Wh a t i s a
CHEMICAL REACTION
MECHANISM?
The complete, step-by-step description of exactly which bonds are broken,
formed, and in which order.
ACTIVE INTERMEDIATE
An active
intermediate is
a high-energy
molecule that
reacts virtually
as fast as il is
formed.
A + M ----> A* + M
Here the activation occurs
when translational kinetic
energy is, transferred into
energy stored in internal
degrees of freedom.
particularly vibrational
degrees of freedom. An
unstable molecule (i.e.,
active intermediate) is not
formed solely as a
consequence of the molecule
moving at a high velocity
(high translational kinetic
energy).
Frederick Alexander Lindemann
1886-1957
The idea of an active intermediate was first
postulated in 1922 by F. A. Lindermann2
used it to explain changes in reaction order
with changes in reactant concentration.
Because the active intermediates were so
short-lived and present in such low
concentrations, their existence was not
really definitively seen.
As a result. it is
present in very small
concentrations.
Active intermediates
(e.g., A*) can he
formed by collision
or interaction with
other molecules.
The energy must be absorbed
into the chemical bonds where
high-amplitude oscillations will
lead to bond ruptures,
molecular rearrangements. and
decomposition. ln the absence
of photochemical effects or
similar phenomena, the
transfer of translational energy
Properties of an active
to vibrational energy to
intermediate A* produce an active intermediate
can occur only as a
consequence of molecuIar
collision or interaction.
Ahmed Zewail
Since the work of Lindermann, it was not
really definitively seen until the work of
Ahmed Zewail who received the Nobel Prize
in 1999 for femtosecond spectroscopy. His
work on cyclobutane showed the reaction
to form two ethylene molecules did not
proceed directly but formed the active
intermediate shown at the top of the energy
reaction coordinate diagram.

 Pseudo-Steady state
Hypothesis
(PSSH)

In the theory of active intermediates, decomposition of the intermediate does not occur instantaneously after internal activation
of the molecule: rather, there is a time lag, although infinitesimally small, during which the species remains activated. Zewail's
work was the first definitive proof of a gas-phase active intermediate that exists for an infinitesimally span time. Because a
reactive intermediate reacts virtually as fast as it is formed, the net rate of formation of an active intermediate is zero. This
condition is referred to as the Pseudo-Steady-State Hypothesis

SIX STEPS IN FINDING THE REACTION

MECHANISM
Once the rate law is found, the search for the mechanism begins.

After writing rate Iaws

Assume an for the rate of formation
of desired product, w the
active rate laws for each of the
intermediate. active intermediates,
and use the PSSH.

Postulate a Eliminate the concentration

mechanism. utilizing of the intermediate species
the rate law obtained in the rate laws by solving
from experiment the simultaneous equations
data, if possible. developed in Steps 4.

If the derived rate law does

not agree with experimental
Model each reaction observat assume a new
in the mechanism mechanism andor
intermediates and gc~ to
sequence as an Step 3. A szn background in
elementary reaction organic and inorganic
chemistry is helpful in
predicting activated
intermediates for the reaction
under consideration.
 Rules of thumb
for the
development of
MECHANISM

A + A*
--> [COLLISION PRODUCTS]

If a constant appears
in the denominator,
one of the reaction A* -->
steps is probably the [DECOMPOSITION
PRODUCTS]

spontaneous
decomposition of the
active intermediate.

Species having the

concentration(s)
appearing in the
numerator of the sate
law probably produce
[REACTANTS] -->
A* + [OTHER PRODUCTS] the active

intermediate in one of
the reaction steps
 Chain Reaction
A chain reaction consists of
the following sequence:

INITIATION
The initiation step is where the formation of an active intermediate. This is the
generation of a reactive intermediate: a short-lived, highly reactive species that is never
present in large concentrations due to its reactive nature. The unpaired electron is
termed the odd electron or radical electron. Species with unpaired electrons are called
free radicals. Normally radicals are electron-deficient and strongly electrophilic.

PROPAGATION
Interaction of an active intermediate with the reactant or product to produce
another active intermediate. The first propagation step is the reaction of the
reactive intermediate. The radical reacts, and generates another radical. (Molecule
and radical  molecule and radical).

TERMINATION
Deactivation of the active intermediate to form products. If a radical undergoes a
reaction which does not generate another radical, then the chain reaction slows
and stops. Therefore side reactions which consume radicals are detrimental to
chain reactions. These side reactions are called Termination Reactions.