Portland State College. Department of Chemistry
Date of Award
Master of Science (M.S.) in Chemistry
1 online resource (iii, 133 leaves)
Chemical kinetics -- Computer programs
Treating the activated complex for unimolecular dissociation as uncoupled fragments simplifies the calculation of transition-state frequencies in the quasi-equilibrium-theory formulation of an isotopic rate-constant ratio. The general method is applied to the specific case of the intramolecular kinetic isotope effect in decarboxylation of malonic acid. The fragment models are further simplified by means of the “cut-off” approximation of Sterm and Wolfsberg. These model calculations are in agreement with the presently available experimental results. Applicability to reactions involving simultaneous multiple bond rupture or formation is noted.
Chang, Paul Chien-Wei, "Theoretical calculations of kinetic isotope effects" (1968). Dissertations and Theses. Paper 785.