LABORATORY REPORT

Title of experiment COMPLEXOMETRIC TITRATION OF METAL ION

Name MOHAMAD NAZRUL BIN RASHID
Matric No U2004770/1
Course Code SIC2004
Lecturer DR ARNIZA KHAIRANI BINTI MOHD JAMIL
Date of Experiment 16 JANUARY 2023
Title:

Complexometric titration of metal ion.

Objectives:

To determine the concentration of Bismuth and Lead ion in the Unknown Sample B, concentration of
Mercury and Cadmium ion in Unknown Sample E using complexometric titration technique by
adjusting pH and the use of masking agent.

Introduction:

By applying complex-forming procedures, complexometric titrations are mainly used to

identify metal ions. Although a lot of complex compounds are suitable for this purpose, iminodiacetic
acid-containing compounds always represent the most of the titrant’s functional groups. One of the
most often used substances in this experiment is ethylenediaminetetraacetic acid (EDTA). The EDTA
structure is shown in Figure 1.

Figure 1: The chemical structure of EDTA.

A metal ion in its fully deprotonated state may receive six pairs of electrons from EDTA, a
Lewis acid with six binding sites made up of two tertiary amino groups, four negatively charged
carboxylate groups, and four negatively charged carboxylate groups. Lewis’s acids include EDTA. It
creates an incredibly stable cage-like structure around the metal ion in the resulting metal-ligand
complex. Regardless of the exact number of coordination sites present on the metal ion, all metal-
EDTA complexes display a 1:1 stoichiometry. EDTA is a hexadentate ligand which is shown in Figure 2.
 Figure 2: The structure of hexadentate ligand.

Additionally, EDTA functions as a chelating agent, binding to metals by means of four different
carboxylic acids. Each metal has a different formation constant for complexation, and because the
ligands are acids, the formation constants are strongly dependent on the ambient pH. Metals will
always bind more tightly as the pH rises because more basic hydrogens are pulled out of the EDTA as
the pH rises.

Moreover, complexometric titrations employ several indicators, some of which are shown in
Figure 3, which is shown below. EDTA is colourless, regardless of whether it is associated with a metal
ion or not. One can look at the complexation titration endpoints by using metal ion indicators. A
complexing agent, the indicator changes colour depending on whether it is in its free form or
combined with ligands to create a complex. Most indicators can only be utilised within specific pH
ranges since the colour of the metal ion indicators varies based on the pH of the solution.

Figure 3: The indicator used in complexometric titrations.

 Results:

Preparation of Zinc Solution

Mass of zinc used = 0.1589 g

Molar mass of zinc = 65.37 𝑔 𝑚𝑜𝑙 −1

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑧𝑖𝑛𝑐 (𝑔)
No of moles of zinc = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑧𝑖𝑛𝑐 (𝑔 𝑚𝑜𝑙−1 )

0.1589 𝑔
=
65.37 𝑔 𝑚𝑜𝑙 −1
= 0.002431 𝑚𝑜𝑙

𝑁𝑜 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑧𝑖𝑛𝑐 (𝑚𝑜𝑙)

The concentration of standardised zinc solution = 𝑉𝑜𝑙𝑢𝑚𝑒 (𝑑𝑚3 )

0.002431 𝑚𝑜𝑙
=
0.25 𝑑𝑚3
= 0.009724 𝑚𝑜𝑙 𝑑𝑚−3

∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑𝑖𝑠𝑒𝑑 𝑧𝑖𝑛𝑐 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑠 0.009724 𝑚𝑜𝑙 𝑑𝑚−3 .

Standardisation of EDTA

Table 1: Result of volume EDTA used for the titration with 25 𝒄𝒎𝟑 zinc solution.

No of titration Initial Reading (𝑐𝑚3 ) Final Reading (𝑐𝑚3 ) Volume of EDTA used
(𝑐𝑚3 )
1 1.00 18.70 17.70
2 18.70 37.00 18.30
3 15.00 30.50 15.50

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑢𝑠𝑒𝑑

The average volume of EDTA used = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛

17.70 + 18.30 + 15.50

=
3
= 17.17 𝑐𝑚3
Since EDTA will react with metal ions in 1:1 ratio, one mole of zinc ions will complex with one mole
of EDTA.

The chemical equation is shown as below.

𝑍𝑛2+ + 𝐸𝐷𝑇𝐴 → 𝑍𝑛 − 𝐸𝐷𝑇𝐴

Therefore, the concentration of EDTA, 𝑀𝐸𝐷𝑇𝐴 is calculated as:
𝑀𝐸𝐷𝑇𝐴 𝑉𝐸𝐷𝑇𝐴 1
𝑀𝑍𝑛2+ 𝑉𝑍𝑛2+
=1

𝑀𝐸𝐷𝑇𝐴 (17.17) 1
(0.009724)(25.00)
=1

(17.17)𝑀𝐸𝐷𝑇𝐴 = 0.2431

𝑀𝐸𝐷𝑇𝐴 = 0.01416 𝑚𝑜𝑙 𝑑𝑚−3

∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑𝑖𝑠𝑒𝑑 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑠 0.01416 𝑚𝑜𝑙 𝑑𝑚−3 .

Determination of Bismuth and Lead Ions in Unknown Sample B

i) Determination of Bismuth ions

Table 2: Result of volume EDTA used for titration with 10.00 𝒄𝒎𝟑 Unknown Sample B
solution to determine the concentration of bismuth ions.

No of titration Initial Reading Final Reading(𝑐𝑚3 ) Volume of EDTA

(𝑐𝑚3 ) used (𝑐𝑚3 )
1 5.00 21.40 16.40
2 29.20 45.40 16.20
3 30.30 46.60 16.30

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑢𝑠𝑒𝑑

The average volume of EDTA used = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛

16.40 + 16.20 + 16.30

=
3
= 16.30 𝑐𝑚3
Since EDTA will react with metal ions in 1:1 ratio, one mole of bismuth ions will complex with one
mol of EDTA.

The chemical equation is shown as below:

𝐵𝑖 3+ + 𝐸𝐷𝑇𝐴 → 𝐵𝑖 − 𝐸𝐷𝑇𝐴
Therefore, the concentration of 𝐵𝑖 3+ in Unknown Sample B, 𝑀𝐵𝑖3+ is calculated as:
𝑀𝐸𝐷𝑇𝐴 𝑉𝐸𝐷𝑇𝐴 1
=
𝑀𝐵𝑖3+ 𝑉𝐵𝑖3+ 1

(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )(16.30) 1

(𝑀𝐵𝑖3+ )(10.00)
=1

𝑀𝐵𝑖3+ = 0.0230808 𝑚𝑜𝑙 𝑑𝑚−3

The concentration of 𝐵𝑖 3+ in the Unknown Sample B in 𝑔 𝑑𝑚−3

= Molarity of 𝐵𝑖 3+( 𝑚𝑜𝑙 𝑑𝑚−3 ) × 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐵𝑖 (𝑔 𝑚𝑜𝑙 −1 )

= 0.0230808 𝑚𝑜𝑙 𝑑𝑚−3 × 209.0 𝑔 𝑚𝑜𝑙 −1

= 4.8238872 𝑔 𝑑𝑚−3

∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐵𝑖 3+ 𝑖𝑛 𝑡ℎ𝑒 𝑈𝑛𝑘𝑛𝑜𝑤𝑛 𝑆𝑎𝑚𝑝𝑙𝑒 𝐵 𝑖𝑠 4.8238872 𝑔 𝑑𝑚−3

ii) Determination of Lead ions

Table 3: Result of EDTA volume used for titration with 10.00 𝒄𝒎𝟑 Unknown Sample B solution to
determine the concentration of Lead ions.

No of titration Initial Reading (𝑐𝑚3 ) Final Reading(𝑐𝑚3 ) Volume of EDTA

used (𝑐𝑚3 )
1 28.30 47.50 19.20
2 18.20 37.60 19.40
3 29.00 19.40 19.30

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑢𝑠𝑒𝑑

The average volume of EDTA used = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛

19.20 + 19.40 + 19.30

=
3
= 19.30 𝑐𝑚3
Since EDTA will react with metal ions in 1:1 ratio, one mole of lead ions will complex with one mole
of EDTA.
The chemical equation is shown as below:

𝑃𝑏 2+ + 𝐸𝐷𝑇𝐴 → 𝑃𝑏 − 𝐸𝐷𝑇𝐴
Therefore, the concentration of 𝑃𝑏 2+ in the Unknown Sample B,
𝑀𝐸𝐷𝑇𝐴 𝑉𝐸𝐷𝑇𝐴 1
𝑀𝑃𝑏2+ 𝑉𝑃𝑏2+
=1

(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )(19.30) 1

=
(𝑀𝑃𝑏2+ )(10.00) 1

𝑀𝑃𝑏2+ = 0.0273288 𝑚𝑜𝑙 𝑑𝑚−3

The concentration of 𝐵𝑖 3+ in the Unknown Sample B in 𝑔 𝑑𝑚−3

= Molarity of 𝑃𝑏 2+( 𝑚𝑜𝑙 𝑑𝑚−3 ) × 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑃𝑏 (𝑔 𝑚𝑜𝑙 −1 )

= 0.0273288 𝑚𝑜𝑙 𝑑𝑚−3 × 207.2 𝑔 𝑚𝑜𝑙 −1

= 5.66252736 𝑔 𝑑𝑚−3

∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑃𝑏 2+ 𝑖𝑛 𝑡ℎ𝑒 𝑈𝑛𝑘𝑛𝑜𝑤𝑛 𝑆𝑎𝑚𝑝𝑙𝑒 𝐵 𝑖𝑠 5.66252736 𝑔 𝑑𝑚−3.

Determination of Cadmium and Mercury in the Unknown Sample E

i) Before KI was added to the analyte

Table 4: Volume of zinc solution used for titration between zinc solution and excess EDTA before
KI was added in the Unknown Sample E.

No of titration Initial Reading (𝑐𝑚3 ) Final Reading (𝑐𝑚3 ) Volume of Zinc

solution used (𝑐𝑚3 )
1 0.90 14.90 14.00
2 14.90 30.60 15.70
3 30.60 46.00 15.40

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑧𝑖𝑛𝑐 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑢𝑠𝑒𝑑

The average volume of zinc solution used = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛

14.00 + 15.70 + 15.40

=
3
= 15.03 𝑐𝑚3
Since EDTA will react with metal ions in 1:1 ratio, one mole of zinc ions will complex with one mole
of EDTA.

The chemical equation is shown as below:

𝑍𝑛2+ + 𝐸𝐷𝑇𝐴 → 𝑍𝑛 − 𝐸𝐷𝑇𝐴

The volume of EDTA solution used, 𝑉𝐸𝐷𝑇𝐴 is calculated as:
𝑀𝐸𝐷𝑇𝐴 𝑉𝐸𝐷𝑇𝐴 1
=
𝑀𝑍𝑛2+ 𝑉𝑍𝑛2+ 1

(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )𝑉𝐸𝐷𝑇𝐴 1

(0.009724 𝑚𝑜𝑙 𝑑𝑚−3 )(15.30)
=1

𝑉𝐸𝐷𝑇𝐴 = 10.51 𝑐𝑚3

Volume of EDTA that reacts with mercury and cadmium ion.

= Volume of excess EDTA – Volume of EDTA used

= 35.00 𝑐𝑚3 – 10.51 𝑐𝑚3

= 24.49 𝑐𝑚3

ii) After KI was added to the analyte

Table 5: Volume of zinc solution used for titration between zinc solution and excess
EDTA after KI was added in the Unknown Sample E.

No of titration Initial Reading (𝑐𝑚3 ) Final Reading (𝑐𝑚3 ) Volume of Zinc

solution used (𝑐𝑚3 )
1 15.50 25.40 9.90
2 25.40 34.00 8.60
3 34.00 44.80 10.80

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑧𝑖𝑛𝑐 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑢𝑠𝑒𝑑

The average volume of zinc solution used = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑜 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛

9.90 + 8.60 + 10.80

=
3
= 9.77 𝑐𝑚3
(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )𝑉𝐸𝐷𝑇𝐴 1
=
(0.009724 𝑚𝑜𝑙 𝑑𝑚−3 )(9.77) 1

𝑉𝐸𝐷𝑇𝐴 = 6.71 𝑐𝑚3

(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )6.71 1

=
(𝑀𝐻𝑔2+ )(10.00) 1

𝑀𝐻𝑔2+ = 0.00950136 𝑚𝑜𝑙 𝑑𝑚−3

= 0.00950136 𝑚𝑜𝑙 𝑑𝑚−3 × 200.6 𝑔 𝑚𝑜𝑙 −1

= 1.906 𝑔 𝑑𝑚−3
∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻𝑔2+ 𝑖𝑛 𝑡ℎ𝑒 𝑈𝑛𝑘𝑛𝑜𝑤𝑛 𝑆𝑎𝑚𝑝𝑙𝑒 𝐸 𝑖𝑠 1.906 𝑔 𝑑𝑚−3

Volume of EDTA that reacts with Cadmium ion

= Volume of EDTA that reacts with mercury and cadmium ion – Volume of EDTA released by 𝐼 − from
Hg-EDTA

= 24.49 𝑐𝑚3 - 6.71 𝑐𝑚3

= 17.78 𝑐𝑚3

(0.01416 𝑚𝑜𝑙 𝑑𝑚−3 )17.78 𝑐𝑚3 1

=
(𝑀𝐶𝑑2+ )(10.00) 1
𝑀𝐶𝑑2+ = 0.02518 𝑚𝑜𝑙 𝑑𝑚−3

= 0.02518 𝑚𝑜𝑙 𝑑𝑚−3 × 112.4 𝑔 𝑚𝑜𝑙 −1

= 2.83 𝑔 𝑑𝑚−3

∴ 𝑇ℎ𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑑 2+ 𝑖𝑛 𝑈𝑛𝑘𝑛𝑜𝑤𝑛 𝑆𝑎𝑚𝑝𝑙𝑒 𝐸 𝑖𝑠 2.83 𝑔 𝑑𝑚−3

Discussion

One of the most important conditions for achieving consistent and transparent
titration readings in this experiment is the standardisation of a volumetric solution used for
titration, either zinc solution or EDTA. The precise concentration can be determined by
standardisation of the answers. Working with the precise volumetric solution concentration
is the only method to provide accurate and reliable titration results. A volumetric solution
used as a titrant in titration has a known nominal concentration. Several variables might cause
the concentration to be different from the actual concentration. The exact concentration
must be ascertained using a titrimetric standard to obtain reliable titration results.

In order to determine the concentration of bismuth and lead ions in Unknown Sample
A and mercury and cadmium ions in Unknown Sample E, it was necessary to first calculate the
concentration of standardised zinc solution and EDTA. After standardisation, the
concentration of lead and bismuth ions in Unknown Sample B was measured using direct
titration. The pH adjustment for this experiment's portion was used. Xylenol orange, which
becomes red when complexed with metal ions, was chosen as the indicator. Free xylol orange
turns violet at pH 6.7, although free indicator colour is yellow below pH 6.7. Bismuth ions
were titrated in the first part of the titration.
 The mixture included In-Bi complexes, which gave the solution its red hue. The
number of In-Bi complexes decreased as the amount of EDTA grew because it started to
dispense indicator from the In-Bi complex. The combination quickly changed from red-purple
to orange-yellow as the In-Bi complexes vanished. The amount of EDTA used for titration was
then used to calculate the concentration of bismuth ions in the Unknown Sample B solution.
The titrated Unknown Sample B was added to a hexamine solution, which functions as a
buffer to change the pH value to one that is favourable for the complexation of lead ions, to
detect the presence of lead. The chemical conditions were also now excellent for the
complexation of 𝑃𝑏 2+ ions and the indicator, Pb-In complexes, which caused the mixture's
colour to shift from orange-yellow to red-purple since the pH value had changed. When the
colour of the analyte changed from red to purple to orange to yellow, EDTA had entirely
replaced the indicator from the Pb-In complexes. The amount of 𝑃𝑏 2+ ions present in the
unknown sample Based on the amount of EDTA used, a solution was calculated.

The concentration of mercury and cadmium ion in Unknown Sample E was then
measured using a back titration. The masking agent was employed during this portion of the
experiment. Considering the potential for analyte precipitation in the lack of EDTA, the
slowness of analyte responses in the presence of EDTA, and the potential for analyte blockage
of the indicator, this possibility exists. As a result, reverse titration rather than direct titration
was employed. By reacting an analyte with a known excess of reagent, back titration is a
technique for measuring an analyte's concentration. In this experiment, EDTA was the extra
reagent that interacted with the unidentified material. The mixture then comprised more
unreacted EDTA as well as EDTA-Hg and EDTA-Cd complexes.

The dark blue colour of the analyte, which had been enhanced with solochrome black
indicator and ammonium chloride solution, was changed to purple by titrating the unreacted
EDTA with zinc solution. As a result, the additional EDTA in the mixture was measured.
Knowing the volume of extra EDTA in the mixture allows one to compute the precise volume
of EDTA complexing with 𝐻𝑔2+ and 𝐶𝑑 2+ ions. The Unknown Sample E solution that had been
titrated with potassium iodide received KI. In comparison to EDTA-Hg complexes, KI is the
masking agent that will result in a significantly more stable combination with 𝐻𝑔2+ ions.
Because I- ions remove EDTA from EDTA-Hg complexes, 𝐻𝑔2+ ions cannot interact with EDTA.

The 𝑍𝑛2+ ions in the solution will react with the "expelled" EDTA burette. When the
colour changed from dark blue to purple, it was clear that all the EDTA molecules had united
with 𝑍𝑛2+ ions to form complexes. Using the quantity of zinc solution from the burette, it was
feasible to calculate the volume of EDTA interacting with 𝐻𝑔2+ ions as well as the
concentration of 𝐻𝑔2+ ions in the sample solution. The amount of 𝐶𝑑 2+ ions in Unknown
Sample E may be measured thanks to the complexing of 𝐶𝑑2+ ions with the remaining amount
of EDTA.
 All titrations in this experiment were run three times. By figuring out the average
volume used, the aim is to reduce mistakes and provide a more precise conclusion. Even
though the numbers are very close, there are some variations in the volume of standard EDTA
or zinc solution for the three times titration based on Tables 1 through Table 5. The problems
listed above may be the result of mistakes made or improperly followed safety procedures.
With all these factors taken into account, the various results found are predictable.

Source of errors
1. The eye-level was not perpendicular to the scale of the pipette, measuring cylinder,
burette and the mark of the volumetric flask and pipette so there might exist parallax
error.

Precaution
1. Ensure that all chemicals were free from contamination and freshly produced to avoid
affecting the reading.

2. A piece of white paper was put below the conical flask during the titration so that the
colour changed at the endpoint of titration could be determined easily.

Suggestion for improvement

1. A digital pipette is used to ensure an accurate result can be obtained and avoid
parallax error.

2. Increase the times of titration process to minimize the error to obtain more accurate
mean readings.

Conclusion
For Unknown Sample B, the concentration of 𝐵𝑖 3+ ions in the sample is
4.8238872 𝑔 𝑑𝑚−3 and the concentration of 𝑃𝑏 2+ ions is 0.0273288 𝑚𝑜𝑙 𝑑𝑚−3. For Unknown
Sample E, the concentration of 𝐻𝑔2+ ions in the sample is 0.00950136 𝑚𝑜𝑙 𝑑𝑚−3 while the
concentration of 𝐶𝑑2+ ions is 2.83 𝑔 𝑑𝑚−3 .
 References:

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