✍ Scribed by P. R. Westmoreland; J. B. Howard; J. P. Longwell; A. M. Dean
No coin nor oath required. For personal study only.
Bimolecular QRRK (Quantum Rice-Ramsperger-Kassel) analysis is a simple method for calculating rate constants of addition and recombination reactions, based on unimolecular quantum-RRK theory. Input parameters are readily derived, and rate constants and reaction branching can be predicted with remarkable accuracy. Such predictive power makes the method especially useful in developing mechanisms of elementary reactions. Furthermore, from the bimolecular QRRK equations, limiting forms of the rate constants in the limits of low and high pressure are developed. Addition / stabilization is pressure-dependent at low pressure but pressure-independent at high pressure, as is conventionally understood for simple decomposition, its reverse. In distinct contrast, addition with chemically activated decomposition has the opposite behavior: pressure independence at low pressure and pressure dependence [as (pressure).'] at high pressure. The method is tested against data and illustrated by calculations for 0 + CO -CO,;
📜 SIMILAR VOLUMES
A reliable QSAR model for estimation of reactivities of radical addition reactions has been developed. The logarithm of the rate constant and the activation energy (reaction barrier) have been chosen to characterize the reactivity. Carbon-centered radicals of very different features and vinyl-type a
## Abstract A competitive method involving the direct measurement of radical concentrations by EPR spectroscopy has been used to show that in solution at 25°C the rate constants for the bimolecular self‐reactions of ethyl, isopropyl, __tert__‐butyl, cyclopentyl, and trichloromethyl are all approxim