The photochemical and thermal decompositions of hydrogen sulphide

The photochemical decomposition of hydrogen sulphide has been investigated at pressures between 8 and 550 mm of mercury and at temperatures between 27 and 650° C, using the narrow cadmium line ( λ 2288) and the broad mercury band (about λ 2550). At room temperature the quantum yield increases with pressure from 1.09 at 30 mm to 1.26 at 200 mm. Above 200 mm pressure there was no further increase in the quantum yield. Temperature had little effect on the quantum yield at λ 2550, but there was a marked increase in the rate of hydrogen production between 500 and 650° C with 2288 Å radiation. This may have been caused by the decomposition of excited hydrosulphide radicals. The results are consistent with a mechanism involving hydrogen atoms and hydrosulphide radicals. The mercury-photosensitized reaction is less efficient than the photochemical decomposition, the quantum yield being only about 0.45. The efficiency increased with temperature and approached unity at high temperatures and pressures. This agrees with the suggestion that a large fraction of the quenching collisions lead to the formation of Hg ( 3 P 0 ) atoms. The thermal decomposition is heterogeneous at low temperatures and becomes homogeneous and of the second order at 650° C. The experimental evidence suggests the bimolecular mechanism 2H 2 S → 2H 2 + S 2 . The activation energies are 25 kcal/mole (heterogeneous) and 50 kcal/mole (homogeneous).