Rate constants, branching fractions, and energy disposal for the H+ClO and H+SF reactions

Autor:	S. J. Wategaonkar, D. W. Setser
Rok vydání:	1989
Předmět:	Hydrogen Infrared Chemistry Radical Inorganic chemistry General Physics and Astronomy chemistry.chemical_element Branching (polymer chemistry) law.invention Reaction rate constant law Thermochemistry Physical chemistry Singlet state Physical and Theoretical Chemistry Chemiluminescence
Zdroj:	The Journal of Chemical Physics. 90:6223-6233
ISSN:	1089-7690 0021-9606
Popis:	The H+ClO and SF reactions have been isolated and studied by infrared chemiluminescence in a fast flow reactor. The OH product channel is favored over the HCl channel by a factor of 4.5 and the total rate constant is (7.7±1.9)×10−11 cm3 s−1 for the H+ClO reaction. Both sets of products are accessed from a bound singlet intermediate with HCl+O(3 P) formed by a singlet–triplet surface crossing in the exit channel; the energy disposal is 〈fV (OH)〉=0.45 and 〈fV (HCl)〉=0.31. The H+SF reaction gives only HF+S(3P), but the energy disposal differs dramatically from the HCl channel of the ClO reaction. This difference arises from changes in the thermochemistry, which result in an earlier crossing to the HSF triplet surface followed by release of repulsive energy as the HF separates from the S(3P) atom.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::437784a03e9c97559a249cc744c6ee77 https://doi.org/10.1063/1.456339 Zobrazit plný text záznamu