Journal of Physical Chemistry A, Vol.102, No.19, 3447-3454, 1998
Diffusion of photochemically generated intermediate radicals in water-ethanol mixed solvents
Diffusion processes of intermediate radicals created by the photoinduced hydrogen abstraction reactions of benzoquinone (BQ) and acetophenone (AP) in ethanol-water mixed solvents are studied by using the transient grating (TG) method. The electrically neutral radicals and the anion radicals are created selectively by adding sodium hydroxide (NaOH) or sulfuric acid (H2SO4) to the solutions. The intermediate species and the chemical stability of the radicals were monitored by the transient absorption and time-resolved EPR methods. The diffusion constants (D) of the radicals and the parent molecules are determined simultaneously. D of the anion radicals are similar to those of the neutral radicals in any mixtures of the solvents. D of the neutral and anion radicals (D-R) are much smaller than those of the parent molecule (D-P) in ethanol (D-P/D-R similar to 2.8 for BQ and D-P/D-R similar to 2.1 for AP in ethanol), While D-P become closer to D-R With increasing water content in the solvent (D-P/D-R similar to 1.3 for BQ and QP in 90% water solution). The temperature dependence of D was also investigated. A possible origin of this water effect is discussed from the point of view of hydrophobic hydration.
Keywords:TRANSIENT GRATING METHOD;X-RAY-SCATTERING;KIRKWOOD-BUFF PARAMETERS;TERT-BUTYL ALCOHOL;LIQUID WATER;TRANSLATIONAL DIFFUSION;HYDROPHOBIC HYDRATION;HYDROGEN ABSTRACTION;MOLECULAR-DYNAMICS;AQUEOUS-SOLUTIONS