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Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions

Abstract

Recent experimental data concerning the rate constants for electron transfer reactions of organic systems in aqueous solutions and their equilibrium constants is examined for possible correlation. The data is correlated quite well by the Marcus theory, if a reorganization parameter, lambda, of 18 kcal/mole is used. Assuming that the only contribution to lambda is the free energy of rearrangement of the water molecules, an effective radius of 5 A for the reacting entities is estimated. For the zero free energy change reaction, i.e., electron exchange between a radical ion and its parent molecule, a rate constant of about 5 X 10/sup 7/ M/sup -1/ s/sup -1/ is predicted. (auth)
Authors:
Publication Date:
Jul 15, 1975
Product Type:
Journal Article
Reference Number:
ERA-01-09157
Resource Relation:
Journal Name: Chem. Phys. Lett.; (Netherlands); Journal Volume: 34:2
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANIC COMPOUNDS; CHARGE EXCHANGE; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; FREE ENERGY; DISPERSIONS; ENERGY; KINETICS; MIXTURES; PHYSICAL PROPERTIES; REACTION KINETICS; SOLUTIONS; THERMODYNAMIC PROPERTIES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
OSTI ID:
7358736
Research Organizations:
Carnegie-Mellon Univ., Pittsburgh
Country of Origin:
Netherlands
Language:
English
Other Identifying Numbers:
Journal ID: CODEN: CHPLB
Submitting Site:
ECN
Size:
Pages: 263-266
Announcement Date:

Citation Formats

Meisel, D. Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions. Netherlands: N. p., 1975. Web. doi:10.1016/0009-2614(75)85269-9.
Meisel, D. Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions. Netherlands. doi:10.1016/0009-2614(75)85269-9.
Meisel, D. 1975. "Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions." Netherlands. doi:10.1016/0009-2614(75)85269-9. https://www.osti.gov/servlets/purl/10.1016/0009-2614(75)85269-9.
@misc{etde_7358736,
title = {Free energy correlation of rate constants for electron transfer between organic systems in aqueous solutions}
author = {Meisel, D}
abstractNote = {Recent experimental data concerning the rate constants for electron transfer reactions of organic systems in aqueous solutions and their equilibrium constants is examined for possible correlation. The data is correlated quite well by the Marcus theory, if a reorganization parameter, lambda, of 18 kcal/mole is used. Assuming that the only contribution to lambda is the free energy of rearrangement of the water molecules, an effective radius of 5 A for the reacting entities is estimated. For the zero free energy change reaction, i.e., electron exchange between a radical ion and its parent molecule, a rate constant of about 5 X 10/sup 7/ M/sup -1/ s/sup -1/ is predicted. (auth)}
doi = {10.1016/0009-2614(75)85269-9}
journal = {Chem. Phys. Lett.; (Netherlands)}
volume = {34:2}
journal type = {AC}
place = {Netherlands}
year = {1975}
month = {Jul}
}