Energy Profiles

ENERGY PROFILES FOR SIMPLE REACTIONS

energy profiles for reactions are slightly different for
reactions involving an intermediate or just a transition
state.

What is an energy profile?

If you have done any work involving activation energy
or catalysis, you will have come across diagrams like
this:

This diagram shows that, overall, the reaction is

exothermic. The products have a lower energy than the
reactants, and so energy is released when the reaction
happens.
It also shows that the molecules have to possess
enough energy (called activation energy) to get the
reactants over what we think of as the "activation
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Energy Profiles

energy barrier".
In this example of a reaction profile, you can see that a
catalyst offers a route for the reaction to follow which
needs less activation energy. That, of course, causes
the reaction to happen faster.
Diagrams like this are described as energy profiles. In
the diagram above, you can clearly see that you need
an input of energy to get the reaction going. Once the
activation energy barrier has been passed, you can
also see that you get even more energy released, and
so the reaction is overall exothermic.
If you had an endothermic reaction, a simple energy
profile for a non-catalysed 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.
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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

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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:

Note: These diagrams have been simplified

in various ways to make the process clearer.
For example, the true arrangement of the lone
pairs of electrons around the oxygen in the
first diagram has been simplified for clarity.
The bromine also has 3 lone pairs as well as
the bonding pair, but they play no part. And, of
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Energy Profiles

course, the other groups attached to the

carbon have been left out in order to
concentrate on what is important.

The second diagram where 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. You 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

Energy Profiles

example.

Energy profiles for reactions which go via an

intermediate
For reasons which you may well meet in the organic
chemistry part of your course, a different organic
bromine-containing compound reacts with hydroxide
ions in an entirely different way.
In this case, the organic compound ionises slightly in a
slow reaction to produce an intermediate positive
organic ion. This then goes on to react very rapidly with
hydroxide ions.

Note: If you haven't come across the use of

curly arrows in organic chemistry yet, all you
need to know for now is that they show the
movement of a pair of electrons. In the first
equation, for example, the bonding pair of
electrons in the C-Br bond moves entirely on
to the bromine to make a bromide ion. In the
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second equation, a lone pair on the hydroxide

ion moves towards the positive carbon to form
a covalent bond.

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.
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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.