Uses and analyses of curtin-hammett/winstein-holness systems involving second order reactions

The Curtin-Hammett (C-H) principle and the Winstein-Holness (W-H) equation approximate the product ratio and overall rate constant of reaction for systems involving a starting material which exists in two forms, each of which reacts via first-order kinetics to give a different product. The C-H/W-H approximations are valid when the rates of isomer interconversion are significantly faster than the rates of product formation. The present treatment encompasses non-first-order reactions to product. A numerical predictor-corrector technique is used to show (1) that relative reagent concentration can affect both the product ratio and the observed rates of product formation; (2) that the absolute concentration of reagent and substrate can affect the kinetics; and (3) that factors (1) and (2) above can affect the validity of the C-H/W-H approximations for non-first-order C-H/W-H schemes.