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

through the four oxygen and the two nitrogen atoms.

Complex Formation Titration

Multidentate ligands are preferred over monodentate ligands.

Chelate covalently attached to an antibody carries a metal


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

ATP

Metal-ATP
Complex

Analytically useful chelating agents


Chelation
therapy and
thalassemia

Orally taken iron chelator

Fractional composition diagram of EDTA

Complexes of EDTA and Metal Ions

Ag+ + Y4 -

Mn+ + Y4-



AgY3-

[MY(n-4)]

KMY = [MY(n-4)] / [Mn+][Y4-]




Mg2+ + Y4- MgY2-





Al3+ + Y4- AlY-

Conditional Formation Constant


4 = [Y4-]/ cT

4 = [Y4-]/ cT
Where:

cT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]

Where:

cT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]


= total molar concentration of uncomplexed EDTA

KMY = [MY(n-4)] / [Mn+][Y4-]


4 =

K1K2K3K4

[H+]4+K1[H+]3+K1K2[H+]2+K1K2K3[H+]+K1K2K3K4

KMY = 4KMY = [MY(n-4)] / [Mn+]cT

Calculate the equilibrium concentration of Ni2+



in a solution with an analytical concentration of

0.0150 M at pH a)3.00 and b) 8.0

KfNiY2- = 4.2 x 1018





Calculate the concentration of Ni2+ in a soln that was

prepared by mixing 50.0 mL of 0.0300 M Ni2+ with

50.0 mL of 0.0500 M EDTA. The mixture was

Buffered to pH 3.0.

KfNiY2- = 4.2 x 1018


Titration curves for the


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

Example. 50.0 mL of 0.0400 Ca2+ is titrated


with 0.0800 M EDTA at pH 10. Calculate pCa
at the ff. volumes of titrant added.
a. 0.00 mL
b. 10.0 mL
c. 25.0 mL
d. 50.0 mL
log Kf = 10.65

Effect of reaction
completeness on
titration curve: As Kf
increases, the reaction
becomes more
complete pM/V
increases (steeper
slope) at the
equivalence point
region.

4 = 0.30 at pH 10

Effect of pH on
titration curve: as
pH increases, the
slope at the
equivalence point
region becomes
steeper (more
distinct break at the
equivalence point).

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

How to improve selectivity of EDTA





1. Interferences can be controlled by pH
regulation

Trivalent cations can be titrated without
interference from divalent cations at pH 1-2



2. Buffer solution to pH 7 for Cd and Zn



3. Add masking reagent/s

(ex: cyanide complexes with Cd, Co, Cu, Ni,
Zn and Pd, so Mg and Ca can be titrated)


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+ D Ag(CN)2-

K ~ 1021

End point: appearance of turbidity due to the


precipitation of silver cyanide.
or

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


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

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.

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.

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