ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the recombination reaction corresponding to the FSO3 + FSO3 ⇔ F2S2O6 equilibrium system has been studied. A time-resolved absorption spectroscopy technique was employed to monitor the appearance of thermally generated FSO3 radicals at 450 nm following a small temperature jump induced after partial laser photodissociation of F2S2O6 at 193 rim. The recombination rate constants have been determined over the temperature range 415-525 K and a N2 pressure range 10-600 torr. The reaction was found to be in its first order regime. The resulting limiting high pressure rate constants were combined with previous values measured in this laboratory at lower temperatures yielding the expression krec, x = (4.5 ± 0.2) × 10-14 (T/300)(1.0 ± 0.1) cm3 molecule-1 s-1 between 293 and 525 K. The temperature coefficient of krec, x is smaller than the one derived from steady-state experiments of the thermal dissociation of F2S2O6 and the equilibrium constant of the system. A recently formulated version of the canonical statistical adiabatic channel model was used to interprete the rate constants.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550220307
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