Proposing ab initio assisted lattice distortion theory for phase equilibrium: Pure and mixed refrigerant gas hydrates

• Published in: AIChE journal 2022-02, Vol.68 (2), p.n/a
• Main Authors: Thakre, Niraj, Jana, Amiya K.
• Format: Article
• Language: English
• Subjects: ab initio; Chemical potential; Cold storage; Desalination; Distortion; Enthalpy; gas hydrate; Gas hydrates; Hydrates; lattice distortion; Model accuracy; Partial differential equations; Phase equilibria; refrigerant; Refrigerants; Seawater; thermodynamic modeling; Thermodynamic models
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.17463

With promising applications in cold storage and seawater desalination, various refrigerant gas hydrates are experimentally studied for their phase equilibrium behavior; however, the theoretical modeling to predict their formation conditions is under development. Although a high degree of lattice distortion is expected in these gas hydrates due to highly polar and nonspherical molecules of refrigerants, this issue is not addressed in the van der Waals–Platteeuw theory. With this research gap, we formulate a lattice distortion theory for both pure and mixed refrigerant hydrates. For the first time, ab initio methodology comprising the spin‐component scaled MP2 method with Dunning's basis set is implemented for estimating cavity potential of refrigerant hydrates. The extent of lattice distortion is documented in terms of reference chemical potential and enthalpy differences, which are obtained by regressing the Holder's equation with the experimental data of refrigerant hydrate formation. A critical observation is made that the reference properties linearly vary with the “Boltzmann weighted energy‐well depth” of the guest. Analyzing the accuracy of the model using average absolute relative deviation between experimental and predicted pressure of hydrate formation, the proposed lattice distortion model outperforms the existing thermodynamic models for variety of pure and mixed refrigerant hydrates.