stock Ethylenediaminetetraacetic acid
(EDTA) solution, 100 mL 0.0500 M stock
Ca2+ solution, and a 250 mL 1.0 M NH3NH4+ pH 10 buffer solution. To avoid
confusion, the aforementioned solutions
will be named solutions A, B, and C
respectively.
Solution A was prepared by adding
approximately 18.61 grams of Na2H2EDTA
* H2O to the nearest 0.1 milligrams in a
400 mL beaker and adding 200 mL of
distilled water and 1.0 gram MgCL2 * H2O
upon the dissolution of the first solid
added. Then the entire solution was
quantitatively transferred in a 500 mL
volumetric flask, filling to mark with
distilled water and mixing.
Next, solution B was prepared by adding
approximately 0.791 grams of pure
CaCO3 (with a purity of 99.97%) to a 250
mL beaker and adding 40 mL distilled
water.
HCl was then added to the solution as it
was being heated and at the same time
gently stirred. This was done in order to
dissolve
the
CaCO3
solids.
Upon
dissolution, the entire solution was
transferred to a 100 mL volumetric flask,
diluted to mark with distilled water and
mixed.
Finally, the solution C was prepared by
mixing the specified values for NH 3 and
NH4Cl (in this case, 14.072 mL of NH3 and
2.06 grams of NH4Cl into a volumetric
flask, diluted to the mark and mixed. The
pH was tested using a strip of pH paper

and adjusted by either adding more acid

or base to attain a pH value of 10.
Additional solutions were also prepared;
250.0 ml .0100 M working EDTA solution
from .1 M EDTA and 50.0 ml .0050 M
working standard Ca2+ from the .0500 M
Ca2+ solution. These solutions will be
labeled
as
Solutions
A1 and
B1
respectively. The solution A 1 will be
prepared by getting 25 ml from the .1000
M EDTA and diluting and storing it to a
specified 250 ml volumetric flask. The
solution B1 was prepared by getting 5 ml
of the .0500 M Ca2+ solution diluting and
storing it to a specified 50 ml volumetric
flask.
Standardization of the .01 M EDTA
solution started by getting three sets of
10 mL aliquots from the .0050M CaCO3
solution. 75 mL of distilled water was
also added to each of the flasks. Three
mL of the buffer solution was then added
to the solution with 2-3 drops of the EBT
indicator before titration.
The volumes (initial and final) of the
titrant were then recorded. The solution
was titrated until a change in color from
wine red to a clear blue was observed.
This part of the experiment was done
within 3 trials.
After doing the standardization, a similar
process was done for the analysis of the
Hidden Spring water sample. However,
instead of 10 mL, 3 sets of 50 mL water
samples were added into 3 separate 250
mL Erlenmeyer flasks before adding 3 mL
of the buffer solution then titrating with
the EDTA solution using the EBT as
indicator. The color change observed for
both was from wine red to dark blue.

RESULTS AND DISCUSSION

During the preparation of stock EDTA
solution, MgCl2 * 6H2O crystals were
added to the dissolved salt EDTA. It was
added to the solution to increase its
solubility via diverse ion effect.
The fact that Mg-EDTA has a higher
formation constant hence a higher
tendency to form complexes than CaEDTA, Mg2+ from EDTA solution can easily
displace Ca2+ ions and form Mg-EDTA
complex
2
4
2
10

Ca + EDTA

CaEDTA K f 5.0 x10

Mg 2 + EDTA 4 MgEDTA 2 K f 4.9 x108

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 Mg2+ 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
errors
can
cause
discrepancies in pH readings so adding
HCl while dissolving CaCO3 during the
solution preparation is important for all
reactions between metal ions and EDTA
that are pH dependent, and for divalent
ions, solutions must be kept basic (and
buffered) for the reaction to go to
completion [5]. 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 a buffer was used
to hold the pH constant. In this
experiment, NH3-NH4Cl buffer was used
since EBT indicator only works when the

pH is at 8 to 10, whereas the buffer has a

pH equal to 10 [4].
Meanwhile NaOH was present to
neutralize the carboxyl groups present in
the EDTA crystals and as such increases
its solubility, therefore ensuring its
complete dissociation into the solution
[5]
Equations (1), (2), and (3) below display
the
reaction
process
the
various
reactants and ions undergo in order to
display a color change from wine red to
dark blue as well as to display a sharper
endpoint for the titration process.
H2Y2 + Ca2+ CaY2 + 2H+ (1)
H2Y2 + Mg2+ MgY2 + 2H+ (2)
H2Y2 + Mg-In MgY2 + HIn2+ H+ (3)
where Mg-In = wine red solution
and HIn2+ = dark blue endpoint
Note how EDTA reacts to both calcium
(equation (1)) and magnesium ions
(equation (2)) before the magnesium
ions bind to the EBT indicator (prior to
titration) then forming a metal-ion
complex post-titration (equation (3)).
Figure 2 below displays the structure of a
metal cation-EDTA complex.

Figure 2. Chemical Structure of a Metal

(M)-EDTA Complexation [7]
The concentration of the two most
common hard water ions, Ca2+ and Mg2+
was then determined by titrating the
water sample with a known chelating

agent, EDTA. It was standardized with

CaCO3 thrice and the resulting average
concentration of EDTA is 0.0095 M.
Table 2.
solution

Standardization

of

EDTA

Trial
Volume of
working
Ca(II) standard,
mL

1
10

2
10

3
10

Net volume
EDTA, mL

8.5

8.3

M EDTA
Average M EDTA

.0098

.0093
.0095

.0095

Titer

MgIn - +Y 4- +H 3O + MgY 2- +HIn 2- +H 2O

.9566187928

The net volume of EDTA used was

obtained experimentally through the
titration process while the MEDTA as
well as the titer were both calculated
from equations (4), (5), (6) and (7).

g CaCO3 (100.09 g /mol )( %purity )

2+=
Lsolution
M stock Ca
(4)

M working standard=

M EDTA =

( M stock Ca ) ( V stock Ca )
V workingstandard

(5)

( M wor king standard ) ( V working standard )

V EDTA

(6)

T =M (FW )

(7)

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 Mg2+ ions in the solution,
and the indicator only exists as wine-red
complex due to the magnesium ions [6].

Mg 2+ + HIn 2- MgIn +H

On the other hand, the water sample

(Hidden Spring) was titrated with the
standardized EDTA. The starting color
sample upon addition of EBT indicator
was wine red due to the existence of
Mg2+ ions and upon titrating with EDTA,
the color gradually changes from wine
red to clear blue, indication that the
endpoint is reached, which occurs when
Ca2+ ions complexes with EDTA, the same
time the Mg2+ complexes with it
sequentially and the Mg-EBT complex
breaks as illustrated in the equation.

(red - wine)

(clear blue)

Table 3. Hidden Spring Water Sample

Analysis
Trial
Volume of
water
sample, mL
Net Volume
of EDTA, mL
Total
Hardness,
ppm CaCO3
Average
RSD
Confidence
Interval

1
50

2
50

3
50

13

13

13

248.7

248.7

248.7

248.7
0 ppt
248.7 +/- 0

The values above were calculated using

the formulas listed below in equations (8)
and (9). While the formulas involving the
RSD and confidence interval are listed
down as equations (10) and (11).

2+=

M EDTRA (V EDTA )
V water sample
M Ca

(8)

Ca2+

1 mol CaCO 3 100.09 g

1000 mg through the burette pre-titration
(
CaCO 3)(
)
1 mol Ca
mol
1 g (increase in ppm CaCO3 due to a most
likely diluted EDTA titrant), too much
ppm CaC O3=M
EBT indicator added (indeterminate

(9)

sx
(1000 ppt)
(10)
mean
t (sx)
(11)
CI =mean
n

RSD=

where t is a given value dependent on n-1 at 95% confidence level and

n is the number of given data

When comparing the obtained values

above with the theoretical values
obtained from the labels indicated in
the water bottle, It can be concluded
that errors were still present in the
experiment, however, the objective of
the experiment was still achieved, that
is to determine the total hardness of a
water sample.
Theoretically,
the
water
sample
contained 25 ppm and 35 ppm of both
Ca2+ and Mg2+ ions respectively; and
the calculated water hardness (CaCO 3
ppm) based on these theoretical
values are 62.44 ppm (from ppm Ca)
and 144.10 ppm (from ppm Mg) for a
total hardness of 206.54 ppm.
Experimentally, the total hardness of
water was 248.70 ppm, which
according to Table 1, falls under the
vey hard category. This fully supports
the theoretical category of the Hidden
Spring water sample to fall to the very
hard category.
As mentioned, certain errors could
have
been
committed
while
performing the experiment that may
have affected the overall result,
primarily the ppm value of calcium
carbonate. Such errors committed that
could have affected the ppm value of
CaCO3 are overtitration (increase in
VEDTA = increase in ppm CaCO3), the
negligence to allow for EDTA to pass

ppm CaCO3 due to a vague shift in

color), too little EBT indicator added
(increase ppm CaCO3 as the time for a
color shift will be delayed), actual pH
of the solution is less than 10
(decrease ppm CaCO3 due to the
possible
precipitation
of
metal
hydroxides.) The addition of indicator
before the 3 mL buffer solution to the
analyte may also affect the overall
process as some of the indicator may
react with the solution before the
buffer can work for an ideal set-up.
SUMMARY AND CONCLUSIONS
Complexometric titration was utilized
to determine the hardness of the 50
mL Hidden Spring water sample.
Water hardness is basically a set of
standards used to determine whether
or not a water sample is suitable for
domestic or industrial use. Generally,
very hard water is mostly suitable for
drinking and not for industrial use for
hard water can; clog pipes due to
formation of precipitates called scales
/mineral deposits when heated,
reduce the life of clothes due to the
slimy film/yellow coating the scales
form in clothes, and it can further
deteriorate
the
performance
of
appliances due to excess mineral
deposits. .
EDTA was used as the titrant because
of its efficiency and stability in forming
metal-ion complexes, specifically with
the Mg2+ and Ca2+ ions found in the
water sample. Because of various
disassociations and formations among
the reactants and ions involved as
expressed in equations (1),(2), and

(3), a color change from wine red to

dark blue may be observed to
determine the MEDTA as well as the ppm
CaCO3.
Various errors such as
overtitration, addition of indicator
before buffer (for the analyte),
addition of too much or too little
indicator,
have
influenced
the
accuracy of the data.
Lastly, after determining the total
hardness of the water sample, and
after comparing the results from the
theoretical values, it can be concluded
that the Hidden Spring water sample
is classified with a total hardness that
falls to the category of very hard
which
signifies
its
high-mineral
content and potability as a type of
drinking water.
REFERENCES

[1] Wurts, William. "WATER HARDNESS

-- CALCIUM & MAGNESIUM."
WATER HARDNESS -- CALCIUM
& MAGNESIUM. Kentucky
State University CEP at UK
Research and Education
Center, 1 Jan. 2008. Web. 1
Apr. 2015.

[2] Spurlock, D. "Determination of

Water Hardness By
Complexometric Titration Class
Notes." Determination of Water
Hardness By Complexometric
Titration Class Notes. Indian
University Southeast, 31 Mar.
2014. Web. 1 Apr. 2015.

[3] "Hardness of Water by EDTA

Titration." Edb.kedcity.net.
Web. 1 Apr. 2015.
<http://cd1.edb.hkedcity.net/cd
/science/chemistry/s67chem/pd
f/sOL_6_Water_hardness.pdf>.
[4] Andersen, Robert A. Algal Culturing
Techniques. Burlington, Mass.:
Elsevier/Academic, 2005. 5455. Print.
5] Beynon, R.J., and J.S. Easterby.
"Determination of Water Total
Hardness by Complexometric
Titration." Titrations.info. 6
Sept. 2009. Web. 1 Apr. 2015.
[6] KIRUTHIGA, B. "Complexometric
Titration." Srmuniv.ac.in. DEPT
OF PHARMACEUTICAL
CHEMISTRY SRMUNIV. Web. 1
Apr. 2015.
<http://www.srmuniv.ac.in/dow
nloads/Complexometric_Titratio
n.pdf>.
[7] Metal-edta.png. Digital image.
Http://figures.boundless.com/1
2142/full/metal-edta.png. Web.
[8] "Buffers & Henderson-Hasselbal."
Mhchem.org. Web. 1 Apr. 2015.
[9] Graphics 9. Digital image.
Http://cnx.org/resources/0418e
3a849c5083ecc35ba9e8c9249
b4/graphics9.jpg. Web.

APPENDIX A - TABLES
Table 1. The water hardness scale.
Table 2. Standardization of EDTA solution [Complete version]
Table 3. Hidden Spring Water Sample Analysis
Trial
1
2
Working
10 mL
10 mL
Ca(II)
standard

3
10 mL

Net Vol of
EDTA

8 mL

8.5 mL

8.3 mL

M of EDTA

9.878915223x103M

9.297802562x103M

9.521845998x103M

APPENDIX B CALCULATIONS
Calculations

1 mol 1 mol Ca 2
mol Ca 2 0.791g

100.0869g 1 mol CaCO3

7.903132178x103 mol Ca 2
M of Ca 2

7.903132178x103 mol Ca 2 1000 mL 1

100 mL
L

10

= 7.903132178x103 M Ca 2
M of EDTA (1)
M of EDTA (2)

A.

M of EDTA (3)

7.903132178x103 M Ca 2 10 mL

9.878915223x10

8 mL
7.903132178x103 M Ca 2 10 mL

8.5 ml
7.903132178x103 M Ca 2 10 mL

rdization of EDTA Solution

8.3 ml

9.297802562x10

9.521845998x10

Standa

++

AVERAGE M =

Titer 9.566187928x103M EDTA 100.0869 g/mol CaCO3

0.9566187928 g/L

B. Analysis of Viva! Water Sample

mol Ca 2 / Mg 2 7.903132178x103 M EDTA 13ml / 1000L

.0001027407183 mol

exp: ppm Ca = mol Ca 2 X 40.08 X 1000mg / .05 ml 99.69 ppm

exp : ppm Mg = mol Mg 2 X 24.305 X 1000mg / .05 ml 60.46 ppm

theo: ppm Ca = 25 ppm
theo: ppm Mg = 35 ppm

ppm CaCO3 from ppm Ca = ppm Ca / 40.08 x 1 x 100.0869 248.9436891 ppm

ppm CaCO3 from ppm Mg = ppm Mg / 24.305 x 1 x 100.0869 248.9436891 ppm

ppm CaCO3 from ppm Ca = ppm Ca / 40.08 x 1 x 100.0869 62.42945359 ppm

ppm CaCO3 from ppm Mg = ppm Mg / 24.305 x 1 x 100.0869 144.1284304 ppm

XX
SD

i 1

n1

248.7 248.7 248.7 248.7 248.7 248.7

2

3 1

= 0 ppm

Confidence Limit X

tSD

ppm CaCO3(1,2,3) =

T x mL EDTA
Vsample

4.30 0
= 248.7

248.7 0

= 248.7208861 ppm

(.9566187928) 13 mL
50 mL

x 1000 mg

1g

RSD

0
X

x1000 ppt

0
x1000 ppt
248.7
0 ppt