Intermolecular Hydrogen Transfer in Isobutane Hydrate

Energies

Naohiro Kobayashi²  Takashi Minami²  Atsushi Tani¹  Mikio Nakagoshi²  Takeshi Sugahara²  Kei Takeya³ 

[1] Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan; E-Mail:;Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan; E-Mail:;Department of Electrical and Electronic Engineering and Information Engineering, Graduate School of Engineering, Nagoya University, Furo, Chikusa-ku, Nagoya, Aichi 464-8603, Japan; E-Mail:

关键词: hydrogen abstraction;    clathrate hydrate;    radical;    electron spin resonance;    activation energy;   

DOI  :  10.3390/en5061705

来源: mdpi

【 摘 要 】

Electron spin resonance (ESR) spectra of butyl radicals induced with γ-ray irradiation in the simple isobutane (2-methylpropane) hydrate (prepared with deuterated water) were investigated. Isothermal annealing results of the γ-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol) of hydrogen picking in the γ-ray-irradiated propane hydrate with deuterated water.

【 授权许可】

CC BY   
© 2012 by the authors; licensee MDPI, Basel, Switzerland.