Complexometric titrations

many metals form complex with a ligand:

Cu++ + NH3 Cu(NH3)++ K f1
Cu(NH3)2+ + NH3 Cu (NH3)22+ K f2
Cu (NH3)22+ + NH3 Cu (NH3)32+ K f3
Cu (NH3)32+ + NH3 Cu (NH3)42+ 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 H2Y2-
to 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
M+ + H2Y2- MHY2- + H+
different M2+ + H2Y2- MY2- + 2H+
metals M3+ + H2Y2- MY- + 2H+
M4+ + H2Y2- 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) + numbers large
KMY = n + 4 so chelates strong
[M ][Y ]
 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
1 2 3 4

[EDTA] known, but not concentrations of

individual species
 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 Y4-
to account for pH
this gives the conditional formation
constant K`MY= KMY
KMY is stability constant for Y4-
varies with pH