Energy profile in Chemistry
we can
clearly see that we need an input of energy to get the reaction
going. Once the activation energy barrier has been passed, we can
also see that we get even more energy released, and so the
reaction is overall exothermic.
If we had
an endothermic reaction, a simple energy profile for a non-catalyzed reaction
would look like this:
Unfortunately, for
many reactions, the real shapes of the energy profiles are slightly different
from these, and the rest of this page explores some simple differences. What
matters is whether the reaction goes via a single transition state or an
intermediate. We will look at these two different cases in some detail.
Energy profiles for
reactions which go via a single transition state only
This is much easier to
talk about with a real example. The equation below shows an organic chemistry
reaction in which a bromine atom is being replaced by an OH group in an
organic compound. The starting compound is bromoethane, and the organic
product is ethanol.
During the reaction
one of the lone pairs of electrons on the negatively charged oxygen in the
-OH group is attracted to the carbon atom with the bromine attached.
That's because the
bromine is more electronegative than carbon, and so the electron pair in the
C-Br bond is slightly closer to the bromine. The carbon atom becomes slightly
positively charged and the bromine slightly negative.
As the hydroxide ion
approaches the slightly positive carbon, a new bond starts to be set up
between the oxygen and the carbon. At the same time, the bond between the
carbon and bromine starts to break as the electrons in the bond are repelled
towards the bromine.
At some point, the
process is exactly half complete. The carbon atom now has the oxygen
half-attached, the bromine half-attached, and the three other groups still
there, of course.
And then the process
completes:
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The bonds are half-made and half-broken is called the transition
state, and it is at this point that the energy of the system is at
its maximum. This is what is at the top of the activation energy barrier.
But the transition
state is entirely unstable. Any tiny change in either direction will send it
either forward to make the products or back to the reactants again. Neither
is there anything special about a transition state except that it has this
maximum energy. We can't isolate it, even for a very short
time.
The situation is
entirely different if the reaction goes through an intermediate. Again, we'll
look at a specific example.
Energy profiles for
reactions which go via an intermediate
For reasons which we may
well meet in the organic chemistry part of we
r course, a different organic bromine-containing compound reacts with
hydroxide ions in an entirely different way.
In this case, the
organic compound ionizes slightly in a slow reaction to produce an
intermediate positive organic ion. This then goes on to react very rapidly
with hydroxide ions.
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The big difference in
this case is that the positively charged organic ion can actually be detected
in the mixture. It is very unstable, and soon reacts with a hydroxide ion (or
picks up its bromide ion again). But, for however short a time, it does have
a real presence in the system. That shows itself in the energy profile.
The stability (however
temporary and slight) of the intermediate is shown by the fact that there are
small activation barriers to its conversion either into the products or back
into the reactants again.
Notice that the
barrier on the product side of the intermediate is lower than that on the
reactant side. That means that there is a greater chance of it finding the
extra bit of energy to convert into products. It would need a greater amount
of energy to convert back to the reactants again.
I've labelled these
peaks "ts1" and "ts2" - they both represent transition
states between the intermediate and either the reactants or the products.
During either conversion, there will be some arrangement of the atoms which
causes an energy maximum - that's all a transition state is.
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