What is the Difference
Between a Transition
State and an
intermediate?
Organic Chemistry > Reactivity: Kinetics, Ther...
Understanding the difference between the
transition state and an intermediate will
help you in drawing the mechanisms,
explaining the mechanistic differences,
and understanding what exactly is going
on in the reaction.
So, let’s start by looking at the picture that,
I'm sure, you have seen quite a few times
by now:eo =Transition States
—e Tot LO
Intermediate
PrA Products
Reaction Coordinate 1
On this diagram we see:
e the x-axis that is a reaction
coordinate: a loosely defined term
meaning the reaction progress in the
general direction from the starting
materials or reagents (SM) to the
products (Pr).e the energy curve describing the
energy states of the components at
a certain point in the reaction.
e the transition states (TS) and an
intermediate (I).
Among other things that you typically see
in these diagrams are the change in
energy and the activation energy, which are
not too important for us at the moment.
Let’s focus on the curve itself for right
now. I've pointed out the transition states
and the intermediate there, but what are
those exactly?Definition of a Transition
State
Transition state is the highest point (or
points) on the reaction coordinate
diagram. Those are the “peaks” or the
“hills” in the picture. A more strict definition
is that a transition state is a molecular
entity that has a lifetime no longer than a
vibration that exhibits some structural
characteristics of both the reactants and
the products. As | couldn't find the “official”
definition, so I've adapted this one from
the Anslyn & Dougherty'’s Modern Physical
Organic Chemistry book. | think, it
describes the transition state the best:¢ it's neither the reactant nor it is a
product
« it resembles both to some extent,
and
« it's not something that can be
isolated (exists only a vibration-long)
The best analogy | can think to describe a
transition state is this: imagine yourself
merrily hopping down the alley in a park.
That moment in time, when you're up in the
air in the mid-jump is your transition state!
You cannot “catch” that state when you're
suspended in the midair, it's neither your
right leg, nor it is your left leg step... it's
something in between. Same applies to
transition states: they are somewhere in
between.Definition of an \ntermediate
Intermediate is a comparatively long-lived
species that can be experimentally
detected and characterized. This means
that an intermediate is an actual molecule
or an ion that you can work with,
sometimes even isolate. That's you
freezing in space as you've landed on one
foot while hopping in a park. It’s not the
beginning of your journey (reactants), nor it
is the end (products). Instead, it’s a
relatively stable midpoint (intermediate).It is also very important to remember that
a reaction doesn’t have to have an
intermediate! You may or may not have one
depending on the nature and the
mechanism of the reaction. There are
plenty of single-step reactions that have
no intermediates at all. A typical first
semester organic chemistry example is an
SN2 reaction that involves no intermediate
whatsoever (we'll see an example later in
this post).
You will always have a transition state
though! Every reaction, no matter how
simple it might be, has a transition state.
For instance, let's consider the following
bromine dissociation reaction giving us
two bromine radicals:% hv “ *
Br? —_—_—_——> :Br- + i Br:
] age Ber | Hy RE be:
eG eG eo
CHS CH
watt Capa
The first transition state is the process of
the C-Br bond elongation that leads to the
eventual bond dissociation and the
formation of the carbocationic
intermediate. This intermediate does exist
long enough (although, still very briefly) so
that we can “catch” it using experimental
techniques and characterize it. The second
step in this reaction has its own transition
state:* CH
A
H,¢- of ma Hae Re ° WE ce
ll _ oH
© Sy be > “o, H-&%
4
om
Ane k
#
4 Nu 4 *
In the second step above we have three
different bonds in the “making-breaking”
state. The H-O and C=C bonds are
forming, while the C-H bond is breaking.
Now, if | were to plot this reaction on the
reaction coordinate vs energy plot, we'll get
something like this:
TI oe eens States
Reaction Ceordinate 4.
