F322 Rates and Equilibrium

Rates and Equilibrium

Candidates should be able to: (a) describe qualitatively, in terms of collision theory, the effect of concentration changes on the rate of a reaction; (b) explain why an increase in the pressure of a gas, increasing its concentration, may increase the rate of a reaction involving gases; (c) state that a catalyst speeds up a reaction without being consumed by the overall reaction; (d) explain that catalysts: (i) affect the conditions that are needed, often requiring lower temperatures and reducing energy demand and CO2 emissions from burning of fossil fuels, (ii) enable different reactions to be used, with better atom economy and with reduced waste, (iii) are often enzymes, generating very specific products, and operating effectively close to room temperatures and pressures, (iv) have great economic importance, eg iron in ammonia production, Ziegler Natta catalyst in poly(ethene) production, platinum/palladium/rhodium in catalytic converters; (e) explain, using enthalpy profile diagrams, how the presence of a catalyst allows a reaction to proceed via a different route with a lower activation energy, giving rise to an increased reaction rate; (f) explain qualitatively the Boltzmann distribution and its relationship with activation energy; (g) describe qualitatively, using the Boltzmann distribution, the effect of temperature changes on the proportion of molecules exceeding the activation energy and hence the reaction rate; (h) interpret the catalytic behaviour in (e), in terms of the Boltzmann distribution; (i) explain that a dynamic equilibrium exists when the rate of the forward reaction is equal to the rate of the reverse reaction; (j) state le Chateliers principle; (k) apply le Chateliers principle to deduce qualitatively (from appropriate information) the effect of a change in temperature, concentration or pressure, on a homogeneous system in equilibrium; (l) explain, from given data, the importance in the chemical industry of a compromise between chemical equilibrium and reaction rate.

Rates of Reaction Rate of reaction is measured in terms of moles of reactant used up or moles of product created per unit time: rate = amount time The units of rate of reaction are therefore mol s-1 The starting point for any study of reaction rates is collision theory: For a reaction to take place, particles of the reactants must collide with one another The particles must collide with energy sufficient to break the necessary bonds in the reactants; they must collide with energy greater than the activation energy for the reaction.

The reaction conditions can affect the rate of a reaction, and we can use collision theory to explain this:

Page 1

F322 Rates and Equilibrium Concentration: Increasing the concentration of a reactant means having more of that reactant per unit volume. Having more particles in the same volume means that collisions, and therefore successful collisions will take place more frequently and the rate will increase. Pressure: Increasing the pressure of a gas compresses the particles into a smaller volume there are more gas particles per unit volume so the effect is the same as increasing the concentration of a reactant. Surface Area: Only the surface of a solid reactant is exposed for collisions to take place with the other reactant(s) so the greater the surface area of a solid, the more frequently collisions between the solid reactant and the other reactant particles will take place, and the more frequently there will be successful collisions. Temperature: Increasing the temperature of a reactant increases the kinetic energy of the particles. The particles move more rapidly and therefore collide more frequently. In addition, the particles collide with greater energy, and so a higher proportion of the collisions which take place will be successful since the particles collided with energy in excess of the activation energy for the reaction. These two effects in combination mean that a small increase in temperature can cause a large increase in rate of reaction. The Boltzmann distribution
lower temp higher temp

number of molecules

energy

EA

The Boltzmann distribution shows the distribution of kinetic energies in a collection of particles (molecules) at a specific temperature. The curve shows that: - no molecules have no energy - there are only a few very energetic molecules - most molecules have average amounts of energy (the peak shows the average energy the particles have)

Page 2

F322 Rates and Equilibrium Note that the area under curve represents the number of molecules in sample (so this mustn't change when the curve is redrawn to represent different temperatures). With increasing temperature: - the curve still starts at 0 - the hump is lower in height - the hump moves to the right (i.e. curve stretches and gets less high) - the area under the curve remains the same Note that the curve never crosses the x-axis, but converges with it at very high energies and at zero energy. Activation energy The activation energy, EA, is the minimum energy that the molecules/particles need to have in order to react when they collide. This is the same as the energy needed to break the necessary bonds in the reactants, in order for new bonds to be formed in the products. At higher temperatures, more molecules have energy > EA therefore more of the collisions which take place will be successful, in addition to there being more collisions taking place overall because the particles are moving faster at higher temperatures. Reactions can be placed in order of increasing activation energy by looking at the bond enthalpies of the reactants and summing the bond enthalpies for the bonds which have to be broken: CH3 + Cl CH3Cl no bonds to break EA = 0 kJmol-1 Br2 2Br one Br-Br bond to break EA = +193 kJmol-1 Cl2 2Cl one Cl-Cl bond to break EA = +243 kJmol-1 CH4 CH3 + H one C-H bond to break EA = +413 kJmol-1 Catalysts Catalysts increase the rate of a reaction, and are not permanently changed by the reaction. They do this by offering an alternative route (reaction pathway) which has a lower activation energy. We can see the effect using an enthalpy profile diagram:

EA enthalpy EA cat N2 + 3H2 2NH3 H still the same but EA and hence rate faster.

Page 3

F322 Rates and Equilibrium This is important in industry as reactions can be carried out at lower temperatures (less energy costs, less use of non-renewable fossil fuel resources, and less effect on the environment from combustion product emissions such as CO2). In an equilibrium reaction, the position of equilibrium is not affected by the use of a catalyst, but equilibrium can be reached more quickly and the plant becomes more cost-effective as product can be obtained faster. The Boltzmann distribution can also be used to show catalytic behaviour. We can see that if EA cat is lower than EA, then a much higher proportion of the reactants have energy sufficient to react. Catalysts in industry Catalysts may also allow different reactions to be used with e.g. better atom economy or less waste produced. Enzymes are biological catalysts, and seeing more widespread use because they generate very specific products and don't need high temperature or pressure to get them to work. Important industrial catalysts: - Haber process (iron catalyst) - Ziegler-Natta catalyst in poly(ethene) production - platinum/palladium/rhodium in automotive catalytic converters Catalysts may be heterogeneous (different state as the reactants). The following examples are of solid catalysts with reactants in the liquid or gaseous state: e.g. - Ni in the hydrogenation of vegetable oils, -CH=CH- + H2 -CH2CH2- Zeolites in petrochemical cracking, reforming, isomerisation The process of heterogeneous catalysis involves adsorbtion of a reactant on the catalyst surface (formation of a weak bond between the reactant and the catalyst) as a result of which the reactant has its bonds weakened, reducing the energy needed to break them. With a lower activation energy, more molecules have energy > EA, so more of the collisions which take place are successful in bringing about a reaction. Desorption of the product molecules then takes place - the weak bond to the catalyst surface breaks and the product is released. This is why catalysts are sometime described as places where reactions occur. Gases may have to be passed over a gauze/porous heterogeneous quite catalyst slowly to allow time for the reaction to take place, or to allow adsorption to take place. Other catalysts are homogeneous (in the same state as the reactants) e.g. - Cl catalysing 2O3 3O2 in the upper atmosphere see notes on atmospheric chemistry - H+(aq) during esterification RCOOH + ROH RCOOR + H2O

Page 4

F322 Rates and Equilibrium Transition metals ions in solution are able to have variable oxidation states often accompanied by characteristic colour changes. They can act has homogeneous catalysts speeding up redox reactions. To do this the catalyst may accept electrons from the species being reduced, (the catalyst will increase its oxidation state), then donate electrons to the species being oxidised (the catalyst will be regenerated to its original oxidation state, ready to go again). Acting as an intermediary for this indirect transfer of electrons may provide a lower activation energy route than direct transfer of the electrons, speeding up the reaction. Equilibria Features of a dynamic equilibrium include: - needs to happen in a closed system - no change in macroscopic properties [concentrations remain same etc.] - forward and backward reactions continue to proceed but at the same rate as each other A dynamic equilibrium can be approached from either direction. (e.g. with NO and N2O4). Initially the rates will be unequal, faster in the direction towards the equilibrium being established. Once established, rates will be equal. Le Chateliers Principle states that: When a system in dynamic equilibrium is subjected to a change in the conditions, the position of the equilibrium (NOT reaction) will shift in the direction that will minimise the effect* of the change, or oppose the change. The shift in position of equilibrium does not "negate" or "cancel" the change ! Effect of Temperature and Pressure changes on Position of Equilibrium Changing the pressure only has an effect if the reaction is accompanied by a change in the space between the particles i.e. when there are different numbers of moles of gases on either side. Increasing the pressure shifts the equilibrium towards the side with the fewer moles of gaseous substances, minimising the effect of particles getting pushed closer together by creating fewer particles in the volume. [An exception is graphite diamond, where the lower density of graphite means that at high pressure the equilibrium shifts toward where the carbon atoms occupy a smaller volume i.e. towards diamond] Increasing the temperature shifts the equilibrium in the direction in which the reaction is endothermic i.e. in the direction where H is positive. (it minimises the effect by taking in the heat). Lowering the temperature shifts the equilibrium in the direction where the reaction is exothermic (i.e. in the direction where H is negative). *

Page 5

F322 Rates and Equilibrium Check your Understanding: Look at the following two equilibrium reactions which are used in the manufacture of methanol. What will be the effect of (i) an increase in pressure and (ii) a decrease in temperature be in each case ? e.g. CH4(g) + H2O(g) Ni at 700C at 100kPa CO(g) + 3H2(g) H = +207 kJ mol-1

CO(g) + 2H2(g)

Cr at 300C and 30,000kPa CH3OH(g) H = -129 kJ mol-1

Effect of conditions on rate of reaction We also have to consider the effects of changing temperature, pressure etc. on the rate of the reaction, quite independently of the effects on the position of equilibrium. It may be possible to select conditions which would increase the amount of product made, but slow the reaction down to the extent where effectively you'd have to wait forever to get it ! Check your understanding: For the two equilibrium reactions above, explain the effect of (iii) increasing the pressure and (iv) decreasing the temperature on the rate of reaction. Effect of concentration changes on Position of Equilibrium Changing the concentration of a reactant or product (e.g. by adding or removing a substance) causes the position of the equilibrium to shift in the direction where the change is opposed. e.g. If a product is removed, the position of equilibrium is shifted so that more of the product is made. It does this by increasing the rate of the forward reaction, because there are more reactant particles in the same volume, therefore more frequent (successful) collisions. More product is made, so the rate of the reverse reaction then speeds up too, and a new equilibrium is established. e.g. Cr2O72-(aq) + H2O(l) 2 CrO42-(aq) + 2H+(aq) (orange) (yellow)

A solution made up from K2CrO4 will therefore contain an equilibrium mixture of the yellow and orange ions (because it doesnt matter which side the equilibrium is approached from). If HCl(aq) is added, the concentration of H+(aq) is increased and the position of equilibrium moves to reduce the concentration of H+ i.e. it moves to the left, using up H+ ions. The solution therefore becomes more orange in colour. The effect of a catalyst on Position of Equilibrium The effect of a catalyst on a reversible reaction is to lower the activation energy for the forward and backward reaction. This has the effect of speeding up both the forward and reverse reaction equally. So there is no change in the position of equilibrium, however equilibrium is reached more rapidly.

Page 6

F322 Rates and Equilibrium Selecting industrial process conditions Many industrial processes require compromise conditions. For example increasing the temperature may increase the rate of a reaction but also shift the equilibrium to the left if the forward reaction is exothermic (and many are). At a high temperature there would be very little of the products at equilibrium, and both forward and reverse reactions are happening quickly at equal rates. At lower temperatures there would be more of the reactant molecules present at equilibrium, but the rate at which the equilibrium is reached would be slow. For example in the manufacture of HNO3 (oxidation of ammonia) 800C represents a medium sort of temperature at which rate is fast enough (with the catalyst helping) and equilibrium far enough to the right. Catalysts are added to increase the rate of both forward and backward reaction instead of elevating the temperature they have no effect on the position of the equilibrium. The effect of a catalyst is therefore to enable the system to reach equilibrium more quickly. Even when the optimum conditions have been selected, the actual %conversion may be less than the theoretical. Reasons include other products than the required ones being formed, not enough time to allow the equilibrium to be established, and possibly poisoning of the catalyst. Check your understanding: (v) For the two equilibrium reactions previously given (manufacture of methanol), explain fully why the chosen reaction conditions have been selected.

Page 7

F322 Rates and Equilibrium

Answers to Check your Understanding questions:

REACTION 1 Ni at 700C at 100kPa CH4(g) + H2O(g) CO(g) + 3H2(g) Cr at 300C and 30,000kPa CO(g) + 2H2(g) CH3OH(g) H = +207 kJ mol-1

REACTION 2

H = -129 kJ mol-1

Effect on position of equilibrium: (i) An increase in pressure will shift the position of equilibrium in Reaction 1 to left (backward), towards the reactants. Less carbon monoxide will be made. This is because there are two moles of gases on the left side of the equation, and four moles of gases on the right side. An increase in pressure will shift the position of equilibrium in Reaction 2 to right (forward), towards the products. More methanol will be made. This is because there are three moles of gases on the left side of the equation, and one mole of gases on the right side. (ii) A decrease in temperature will shift any equilibrium reaction in the direction which is exothermic (i.e. the direction in which H is negative). This means that the position of equilibrium in Reaction 1 will shift towards the reactants (backwards direction) and less CO will be made. The position of equilibrium in Reaction 2 will shift in the forward direction (towards the products) producing more methanol. Effect on rate of reaction: (iii) increasing the pressure will increase the rate of both forward and backward reactions in both cases, because the gas particles will be closer together and therefore there will be more frequent collisions. An equilibrium will be established more quickly. (iv) decreasing the temperature will reduce the rate of reaction in both cases because the particles move less rapidly and collide both less frequently and with less energy. It will therefore take a lot longer to reach equilibrium. Choice of conditions: (v) Reaction 1: A moderately high temperature is chosen since at high temperatures the reaction is fast, and the position of equilibrium shifts towards the products. Too high a temperature would be expensive in terms of energy costs, and fuel use, so a catalyst is used to speed up the reaction as well, rather than using an even higher temperature. A low pressure is used because at high pressures the position of equilibrium shifts towards the reactants. Reaction 2: A moderately low temperature is chosen as a compromise between getting a fast enough rate of reaction and getting a reasonable yield of product, since at high temperatures the position of equilibrium shifts in the backward direction. A lower temperature can be used and still get a reasonable rate of reaction because a catalyst is being used to increase the rate. A high pressure is used which helps increase the rate of reaction as well as shifting the position of equilibrium towards the products, increasing the yield of methanol. An excessively high pressure would result in safety and cost issues, however, so the pressure chosen represents a compromise. Page 8