Abstract
The thermodynamic stability of clathrate hydrates I and II encaging xenon or argon has been investigated by examining the temperature dependence of the dissociation pressure. The evaluation of the stability is made based on the generalized van der Waals and Platteeuw theory developed by Tanaka and Kiyohara [J. Chem. Phys. 98, 4098 (1993)]. In the new treatment, the free energy of formation of hydrates in equilibrium with ice is calculated by taking the coupling of the host lattice vibrations with guests into consideration. The predicted dissociation pressures of Xe and Ar hydrates agree well with experiments in higher temperature range. A poor agreement between experiment and calculation for Ar clathrate hydrate at low temperature is improved by the use of a quantum mechanical partition function for a harmonic oscillator in evaluating the free energy difference between ice and empty hydrate.
| Original language | English |
|---|---|
| Pages (from-to) | 317-327 |
| Number of pages | 11 |
| Journal | Molecular Simulation |
| Volume | 12 |
| Issue number | 3-6 |
| DOIs | |
| Publication status | Published - Mar 1 1994 |
| Externally published | Yes |
Keywords
- Clathrate hydrate
- generalized vdWP theory
- thermodynamic stability
ASJC Scopus subject areas
- Chemistry(all)
- Information Systems
- Modelling and Simulation
- Chemical Engineering(all)
- Materials Science(all)
- Condensed Matter Physics