High-temperature collisional energy transfer in highly vibrationally excited molecules II: Isotope effects in isopropyl bromide systems

Brown, Trevor C., King, Keith D. and Gilbert, Robert G. (1987) High-temperature collisional energy transfer in highly vibrationally excited molecules II: Isotope effects in isopropyl bromide systems. International Journal of Chemical Kinetics, 19 9: 851-867. doi:10.1002/kin.550190906


Author Brown, Trevor C.
King, Keith D.
Gilbert, Robert G.
Title High-temperature collisional energy transfer in highly vibrationally excited molecules II: Isotope effects in isopropyl bromide systems
Journal name International Journal of Chemical Kinetics   Check publisher's open access policy
ISSN 0538-8066
1097-4601
Publication date 1987-09
Sub-type Article (original research)
DOI 10.1002/kin.550190906
Volume 19
Issue 9
Start page 851
End page 867
Total pages 17
Place of publication Hoboken, NJ, United States
Publisher John Wiley & Sons
Language eng
Formatted abstract
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.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown
Additional Notes Article first published online: 19 October 2004.

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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Created: Mon, 07 Mar 2011, 15:37:50 EST