Chemical Kinetics

The objective of a kinetics experiment is to determine the rate of a chemical reaction. To do this, you measure changes in the concentration of one or more of the reactants or products as a function of time. In NMR, one measures the rate of the reaction by mixing precisely known concentrations of the reactant solutions and recording several proton (or 13C, 31P, etc.) spectra at carefully timed intervals.

More important than the rate of the reaction is the dependence of the rate on the concentrations of the reagent and/or reactant. In order to determine this you have to perform a series of experiments in which you first vary the concentration of the reagent solution. Then you perform another series in which you vary the concentration of the reactant solution. Such measurements allow you to determine the order of the reaction. If the rate of a reaction doubles when you double the reagent concentration, the reaction is said to be first order with respect to the reagent. If the rate of a reaction doubles when you double the concentration of the reactant, the reaction is said to be first order with respect to the reactant. A reaction that is first order with respect to both the reagent and the reactant is said to be second order overall. Such a reaction is described as a bimolecular reaction because its rate depends upon the concentration of both species.

   

In one simple experiment, stoichiometric amounts of trifluoroacetic acid and methanol form the ester and water.

   
   

The OH chemical shift is a  weighted-average of the exchangeable proton shifts for the acid, alcohol and water. This shift value is used to track the extent of the reaction in many condensation reactions.

   
The integral values for the two methyl peaks in both the reactant and product are used to extract rate constants from the first 10 minutes of this reaction or to calculate Keq after several hours.