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. 2017 Apr 24;2(4):1601-1607.
doi: 10.1021/acsomega.7b00264. eCollection 2017 Apr 30.

Thermodynamic Stability of Structure II Methyl Vinyl Ketone Binary Clathrate Hydrates and Effects of Secondary Guest Molecules on Large Guest Conformation

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Free PMC article

Thermodynamic Stability of Structure II Methyl Vinyl Ketone Binary Clathrate Hydrates and Effects of Secondary Guest Molecules on Large Guest Conformation

Yun-Ho Ahn et al. ACS Omega. .
Free PMC article

Abstract

Clathrate hydrates have received massive attention because of their potential application as energy storage materials. Host water frameworks of clathrate hydrates provide empty cavities that can capture not only small molecular guests but also radical species induced by γ-irradiation. In this work, we investigated structure II methyl vinyl ketone (MVK) binary clathrate hydrates with CH4, O2, and N2 and the effects of secondary guest species on MVK conformation in the cavity of hydrate and on the thermodynamic stability of unirradiated and γ-irradiated hydrate phases. The present findings provide meaningful information to understand the nature of guest-host interactions in γ-irradiated clathrate hydrates and to open up practical applications for hydrate-based nanoreactors.

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
HRPD patterns of (a) MVK + O2 and (b) MVK + N2 hydrates [red circles, observed HRPD pattern; black solid line, calculated HRPD pattern; and tick marks, cubic Fdm (top, green) and hexagonal P63/mmc phases (bottom, blue)].
Figure 2
Figure 2
Phase equilibrium curve of the pure CH4 and MVK (3.0, 5.6, 8.0 mol %) + CH4 hydrates. Data points for CH4 + water are adapted with permission from the original publishers (ref (26), copyright 1997, Elsevier).
Figure 3
Figure 3
Phase equilibrium curve of the pure O2, and MVK (3.0, 5.6, 8.0 mol %) + O2 hydrates. Data points for O2 + water are adapted with permission from the original publishers (ref (27), copyright 2003, American Chemical Society).
Figure 4
Figure 4
Phase equilibrium curve of the pure N2, and MVK (3.0, 5.6, 8.0 mol %) + N2 hydrates. Data points for N2 + water are adapted with permission from the original publishers (ref (26), copyright 1997, Elsevier).
Figure 5
Figure 5
Raman spectra of (a) nonirradiated MVK + O2 hydrate and (b) γ-irradiated MVK + O2 hydrate measured at various temperatures.
Figure 6
Figure 6
Raman spectra of (a) nonirradiated MVK + N2 hydrate and (b) γ-irradiated MVK + N2 hydrate measured at various temperatures.

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