Infrared matrix isolation study of the oxidation of H2S by CrCl2O2

The thermal and photochemical reactions between CrO2Cl2 and H2S have been investigated using matrix isolation infrared spectroscopy. Twin-jet co-deposition of the two reagents into argon matrices at 14 K followed by irradiation with light of lambda > 300 nut led to the growth of a number of new bands. These have been assigned to the HSOH-CrCl2O complex, and to SO2. These assignments were supported by deuterium isotopic substitution and high level density functional calculations. Merged-jet deposition with the reaction zone at temperatures above 125 degrees C led to substantial yields Of SO2 and HCl, as well as the complex of HCl with excess parent H2S. The evidence suggests that the thermal and photochemical reactions may follow different pathways.