Is a Proposed Reaction Mechanism Free from Unnecessary Assumptions?: Occam's Razor Applied in a Mathematical Way To Complex First-Order Reaction Systems
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, no 112, 4235-4240 p.Article in journal (Refereed) Published
Following Occam's principle, a proposed reaction mechanism should not contain assumptions about the existence of reactive intermediates and reaction paths that are unnecessary for a full description and interpretation of the available facts. A mechanism refers, in this paper, to a proposed reaction scheme or network that represents the reactions supposed to be going on in a complex reaction system with observable species as well as unobservable reactive intermediates. The scope is limited here to (pseudo) first-order reactions and the steady-state approximation is invoked in order to relate unknown mechanistic rate constants to experimentally determined ones, and, when available, theoretically calculated quantities. When the resulting, nonlinear system of equations admits a unique solution within a physically reasonable domain, it is concluded that the reaction mechanism fulfills Occam's principle. Otherwise, there are many or no solutions. No subjective or qualitative arguments enter the procedure and the outcome is not negotiable.
Place, publisher, year, edition, pages
2008. no 112, 4235-4240 p.
IdentifiersURN: urn:nbn:se:uu:diva-16334DOI: 10.1012/jp711004kISI: 000255486400010OAI: oai:DiVA.org:uu-16334DiVA: diva2:44105