QUANTITATIVE DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA

TITRATION
Z.C. HACHERO
DEPARTMENT OF MINING, METALLURGICAL AND MATERIALS ENGINEERING
COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 30, 2015
INSTRUCTORS NAME: SEARLE AICHELLE DUAY

1. Discuss
the
concept
of
complexometric
titration
and
water
hardness
(why
is
it
expressed as ppm CaCO3?)
Complexometric titration is 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. [1]
Water hardness is an expression for
the sum of the calcium and
magnesium cation concentration in
a water sample. These cations form
insoluble salts with a reagent in
soap, decreasing its cleaning
effectiveness. The standard way to
express water hardness is in ppm
CaCO3 which has the formula
weight of 100.1 g/mole. [3]
2. Discuss the use of EDTA as
complexing agent and titrant.
EDTA is a hexadentate ligand. The
EDTA molecule has six potential
sites for bonding a metal ion: the
four carboxyl groups and the two
amino groups, each of the latter

with an unshared pair of electrons.

It has high formation constant
values for its complexes in
complexation
reactions
and
titration. Solutions of EDTA are
particularly valuable as titrants
because the EDTA combines with
metal ions in a 1:1 ratio regardless
of the charge on the cation. [1]
3.
4. Discuss the use of EBT as
indicator; significance of adding
MgCl26H2O crystals to the titrant.
Eriochrome Black T, or EBT, has a
pH range of 6.3 to 11.5, and
exhibits the following behavior:
with red as its acidic color and
orange its basic color. Because of
this, it becomes useful in
titrations involving more than 2
dozens of metal ions which form
red complexes at pH 7-11 like
those
measured
in
this
2+
2+
experiment (Mg and Ca ). It is
important that the pH is kept
above
7
so
that
HIn2predominates and reacts with the

cations accordingly to form the

necessary wine red and blue
colored solution. [4]
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, Mg2+
from EDTA solution can easily
displace Ca2+ions and form MgEDTA complex.
5.
6. Discuss the pertinent chemical
equations
involved
during
titration.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Discuss the relationship of
pH and feasibility of titration
using EDTA method for cation
analysis; the minimum pH values
for cations in EDTA titration.
EDTA is a remarkable reagent not
only because it forms chelates with
all cations but also because most
of these chelates are sufficiently
stable for titrations.. Prior to the
equivalence point, the cation is in
excess, and its concentration can
be found from the reaction
stoichiometry. At the equivalence
point and in the postequivalencepoint region, however, the
conditional formation constant of
the complex must be used to

calculate the cation concentration.

[1]

18.
Discuss
the
other
applications
of
EDTA
complexation.
The complexation of EDTA can also
be applied in the field of medicine.
It is used specifically to detoxify
patients
poisoned
with
lead,
mercury or arsenic which are
converted by EDTA into a form that
can be excreted by the body
without interacting first with the
body. In the field of analytical
chemistry, it is used to bond with
metal cations to prevent the
interference of these to the desired
reaction. [1]
19.
20.
Discuss
the
difference
between experimental and actual
value.
The theoretical value of ppm
CaCO3 is 192.5 ppm while the
experimental value obtained was
21.
22.
Discuss the rationale behind
performing the analysis of Ca and
Mg at pH 10.
EDTA is a weak acid, so for this
experiment, the pH was buffered at
10 with NH3-NH4Cl to produce the
aimed amount of Y4-. The pH value
of 10 is enough to allow the specie
Y4- to predominate and react to
yield MgY2-,HIn2-(blue) and H+ in the
final reaction. At higher pH levels,
excess hydroxide concentrations
can cause the formation of metal
hydroxide precipitate. The Ca-EDTA
complex begins to form at ph 8,
however, it is only at pH 10 where
Mg-ESTA complex forms; which is

why
the
solution
must
be
[1]
maintained at pH 10.
23.
Discuss the effect of using
too much buffer in the analysis of
Ca and Mg using EDTA titration.
At higher pH levels, excess
hydroxide
concentrations
can
cause the formation of metal
hydroxide precipitate.
24.
25.
Discuss
the
correlation
between stability of Mg-EDTA
complex, Ca-EDTA complex, MgInand CaIn- and their corresponding
Kf values.
The stability of the complex are
listed as follows: Ca-EDTA> MgEDTA> MgIN->CaIn-. The higher
the Kf value, the more stable the
complex is. [1]
26.
27.
Discuss the rationale behind
adding NaOH to the EDTA solution
if the sodium-EDTA crystals do not
dissolve.
CaIn complex is not very stable and
will be easily affected when EDTA is
added, so by adding Mg ions, the
endpoint will become sharp and
will not come too early in the
titration.
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. [4]
28.
29.
Discuss the possible sources
of errors and their effect on
calculated parameters.
Overtitration of the sample analysis
is a 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 for
overtitration. The indicator used
must be suitable for the type of
titration, which in this experiment
we used EBT since it selectively
binds with the Mg2+ 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.
30.
31.
REFERENCES:
32. [1] Skoog, D., West, D., Holler, F.J., Crouch,
S., Chen, S. Introduction to Analytical
Chemistry 8th ed.
33.
Cengage Learning, Singapore. 2012.
34.
35. [2] Harris, D. Quantitative Chemical
Analysis 8th ed. W.H. Freeman and Company,
New York. 2010.
36.
37.
[3] EDTA determination of
water hardness
http://www.titrations.info/EDTA-titrationwater-hardness. (Accessed October 5, 2015)
38.
39.
[4] Experiment 3: EDTA
Determination of Total Water Hardness
http://web.utk.edu/~kcook/319S02/exp3m.pdf.
(Accessed October 5, 2015)
40.
41.
[5] A Volumetric Analysis
(Complexometric Titration) of Calcium in Hard
Water
http://infohost.nmt.edu/~jaltig/VolAnalWater.pd
f (Accessed October 5, 2015)
42.