Solvent reorganization energies measured by an electron transfer reaction in supercritical ethane.

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The intermolecular electron transfer reaction between a biphenyl anion and pyrene in supercritical ethane was studied using pulse radiolysis. Second-order electron transfer rates were found to be of the order of 10{sup 11} M{sup {minus}1} s{sup {minus}1}. The rate constants appear to be approximately constant over the pressure range 55-133 bar. Two possibilities are discussed that could explain the present results: solvent clustering; or a dependence of the solvent reorganization energy on pressure. Reorganization energies E{sub r} of non-polar supercritical ethane were estimated from the observed rate constant using the modified Marcus equation. E{sub r} may be larger than normally ... continued below

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6 p.

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Feng, W.; Jonah, C. D.; Sawamura, S. & Takahashi, K. April 14, 1997.

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The intermolecular electron transfer reaction between a biphenyl anion and pyrene in supercritical ethane was studied using pulse radiolysis. Second-order electron transfer rates were found to be of the order of 10{sup 11} M{sup {minus}1} s{sup {minus}1}. The rate constants appear to be approximately constant over the pressure range 55-133 bar. Two possibilities are discussed that could explain the present results: solvent clustering; or a dependence of the solvent reorganization energy on pressure. Reorganization energies E{sub r} of non-polar supercritical ethane were estimated from the observed rate constant using the modified Marcus equation. E{sub r} may be larger than normally expected for non-polar solvents because of density fluctuations.

Physical Description

6 p.

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OSTI as DE00012351

Medium: P; Size: 6 pages

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  • 4th International Symposium on Supercritical Fluids, Sendai (JP), 05/11/1997--05/14/1997

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  • Report No.: ANL/CHM/CP-92836
  • Grant Number: W-31109-ENG-38
  • Office of Scientific & Technical Information Report Number: 12351
  • Archival Resource Key: ark:/67531/metadc627974

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  • April 14, 1997

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  • June 16, 2015, 7:43 a.m.

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  • April 11, 2017, 2:49 p.m.

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Feng, W.; Jonah, C. D.; Sawamura, S. & Takahashi, K. Solvent reorganization energies measured by an electron transfer reaction in supercritical ethane., article, April 14, 1997; Illinois. (digital.library.unt.edu/ark:/67531/metadc627974/: accessed September 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.