Hydrogen/deuterium exchange in the reactions of methyl cation with methane
作者： Lee Hack Sung , Veronica M. Bierbaum , Charles H. DePuy
DOI: 10.1016/S0168-1176(97)00103-1
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摘要: Abstract The reaction of methyl cation with methane to form C 2 H 5 + and molecular hydrogen has been studied for several combinations deuterated reactants. experiments were carried out at room temperature a tandem flowing afterglow-selected ion flow tube (FA-SIFT). We observed small deviations from statistical loss /HD/D some reactions, notably the 3H/4D 4H/3D cases, exhibit an asymmetry in product distributions. A matrix method solving coupled rate equations, originally developed by J. Weiner et al. ( Am. Chem. Soc. 95 (1973) 4115), extended include isotope effects dissociation intermediate complex, provides very good fits experimental data. data analysis suggest that even highly exothermic reactions such as title reaction, distributions can deviate depending on relative rates H/D scrambling within collision complex its products. effect is approximately equal reciprocal square root masses , HD, D
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Jose Walkimar de M. Carneiro, Paul v. R. Schleyer, Martin Saunders, Richard Remington, Henry F. Schaefer, Arvi Rauk, Theodore S. Sorensen, Protonated Ethane. A Theoretical Investigation of C2H7+ Structures and Energies Journal of the American Chemical Society. ,vol. 116, pp. 3483- 3493 ,(1994) , 10.1021/JA00087A039
Shuang‐Ling Chong, J. L. Franklin, Ion–Molecule Reactions of CH4–CD4 Mixtures at High Pressures The Journal of Chemical Physics. ,vol. 55, pp. 641- 646 ,(1971) , 10.1063/1.1676131
Richard Wolfgang, Energy and chemical reaction. II. Intermediate complexes vs. direct mechanisms Accounts of Chemical Research. ,vol. 3, pp. 48- 54 ,(1970) , 10.1021/AR50026A002
Fred P. Abramson, Jean H. Futrell, Ion—Molecule Reactions of Methane The Journal of Chemical Physics. ,vol. 45, pp. 1925- 1931 ,(1966) , 10.1063/1.1727873
Jane M. Van Doren, Stephan E. Barlow, Charles H. Depuy, Veronica M. Bierbaum, The tandem flowing afterglow-shift-drift International Journal of Mass Spectrometry and Ion Processes. ,vol. 81, pp. 85- 100 ,(1987) , 10.1016/0168-1176(87)80007-1
Richard D. Smith, Jean H. Futrell, Proton- and deuteron-transfer reactions to ethane and ethane-d6: Internal-energy effects in the formation and decomposition of C2H7+ International Journal of Mass Spectrometry and Ion Physics. ,vol. 20, pp. 347- 378 ,(1976) , 10.1016/0020-7381(76)80052-6
Kenzo Hiraoka, Paul Kebarle, Stabilities and energetics of pentacoordinated carbonium ions. The isomeric protonated ethane ions and some higher analogs: protonated propane and protonated butane Journal of the American Chemical Society. ,vol. 98, pp. 6119- 6125 ,(1976) , 10.1021/JA00436A009
Albert J.R. Heck, Leo J. de Koning, Nico M.M. Nibbering, Chemical behavior of the gas-phase pentacoordinated carbonium ion, C2H+7 International Journal of Mass Spectrometry and Ion Processes. ,vol. 117, pp. 145- 169 ,(1992) , 10.1016/0168-1176(92)80091-E
Michael Henchman, David Smith, Nigel C. Adams, Proton motion within proton-bound dimers: H3O+ · H2O ⇌ H2O · H3O+, NH+4 · NH3 ⇌ NH3 · NH+4 and CH+5 · CH4 ⇌ CH4 · CH+5 A Kinetic model for isotope-exchange reactions International Journal of Mass Spectrometry and Ion Processes. ,vol. 109, pp. 105- 132 ,(1991) , 10.1016/0168-1176(91)85100-Z
L. I. Yeh, J. M. Price, Yuan T. Lee, Infrared spectroscopy of the pentacoordinated carbonium ion C2H7 Journal of the American Chemical Society. ,vol. 111, pp. 5597- 5604 ,(1989) , 10.1021/JA00197A015