1

QUANTITATIVE DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA
TITRATION
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
______________________________________________________________________________
ABSTRACT
The determination of water hardness is a useful tool to provide a measure for quality of water within
households and for industrial uses. In this experiment complexometric EDTA titration was used to determine
the mineral content of Hidden Spring Mineral Water. A 0.0500 M EDTA solution was standardised with 99.5%
pure calcium carbonate. Using the ammonia-ammonium buffer the environment of the reaction was kept
alkaline at pH = 10 and the indicator used was Eriochrome Black T or EBT. The analysis of the water sample
involved the the titration of 50 mL of the mineralised water mixed with buffer solution and indicator solution
with EDTA solution. The change of color from red wine (color of EBT bound to metal ion) to clear blue (color
of free EBT ion) indicated the endpoint. The method yielded the hardness to be 219.63 ppm CaCO3 which
classifies the water as very hard. The total cation content computed from the content given on the waters
label was 206.87 ppm. The relative standard deviation was computed and it resulted to 0 ppm and
confidence interval at 95% confidence level obtained was 217.7 0. During the experiment intrinsic errors of
the method and typical errors like human errors may have occurred.

______________________________________________________________________________

INTRODUCTION

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Complexometric titration is considered to be one of
the best ways to determine water hardness.

METHODOLOGY
In this experiment the total hardness of Hidden
Spring
Mineral
Water
was
determined
quantitatively using complexometric titration with
ethylenediaminetetraacetic acid (EDTA) as the
titrant. The large molecule known as EDTA forms a
complex with calcium and magnesium. A blue dye
known as Eriochrome Black T (EBT) was used as
an indicator. EBT also forms a complex with
calcium and magnesium ions which causes the

Minerals that are dissolved in groundwater produce

metal ions like manganese, calcium, strontium,
aluminum, barium, zinc, magnesium and iron.
These metal ions are considered to be good for the
body, which is why mineralised water contains
these ions. Calcium and magnesium are the most
abundant ions in mineralised water because they
have become commercialised. The ions present in
water give it a hardness. The determination of
water hardness is a useful test to measure the
quality of mineral water for households and
industrial uses. The hardness of water a concern
because hard water increases soap consumption,
leaving a soapy sink, causing burn out of
electrodes or discolouring plumbing fixtures and
utensils. [1]
The total hardness of water is determined by the
sum of the calcium and magnesium salts dissolved
in water. This is expressed as milligrams per litre
(mg/L) of water, or for more practical reasons parts
per million (ppm) of CaCO3. The hardness of water
can be determined by the table below.

change of the solutions color from red wine to clear

blue endpoint. [3]

Figure 1. Ethylenediaminetetraacetic acid

(EDTA)
Figure 2. Eriochrome Black T (EBT)

Table 1. The water hardness scale. [2]

Water Hardness

ppm CaC

Soft

0-20

Moderately Soft

21-60

Moderately Hard

61-120

Hard

121-180

Very Hard

> 180

Water hardness is usually determined in one of two

ways. One of these methods would be
complexometric
titration,
also
known
as
chelatometry. Complexometric titration is a form of
volumetric analysis where the formation of a
colored complex is used to indicate the end point of
a titration. This titration depends on the
combination of ions to form a soluble complex of
ions like magnesium, calcium, iron, zinc and lead.
These titrations are useful for determining the
mixture of different metal ions in a solution. [1]

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this experiment NaOH pellets, facilitates dissolution
of acid form of EDTA.
A carbonate error can cause discrepancies in the
pH reading. The addition of HCl while dissolving
CaCO3 during solution preparation is important for
all reactions because the metal ions and EDTA are
pH dependent. The divalent ions, solutions must be
kept basic for the reaction to complete. [4] Ligands
are mostly basic and they bind to H+ ions
throughout a wide range of pH. Some of the H+
ions displace from the ligands by the metal during
chelate formation. The buffer was used to hold the
pH constant.
As observed, the standard was allowed to react in a
basic medium by the addition of the basic buffer of
pH 10. In this experiment, NH3-NH4Cl buffer was
used. A buffer was added for the pH of the whole
reaction to remain constant. A constant pH is
needed in the titration process since the EDTA and
EBT have polyprotic properties, making them
unstable. At different pH levels the hydronium ion
concentration may interfere with the complexation
of the EDTA with the calcium and magnesium ions.
Also, the effective stability constant of EDTA varies
with the pH because it depends on its degree of
ionization. [4]
EBT was used as an indicator in this experiment.
Most complexometric titrations use indicators that
are chelating agents and have metal complexes
that have different color from the reagents
themselves. The same principle on the ionization
and dissociation of EDTA also applies to EBT since
it is also polyprotic. [5]
At the beginning of the titration of EDTA to 10mL
0.0050 M working standard CaCO3 with 3mL buffer
and 2-3 drops of EBT, the solution becomes wine
red. This is due to the complexation of the Mg 2+
ions with the indicator. Upon titrating with EDTA, the
color gradually changed from wine red to clear
blue, indicating that the endpoint was reached. The
endpoint occurs when Ca2+ ions complexes with
EDTA, and at the same time the Mg 2+ complexes
with it. The Mg-EBT complex breaks as illustrated
in the equation.

MgIn- + Y4- + H+ MgY2- + Hln2-

For the standardisation of 0.01M EDTA solution

three 250mL erlenmeyer flasks were set and 10mL
of 0.0050M working standard, CaCO 3 solution, was
measured in to each. Then 75 mL of distilled water
was added into the 10mL working standard. Three
mL of the buffer solution NH3-NH4 Cl with pH = 10,
followed by 2-3 drops of EBT indicator was added
to the solution. Immediately after the addition of the
buffer and indicator the titration with the standard
EDTA solution followed. The solution was titrated
until the clear blue endpoint was reached.
For the analysis of the Hidden Spring Mineral Water
50mL of the water sample was measured into three
separate 250mL erlenmeyer flasks. Then three mL
of the buffer and 2-3 drops of the indicator was
added to the sample immediately followed by
titration with standard EDTA solution until the clear
blue endpoint was observed.

RESULTS AND DISCUSSION

During the preparation of the EDTA solution MgCl 2
x 6H2O crystals were added to the dissolved EDTA
salt. When determining the hardness of water it is
determining
the
concentration
of
calcium
carbonate. Calcium ion determination via EDTA is
also known as displacement titration because
EDTA binds with calcium ions very slowly. By
addition of another metal, like magnesium in the
form of salt it could bind to EDTA quicker forming a
Mg-EDTA complex which is less stable than CaEDTA complex. The Mg-EDTA has a higher
formation constant giving it a higher tendency to
form complexes than Ca-EDTA. Then the free Ca 2+
ions in the solution replace the Mg forming CaEDTA complex and resulting in free Mg 2+ ions which
can be titrated easily. The amount of liberated Mg 2+
is equivalent to the original concentration of Ca 2+.
Ca2+ + EDTA4- CaEDTA

22-

Kf = 5.0x1010
Kf = 4.9x108

Mg2+ + EDTA4- MgEDTA

There is a greater energy for the complex to form
since the Ca-EDTA has a lower Kf, formation
constant making it is less stable. Adding more Mg 2+
ions will make the endpoint sharper. EDTA is
considerably insoluble in water, and only dissolves
when pH is neutralized at 8. Addition of base, in

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indicator used and determine whether it is suitable
for the type of titration. In this experiment EBT was
used since it selectively binds with the ions.
Neglecting to add a buffer can also cause error in
the concentration of the standardised EDTA. The
reaction is very sensitive to pH change, so it is
important to note that proper selection of kind of
buffer based on each pH range, in this experiment
it is at 10.

SUMMARY AND CONCLUSIONS

The standardized EDTA resulted to a 0.0084 M
after titrating it thrice with primary standard CaCO 3.
Hidden Spring Mineral Water was used as the
sample and has an initial Ca2+ content of 25 ppm
and Mg2+ content with 35 ppm.
The water sample was titrated with standardized
EDTA and EBT was used as an indicator. The
selection of the indicator was based on the range of
its pH, 8 to 10. NH3-NH4Cl buffer with pH at 10 was
used to maintain the pH of the solution because
EDTA is pH dependent. After three trials of titration,
the computed hardness of water were 219.36 ppm,
214.30 ppm, 219.36 ppm and making the average
hardness 217.67 ppm.
The values were checked using the Grubbs-test to
eliminate outliers. In this experiment the outlier was
214.30 ppm making the new average 219.36 ppm.
After computing the relative standard deviation
obtained was 0 ppm. The calculated confidence
interval at 95% confidence level was 217.7 ppm to
217.7 ppm. Based from the labels ion content the
total ion content was computed to be 206.8665931
ppm which was smaller than the value obtained
through titration.
The difference in the value may be caused by either
over titration or even inaccurate solution
preparation. These factors may have affected
parameters such as the concentration of
standardised EDTA and total hardness based from
the titration data.
The two calculated hardness have showed the level
of hardness of Hidden Spring Miner Water which is
very hard. The hardness of the water shows that

wine red

clear blue

The computed average hardness from the three

trials is 217.67382700 ppm (see Appendix C for
calculations). According to the water hardness
scale in Table 1 the water sample is very hard.

Table 2.
Mineral Water.
Trial

Analysis of Hidden Spring

Water Sample

50mL

Final volume EDTA

13mL

Initial volume EDTA

0mL

Net volume EDTA

13mL

Total Hardness

219.36

The Grubbs test was first conducted to determine

which values will be accepted, and only the values
from trial 1 and trial 3 were accepted from the
calculations making the new average 219.63 ppm.
The standard deviation computed was 0 ppm and
the relative standard deviation was also 0 ppt. The
confidence limit was also computed with confidence
interval at 95% and the resulting interval was 217.7
0.
From the Hidden Springs given ion content of Ca 2+
and Mg2+ the total ion content could be computed.
This is done adding the total CaCO 3 ppm from
CaCO3 and MgCO3. The computed value was
206.87 ppm (see Appendix for calculations). Based
on Table 1, the calculated ion content classifies the
water as very hard.
The values obtained and calculated may be
effected by certain errors made throughout the
experiment. Discrepancies may be caused by
several factors. Over titration of the sample analysis
is a common source of error. The delayed change
of color of the solution could be a possible cause
for over titration. It is important to take note of the

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pertinent ions such as Ca and Mg , are present
and are acceptable for human consumption.
2+

[3] N.p.. Web. 29 Jan 2014.

<http://www.titrations.info/EDTA-titration-waterhardness>

2+

REFERENCES

[4] N.p.. Web. 29 Jan 2014.

<http://amrita.vlab.co.in/?
sub=2&brch=193&sim=352&cnt=1>.

[1] Spellman, F. The Science of Water: Concepts

and Applications, Second Edition. 2000. Boca
Raton, Florida: CRC Press.

[5] Chang, R. 2007. Chemistry: Ninth Edition. New

York: McGraw Hill. 549-553.

[2]
Institute
of
Chemistry,
University
of
thePhilippines. Analytical Chemistry: Laboratory
Manual. 2013.