High-pressure reactivity of model hydrocarbons driven by near-UV photodissociation of water.

The ambient temperature photoinduced reactivity of mixtures containing water and some of the simplest model hydrocarbons has been studied in a diamond anvil cell below 1 GPa. The near-UV 350 nm emission of an Ar ion laser has been employed to photodissociate water molecules through two-photon absorption processes. The hydroxyl radicals generated through this process are able to trigger a chemical reaction in the mixtures containing ethane and acetylene, which are otherwise stable under the same P-T-hnu conditions, whereas the contribution of water has no effect or is very limited in the case of the ethylene and propene mixtures, respectively. The reaction evolution and the reaction products were characterized by using FTIR spectroscopy. The formation of fluorescent products limits or prevents, as in the case of acetylene, the characterization by Raman spectroscopy. Particularly relevant is the in situ efficient sequestration of the CO(2) formed during the reaction, through the formation of a clathrate hydrate, in the mixtures where water is largely in excess.