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Photochemical Kinetics: Reaction Orders and Analogies with Molecular Beam Scattering and Cavity Ring-Down Experiments
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Abstract
Despite its fundamental importance, photochemical kinetics is not often treated in much detail in physical chemistry courses and concepts often remain unclear. One topic of recent debate concerns reaction orders of photochemical reactions. In this article, we emphasize that a photochemical reaction system is composed of several elementary steps, each of which has a defined molecularity and reaction order. The elementary, primary absorption step can be considered a bimolecular reaction. Depending on the experimental conditions, the apparent total reaction order of the mechanism may have different values, but will still be defined in most cases. Possible conceptual difficulties may be avoided by realizing two analogies between experiments involving light and kinetic experiments not involving light: a standard absorption measurement has an analogy with a molecular beam scattering experiment, and cavity ring-down spectroscopy has an analogy with a conventional static reactor experiment.
Keywords (Audience):
Upper-Division UndergraduateKeywords (Domain):
Physical ChemistryKeywords (Feature):
Advanced Chemistry Classroom and LaboratoryKeywords (Subject):
Instrumental MethodsCiting Articles
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This article has been cited by 3 ACS Journal articles (3 most recent appear below).
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Does a Photochemical Reaction Have a Kinetic Order? (the author replies)
Michael HipplerJournal of Chemical Education2005 82 (1), 37Does a Photochemical Reaction Have a Kinetic Order? (the author replies)
Michael HipplerJournal of Chemical Education2005 82 (1), 37Light absorption in photochemistry can be described by standard kinetic concepts, without inconsistencies or anomalies.
Does a Photochemical Reaction Have a Kinetic Order?
Sidney TobyJournal of Chemical Education2005 82 (1), 37Does a Photochemical Reaction Have a Kinetic Order?
Sidney TobyJournal of Chemical Education2005 82 (1), 37There are anomalies associated with the characterization of photochemical reactions in terms of rate constants.
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- Received: August 03, 2009
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