Complexes will undergo ligands substitution

reaction.
This ability is known as lability.
If the reaction completes in less than 30 s,
the reaction is called labile.
If not it is called inert.
The dynamics of the reaction can be studied in
the form
of stability constant.

Stability Constant Expressions

For complexes that contain more than one ligand or central
metal ion,
[Cr(H2O)6] 3 + + 6NH3
[Cr(NH 3) 6] 3 + + 6H2O
there are two ways of writing stability constants, depending on
the mechanism taken by the reaction.
Stepwise formation constants, Kn are equilibrium constants
for the reaction in which the central ion consecutively adds
one ligand.

[Cr(H2O)6]3 + + NH3

1 =

[Cr(NH3) (H2O)5]3 + + H2O

[Cr (NH 3 ) (H 2 O)5 ]3+ H 2 O

[Cr (H 2 O)6 ] 3+ NH 3

[Cr(H2O)5(NH3)]3 + + NH3

[Cr(NH3)2 (H2O)4]3+ + H2O

[Cr(NH3 ) (H2 O)5 ]3 + H2 O

2 =
[Cr(NH3 )2 (H2 O)4 ]3 + NH3

[Cr(H2O)4(NH3)2]3+ + NH3

3=

[Cr(NH 3)3 (H2O)3]3+ +H2O

[Cr (NH 3 )3 (H 2 O)3 ]3+ H 2 O

[Cr (NH 3 )2 (H 2 O)4 ]3+ NH 3

[Cr(H2O)3(NH3)3]3+ + NH3 [Cr(NH3)4 (H2O)2]3+ +H2O

4=

[Cr (NH 3 )4 (H 2 O)2 ]3+ H 2 O

[Cr (NH 3 )3 (H 2 O)3 ]3+ NH 3

[Cr(H2O)2(NH3)4]3 + + NH3

[Cr(NH 3)5 (H2O)]3+ + H2O

[Cr(NH3 )5 (H2 O) ]3 + H2 O
5 =
[Cr(H2 O)2 (NH3 )4 ]3 + NH3

[Cr(H2O) (NH3)5]3 + + NH3 [Cr(NH 3)6]3 + + H2O

6=

[Cr (NH 3 )6 ]3+ H 2 O

[Cr (NH 3 )5 (H 2 O) ]3 + NH 3

1 > 2 > 3> 4 > 5 > 6

An Overall formation constant , n is the equilibrium constant for

the reaction in which the central metal ion combines with all of the
ligands necessary to form a specific complex:

[Cr(H2O)6]3 + + NH3 [Cr(NH3) (H2O)5]3 + + H2O

3+

[Cr(NH3 ) (H2 O)5 ]

H2 O
1 =
[Cr(NH3 )6 ]3+ NH3

[Cr(H2O)6] 3 + + 2NH3 [Cr(NH3)2 (H2O)4]3+ + 2H2O

[Cr(NH3 )2 (H2 O)4 ]3+ H2 O
2 =
[Cr(NH3 ) ]3 + NH3 2
3+

[Cr(H2O)6]

+ 3NH3 [Cr(NH3)3 (H2O)3] + 3H2O

3+

3+

[Cr(NH3 )3 (H2 O)3 ]

H2 O
3 =
[Cr(NH3 )6 ]3 + NH3 3

[Cr(H2O)6]3 + + 4NH3 [Cr(NH3)4(H2O)2]3 + + 4H2O

[Cr(NH3 )4 (H2 O)2 ]3+ H2 O
4 =
[Cr(H2 O)6 ]3+ NH3 4

[Cr(H2O)6]3+ + 5NH3 [Cr(NH 3)5(H2O)]3+ + 5H2O

3+

[Cr(NH3 )5 (H2 O) ]
H2 O
5 =
[Cr(H2 O)6 ]3+ NH3 5

[Cr(H2O)6]3 + + 6NH3 [Cr(NH3)6]3+ + 6H2O

[Cr(NH3 )6 ]3 + H2 O
6 =
[Cr(H2 O)6 ]3+ NH3 6
=123 456
Factors affecting the stability constant:
Nature of the central ion (effective charge)
Nature of the ligand (field strength)
Chelating Effect

This greater stability for complexes of chelate

complexes is termed the chelate effect.
Its origin is primarily in the differences in entropy
between chelate and non-chelate
complex reactions.
The formation of chelate complexes results in
greater disorder
because of the formation of a larger number of
free particles in the products whereas
there is no change in the number of particles in the
formation of comparable nonchelate
complexes.

[Cu(OH2)4]2+ + en [Cu(OH2)2(en)]2+ + 2 H2O

H = -54 kJ mol-1, S = 23 J K-1 mol-1
[Cu(OH2)4]2++2NH3 [Cu(OH2)2(NH3)2]2++ 2H2O
H = -46 kJ mol-1, S = -8.4 J K-1 mol-1
The formation of chelate complexes results in greater
disorder because of the formation of a larger number
of free particles in the products whereas there is no
change in the number of particles in the formation of
comparable nonchelate complexes