nip Rates, equilibria and further organic chemistryIntroduction )Thevalueof Afteactant) i The rate of a chemical reaction is the rate of change of concentration of a negative because its reactant or product with time. concentration decreases with time. Therefore, a more correct dfiiton of rates Its units are moldm~*s ‘The average rate of reaction is defined as: concentration rate - Atime rate Afreactant] ~ atime where Aconcentration is the change in concentration of a reactant or product. oy and Atime is the time over which this change takes place. Bree Aioroduct] ‘This is only a reasonable assumption if the concentration of a reactant has fallen Bsns by less than 10% during the time elapsed. Tis gives a postive value forthe ratein both cases, Collision theory For a reaction to take place, reactant molecules must collid = with kinetic energy greater than or equal to the activation energy of the reaction = with the correct orientation Maxwell-Boltzmann distribution of energy ‘The molecules in a gas or liquid and the molecules or ions in a solution move at different speeds. They possess different amounts of kinetic energy. This is shown by the blue line in Figure 1.1. The total number of molecules with energy equal to or greater than a particular energy value is given by the area under the graph to the right of that energy. Thus the blue area to the right of the aetivation energy, £, is the fraction of molecules that have sufficient energy (at temperature T,) to react on collision, providing that the orientation of collision is correct. Effect of temperature on rate When the temperature is increased, the molecules or ions gain kinetic energy. ‘They have a greater range of energies (greater entropy) and the average energy is inereased. This means that the peak of the Maxwell-Boltzmann distribution is lowered and moved to the right. This is shown by the red line (at temperature 7,) in Figure 1.1. The red area to the right of the activation energy is greatly increased because a much greater proportion of the colliding molecules have energy greater than or equal to the activation energy. Therefore, a greater proportion of collisions will result in reaction.Fraction of molecules with energy & Kinetic 5 ‘energy, E A reaction that takes place fairly quickly at room temperature has an activation energy of about 60kJmol”. This means that less than one in a billion collisions will have the necessary energy for a reaction to take place. ‘An approximate guide is that the rate doubles for a 10K increase in temperature. ‘The magnitude of the effect of increasing temperature depends on the value of the activation energy. A rise from 298K to 308K will cause the rate to increase by a factor of: where R is the gas constant (8.13.JK-! mol") and F, is the activation energy for the reaction. iF = 60kJ mol, the rate increases by a factor of 1.96 = or 100%, ‘An increase in temperature also increases the average speed of the molecules and so increases the collision frequency. For a 10K rise from 298K, this increases the rate by a factor of 1.02 (2%). This is negligible compared with the increase in rate caused by the increased proportion of collisions that result in reaction. Effect of pressure on the rate of a gaseous reaction If the pressure on a gaseous system is increased at constant temperature, the molecules become packed more closely together. There is no change in their speed or energy, but the collision frequency increases. The same proportion of the collisions results in reaction. However, because the frequency of collisions increases, the rate of reaction also goes up. ‘The situation is different if a gas is reacting with a solid, such as a catalyst. The surface area of the solid is usually the limiting factor, so the rate is independent of the pressure of the gas (p. 25). Figure 1.1 Maxwell-Boltzmann distribution of kinetic energy