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# explain, using collision theory, how temperature, concentration/ pressure, surface area and nature of reactants affect the

## rate of reaction describe the effect of a catalyst on the rate of reaction

where [A] and [B] express the concentration of the species A and B, respectively (usually in moles per liter (molarity, M)); x and y are not the respective stoichiometric coefficients of the balanced equation; they must be determined experimentally. k is the rate coefficient or rate constant of the reaction. The value of this coefficient k depends on conditions such as temperature, ionic strength, surface area of the adsorbent or light irradiation. For elementary reactions, the rate equation can be derived from first principles using collision theory. Again, x and y are NOT always derived from the balanced equation.

## 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.

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.

he 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.
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).

## Electrophilic addition reactions involving hydrogen bromide

Hydrogen bromide is chosen as a typical hydrogen halide. Bromine is more electronegative than hydrogen. That means that the bonding pair of electrons is pulled towards the bromine end of the bond, and so the hydrogen bromide molecule is polar.

The reaction of ethene with hydrogen bromide The structure of ethene is shown in the diagram on the right. The pi bond is an orbital above and below the plane of the rest of the molecule, and relatively exposed to things around it. The two electrons in this orbital are highly attractive to anything which is positively charged.

The slightly positive hydrogen atom in the hydrogen bromide acts as an electrophile, and is strongly attracted to the electrons in the pi bond.

Electrophile: A substance with a strong attraction to a negative region in another substance. Electrophiles are either fully positive ions, or the slightly positive end of a polar molecule.

The electrons from the pi bond move down towards the slightly positive hydrogen atom. In the process, the electrons in the H-Br bond are repelled down until they

## are entirely on the bromine atom, producing a bromide ion.

That leaves you with these two ions at this half-way stage of the reaction:

The ion with a positive charge on the carbon atom is called a carbocation or carbonium ion (an older term). Why is there a positive charge on the carbon atom? The pi bond was originally made up of an electron from each of the carbon atoms. Both of those electrons have been used to make a new bond to the hydrogen. That leaves the right-hand carbon an electron short - hence positively charged. In the second stage of the mechanism, the lone pair of electrons on the bromide ion is strongly attracted to the positive carbon and moves towards it until a bond is formed.

Note: For clarity only one of the lone pairs around the bromide ion is shown. That's perfectly acceptable, because the other three lone pairs aren't involved in the process - they are pointing in the wrong directions.

## The overall mechanism is therefore

The reaction of cyclohexene with hydrogen bromide Cyclohexene is chosen an an example of a fairly commonly used symmetrical alkene. The fact that it is a ring structure doesn't make any difference to the mechanism. The full structure of cyclohexene is

## but it is often abbreviated to

In this diagram, there is a carbon atom at each corner, and enough hydrogens attached to each carbon to bring the total number of bonds per carbon atom up to 4. The double bond has an easily attacked pi bond exactly as in ethene, and the electrons in that bond are attracted towards the slightly positive hydrogen atom in the HBr. Once again, the pi bond electrons swing to make a bond with the hydrogen, and push the electrons in the H-Br bond fully onto the bromine, making a bromide ion.

Care! Think carefully about which way the pi bond electrons swing. In this case, think of them as being pivotted about the top carbon atom. It is therefore that carbon atom which is joined to the new hydrogen.

In the second stage, one of the lone pairs of electrons on the bromide ion is attracted to the positively charged carbon atom and forms a bond with it.

## Electrophilic addition reactions involving the other hydrogen halides

The mechanisms The other hydrogen halides behave in exactly the same way as hydrogen bromide. For example, compare the reaction between ethene and hydrogen bromide with the one between ethene and hydrogen chloride.

There's no need to learn both mechanisms. As long as you know one of them, all you have to do is swap one halogen atom for another. That's equally true for hydrogen fluoride or hydrogen iodide. The different rates of reaction The rate of reaction increases as you go from HF to HCl to HBr to HI. HF HCl HBr HI fastest reaction slowest reaction

The reason for this is that as the halogen atoms get bigger, the strength of the hydrogen-halogen bond falls. Bond strengths (measured in kilojoules per mole) are: H-F H-Cl H-Br H-I 568 432 366 298

In the first step of these mechanisms, the hydrogen-halogen bond breaks as the electron pair is forced down onto the halogen atom. Breaking bonds needs energy, and if the bond is weaker, it will break more easily needing less energy. That means that the activation energy for the reactions will fall as you go from hydrogen fluoride to hydrogen iodide. The lower the activation energy, the faster the reaction.

Activation energy: The minimum energy needed before a reaction will occur. In this case it is the energy needed to break the various bonds and make the carbocation and the halide ion.

Beware! A red herring! People sometimes get confused because there is another tempting place to look for the reason why the reaction rates are different between the various hydrogen halides. The halogens have different electronegativities - with fluorine being the most electronegative and iodine the least. That means that the hydrogen in HF will have the greatest positive charge and so will be attracted most strongly to the pi bond. It would be tempting to think that that would produce the fastest reaction - but not so! Although the HF may well be attracted most strongly, attraction alone isn't enough. If anything is to happen, bonds have to be broken - and here HF is at a disadvantage, because the bond is very strong. The lesson from all this When you are trying to find reasons for differing rates of reactions, always look first at differences in bond strengths. Electronegativity differences may be interesting, but rarely give you the answer you want!

## THE EFFECT OF TEMPERATURE ON REACTION RATES

This page describes and explains the way that changing the temperature affects the rate of a reaction. It assumes that you are already familiar with basic ideas about the collision theory, and with the Maxwell-Boltzmann distribution of molecular energies in a gas.

The facts
What happens? 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 10C rise in temperature. You have to be careful not to take this too literally. It doesn't apply to all reactions. Even where it is approximately true, it may be that the rate doubles every 9C or 11C or whatever. The number of degrees needed to double the rate will also change gradually as the temperature increases.

Note: You will find the effect of temperature on rate explored in a slightly more mathematical way on a separate page.

Examples Some reactions are virtually instantaneous - for example, a precipitation reaction involving the coming together of ions in solution to make an insoluble solid, or the reaction between hydrogen ions from an acid and hydroxide ions from an alkali in solution. So heating one of these won't make any noticeable difference to the rate of the reaction.

Almost any other reaction you care to name will happen faster if you heat it - either in the lab, or in industry.

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 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 (20C to 30C), 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 . . .

The key importance of activation energy 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 don'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 Increasing the temperature increases reaction rates because of the disproportionately large increase in the number of high energy collisions. It is only these collisions (possessing at least the activation energy for the reaction) which result in a reaction.

## THE EFFECT OF PRESSURE ON REACTION RATES

This page describes and explains the way that changing the pressure of a gas changes the rate of a reaction.

The facts

What happens? 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.

Note: If you want to explore equilibria you will find the topic covered in a separate section of the site.

The explanation
The relationship between pressure and concentration 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:

## Rearranging this gives:

Because "RT" is constant as long as the temperature is constant, this shows that the pressure is directly proportional to the concentration. If you double one, you will also double the other.

Note: If you should be able to do calculations involving the ideal gas equation, but aren't very happy about them, you might be interested in my chemistry calculations book.

The effect of increasing the pressure on the rate of reaction Collisions involving two particles 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.

Reactions involving only one particle If a reaction only involves a single particle splitting up in some way, then the number of collisions is irrelevant. What matters now is how many of the particles have enough energy to react at any one time.

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.

## 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.

Note: The mathematical relationship between concentration and rate of reaction is dealt with on the page about orders of reaction. If you are interested, you can use this link or read about it later via the rate of reaction menu (link at the bottom of the page).

Some examples The examples on this page all involve solutions. Changing the concentration of a gas is achieved by changing its pressure. This is covered on a separate page.

Note: If you want to explore the effect of changing pressure on the rate of a reaction, you could use this link. Alternatively, use the link to the rates of reaction menu at the bottom of this page.

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.

As the sodium thiosulphate solution is diluted more and more, the precipitate takes longer and longer to form.

The explanation
Cases where changing the concentration affects the rate of the reaction This is the common case, and is easily explained. Collisions involving two particles 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 solution, or whether one is in solution and the other a solid. If the concentration is higher, the chances of collision are greater.

Reactions involving only one particle If a reaction only involves a single particle splitting up in some way, then the number of collisions is irrelevant. What matters now is how many of the particles have enough energy to react at any one time.

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 concentration.

Cases where changing the concentration doesn't affect the rate of the reaction At first glance this seems very surprising!

Where a catalyst is already working as fast as it can Suppose you are using a small amount of a solid catalyst in a reaction, and a high enough concentration of reactant in solution so that the catalyst surface was totally cluttered up with reacting particles. Increasing the concentration of the solution even more can't have any effect because the catalyst is already working at its maximum capacity. In certain multi-step reactions This is the more important effect from an A' level point of view. 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.
Note: The overall rate of reaction isn't entirely independent of the concentration of B. If you lowered its concentration enough, you will eventually reduce the rate of the second reaction to the point where it is similar to the rate of the first. Both concentrations will matter if the concentration of B is low enough. However, for ordinary concentrations, you can say that (to a good approximation) the overall rate of reaction is unaffected by the concentration of B.

The best specific examples of reactions of this type comes from organic chemistry. These involve the reaction between a tertiary halogenoalkane (alkyl halide) and a

number of possible substances - including hydroxide ions. These are examples of nucleophilic substitution using a mechanism known as SN1.
Note: If you are interested in exploring nucleophilic substitution reactions further, you could follow this link. Otherwise, you can find more about how the relationship between concentration and rate of reaction is affected by reaction mechanisms by exploring the topics at the bottom of the rates of reaction menu (link below).

## THE EFFECT OF SURFACE AREA ON REACTION RATES

This page describes and explains the effect of changing the surface area of a solid on the rate of a reaction it is involved in. This applies to reactions involving a solid and a gas, or a solid and a liquid. It includes cases where the solid is acting as a catalyst.

The facts
What happens? 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 catalytic decomposition of hydrogen peroxide This is another familiar lab reaction. Solid manganese(IV) oxide is often used as the catalyst. Oxygen is given off much faster if the catalyst is present as a powder than as the same mass of granules.

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.

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

## THE EFFECT OF CATALYSTS ON REACTION RATES

This page describes and explains the way that adding a catalyst affects the rate of a reaction. It assumes that you are already familiar with basic ideas about the collision theory of reaction rates, and with the Maxwell-Boltzmann distribution of molecular energies in a gas.

Note that this is only a preliminary look at catalysis as far as it affects rates of reaction. If you are looking for more detail, there is a separate section dealing with catalysts which you can access via a link at the bottom of the page.

The facts
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. Some examples Some common examples which you may need for other parts of your syllabus include: reaction Decomposition of hydrogen peroxide catalyst manganese(IV) oxide, MnO2 concentrated sulphuric acid Iron vanadium(V) oxide, V2O5 nickel

Nitration of benzene Manufacture of ammonia by the Haber Process Conversion of SO2 into SO3 during the Contact Process to make sulphuric acid Hydrogenation of a C=C double bond

Note: You can find details of these and other catalytic reactions by exploring the menu for the main section on catalysis. You will find a link at the bottom of this page.

The explanation

The key importance of activation energy Collisions only result in a reaction if the particles collide with a certain minimum energy 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 don't have enough energy, and will simply bounce apart. 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: