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Introduction
These pages describe the collision theory of reaction rates. They cover collision theory,
and describe and explain the individual factors which affect the rate of a reaction that is
surface area, concentration, pressure, temperature and catalysts on reaction rates. The
first part 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).We are
going to look in detail at reactions which involve a collision 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.
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.
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. It looks like this:
The state of maximum energy of the system is called the activated complex or its
transition state. For a simple over-all exothermic reaction (the products are less
energetic than the reactants), energy is released as heat or eventually light. 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.
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.
The area under the curve is a measure of the total number of particles present. The
reason for this lies in some maths that you will learn at the end of this year. 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!
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. To enable them to react we either have to change the shape of the curve, or
move the activation energy further to the left.
THE EFFECT OF SURFACE AREA ON REACTION RATES
The more finely divided the solid is, the faster the reaction happens. A powdered solid
will normally produce a faster reaction than if the same mass is present as a single lump.
The powdered solid has a greater surface area than the single lump.
Some examples
In the lab, powdered calcium carbonate reacts much faster with dilute hydrochloric acid
than if the same mass was present as lumps of marble or limestone.
Catalytic converters
Catalytic converters use metals like platinum, palladium and rhodium to convert
poisonous compounds in vehicle exhausts into less harmful things. For example, a
reaction which removes both carbon monoxide and an oxide of nitrogen is:
Because the exhaust gases are only in contact with the catalyst for a very short time, the
reactions have to be very fast. The extremely expensive metals used as the catalyst are
coated as a very thin layer onto a ceramic honeycomb structure to maximise the surface
area.
The explanation
You are only going to get a reaction if the particles in the gas or liquid collide with the
particles in the solid. Increasing the surface area of the solid increases the chances of
collision taking place. Imagine a reaction between magnesium metal and a dilute acid
like hydrochloric acid. The reaction involves
collision between magnesium atoms and
hydrogen ions.
For many reactions involving liquids or gases, increasing the concentration of the
reactants increases the rate of reaction. In a few cases, increasing the concentration of
one of the reactants may have little noticeable effect of the rate. These cases are
discussed and explained further. Don't assume that if you double the concentration of
one of the reactants that you will double the rate of the reaction. It may happen like that,
but the relationship may well be more complicated.
Some examples
The examples on this page all involve solutions. Changing the concentration of a gas is
achieved by changing its pressure.
Zinc and hydrochloric acid: In the lab, zinc granules react fairly slowly with dilute
hydrochloric acid, but much faster if the acid is concentrated.
The explanation
At first glance this seems very surprising but in certain multi-step reactions in fact it is
so.
Suppose you have a reaction which happens in a series of small steps. These steps are
likely to have widely different rates - some fast, some slow.
For example, suppose two reactants A and B react together in these two stages:
The overall rate of the reaction is going to be governed by how fast A splits up to make
X and Y. This is described as the rate determining step of the reaction.
If you increase the concentration of A, you will increase the chances of this step
happening for reasons we've looked at above. If you increase the concentration of B,
that will undoubtedly speed up the second step, but that makes hardly any difference to
the overall rate. You can picture the second step as happening so fast already that as
soon as any X is formed, it is immediately pounced on by B. That second reaction is
already "waiting around" for the first one to happen.
Increasing the pressure on a reaction involving reacting gases increases the rate of
reaction. Changing the pressure on a reaction which involves only solids or liquids
has no effect on the rate.
An example
In the manufacture of ammonia by the Haber Process, the rate of reaction between the
hydrogen and the nitrogen is increased by the use of very high pressures.
In fact, the main reason for using high pressures is to improve the percentage of
ammonia in the equilibrium mixture, but there is a useful effect on rate of reaction as
well.
The explanation
Increasing the pressure of a gas is exactly the same as increasing its concentration. If
you have a given mass of gas, the way you increase its pressure is to squeeze it into a
smaller volume. If you have the same mass in a smaller volume, then its concentration
is higher. You can also show this relationship mathematically if you have come across
the ideal gas equation:
The same argument applies whether the reaction involves collision between two
different particles or two of the same particle.
In order for any reaction to happen, those particles must first collide. This is true
whether both particles are in the gas state, or whether one is a gas and the other a solid.
If the pressure is higher, the chances of collision are greater.
Suppose that at any one time 1 in a million particles have enough energy to equal or
exceed the activation energy. If you had 100 million particles, 100 of them would react.
If you had 200 million particles in the same volume, 200 of them would now react. The
rate of reaction has doubled by doubling the pressure.
Examples
The explanation
Particles can only react when they collide. If you heat a substance, the particles move
faster and so collide more frequently. That will speed up the rate of reaction.
That seems a fairly straightforward explanation until you look at the numbers! It turns
out that the frequency of two-particle collisions in gases is proportional to the square
root of the Kelvin temperature. If you increase the temperature from 293 K to 303 K
you will increase the collision frequency by a factor of just 1.7% for a 10° rise. The rate
of reaction will probably have doubled for that increase in temperature - in other words,
an increase of about 100%. The effect of increasing collision frequency on the rate of
the reaction is very minor. The important effect is quite different.
Collisions only result in a reaction if the particles collide with enough energy to get the
reaction started. This minimum energy required is called the activation energy for the
reaction. You can mark the position of activation energy on a Maxwell-Boltzmann
distribution to get a diagram like this:
Only those particles represented by the area to the right of the activation energy will
react when they collide. The great majority doesn't have enough energy, and will simply
bounce apart. To speed up the reaction, you need to increase the number of the very
energetic particles - those with energies equal to or greater than the activation energy.
Increasing the temperature has exactly that effect - it changes the shape of the graph.
In the next diagram, the graph labelled T is at the original temperature. The graph
labelled T+t is at a higher temperature.
If you now mark the position of the activation energy, you can see that although the
curve hasn't moved very much overall, there has been such a large increase in the
number of the very energetic particles that many more now collide with enough energy
to react.
Remember that the area under a curve gives a count of the number of particles. On the
last diagram, the area under the higher temperature curve to the right of the activation
energy looks to have at least doubled - therefore at least doubling the rate of the
reaction.
Summary
Some examples
Some common examples which you may need for other parts of your syllabus include:
reaction catalyst
Conversion of SO2 into SO3 to make sulphuric acid vanadium(V) oxide, V2O5
The explanation
Collisions only result in a reaction if the particles collide with enough energy to get the
reaction started. This minimum energy required is called the activation energy for the
reaction. You can mark the position of activation energy on a Maxwell-Boltzmann
distribution to get a diagram like this:
Only those particles represented by the area to the right of the activation energy will
react when they collide. The great majority doesn't have enough energy, and will simply
bounce apart.
To increase the rate of a reaction you need to increase the number of successful
collisions. One possible way of doing this is to provide an alternative way for the
reaction to happen which has a lower activation energy.
In other words, to move the activation energy on the graph this way:
Adding a catalyst has exactly this effect on activation energy. A catalyst provides an
alternative route for the reaction. That alternative route has a lower activation energy.
Showing this on an energy profile:
PROBLEMS ON REACTION RATES
2- A similar experiment to the one with manganese (IV) oxide was carried out but
at a higher temperature. The data are shown in the table below.
Time (min) 1 2 3 4 5 6 7 8
0
Vol. of gas (cm3) 4 6 9 10 11 12 12 120
0 0 5 2 7 5 0 0