Solvation of hydrocarbon radicals in sub-CW and SCW: An ab initio MD study

Solvation of methyl radicals in subcritical and supercritical water was investigated with the ab initio MD simulation to increase the understanding of the thermal cracking of hydrocarbons under the severe hydrothermal environments. The calculation results show that water clusters around the radical could be formed with the following prerequisites: the bulk density of water is close to liquid phase, and the state point of water on its phase diagram is far away from the critical point and from the vapor–liquid equilibrium boundary. The occurrence of water clusters superimposes a negative influence on the originally depressed diffusivity of the radical under the dense hydrothermal environments, and the interference from the immediately adjacent water molecules with the frontier orbitals of the radical results in randomly reduced activity of the radical. Regardless of whether there are water clusters around the radical or not, in subcritical and supercritical water the bimolecular reactions participating via hydrocarbon radicals should be partially suppressed by the reduced diffusivity and lower activity of the radical.

Figure optionsDownload as PowerPoint slideHighlights
► Solvation of methyl radicals in sub-CW and SCW was characterized by ab initio MD.
► Solvent clusters around the radical occur under specific hydrothermal environments.
► Formation of solvent clusters results in depressed diffusivity of the radical.
► Activity of the hydrocarbon radical is suppressed by hydrothermal environments.