Estabilidad termodinmica.

Sabemos que, al hablar de estabilidad termodinmica nos referimos al grado

de asociacin entre dos especies en estado de equilibrio (cualitativamente,
entre mayor la asociacin, mayor la estabilidad). La magnitud de la constante
de equilibrio representa el grado de asociacin, por lo tanto, nos da
informacin acerca de la estabilidad.

Efecto quelato.

Recordemos que, se les denomina quelatos a las molculas capaces de formar

anillos que incluyen al centro metlico en un compuesto de coordinacin. La
formacin de quelatos genera compuestos con mayor estabilidad. El efecto
estabilizante es el resultado de varios factores como el obvio incremento en la
rigidez de la molcula, probabilidad de unin del el ligante, etc.

El requisito ms evidente es que los anillos que se formen no debe de estar

muy tensionados, un anillo con muy pocos miembros producir una gran
tensin y por lo tanto una ruptura muy fcil. Por el contrario, un anillo de
muchos miembros, tambin produce tensin en el anillo, adems de que
disminuye la probabilidad de la unin del segundo grupo donador del par
electrnico durante el proceso de formacin del anillo dando como resultado
una menor estabilidad.

Este efecto puede apreciarse cuando se compara la reaccin entre un ion

metlico y un ligante bidentado y un monodentado. Por ejemplo, al agregarse
2,2-bipiridina (relacin 1:2, bipiridina: in metlico) y la piridina (relacin 2:1)
o etilendiamina (2:1) y amoniaco (4:1).

Tabla de datos terodinmicos.

Reaction of ammonia and 1,2-diaminoethane with Cd2+.

# of S /JK-
G /kJmol-1 H /kJmol-1 log
ligands 1
mol-1
2 NH3(1 -28.24 (- -29.79 (- -5.19 4.95
en) 33.30) 29.41) (+13.05) (5.84)
4 NH3(2 -42.51 (- -53.14 (- -35.50 7.44
en) 60.67) 56.48) (+13.75) (10.62)

Reaction of pyridine and 2,2'-bipyridine

with Ni2+.
# of ligands log G /kJmol-1
2 py (1 bipy) 3.5 (6.9) -20 (-39)
 4 py (2 bipy) 5.6 (13.6) -32 (-78)
6 py (3 bipy) 9.8 (19.3) -56 (-110)

Reaction of ammonia and 1,2-

diaminoethane with Ni2+.
# of ligands log G /kJmol-1
1 NH3 2.8 -16
2 NH3 (1 en) 5.0 (7.51) -28.5 (-42.8)
3 NH3 6.6 -37.7
4 NH3 (2 en) 7.87 (13.86) -44.9 (-79.1)
5 NH3 8.6 -49.1
6 NH3 (3 en) 8.61 (18.28) -49.2 (-104.4)

A number of points can be highlighted from this data.

In the first table, it can be seen that the H values for the formation steps are
almost identical, that is, heat is evolved to about the same extent whether forming
a complex involving monodentate ligands or bidentate ligands.
What is seen to vary significantly is the S term which changes from negative
(unfavourable) to positive (favourable). Note as well that there is a dramatic
increase in the size of the S term for adding two compared to adding four
monodentate ligands. (-5 to -35 JK-1mol-1).
What does this imply, if we consider S to give a measure of disorder?

In the case of complex formation of Ni2+ with ammonia or 1,2-diaminoethane, by

rewriting the equilibria, the following equations are produced.

Using the equilibrium constant for the reaction (3 above) where the three
bidentates replace the six monodentates, it has been found that at a temperature
of 25 C (298 K):
G = -2.303 RT log10 (K)
= -2.303 R T (18.28 - 8.61)
= -54 kJ mol-1
Based on measurements made over a range of temperatures, it is possible to
break the G term down into its enthalpy and entropy components. G =
H - TS
The result is that:
H = -29 kJ mol-1
- TS = -25 kJ mol-1
and at 25 C (298 K)
S = +88 J K-1 mol-1

Note that for many years, these numbers were incorrectly recorded in textbooks.
For example, the third edition of "Basic Inorganic Chemistry" by F.A. Cotton, G.
Wilkinson and P.L. Gaus, John Wiley & Sons, Inc, 1995, on page 186 gave the
values as:
G = -67 kJ mol-1
H = -12 kJ mol-1
- TS = -55 kJ mol-1
The conclusion they drew from these incorrect numbers was that the chelate
effect was essentially an entropy effect, since the TS contribution was nearly 5
times bigger than that of H.

In fact, the breakdown of the G into H and TS shows that the two terms
are nearly equal (-29 cf. -25 kJ mol -1) with the H term a little larger! The
entropy term found is still much larger than for ordinary reactions involving
substitution of a non-chelating ligand at a metal ion.
How can we explain this enhanced contribution from entropy? One explanation
is to count the number of species on the left and right hand side of the equation
above.
It will be seen that on the left-hand-side there are 4 species, whereas on the right-
hand-side there are 7 species, that is a net gain of 3 species occurs as the reaction
proceeds. This can account for the increase in entropy since it represents an
increase in the disorder of the system.

An alternative view comes from trying to understand how the reactions might
proceed. To form a complex with 6 monodentates requires 6 separate favourable
collisions between the metal ion and the ligand molecules. To form the tris-
bidentate metal complex requires an initial collision for the first ligand to attach
by one arm but remember that the other arm is always going to be nearby and
only requires a shift in position of the other end to enable the ligand to form the
chelate ring.
If you consider dissociation steps, then when a monodentate group is displaced, it
is lost into the bulk of the solution. On the other hand, if one end of a bidentate
group is displaced the other arm is still attached and it is only a matter of the arm
shifting around and it can be reattached again.

Both sets of conditions favour the formation of the complex with bidentate
groups over that with monodentate groups.