Complexometric titrations

many metals form complex with a ligand:

Cu
++
+ NH
3
Cu(NH
3
)
++
K
f
1
Cu(NH
3
)
2+
+ NH
3
Cu (NH
3
)
2
2+
K
f
2
Cu (NH
3
)
2
2+
+ NH
3
Cu (NH
3
)
3
2+
K
f
3
Cu (NH
3
)
3
2+
+ NH
3
Cu (NH
3
)
4
2+
K
f4
Zn (NH
3
) complexes vs lg NH
3
theoretically could titrate Zn with
ammonia
stepwise K
f
very similar and small
difficult to know stoichiometry
to ensure all one form, need excess NH
3
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
Na
2
H
2
Y (H
4
Y 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
Y
4-
present at pH>10
H
4
Y has low solubility in water
Na
2
H
2
Y 2H
2
O usually used (i.e. two acid
groups neutralized) dissociates to H
2
Y
2-

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
+
+ H
2
Y
2-
MHY
2-
+ H
+
M
2+
+ H
2
Y
2-
MY
2-
+ 2H
+
M
3+
+ H
2
Y
2-
MY
-
+ 2H
+
M
4+
+ H
2
Y
2-
MY + 2H
+
species present in
moderately acid solution
different
metals
In neutral to moderately basic solutions
M
n+
+ HY
3-
MY
(n-4)+
+ H
+
M
n+
(Y
4-
)
(n-4)+
EDTA chelates with almost all cations
except alkali metals
chelates sufficiently stable for volumetric
analysis
formation constants (next slide) refer to:
M
n+
+ Y
4-
MY
(n-4)+
K
MY
=
MY
( n4) +
[M
n +
][Y
4
]
numbers large
so chelates strong
pH dependence of M-EDTA
M-EDTA formation constant depends on
pH because H
+
competes with MY
formation
M
n+
+ HY
3-
MY
(n-4)+
+ H
+
add H
+
, eqn moves to LHS, and depends
on K
a1
, K
a2
, K
a3
, K
a4
and [EDTA] added
[EDTA] known, but not concentrations of
individual species
define
Y
4-
= fraction of EDTA as Y
4-
=
alpha
Y
4
H
4
Y + H
3
Y

+ H
2
Y
2
+ HY
3
=
Y
4
C
tot
where C
tot
is the total EDTA conc.
conditional formation constant
a modifies the formation constant for Y
4-
to account for pH
this gives the conditional formation
constant K`
MY
= K
MY
K
MY
is stability constant for Y
4-
varies with pH