THE COLLISION THEORY OF
REACTION RATES
This page describes the collision theory of reaction rates. It
concentrates on the key things which decide whether a
particular collision will result in a reaction - in particular, the
energy of the collision, and whether or not the molecules hit
each other the right way around (the orientation of the collision).
The individual factors which affect the rate of a reaction
(temperature, concentration, and so on) are discussed on
separate pages. You can get at these via the rates of reaction
menu - there is a link at the bottom of the page.
We are going to look in detail at reactions which involve a
collision between two species.
Species: This is a useful term which covers any sort of
particle you like - molecule, ion, or free radical.
Reactions where a single species falls apart in some way are
slightly simpler because you won't be involved in worrying about
the orientation of collisions. Reactions involving collisions
between more than two species are going to be extremely
uncommon (see below).
Reactions involving collisions between two species
It is pretty obvious that if you have a situation involving two
species they can only react together if they come into contact
with each other. They first have to collide, and then they may
react.
Why "may react"? It isn't enough for the two species to collide -
they have to collide the right way around, and they have to
collide with enough energy for bonds to break.
(The chances of all this happening if your reaction needed a
collision involving more than 2 particles are remote. All three (or
more) particles would have to arrive at exactly the same point in
space at the same time, with everything lined up exactly right,
and having enough energy to react. That's not likely to happen
very often!)
The orientation of collision
Consider a simple reaction involving a collision between two
molecules - ethene, CH2=CH2, and hydrogen chloride, HCl, for
example. These react to give chloroethane.
As a result of the collision between the two molecules, the
double bond between the two carbons is converted into a single
bond. A hydrogen atom gets attached to one of the carbons and
a chlorine atom to the other.
Note: The mechanism for this reaction is dealt with on a
separate page. This might help you to understand why the
orientation of the two molecules is so important.
If you want to read a bit more about this, follow this link and
use the BACK button on your browser to return to this page.
The reaction can only happen if the hydrogen end of the H-Cl
bond approaches the carbon-carbon double bond. Any other
collision between the two molecules doesn't work. The two
simply bounce off each other.
Of the collisions shown in the diagram, only collision 1 may
possibly lead on to a reaction.
If you haven't read the page about the mechanism of the
reaction, you may wonder why collision 2 won't work as well.
The double bond has a high concentration of negative charge
around it due to the electrons in the bonds. The approaching
chlorine atom is also slightly negative because it is more
electronegative than hydrogen. The repulsion simply causes the
molecules to bounce off each other.
Note: If you aren't sure about electronegativity , you might
like to follow this link.
Use the BACK button on your browser to return to this page.
In any collision involving unsymmetrical species, you would
expect that the way they hit each other will be important in
deciding whether or not a reaction happens.
The energy of the collision
Activation Energy
Even if the species are orientated properly, you still won't get a
reaction unless the particles collide with a certain minimum
energy called the activation energy of the reaction.
Activation energy is the minimum energy required before a
reaction can occur. You can show this on an energy profile for
the reaction. For a simple over-all exothermic reaction, the
energy profile looks like this:
Note: The only difference if the reaction was endothermic
would be the relative positions of the reactants and products
lines. For an endothermic change, the products would have a
higher energy than the reactants, and so the green arrow
would be pointing upwards. It makes no difference to the
discussion about the activation energy.
If the particles collide with less energy than the activation
energy, nothing important happens. They bounce apart. You can
think of the activation energy as a barrier to the reaction. Only
those collisions which have energies equal to or greater than the
activation energy result in a reaction.
Any chemical reaction results in the breaking of some bonds
(needing energy) and the making of new ones (releasing
energy). Obviously some bonds have to be broken before new
ones can be made. Activation energy is involved in breaking
some of the original bonds.
Where collisions are relatively gentle, there isn't enough energy
available to start the bond-breaking process, and so the
particles don't react.
The Maxwell-Boltzmann Distribution
Because of the key role of activation energy in deciding whether
a collision will result in a reaction, it would obviously be useful to
know what sort of proportion of the particles present have high
enough energies to react when they collide.
In any system, the particles present will have a very wide range
of energies. For gases, this can be shown on a graph called the
Maxwell-Boltzmann Distribution which is a plot of the number of
particles having each particular energy.
Note: The graph only applies to gases, but the conclusions
that we can draw from it can also be applied to reactions
involving liquids.
The area under the curve is a measure of the total number of
particles present.
Note: The reason for this lies in some maths beyond the
scope of an A'level chemistry course. It is important that you
remember that the area under the curve gives a count of the
number of particles even if you don't understand why!
The Maxwell-Boltzmann Distribution and activation energy
Remember that for a reaction to happen, particles must collide
with energies equal to or greater than the activation energy for
the reaction. We can mark the activation energy on the Maxwell-
Boltzmann distribution:
Notice that the large majority of the particles don't have enough
energy to react when they collide. Does this mean that they can
never react? No, it doesn't!
There are exchanges of energy between the particles all the
time - some speed up, others slow down as they collide with
each other. At a constant temperature, the shape of the curve
won't change, but individual particles will spend some of their
time in the lower energy, unreactive region, and some time in the
area where they have enough energy to react if they collide.
If you want to speed the reaction up, one of two things has to
happen. We either have to change the shape of the curve, or
move the activation energy further to the left so that at any one
time there are more particles with enough energy to react. This
is described on other pages.
Note: You can change the shape of the curve by changing
the temperature of the reaction. You can change the position
of the activation energy by adding a catalyst to the reaction.
You could either go straight to these pages if you are
interested, or access them later via the rates of reaction
menu (link at the bottom of the page).
Questions to test your understanding
If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK BUTTON
on your browser to come back here afterwards.
questions on the collision theory
answers
Where would you like to go now?
To the rates of reaction menu . . .
To the Physical Chemistry menu . . .
To Main Menu . . .
© Jim Clark 2002 (last modified October 2018)
