TITLE : COMPLEXOMETRIC TITRATION OF METAL ION

OBJECTIVE : 1. To apply the concept of titration of metal by chelating agents such as

EDTA
2. To determine the concentration of metal ions using complexometric
titration technique.
3. To determine the concentration of metal ions in mixture by pH
adjustment and masking agent.
INTRODUCTION :
Complexometric titration of metal ion is the concept of titration of metal by
chelating agents. The chelating agents that use in this experiment is EDTA
(ethylenediaminetetraacetic acid). EDTA will undergoes successive acid dissociation to form
negatively charged ion. This ion will react will positive metal ion to form complex formation
in the mol ratio 1 to 1.
In the pH adjustment, bismuth and lead is determined in one solution using the same
indicator. The indicator that used in this procedure is xylenol orange. The bismuth is first
determined at pH 1-3, then lead at pH 5-6.
Back titration is for the determination of several metal ions that cannot be tirated directly
but form stable EDTA complexes. A blue dye solochrome black T/KCl is used as the indicator. This
blue dye also forms a complex with the metal ions, changing colour from blue to purple in the
process. The dye–metal ion complex is less stable than the EDTA–metal ion complex. The known
amount of EDTA is added to the analyte sample solution and the excess is back titrated with a
standard zinc solution until the colour changed from blue to purple. Potassium iodide is used in the
masking of mercury in the determination of cadmium.

RESULTS AND DISCUSSION :

Standardization of EDTA
Mass of zinc : 0.1606g

Titration 1 Titration 2 Titration 3

Initial (ml) 23.72 3.45 12.45
Final 47.41 23.39 35.21
Used 23.69 19.94 22.76

𝑚𝑎𝑠𝑠 𝑍𝑛 0.1606𝑔
Mol of zinc = = = 2.4564×10-3 mol
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑍𝑛 65.38𝑔/𝑚𝑜𝑙

𝑚𝑜𝑙 2.4564×10−3 mol

MZn = = = 0.0098256M (0.00983 M)
𝑣𝑜𝑙𝑢𝑚𝑒 0.250 𝐿
Mole zinc solution = mole EDTA
Titration 1 Titration 2 Titration 3
MEDTAVEDTA = MZnVZn MEDTAVEDTA = MZnVZn MEDTAVEDTA = MZnVZn
0.00983 M ×0.025 L 0.00983 M ×0.025 L 0.00983 M ×0.025 L
MEDTA = MEDTA = MEDTA =
0.02369𝐿 0.01994𝐿 0.02276𝐿

= 0.01037M =0.01232M =0.01080M

Average : (0.01037M + 0.012324M + 0.01080M)/3 = 0.01116M

(0.01037−0.01116)2 (0.01232−0.01116)2 (0.01080−0.01116)2

Standard deviation :√ = 1.0497 x 10-6M
3−1

Molarity of EDTA is (0.01116±1.0497 x 10-6)M

The EDTA solution can be standardize using many reagents which is metal solution.
In this experiment the EDTA is standardized using zinc solution.
Zn2+ + EDTA4- ZnEDTA2-
The different of the volume EDTA used in this experiment is a bit large because there
is an error while conducting the titration. So that there will be negative or positive error in
calculating the molarity.

Determination of bismuth and lead (pH adjustment)

Unknown : 2D

Titration 1 Titration 2 Titration 3

Bismuth Initial 0.48 10.35 3.19
Final (before adding 33.42 42.95 36.03
hexamine solution
(10% w/v)
Used 32.94 32.60 32.84
Lead Final (after adding 33.52 43.15 36.17
hexamine solution
(10% w/v)
Used 0.10 0.20 0.14

Bismuth :
Concentration of EDTA : 0.01116 moldm-3
32.94 + 32.60 + 32.84
Average of EDTA used : = 32.79 ml (0.03279dm3)
3

Volume of the unknown solution : 10 ml (0.010 dm3)

Mole of unknown = mole EDTA
= MEDTAVEDTA
= 0.01116 moldm-3 ( 0.03279dm3)
= 3.6594 x 10-4mol
Molar mass of bismuth = 208.9804g/mol
Mass of bismuth = mole x molar mass
= 3.6594 x 10-4mol x 208.9804g/mol
= 0.07647g
0.07647
Concentration of bismuth = 0.010𝑑𝑚3 = 7.6474gdm-3

The bismuth is a component of many alloys.it will react easily with EDTA forming the
stable coordination compounds even in the acid. The complexation reaction of bismuth with
EDTA should be carried in the acidic condition at pH 1-3. Xylenol orange is use as the
indicator that show the end point from red-purple colour to orange -yellow colour.
Bi3++ EDTA4- BiEDTA1-
Lead :
Concentration of EDTA : 0.01116 moldm-3
0.10+0.20+0.14
Average of EDTA used : = 0.1467(0.00015dm3)
3

Volume of the unknown solution : 10 ml (0.010 dm3)

Mole of unknown = mole EDTA
= MEDTAVEDTA
= 0.01116 moldm-3 ( 0.00015dm3)
= 1.674 x 10-6mol
Molar mass of lead = 208.9804g/mol
Mass of lead = mole x molar mass
= 1.674 x 10-6mol x 207.2g/mol
= 3.4685 x 10-4 g
0.00034685
Concentration of lead = = 0.034685gdm-3
0.010𝑑𝑚3
 The lead is titrated with EDTA at pH 5-6. It use the same indicator as bismuth which
is xylenol orange the bismuth is first determined at pH 1-3 forming the stable complex then
the remaining will react with lead at pH 5-6.
Pb2+ + EDTA4- PbEDTA2-
Determination of Cadmium and Mercury (back titration and masking agent)
Unknown : 2H

Titration 1 Titration 2
Cadmium Initial 4.48 16.65
Final (before adding 22.41 33.12
potassium iodide)

Used 17.93 16.47

Mercury Final (after adding 38.42 49.05
potassium iodide)

Used 16.01 15.93

Cadmium :
1 mole of Zn2+ = 1 mole of EDTA
17.93+16.47
Average volume of zinc solution = : =17.195 ml (0.017195dm3)
2

Mole of Zn2+ = 0.00983 moldm-3 (0.01720dm3)

=1.691 x 10 -4 mol
1 mole of Zn2+ = 1 mole of EDTA
Mole of excess EDTA = 1.691 x 10-4mol
Mole of EDTA = 0.01116 moldm-3 (0.035dm3)
=3.906 x 10-4 mol
Mole EDTA react with cadmium = mole of EDTA used -mole EDTA excess
= 3.906 x 10-4mol -1.691 x 10-4mol
= 2.215 x 10-4mol
1 mole of EDTA = 1 mol of Cd2+
Molar mass of cadmium =112.411g/mol
 1
Concentration of Cd2+ = 0.010𝑑𝑚3 x 2.215 x 10-4mol x 112.411g/mol

= 2.4899gdm-3
Mercury :
1 mole of Zn2+ = 1 mole of EDTA
16.01+15.93
Average volume of zinc solution used = =15.97 ml (0.01597dm3)
2

Mole of zinc solution = 0.00983 moldm-3 X 0.01597dm3

= 1.570 10-4mol
Mole liberated of EDTA = 1.570 10-4mol
Mole of EDTA = mole of Hg2+
Mole of Hg2+ = 1.570 10-4mol
Molar mass of mercury = 200.59g/mol
1
Concentration of Hg2+ = 0.010𝑑𝑚3 x 1.570 x 10-4mol x 200.59g/mol

=3.1493 gdm-3
In this part , the concentration of the cadmium and mercury is determined. It is
determined by the reaction with EDTA and back-titration with standar zinc (ii) solution. It
will followed by masking of mercury and continued with back titration of the released EDTA.
The masking agent used in this part is potassium iodide.
The reaction involve is
Cd2+ + EDTA4- CdEDTA2-
Hg2+ + EDTA4- HgEDTA2-

Conclusion : 1) Molarity of EDTA is (0.01116±1.0497 x 10-6)M

2) Concentration of bismuth = 7.6474gdm-3
3) Concentration of lead = 0.034685gdm-3
4) Concentration of bismuth = 7.6474gdm-3
5) Concentration of Cd2+ = 2.4899gdm-3
6) Concentration of Hg2+ =3.1493 gdm-3
References :
Complexation Reaction And Complexometric Titration. (2013). Quantitative

Chemical Analysis, 108–145. doi: 10.1142/9789814452304_0005

Isco. (1975). Analytical Chemistry, 47(2). doi: 10.1021/ac60352a840

Raoot, S. (1985). Selective complexometric determination of bismuth with

mercaptans as masking agents, and its estimation in alloys. Talanta, 32(10), 1011–1012. doi:

10.1016/0039-9140(85)80225-3

Sun, P.-J. (1961). Consecutive Chelatometric Determination of Bismuth and Lead Using

Gallein as Indicator. Journal of the Chinese Chemical Society, 8(4), 314–319. doi:

10.1002/jccs.196100033

Questions :
1) What is direct titration and back titration?
Back titration is a known amount of EDTA is added to the analyte sample solution
and the excess is back titrated with a standard solution of metal ion. Meanwhile,
the direct titration is solution of metal ion is a analyte that is titrated with EDTA
solution.

2) Why should heating assist an EDTA reaction?

EDTA is almost insoluble in water with very little solubility. Heating an EDTA will
make EDTA dissolve completely in the solution. This is because heating will
increase the kinetic energy of the molecules which make increasing the rate of
reaction.

3) Would you expect positive or negative errors in the determination of Cd and Hg ions
(or no error) if so , why?
Yes , if EDTA is added inaccurately into the sample of Cd-Hg solution using
measuring cylinder or beaker. So that the there will be negative error in the
titration of determining of Cd.

4) What would happen in titration n of metal M with EDTA with indicator HxIn in the
presence of a metal ion n that formed an indicator complex Nin that was more stable
than the complex NY and the complex Mln
The concentration of metal M cannot be determined accurately on the titration
values as the EDTA could not displace the metal ion.