FREE-RADICAL CHLORINATION OF ALKANES IN SUPERCRITICAL CARBON-DIOXIDE - THE CHLORINE ATOM CAGE EFFECT AS A PROBE FOR ENHANCED CAGE EFFECTS IN SUPERCRITICAL-FLUID SOLVENTS
B. Fletcher et al., FREE-RADICAL CHLORINATION OF ALKANES IN SUPERCRITICAL CARBON-DIOXIDE - THE CHLORINE ATOM CAGE EFFECT AS A PROBE FOR ENHANCED CAGE EFFECTS IN SUPERCRITICAL-FLUID SOLVENTS, Journal of the American Chemical Society, 120(46), 1998, pp. 11839-11844
The chlorine atom cage effect was used as a highly sensitive probe for
studying the effect of viscosity and the possible role of solvent clu
sters on cage lifetimes and reactivity for reactions carried out in su
percritical fluid solvents. These experiments were conducted in superc
ritical carbon dioxide (SC-CO2, 40 degrees C, at various pressures) wi
th parallel experiments in conventional solvents and in the gas phase.
The results of these experiments provide no indication of an enhanced
cage effect near the critical point in SC-CO2 solvent. The magnitude
of the cage effect observed in SC-CO2 at all pressures examined is wel
l within what is anticipated on the basis of extrapolations from conve
ntional solvents.