QUANTITATIVE DETERMINATION OF TOTAL HARDNESS IN

DRINKING WATER BY COMPLEXOMETRIC EDTA TITRATION

______________________________________________________________________________________________________________________________

1. What is the significance of determining

the hardness of water?

Water that we use may contain

metal cations. Due to the presence of
the cations, it could affect the quality of
water. The cations present such as
calcium and magnesium may react
with its surrounding, thus forming
precipitates which may affect objects
and equipment wherein the water
runs through. Also, hard water may
have may affect industrial functions,
such as for food production. The
harder the water is the more it is
possible that precipitates would form.
To avoid this happening either in the
household or in an industrial use it is
better to check the water hardness and
adjust according to findings.[1]
2. Why do we express water in hardness as
ppm CaCO3?

The hardness water is due to

the cations present. It is measured in
terms of the concentration of CaCO3,
particularly in ppm but it does not
mean that Ca+ is the only ion present,
other cations are already accounted
when we say ppm CaCO3.

3. Discuss the use of EDTA as a complexing

agent and titrant.

EDTA as a complexing agent

forms chelates with all cations except
akali metal ions. Also, the chelates
formed are stable enough for

titrations. A factor behind this is

because EDTA is hexadentate, there
are relatively many complexing sites,
thus resulting to a cage-like structure.
This structure helps cations to be
separated from solvent molecules
deeming it stable.
EDTA as titrant react with
metal ions in a 1:1 ratio. The charge
does not matter. Due to this EDTA as
titrant makes titrant calculations more
convenient. [1]
4. Discuss the use of EBT as indicator. Why
do we add MgCl26H2O crystals to the
titrant?

Eriochrome Black T (EBT) a

typial metal ion indicator, also it can
also be used as acid/base indicator. In
the experiment it is used as a metal ion
indicator. Ca-EBT complexes are not
stable, thus in the experiment Mg-EBT
complex, denoted as MgIn- (wine-red),
is present. When titrated with EDTA,
the Mg-EBT complex breaks up and to
form the Mg-EDTA complex. The EBT
then becomes, HIn2(blue)-. The
titration depends on the color change
of the indicator.
MgCl2 crystals are added to the
EDTA titrantso that Mg+ ions are
introduced because CaIn- is less stable
that MgIn-. With that the Ca+ becomes
completely free, and the analyte turns
int o wine red. So Basically, Mg was
added because Ca-EBT is not a good
indicator.

5. Why do we add NaOH to the EDTA

solution if the disodium EDTA crystals do
not dissolve?

EDTA crystals do not dissolve

easily because it tetraprotic. In order
for the EDTA to dissolve further the pH
must be high so that the protons will
neutralize. When the pH becomes
more basic, the EDTA becomes more
unprotonated, thus more soluble.
6. Outline and explain the pertinent
chemical equations involved during
titrations.

The important chemical equations in

the experiment are the ff:

[1] 2H2Y2-+Ca2++Mg2+ CaY2-+MgY2-+4H[2]

H2Y2- + MgIn- HIn2- + MgY2- + H+
The first equation shows that
when the EDTA titrant is added the
free Ca2+ and Mg2+ reacts with the
EDTA for the respective EDTA
complex. When the free cations are
already tirated. The MgIn- complex
will then react with the EDTA titrant.
Due to the Mg-EDTA being more stable
than the Mg-EBT, the formation of the
EDTA complex is more preferred. Thus
when all the Mg-EBT complex is
titrated the EBT becomes HIn2-, which
makes the analyte change color from
wine red to blue.

7. Discuss the relationship of pH and

feasibility of titration of cations using
EDTA.

EDTA basically is a tetraprotic

acid. Due to this, EDTA at lower pH
comes takes the fully protonated form.
As the pH gets higher the EDTA slowly
become unprotonated. Specifically at
ph range 3-10 the diprotic and

monoprotic form of it dominates.

When pH is greater than 10 the
unprotonized form is dominant. The
triprotic form is not usually there
because the formation of it is less
probable. With this it can be said that
cations with charge 2-3+ are titrated
better at pH 3-10. For 4+ it is at pH
greater than 10, lastly for 1+ cations
EDTA titration, it is more difficult. [1]
8. Enumerate some other applications of
EDTA complexation(besides
complexometric titration).

Other than doing volumetric

analysis on an EDTA complexation
other applications are Potentiometric
and Spectrophotometric methods. In
Potentiometric method, potential are
used to determine EDTA titration
endpoints. In spectrophotometric
methods, UV/visible light absorption
is measure to determine the endpoint
of titration.
9. Why do we perform the analysis of Ca
and Mg at pH 10?

The formation of Ca and MgEDTA occurs at high pH. Particularly,

Ca-EDTA is at around pH=7.3, and on
the other hand Mg-EDTA is at around
pH=10. Therefore the minimum
possible pH to achieve complexation is
at pH=10. In addition to that EDTA as a
tetraprotonic acid is amphoteric in its
other forms, to avoid the tendency of
EDTA to change properties drastically
it better to maintain the pH high.[2]
10. What is the effect, if any, of using too
much buffer in this analysis?

The buffers purpose is to

regulate the possibility of a sudden
change in pH. The complex formation
used in the experiment are mostly pH
dependent. It is a right thing to use a
2

buffer in this case. If too much buffer is

used pH changes will be very much
resistant. Due to this there is a
possibility that pH would remain very
much constant thus affecting other
components in the experiment that
may need lower pH to thrive.
11. What is the purpose of auxiliary
complexing agents? What reagent, if any,
served as auxiliary complexing agent in
this titration? Discuss.

An auxiliary complexing agent

purpose is bind to metal strongly to
avoid the formation of metal
hydroxide especially in high pH. It will
also be readily able to give away its
metal when EDTA comes. In the
experiment, the agent that acted as an
auxiliary complexing agent is the EBT
complex. It acted as the complexing
agent because it reacted with Mg2+, but
when EDTA was started to be titrated,
the formation of Mg-EDTA complex
was preferred.[3]
12. Correlate the stability of the Mg-EDTA,
Ca-EDTA, Mg-EBT, and Ca-EBT complexes
with the values of the formation constant.
Ca-EDTA Kf = 5.0 x 1010
Mg-EDTA Kf = 4.9 x 108
Ca-EBT
Kf = 2.5 x 105
Mg-EBT Kf = 1.0 x 107
Base on the Kf values above the
extent of formation is ranked as CaEDTA > Mg-EDTA > Mg-EBT > Ca-EBT.
This means that Ca-EDTA would be the
most stable. Ca-EDTA is preferred than
Mg-EDTA. When EDTA is introduced
to a Mg-EBT complex, it become MgEDTA because this is more preferred.
Lastly, Ca-EBT would be the most
unstable become it will most likely not
form among the four complexes.

13. Discuss the difference between the

experimental value of water hardness and
the stated value of water hardness on the
label of your water sample.

The water hardness on the

label of the water sample is at 58.05
ppm CaCO3. On the other hand the
experimental value was calculated as
41.43 ppm CaCO3. The experimental
titrated cations is lower than what is
stated in the water sample. This means
that the cations present in the water
sample is not in accordance to what is
stated in the water sample, relative to
what was measured in the experiment.
The stated hardness by the company is
assumedly measured with higher
precision and accurancy. Therefore,
the experiment that was done had
many errors.
14. Enumerate and discuss some possible
sources of error. Determine their effect on
your calculated parameters.

Besides the normal equipment

and human error that occurs there are
also other errors that may affect
calculated parameters.
An example of this error is the
parallax error. Reading burettes
graduation, might be a cause of error if
not done right, specifically reading it
not in an eye level.
Another error is because of
carbonate error. Due to present
carbonates in solution, it may react
with the cations present. Due to the
carbonate present titration will be
more than what is really needed.[4]

REFERENCES

[1] Skoog, D. A., West D. M. Holler F. J.,

Crouch S. R., Fundamentals of Analytical
Chemistry 8th ed. Thomson Learning Asia.
3

Singapore, 2004. pg 338, 461, 476, 459

[2] Khopka, S.M. Basic Concepts of Analytical
Chemistry. New Age Ineternationals, 2004. Pg
63-76.
[3] Harris, D. Quantitative Chemical Analysis
8th edition.
[4]Determination of water total hardness by
complexometric titration.
http://www.titrations.info/EDTA-titrationwater-hardness. Web. (accessed 15 Mar, 2016)