QUANTITATIVE DETERMINATION OF TOTAL

HARDNESS IN DRINKING WATER BY

COMPLEXOMETRIC EDTA TITRATION
W. YBAEZ1
NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 21 MARCH 2016
DATE PERFORMED: 17 MARCH 2016
1

ANSWERS TO QUESTIONS
1. What is water hardness and why is it expressed as ppm CaCO3?
The most straightforward definition of water hardness is the amount of calcium and
magnesium ions dissolved in water[1]. It is further defined as the capacity of cations in water
to replace the Na+ or K+ ions in soaps and form precipitates that cause scum in the sink or
bathtub. The precipitate formation lessens the cleansing action of the soap. Moreover, hard
water, on being heated, also forms precipitates, resulting to clogging of pipes and broiler
equipment[2].
Most cations with charge greater than +1 have this undesirable property. And in most
water sources, the concentrations of Mg2+ and Ca2+ far exceed those of any other metal, making
sense of the definition that water hardness is dependent on [Mg2+] and [Ca2+]. Water hardness
is usually expressed in terms of ppm CaCO3 (or a variant thereof, such as mg/L), equivalent
to the concentration of roughly all the multicharged ions in the sample. Also, part of the reason
why it is expressed in ppm CaCO3 is because when hard water is heated it precipitates
CaCO3[3].
2. How does complexometric titration work?
Complexometric titration, as the name implies, involves reactions where complexes are
formed. The ligand (can be an ion or a molecule) forms a coordination bond with a metal atom
by donating an electron pair which is then shared by them both[3].
In this type of titration, a solution containing the free metal ion(s) of interest is titrated
with the solution of the ligand until all the metal ions are completely complexed. The
formation of a colored complex is used to indicate the endpoint of a titration. Complexometric
titration is particularly useful for the determination of a mixture of different metal ions in a
solution. An indicator capable of producing an ambiguous color change is usually used to
detect the endpoint of the titration[4].
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Complexometric titration is valid (1) the reaction reaches equilibrium rapidly, (2) stepwise
formation of different complexes does not occur, resulting to the presence of more than one
complex in the titration process and lastly (3) a complexometric indicator capable of locating
the equivalence point, with acceptable accuracy, is available[5].
3. Why was EDTA used as complexing agent/titrant?
Ethylenediaminetetraacetic acid (EDTA) is an important reagent in analytical chemistry
and other applications. As seen from figure 1 below, it is a hexadentate ligand; each of the
carboxyl groups and each of the amine groups can donate one pair of electrons[4].

Figure 1. The EDTA4- ion

Among the reasons that EDTA was used as a complexing agent is its multiple denticity.
As titrants, multidentate ligands, like EDTA, have two advantages over their unidentate
counterparts. First, EDTA reacts more completely with metal cations and thus provide sharper
endpoints. It also reacts with metal ions in a single step process, whereas complex formation
with unidentate ligands usually involves two or more intermediate species[3].

Figure 2. Complexometric Titration Curves

Figure 2 above shows the different titration curves for the same metal with titrants
containing ligands with different denticities. It can be noted that A, which shows the curve
with a tetradentate ligand, has a single step and is very sharp. Curve B represents the
titration with a bidentate ligand, occurring in two steps. Lastly, C shows the titration with
a unidentate ligand, occurring in four steps. Notice that the curve is a gentle slope and

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there is no distinction between the steps. For this reason, EDTA and its multidenticity is a
good titrant for the determination of water hardness in water[3].
4. Why were MgCl26H2O crystals and NaOH pellets added in the preparation of the EDTA
solution?
The determination of water hardness by EDTA titration is more aptly classified as a
displacement titration. The direct analysis of Ca2+ concentration by EDTA, which will be
represented as Y in equations hereinafter, in (1) has no suitable indicator.
Ca2+ + Y 4 CaY 2

(1)

This is where the addition of MgCl26H2O makes sense. Alternatively, to analyze the
concentration of Ca2+, Mg2+ is added since the complex MgY2- forms faster than the CaY2- does.
In the course of the titration Mg2+ is released from complexation and titrating the free Mg2+
with EDTA gives a suitable endpoint for detection of the Eriochrome Black T (EBT) indicator.
In the preparation of the EDTA solution, the EDTA solid did not immediately dissolve in
water. The addition of NaOH, along with the heating, compensates for this.
Na2H2EDTA2H2O was used to prepare the EDTA solution and it dissociates into Na+, EDTA4, and H+ (bound to two of the carboxyl groups). The addition of OH- from the NaOH reduces
the H+ in the solution. By the Le Chateliers Principle, this increases the solubility of the solid
Na2H2EDTA2H2O and maintains the high pH, the importance of which will be discuss
shortly[6].
5. Why was HCl added in the preparation of the CaCO3 solution?
Calcium carbonate is a slightly soluble compound, with Ksp only equal to 4.5 10-9. The low
Ksp means that not all the solid added dissolves in the solution and the concentration that is
attained is not equal to that of the calculated[3]. This isnt favorable since the CaCO3 solution is
to be used as the standard for the determining the precise concentration of the EDTA solution.
Calcium carbonate dissociates into Ca2+ and CO32- as shown in (2).
2
CaCO3(s) Ca2+
(aq) + CO3(aq) (2)

In solution, CO32- behaves as a Brnsted-Lowry base, able to accept protons from an acid.
When HCl is added it reacts with the carbonate in the solution and shifts the equilibrium to
the right. This increases the solubility of CaCO3 and ensures that the actual molarity of the
solution is close to that of the calculated one.

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6. What are the pertinent chemical equations involved during titration? Explain how the
color of the solution turns clear blue using the stability of the complexes involved in
the titration.
Mg2+ forms the least stable EDTA complex of all the common multicharged ions in typical
water samples. This is supported by the data on the Kf for the formation of the complexes of
Mg2+ and Ca2+ with EDTA in table 1 below[3].
Table 1. Formation Constants
Cations
Mg2+
Ca2+

Kf (EDTA)
4.9108
5.01010

Kf (In)
1.0107
2.5105

See a hyphothetical complex formation reaction on (3) below.

+ + 4 (4)+
=

[ (4)+ ]
[ + ][ 4 ]

(3)
(4)

When Kf values are large, it means that more complex ions exist in comparison to the
original metal ion and ligand, as seen in (4). This translates to a measure of stability. The
larger the Kf value of a complex ion, the more stable it is[3].
+ 3 2 + 2 (5)
+ 3 2 + 2 (6)
EBT also forms complexes with the metal ions as shown in (5) and (6). As evident in their
Kf, these metal-EBT complexes are less stable than those complexes formed with EDTA as
the ligand[3].
Integrating everything: in the titration process, Ca2+ in the analyte displaces Mg2+ from
being bonded to EDTA (as was from the titrant) forming the Ca-EDTA complex, as predicted
by its higher Kf as seen in the reaction in (7). This reaction also release an equivalent amount
of Mg2+ which is then binded by the EBT (Mg-EBT having higher Kf than Ca-EBT) which
makes the solution appear red [see (5)]. When enough amount of EDTA is added during the
titration of Mg-EBT complex, EBT is liberated (Mg-EDTA has higher Kf than Mg-EBT) from
the complex and the solution then turns blue as seen in (8)[5].
2+
2+
2
2
()
+ ()
()
+ ()

(7)

4
2
2
()
+ ()
+ ()
()
+ ()

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(8)

7. What is the importance of maintaining the pH at 10 and choosing the NH3-NH4Cl as the
buffer?
Owing to the possibility of metal hydrolysis and ligand protonation reactions, formation
of a metal-ligand complex is pH dependent. At higher pH values, metal hydrolysis occurs
when either Ca2+ or Mg2+ reacts with aqueous OH- in water to form its respective metal
hydroxide. At lower pH, EDTA4- will be protonated; it is in its acid form and the electron
pairs of its carboxyl groups is not available for ligand formation[7].
How the pH will affect the complex formation will depend on the pKa of the metal and
the pKb of the ligand. For the determination of the optimal pH in which the complexometric
titration should work, alpha plots of EDTA4-, Ca2+ and Mg2+ as a function of pH. These alpha
plots show us the relative concentration of each species in the solution. Through alpha plots,
it is determined that the optimal working pH for Mg2+ and Ca2+ is 11 and 12 respectively[7].
NH3-NH4Cl was chosen as the buffer specifically because of its Ka of NH4Cl (or the Kb of
NH3, its the same logic, otherwise). Buffer solutions are generally governed by the
Henderson-Hasselbalch equation (9).
pH = pKa + log

[base]
[acid]

(9)

Since the Ka of NH4+ is 5.56 10-10, its pKa is equal to 9.26 which is quite close to pH = 10.
Even though pH 10 is not equal to the optimal pH value in which the titration of Ca2+ and Mg2+
with EDTA must occur, the effective formation constants is still large enough to allow
complete reaction during titration, even for the reduced of EDTA4- [7]. Moreover, NH3 and
NH4Cl is widely available and has reasonable cost.
8. What are the possible sources of errors and their effects on the calculated parameters?
Rationalize.
Several possible sources of errors can be found throughout the experiment. This may include,
but is not limited to the entire titrimetry itself. The complexometric titration might be done
too rapidly and thus resulted to overtitration which will cause errors in the calculated total
water hardness. Another error in titrimetry is the addition of too much EBT which makes the
endpoint not sharp and hard to detect.
Another possible source of error in the experiment are errors in solution preparation. The
NH3-NH4Cl buffer might not be well prepared and unable to maintain the optimal pH range
in which the titration must occur. The preparation of the CaCO3 solution might not be
saturated enough and the actual concentration may have disparities on the calculated
molarity. Same goes for the preparation of EDTA. Lastly, aliquots might not be measured
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properly so as the preparation of the working solutions are erroneous. Faulty calibration of
equipment, such as the analytical balance, and glassware, such as measuring pipettes and
volumetric flasks also cause errors in solution preparation.
Another possible source of error is personal uncertainties such as personal judgments, bias
and shortcomings. The indicator method is based on colors and color judgment is subjective.
This may cause variation in the data obtained from experimenter to experimenter. Another
error may be due to wrong interpretation of meniscus. This may affect the accuracy of the
calculated total hardness since it is also dependent on the accuracy of the titrimetric
procedure.

REFERENCES
[1] US Geological Survey. (2015). The USGS Water Science School: Water Hardness. Retrieved
from http://water.usgs.gov/edu/hardness.html, on March 19, 2016
[2] Analytical Chemistry Group. (2013). Analytical Chemistry Lab Manual. Quezon City:
University of the Philippines Institute of Chemistry
[3] Skoog, D., West, D., Holler, F., Crouch, S. (2014). Fundamentals of Analytical Chemistry. (9th
Edition). (p. 437-438). California: Cengage Learning
[4] Kiruthiga,

B.

SRM

University:

Complexometric

Titration.

Retrieved

from

http://www.srmuniv.ac.in/sites/default/files/downloads/Complexometric_Titration.pdf,
on March 20, 2016
[5] Harvey, D. (2000). Modern analytical chemistry. Texas: McGraw-Hill
[6] Quantitative Analysis Laboratory. (n.d.) New Mexico Tech: A Volumetric Analysis
(Complexometric

Titration)

of

Calcium

in

Hard

Water.

Retrieved

from

http://infohost.nmt.edu/~jaltig/VolAnalWater.pdf, on February 21, 2016

[7] Tissue, B. (2013). Basics of Analytical Chemisty and Chemical Equilibria. New Jersey: John
Wiley and Sons, Inc.

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