Introduction

The concept of stoichiometry is used in chemistry in different contexts. One use refers to an abstract, balanced transformation of a set of species (reactants) into another set of species (products), characterized well by Smith and Missen [1979]. Another use refers to the stoichiometry of a reaction mechanism, and is concerned roughly with a balanced transformation of starting materials into final products that is implied by the mechanism. This note examines the concept of stoichiometry only in this sense of a balanced transformation implied by a mechanism.

The stoichiometric coefficients of starting materials are often construed as the ideal proportions of starting materials, in the sense of not providing more initial concentration than needed to obtain, in the idealized case, a certain yield of a target product.

The purpose of this note is to formalize the concept of reaction-mechanism stoichiometry by relating the concept explicitly to ideal yield. The current, semi-formal notion of mechanism stoichiometry, as described by Corio [1989], has an ambiguity due to an uncertain, somewhat arbitrary decision of which mechanism species to regard as intermediates. This ambiguity makes the concept of stoichiometry less valuable for the discussion of ideal mechanism yields. We shall illustrate by example how our formalization in terms of linear programming removes this ambiguity, while gaining a clearer understanding of the relation between stoichiometry and ideal yield.

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