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Is it always correct to use the Marcus cross relation for calculations of electron self-exchange rates? by Ariela Burg; Dan Meyerstein is a Chemistry article available to read on EtoBox.
What is Is it always correct to use the Marcus cross relation for calculations of electron self-exchange rates? about?
The rate constant of the electron self-exchange reaction, which proceeds via the outer sphere mechanism, k 11 , of a redox couple, reflects the basic tendency of the reaction to participate in redox processes. Often k 11 is derived from the rate constant of a redox reaction, k 12 , by applying the Marcus cross relation: This derivation is based on the assumption that the products of the cross reaction are formed in their ground states. However, the k 11 values obtained by this method for several redox systems, e.g. for [Co(NH 3 ) 6 ] 3+/2+ , Cu 2+/+ (aq) and Eu 3+/2+ (aq), depend strongly on the redox reaction studied for its derivation. It is proposed that these discrepancies are due to the formation, in some of these reactions, of products in vibrationally excited states and/or as isomers of the final products. Thus, the lowest value of k 11 obtained experimentally is either correct or an upper limit for the correct value if correct k 22 are used.
Who reads Is it always correct to use the Marcus cross relation for calculations of electron self-exchange rates??
It is typically read by researchers, students, and practitioners in Chemistry.
- Author
- Ariela Burg; Dan Meyerstein
- Publisher
- Elsevier Science; Elsevier ; Elsevier BV (ISSN 0020-1693)
- Published
- 2010
- Language
- EN
- Field
- Chemistry (Physical Sciences)