Photochemistry of the SO/sub 2/, 2-pentene system at 3660 A
The photolysis of SO/sub 2/ in the presence of cis- and trans-2-pentene has been investigated at 3660 A and 22/sup 0/C. Quantum yield measurements of the SO/sub 2/ photosensitized conversion of one isomer into the other are consistent with a mechanism in which the only participating excited electronic state of SO/sub 2/ is the SO/sub 2/(/sup 3/B/sub 1/) state. Quantum yield measurements were made for a variation in P/sub SO/sub 2///P/sub isomer/ reactant ratios of 4.01 -283 and 57.5-351 for the cis and trans isomers, respectively. The data are consistent with a mechanism in which a (SO/sub 2/-olefin)/sup 3/ collision intermediate is the precursor to the photosensitized isomeric products. The intermediate undergoes unimolecular decay to yield the cis and trans isomers with probabilities of 0.26 +- 0.05 and 0.69 +- 0.04, respectively. Estimates of the quenching rate constants at 22/sup 0/C for removal of SO/sub 2/(/sup 3/B/sub 1/) molecules by cis- and trans-2-pentene are (0.633 +- 0.125) x 10/sup 11/ l./mole.sec and (1.00 +- 0.27) x 10/sup 11/ l./mole.sec, respectively. An experimentally determined photostationary composition, (trans-2-pentene)/(cis-2-pentene) = 2.3 +- 0.1 was in fair agreement with that of 1.7 +- 0.7 as predicted from kinetic data derived in this study.
- Research Organization:
- Los Alamos Scientific Lab., NM
- OSTI ID:
- 7300564
- Journal Information:
- Int. J. Chem. Kinet.; (United States), Journal Name: Int. J. Chem. Kinet.; (United States) Vol. 8; ISSN IJCKB
- Country of Publication:
- United States
- Language:
- English
Similar Records
SO/sub 2/(/sup 3/B/sub 1/) photosensitized isomerization of cis- and trans-1,2-dichloroethylene
SO/sub 2/(/sup 3/B/sub 1/) photosensitized isomerization of cis and trans-1,2-dichloroethylene