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The mercury‐sensitized oxidation of carbon monoxide
Author(s) -
Simonaitis R.,
Heicklen Julian
Publication year - 1971
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550030404
Subject(s) - chemistry , excited state , carbon monoxide , reaction rate constant , quantum yield , mercury (programming language) , photochemistry , oxygen , redox , chemical reaction , analytical chemistry (journal) , inorganic chemistry , kinetics , catalysis , fluorescence , organic chemistry , atomic physics , physics , quantum mechanics , computer science , programming language
Abstract The mercury‐photosensitized oxidation of CO was studied at 275°C over a wide range of [O 2 ]/[CO] ratios in the absence and presence of the oxygen atom scavenger 2‐trifluoromethylpropene (TMP) and at 25°C at low [O 2 ]/[CO] ratios in the presence of TMP. By following the quantum yield of CO 2 production, Φ {CO 2 }, as a function of the [O 2 ]/[CO] ratio, the reactions of vibrationally excited CO ( v υ 9) and electronically excited O 2 , probably in the c 1 Σ − u state, were studied. At low [O 2 ]/[CO] ratios the predominant reactions are of vibrationally excited CO ( v υ 9). Relative rate constants for chemical reaction versus deactivation of CO ( v υ 9) were obtained. At higher [O 2 ]/[CO] ratios, the principal reactions are of electronically excited O 2 . Relative rate constants for chemical reactions and deactivation of this electronically excited O 2 with CO, O 2 , and TMP were obtained. From the effect of total pressure on Φ {CO 2 }, it is proposed that an intermediate CO 3 is formed in the reaction of electronically excited O 2 with CO.