990 K
20 pp.
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TitleOn the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants
Author(s)Marcus, R. A.
Publication Date1962
Report NumberBNL-6422
Unique IdentifierACC0262
Other NumbersOSTI ID: 4712863
Research OrgBrookhaven National Laboratory (BNL), Upton, N.Y.; Polytechnic Institute, Brooklyn
Contract NoA(30-2)-Gen-16
Sponsoring OrgU.S. Atomic Energy Commission (AEC)
Other InformationJournal of Physical Chemistry (U.S.); Vol: 67
SubjectChemistry; Atoms; Binding Energy; Complexes; Electrochemistry; Electrolytes; Electrons; Interactions; Oxidation; Reduction; Standards
Related Web PagesRudolph A. Marcus and His Theory of Electron Transfer Reactions
AbstractUsing a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)
990 K
20 pp.
View Document 

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