Relation of reaction mechanism to reaction kinetics

In a nutshell, the rate equation is made up of reactants which are involved in the rate liming step or the slow step.

When chemists study reaction mechanisms, they are interested to know how the reaction actually occurs, for example which bonds are boken first, which bonds are formed first etc. We cannot determine the reaction mechanism from the balanced chemical reaction.


Let us consider the reaction of propanonne with iodine. From the balanced chemical equation, we can see that there are 2 reactants propanone and iodine. In order to determine the order of reaction w.r.t iodine, we use an excess of propanone and vary the concentration iodine, i.e. iodine will be the limiting reactant. Using the initial rates method, we can determine the order of reaction w.r.t iodine. It was determined that the reaction is zero order w.r.t iodine which means that the rate of reaction is independent of the concentration of iodine. Iodine will not appear in the rate equation

Next we determine the order of reaction w.r.t propanone and it was determined that the order of reaction w.r.t propanone is first order . Hence propanone will appear in the rate equation . Similarly we determine the order of reaction with respect to hydrogen ion concentration to be first order. Hence from the above data, we can write the following rate equation:

The rate equation also indicates that H+ and propanone are reactants in the rate determining step and a reaction mechanism can be proposed based on this data.

Note that the rate equation cannot be used to prove that a particular reaction mechanism is correct, it can only be used to prove that a particular reaction mechanism is wrong. If some one suggests that iodine is a reactant in the rate determining step, we can use the data from the kinetic analysis to say that he is wrong because the rate of reaction is independent of the concentration of iodine and hence iodine cannot be a reactant in the rate determining step.