Reactions of NO<sub>2</sub><sup>+</sup> and solvated NO<sub>2</sub><sup>+</sup> ions with aromatic compounds and alkanes

International Journal of Chemical Kinetics - Tập 10 Số 7 - Trang 657-667 - 1978
P. Ausloos1, Sharon G. Lias1
1Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20034

Tóm tắt

AbstractThe rate constants and modes of reaction of NO2+ and C2H5ONO2NO2+ with aromatic compounds and alkanes have been determined in a pulsed ion cyclotron resonance mass spectrometer. Both ions undergo competing charge transfer and substitution reactions (NO2+ + M → MO+ + NO; C2H5ONO2NO2+ + M → MNO2+ + C2H5ONO2) with aromatic molecules. In both cases, the probability that a collision results in charge transfer increases with increasing exothermicity of that process. The C2H5ONO2NO2+ ion does not undergo charge transfer with molecules having an ionization potential greater than about 212 kcal/mol (9.2 eV); this observation leads to an estimate of 13 kcal/mol for the binding energy between NO2+ and C2H5ONO2. The importance of the substitution reaction depends on the number of substituents on the aromatic ring and the molecular structure, and, in the case of C2H5ONO2NO2+ ions, on the energetics of the competing charge transfer process. Both NO2+ and C2H5ONO2NO2+ undergo hydride transfer reactions with alkanes. For both these ions, k(hydride transfer)/k (collision) increases with increasing exothermicity of reaction, but in both cases the rate constants of reaction are unusually low when compared with other hydride transfer reactions of comparable exothermicity which have been reported in the literature. This is interpreted as evidence that the attack on the alkane preferentially involves the nitrogen atom (where the charge is localized) rather than one of the oxygen atoms of NO2+.

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Tài liệu tham khảo

10.1021/ja00708a004

10.1016/0009-2614(77)85024-0

10.1021/ja00728a060

10.1021/ja00774a053

10.1016/0020-7381(76)80006-X

Rosenstock H. M., 1977, J. Phys. Chem. Ref. Data, 6

Langevin P., 1905, Ann. Chim. Phys., 5, 245

10.1063/1.1744477

10.1016/0020-7381(73)80104-4

10.1021/ja00786a003

10.1007/978-1-4613-4455-1_9

Maryott A. A., 1953, NBS Circular 537

Stull D. R., 1971, JANAF Thermochemical Tables

10.1002/9783527619825

10.1021/ja00720a006

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Thông tin xuất bản

International Journal of Chemical Kinetics

Tập 10 Số 7

657-667

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