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The nature of the CH2Cl2 neutral/acidic hydrolysis reaction from ambient tosupercritical conditions (25 C to 600 C at 246 bar) is explored. Of primaryinterest is the effect of the changing dielectric behavior of the water solventover this temperature range on this reaction. Experiments reveal thatsignificant CH2Cl2 hydrolysis occurs under subcritical temperatures, whilerelatively little hydrolysis occurs under supercritical conditions. Thesetrends cannot be explain by simple Arrhenius behavior. A combination ofKirkwood theory and ab initio modeling provides a means of successfullyaccounting for this behavior both qualitatively and quantitatively. The resultsshow that increases in the activation energy and a changing reaction profilewith a decreasing dielectric constant provide a mechanism for a slowing of thereaction at higher temperatures by as much as three orders of magnitude. Thesesolvent effects are captured quantitatively in a correction factor to theArrenius form of the rate constant, which is incorporated into a global rateexpression proposed for CH2Cl2 hydrolysis that provides good predictions of theexperimental data.Comment: Deals with solvation as a multiscale problem. Presently accepted for  publication in the Journal of Physical Chemistry A: 46 pages, 12 figures, 8  table

Solvation Effects on Kinetics of Methylene Chloride Reactions in Sub- and Supercritical Water: Theory, Experiment, and Ab Initio Calculations