STABILITY of COORDINATION

COMPOUND

AMARIA
Jurusan Kimia FMIPA
 Sub-CLO (Course Learning Outcome)

 Students are able to explain the stability of coordination

compounds and the factors that influence

Indicator
1. Students are able to explain the stability constants
2. Students are able to explain the thermodynamic parameters of
complex compounds
3. Students are able to explain the factors that affect the stability of
complex compounds
4. Students are able to predict the stability of complex compounds based
on their reaction data
CoCl3.6NH3 CoCl3.5NH3
 Write complexes in square brackets, with charge on
outside
Ex: Cu2+(aq) + 4NH3 (aq) → [Cu(NH3)4]2+ (aq)

2+

:NH3
H
| H 3
Cu (aq) + 4 :N ─ H (aq) →
2+
Cu :N
:
| H 3N

:N
H

H3
 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 of
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:
1. 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      β4 = [ML4]/ [M] [L]4
The stepwise and overall stability constants are therefore
related as follows:
β4 =K1.K2.K3.K4 or more generally,
βn =K1.K2.K3.K4 ..................Kn
 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:

[M(H2O)6]z+ (aq) + L(aq) [M(H2O)5L]z+ (aq) + H2O (l) (1)

[M(H2O)5L]z+ (aq) + L (aq) [M(H2O)4L2]z+ (aq) + H2O (l) (2)

[M(H2O)4L2]z+(aq) + L (aq) [M(H2O)3L3]z+(aq) + H2O (l) (3)

[M(H2O)3L3]z+(aq) + L (aq) [M(H2O)2L4]z+(aq) + H2O (l) (4)

[M(H2O)2L4]z+(aq) + L(aq) [M(H2O)L5]z+(aq) + H2O (l) (5)

[M(H2O)L5]z+(aq) + L(aq) [ML6]z+ (aq) + H2O (l) (6)

 TASK 1
1. Please write of stepwise stability of constant of
K1 until K6
2. Please write of formula for β6
 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
logβ4 = 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.

ΔG° = -RTLnβ
ΔG° = -2.303 RTLog10β
ΔG° = ΔH° - TΔS°
Worked Example
Formation of [Ni(H2O)6 – x (NH)x]2+
Results of pH study using a glass electrode (in 2M
NH4NO3 aqueous solution) give values of the stepwise
stability constant (at 303 K) of [Ni(H2O)6-x(NH3)x]2+
(x = 1- 6) as: log K1 = 2.79; log K2 = 2.26; log K3 = 1.69;
log K4 = 1.25; log K5 = 0.74; log K6 = 0.03.
Calculate (a) β­6 for [Ni(NH3)6]2+, and (b) ΔG°1 (303 K). (c) if
the value of ΔH°1 (303 K) = -16.8 kJ mol-1, calculate ΔS°1
(a) β6 =(R
(303 K). 𝐾1=𝑥 8.314
𝐾2 𝑥 𝐾3 J𝑥 𝐾
K4-1𝑥mol
𝐾5 𝑥-1𝐾)6
log β6 = 𝑙𝑜𝑔 𝐾1 + 𝑙𝑜𝑔 𝐾2 + 𝑙𝑜𝑔 𝐾3 + 𝑙𝑜𝑔 𝐾4 + 𝑙𝑜𝑔 𝐾5 + 𝑙𝑜𝑔 𝐾6
log β6 = 2.79 + 2.26 + 1.69 + 1.25 + 0.74 + 0.03
log β6 = 8.76
β6 = 5.75 𝑥 108
 (b) ΔG°1 (303 K) refers to the stepwise formation
of [Ni(H2O)5(NH3)]2+
ΔG°1 (303 K) = −𝑅𝑇 ln 𝐾1
= −ሺ8.314 𝑥 10−3 𝑥 303ሻln 102.79
= −16.2 𝑘𝐽 𝑚𝑜𝑙 −1 A negative free energy
indicates spontaneity

(c) ΔS°1 (303 K)

ΔG°1 = ΔH°1 - T ΔS°1
ΔH°1− ΔG°1
ΔS°1 =
𝑇
−16.8 −(−16.2)
ΔS°1 (303 K) =
303
= −1.98 𝑥 10−3 𝑘𝐽 𝐾 −1 𝑚𝑜𝑙 −1 A negative entropy indicates
the surrounding water is
ΔS°1 = −1.98 𝐽 𝐾 −1 𝑚𝑜𝑙 −1 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 - TSo

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
Stability Constants of Some Fe(II) and Fe(III) Complexes

Oxidation State +2 Oxidation State +3

Complex Ion β n (25°C) Complex Ion β n (25°C)

[Fe II(CN)6]4- ~1035 [Fe III(CN)6]3- ~1042

[Fe II(phen)3]2+ ~1021 [Fe III(phen)3]3+ ~1014

[Fe II(oxalato)3]4- ~105 [Fe III(oxalato)3]3- ~1018

[Fe II(bipy)3]2+ ~1017 [Fe III(bipy)3]3+ ~1012

The influence of the Size of metal ion
Stepwise Formation Constants of Some Alkaline-Earth Complexes* (arrows
indicate increasing stability

Metal Ion Mg2+ Ca2+ Sr2+ Ba2+

Ionic Radius, Å 0.65 0.99 1.13 1.35

Complex K1 [Mg(C2O4)] [Ca(C2O4)] [Sr(C2O4)] [Ba(C2O4)]

3.7 x 103 1.0 x 103 7.3 x 102 4.9 x 102

Complex K1 [Mg(S2O3)] [Ca(S2O3)] [Sr(S2O3)] [Ba(S2O3)]

0.9 x 102 1.0 x 102 2.1 x 103 4.7 x 103

Complex K1 [Mg(EDTA)]2- [Ca(EDTA)]2- [Sr(EDTA)]2- [Ba(EDTA)]2-

2.0 x 109 2.6 x 1011 2.3 x 109 1.7 x 108

* The coordinated H2O molecules are not shown in the formulas of the complexes
 The influence of the electronic configuration
of metal
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu (II) > Zn(II) disebut deret Irving Wiliam

Stability Constants of Som e Metal-Halide Com plexes

Compd. βn Compd. βn Compd. βn

[SnF3]- ~1010 (25°) [SnCl3]- 9.3 x 103 (25°) [SnBr3]- 3.6 x 102 (25°)

[PtF4]2- not known [PtCl4]2- ~1016 (25°) [PtBr4]2- ~1020 (25°)

[CuF4]2- not known [CuCl4]2- 2.4 x 106 (18°) [CuBr4]2- 5.2 x 108 (18°)
 Effect of Chelation on Stability Constants of Zn(II) Com plexes
(arrows indicate increasing stability)
Complex β n (20°C) Chelate Rings
[Zn(NH3)4]2+ 3.1 x 1010 none
[Zn(NH2CH2CH2NH2)2]2+ 7.9 x 1012 two, isolated
[Zn{N(CH2CH2NH2)3}]2+ 2.5 x 1015 three, fused
[Zn(NH3)2(H2O)2}]2+ 1.6 x 105 none
[Zn(NH2CH2CH2NH2) (H2O)2]2+ 1.2 x 106 one
[Zn(NH3)3(H2O)]2+ 5.0 x 108 none
[Zn{NH(CH2CH2NH2)2}(H2O)]2+ 1.6 x 1010 two, fused
 Task 2

1. (a) Write all the stepwise (K’s) and overall (β’s) stability
constants for the following reactions
(b) Estimate which of all the stepwise constants will be the
greatest
(c) Predict which of all the stepwise constants will be the
smallest

2. The value for formation constants for each step in the

formation of [Ni(en)3]2+ are log K1 = 7.52, log K2 = 6.28, and
log K3 = 4.26 at 30oC in 1.0 M KCl. (a) What is log β3 for
overall formation from Ni2+ and 3 en?, (b) Why do value of K
decrease with K1 > K2 > K3 ?
 Kinetic stability

 Inert: not easily replaced by other ligands

 labile: easily replaced by other ligands

Influenced by external factors, such as ligands

Read text books of Fred Basolo p. 97-106, or

Quagliano, J. V. and Vallarino, L.M. P. 80-90