Energies 2012, 5(6), 1705-1712; doi:10.3390/en5061705
Article

Intermolecular Hydrogen Transfer in Isobutane Hydrate

1 Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan 2 Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan 3 Department of Electrical and Electronic Engineering and Information Engineering, Graduate School of Engineering, Nagoya University, Furo, Chikusa-ku, Nagoya, Aichi 464-8603, Japan
* Author to whom correspondence should be addressed.
Received: 5 April 2012; in revised form: 18 May 2012 / Accepted: 22 May 2012 / Published: 25 May 2012
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Abstract: 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.
Keywords: hydrogen abstraction; clathrate hydrate; radical; electron spin resonance; activation energy

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MDPI and ACS Style

Kobayashi, N.; Minami, T.; Tani, A.; Nakagoshi, M.; Sugahara, T.; Takeya, K.; Ohgaki, K. Intermolecular Hydrogen Transfer in Isobutane Hydrate. Energies 2012, 5, 1705-1712.

AMA Style

Kobayashi N, Minami T, Tani A, Nakagoshi M, Sugahara T, Takeya K, Ohgaki K. Intermolecular Hydrogen Transfer in Isobutane Hydrate. Energies. 2012; 5(6):1705-1712.

Chicago/Turabian Style

Kobayashi, Naohiro; Minami, Takashi; Tani, Atsushi; Nakagoshi, Mikio; Sugahara, Takeshi; Takeya, Kei; Ohgaki, Kazunari. 2012. "Intermolecular Hydrogen Transfer in Isobutane Hydrate." Energies 5, no. 6: 1705-1712.

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