ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Changes in the magnitude of 〈ΔEdown〉, the average downward collisional energy transferred between a highly vibrationally excited reactant molecule and an inert bath gas, upon perdeuteration of the substrate are reported for tert-butyl bromide dilute in Ar, Kr, N2, and CO2. The technique of pressure-dependent very low-pressure pyrolysis (VLPP) was used to obtain the absolute values of 〈ΔEdown〉, which are for C4H9Br, 230 (Ar), 285 (Kr), 270 (N2), and 365 (CO2) while for C4D9Br, 200 (Ar), 250 (Kr), 220 (N2), and 335 (CO2), all in cm-1 at ca. 720 K. The estimated uncertainties in these values are ca. ± 10%. These observed 〈ΔEdown〉, values and trends found with results from this series of isotope studies, are compared with current theoretical models. Extrapolated high-pressure temperature-dependent rate coefficients (s-1) for the thermal decomposition of reactant are 1013.8±0.3 exp(-175 ± 8 kJ mol-1/RT) for C4H9Br and 1014.3±0.3 exp(-183 ± 8 kJ mol-1/RT) for C4D9Br. These results are in accord with other studies and the expected isotope effect.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550200705
