Volumes and Entropy of Activation

Background
This follows on from the rate constant work:
k
2nd
= K

kT/hc
0
(1)
Where K

= exp[-G

/RT], and G

= H

- TS

This gives you how the rate varies with the enthalpy and entropy of activation;
it is the Arrhenius Equation on steroids.
N.B. Only applies to the formation of the transition state (TS)
We can also get the variation of the rate with pressure.
Since dG = Vdp SdT
dG/dP|
T
= V
Hence from (1), -RT d(lnk
2nd
)/dp|
T
= dG

/dP|
T
= V


What is this for?
We can measure these two quantities, and thusly prove the mechanism by which the reaction
proceeds (for simple reactions!).

Consider a reaction in solution. There are two contributions to the entropy and volume: the
reactants, and the solvent. We shall therefore consider the two contributions separately, and
combine them at the end. The effect of the reactants forming the transition state shall be referred to
as the intrinsic effect (IE), and the behaviour of the solvent in the presence of the transition state
the solvent effect (SE).
Consider the two cases:
1) A Dissociative mechanism (DS)
2) An Associative mechanism (AS)

The signs of S

and V

for IE are given below:
Dissociative Associative
S

+ve -ve
V

+ve -ve

For SE we need to consider if the TS is more, or less, solvated. Solvation removes degrees of freedom
from the solvent [electrostriction]. Hence a similar table:
Less solvated More solvated
S

+ve -ve
V

+ve -ve

The method is therefore: to suppose each case, calculate which columns are relevant, add the
columns, and compare with data. If no decision can be reached then a qualitative assessment of
which effect is stronger must be made.
N.B. SE ~ charge
2
/radius



Worked Examples (Q46. Of example sheet)

Reaction 1 (easy)
Let TS be DS [S

and V

> 0]
Then SE small, since metal
3+
-> metal
3+
+ HCONH
2

Hence TS not DS, since S

and V

< 0

Let TS be AS [S

and V

< 0]
Then SE small, since charge on metal/ligands also not changing
Hence TS is AS, since S

and V

< 0

Reaction 3 (medium)
Let TS be DS
Then SE is more solvated, since metal
+
-> metal
2+
+ Cl
-

IE and SE are of opposite sign

Let TS be AS
SE is small since no change in charge
S

and V

< 0
Not what is seen, so not AS

Therefore TS is DS with IE>SE

Reaction 4 (hard)
Let TS be DS
SE is more solvated, since metal
+
-> metal
2+
+ Cl
-
IE and SE are of opposite sign [require SE > IE to fit data]

Let TS be AS
SE is less solvated, since metal
+
+ Br
-
-> neutral complex
IE and SE are of opposite sign [require SE < IE to fit data]

In the case of DS, it is possible that SE > IE, since we have a 2+ species (goes like charge
2
), however
the ions are very large (goes like 1/radius).
In the case of AS, it is more likely that IE > SE, since the ions are both large and only of unit charge.

Hence predict TS is AS, on the balance.