High‐temperature dissociation of ethyl radicals and ethyl iodide
作者： Xueliang Yang , Robert S. Tranter
DOI: 10.1002/KIN.20601
关键词: Ethyl iodide 、 Analytical chemistry 、 Shock wave 、 Torr 、 Chemistry 、 Dissociation (chemistry) 、 Shock tube 、 Radical 、 Computational chemistry 、 Bond cleavage 、 Fission
摘要: The decomposition of ethyl iodide and subsequent dissociation radicals have been investigated behind incident shock waves in a diaphragmless tube by laser-schlieren (LS) densitometry (1150–1870 K, 55 ± 2 Torr 123 3 Torr). LS density-gradient profiles were simulated assuming that the initial C2H5I proceeded 87% C–I fission 13% HI elimination. Excellent agreement was found between simulations experimental profiles. Rate coefficients for scission reaction obtained show strong falloff. Gorin model RRKM (Rice, Ramsperger, Kassel, Marcus) calculations are excellent with data E0 = 55.0 kcal/mol, which is very good recent thermochemical measurements evaluations. However, approximately 2.7 kcal/mol higher than previous estimates. First-order rate determined to be k55Torr 8.65 × 1068T−16.65 exp(−37,890/T) s−1, k123Torr 3.01 1069T−16.68 exp(−38,430/T) k∞ 2.52 1019T−1.01 exp(−28,775/T) s−1. Rates also obtained, these theoretical predictions (Miller J. A. Klippenstein S. Phys Chem 2004, 6, 1192–1202). at low temperatures consumed through recombination reactions as well dissociation, whereas high temperatures, dominates. © 2012 Wiley Periodicals, Inc. Int J Kinet 44: 433–443,
sci-hub.se 参考文章(41)
Y. Feng, J. T. Niiranen, A. Bencsura, V. D. Knyazev, D. Gutman, W. Tsang, Weak collision effects in the reaction C2H5 ⇌ C2H4 + H The Journal of Physical Chemistry. ,vol. 97, pp. 871- 880 ,(1993) , 10.1021/J100106A012
Jorma A. Seetula, John J. Russell, David Gutman, Kinetics and thermochemistry of the reactions of alkyl radicals (methyl, ethyl, isopropyl, sec-butyl, tert-butyl) with hydrogen iodide: a reconciliation of the alkyl radical heats of formation Journal of the American Chemical Society. ,vol. 112, pp. 1347- 1353 ,(1990) , 10.1021/JA00160A009
Mark A. Hanning-Lee, Nicholas J. B. Green, Michael J. Pilling, Struan H. Robertson, Direct observation of equilibration in the system hydrogen atom + ethylene .dblharw. ethyl radical. Standard enthalpy of formation of the ethyl radical The Journal of Physical Chemistry. ,vol. 97, pp. 860- 870 ,(1993) , 10.1021/J100106A011
James A. Miller, Stephen J. Klippenstein, The H + C2H2(+M) ⇄ C2H3(+M) and H + C2H2(+M) ⇄ C2H5(+M) reactions: Electronic structure, variational transition-state theory, and solutions to a two-dimensional master equation Physical Chemistry Chemical Physics. ,vol. 6, pp. 1192- 1202 ,(2004) , 10.1039/B313645K
J. H. Kiefer, M. Z. Al-Alami, J-C. Hajduk, Physical optics of the laser-schlieren shock tube technique Applied Optics. ,vol. 20, pp. 221- 230 ,(1981) , 10.1364/AO.20.000221
J.H. Kiefer, S. Santhanam, N.K. Srinivasan, R.S. Tranter, S.J. Klippenstein, M.A. Oehlschlaeger, Dissociation, relaxation, and incubation in the high-temperature pyrolysis of ethane, and a successful RRKM modeling Proceedings of the Combustion Institute. ,vol. 30, pp. 1129- 1135 ,(2005) , 10.1016/J.PROCI.2004.08.215
J.V Michael, S.S Kumaran, M.-C Su, K.P Lim, Thermal rate constants over thirty orders of magnitude for the I+H2 reaction Chemical Physics Letters. ,vol. 319, pp. 99- 106 ,(2000) , 10.1016/S0009-2614(00)00072-5
Sidney W. Benson, A. N. Bose, Kinetics of the Gas‐Phase Addition of HI to C2H4 and the Pyrolysis of Ethyl Iodide The Journal of Chemical Physics. ,vol. 37, pp. 2935- 2940 ,(1962) , 10.1063/1.1733121
Robert S. Tranter, Xueliang Yang, John H. Kiefer, Dissociation of C3H3I and rates for C3H3 combination at high temperatures Proceedings of the Combustion Institute. ,vol. 33, pp. 259- 265 ,(2011) , 10.1016/J.PROCI.2010.05.030
J. H. Kiefer, A. C. Manson, Refractive index change and curvature in shock waves by angled beam refraction Review of Scientific Instruments. ,vol. 52, pp. 1392- 1396 ,(1981) , 10.1063/1.1136779