Complexometric titrations

many metals form complex with a ligand:

Cu(NH3)++
Cu++ + NH3
Cu (NH3)22+
Cu(NH3)2+ + NH3
Cu (NH3)32+
Cu (NH3)22+ + NH3
Cu (NH3)42+
Cu (NH3)32+ + NH3

K f1
K f2
K f3
K f4

Zn (NH3) complexes vs lg NH3

 theoretically could titrate Zn with

ammonia
stepwise Kf very similar and small
difficult to know stoichiometry
to ensure all one form, need excess NH3
titration never gives good equivalence
point
cant use monodentate ligand to titrate
metals

Titrations with EDTA

use multidentate ligands e.g. EDTA

tetraprotic, always forms 1:1 complexes
different stabilities depending on metal
usually use more soluable sodium form
Na2H2Y (H4Y is insoluble)

Example EDTA- metal complex

Mn-EDTA

EDTA - weak acid, ionizes stepwise

Fraction of EDTA species f(pH)

specie that reacts with metal depends on pH

The formation constant

vary pH of EDTA solution
different forms of EDTA present
smaller stability constant complexes need
higher pH to give particular form of
complex
Y4- present at pH>10
H4Y has low solubility in water
Na2H2Y 2H2O usually used (i.e. two acid
groups neutralized) dissociates to H2Y2to give a solution of pH 4-5

 lg formation constants for various metals

numbers large
so chelates strong

 metal chelates very stable - many sites for

bonding
charge on EDTA-metal complex depends
on metal and pH
different
metals

M+ + H2Y2M2+ + H2Y2M3+ + H2Y2M4+ + H2Y2-

MHY2- + H+
MY2- + 2H+
MY- + 2H+
MY + 2H+

species present in
moderately acid solution

 In neutral to moderately basic solutions

Mn+ + HY3- MY(n-4)+ + H+
Mn+ (Y4-)(n-4)+

EDTA chelates with almost all cations

except alkali metals
chelates sufficiently stable for volumetric
analysis
formation constants (next slide) refer to:
Mn+ + Y4- MY(n-4)+
MY ( n 4) +
KMY = n + 4
[M ][Y ]

numbers large
so chelates strong

pH dependence of M-EDTA
M-EDTA formation constant depends on
pH because H+ competes with MY
formation
Mn+ + HY3- MY(n-4)+ + H+

add H+, eqn moves to LHS, and depends

on Ka , Ka , Ka , Ka and [EDTA] added
[EDTA] known, but not concentrations of
individual species
1

alpha
define Y4- = fraction of EDTA as Y4=

Y 4
H4Y + H3Y + H2Y 2 + HY 3
Y 4
=
where C tot is the total EDTA conc.
Ctot

conditional formation constant

a modifies the formation constant for Y4to account for pH
this gives the conditional formation
constant K`MY= KMY
KMY is stability constant for Y4varies with pH