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

Tohru Kamo, Muneyoshi Yamada

Research output: Contribution to journalArticlepeer-review

Abstract

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 (k1,/k2). 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-C4H9SH + H → 1-C4H9̇ + H2S (1) 1-C4H9SH + H → 1-C4H9Ṡ + H2 (2) 1-C4H9Ṡ + H → 1-C4H9SH* (3) Relative rates of molecular elimination of hydrogen sulfide and C - S bond fission for the chemically activated 1-butanethiol, k5/k4 and k6/k4, 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. 1-C4H9SH* + M → 1-C4H9SH (4) 1-C4H9SH* → 1-C4H8 + H2S (5) 1-C4H9SH* → 1-C4H9̇ + HṠ (6)

Original languageEnglish
Pages (from-to)923-932
Number of pages10
JournalInternational Journal of Chemical Kinetics
Volume30
Issue number12
DOIs
Publication statusPublished - 1998
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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