Complexometric Titration

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Complex Formation Titration

L. dlC. Coo

Analytically useful chelating agents

Chelate covalently attached to an antibody carries a metal


isotope (M) to deliver lethal doses of radiation to tumor cells.

Orally taken iron chelator


Part of treatment of thalassemia

EDTA forms 1:1 complexes with most metal ions, binding


through the four oxygen and the two nitrogen atoms.

Titration Reaction:
Mn+ + H2Y2-

MY4-n + 2H+

Titration curves for the


reaction of 50.0 mL of
0.0400 M metal ion
with 0.0800 M EDTA
at pH 10.

KFeYKFeY-2
KCaY-2
KHgY-2
KZnY-2

=
=
=
=
=

KFeY- = 1.3 x 1025


KZnY-2 = 3.2 x 1016
KCaY-2 = 5.0 x 1012

1.3 x 1025
2.1 x 1014
5.0 x 1012
6.3 x 1021
3.2 x 1016

KHgY-2 = 6.3 x 1021


KFeY-2 = 2.1 x 1014

Techniques
1. Back titration

2. Displacement Titration
-unavailability of a suitable indicator

An auxiliary
complexing agent
like NH3, tartrate,
citrate or
triethanolamine,
prevents precipitation
of metal hydroxide.

Metal ion indicators change color when they bind to a metal ion.

Hardness of water
A 100-mL sample of water containing Ca2+ and
Mg2+ ions is titrated with 15.28 mL of 0.01016
M EDTA in an ammonia buffer at pH 10.00.
Another sample of 100 mL is treated with
NaOH to precipitate Mg(OH)2, and then
titrated at pH 13.00 with 10.43 mL of the same
EDTA solution. Calculate the ppm of CaCO3
(100.09) and of MgCO3 (84.314) in the sample.

Liebig Titration of Cyanide with AgNO3


Basis: 2 CN + Ag+  Ag(CN)2

K ~ 1021

End point: appearance of turbidity due to the


precipitation of silver cyanide.

or

Ag+ + Ag(CN)2  2 AgCN (s)


Ag+ + Ag(CN)2  Ag[Ag(CN)2] (s)

Deniges modification: iodide ion is added since AgI is


less soluble than silver cyanide; NH3 is added
Ag(NH3)2+ forms which retards the precipitation of
AgI until very near the equivalence point.

Example. A 0.7562-g sample containing


NaCN is dissolved in H2O and then
concentrated NH3 and some KI solution are
added. The solution requires 23.58 mL of
0.0988 M AgNO3 for titration. Calculate the
percentage of NaCN (49.007) in the sample.

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