Collision Theory

Collision theory is used to explain how different variables affect the rate of a
reaction. Its basic premise is that for a reactants to form into products, the
reactant particles must collide however only a small percentage of these
particles have the orientation and have enough kinetic energy to overcome the
energy barrier to produce said products.
In order for molecules to react, the colliding molecules must possess enough
kinetic energy to overcome the bonds and repulsive energies of the reactants.
The activation enthalpy is the minimum amount of kinetic energy required by a
pair of colliding particles before the reaction will occur and is denoted E a.
The higher the Ea of a reaction, the smaller the amount of collision present and
the slower the reaction as more energy is needed by the colliding molecules.
However, the opposite is also true, the smaller the E a of a reaction, the greater
the amount of collisions present and the faster the reaction as less energy is
needed by the colliding molecules.

Effect of orientation of molecules

The orientation of unsymmetrical molecules can determine whether a reaction
will occur as without proper orientation, the reaction will not occur. An example
of how orientation effects reactions can be seen below. The reaction can only
occur if the hydrogen end of the H-Cl bond approaches the Carbon-Carbon
double bound else they simply bounce off each other because of repulsion
caused by the bonds.
Figure 5 - The Collision of Hydrogen Chloride with ethane to form chloroethane :
(Carbon is shown in black, hydrogen in white, and chloride in green.)

From this we can conclude that an orientation favourable for breaking the bonds
and allowing rearrangement is needed for a successful reaction.

Activation enthalpy and Enthalpy profiles

An enthalpy profile is when a plot is drawn of a reactions progress against the
enthalpy (or energy) profile. They show the energy changes that take place
during a reaction. The highest peak on the graph shows the point in the reaction
where the old bonds are stretched and broken and new bonds have started to
form and the activation enthalpy needed can be seen from the size of the peak.
The curve on the graph below applies to a simple one step reaction however
many reactions take place in a series of steps and drawing a single curve would
be meaningless.

The difference in endothermic and exothermic reactions can be seen in their

respective enthalpy profiles as the energy of the products is higher than the
reactants towards the end of a reaction in an endothermic reaction due to heat
being absorbed from the surrounding whereas the opposite is true for the
exothermic reactions. As the iodine clock reaction is an exothermic reaction, its
enthalpy profile would be similar to the exothermic enthalpy profile.

Effect of Temperature:
Temperature is a measure of the average kinetic energy of
particles. Kinetic energy is the energy possessed by objects in
motion and can be found using the equation:
1
KE= m v 2
2

As temperature increases, molecules move faster and collide

more frequently because of the increased average kinetic
energy. At any temperature the kinetic energy of particles in a
system are spread over a wide range. The Boltzmann is the
distribution function for the distribution of an amount of energy
between identical but distinguishable particles.

The Boltzmann distribution curve can be seen in figure 6.

(Figure 6)

Only the particles represented in the area shaded green have a

high enough energy to react where as those in the area shaded
in blue in the graph will simply bounce apart elastically due to
the repulsion caused by the charges in bonds. So to speed up
the reaction there needs to be an increase in the number of
particles possessing activation energy during collision to cause
a reaction as they possess enough energy to break bonds and
initiate the reaction. The Boltzmann distribution for a graph

with the temperature T and the graph of an increased

temperature labelled T + t is shown below:

From the graph you can see that by increasing the temperature
that the number of molecules with an energy greater or equal
to the activation energy has increased as the peak of the graph
has moved towards the right, closer to the activation energy
which means that more successful collisions will take place
resulting in an increased reaction rate. Increasing the
temperature may not have a difference on the individual
particles within a system but there is a bigger difference to the
proportion of particles that have enough energy to react.
Kinetic Energy
Type equation
here(Initial
.
P=mu
momentum
before collision)

P=mu

(final momentum

after collision

Consider a single gas particle of the mass m and travelling at

a velocity u in a two dimensional box of the length L.
The initial momentum,

P , of the particle is

P=mu

Once the particle bounces off the wall and heads in the
opposite direction the momentum is
P=mu

The change in momentum is therefore, P=mu(mu )=2 mu .

Since force is the change in momentum per unit time, the force
on one wall following the collision can be expressed as
F wall=

2 mu
t

The time between collisions, t , can be found as the time

taken to travel the given distance can be expressed as distance
over the velocity.
t=

d
u

The distance is 2 L as the particle must travel to the wall and

2L
back thus t= u

We can then substitute t

F wall=( 2 mu )

u mu
=
2l
l

into our previous equation to get

Suppose that a large number of molecules,

N , of the mass

are moving independently in the box. Each particle will

have a different velocity so the equation is now
u
( 1 +u22 +...+u2n)
m
l
F wall=
2

Now by calculating the mean value of the squares of all the

velocities

u
( 1 +u22 +...+u2n )
N
2
U =
2

u
( 1 +u22 +...+ u2n )
N U 2=
2

Substituting this into the equation for the force we get

F wall =

Nm U 2
l

Pressure is defined as force over area:

P=

Force
Area

P=

thus

Nm U 2
Area x( l)

2
Now the area is l and multiplied

3
by l we get l which is the volume of the box, v , so
the equation becomes

P=

Nm U
V

or

PV =Nm U 2

However this only considers particles moving along one

dimension so we now considering the problem in three
dimensions.
In two dimensions Pythagorean Theorem states that for a right
angle triangle the length of the hypotenuse is:
Y
X
2

y =x + z
Z

Extending this into three dimensions we get:

Y
C

By
x

Thick
2
2
B (line)=Z + X
2

C2 ( kube)=Y 2 + B2
Combining the two equations we get:
2

C =Y + X +Z

Now as the particles move randomly it means that the mean values for the
velocities X2, Y2 and Z2 are all equal so:

1
C2 =3u 2 therefore C2=u 2
3

Substituting this into our equation we now have the pressure of the gas in three
dimensions:

1
PV = Nm C2
3
N

is the number of particles which is equal to Avogadros number,

multiplied by the number of moles,

N=n(6.02214179 x 1023)
For one mole,

N=L

therefore:

n .

L ,

1
PV = Lm C 2
3
Which can be written as follows using the equation to work out Kinetic Energy

1
2
KE= mu :
2

2 1
PV = L( mC 2)
3 2
Now using the Ideal Gas equation
-1

PV =RT

where

is the molar gas

-1

constant (8.31J mol K ):

2 1
L mC 2 =RT
3 2

Therefore,
Now

( 12 mC )= 32 ( RL ) T
2

R
=1.38 x 1023 J K1
L

which is the Boltzmann constant, k , hence

( 12 mC )= 32 kT
2

Where

m=mass

C=velocity
k =Boltzmann constant

T =temperatureKelvin
This equation allows to calculate the average kinetic energy of the particles in
the reaction.

Effect of Concentration:
Concentration is the number of molecules in a given volume of
a solution.In the iodine clock experiment, the concentration of a
chemical is found using the following equation:
Concentration (moldm-3) = moles (mol) / total volume of
solution (dm-3)
By altering the moles or the total volume of the solution the
concentration of a chemical can be altered which can in turn
have an effect on the rate of reaction.

A mole is a unit of measurement used in chemistry to express

the amount of a chemical substance that contains the number
of particles equivalent to the number of atoms in 12 grams of
pure Carbon-12 (12C). The number of particles in 12 grams of
12
C is 6.02214179 x1023 which is known as Avogadros number.
So essentially one mole contains 6.02214179 x1023 so by
altering the moles of a chemical we can increase or decrease
the number of particles of that chemical within a given volume.
By increasing the concentration we can increase the rate of
reactions as for a reaction to occur, two particles must collide
with the minimum amount of kinetic energy needed to
overcome the bonds and repulsion. Increasing the
concentration means that there is a greater number of particles
of that chemical in a given volume as seen in figure 5 which
means that the frequency of collisions will increase. As the
frequency of collisions will increase due to particles being more
crowded together, the chance that a collision between two
particles has the correct conditions - as discussed previously needed for a reaction to occur will increase which can be seen
in figure 6 leading to an increased the rate of reaction.

(Figure 5)

(Figure 6)

In the case of most reactions, by increasing the concentration,

the rate of reaction increase. However, in certain multi-step
reactions where the reaction occurs in a series of small steps,
increasing the concentration of one constituent may not
increase the overall rate of the reaction. Take the following
reaction:

The pace at which A splits into X and Y dictates the rate of as it

is the slowest step in the reaction; this is known as the ratedetermining step. If you increase the concentration of A, the
frequency of the rate-determining step will increase due to the
abundance of A and lead to an increase in overall rate.
However, increasing the concentration of B will increase the
frequency of the second step but makes little difference to the
overall rate as for the second step to occur as it depends on the
rate-determining step to occur first and the frequency of that
has not changed.
The reason for the difference in the reaction speed for the
multi-step reaction is due to the different activation enthalpies
needed for the different steps. The rate-determining step
requires colliding particles to have a higher total kinetic energy
to overcome the energy barrier for the reaction to occur leading
to a slower reaction rate; this can be seen in figure 7. This is
why increasing the concentration of the chemicals in the ratedetermining step has a greater effect on the overall rate.
Whereas the second step in the reaction requires a smaller total
kinetic energy between colliding particles so can occur much
faster as seen in figure 8 but it still depends on the speed at
which products are made in the rate determining step; the
faster the products are made, the more frequently the second
step can occur so increasing the concentration of the chemicals
in the second step is less likely to affect the overall rate.

(Figure 11)

(Figure 12)

Catalyst
Catalyst
When a catalyst is added to a reaction, the change in energy can also be seen in
a enthalpy profile as the catalyst provides a different pathway for the reaction so
that less energy is needed during the collision for products to be made. The
enthalpy profile of an endothermic reaction with a catalyst can be seen below.
After adding a catalyst to my reaction I will also draw an enthalpy profile to
compare to my previous one.

Rate equation and Orders of Reactions