The Photochemical and Thermal Decompositions of Hydrogen Sulphide

Details The Photochemical and Thermal Decompositions of Hydrogen Sulphide The Photochemical and Thermal Decompositions of Hydrogen Sulphide

Feb 1953

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1953rspsa.216..344d&link_type=abstract

Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, Volume 216, Issue 1126, pp. 344-361

Physics

3

Scientific paper

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 degrees 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\cdot 09 at 30 mm to 1\cdot 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 degrees C with 2288 angstrom 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\cdot 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 (3P0) atoms. The thermal decomposition is heterogeneous at low temperatures and becomes homogeneous and of the second order at 650 degrees C. The experimental evidence suggests the bimolecular mechanism 2H2S-> 2H2+S2. The activation energies are 25 kcal/mole (heterogeneous) and 50 kcal/mole (homogeneous).

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