ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Br-atom atomic resonance absorption spectrometry (ARAS) has been developed and applied to measure thermal decomposition rate constants for CF3Br (+ Kr)→CF3+Br (+ Kr) over the temperature range, 1222-1624 K. The Br-atom curve-of-growth (145〈λ〈163 nm) was determined using this reaction. For [Br]≤1×1012 molecules cm-3, absorbance, (ABS)=1.410×10-13 [Br], yielding σ=1.419×10-14 cm2. The curve-of-growth was then used to convert (ABS) to Br-atom profiles which were then analyzed to give measured rate constants. These can be expressed in second-order by k1=8.147×10-9 exp(-24488 K/T) cm3 molecule-1 s-1 (±33%, 1222≤T≤1624 K). A unimolecular theoretical approach was used to rationalize the data. Theory indicates that the dissociation rates are closer to second- than to first-order, i.e., the magnitudes are 30-53% of the low-pressure-limit rate constants over 1222-1624 K and 123-757 torr. With the known, E0=ΔH00=70.1 kcal mole-1, the optimized theoretical fit to the ARAS data requires 〈ΔE〉down=550 cm-1. These conclusions are consistent with recently published data and theory from Kiefer and Sathyanarayana. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 859-867, 1998
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
