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THE COLLISION THEORY OF REACTION RATES

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 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 H­Cl bond approaches the carbon­carbon  double bond. Any other collision between the two molecules doesn't work. The  two simply bounce off each other.

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.

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 bond­breaking process, and so the particles don't react.

THE EFFECT OF CONCENTRATION ON  REACTION RATES

This page describes and explains the way that changing the concentration of a  solution affects the rate of a reaction. Be aware that this is an introductory page  only. If you are interested in orders of reaction, you will find separate pages 

dealing with these. You can access these via the rates of reaction menu (link at  the bottom of the page).

The facts What happens?
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 down this page. 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 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 catalytic decomposition of hydrogen peroxide Solid manganese(IV) oxide is often used as a catalyst in this reaction. Oxygen is  given off much faster if the hydrogen peroxide is concentrated than if it is dilute.

The reaction between sodium thiosulphate solution and hydrochloric acid This is a reaction which is often used to explore the relationship between  concentration and rate of reaction in introductory courses (like GCSE). When a  dilute acid is added to sodium thiosulphate solution, a pale yellow precipitate of  sulphur is formed.

THE EFFECT OF TEMPERATURE ON REACTION  RATES
As you increase the temperature the rate of reaction increases. As a rough  approximation, for many reactions happening at around room temperature, the  rate of reaction doubles for every 10°C rise in temperature.

The explanation
Increasing the collision frequency 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 two­particle collisions in gases is proportional to  the square root of the kelvin temperature. If you increase the temperature from  293 K to 303 K (20°C to 30°C), you will increase the collision frequency by a  factor of:

That's an increase of 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 . . . You can mark the position of activation energy on a Maxwell­Boltzmann  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 don't have enough energy, and  will simply bounce apart. 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.
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

What are catalysts? A catalyst is a substance which speeds up a reaction, but is chemically  unchanged at the end of the reaction. When the reaction has finished, you would  have exactly the same mass of catalyst as you had at the beginning. Catalysts  and activation energy 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 like this:

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:

 effect of changing the surface area of a solid on the rate of a reaction it is  involved in. 

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
Note:  Why normally? What exceptions can there be? 

Imagine a case of a very fine powder reacting with a gas. If the powder was in one big heap, the  gas may not be able to penetrate it. That means that its effective surface area is much the same  as (or even less than) it would be if it were present in a single lump. A small heap of fine magnesium powder tends to burn rather more slowly than a strip of  magnesium ribbon, for example.

Some examples Calcium carbonate and hydrochloric acid 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.

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.

Increasing the number of collisions per second increases the rate of reaction.

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: What will happen to the rate of the reaction when I increase the temperature? or What will happen to the rate of the reaction if I increase the concentration of one of the reactants? 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: Why will the reaction go faster if I increase the temperature? or Why will the reaction go faster if I increase the concentration of one of the reactions? 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. How does temperature affect the rate of a chemical reaction? 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. How do catalysts affect the rate of a reaction? 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. How does concentration affect the rate of a reaction? 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. How does surface area affect a chemical reaction? 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. What affect does pressure have on the reaction between two gasses? 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. A catalyst is a substance which alters the rate of a chemical reaction but is chemically unchanged at the end of the reaction. Why not memorise this definition? "..... but is chemically unchanged at the end of the reaction." This means that there is just as much catalyst at the end of a reaction as there was at the beginning. The catalyst is used over and over again. Because catalysts work so rapidly and are used again and

again, it is only necessary to have very small quantities of catalyst present to make a chemical reaction go faster. You might have a "catalytic converter" in the exhaust pipe of your car. If the catalyst was Platinum you might expect silly people to start stealing car exhaust pipes; but there is so little catalyst there that it would not be worthwhile for them. A little bit of catalyst goes a long way! What does the catalytic converter do? Well without it the fumes from your car would cause too much pollution and the car might fail its MOT. Perhaps you don't think that catalysts are very important. "..... alters the rate of a chemical reaction ....." This means that catalysts make chemical reactions go faster. I am still looking for one which will make you do your homework faster, and another which will make me mark it faster. What about chemical reactions. Some of them go very slowly, your chemistry experiment might take hours, days, weeks, or ever years. Imagine if your chemistry teacher asked you to find out what gas is released from Hydrogen Peroxide: you might have to sit there watching your test tube for weeks; your chemistry teacher would keep on asking why you had not finished your work. Eventually you would have enough gas to test; so weeks later you would say "Oh, it is Oxygen Miss." If you had put a little pinch of Manganese Dioxide into the test tube, the gas would be produced in a few minutes. So, you would be able to go long before the end of the lesson. Even better, you would still have the Manganese Dioxide catalyst which you would be able to sell back to your teacher to use with another class. How about the chemical industry. Well they will make much more money if they can make their products quickly. The manufacturers of Nitric Acid use Platinum as a catalyst. Even though this is a very expensive metal, it does not cost too much to use it because they are only using small amounts of it. "A catalyst is a substance ....." This means that it is some kind of chemical substance! It could be a pure element; e.g. Platinum, Nickel; or it could be a pure compound, e.g. Manganese Dioxide, Silica, Vanadium V Oxide, Iron III Oxide; it coulb be dissolved ions, e.g. Copper ions, Cobalt II ions; or it could be a mixture, e.g. Iron-Molybdenum, or it could be a much more complicated compound such as protein (all enzymes are proteins; you learn about them in your biology; they are special cases.) Enzymes are biological catalysts. They are slightly different in that they are easily denatured by heat. If you want to know more about enzymes, jump to the enzyme page (look at the Biology Index). Most catalysts make chemical reactions go faster. Chemists call such catalysts "positive catalysts" or "promoters". However, sometimes we want a chemical reaction to go more slowly. So we choose a "negative catalyst"; we could call this an "inhibitor". My wife put a negative catalyst in our central heating system. She did this to stop the iron bits from rusting. We did not have a problem with the Copper pipes (Copper does not rust), but we might have had a problem with the old Iron radiators: we wanted to stop them

from rusting so we used an inhibitor. I think that we also have an inhibitor in the water cooling system of our car so that the car radiator does not rust. This is cheaper than buying a new car every year when the old one has got too rusty. My baker puts an inhibitor into the bread he makes. This slows down the chemical reactions which make bread go stale. This is important since we only go shopping once a week. We used to put Lead in our petrol; this stops the engine from "knocking". Now we have a better car which uses lead free petrol but the engine can burn it without knocking. You might wonder how catalysts work. There are two ways in which catalysts work. You already know that when two different molecules bump into each other, they might react to make new chemicals. We usually talk about "collisions" between molecules, it would be much simpler to say that the molecules bumped into each other. How fast a chemical reaction is depends upon how frequently the molecules collide. You have probably been told about the "kinetic theory" which is all about heat and how fast molecules move around. What catalysts are doing when they make a chemical reaction go faster is to increase the chance of molecules colliding. The first method is by "adsorption", the second method is by the formation of intermediate compounds. Adsorption This occurs when a molecule sticks onto the surface of a catalyst. Make sure that you spell this word correctly; it is not the same as absorption. Here is an example: it is possible to use Platinum as a catalyst to make sulphur Trioxide from Sulphur Dioxide and Oxygen. Sulphur Trioxide is very important because it is used to make Sulphuric acid which is needed for car batteries. The molecules of the two gases (Sulphur Dioxide and Oxygen) get adsorbed (stuck onto) the surface of a Platinum catalyst. Because the two molecules are held so close together, it is more likely that they will collide and therefore react with each other. The Sulphur Trioxide easily falls off the catalyst leaving space for more Sulphur Trioxide and Oxygen. Intermediate Compounds Many catalysts, including all enzymes" work by forming intermediate compounds. What happens is very simple: the chemicals involved in the reaction combine with the catalyst making an intermediate compound, but this new compound is very unstable. When the intermediate compound breaks down it releases the new compounds and the original catalyst. Well: if you have understood all this, it should be easy to memorise the definition of a catalyst given at the top of the page.