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Topic 4.

2 EQUILIBRIA Dynamic equilibria Equilibrium constants Changing the position of equilibrium


REVERSIBLE REACTIONS A reversible reaction is one which can be made to go in either direction depending on the conditions. If you pass steam over hot iron the steam reacts with the iron to produce a black, magnetic oxide of iron called triiron tetroxide, Fe3O4.

The hydrogen produced in the reaction is swept away by the stream of steam.

Under different conditions, the products of this reaction will also react together. Hydrogen passed over hot triiron tetroxide reduces it to iron. Steam is also produced.

This time the steam produced in the reaction is swept away by the stream of hydrogen.

These reactions are reversible, but under the conditions normally used, they become one-way reactions. The products aren't left in contact with each other, so the reverse reaction can't happen.

Reversible reactions happening in a closed system A closed system is one in which no substances are either added to the system or lost from it. Energy can, however, be transferred in or out at will. In the example we've been looking at, you would have to imagine iron being heated in steam in a closed container. Heat is being added to the system, but none of the substances in the reaction can escape. The system is closed. As the triiron tetroxide and hydrogen start to be formed, they will also react again to give the original iron and steam. So, if you analysed the mixture after a while, what would you find? You would find that you had established what is known as a dynamic equilibrium.

Dynamic equilibria
Explaining the term "dynamic equilibrium" The reaction has reached equilibrium in the sense that there is no further change in the numbers of blue and orange squares. However, the reaction is still continuing. For every orange square that turns blue, somewhere in the mixture it is replaced by a blue square turning orange. This is known as a dynamic equilibrium. The word dynamic shows that the reaction is still continuing. You can show dynamic equilibrium in an equation for a reaction by the use of special arrows. In the present case, you would write it as:

It is important to realise that this doesn't just mean that the reaction is reversible. It means that you have a reversible reaction in a state of dynamic equilibrium.

The "forward reaction" and the "back reaction" The change from left to right in the equation (in this case from blue to orange as it is written) is known as the forward reaction. The change from right to left is the back reaction. Position of equilibrium In the example we've used, the equilibrium mixture contained more orange squares than blue ones. Position of equilibrium is a way of expressing this. You can say things like:

"The position of equilibrium lies towards the orange." "The position of equilibrium lies towards the right-hand side."

If the conditions of the experiment change (by altering the relative chances of the forward and back reactions happening), the composition of the equilibrium mixture will also change. For example, if changing the conditions produced more blue in the equilibrium mixture, you would say "The position of equilibrium has moved to the left" or "The position of equilibrium has moved towards the blue". A more formal look at dynamic equilibria Thinking about reaction rates This is the equation for a general reaction which has reached dynamic equilibrium:

How did it get to that state? Let's assume that we started with A and B. At the beginning of the reaction, the concentrations of A and B were at their maximum. That means that the rate of the reaction was at its fastest. As A and B react, their concentrations fall. That means that they are less likely to collide and react, and so the rate of the forward reaction falls as time goes on.

In the beginning, there isn't any C and D, so there can't be any reaction between them. As time goes on, though, their concentrations in the mixture increase and they are more likely to collide and react. With time, the rate of the reaction between C and D increases

Eventually, the rates of the two reactions will become equal. A and B will be converting into C and D at exactly the same rate as C and D convert back into A and B again.

At this point there won't be any further change in the amounts of A, B, C and D in the mixture. As fast as something is being removed, it is being replaced again by the reverse reaction. We have reached a position of dynamic equilibrium.

Le Chatelier's Principle
A statement of Le Chatelier's Principle

If a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to counteract the change.

Using Le Chatelier's Principle with a change of concentration Suppose you have an equilibrium established between four substances A, B, C and D.

What would happen if you changed the conditions by increasing the concentration of A? According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the change. That means that the position of equilibrium will move so that the concentration of A decreases again - by reacting it with B and turning it into C + D. The position of equilibrium moves to the right.

This is a useful way of converting the maximum possible amount of B into C and D. You might use it if, for example, B was a relatively expensive material whereas A was cheap and plentiful. What would happen if you changed the conditions by decreasing the concentration of A? According to Le Chatelier, the position of equilibrium will move so that the concentration of A increases again. That means that more C and D will react to replace the A that has been removed. The position of equilibrium moves to the left.

This is esssentially what happens if you remove one of the products of the reaction as soon as it is formed. If, for example, you removed C as soon as it was formed, the position n of equilibrium would move to the right to replace it. If you kept on removing it, the equilibrium position would keep on moving rightwards - turning this into a one-way reaction.

. Using Le Chatelier's Principle with a change of pressure This only applies to reactions involving gases:

What would happen if you changed the conditions by increasing the pressure? According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the change. That means that the position of equilibrium will move so that the pressure is reduced again. Pressure is caused by gas molecules hitting the sides of their container. The more molecules you have in the container, the higher the pressure will be. The system can reduce the pressure by reacting in such a way as to produce fewer molecules. In this case, there are 3 molecules on the left-hand side of the equation, but only 2 on the right. By forming more C and D, the system causes the pressure to reduce. Increasing the pressure on a gas reaction shifts the position of equilibrium towards the side with fewer molecules.

What would happen if you changed the conditions by decreasing the pressure? The equilibrium will move in such a way that the pressure increases again. It can do that by producing more molecules. In this case, the position of equilibrium will move towards the left-

hand side of the reaction.

What happens if there are the same number of molecules on both sides of the equilibrium reaction? In this case, increasing the pressure has no effect whatsoever on the position of the equilibrium. Because you have the same numbers of molecules on both sides, the equilibrium can't move in any way that will reduce the pressure again.

Using Le Chatelier's Principle with a change of temperature For this, you need to know whether heat is given out or absorbed during the reaction. Assume that our forward reaction is exothermic (heat is evolved):

This shows that 250 kJ is evolved (hence the negative sign) when 1 mole of A reacts completely with 2 moles of B. For reversible reactions, the value is always given as if the reaction was one-way in the forward direction. The back reaction (the conversion of C and D into A and B) would be endothermic by exactly the same amount.

What would happen if you changed the conditions by increasing the temperature? According to Le Chatelier, the position of equilibrium will move in such a way as to counteract the change. That means that the position of equilibrium will move so that the temperature is reduced again. Suppose the system is in equilibrium at 300C, and you increase the temperature to 500C. How can the reaction counteract the change you have made? How can it cool itself down again? To cool down, it needs to absorb the extra heat that you have just put in. In the case we are looking at, the back reaction absorbs heat. The position of equilibrium therefore moves to the left. The new equilibrium mixture contains more A and B, and less C and D.

If you were aiming to make as much C and D as possible, increasing the temperature on a

reversible reaction where the forward reaction is exothermic isn't a good idea! What would happen if you changed the conditions by decreasing the temperature? The equilibrium will move in such a way that the temperature increases again. Suppose the system is in equilibrium at 500C and you reduce the temperature to 400C. The reaction will tend to heat itself up again to return to the original temperature. It can do that by favouring the exothermic reaction. The position of equilibrium will move to the right. More A and B are converted into C and D at the lower temperature.

Summary

Increasing the temperature of a system in dynamic equilibrium favours the endothermic reaction. The system counteracts the change you have made by absorbing the extra heat. Decreasing the temperature of a system in dynamic equilibrium favours the exothermic reaction. The system counteracts the change you have made by producing more heat..

Le Chatelier's Principle and catalysts adding a catalyst makes absolutely no difference to the position of equilibrium, and Le Chatelier's Principle doesn't apply to them. This is because a catalyst speeds up the forward and back reaction to the same extent. Because adding a catalyst doesn't affect the relative rates of the two reactions, it can't affect the position of equilibrium. So why use a catalyst? For a dynamic equilibrium to be set up, the rates of the forward reaction and the back reaction have to become equal. This doesn't happen instantly. For a very slow reaction, it could take

years! A catalyst speeds up the rate at which a reaction reaches dynamic equilibrium.

THE HABER PROCESS

A brief summary of the Haber Process


The Haber Process combines nitrogen from the air with hydrogen derived mainly from natural gas (methane) into ammonia. The reaction is reversible and the production of ammonia is exothermic.

A flow scheme for the Haber Process looks like this:

Some notes on the conditions The catalyst The catalyst is actually slightly more complicated than pure iron. It has potassium hydroxide added to it as a promoter - a substance that increases its efficiency.

The pressure The pressure varies from one manufacturing plant to another, but is always high. Recycling At each pass of the gases through the reactor, only about 15% of the nitrogen and hydrogen converts to ammonia. (This figure also varies from plant to plant.) By continual recycling of the unreacted nitrogen and hydrogen, the overall conversion is about 98%.

Explaining the conditions


The proportions of nitrogen and hydrogen The mixture of nitrogen and hydrogen going into the reactor is in the ratio of 1 volume of nitrogen to 3 volumes of hydrogen. Avogadro's Law says that equal volumes of gases at the same temperature and pressure contain equal numbers of molecules. That means that the gases are going into the reactor in the ratio of 1 molecule of nitrogen to 3 of hydrogen. That is the proportion demanded by the equation. In some reactions you might choose to use an excess of one of the reactants. You would do this if it is particularly important to use up as much as possible of the other reactant - if, for example, it was much more expensive. That doesn't apply in this case. There is always a down-side to using anything other than the equation proportions. If you have an excess of one reactant there will be molecules passing through the reactor which can't possibly react because there isn't anything for them to react with. This wastes reactor space particularly space on the surface of the catalyst.

The temperature Equilibrium considerations You need to shift the position of the equilibrium as far as possible to the right in order to produce the maximum possible amount of ammonia in the equilibrium mixture. The forward reaction (the production of ammonia) is exothermic.

According to Le Chatelier's Principle, this will be favoured if you lower the temperature. The system will respond by moving the position of equilibrium to counteract this - in other words by producing more heat. In order to get as much ammonia as possible in the equilibrium mixture, you need as low a temperature as possible. However, 400 - 450C isn't a low temperature! Rate considerations The lower the temperature you use, the slower the reaction becomes. A manufacturer is trying to produce as much ammonia as possible per day. It makes no sense to try to achieve an equilibrium mixture which contains a very high proportion of ammonia if it takes several years for the reaction to reach that equilibrium. You need the gases to reach equilibrium within the very short time that they will be in contact with the catalyst in the reactor. The compromise 400 - 450C is a compromise temperature producing a reasonably high proportion of ammonia in the equilibrium mixture (even if it is only 15%), but in a very short time.

The pressure Equilibrium considerations

Notice that there are 4 molecules on the left-hand side of the equation, but only 2 on the right. According to Le Chatelier's Principle, if you increase the pressure the system will respond by favouring the reaction which produces fewer molecules. That will cause the pressure to fall again. In order to get as much ammonia as possible in the equilibrium mixture, you need as high a pressure as possible. 200 atmospheres is a high pressure, but not amazingly high. Rate considerations Increasing the pressure brings the molecules closer together. In this particular instance, it will increase their chances of hitting and sticking to the surface of the catalyst where they can react. The higher the pressure the better in terms of the rate of a gas reaction.

Economic considerations Very high pressures are very expensive to produce on two counts. You have to build extremely strong pipes and containment vessels to withstand the very high pressure. That increases your capital costs when the plant is built. High pressures cost a lot to produce and maintain. That means that the running costs of your plant are very high. The compromise 200 atmospheres is a compromise pressure chosen on economic grounds. If the pressure used is too high, the cost of generating it exceeds the price you can get for the extra ammonia produced.

The catalyst Equilibrium considerations The catalyst has no effect whatsoever on the position of the equilibrium. Adding a catalyst doesn't produce any greater percentage of ammonia in the equilibrium mixture. Its only function is to speed up the reaction. Rate considerations In the absence of a catalyst the reaction is so slow that virtually no reaction happens in any sensible time. The catalyst ensures that the reaction is fast enough for a dynamic equilibrium to be set up within the very short time that the gases are actually in the reactor.

Separating the ammonia When the gases leave the reactor they are hot and at a very high pressure. Ammonia is easily liquefied under pressure as long as it isn't too hot, and so the temperature of the mixture is lowered enough for the ammonia to turn to a liquid. The nitrogen and hydrogen remain as gases even under these high pressures, and can be recycled.

EQUILIBRIUM CONSTANTS 1. Expressions for equilibrium constant (Kc) C + 2D

Consider the reversible reaction A + 3B

The rate expression for the forward reaction can be written: Rate = kf[A][B]3, where kf is the rate constant for the forward reaction. The rate expression for the reverse reaction can be written: Rate = kr[C][D]2, where kr is the rate constant for the reverse reaction. At equilibrium, the rates of the forward and reverse reactions are equal: kf[A][B]3 = kr[C][D]2 This can be rearranged to give kf/ kr = [C][D]2 [A][B]3 Since the rate constants are constant at a given temperature, it follows that the term kf/ kr is also constant at a given temperature. It is therefore normally regarded as a single constant Kc and is known as the equilibrium constant of the reaction. Kc = [C][D]2 [A][B]3

2.

Units for equilibrium constants (Kc)

The units of the equilibrium constant vary, depending on the number of species involved. The units can be deduced by multiplying out the units of concentration and cancelling as appropriate. The units of the above equilibrium constant are mol-1dm3. Eg H2(g) + I2(g) 2HI(g) Kc = [HI]2 It has no units. [H2][I2] Eg PCl5(g) PCl3(g) + Cl2(g)

Kc = [PCl3][Cl2] It has units of moldm-3. [PCl5] Extension equilibrium constants The value and units of equilibrium constant depends on the way the reaction is written. Eg consider the equilibrium 2SO2(g) + O2(g) K1c = [SO3]2 units mol-1dm3. [SO2]2[O2] 2SO3(g)

If written in the following way, however: SO2(g) + 1/2O2(g) K2c = [SO3] units mol-1/2dm3/2. [SO2][O2]1/2

SO3(g)

K1c and K2c do not have the same units or the same numerical value; in fact K1c = (K2c)2. The equilibrium constants of the forward and reverse reactions are not the same, but are related by a simple relationship: Eg for the reaction 2SO2(g) + O2(g) Kc(f) = [SO3]2 [SO2]2[O2] Kc(r) = 2SO3(g)

[SO2]2[O2] [SO3]2

The two equilibrium constants can be related by the relationship Kc(f)= 1/Kc(r)

3.

Calculations of equilibrium constants (Kc)

If the concentrations of all the reacting species are known, the equilibrium constant can be calculated by putting the values into the expression for the equilibrium constant and computing the value. Often, however, the concentration of only one of the species at equilibrium is given, and the others must be deduced. This is done by considering the way in which the species react: Eg Consider the equilibrium H2(g) + I2(g) 2HI(g)

If the initial amounts of hydrogen and iodine are a and b, and x moles of hydrogen react with x moles of iodine to give 2x moles of hydrogen iodide, then the amounts of hydrogen and iodine in the mixture at equilibrium are (a-x) and (b-x) respectively. H2(g) + I2(g) Initially: a b 0 At equilibrium: (a-x) (b-x) 2x 2HI(g)

If a, b and the amount of one of the species present at equilibrium is known, then the value of x can be deduced and the amounts of all the other species at equilibrium can also be deduced. Eg If 1.5 mol of hydrogen and 1.2 mole of iodine are mixed together and allowed to reach equilibrium, the amount of hydogen iodide present at equilibrium is found to be 1.6 mol. 2x = 1.6, so x = 0.8, (a-x) = 0.7 and (b-x) = 0.4 Therefore at equilibrium there are 0.7 moles of hydrogen, 0.4 moles of iodine and 1.6 moles of hydrogen iodide. These amounts can be converted into concentrations, and then inserted into the expression for equilibrium constant.

CHANGING THE POSITION OF EQUILIBRIUM If the conditions are changed after equilibrium has been established, the system may no longer be at equilbrium and may move in one direction or another to re-establish equilibrium. The direction in which the system will move to re-establish equilibrium can be predicted by Le Chatelier's principle: "If a constraint is imposed on a system at equilibrium, then the system will respond in such a way as to counteract the effect of that constraint." Such constraints can be the addition or removal of one of the reactants or products, a change in pressure, a change in temperature or the addition of a catalyst.

Each must be treated separately: 1. Concentration Le Chatelier's principle predicts that if a reactant's concentration in a system is increased, the system will move to the right in order to decrease the concentration of that reactant. If the reactant's concentration is decreased, the system will move to the left in order to replace that reactant. Similarly, if a product's concentration is increased then the system will move to the left and if a product's concentration is decreased then the system will move to the right. Changing the concentrations of reactants and products has no effect on the rate constants of the forward or reverse reactions. Therefore it has no effect on the equilibrium constant. Given that Kc is unchanged, the effect of changing the concentration of one of the species can be shown with reference to Kc: Consider the reaction: aA + bB cC + dD

Kc = [C]c [D]d [A]b [B]b If the concentration of A or B is increased, then [C] and [D] must increase to maintain Kc. Similarly if the concentration of C or D is increased, then [A] and [B] must increase to maintain Kc. 2. Pressure The pressure in a system depends on the number of gas molecules in the system. Le Chatelier's principle therefore predicts that if the pressure of the system is increased, the system will move towards the side which has fewer gas moles. If the pressure of the system is decreased, the system will move towards the side which has more gas moles. If the number of gas moles on both sides in the same, then pressure has no effect on the equilibrium position. Eg PCl5(g) PCl3(g) + Cl2(g) If the pressure is increased, the system will move to the left. If the pressure is decreased, the system will move to the right. Eg 2SO2(g) + O2(g) 2SO3(g) If the pressure is increased, the system will move to the right. If the pressure is decreased, the system will move to the left. Eg 2H2S(g) + SO2(g) 3S(s) + 2H2O(l) If the pressure is increased, the system will move to the right. If the pressure is decreased, the system will move to the left. Eg H2(g) + I2(g) 2HI(g) Changing the pressure will have no effect on the position of this equilibrium.

Since changes in pressure affect the reactant concentrations and not the rate constants, it follows that the equilibrium constant is not affected by changes in pressure. 3. Temperature

If the forward reaction is exothermic, then the temperature of the system will rise if the forward reaction takes place. The reverse reaction will therefore be endothermic, and the temperature of the system will fall if the reverse reaction takes place. Le Chatelier's principle therefore predicts that an increase in temperature will favour the endothermic reaction, and that a decrease in temperature will favour the exothermic reaction. If the forward reaction is exothermic, then an increase in temperature will cause the system to shift to the left, and a decrease in temperature will cause the system to shift to the right. If the forward reaction is endothermic, than an increase in temperature will cause the system to shift to the right, and a decrease in temperature will cause the system to shift to the left. If H = 0, then a change in temperature will have no effect on the position of equilibrium. Eg 2SO2(g) + O2(g) 2SO3(g), H = -ve The forward reaction is exothermic so is favoured by decreasing the temperature. The reverse reaction is endothermic so is favoured by increasing the temperature. Eg CaCO3(s) CaO(s) + CO2(g), H = +ve The forward reaction is endothermic so is favoured by increasing the temperature. The reverse reaction is exothermic so is favoured by decreasing the temperature. A change in temperature changes the rate constants for both forward and reverse reactions and is therefore likely to change the value of the equilibrium constant. If the reaction is exothermic, then an increase in temperature will cause the value of Kc to decrease, and if the reaction is endothermic, then an increase in temperature will cause the value of Kc to increase. 4. Catalysts

The addition of a catalyst will have no effect on the position of equilibrium. It will increase the rate of the forward and reverse reactions, but by the same amount. The position of equilibrium will thus be unchanged. As the position of equilibrium is unchanged, it follows that adding a catalyst has no effect on the equilibrium constant.

5. Summary Effect of changing conditions on a system at equilibrium Change Concentratio n Type of change Add reactant or remove product Add product or remove reactant Increase pressure or decrease volume Decrease pressure or increase volume Increase temperature Decrease temperature Catalyst Add or remove catalyst Effect on equilibrium position Moves to right Moves to left Moves towards side with fewer gas moles (right if n = -ve, left if n = +ve) Moves towards side with more gas moles (left if n = -ve, right if n = +ve) Moves in endothermic direction (right if H = +ve, left if H = -ve) Moves in exothermic direction (left if H = +ve, right if H = -ve) No effect Effect on equilibrium constant No effect No effect No effect

Pressure (or volume)

No effect Increases (if H = +ve) Decreases (if H = ve) Decreases (if H = +ve) Increases (if H = -ve) No effect

Temperature