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1

COORDINATION
CHEMISTRY
(COMPLEXATION)
2
WHY IS CHEMICAL SPECIATION SO
IMPORTANT?
• The biological availability (bioavailability) of
metals and their physiological and toxicological
effects depend on the actual species present.
– Example: CuCO
3
0
, Cu(en)
2
0
, and Cu
2+
all affect the
growth of algae differently
– Example: Methylmercury (CH
3
Hg
+
) is readily formed
in biological processes, kinetically inert, and readily
passes through cell walls. It is far more toxic than
inorganic forms.
• Solubility and mobility depend on speciation.
3
Figure 6-20 from Stumm & Morgan: Effect of free Cu
2+
on
growth of algae in seawater.
4
DEFINITIONS - I
Coordination (complex formation) - any combination of
cations with molecules or anions containing free pairs
of electrons. Bonding may be electrostatic, covalent or a
mix.
Central atom (nucleus) - the metal cation.
Ligand - anion or molecule with which a cation forms
complexes.
Multidentate ligand - a ligand with more than one possible
binding site.
Chelation - complex formation with multidentate ligands.
Multi- or poly-nuclear complexes - complexes with more
than one central atom or nucleus.
5
N H
2
N H
2
M
N
N
HO O
OH
O
OH
O
HO O
MULTIDENTATE LIGANDS
Oxalate (bidentate)
Ethylendiamine (bidentate)
Ethylendiaminetetraacetic acid
or EDTA (hexadentate)
O
O
O
O
M
6
Chelation
NH
2
NH
2
Ni
H
2
N
H
2
N
Polynuclear complexes
Sb
2
S
4
2-

OH
Hg
OH
Hg
OH
OH
Hg
2+
Hg
3
(OH)
4
2+

Sb Sb
S
S S
S
2-
7
DEFINITIONS - II
Species - refers to the actual form in which a molecule or
ion is present in solution.
Coordination number - total number of ligands
surrounding a metal ion.
Ligation number - number of a specific type of ligand
surrounding a metal ion.
Colloid - suspension of particles composed of several
units, whereas in true solution we have hydration of a
single molecule, atom or ion.

8
FORMS OF OCCURRENCE OF
METAL SPECIES
Free metal
ion
Inorganic
ion pairs
and
complexes
Organic
complexes,
chelates
Metals
bound to
high mol.
wt.
species
Highly
dispersed
colloids
Metals
sorbed on
colloids
Cu
2+
Cu
2
(OH)
2
2+
Me-SR Me-lipids FeOOH Me
x
(OH)
y
Fe
3+
PbCO
3
0
Me-OOCR Me-
humic
acid
Fe(OH)
3
MeCO
3
,
MeS,etc.
on clays
Pb
2+
CuCO
3
0
Mn(IV)
oxides
FeOOH or
Mn(IV) on
oxides
Na
+
AgSH
0
Ag
2
S
Al
3+
CdCl
+
Zn
2+
CoOH
+
1000 Å 100 Å 10 Å
9
Coordination numbers
Me
L
L L
L
Me
L
L
L
L
Me L L
Me
L
L
L
L
L
L
CN = 2 (linear)
CN = 4 (tetrahedral)
CN = 6 (octahedral)
CN = 4 (square planar)
Coordination numbers 2, 4, 6, 8, 9 and 12 are most common
for cations.
10
STABILITY CONSTANTS MEASURE THE
STRENGTH OF COMPLEXATION
Stepwise constants
ML
n-1
+ L ÷ ML
n


Cumulative constants
M + nL ÷ ML
n
] ][ [
] [
1
L ML
ML
K
n
n
n
÷
=
n
n
n
L M
ML
] ][ [
] [
= |
|
n
= K
1
· K
2
· K
3
· · · K
n

11
For a protonated ligand we have:
Stepwise complexation
ML
n-1
+ HL ÷ ML
n
+ H
+

Cumulative complexation
M + nHL ÷ ML
n
+ nH
+

] ][ [
] ][ [
1
*
HL ML
H ML
K
n
n
n
÷
+
=
n
n
n
n
HL M
H ML
] ][ [
] ][ [
*
+
= |
The larger the value of the stability constant, the more
stable the complex, and the greater the proportion of
the complex formed relative to the simple ion.
12
STABILITY CONSTANTS FOR
POLYNUCLEAR COMPLEXES
mM + nL ÷ M
m
L
n



mM + nHL ÷ M
m
L
n
+ nH
+


n m
n m
nm
L M
L M
] [ ] [
] [
= |
n m
n
n m
nm
HL M
H L M
] [ ] [
] ][ [
*
+
= |
If m = 1, the second subscript on |
nm
is omitted and
the expression simplifies to the previous expressions
for mononuclear complexes.
13
METAL-ION TITRATIONS
• Metal ions can be titrated by ligands in the
same way that acids and bases can be
titrated.
• According to the Lewis definition, metal
ions are acids because they accept
electrons; ligands are bases because they
donate electrons.
14
Figure 6-3 from Stumm & Morgan: Titration of H
+
and Cu
2+
with
ammonia and tetramine (trien)
15
HYDROLYSIS
The waters surrounding a cation may function as acids. The
acidity is expected to increase with decreasing ionic
radius and increasing ionic charge. For example:
Zn(H
2
O)
6
2+
÷ Zn(H
2
O)
5
(OH)
+
+ H
+

Hydrolysis products may range from cationic to anionic.
For example:
Zn
2+
÷ ZnOH
+
÷ Zn(OH)
2
0
(ZnO
0
)
÷ Zn(OH)
3
-
(HZnO
2
-
) ÷ Zn(OH)
4
2-
(ZnO
2
2-
)
May also get polynuclear species.
Kinetics of formation of mononuclear hydrolysis products
is rather fast, polynuclear formation may be slow.
16
GENERAL RULES OF HYDROLYSIS
• The tendency for a metal ion to hydrolyze will
increase with dilution and increasing pH
(decreasing [H
+
])
• The fraction of polynuclear products will decrease
on dilution
• Compare
Cu
2+
+ H
2
O ÷ CuOH
+
+ H
+
log
*
K
1
= -8.0
Mg
2+
+ H
2
O ÷ MgOH
+
+ H
+
log
*
K
1
= -11.4
] [
] ][ [
2
1
*
+
+ +
=
M
H MOH
K
17
At infinite dilution, pH ~ 7 so
o
CuOH
+
= (1 + 10
-7
/10
-8
)
-1
= 1/11 = 0.091
o
MgOH
+
= (1 + 10
-7
/10
-11.4
)
-1
= 1/25119 = 4x10
-5

Only salts with p
*
K
1
< (1/2)pK
w
or p
*
|
n
< (n/2)pK
w

will undergo significant hydrolysis upon dilution.
Progressive hydrolysis is the reason some salts
precipitate upon dilution. This is why it is necessary
to add acid when diluting standards.
1
*
2
] ][ [
] [
] [
] [ ] [
] [
K
H MOH
MOH
MOH
M MOH
MOH
MOH
+ +
+
+
+ +
+
+
=
+
=
+
o
1
*
] [
1
1
K
H
MOH
+
+
=
+
o
18
POLYNUCLEAR SPECIES DECREASE IN
IMPORTANCE WITH DILUTION
Consider the dimerization of CuOH
+
:
2CuOH
+
÷ Cu
2
(OH)
2
2+
log
*
K
22
= 1.5
Assuming we have a system where:
Cu
T
= [Cu
2+
] + [Cu(OH)
+
] + 2[Cu
2
(OH)
2
2+
]
we can write:
22
*
2 2
2 2
2
2
2 2
2
2
2 2
]) ) ( [ 2 ] [ (
] ) ( [
] [
] ) ( [
K
OH Cu Cu Cu
OH Cu
CuOH
OH Cu
T
=
÷ ÷
=
+ +
+
+
+
So [Cu
2
(OH)
2
2+
] is clearly dependent on total Cu
concentration!
19
HYDROLYSIS OF IRON(III)
Example 1: Compute the equilibrium composition of a
homogeneous solution to which 10
-4
(10
-2
) M of
iron(III) has been added and the pH adjusted in the
range 1 to 4.5 with acid or base.
The following equilibrium constants are available at I =
3 M (NaClO
4
) and 25°C:
Fe
3+
+ H
2
O ÷ FeOH
2+
+ H
+
log
*
K
1
= -3.05
Fe
3+
+ 2H
2
O ÷ Fe(OH)
2
+
+ 2H
+
log
*
|
2
= -6.31
2Fe
3+
+ 2H
2
O ÷ Fe
2
(OH)
2
4+
+ 2H
+
log
*
|
22
= -2.91
Fe
T
= [Fe
3+
] + [FeOH
2+
] + [Fe(OH)
2
+
] + 2[Fe
2
(OH)
2
4+
]

20
Now we define: o
0
= [Fe
3+
]/Fe
T
; o
1
= [FeOH
2+
]/Fe
T
;
o
2
= [Fe(OH)
2
+
]/Fe
T
; and o
22
= 2[Fe
2
(OH)
2
4+
]/Fe
T
.
|
|
.
|

\
|
+ + + =
+
+
+ +
+
2
22
* 3
2
2
*
1
*
3
] [
] [ 2
] [ ] [
1 ] [
H
Fe
H H
K
Fe Fe
T
| |
1
2
22
*
0
2
2
*
1
*
0
] [
2
] [ ] [
1
÷
+ + +
|
|
.
|

\
|
+ + + =
H
Fe
H H
K
T
| o |
o
0 1
] [ ] [
1
] [
2
2
2
*
1
*
0
2
22
*
2
0
= ÷
|
|
.
|

\
|
+ + +
+ + +
H H
K
H
Fe
T
|
o
| o
21
These equations can then be employed to calculate
the speciation diagrams on the next slide.
2
22
*
2
0
22
] [
2
+
=
H
Fe
T
| o
o
] [
1
*
0
1
+
=
H
K o
o
2
22
*
0
2
] [
+
=
H
| o
o
This last equation can be solved for o
0
at given values
of Fe
T
and pH. The remaining o values are obtained
from the following equations:
22
Fe
T
= 10
-4
M
%
F
e
0
20
40
60
80
100
Fe
T
= 10
-2
M
pH
1 2 3 4
%
F
e
0
20
40
60
80
100
Fe
3+
FeOH
2+
Fe(OH)
2
+
Fe
2
(OH)
2
4+
Fe
3+
FeOH
2+
Fe(OH)
2
+
23
Example 2: Compute the composition of a Fe(III)
solution in equilibrium with amorphous ferric
hydroxide given the additional equilibrium
constants:
Fe(OH)
3
(s) + 3H
+
÷ Fe
3+
+ 3H
2
O log
*
K
s0
= 3.96
Fe(OH)
3
(s) + H
2
O ÷ Fe(OH)
4
-
+ H
+
log
*
K
s4
= -18.7

Fe
3+

log [Fe
3+
] = log
*
K
s0
- 3pH

Fe(OH)
4
-

log [Fe(OH)
4
-
] = log
*
K
s4
+ pH
24
FeOH
+

Fe(OH)
3
(s) + 3H
+
÷ Fe
3+
+ 3H
2
O log
*
K
s0
= 3.96
Fe
3+
+ H
2
O ÷ FeOH
2+
+ H
+
log
*
K
1
= -3.05
Fe(OH)
3
(s) + 2H
+
÷ FeOH
2+
+ 2H
2
O log
*
K
s1
= 0.91

log [FeOH
2+
] = log
*
K
s1
- 2pH

Fe(OH)
2
+

Fe(OH)
3
(s) + 3H
+
÷ Fe
3+
+ 3H
2
O log
*
K
s0
= 3.96
Fe
3+
+ 2H
2
O ÷ Fe(OH)
2
+
+ 2H
+
log
*
|
2
= -6.31
Fe(OH)
3
(s) + H
+
÷ Fe(OH)
2
+
+ H
2
O log
*
K
s2
= -2.35

log [Fe(OH)
2
+
] = log
*
K
s2
- pH

25
Fe
2
(OH)
2
4+

2Fe(OH)
3
(s) + 6H
+
÷ 2Fe
3+
+ 6H
2
O 2log
*
K
s0
= 7.92
2Fe
3+
+ 2H
2
O ÷ Fe
2
(OH)
2
4+
+ 2H
+
log
*
|
22
= -2.91
2Fe(OH)
3
(s) + 4H
+
÷ Fe
2
(OH)
2
4+
+ 4H
2
O
log
*
K
s22
= 5.01

log [Fe
2
(OH)
2
4+
] = log
*
K
s22
- 4pH

These equations can be used to obtain the concentration of
each of the Fe(III) species as a function of pH. They can
all be summed to give the total solubility.
26
pH
0 2 4 6 8 10 12 14
l
o
g

c
o
n
c
e
n
t
r
a
t
i
o
n
-15
-10
-5
0
5
Fe(OH)
3
(s)
Fe(OH)
4
-
Fe(OH)
2
+
FeOH
2+
Fe
2
(OH)
2
4+
Fe
3+
27
Figure 6-4a from Stumm and Morgan: Predominant pH range
for the occurrence of various species for various oxidation states
28
Figure 6-4b from Stumm & Morgan: The linear dependence of the
first hydrolysis constant on the ratio of the charge to the M-O
distance (z/d) for four groups of cations at 25°C.
29
Figure 6-6 from
Stumm & Morgan:
Correlation
between solubility
product of solid
oxide/hydroxide
and the first
hydrolysis constant.
30
PEARSON HARD-SOFT ACID-BASE
(HSAB) THEORY
• Hard ions (class A)
– small
– highly charged
– d
0
electron
configuration
– electron clouds not
easily deformed
– prefer to form ionic
bonds
• Soft ions (class B)
– large
– low charge
– d
10
electron
configuration
– electron clouds easily
deformed
– prefer to form covalent
bonds
31
Pearson’s Principle - In a competitive
situation, hard acids tend to form complexes
with hard bases, and soft acids tend to form
complexes with soft bases.
In other words - metals that tend to bond covalently
preferentially form complexes with ligands that
tend to bond covalently, and similarly, metals that
tend to bond electrostatically preferentially form
complexes with ligands that tend to bond
electrostatically.
32
Classification of metals and ligands in terms of Pearson’s (1963) HSAB principle.
Hard Borderline Soft
Acids
H
+
Li
+
> Na
+
> K
+
> Rb
+
> Cs
+
Be
2+
> Mg
2+
> Ca
2+
> Sr
2+
> Ba
2+
Al
3+
> Ga
3+
Sc
3+
> Y
3+
; REE
3+
(Lu
3+
> La
3+
);
Ce
4+
; Sn
4+
Ti
4+
> Ti
3+
, Zr
4+
~ Hf
4+
Cr
6+
> Cr
3+
; Mo
6+
> Mo
5+
>
Mo
4+
; W
6+
> W
4+
; Nb
5+
, Ta
5+
;
Re
7+
> Re
6+
> Re
4+
; V
6+
> V
5+
>
V
4+
; Mn
4+
; Fe
3+
; Co
3+
; As
5+
; Sb
5+
Th
4+
; U
6+
> U
4+
PGE
6+
> PGE
4+
, etc. (Ru, Ir, Os)
Acids
Fe
2+
, Mn
2+
, Co
2+
, Ni
2+
,
Cu
2+
, Zn
2+
, Pb
2+
, Sn
2+
,
As
3+
, Sb
3+
, Bi
3+
Acids
Au
+
> Ag
+
> Cu
+
Hg
2+
> Cd
2+
Pt
2+
> Pd
2+
other PGE
2+
Tl
3+
> Tl
+
Bases
F
-
; H
2
O, OH
-
, O
2-
; NH
3
; NO
3
-
;
CO
3
2-
> HCO
3
-
; SO
4
2-
> HSO
4
-
;
PO
4
3-
> HPO
4
2-
> H
2
PO
4
-
;
carboxylates (i.e., acetate,
oxalate, etc.);
MoO
4
2-
; WO
4
2-
Bases
Cl
-
Bases
I
-
> Br
-
; CN
-
; CO;
S
2-
> HS
-
> H
2
S;
organic phosphines (R
3
P);
organic thiols (RP);
polysulfide (S
n
S
2-
),
thiosulfate (S
2
O
3
2-
),
sulfite (SO
3
2-
);
HSe
-
, Se
2-
, HTe
-
, Te
2-
;
AsS
2
-
; SbS
2
-
33
ION PAIRS VS. COORDINATION
COMPLEXES
• ION PAIRS
– formed solely by
electrostatic attraction
– ions often separated by
coordinated waters
– short-lived association
– no definite geometry
– also called outer-
sphere complexes
• COORDINATION
COMPLEXES
– large covalent
component to bonding
– ligand and metal joined
directly
– longer-lived species
– definite geometry
– also called inner-
sphere complexes
34
STABILITY CONSTANTS OF ION PAIRS
CAN BE ESTIMATED FROM
ELECTROSTATIC MODELS
For 1:1 pairs (e.g., NaCl
0
, LiF
0
, etc.)
log K ~ 0 - 1 (I = 0)
For 2:2 pairs (e.g., CaSO
4
0
, MgCO
3
0
, etc.)
log K ~ 1.5 - 2.4 (I = 0)
For 3:3 pairs (e.g., LaPO
4
0
, AlPO
4
0
, etc.)
log K ~ 2.8 - 4.0 (I = 0)
Stability constants for covalently bound coordination
complexes cannot be estimated as easily.
35
COMPLEX FORMATION AND
SOLUBILITY
• Total solubility of a system is given by:
[Me]
T
= [Me]
free
+ E[Me
m
H
k
L
n
(OH)
i
]
• Solubilities of relatively “insoluble” phases such as:
Ag
2
S (pK
s0
= 50); HgS (pK
s0
= 52); FeOOH (pK
s0
=
38); CuO (pK
s0
= 20); Al
2
O
3
(pK
s0
= 34) are probably
not determined by simple ions and solubility products
alone, but by complexes such as: AgHS
0
, HgS
2
2-
or
HgS
2
H
-
, Fe(OH)
+
, CuCO
3
0
and Al(OH)
4
-
.
36
Calculate the concentration of Ag
+
in a solution in
equilibrium with Ag
2
S with pH = 13 and S
T
= 0.1
M (20°C, 1 atm., I = 0.1 M NaClO
4
).
K
s0
= 10
-49.7
= [Ag
+
]
2
[S
2-
]
At pH = 13, [H
2
S
0
] << [HS
-
] because pK
1
= 6.68 and
pK
2
= 14.0 so
S
T
= [HS
-
] + [S
2-
] = 0.1 M
] [
] ][ [
10
2
14
2
÷
÷ +
÷
= =
HS
S H
K
14
2
10
] ][ [
] [
÷
÷ +
÷
=
S H
HS
] [
10
] ][ [
1 . 0
2
14
2
÷
÷
÷ +
+ = S
S H
37
[S
2-
] = 9.1x10
-3
M
[Ag
+
]
2
= 10
-49.7
/10
-2.04
= 10
-47.66

[Ag
+
] = 10
-23.85
= 1.41x10
-24
M
Obviously, in the absence of complexation, the solubility
of Ag
2
S

is exceedingly low under these conditions.
The concentration obtained corresponds to ~1 Ag ion per
liter. What happens if we take 100 mL of such a
solution? Do we then have 1/10 of an Ag ion? No, the
physical interpretation of concentration does not make
sense here. However, an Ag
+
ion-selective electrode
would read [Ag
+
] = 10
-23.85
nevertheless.
] [ 11 ] [
10
] [ 10
1 . 0
2 2
14
2 13
÷ ÷
÷
÷ ÷
= + = S S
S
38
Estimate the concentration of all species in a solution of
S
T
= 0.02 M and saturated with respect to Ag
2
S as a
function of pH (in other words, calculate a solubility
diagram).
[Ag]
T
= [Ag
+
] + [AgHS
0
] + [Ag(HS)
2
-
] + 2[Ag
2
S
3
H
2
2-
]
K
s0
= [Ag
+
]
2
[S
2-
], but [S
2-
] = o
2
S
T
so
K
s0
= [Ag
+
]
2
o
2
S
T

2
0
] [
o
T
s
S
K
Ag =
+
Ag
+
+ HS
-
÷ AgHS
0
log K
1
= 13.3
AgHS
0
+ HS
-
÷ Ag(HS)
2
-
log K
2
= 3.87
Ag
2
S(s) + 2HS
-
÷ Ag
2
S
3
H
2
2-
log K
s3
= -4.82
39
] ][ [
] [
0
1
÷ +
=
HS Ag
AgHS
K
T
S Ag
AgHS
K
1
0
1
] [
] [
o
+
=
T
S HS
1
] [ o =
÷
] [ ] [
1 1
0 +
= Ag S K AgHS
T
o
2
0
1 1
0
] [
o
o
T
s
T
S
K
S K AgHS =
] ][ [
] ) ( [
0
2
2
÷
÷
=
HS AgHS
HS Ag
K
] ][ [ ] ) ( [
0
2 2
÷ ÷
= HS AgHS K HS Ag
2
0
2
1
2
1 2 2
] ) ( [
o
o
T
s
T
S
K
S K K HS Ag =
÷
40
2
2
2 3 2
3
] [
] [
÷
÷
=
HS
H S Ag
K
s
2
1
2
3
2
2 3 2
] [ o
T s
S K H S Ag =
÷
( )
2
1
2
3
2
1
2
1 2 1 1
2
0
2 1 ] [ o o o
o
T s T T
T
s
T
S K S K K S K
S
K
Ag + + + =
41
pH
0 2 4 6 8 10 12 14
l
o
g

c
o
n
c
e
n
t
r
a
t
i
o
n
-24
-22
-20
-18
-16
-14
-12
-10
-8
-6
Ag
+
AgHS
0
Ag(HS)
2
-
Ag
2
S
3
H
2
2-
pH = pK
1
(H
2
S)
42
pH
0 2 4 6 8 10 12 14
l
o
g

c
o
n
c
e
n
t
r
a
t
i
o
n
-10
-9
-8
-7
AgHS
0
Ag(HS)
2
-
Ag
2
S
3
H
2
2-
pH = pK
1
(H
2
S)
1
2
3
4
5
43
Region 1: AgHS
0
and H
2
S
0
are predominant
Ag
2
S(s) + H
2
S
0
÷ 2AgHS
0
log [AgHS
0
] = 1/2log [H
2
S
0
] + 1/2log K
0
] log[
2
=
|
|
.
|

\
|
c
c
S H
T
pH
Ag
Region 2: Ag(HS)
2
-
and H
2
S
0
are predominant
Ag
2
S(s) + 3H
2
S
0
÷ 2Ag(HS)
2
-
+ 2H
+
log [Ag(HS)
2
-
] = 3/2log [H
2
S
0
] + 1/2log K + pH
1
] log[
2
=
|
|
.
|

\
|
c
c
S H
T
pH
Ag
44
Region 3: Ag(HS)
2
-
and HS
-
are predominant
Ag
2
S(s) + 3HS
-
+ H
+
÷ 2Ag(HS)
2
-


log [Ag(HS)
2
-
] = 3/2log [HS
-
] + 1/2log K - 1/2pH
2 / 1
] log[
÷ =
|
|
.
|

\
|
c
c
÷
HS
T
pH
Ag
Region 4: Ag
2
S
3
H
2
2-
and HS
-
are predominant
Ag
2
S(s) + 2HS
-
÷ Ag
2
S
3
H
2
2-


log [Ag
2
S
3
H
2
2-
] = 2log [HS
-
] + log K
0
] log[
=
|
|
.
|

\
|
c
c
÷
HS
T
pH
Ag
45
Region 5: Ag
2
S
3
H
2
2-
and S
2-
are predominant
Ag
2
S(s) + 2S
2-
+ 2H
+
÷ Ag
2
S
3
H
2
2-


log [Ag
2
S
3
H
2
2-
] = 2log [S
2-
] + log K - 2pH
2
] log[
2
÷ =
|
|
.
|

\
|
c
c
÷
S
T
pH
Ag
46
THE CHELATE EFFECT
• Multidentate ligands are much stronger
complex formers than monodentate ligands.
• Chelates remain stable even at very dilute
concentrations, whereas monodentate
complexes tend to dissociate.
47
WHAT IS THE CAUSE OF THE
CHELATE EFFECT?
AG
r
o
= AH
r
o
- TAS
r
0
For many ligands, AH
r
o
is about the same in multi-
and mono-dentate complexes, but there is a larger
entropy increase upon chelation!

Cu(H
2
O)
4
2+
+ 4NH
3
0
÷ Cu(NH
3
)
4
2+
+ 4H
2
O
Cu(H
2
O)
4
2+
+ N
4
÷ Cu(N
4
)
2+
+ 4H
2
O

The second reaction results in a greater increase in
AS
r
0
.

48
Figure 6-11 from Stumm and Morgan. Effect of dilution on degree of complexation.
49
Figure 6-12a from
Stumm & Morgan.
Complexing of Fe(III).
The degree of
complexation is
expressed as ApFe for
various ligands at a
concentration of 10
-2

M. The complexing
effect is highly pH-
dependent because of
the competing effects of
H
+
and OH
-
at low and
high pH, respectively.
50
Figure 6-12b from Stumm & Morgan. Chelation of Zn(II).
51
METAL-ION BUFFERS
Analogous to pH buffers. Consider:
Me + L ÷ MeL
] [
] [
] [
L
MeL K
Me =
If we add MeL and L in approximately equal
quantities, [Me] will be maintained approximately
constant unless a large amount of additional metal
or ligand is added.
If [MeL] = [L], then pMe = pK!
52
Example: Calculate [Ca
2+
] of a solution with the
composition - EDTA = Y
T
= 1.95x10
-2
M, Ca
T
=
9.82x10
-3
M, pH = 5.13 and I = 0.1 M (20°C).
For EDTA, pK
1
= 2.0; pK
2
= 2.67; pK
3
= 6.16; and
pK
4
= 10.26.

6 . 10
4 2
2
10
] ][ [
] [
= =
÷ +
÷
CaY
K
Y Ca
CaY
5 . 3
3 2
10
] ][ [
] [
= =
÷ +
÷
CaHY
K
HY Ca
CaHY
( )
1 2
4 1
4
4 2
2 2
] [
] ][ [ ] [ 1 ] [
] [ ] [ ] [ ) (
÷ +
÷ + ÷ ÷ +
÷ ÷ +
=
+ + =
+ + =
Ca
CaHY CaY
T
Ca
Y H K K Y K Ca
CaHY CaY Ca Ca i
o
T
Ca
Ca
Ca ] [
2+
= o
53
CaHY CaY
T
K K Y H Ca K Y Ca Y
CaHY CaY Y HY Y H Y H Y H Y ii
1
4
4 2 4 2 1 *
4
4
2 4 3 2
2 3
0
4
] ][ ][ [ ] ][ [ ) ]( [
] [ ] [ ] [ ] [ ] [ ] [ ] [ ) (
÷ ÷ + + ÷ + ÷ ÷
÷ ÷ ÷ ÷ ÷ ÷
+ + =
+ + + + + + =
o
1
1 2 3 4
4
2 3 4
3
3 4
2
4
4
0
4
4
*
4
] [ ] [ ] [ ] [
1
] [
] [
÷
+ + + +
=
÷
÷
|
|
.
|

\
|
+ + + + = =
¿
K K K K
H
K K K
H
K K
H
K
H
Y H
Y
i
i
i
o
Equations (i) and (ii) must be solved by trial and error.
We know pH so we can calculate o
4
*
directly. We can
then assume that E[H
i
Y
4-i
] ~ Y
T
- Ca
T
. This permits us
to calculate [Y
4-
] and then solve (i) for [Ca
2+
]. This
approach leads to: [CaY
2-
] = 9.66x10
-3
M; [CaHY
-
] =
1.09x10
-4
M; [Ca
2+
] = 4.12x10
-5
M; [Y
4-
] = 6.05x10
-9

M; [H
3
Y
-
] = 3.07x10
-5
M; [H
2
Y
2-
] = 8.8x10
-3
M; [HY
3-
]
= 8.21x10
-4
M; [H
4
Y
0
] = 2.26x10
-8
M.
54
MIXED COMPLEXES
Examples: Zn(OH)
2
Cl
2
2-
, Hg(OH)(HS)
0
, PdCl
3
Br
2-
, etc.
Generalized complexation reaction:
M + mA + nB ÷ MA
m
B
n
S
n m
n
n m
m
n m n m n m
MB MA B MA
log log log log +
+
+
+
=
+ +
| | |
Log S is a statistical factor. For example, the probability
of forming MAB relative to MA
2
and MB
2
is S = 2
because there are two distinct ways of forming MAB,
i.e., A-M-B and B-M-A. The probability of forming
MA
2
B relative to MA
3
and MB
3
is S = 3.

55
In general, mixed complexes usually only
predominate under a very restricted set of
conditions.
! !
)! (
n m
n m
S
+
=
In simple cases we can use the following
formula:
56
Figure 6-15 from
Stumm and
Morgan.
Predominance of
Hg(II) species as a
function of pCl
and pH. In
seawater, HgCl
4
2-

predominates.
57
COMPETITION FOR LIGANDS
• The ratio of inorganic to organic substances in most
natural waters are usually very high.
• Does a large excess of, say, Ca
2+
or Mg
2+
, decrease the
potential of organic ligands to complex trace metals?
• Example: Fe
3+
, Ca
2+
and EDTA

Fe
3+
+ Y
4-
÷ FeY
-
log K
FeY
= 25.1
Ca
2+
+ Y
4-
÷ CaY
2-
log K
CaY
= 10.7

These data suggest that Fe
3+
should be complexed by
EDTA.
58
But, let us combine the two above expressions to get:
CaY
2-
+ Fe
3+
÷ FeY
-
+ Ca
2+
log K
exchange
= 14.4
] [
] [
4 . 14
] [
] [
2
3
2
÷
÷
+
+
=
FeY
CaY
Fe
Ca
Thus, the relative importance of the two EDTA
complexes depends also on the ratio of calcium to
iron in solution.
For an exact solution to this problem, we also need
to consider the species FeYOH and FeY(OH)
2
.
59
Figure 6.17a from Stumm & Morgan. Competitive effect of Ca
2+
on
complexation of Fe(III) with EDTA. Fe(OH)
3
(s) precipitates at pH > 8.6.
60
Figure 6.17b from Stumm & Morgan. Competitive effect of Ca
2+
on
complexation of Fe(III) with EDTA.
61
Figure 6.17c from Stumm & Morgan. Competitive effect of Ca
2+
on
complexation of Fe(III) with citrate.