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STABILITY of COORDINATION

COMPOUND

Jurusan Kimia FMIPA


Write complexes in square brackets, with charge
on outside
Ex: Cu2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq)

2+

:NH3
H
|
Cu2+ (aq) + 4 :N H (aq) Cu
|
H
Oxidation Numbers

+2 +4(0) = +2

[Cu(NH3)4]2+
Knowing the charge on a complex ion and the
charge on each ligand, one can determine the
oxidation number for the metal.
Thermodynamic Stability

Stability of a complex in solution (in Lab)


refers to the degree of association between
the two species involved in the state of
equilibrium
the greater the association, the greater the
stability of the compound
The factor which actually determines whether a
chemical process can take place spontaneously is
the change in free energy (G) of system
A reaction can proceed spontaneously in the
direction corresponding to a decrease in the free
energy of the system (negative value of G)
The more greater negative G is the greater the
tendency of the reaction to occur and the greater
the capacity of the system to do useful work
when undergoing the reaction
G = 0, The system is in a state of equilibrium
At the constant temperature and pressure the
change in free energy, accompanying a reaction at
absolut T is equal to the change in enthalpy H- T.
S
The entropy S is a measure of disorder of system.
The change in entropy S is the increase ( S
positif) or decrease (S negatif) in the disorder of
the system accompanying o reaction.
Example : an increase a number particles of system,
The magnitude of the (stability or formation)
equilibrium constant for the association,
quantitatively expresses the stability.
Thus, if we have a reaction of the type:
M + 4L ML4
Then the larger the stability constant, the higher
the proportion of ML4 that exists in the solution.
Free metal ions rarely exist in solution so that M,
will usually be surrounded by solvent molecules
which will compete with the ligand molecules, L,
and be successively replaced by them
For simplicity, we generally ignore these solvent
molecules and write four stability constants as
follows:

l. M + L ML K1 = [ML] / [M] [L]


2. ML + L ML2 K2 = [ML2] / [ML] [L]
3. ML2 + L ML3 K3 = [ML3] / [ML2] [L]
4. ML3 + L ML4 K4 = [ML4] / [ML3] [L]
where K1, K2 etc. are referred to as "stepwise stability
constants".
Alternatively, we can write the
"Overall Stability Constant" thus:
M + 4L ML4 4 = [ML4]/ [M] [L]4
The stepwise and overall stability constants are therefore
related as follows:
4 =K1.K2.K3.K4 or more generally,
n =K1.K2.K3.K4--------------K n
Formation of complex in water does not take
place by the simultaneous formation of all metal-
to ligand bonds, but the ligand replace the H2O
molecules in successive step
For formation of complex [MLn] we can write a
series of stepwise equilibrium reaction:
r
1. Please write of stepwise stability of constant of
K1 until K6
2. Please write of formula for 6
If we take as an example, the steps involved in the
formation of the cuprammonium ion, we have the
following:
Cu2+ + NH3 Cu(NH3)2+ K1 = [Cu(NH3)2+]/[Cu2+] [NH3]

CuNH32+ + NH3 Cu(NH3)22+


K2 = [Cu(NH3)22+]/[Cu(NH3)2+] [NH3]
etc. where K1, K2 are the stepwise stability constants.
Also:
4 = [Cu(NH3)42+]/[Cu2+] [NH3]4
The addition of the four ammine groups to copper
shows a pattern found for most formation constants,
in that the successive stability constants decrease.
The four constants are:
logK1 =4.0, logK2 =3.2, logK3 =2.7, logK4 =2.0 or
log4 =11.9
A number of texts refer to the instability constant
or the dissociation constant of coordination
complexes. This value corresponds to the reciprocal
of the formation constant, since the reactions referred
to are those where fully formed complexes break
down to the aqua ion and free ligands.
G = -RTLn
G = -2.303 RTLog10
G = H - TS
6.12 Stability constants of coordination
complexes

A negative free energy


indicates spontaneity

A negative entropy indicates


the surrounding water is
becoming more ordered
Metal complex formation is governed by thermodynamic processes
in aqueous solution. Free energy change (Go) is negative if the
process is spontaneous and favored---which is based on enthalpy and
entropy. Go = Ho - TSo

When complex formation occurs between charged cations and anions,


with a resulting partial or total cancellation of charge, the changes in
enthalpy for these processes are significantly negative and usually
the predominant factor in complex formation.

However, the accompanying changes in entropy are significantly


more positive because less order is imposed on the H2O molecules
around the uncomplexed metal cations and anionic ligands.

The corresponding values for Go are substantially negative indicating


that very stable complexes are formed.
FACTORS INFLUENCING THE
STABILITY CONSTANTS OF
COORDINATION COMPOUND

The infuence of Oxidation state of metal


The influence of the Size of metal ion
The influence of the electronic
configuration of metal
Mn(II)< Fe(II) < Co(II) < Ni(II) < Cu (II)
>Zn(II) disebut deret Irving Wiliam