Pressure dependence of the reaction of 1-butanethiol with hydrogen atoms

✍ Scribed by Tohru Kamo; Muneyoshi Yamada

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 199 KB
• Volume: 30
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/(sici)1097-4601(1998)30:12<923::aid-kin7>3.0.co;2-1

✦ Synopsis

The reaction of 1-butanethiol with hydrogen atoms was investigated at room temperature under pressures of 133, 266, 532, 2660, and 5320 Pa, using two types of fast-flow discharge reactors; the main products were n-butane and 1-butene with total yields of more than 90%. In the reaction of 1-butanethiol and deuterium atoms, monodeuterated 1-butanethiol was observed by a photo-ionizing mass spectrometer. The relative rate of the two initial reactions of 1-butanethiol with hydrogen atoms was 0.272 (k 1 /k 2 ). The n-butane and 1-butene are considered to be produced via chemically activated 1-butanethiol on the basis of the pressure dependence of the two main products.

1-C H SH ϩ H

Relative rates of molecular elimination of hydrogen sulfide and C-S bond fission for the chemically activated 1-butanethiol, k 5 /k 4 and k 6 /k 4 , were 0.114 and 0.0552 under 532 Pa of pressure at room temperature. Activation energies of the two reactions were calculated to be 228 [kJ/mol] and 297 [kJ/mol], respectively, by use of RRKM on the base of estimated A factors.