COMPLEXIMETRIC DETERMINATION OF CACIUM IN WATER SAMPLES

DAVID, Frances Erika H.1, DEVILLES, Jallyssa Jannel J.2, EBON, Alyssa Mae P.3, ERODIAS, Claro Ven T.4
1
Department of Biology, College of Science, University of the Philippines Baguio
August 14, 2013
ABSTRACT
The experiment aimed for the students to get acquainted with chelating agents; strengthen technical
skills involved in titrimetric analyses; learn and apply the concept of titer; and to study the physicchemical characteristics of water. The experiment was divided into two parts wherein in the first part,
the EDTA solution was prepared and standardized by the titration of a prepared Calcium chloride
solution using the EDTA solution; the second part was the analysis of the water sample win which
Calcium content was analyzed by obtaining a water sample where a buffer solution and an indicator
was added and titrated with the standardized EDTA solution. The water sample used was a
commercial mineral bottled water. Its mineral contents were determined by titrating it in the EDTA
solution. And computed for the hardness of the water.

Introduction
In a complexometric titration, a
solution containing the free metal ion of
interest is titrated with a solution of chelating
agent until all of the metal ions are completely
complexed. The endpoint is usually measured
with an indicator ligand that forms a colored
complex with the free metal ion.
The most important chelating agent in
analytical
chemistry
is
ethelyenediaminetetraacetic acid (EDTA). The
tetrabasic form of this acid forms complexes
with virtually all metal ions. EDTA is a
hexadentate ligand; each of the acid oxygens
and each of the amine nitrogens can donate
one electron pair. The metal ion is usually held
in a one-to-one complex with EDTA. The
complexes have four or five
5-membered
rings, contributing significantly to their
stability. Unfortunately, EDTA cannot be easily
used as a primary standard. It is available in
several days to obtain the precise composition
of the dihydrate. In any case, standardization
of EDTA titrant against a solution of the metal
ion to be determined helps to eliminate any
errors in endpoint selection.

COOH

HOOC
N
HOOC

N
COOH

Ethylenediaminetetraacetic acid (EDTA)

pKa-2 = 0.0
pKa-1 = 1.5
pKa1 = 2.0
This experiment shows the way how to get
acquainted with chelating agents and also to
strengthen technical skills involved in
titrimetric analyses, to learn and apply the
concept of titer and to study one physicochemical characteristic of water.
Results
A. Preparation and Standardiztion of
EDTA solution
It took 25 drops of 1:1 HCl to clear soln.
Table 1 Calcium Carbonate Titrations
Molarity
Initial
Final
Trial
of EDTA
volume
volume
solution
1
50
24.9
0.00843
2
50
23.7
0.00861
3
50
24.1
0.00871

Average

0.00858

B. Analysis of Water Samples

Table 2
Initial
Tria
volum
l
e (mL)

Final
volum
e (mL)

Ca 2+
Concentrati
on

1
2
3

25.5
27.2
24

0.00219 M
0.00233 M
0.00206 M

50
50
50

Total
Hardne
ss of
Water
(ppm)
219
233
206

Discussions
Three tests were executed in order
to determine how much Calcium
Carbonate solution was spent in every
trial. In Trial 1, with the initial volume of
50 ml, 25.1 ml Calcium Carbonate solution
was put to use. Accordingly, its final
volume was 24.9 ml making it the lowest
volume of Calcium Carbonate used with
regards to the three trials performed.
Trial 2 with its initial volume of 50 ml
yielded to a 23.7 ml final volume. So, only
26.3 ml Calcium Carbonate solution was
depleted. As for the terminal trial, again
50 ml as the initial volume, which resulted
to 24.1 ml final volume. In the latter, 25.9
ml Calcium Carbonate was used. Alongside
its high volume amount utilization, the
pure blue color indicator was acquired
here for which the process aborts. All of
which resulted to the said blue color. The
Molarity of the EDTA solution was
calculated. For Trial 1, a Molarity of
0.00843 M was obtained, the lowest of the
three. For Trial 2 and Trial 3, 0.00861 M
and 0.00871 M was reckoned respectively.

In analyzing the water sample

obtained from drinking water, the concept
of titer was operated. Three trial runs
were executed in this section of the
experiment. From the collected drinking
water, given their initial volume of 50 ml
for Trial 1, only 24.5 ml usage of EDTA
solution was computed, with a final
volume of 25.5 ml. Performing Trial 2,
22.8 ml was consumed, a final volume of
27.2 ml was calculated. Finally, with a 50
ml initial volume, 26 ml was used up
resulting to a final volume of 24 ml.
Likewise, a pure blue indicator was
obtained for which the process aborts. All
of the trial runs completed resulted to the
above said final solution. None of the three
runs terminated as overtitrated. In
addition, the concentration total hardness
of water as ppm of Ca2+ was known. A
0.00219 M Ca2+ concentration, with a 219
CaCO3 ppm was obtained in Trial 1. For
Trial 2, a Ca2+ concentration of 0.00233 M
and a 233 CaCO3 ppm. Lastly, the Ca2+
concentration of Trial 3 was 0.00206 M
and a CaCO3 ppm of 206, the lowest of the
three.
Conclusion
The experiment tests the hardness of
the water sample. It is said that the water is
considered hard if it contains Ca+2, Mg+2,
and/or Fe+3 ions. And the mineral water used
contains Ca+2 and Mg+2 ,Viva Mineral water
which is commercially sold bottled water. This
experiment shows how much minerals are
contained in the water sample. Because
certain minerals have effect on human
nutrition especially those who have
intolerance with such minerals.

M CaCO3= 0.21g CaCO3

(

References
[1]
Giron,
Ofelia.
ANALYTICAL
CHEMISTRY (chem26.1) Laboratory Manual.
Philippines: University of the Philippines
Baguio
[2]
Skoog, West, Holler & Crouch.
(2010).
Fundamentals of Analytical
Chemistry. USA, Cengage Learning
[3]
The Complexometric Titration.
Retrieved
August
13,
2013,
from
http://www.nmt.edu/~fletcher/labs/lab03/La
b03_EDTA_Complex_Titration.html
Retrieved August 13, 2013, from
http://homepages.ius.edu/DSPURLOC/c121/w
eek13.htm
Retrieved August 13, 2013, from
http://answers.yahoo.com/question/index?qi
d=20080303075816AAAGr5n

)(

M CaCO3= 0.008393 M
EDTA Solution
Since 25 mL aliquot was taken,
25 mL (

)= moles CaCO3 in

aliquot
25 mL (
)= 0.00021
moles CaCO3 in aliquot
MEDTA= moles CaCO3 in aliquot * 1000ml
Final Volume of EDTA
Trial 1:
)

MEDTA=(
MEDTA= 0.00843 M
Trial 2:
MEDTA=(
MEDTA= 0.00861M
Trial 3:

MEDTA=(
MEDTA= 0.00871M

[4]

Brown, LeMay, Bursten. 2002.

CHEMISTRY, The Central Science, 8th ed.
Philippines: Pearson Education Asia Pte. Ltd.

Calculations for the Total Hardness of Water:

Find the concentration of Ca2+:
(

Harvey, David. 2000. Modern

Analytical Chemistry. United States of
America: The McGraw-Hill Companies, Inc.
[5]

http://www.csudh.edu/oliver/che23
0/labmanual/calcium.htm
[6]

http://www.lasalle.edu/~prushan/W
ater-lab7.pdf

)(

M Ca2+= (

[5]

Trial 1:

)(

)(

)(

M Ca2+= (
M Ca2+= 0.00219 M
Trial 2:
M Ca2+= (
M Ca2+= 0.00233 M
Trial 3:
M Ca2+= (
M Ca2+= 0.00206 M

Appendix

To Compute for Total Hardness:

ppm CaCO3=

Calculations for Molarity:

CaCO3 Titer:

M CaCO3= g CaCO3 (

)(

Trial 1:

)(

)(

)(

)(

)
)

)(

ppm CaCO3=
(

)(

)(
(

)(

= 219
Trial 2:
ppm CaCO3=
(

)(
)(

AVERAGE DEVIATION:

)(

)(
(

)(

)(

)(

)(

)(

= 233
Tria 3:
(

76.7
3 = 25.6

ppm CaCO3=
)(

)(

)(

25.6 25.5 = 0.1

25.6 27.2 = 1.6
25.6 - 24 = 1.6
3.3
3.3
3 = 1.1

= 206
STANDARD DEVIATION
Analysis of Water Sample
S2 = (0.1)2 + (1.6)2 + (1.6)2
3-1
= 0.01 + 2.56 + 2.56
2
= 2.57
Red wine colored Solution (Initial)

Pure Blue Solution (Final)

Answers to Questions
1. Determine the precision of your
analyses using standard deviation and
relative range in parts per thousand.

2. Explain the advantage / disadvantage

of using Eriochrome Black T over
Calgamite as indicator.
The color of the Eriochrome
Black T complexes with Mg2+ in the
solution and it forms red color. Then,
the metal is displaced from the
solution and complexes with EDTA
which causes a color change from red
to blue. And by titration, the color
change from red to blue. And it cannot
be cannot be used to indicate the
titration of Ca2+ alone because it forms
too weak that thus not gives a distinct
end point.

MEAN :
25.5 ml
27.2 ml
24 ml
76.7

3. A 20.0 ml volume of EDTA titrant is

required to titrate 25.0 ml of standard
0.0100 M CaCO3. A 75.0 ml sample
solution of chalk requires 30.0 ml of
this EDTA titrant in the analysis of

calcium content. Calculate both the

ppm Ca and ppm CaCO3 in the sample
solution of chalk. If the 75.0 ml sample
solution is withdrawn from a stock
solution of 500.0 ml which contains
2.1345 g of chalk, what is the % Ca in
the solid sample?
EDTA = CaCO3
20ml x M = 25ml x 0.0100
M = 0.0125 M EDTA
ppm of Ca
= M EDTAxV EDTAxMW Ca/volsample
=0.0125Mx30.0mlx(40mg/mmol)/ 75.0ml
= 0.2 ppm Ca
ppm CaCO3
=M EDTAxV EDTAxMW Ca/volsample
=0.0125Mx30.0mlx(100mg/mmol)/75.0ml
= 0.5 ppm CaCO3

mass of Ca
=mass of CaCO3 x (MW Ca/ MW CaCO3)
= 2.1345g x (40 g/mol)/(100g/mol)
= 0.8538 g
% Ca = (mass of Ca/ mass of CaCO3) x 100
=(0.8538 g/ 2.1345g) x 100
=40% Ca in the sample

4. The titration of a 50.0 ml water sample

for total hardness required 4.08 ml of
0.0100 M EDTA. Calculate the hardness
of the water as ppm CaCO3.
ppm CaCO3=M EDTAxV EDTAxMW CaCO3/vol sample
= 0.0100M x 4.08ml x (100mg/mmol)/ 50.0ml
= 0.0816 ppm CaCO3