ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Values for 〈ΔEdown〉, the average downward energy transferred from the reactant to the bath gas upon collision, have been obtained for highly vibrationally excited undeuterated and per-deuterated isopropyl bromide with the bath gases Ne, Xe, C2H4, and C2D4, at ca. 870 K. The technique of pressure-dependent very low-pressure pyrolysis (VLPP) was used to obtain the data. For C3H7Br, the 〈ΔEdown〉 values (cm-1) are 490 (Ne), 540 (Xe), 820 (C2H4), and 740 (C2D4), and for C3D7Br, 440 (Ne), 570 (Xe), 730 (C2H4), and 810 (C2D4). The uncertainties in these values are ca. ±10%. The 〈ΔEdown〉 values for the inert bath gases Ne and Xe show excellent agreement with the theoretical predictions of the semi-empirical biased random walk model for monatomic/substrate collisional energy exchange [J. Chem. Phys., 80, 5501 (1984)]. The relative effects of deuteration of the reactant molecule on 〈ΔEdown〉 also compare favorably with the predictions of this theoretical model. Extrapolated high-pressure rate coefficients (s-1) for the thermal decomposition of reactant are 1013.6±0.3 exp(-200 ± 8 kJ mol-1/RT) for C3H7Br and 1013.9±0.3 exp(-207 ± 8 kJ mol±1/RT) for C3D7Br, which are consistent with previous studies and the expected isotope effect.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550190906
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