Determination of Calcium by Complexometric Titration

Yuriann Angelica Pempengco, Alexandra Portillo and Alpha Divina Nolasco1

Chemistry Department, College of Humanities and Sciences, De La Salle Health Sciences
Institute, Dasmarinas Cavite
DATE PERFORMED: September 29, 2016
DATE SUBMITTED: October 25, 2016

ABSTRACT
Determining the calcium content through complexometric titration is the goal of this experiment. This
will help understand the covalent coordinating bonding based on experiment in titration. The main
procedure of this experiment is to titrate CaCO3 using EDTA solution at pH 10 with EBT as the indicator
which was performed to standardized and to determine water hardness. The end point is from red to blue
after being titrated resulting to complete reaction of metal ion and EDTA and its excess. The water
hardness is being determined based on the metal ion content of the water sample using the EDTA solution
as titrant.
____________________________________________________________________________________
Keywords: covalent coordinating bond, complexometric titration, calcium, EBT, end point

INTRODUCTION
Complexometric titration is a chemical technique using the formation of a colored complex to
signifies the end of titration. These bonds are called covalent coordinating bonds where in there is the
complexation of a chelating agent with metal. The most common reagent used is EDTA where it is a
hexadentate ligand. Among the six protons, only Y -4 has 1:1 mole ratio with metals and the forms stable
complexes metals so a pH 10 buffer is needed to add to adjust the pH. The The Eriochrome black T is an
indicator which is metallochromic; there are indicators that are complexing agents that color change from
blue to red when reacted with metals.
The combined concentration of calcium and magnesium determines the water hardness of a
sample. Most of the water hardness is found in lathering soap and the formation of a scum in a bathtub
because these ions are insoluble salts causing precipitation of soap scum.

+
2+ H
2+ HIn
2+ HEBT
MgEDTA
2+ MgEBT
H 2 EDTA

OBJECTIVES
The main objective of this experiment is to understand the concept about complexometric titration by
titrating CaCO3 using EDTA as the titrant. This also aims to determine the water hardness of the sample in
ppm depending on the amount of CaCO3 content. The purpose of this experiment is to master the
calculation of complexometric based on the data gathered.

METHODOLOGY
A. Preparation of EDTA solution
Using an analytical balance, an EDTA disodium dihydrate (0.9610g) and MgCl 2 6H2O (0.0517g) were
weighed and were transferred into volumetric flask. EDTA disodium dihydrate was dissolved into
deionized water (150ml) and MgCl2 6H2O was dissolved in beaker first using deionized water (20ml). The
solution was diluted to mark and was transferred into a labeled plastic bottle.

B. Standardization of EDTA solution

On a weighing paper, standard calcium carbonate was measured (0.012-0.015g) and was transferred into
an erlenmeyer flask with deionized water (20ml). There was an addition of 6M HCl (2ml) by the used of
serological pipette, was shaken and was added with deionized water (80ml). The solution was boiled
gently for 2 minutes. After being cooled down, methyl red indicator (3 drops), 6M NaOH (drops until
yellow), pH 10 buffer (2 ml), and EBT indicator (3 drops) were added on the solution. The CaCO 3 was
titrated by the used of standard EDTA solution until color changed from red to blue. This was perfromed
in triplicates.

C. Determination of Water Hardness

Water sample (100ml) was transferred into an erlenmeyer flask and concentrated HCl (3 drops) was
added into the solution. The solution was boiled gently for 2 minutes. After being cooled down the steps
were repeated from B.

RESULTS AND DISCUSSIONS

Table 1: Preparation of EDTA

Mass of dry of EDTA disodium dihydrate

Moles of EDTA
Mass of dry Magnesium chloride hexahydrate
Volume of solution
Molarity of EDTA

0.9610 g EDTA x

0.9610g
2.58x10-3 mol
0.0517g
0.25L
0.0103M

1 mol EDTA
=2.58 x 103 mol EDTA
372.24 g EDTA

The magnesium chloride hexahydrate is added on the standard solution to occur a back titration because
once EDTA solution is added to the analyte the excess EDTA added will react to Mg 2+and then start
complexing with EBT indicator resulting to change in color.

Table 2: Standardization of EDTA solution

TRIAL 1
0.0360
3.60x10-4
3.60x10-4
0.00
42.0
0.0420
8.55x10-3

Mass of standard CaCO3 (g)

Moles of CaCO3 (mol)
Moles EDTA (mol)
Vo reading of EDTA (mL)
Vf reading of EDTA (mL)
Volume of EDTA used (L)
Molarity of EDTA
Average molarity of EDTA
Trial 1:

TRIAL 2
0.0186
1.86x10-4
1.86x10-4
0.00
20.0
0.0200
9.29x10-3
9.17x10-3M

TRIAL 3
0.0121
1.21x10-4
1.21x10-4
20.0
32.5
0.0125
9.67x10-3

1 mol CaCO3
100.09 g CaCO3
4
=8.54 x 10 M EDTA
(42 mL 1000 mL)

0.036 g CaCO3 x

8.55 x 10 + 9.29 x 10 +9.67 x 10

=9.17 x 103 M EDTA
3
*Same computation for trial 2 and 3*
Since EDTA and metals always usually have 1:1 mole ratio the moles of EDTA and CaCO 3 is the same
moles when reaction occurs. When there is no EDTA added yet the reaction is between Ca-EBT which
has a weak bond so once EDTA is added Ca2+ will bond to EDTA and the excess EDTA will interact with
the Mg2+ causess the color change from red to blue. The data shows that when there is a higher amount of
standard calcium carbonate on the analyte, the higher amount of EDTA solution is needed to complete the
reaction resulting to a complex covalent coordinating bond.
Table 3: Determination of Water Hardness in an Unknown Sample

Molarity of EDTA
Vo reading of EDTA (ml)
Vf reading of EDTA (ml)
Volume of EDTA used (ml)
Moles of EDTA (mol)
Moles of CaCO3 (mol)
Mass of CaCO3 (mg)
Volume of water sample (L)

TRIAL 1
0.0100
0.00
17.9
17.9
1.79x10-4
1.79x10-4
17.9
0.100

TRIAL 2
0.100
0.00
35.0
17.2
1.72x10-4
1.72x10-4
17.2
0.100

TRIAL 3
0.0100
0.00
51.2
17.7
1.77x10-4
1.77x10-4
17.7
0.100

Hardness as ppm CaCO3 (mg/L)

179

Average ppm CaCO3 (mg/L)

Type of Water Hardness

172
176
Hard

177

Trial 1:

0.9610 g EDTA x

17.9 ml EDTA x

1 mol EDTA
3
=2.58 x 10 mol EDTA
372.24 g EDTA

1L
0.0100 mol EDTA 1 mol CaCO3
x
x
=1.79 x 104 mol CaCO 3
1000 ml
L EDTA
1 mol EDTA

1.79 x 104 mol CaCO3 x

100.09 g CaCO3 1000 mg 17.9 mg

x
=
=179 mg/ L
1 mol CaCO3
1g
0.100 L

*Same computation for trial 2 and 3

The higher the hardness in ppm of CaCO3, the higher amounts of Ca2+ and Mg2+ is found on the
water sample since hardness is dependent on the ions present. As seen on the data, the type of
hardness is hard which tells that the sample should not be taken up by humans since the
concentrations of ions is high and it is insoluble in our body.
CONCLUSION
Complometric titration is used when there is an involvement between metal ions and complexing agents
to give coordinate complex. This is useful for determining a mixture with different components of metal
ion in a solution. The most common used solution is EDTA since it is readily available and primarily
graded already and efficient to used. The EDTA solution chelates the metal ion preventing their
interference. In this experiment, one of the error that may occur is when the pH is higher Mg 2+will
precipitate to Mg(OH)2 and reacts only with Ca 2+ this is the one avoided in this classical method. The
hardness of water sample is sensible since the sample was from a tap which is usually not drank by
humans. The calcium and magnesium content of the sample were very high and fell on the range of hard
water sample.
REFERENCES
[1] (n.d.).Faculty of Chemistry, University of Wrocaw, Analytical Chemistry Dept., quantitative analysis.
Task 14 - p. 1 /react-text
react-text: 179
[2] Bonifacio, M. Analytical Chemistry 1 Laboratory experiments Edition B (2016). De La Salle Health
Sciences Institute. 2016

[3] UC University of Canterbury, College of Science (n.d). Detemination of Total Calcium and
Magnesium

ion

concentration

[pdf

document].

Retrieved

from

http://www.outreach.canterbury.ac.nz/chemistry/documents/magnesium_calcium.pdf

/react-text