A time-resolved lif study of the kinetics of OH(ν = 0) and OH(ν = 1) with HCl and HBr

✍ Scribed by Bret D. Cannon; John S. Robertshaw; Ian W.M. Smith; Martin D. Williams

• Publisher: Elsevier Science
• Year: 1984
• Tongue: English
• Weight: 618 KB
• Volume: 105
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(84)80045-7

✦ Synopsis

The kinetics 01 OH(u = 0) and OH@ = 1) have been followed using pulsed photolysis of Hz0 or HN03 to generate hydrosyl radicals. and time-resolved, laser-induced fluorevence to observe the rates of their subsequent removal in the presence of HCI or HBr The experiments yield the following rate constants (cm3 molecule-' s-t) at 298 f_ 4 KI OH@ = 0) + HCI: k. = (6.8 ? 0.25) X lo-13; OH(u = 0)+ HBrr k. = (11.2 f 0.45) lo-I*; OH(u = 1) + HCl. k, = (9.7 i 1.0) x 10-13;0H(,=1)+HBr.k, =(8.1 f 1.05)~ lo-I2 For OH(v = 1). the measurements do not distinguish between low by reaction and relaxation. and the fact that k, > k, for HCI is tentatrvely attributed to relaxation, probably by nearresonant vibrational-vibrational energy transfer Clearly, neither of these exothermic. low-activation-energy reactions IS enhanced to any grat extent. if at all, by nbrational excrtation of the OH radical.