Chemical Reactions and Kinetic2.docVIP

Chemical Reactions and Kinetics The Mechanisms of Chemical Reactions The Relationship Between Rate Constants and Equilibrium Constants Determining the Order of a Reaction from Rate of Reaction Data The Integrated Form of First-Order and Second-Order Rate Laws Determining the Order of a Reaction with the Integrated Form of Rate Laws Reactions that are First Order in Two Reactants The Mechanisms of Chemical Reactions What happens when the first step in a multi-step reaction is not the rate-limiting step? Consider the reaction between NO and O2 to form NO2, for example. 2 NO g + O2 g 2 NO2 g This reaction involves a two-step mechanism. The first step is a relatively fast reaction in which a pair of NO molecules combine to form a dimer, N2O2. The product of this step then undergoes a much slower reaction in which it combines with O2 to form a pair of NO2 molecules. Step 1: 2 NO N2O2 fast step Step 2: N2O2 + O2 2 NO2 slow step The net effect of these reactions is the transformation of two NO molecules and one O2 molecule into a pair of NO2 molecules. 2 NO N2O2 N2O2 + O2 2 NO2 _______________ 2 NO + O2 2 NO2 In this reaction, the second step is the rate-limiting step. No matter how fast the first step takes place, the overall reaction cannot proceed any faster than the second step in the reaction. As we have seen, the rate of any step in a reaction is directly proportional to the concentrations of the reactants consumed in that step. The rate law for the second step in this reaction is therefore proportional to the concentrations of both N2O2 and O2. Step 2: Rate2nd k N2O2 O2 Because the first step in the reaction is much faster, the overall rate of reaction is more or less equal to the rate of this rate-limiting step. Rate k N2O2 O2 This rate law is not very useful because it is difficult to measure the concentrations of intermediates, such as N2O2, that are simultaneously formed and consumed in the reaction. It would be better to have an