High Mobility Solvent Holes in Methylcyclohexane

Autor:	Myran C. Sauer, Ilya A. Shkrob, Alexander D. Trifunac, A. D. Liu
Rok vydání:	2001
Předmět:	Solvent chemistry.chemical_compound Electron mobility Electron transfer chemistry Ionization Photoconductivity Analytical chemistry Activation energy Physical and Theoretical Chemistry Methylcyclohexane Ionization energy Photochemistry
Zdroj:	The Journal of Physical Chemistry A. 105:7211-7215
ISSN:	1520-5215 1089-5639
Popis:	Using time-resolved dc photoconductivity, the migration patterns and reactions of solvent hole in liquid methylcyclohexane between 230 and 350 K have been studied. It is shown that solvent holes in liquid methylcyclohexane are reversibly scavenged by solutes whose liquid-state ionization potentials are 0.2-0.3 eV below that of the solvent. The reversible electron transfer is driven mainly by the reaction heat (60-90%); further decrease in the free energy is due to increase in entropy following the destruction of solvent structure around the hole. Between 133 and 360 K, the solvent hole diffuses with activation energy of 7.8 kJ/mol; the fastest electron-transfer reactions (ca. 8.7 x 10{sup 10} M{sup -1} s{sup -1} at 25 {sup o}C) have activation energies between 3.9 and 5.3 kJ/mol (250 to 350 K). Unusually large scavenging radii, 1.5-3 nm, were obtained for these charge-transfer reactions.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::b952062e1c9847379df6c0c7e0f3e601 https://doi.org/10.1021/jp003052j Zobrazit plný text záznamu