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

Authors :
Vernon D. Parker
Source :
Pure and Applied Chemistry. 77:1823-1833
Publication Year :
2005
Publisher :
Walter de Gruyter GmbH, 2005.

Abstract

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.

Details

ISSN :
13653075 and 00334545
Volume :
77
Database :
OpenAIRE
Journal :
Pure and Applied Chemistry
Accession number :
edsair.doi...........3126a28d2dfcbf82fab8128ed21c3da3
Full Text :
https://doi.org/10.1351/pac200577111823