c




  
 
  

 


Temperature
Concentrations of reactants
Catalysts
Surface area of a solid reactant
Pressure of gaseous reactants or products

If you are planning an investigation, I suggest that you investigate the

effects of temperature or the effects of the concentration of the reactants
because these will allow you to choose a suitable range of values for the
controlled or independent variable. The dependent variable will be the
rate of the reaction. Keep all the other variables fixed.

To make a prediction for your investigation you will have to ask yourself
the question: c

 
 

 

  
 
 
 or c

 
 

 


 
 
 




 

 The
answer to that question is your prediction. The next thing to do is to
explain your prediction. You will have to answer the question: c 
 



 
 
 or c  




 
 
 




 


The answer to this question is your explanation, and to get the highest
possible marks, you will have to provide a full scientific explanation.

Once you have written your hypothesis (prediction with explanation) you
will decide how to do the experiments, i.e. write the proposed method.

½   
 
  
 
  

 



When two chemicals react, their molecules have to collide with each
other with sufficient energy for the reaction to take place. This is collision
theory. The two molecules will only react if they have enough energy. By
heating the mixture, you will raise the energy levels of the molecules
involved in the reaction. Increasing temperature means the molecules
move faster. This is kinetic theory. If your reaction is between atoms
rather than molecules you just substitute "atom" for "molecule" in your
explanation.

½


  
 

 



Catalysts speed up chemical reactions. Only very minute quantities of

the catalyst are required to produce a dramatic change in the rate of the
reaction. This is really because the reaction proceeds by a different
pathway when the catalyst is present. Adding extra catalyst will make
absolutely no difference. There is a whole page on this site devoted to
catalysts.

½ 


 

  
 

 


Increasing the concentration of the reactants will increase the frequency

of collisions between the two reactants. So this is collision theory again.
You also need to discuss kinetic theory in an experiment where you vary
the concentration. Although you keep the temperature constant, kinetic
theory is relevant. This is because the molecules in the reaction mixture
have a range of energy levels. When collisions occur, they do not
always result in a reaction. If the two colliding molecules have sufficient
energy they will react.

If reaction is between a substance in solution and a solid, you just vary

the concentration of the solution. The experiment is straightforward. If
the reaction is between two solutions, you have a slight problem. Do you
vary the concentration of one of the reactants or vary the concentration
of both? You might find that the rate of reaction is limited by the
concentration of the weaker solution, and increasing the concentration
of the other makes no difference. What you need to do is fix the
concentration of one of the reactants to excess. Now you can increase
the concentration of the other solution to produce an increase in the rate
of the reaction.

½ 
 


 
  

 



If one of the reactants is a solid, the surface area of the solid will affect
how fast the reaction goes. This is because the two types of molecule
can only bump into each other at the liquid solid interface, i.e. on the
surface of the solid. So the larger the surface area of the solid, the faster
the reaction will be.

Smaller particles have a bigger surface area than larger particle for the
same mass of solid. There is a simple way to visualize this. Take a loaf
of bread and cut it into slices. Each time you cut a new slice, you get an
extra surface onto which you can spread butter and jam. The thinner
you cut the slices, the more slices you get and so the more butter and
jam you can put on them. This is "Bread and Butter Theory". You should
have come across the idea in your biology lessons. By chewing your
food you increase the surface area so that digestion can go faster.

c

    
 

 
 
 


 
You should already know that the atoms or molecules in a gas are very
spread out. For the two chemicals to react, there must be collisions
between their molecules. By increasing the pressure, you squeeze the
molecules together so you will increase the frequency of collisions
between them. This is collision theory again.

In a diesel engine, compressing the gaseous mixture of air and diesel

also increases the temperature enough to produce combustion.
Increasing pressure also results in raising the temperature. It is not
enough in a petrol engine to produce combustion, so petrol engines
need a spark plug. When the petrol air mixture has been compressed, a
spark from the plug ignites the mixture. In both cases the reaction
(combustion) is very fast. This is because once the reaction has started,
heat is produced and this will make it go even faster.
Faster reaction rates are achieved by increasing the probability of a successful collision.
Particles require a certain level of energy, called
 
 

 or  before a
successful collision can occur.

Ways to measure rate of reaction:

- measure volume of gas evolved at regular time intervals
- measure rate of decrease in mass of reactant
- measure time taken for a precipitate to appear

Rates of reaction are based on five factors:

1. Concentration of substance
2. Pressure
3. Temperature
4. Catalyst
5. Surface area (per volume ratio)

1. Concentration of reactant
Increased concentration of reactants = Increased rate of reaction
As the concentration of reactants increases, the number of 



   



increases. This in turn increases the chances of successful collisions, increasing
the rate of reaction.

2. Pressure
Increased pressure = increased rate of reaction
 


 
 

When there is an increase in pressure, the  



 
 
 

    
  and this increases the chances of successful collisions. Thus
the rate of reaction is increased.

3. Temperature
Increased temperature = increased rate of reaction
The molecules 


 
 and  


  . Increased chances of
successful collisions leading to a faster rate of reaction.
More molecules may also



 
 

 and the number of successful
collisions also increases. Thus increased temperature leads to a faster rate of reaction.

4. Catalyst
Use of catalyst increases rate of reaction.
A catalyst   
 
 

 and so  
  





 
 


, thus a faster rate of reaction.







     Increasing the amount of catalyst used
will not increase the rates of reaction beyond a cerain point.

5. Surface area
Increased surface area = increased rate of reaction
A larger surface area per volume ratio

  



 between
reactant particles. This increases the chances of successful collisions. Thus the rate of
reaction is increased

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

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.

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.

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. To enable them to react we either have to
change the shape of the curve, or move the activation energy further to
the left. This is described on other pages.
 
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