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Validity of local equilibrium has been questioned for non-equilibrium systems which are characterized by delayed response. In particular, for systems with non-zero thermodynamic inertia, the assumption of local equilibrium leads to negative values of the entropy production, which is in contradiction with the second law of thermodynamics. In this paper, we address this question by suggesting a variational formulation of irreversible evolution of a system with non-zero thermodynamic inertia. We introduce the Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" systems. We show that the standard evolution equations, in particular, the Maxwell-Cattaneo-Vernotte equation, can be derived from the variational procedure without going beyond the assumption of local equilibrium. We also argue that the second law of thermodynamics in non-equilibrium should be understood as a consequence of the variational procedure and the property of local equilibrium. For systems with instantaneous response this leads to the standard requirement of the local instantaneous entropy production being always positive. However, if a system is characterized by delayed response, the formulation of the second law of thermodynamics should be altered. In particular, the quantity, which is always positive, is not the instantaneous entropy production, but the entropy production averaged over a proper time interval. [ABSTRACT FROM AUTHOR]

We show that the equations which describe irreversible evolution of a system can be derived from a variational principle. We suggest a Lagrangian, which depends on the properties of the normal and the so-called "mirror-image" system. The Lagrangian is symmetric in time and therefore compatible with microscopic reversibility. The evolution equations in the normal and mirror-imaged systems are decoupled and describe therefore independent irreversible evolution of each of the systems. The second law of thermodynamics follows from a symmetry of the Lagrangian. Entropy increase in the normal system is balanced by the entropy decrease in the mirror-image system, such that there exists an "integral of evolution" which is a constant. The derivation relies on the property of local equilibrium, which states that the local relations between the thermodynamic quantities in non-equilibrium are the same as in equilibrium. [ABSTRACT FROM AUTHOR]

Nucleation is often accompanied by heat transfer between the surroundings and a nucleus of a new phase. The interface between two phases gives an additional resistance to this transfer. For small nuclei the interfacial curvature is high, which affects not only equilibrium quantities such as surface tension, but also the transport properties. In particular, high curvature affects the interfacial resistance to heat and mass transfer. We develop a framework for determining the curvature dependence of the interfacial heat and mass transfer resistances. We determine the interfacial resistances as a function of a curvature. The analysis is performed for a bubble of a one-component fluid and may be extended to various nuclei of multicomponent systems. The curvature dependence of the interfacial resistances is important in modeling transport processes in multiphase systems. [ABSTRACT FROM AUTHOR]

We analyze the stability of small bubbles in a closed system with fixed volume, temperature, and number of molecules. We show that there exists a minimum stable size of a bubble. Thus there exists a range of densities where no stable bubbles are allowed and the system has a homogeneous density which is lower than the coexistence density of the liquid. This becomes possible due to the finite liquid compressibility. Capillary analysis within the developed 'modified bubble' model illustrates that the existence of the minimum bubble size is associated to the compressibility and it is not possible when the liquid is strictly incompressible. This finding is expected to have very important implications in cavitation and boiling. [ABSTRACT FROM AUTHOR]

In this paper we calculate the interfacial resistances to heat and mass transfer through a liquid-vapor interface in a binary mixture. We use two methods, the direct calculation from the actual nonequilibrium solution and integral relations, derived earlier. We verify, that integral relations, being a relatively faster and cheaper method, indeed gives the same results as the direct processing of a nonequilibrium solution. Furthermore we compare the absolute values of the interfacial resistances with the ones obtained from kinetic theory. Matching the diagonal resistances for the binary mixture we find that kinetic theory underestimates the cross coefficients. The heat of transfer is, as a consequence, correspondingly larger. [ABSTRACT FROM AUTHOR]

We present a theory that describes the transport properties of the interfacial region with respect to heat and mass transfer. Postulating the local Gibbs relation for a continuous description inside the interfacial region, we derive the description of the Gibbs surface in terms of excess densities and fluxes along the surface. We introduce overall interfacial resistances and conductances as the coefficients in the force-flux relations for the Gibbs surface. We derive relations between the local resistivities for the continuous description inside the interfacial region and the overall resistances of the surface for transport between the two phases for a mixture. It is shown that interfacial resistances depend among other things on the enthalpy profile across the interface. Since this variation is substantial, the coupling between heat and mass flow across the surface is also substantial. In particular, the surface puts up much more resistance to the heat and mass transfer than the homogeneous phases over a distance comparable to the thickness of the surface. This is the case not only for the pure heat conduction and diffusion but also for the cross effects such as thermal diffusion. For the excess fluxes along the surface and the corresponding thermodynamic forces, we derive expressions for excess conductances as integrals over the local conductivities along the surface. We also show that the curvature of the surface affects only the overall resistances for transport across the surface and not the excess conductivities along the surface. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulations to investigate the linear and nonlinear density response functions for simple fluids under the influence of spatially periodic external fields. Using a direct Fourier space decomposition of the instantaneous microscopic density for the perturbed fluid we can clearly identify the distinct order of response. Using a single component sinusoidal longitudinal force for a set of wavelengths and amplitudes we show that in the linear response regime the proportionality between the external field amplitude and the density perturbation can be used to determine the linear density response function, and hence the pair correlation function, static liquid structure factor, and lowest order direct correlation function. We show also that for large external field amplitudes a single component external field can be used to determine the form for lowest order and second lowest order nonlinear response functions for restricted regions of the total response function spaces. [ABSTRACT FROM AUTHOR]