Revisiting the thermodynamic modelling of type I gas-hydroquinone clathrates.
Revisiting the thermodynamic modelling of type I gas-hydroquinone clathrates.
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重新审视 I 型气体-氢醌包合物的热力学模型。
DOI：
10.1039/c5cp07202f
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
C. Miqueu
中科院分区：
文献类型：
--
作者：
M. M. Conde;J. Torré;C. Miqueu
在特定的压力和温度条件下，某些气体物质可以参与对苯二酚分子的主体晶格，形成称为气体对苯二酚笼形物的超分子实体。本研究致力于热力学模型的I型氢醌包合物。在这项工作中考虑的气体是氩，氪，氙，甲烷，氮气，氧气和硫化氢。例如，基本的货车德瓦耳斯和普拉特模型不能很好地预测这种笼形物在高温下的相平衡性质，通过首先考虑客体在固体HQ中的溶解度，然后考虑笼形物结构内部的气体分子之间的相互作用（即客体-客体相互作用）来修改和扩展该模型。其他的改进的基本理论，如参考状态的选择，提出了，并最终计算出一套独特的热力学参数有效的所有研究的客人。模型预测和文献中的实验数据之间获得了很好的一致性。我们的结果清楚地表明，最高水平的理论是必要的，以很好地描述三相平衡线（其中HQ包合物，天然氢醌HQα和气体共存），客体在包合物中的占有率，和嵌入焓。
Under specific pressure and temperature conditions, certain gaseous species can be engaged in a host lattice of hydroquinone molecules, forming a supramolecular entity called a gas hydroquinone clathrate. This study is devoted to the thermodynamic modelling of type I hydroquinone clathrates. The gases considered in this work are argon, krypton, xenon, methane, nitrogen, oxygen and hydrogen sulphide. The basic van der Waals and Platteeuw model, which is, for example, not able to predict well the phase equilibrium properties of such clathrates at high temperature, is modified and extended by considering first the solubility of the guest in solid HQ and then the mutual interactions between the gaseous molecules inside the clathrate structure (i.e. guest-guest interactions). Other improvements of the basic theory, such as the choice of the reference state, are proposed, and a unique set of thermodynamic parameters valid for all the studied guests are finally calculated. Very good agreement is obtained between the model predictions and the experimental data available in the literature. Our results clearly demonstrate that the highest level of theory is necessary to describe well both the triphasic equilibrium line (where the HQ clathrate, the native hydroquinone HQα and the gas coexist), the occupancy of the guest in the clathrate, and the intercalation enthalpy.