ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The average downward collisional energy transfer (〈ΔEdown〉) is obtained for highly vibrationally excited tert-butyl chloride, both undeuterated and per-deuterated, with Kr, N2, CO2, and C2H4 bath gases, at ca. 760 K. Data are obtained using the technique of pressure-dependent very low-pressure pyrolysis. Reactant internal energies to which the data are sensitive are in the range 200-250 kJ mol-1. For C4H9Cl, the 〈ΔEdown〉 values (cm-1) are 255 (Kr), 265 (N2), 440 (CO2), and 585 (C2H4), and for C4D9Cl, 245 (N2), 370 (CO2), and 540 (C2H4). The uncertainties in these values are ca. 20% (40% for Kr); the uncertainties in the deuteration ratios are 10-15%. The value for Kr is in agreement with theoretical predictions of a biased random walk model for internal energy change in monatomic/substrate collisions. The effect of deuteration of 〈ΔEdown〉 is also in accord with that predicted by a modification of the theory. Extrapolated highpressure rate coefficients for the thermal decomposition of reactant are 1013.6 exp(-187 kJ mol-1/RT) s-1 (C4H9Cl) and 1014.2 exp(-196 kJ mol-1/RT) s-1 (C4D9Cl), in accord with other studies and the expected isotope effect.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550161113
