Low-Temperature Thermodynamic Study of the Metastable Empty Clathrate Hydrates Using Molecular Simulations

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The thermodynamics of metastable empty sI-clathrate hydrates are probed over broad temperature and pressure ranges, 100 ≤ T (K) ≤ 220 and 1 ≤ p (bar) ≤ 5000, respectively, by large-scale simulations and compared with experimental data at 1 bar. The whole p-V-T surface obtained is fitted by the universal form of the Parsafar and Mason equation of state with an accuracy of 99.7-99.9%. Framework deformation brought about by the applied temperature follows a parabolic law, and there is a critical temperature above which the isobaric thermal expansion becomes negative, ranging from 194.7 K at 1 bar to 166.2 K at 5000 bar. That response to the applied (p, T) field is analyzed in terms of angle and distance descriptors of a classical tetrahedral structure and observed to occur essentially by means of angular alteration for (p, T) > (2000 bar, 200 K). The length of the hydrogen bonds responsible for framework integrity is insensitive to the thermodynamic conditions and its average value is r (O-H)=0.25 nm.

Original languageEnglish
Pages (from-to)789-799
Number of pages11
JournalACS Earth and Space Chemistry
Issue number5
Publication statusPublished - 16 May 2019


  • Empty clathrate hydrates
  • isobaric expansivity
  • isobaric heat capacity
  • molecular dynamics
  • p- V- T data
  • structure
  • thermodynamics


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