Continuous Fractional Component Monte Carlo (CFCMC) and molecular dynamics (MD) simulations are performed to calculate the solubilities and self-diffusion coefficients of four light n-alkanes (methane, ethane, propane, and n-butane) in aqueous NaCl solutions as well as the thermodynamic properties of their corresponding hydrate crystals. Correction factors k_ij to the Lorentz-Berthelot combining rules for alkane groups (CH₃) and water are optimized (k_ij = 1.04) by fitting excess chemical potentials to experimental data at 1 bar and 298.15 K. Using these values of k_ij, we calculate the solubilities of the four alkanes in aqueous NaCl solutions with different molalities (0-6) mol/kg at different temperatures (278.15-308.15) K and pressures (1, 100, 200, 300) bar. The diffusion coefficients of the four alkanes in NaCl solutions (0-6) mol/kg are calculated at different temperatures (278.15-308.15) K and 1 bar and corrected for the finite-size effects. The lattice parameters of the corresponding hydrates with different guest molecules are computed using MD simulations at different temperatures (150-290) K and pressures (5-700) MPa. Isothermal compressibilities at 287.15 K and thermal expansion coefficients at 14.5 MPa for the corresponding hydrates are calculated. We present an extensive collection of thermodynamic data related to gas hydrates that contribute to a fundamental understanding of natural gas hydrate science.

Knowledge on the kinetics of gas hydrate dissociation in clay pores at static and dynamic fluid conditions is a fundamental scientific issue for improving gas production efficiency from hydrate deposits using thermal stimulation and depressurization respectively. Here, molecular dynamics simulations were used to investigate poly- and mono-crystalline methane hydrates in Na-montmorillonite clay nanopores. Simulation results show that hydrate dissociation is highly sensitive to temperature and pressure gradients, but their effects differ. Temperature changes increase thermal instability of water and gas molecules, leading to layer-by-layer dissociation from the outer surface. Under flow conditions, laminar flow predominates in nano-pores, and non-Darcy flow occurs due to clay-fluid interactions. Viscous flow disrupts hydrogen bonding at the hydrate surface, enhancing kinetic instability of water. Grain boundaries of polycrystalline hydrates are less stable compared to bulk phases and preferentially decompose, forming new dissociation fronts. This accelerates dissociation compared to monocrystalline hydrates. Fracture occurs at the grain boundaries of polycrystalline hydrate in the fluid, resulting in separate hydrate crystal grains. This fracture process further accelerates hydrate dissociation. In flow systems, methane nanobubbles form in fluid and readily transport with fluid flow. Unlike surface nanobubbles at static conditions, these liquid nanobubbles exhibit mobility. The findings of this study can contribute to a better understanding of the complex phase transition behavior of hydrate in confined environment, and provide theoretical support for improving production control technology.

This work addresses the contribution of the wavelength composition of the spectrum of the rail support stiffness profile to the expected long-term settlement. To that aim, purely harmonic stiffness variations of different wavelength are studied. The frequency-domain model with a double periodicity level previously developed by the first and last authors is adopted to embed the stiffness profile in one of the periodicity layers. Additional resonance velocities at which the resonance frequency of the track system coincides with the support-passing frequency or its multiples are found. The susceptibility to degradation is assessed both by quantifying the mechanical energy dissipated in the substructure under a moving train axle within one wavelength of the support stiffness variation, and the work performed by the wheel-rail contact force. It is shown that shorter wavelengths and larger standard deviations of varying ballast/subgrade stiffness result in an increasing energy dissipation in the substructure, and increase the work performed by the wheel-rail contact force, therefore leading to a reduced lifetime of the track. The energetic quantities increase for lower mean values of the stiffness profile, confirming the proneness of tracks on soft soils to degradation. The influence of varying stiffness vanishes for wavelengths of approximately 16 times the sleeper span, which is equivalent to a track length of about 10 m. High railpad stiffness values result in increased energy dissipation but the influence is limited. In general, an increasing train velocity amplifies the rate of track degradation, with no stabilizing trend in the high-speed regime (300 km/h).