K. Takahashi et Cd. Jonah, THE MEASUREMENT OF AN ELECTRON-TRANSFER REACTION IN A NONPOLAR SUPERCRITICAL-FLUID, Chemical physics letters, 264(3-4), 1997, pp. 297-302
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 o
f 10(11) M(-1) s(-1). The rate constants appear to be approximately co
nstant over the pressure range 55-133 bar. Two possibilities are discu
ssed that could explain the present results: solvent clustering, or a
dependence of the solvent reorganization energy on pressure. Reorganiz
ation energies of non-polar supercritical ethane were estimated from t
he observed rate constant using the modified Marcus equation.