We have established that in order for a reaction to occur at all,
ΔG < 0, however, we still have not
concluded anything about the rate of reaction. This is the
realm of kinetics.
For example, petrol at room temperature is stable, although volatile.
Cars do not spontaneously explode; the petrol sits in the tank essentially
for any length of time without burning. This is despite the
fact that the combustion of petrol is highly exothermic (there is
a large enthalpy change (ΔH), and accompanied
by a favourable entropy increase (ΔS).
Petrol at room temperature is kinetically
stable, because although the Gibb's energy change will be
very large, and K will be enormous (i.e. essentially no product
left), this reaction at room temperature takes a very long time.
At elevated temperatures (i.e. that of a match, or spark-plug spark),
this reaction proceeds much faster (hence cars work!).
What we have stumbled across is that the rate of reaction is not
determined by ΔG, but by something else;
the energy of activation:
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ΔG‡ is
this energy of activation; in simple terms, it is the energy hump
that the system must overcome before the reaction can proceed.
This basic scheme shown above is a very useful representation that
we shall refer to in the future. |
The peak of the graph shown above is known variously
as; the transition state, or activated complex. It is definitely
not an intermediate, which we will discuss later. The transition
state is an unstable state which is passed through momentarily by
a reacting species:
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| Transition State |
The species above in brackets is the transition state
of that particular reaction. The more unstable this transition
state is, the higher the energy of activation, and hence the slower
the reaction is.
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