QUANTITATIVE DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA

TITRATION
R.J. TORING1 AND R.J.H. BAGUINON2
1
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
2
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 24,
INSTRUCTORS NAME: MR. AMADO

2015
LUIS ORDEN

1. The concept of complexometric

titration and water hardness (why
is it expressed as ppm CaCO3?).
In a complexometric titration, a
metal ion reacts with a suitable ligand
to produce a complex. Just like other
titration, the equivalence point can
then be determined by an indicator.
And, water hardness was originally a
measure of the waters ability to
precipitate soap. But since calcium
and magnesium are the main cause of
this, water hardness can now be
defined as the amount of calcium and
magnesium present which can be
expressed into ppm of calcium
carbonate. In this experiment, EDTA

(a ligand) was allowed to react with

the Ca2+ and Mg2+ ions (metal ions)
present in the water during the
titration
process.
The
water
hardness will then be measured as
the ppm of calcium carbonate. [1][2][3]
2. The use of EDTA as complexing
agent and titrant.
The ethylenediaminetetraacetic
acid (EDTA) can react with metal ions
in a 1:1 ratio to form very stable
complexes at high pH. For this
experiment, EDTA would readily react
with Ca2+ and Mg2+ in a 1:1 ratio to

form complexes at about pH 10,

making it a good complexing agent

and titrant. These behavior is due
to its hexadentate structure which
allows it to have six donor atoms
and thus six sites of attachment for
the metal ions, making the formed
complexes to be more stable. [1][2][3]
3. The use of EBT as indicator;
significance of adding MgCl26H2O
crystals to the titrant.
The indicator used in this
experiment is the Eriochrome Black T
(EBT) gives a good endpoint. EBT
forms a colored metal complex at the
start which gives the color of wine red.
At the equivalence point, the metal
ions from the metal complex formed
by EBT were removed by EDTA
through chelation, making the color
turn into blue. This is possible since
EDTA binds more strongly to the metal
ions than EBT. However, EBT indicator
does not react well with Ca 2+ ions
because the complex MgIn- is not that
strong and wouldnt give much color.
To correct that, MgCl26H2O crystals
were added to give a sharper
endpoint. [2][4]
4.
The
equations
titration.

pertinent
involved

chemical
during

Initially, EBT reacts with the

Mg2+ ions by the equation:
Mg2+ + HIn2- MgIn- + H+
(blue) (wine red)
When EDTA is added, EDTA
reacts with the metal ions to form
complexes removing the metal ions
in the EBT complex shown by the
equations:
Ca2+ + H2Y2- CaY2- + 2H+
Ca2+ + MgY2 CaY2- + Mg2+
Mg2+ + HIn2- MgIn- + H+
MgIn- + H2Y2- MgY2- + 2H+
Combining the equations, it would
yield the equations that occurs at the
endpoint:
2H2Y2- + Ca2+ + Mg2+ CaY2- + MgY2- +
4H+
2H2Y + MgIn MgY2- + HIn2- + H+
5. The relationship of pH and
feasibility of titration using EDTA
method for cation analysis; the
minimum pH values for cations in
EDTA titration.
At lower pH, EDTA has its
complete 4 protons and exist as H 4Y,
decreasing the number of bonding
possible to the metal ions. While at
higher pH (>10), EDTA is deprotonated
and exists as Y4-, giving more sites of
attachment for the metal ions. With
more sites of attachment, the stable
the formed complex will be. The
minimum pH values to form a complex
for Ca2+ and Mg2+ with EDTA is 7.3 and
10, respectively. [1]
6. Other applications of EDTA
complexation.
Other uses for EDTA includes
industrial, and medicinal and healthsciences uses. For industrial uses,
EDTA is helpful in making cosmetic
products resistant to air molecules, as
purifying agent and preservative,

soften water for more efficient

cleansing
,
preventing
the
discoloration of dyed fabrics, and
reducing reactivity of metal. For
medicinal and health-sciences uses,
EDTA can be used to treat lead,
mercury, chromium, cobalt, zinc (and
some
other)
poisoning
through
chelation therapy. It can also help to
clear bloodstream from unused ions. [5]
7.
Difference
between
experimental and actual value.
In the experiment, the sample
water isnt boiled which makes it
possible for some carbon dioxide to
dissolve. These carbon dioxide may
interfere in the test giving some
difference of the experimental to the
actual value.
8.
The
rationale
behind
performing the analysis of Ca and
Mg at pH 10.
As mentioned in the previous
answer (number 5), EDTA has more
sites for attachment at higher pH,
making the complex formed stable.
With more stable complexes, the
better the result of the experiment is.
Also, the minimum required pH for
Mg2+ to form a complex with EDTA is at
pH 10. Thus, at least pH 10 is required
for the complex to form. [1]
9. The effect of using too much
buffer in the analysis of Ca and
Mg using EDTA titration.
With too much buffer, the
solution would become too basic. With
that, pH changes through titration
would hardly affect the solution. This
would result to a less sharp endpoint.
[1]

10.
The
correlation
between
stability of Mg-EDTA complex, CaEDTA complex, MgIn- and CaInand their corresponding Kf values.

The
higher
the
formation
constant of a complex, Kf, the more
favored the formation that complex
would be thus, the more stable it
becomes.
Since
Ca-EDTA
(Kf
=5.0x1010) has higher Kf than Mg-EDTA
(Kf =4.9x108), Ca-EDTA is more stable
than Mg-EDTA. Also, since MgIn- (K f
=1.0x107) has higher Kf than CaIn- (Kf
=2.5x105), MgIn- is more stable than
CaIn-. Additionally, since the EDTA
complexes have relatively higher Kf
values than the EBT complexes, thus,
the EDTA complexes are more stable
than the EBT complexes. [1][4]
11. The rationale behind adding
NaOH to the EDTA solution if the
sodium-EDTA
crystals
do
not
dissolve.
The dissolution of sodium-EDTA
crystals is normally very slow and is
more favorable at higher pH ( 8). By
adding NaOH, the pH becomes higher
and makes the dissolution of sodiumEDTA crystals more favorable. Thus,
the crystals would be dissolved faster.
[1]

12. Possible sources of errors and

their
effect
on
calculated
parameters.
Possible
sources
of
errors
include too much addition of EBT, too
much addition of buffer, too fast
addition
of
HCl
during
CaCO3
dissolution, and overtitration. Too
much addition of EBT indicator and
buffer can lead to a less sharp
endpoint, making inaccurate volume

readings. Too fast addition of HCl

during CaCO3 dissolution can make
excess formation of CO2 leading to a
loss of material. Lastly, overtitration
can also make inaccurate data. [1]
REFERENCES
[1] Skoog, D.A.; West, D.M.; Holler, F.J.;
Crouch,
S.R.
Fundamentals
of
Analytical
Chemistry,
9th
ed.;
California:
Brooks/Cole
Cengage
Learning, 2014.
[2]
Winona
State
University.
Determination of the Hardness of
Natural
Waters.
http://course1.winona.edu/mengen/Ch
emistry%20320/Lab/Hardness%20of
%20Water.pdf (accessed September
30, 2015)
[3] The University of Tennessee,
Knoxville.
Experiment
3:
EDTA
Determination
of
Total
Water
Hardness.
http://web.utk.edu/~kcook/319S02/ex
p3m.pdf (accessed September 30,
2015)
[4] The University of Texas at Austin.
Coordination
Chemistry
.
http://www.geo.utexas.edu/courses/37
6m/coord_chem.htm
(accessed
September 30, 2015)
[5] UC Davis ChemWiki. EDTA.
http://chemwiki.ucdavis.edu/Inorganic_
Chemistry/Coordination_Chemistry/Lig
ands/EDTA (accessed September 30,
2015)