On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. [Part] 5. Comparison and Properties of Electrochemical and Chemical Rate Constants

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Using 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 ... continued below

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Pages: 853-7

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Marcus, R. A. April 1, 1963.

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Using 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)

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Pages: 853-7

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"V."

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  • Journal Name: Journal of Physical Chemistry (U.S.); Journal Volume: Vol: 67

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  • Report No.: BNL-6422
  • Grant Number: A(30-2)-Gen-16
  • Office of Scientific & Technical Information Report Number: 4712863
  • Archival Resource Key: ark:/67531/metadc1028946

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  • April 1, 1963

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  • Oct. 18, 2017, 7:39 a.m.

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  • Jan. 2, 2018, 12:06 a.m.

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Marcus, R. A. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. [Part] 5. Comparison and Properties of Electrochemical and Chemical Rate Constants, article, April 1, 1963; Upton, New York. (digital.library.unt.edu/ark:/67531/metadc1028946/: accessed April 25, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.