Infrared laser-induced decomposition of tert-butyl alcohol

Autor:	Kenneth A. Holbrook, G. A. Oldershaw, Peter E. Dyer, Charles Shaw
Rok vydání:	1992
Předmět:	tert-Butyl alcohol Infrared Analytical chemistry chemistry.chemical_element Photochemistry Decomposition chemistry.chemical_compound Reaction rate constant Xenon chemistry Irradiation Physical and Theoretical Chemistry Total pressure Absorption (chemistry)
Zdroj:	Journal of the Chemical Society, Faraday Transactions. 88:2617
ISSN:	1364-5455 0956-5000
DOI:	10.1039/ft9928802617
Popis:	The decomposition of tert-butyl alcohol (2-methylpropan-2-ol) by pulsed infrared radiation from a TEA CO2 laser has been examined, using the 10P30 line at 934.9 cm–1. Over the pressure range 0.007–1,3 kPa the absorption cross-section increases with increasing pressure due to hole-filling by collisional rotational relaxation. Experiments on the decomposition were carried out at low total pressure (6.7 Pa) to minimise the effects of collisions during the pulse. The fluence range used was 3.3–6.4 J cm–2. Under these conditions the only decomposition product detected was isobutene (2-methylpropene) generated in the reaction:(CH 3 ) 3 COH →(CH 3 ) 2 CCH 2 + H 2 OAddition of the diluent gases hexane and xenon reduced the extent of decomposition, and product yields from the diluted tert-butyl alcohol were compared with values calculated by assuming particular forms of the intermolecular energy distribution and by using RRKM rate constants. The comparison indicates that about half the irradiated molecules absorb the 10P30 radiation. The fraction of absorbing molecules deduced from the absorption measurements is considerably smaller than this, and reasons for the discrepancy are discussed.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::837813a1c6000eace1edaf30423bb1ef https://doi.org/10.1039/ft9928802617 Zobrazit plný text záznamu