Is the single transition-state model appropriate for the fundamental reactions of organic chemistry?

Autor:	Vernon D. Parker
Rok vydání:	2005
Předmět:	State model Reaction rate constant Organic reaction Chemistry Computational chemistry General Chemical Engineering Reagent Kinetics Physical chemistry Product formation General Chemistry Kinetic energy Volume concentration
Zdroj:	Pure and Applied Chemistry. 77:1823-1833
ISSN:	1365-3075 0033-4545
DOI:	10.1351/pac200577111823
Popis:	In recent years, we have reported that a number of organic reactions generally believed to follow simple second-order kinetics actually follow a more complex mechanism. This mechanism, the reversible consecutive second-order mechanism, involves the reversible formation of a kinetically significant reactant complex intermediate followed by irreversible product formation. The mechanism is illustrated for the general reaction between reactant and excess reagent under pseudo-first-order conditions in eq. i where k f' is the pseudo-first-order rate constant equal to k f[Excess Reagent]. Reactant + Excess reagent = Reactant complex = Products (i) The mechanisms are determined for the various systems, and the kinetics of the complex mechanisms are resolved by our "non-steady-state kinetic data analysis". The basis for the non-steady-state kinetic method will be presented along with examples. The problems encountered in attempting to identify intermediates formed in low concentration will be discussed.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::3126a28d2dfcbf82fab8128ed21c3da3 https://doi.org/10.1351/pac200577111823 Zobrazit plný text záznamu