EXPERIMENT NO.
7
Determination of Water Hardness by EDTA Titration
Santillan, H.S.Y.1
1
Chemistry Department, College of Science, Adamson University, Ermita, Manila 1000
Philippines
Keywords: Water Hardness, Temporary Water hardness, Permanent water Hardness,
Complexometric Titration, EDTA, Eriochrome Black T
1.0 Introduction
Water Hardness is defined as the total
concentration of cations such as Ca2+ and
Mg2+ in water that when reacted with soap
forms insoluble complexes. Enough soap to
consume the said cations is useful for
cleaning (Harris, D., 2007). Temporary hard
water, a type of water hardness, is water
that has carbonates of magnesium, calcium
or both. When temporary hard water was
boiled, precipitation of CaCO3 or MgCO3
occurs which will remove the hardness of
the water. Another type is the permanent
hard water where chlorides or sulfates of
magnesium, calcium or both are contained
in the water. These compounds are soluble
in water which cannot be removed by
boiling (http://www.citycollegiate.com/, n.d.).
Water hardness can be determined by
complexometric titration. It is a kind of
titration method wherein a complex is
formed when a metal ion reacts with a
ligand (Skoog, D. et. al., 2014). EDTA is
used as the titrant for this method.
Ethylenediaminetetraacetic acid, or EDTA,
contains tertiary amines and a carboxylic
acid group that can form a cage-like
structure around the metal ion and is
considered very stable (Harvey, D., 2008).
The equivalence point can be determined
by the use of Eriochrome Black T as an
indicator.
The objective of this experiment is to
determine the hardness of a water sample
in terms of mg/L of Ca2+.
2.0 Experimental
The reagents used in this experiment
are 0.1 M HNO3, Disodium EDTA dihydrate,
NH4Cl, conc. NH4OH, Eriochrome Black T
(EBT), methanol, CaCO3, and conc. HCl.
The fume hood was used as equipment for
this experiment.
2.1 Preparation of Glasswares
All the glasswares were rinsed with 0.1
M HNO3.
2.2 Preparation of Reagents
For the preparation of EDTA titrant, 1 g
of disodium EDTA dihydrate was dissolved
in 500-mL volumetric flask and diluted to
mark using distilled deionised water. The
buffer solution of NH3-NH4Cl was prepared
by dissolving 32 g of NH4Cl in 200 mL
distilled deionised water. Two hundred
eighty-five milliliters of concentrated
ammonia was carefully added to the
solution while stirring. Enough amount of
water was added to make a 500 mL volume.
For the indicator, 0.25 g of EBT was
dissolved in 50 mL of ethanol. The solution
was then stored in an amber reagent bottle
and was labelled with the date of
preparation. The indicator was placed in a
refrigerator and should be away from the
sunlight. The standard CaCO3 was prepared
by adding drop by drop of concentrated HCl
into weighed 0.25 g of CaCO3 placed in a
250-mL beaker. The beaker was covered
with watch glass and the HCl was
evaporated to incipient dryness. The
residue was then transferred to a 500-mL
volumetric flask and diluted to mark.
2.3 Blank Titration
A 50 mL distilled deionised water was
used for blank titration. Five millilitres of the
buffer solution and 5 drops of the indicator
were added. The solution was then titrated
and the volume of the EDTA was subtracted
to the volume on each test.
2.4 Standardization of EDTA
In a 10 mL aliquot of standard CaCO3
solution, 5 mL of the buffer solution and 5
drops of the EBT indicator was added. The
solution was titrated with the EDTA
prepared on 2.2 until the color of the
solution turned blue. Triplicate determination
was done. The molarity of EDTA was
computed.
2.5 Analysis of Sample
A 20 mL of the sample in the
reagent bottle was pipette into 250-
mL Erlenmeyer flask. Five milliliters
of the buffer solution and 5 drops of
the EBT indicator was added to the
sample. The same titration
procedure in 2.3 was done. The
analysis was done three times. The
ppm Ca2+ in the sample was
computed. The mean, standard
deviation and %RSD was also
computed.
3.0 Results and Discussion
3.1 Preparation of Glasswares
The glasswares were prepared
by rinsing it with 0.1 M HNO 3 so any
heavy metals on the glassware will
be solubilised and removed. These
metals could interfere with the
analysis (LeFevre, J., n.d.).
3.2 Preparation of Reagents
During the entire experiment,
only deionised water was used
because it does not contain ions.
Any ions should not be present on
the reagents to be used because it
can already react with the reagent
causing an error in the analysis
(http://www.ausetute.com.au/, 2014).
A buffer solution of NH3-NH4Cl was
also prepared to make the sample
alkaline. For indicator, Eriochrome
Black T was used because it is a
metal ion indicator and it should be
stored away from sunlight because it
has a low boiling point (65 C). The
preparation of standard CaCO3
should be very careful especially
with the addition of concentrated HCl
because too much addition will make
the pH adjustment on the analysis
more difficult
(http://classes.uleth.ca/, n.d.). The
molarity of the standard CaCO3 was
4.356 x 10-3 M.
3.3 Blank Titration
Blank titration is done to determine the
amount of titrant reacting on the solvent
without the analyte
(http://education.seattlepi.com/, 2015). The
volume of EDTA titrant used was 0.57 mL
and this volume should be deducted to all
the volumes on each analysis.
3.4 Standardization of EDTA
A 5 mL of NH3-NH4Cl solution
was added to 10 mL aliquot of
CaCO3 solution to make the solution
weakly alkaline. The pH should be
10 because calcium ions can only be
titrated at pH 8 while magnesium
ions at pH 10 (Cash, D., 2008). EBT
indicator was added to the solution.
The picture below shows the wine
red color of the solution when EBT
indicator was added.

Figure 1. Initial color of solution with
EBT indicator
Source:
http://homepages.ius.edu/DSPURLOC/c121/
week13.htm
The solution was then titrated
with EDTA and a volume of 8.21 mL,
8.15 mL and 8.15 mL was needed to
reach the equivalence point. The
picture on the next page shows the
blue color of the solution when it
reached its equivalence point.
%20161/Chem%20161%20Labs/Lab
%207%20Analysis%20of%20Hard
%20Water/Eriochrome%20black-T%20Indicator.htm
The molarity of EDTA was computed
from the volume used. The mean molarity
was 5.332 x 10-3 M while standard deviation
was 2.552 x 10-5 M and the %RSD was
0.4223%.
3.5 Analysis of Sample
A 20 mL aliquot was made from
the sample given. The solution was
made alkaline by adding 5 mL NH3-
NH4Cl buffer solution and 5 drops of
the indicator was added. EDTA was
used to titrant for the sample. The
formation of the complex occurs
because EDTA acts as a
dicarboxylic acid and could be
written as H4Y, its disodium salt,
Na2H2Y and the complex forming ion
is H2Y2-. The reactions below show
the possible complex formation.

M2+ + H2Y 2- MY2- + 2H+ (eq. 1)

M3+ + H2Y 2- MY- + 2H+ (eq. 2)
M4++ H2Y 2- MY + 2H+ (eq. 3)

One gram of H2Y2- always reacts

with one gram of the metal ion. The
complex will only form in basic
condition (http://amrita.vlab.co.in/,
2015). The indicator will form a
complex ion with Ca2+ and Mg2+ but
the Mg2+ complex is stronger than
that of Ca2+. On the first few drops of
the EBT indicator, (Mg-EBT)2+ was
formed giving a wine red coloration
of the solution. The equation below
shows the equilibrium reaction of the
formation of (Mg-EBT)2+ (Beran, J.,
2011).

2+( aq)


2+ ( aq )+EBT ( aq ) ( MgEBT )
Mg
Figure 2. Equivalence Point of EBT (eq. 4)
Indicator
Source:
http://www.instruction.greenriver.edu/kmarr/Chem
 When EDTA (titrant) was added, No Author. (n.d.). Determination of
it will react first with the free Mg 2+ Hardness of Water with EDTA.
ion. The color of this complex is Website:
colorless. After all the Mg2+ reacted, http://classes.uleth.ca/200703/chem24
the (Mg-EBT)2+ reacted with EDTA 102/Expt%206_7_8_07.pdf
replacing the indicator. If the Cash, D. (2008). EDTA Titrations 2:
indicator was already replaced, it will Analysis of Calcium in a Supplement
give a blue solution indicating that Tablet; Analysis of Magnesium in
the solution reached its equivalence Epsom Salt; Hardness of Water.
point (Harris, D., 2007). Ontario,Canada: Mohawk College
Markings, S. (2015). Why is a Blank
The volumes of EDTA used were Titration Needed?. Website:
5.93 mL, 5.81 mL and 5.76 mL. The http://education.seattlepi.com/blank-
amounts of Ca2+ present in each titration-needed-4452.html
sample were 63.36 ppm, 62.08 ppm Amrita University. (2015). Acid Base
and 61.55 ppm. Titration. Website:
http://amrita.vlab.co.in/?
4.0 Conclusion sub=2&brch=193&sim=352&cnt=1
The water hardness of the Beran, J. (2011). Laboratory Manual
sample was determined through for Principles of General Chemistry.
complexometric titration. The USA: John Wiley & Sons, Inc.
2+
computed average ppm of Ca is
62.33 ppm, standard deviation is Sample Calculation
0.9305 ppm and the %RSD is
Standardization of EDTA
1.493%.
4.356 103 mmolCaCO 3 1mmol ED
10 mL CaCO3
References 1 mL CaCO 3 1 mmolCa
Harris, D. (2007). Quantitative
Chemical Analysis 7th Edition. USA: W.
H. Freeman and Company
No Author. (n.d.). Hard Water and Soft
Water. Website:
http://www.citycollegiate.com/chapter3
e.htm
Skoog, D., West, D., Holler, F, et. al.
(2014). Fundamentals of Analytical
Chemistry. Pasig City, Philippines: Analysis of Sample
Cengage Learning 2+
Harvey, D. (2008). Analytical 1 mg
1 mmolCa 2+ =63.36 ppmCa
Chemistry 2.0. California, USA: 0.02 L L
McGraw-Hill Companies Ca2+
LeFevre, J. (n.d.). Metal Analysis of 40.08 mg
Sediment by Atomic Absorption Ca 2+
Spectroscopy: A New Laboratory 1 mmol
Exercise. New York: Oswego
1 mmol EDTA
No Author (2014). Determining Total 5.332 103 mmol EDTA
5.93 mL EDTA
Hardness in Water. Website: 1 mL EDTA
http://www.ausetute.com.au/camgedta
.html