ABSTRACT

In the last few chapters, discussion has focused on the use of initial rate studies to obtain information on kinetic mechanism. The conventional means of determining the order of addition of reactants makes use of initial velocity studies in the absence and presence of product and dead-end inhibitors, as described in Chapters 5 and 6. These studies may not be conclusive, however, and information obtained from other techniques is often required to confirm conclusions based on initial rate studies and provide additional documentation of the kinetic mechanism. Complementary techniques include but are not limited to isotope exchange at equilibrium, isotope partitioning, positional isotope exchange, and rapid or pre-steady-state kinetics. In this chapter, some of these alternative methods that make use of isotopes will be introduced. The techniques discussed in this chapter are generally thought to be complementary to those discussed previously. Thus, although the results of methods discussed in this chapter overlap with those obtained from initial rate studies, new information is generated that extends knowledge of a given mechanism. In particular, these methods allow determination of the relative rates of steps in the mechanism. Isotope effects will be discussed separately in Chapter 9.