Density Functional Theory Probe of the Hydrolysis of Heavy Hydrocarbon Structural Moieties in Supercritical Water

The thermochemistry and kinetics of hydrolysis in supercritical water were probed using density function theory (DFT). Four molecules (propane, dimethyl ether, 1,3-diphenylpropane, and dibenzyl ether) were selected for this study to compare the reactivity of molecules with and without a heteroatom on a saturated carbon. We found that the activation energy for compounds with a heteroatom attached to saturated carbon was lower than that for fully hydrocarbon systems. The fastest reaction among the four molecules was that for dibenzyl ether with water. The activation energy and pre-exponential factor of the dibenzyl ether reaction with water is rationalized in the context of experimental values.