期刊
CHEMICAL ENGINEERING SCIENCE
卷 236, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ces.2021.116514
关键词
Semiclathrate hydrate; Phase equilibrium; Quaternary phosphonium cation; Dissociation enthalpy
资金
- Ministry of Education, Culture, Sports, Science and Technology, Japan [18K05032, 26410104, 17H06456, 17H03535]
- Kato Foundation for Promotion of Science
- Grants-in-Aid for Scientific Research [18K05032, 26410104, 17H06456, 17H03535] Funding Source: KAKEN
This study investigated the impact of cation size and shape on the thermodynamic properties of semiclathrate hydrates, finding that branched alkyl groups raised the equilibrium temperature while shorter alkyl groups lowered it. Among the orthorhombic systems studied, semiclathrate hydrates with higher equilibrium temperatures had larger dissociation enthalpies.
Semiclathrate hydrate (SCH) is one of the phase change materials suitable for cold storage. The thermodynamic properties of SCHs, such as an equilibrium temperature and a dissociation enthalpy, depend on the size and shape of guest substances. In this study, to reveal the effect of cation size and shape on the thermodynamic properties, tri-n-butylalkylphosphonium bromide (P444R-Br) SCHs, where the alkyl group was n-propyl (R = 3), n-butyl (R = 4), n-pentyl (R = 5), i-butyl (R = i-4), i-pentyl (R = i-5), or allyl (R = Al)), were investigated. The branched alkyl groups (R = i-4 or i-5) raised the equilibrium temperature, whereas the shorter alkyl groups (R = 3 or Al) lowered one. Except for P4445-Br and P444(Al)-Br SCHs, the other P444R-Br SCHs had the same orthorhombic structure. Among the orthorhombic systems in the present study, the semiclathrate hydrate with a higher equilibrium temperature had a larger dissociation enthalpy. (c) 2021 Elsevier Ltd. All rights reserved.
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