Abstract
The quantum yield of formation of CH3 and CH3CO in the pulsed laser photo-excitation of acetone at 300 and 308 nm was investigated at several pressures (60 to 740 Torr) and at either 298 or 228 K. The organic radicals generated were monitored indirectly following conversion (by reaction with Br2) to Br atoms, which were detected by resonance fluorescence. The photolysis of Cl2 in back-to-back experiments at the same wavelength and under identical experimental conditions served as chemical actinometer. The pressure and temperature dependent quantum yields obtained with this method are in good agreement with previous literature values and are reproduced using the parameterisation developed by Blitz et al. The Br formation kinetics deviated from that expected from reactions of CH3 and CH3CO alone and Br atoms were still observed at high yield even when the quantum yield of formation of CH3 and CH3CO was low. This is explained by the reactive quenching of thermalized triplet acetone (T1) by Br2. High yields of T1 (>80%) at the highest pressure in this study indicate that any dissociation from the first excited singlet state (S1) occurs in competition with intersystem crossing, and that physical quenching of S1 to the electronic ground (S0) is not a major process at these wavelengths. The rate coefficient for reaction of T1 with Br2 was found to be ∼3 × 10(-10) cm(3) molecule(-1) s(-1), independent of pressure or temperature.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.