On the thermodynamic stability and structural transition of clathrate hydrates

Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure

A branch-point approximant for the equation of state of hard spheres

Using the first seven known virial coefficients and forcing it to possess two branch-point singularities, a new equation of state for the hard-sphere fluid is proposed. This equation of state predicts accurate values of the higher virial coefficients, a radius of convergence smaller than the close-packing value, and it is as accurate as the rescaled virial expansion and better than the Pad\'e [3/3] equations of state. Consequences regarding the convergence properties of the virial series and the use of similar equations of state for hard-core fluids in $d$ dimensions are also pointed out.Comment: 6 pages, 4 tables, 3 figures; v2: enlarged version, extension to other dimensionalities; v3: typos in references correcte

Droplet minimizers for the Gates-Lebowitz-Penrose free energy functional

We study the structure of the constrained minimizers of the Gates-Lebowitz-Penrose free-energy functional ${\mathcal F}_{\rm GLP}(m)$, non-local functional of a density field $m(x)$, $x\in {\mathcal T}_L$, a $d$-dimensional torus of side length $L$. At low temperatures, ${\mathcal F}_{\rm GLP}$ is not convex, and has two distinct global minimizers, corresponding to two equilibrium states. Here we constrain the average density L^{-d}\int_{{\cal T}_L}m(x)\dd x to be a fixed value $n$ between the densities in the two equilibrium states, but close to the low density equilibrium value. In this case, a "droplet" of the high density phase may or may not form in a background of the low density phase, depending on the values $n$ and $L$. We determine the critical density for droplet formation, and the nature of the droplet, as a function of $n$ and $L$. The relation between the free energy and the large deviations functional for a particle model with long-range Kac potentials, proven in some cases, and expected to be true in general, then provides information on the structure of typical microscopic configurations of the Gibbs measure when the range of the Kac potential is large enough

Laterally driven interfaces in the three-dimensional Ising lattice gas

We study the steady state of a phase-separated driven Ising lattice gas in three dimensions using computer simulations with Kawasaki dynamics. An external force field F(z) acts in the x direction parallel to the interface, creating a lateral order parameter current j^x(z) which varies with distance z from the interface. Above the roughening temperature, our data for `shear-like' linear variation of F(z) are in agreement with the picture wherein shear acts as effective confinement in this system, thus supressing the interfacial capillary-wave fluctuations. We find sharper magnetisation profiles and reduced interfacial width as compared to equilibrium. Pair correlations are more suppressed in the vorticity direction y than in the driving direction; the opposite holds for the structure factor. Lateral transport of capillary waves occurs for those forms of F(z) for which the current j^x(z) is an odd function of z, for example the shear-like drive, and a `step-like' driving field. For a V-shaped driving force no such motion occurs, but capillary waves are suppressed more strongly than for the shear-like drive. These findings are in agreement with our previous simulation studies in two dimensions. Near and below the (equilibrium) roughening temperature the effective-confinement picture ceases to work, but the lateral motion of the interface persists.Comment: 20 pages, 11 figures, submitted to Phys. Rev.

New results for virial coefficients of hard spheres in D dimensions

We present new results for the virial coefficients B_k with k <= 10 for hard spheres in dimensions D=2,...,8.Comment: 10 pages, 5 figures, to appear in conference proceedings of STATPHYS 2004 in Pramana - Journal of Physic

Free Energy Minimizers for a Two--Species Model with Segregation and Liquid-Vapor Transition

We study the coexistence of phases in a two--species model whose free energy is given by the scaling limit of a system with long range interactions (Kac potentials) which are attractive between particles of the same species and repulsive between different species.Comment: 32 pages, 1 fig, plain tex, typeset twic

On the relation between virial coefficients and the close-packing of hard disks and hard spheres

The question of whether the known virial coefficients are enough to determine the packing fraction $\eta_\infty$ at which the fluid equation of state of a hard-sphere fluid diverges is addressed. It is found that the information derived from the direct Pad\'e approximants to the compressibility factor constructed with the virial coefficients is inconclusive. An alternative approach is proposed which makes use of the same virial coefficients and of the equation of state in a form where the packing fraction is explicitly given as a function of the pressure. The results of this approach both for hard-disk and hard-sphere fluids, which can straightforwardly accommodate higher virial coefficients when available, lends support to the conjecture that $\eta_\infty$ is equal to the maximum packing fraction corresponding to an ordered crystalline structure.Comment: 10 pages, 6 figures; v2: discussion about hard-square and hard-hexagon systems on a lattice added; five new reference

On the thermodynamic stability of clathrate hydrates IV: Double occupancy of cages

We have extended the van der Waals and Platteeuw theory to treat multiple occupancy of a single cage of clathrate hydrates, which has not been taken into account in the original theory but has been experimentally confirmed as a real entity. We propose a simple way to calculate the free energy of multiple cage occupancy and apply it to argon clathrate structure II in which a larger cage can be occupied by two argon atoms. The chemical potential of argon is calculated treating it as an imperfect gas, which is crucial to predict accurate pressure dependence of double occupancy expected at high pressure. It is found that double occupancy dominates over single occupancy when the guest pressure in equilibrium with the clathrate hydrate exceeds 270 MPa. (C) 2004 American Institute of Physics

Master crossover behavior of parachor correlations for one-component fluids

The master asymptotic behavior of the usual parachor correlations, expressing surface tension $\sigma$ as a power law of the density difference $\rho_{L}-\rho_{V}$ between coexisting liquid and vapor, is analyzed for a series of pure compounds close to their liquid-vapor critical point, using only four critical parameters $(\beta_{c})^{-1}$, $\alpha_{c}$, $Z_{c}$ and $Y_{c}$, for each fluid. ... The main consequences of these theoretical estimations are discussed in the light of engineering applications and process simulations where parachor correlations constitute one of the most practical method for estimating surface tension from density and capillary rise measurements