We derive the entropy production for transport of multi-phase fluids in a non-deformable, porous medium exposed to differences in pressure, temperature, and chemical potentials. Thermodynamic extensive variables on the macro-scale are obtained by integrating over a representative elementary volume (REV). Contributions come from porous media specific properties, phase volumes, surface areas, and contact lines. Curvature effects are neglected. Using Euler homogeneity of the first order, we obtain the Gibbs equation for the REV. From this we define the intensive variables, the temperature, pressure, and chemical potentials, and, using the balance equations, we derive the entropy production for the REV. The entropy production defines sets of independent conjugate thermodynamic fluxes and forces in the standard way. The transport of two-phase flow of immiscible components is used to give a first illustration of the equations.

We define a representative elementary volume of a porous medium in terms of lumped extensive variables, including properties of homogeneous phases, interfaces, and contact lines. Using the grand potential, we define the pressure of the REV in a porous medium in a new manner. From the entropy production expressed in these variables, we develop new constitutive equations for multi-component, multi-phase, macro-scale flow. The system is exposed to temperature, composition, and pressure gradients. New contributions due to varying porosity or surface tension offer explanations for non-Darcy behavior, and predict thermal osmosis special for porous media. An experimental program is suggested to verify Onsager symmetry in the transport coefficients. The analysis is limited to non-deformable systems, which obey Euler homogeneity on the REV level.

We define the pressure of a porous medium in terms of the grand potential and compute its value in a nano-confined or nano-porous medium, meaning a medium where thermodynamic equations need be adjusted for smallness. On the nano-scale, the pressure depends in a crucial way on the size and shape of the pores. According to Hill [1], two pressures are needed to characterize this situation; the integral pressure and the differential pressure. Using Hill's formalism for a nano-porous medium, we derive an expression for the difference between the integral and the differential pressures in a spherical phase α of radius ${\widehat{p}}^{\alpha }-p^{\alpha }=\gamma /R$. We recover the law of Young-Laplace for the differential pressure difference across the same curved surface. We discuss the definition of a representative volume element for the nano-porous medium and show that the smallest REV is a unit cell in the direction of the pore in the fcc lattice. We also show, for the first time, how the pressure profile through a nano-porous medium can be defined and computed away from equilibrium.

It is known that thermodynamic properties of a system change upon confinement. To know how, is important for modelling of porous media. We propose to use Hill’s systematic thermodynamic analysis of confined systems to describe two-phase equilibrium in a nanopore. The integral pressure, as defined by the compression energy of a small volume, is then central. We show that the integral pressure is constant along a slit pore with a liquid and vapor in equilibrium, when Young and Young–Laplace’s laws apply. The integral pressure of a bulk fluid in a slit pore at mechanical equilibrium can be understood as the average tangential pressure inside the pore. The pressure at mechanical equilibrium, now named differential pressure, is the average of the trace of the mechanical pressure tensor divided by three as before. Using molecular dynamics simulations, we computed the integral and differential pressures, $\widehat{p}$ and p, respectively, analysing the data with a growing-core methodology. The value of the bulk pressure was confirmed by Gibbs ensemble Monte Carlo simulations. The pressure difference times the volume, V, is the subdivision potential of Hill, $(p-\widehat{p})V=ϵ$ . The combined simulation results confirm that the integral pressure is constant along the pore, and that $ϵ/V$ scales with the inverse pore width. This scaling law will be useful for prediction of thermodynamic properties of confined systems in more complicated geometries.

The accurate description of the behavior of fluids in nanoporous materials is of great importance for numerous industrial applications. Recently, a new approach was reported to calculate the pressure of nanoconfined fluids. In this approach, two different pressures are defined to take into account the smallness of the system: the so-called differential and the integral pressures. Here, the effect of several factors contributing to the confinement of fluids in nanopores are investigated using the definitions of the differential and integral pressures. Monte Carlo (MC) simulations are performed in a variation of the Gibbs ensemble to study the effect of the pore geometry, fluid-wall interactions, and differential pressure of the bulk fluid phase. It is shown that the differential and integral pressure are different for small pores and become equal as the pore size increases. The ratio of the driving forces for mass transport in the bulk and in the confined fluid is also studied. It is found that, for small pore sizes (i.e., < $5{\sigma }_{\mathrm{fluid}}$ ), the ratio of the two driving forces considerably deviates from 1.

We have described for the first time the thermodynamic state of a highly confined single-phase and single-component fluid in a slit pore using Hill’s thermodynamics of small systems. Hill’s theory has been named nanothermodynamics. We started by constructing an ensemble of slit pores for controlled temperature, volume, surface area, and chemical potential. We have presented the integral and differential properties according to Hill, and used them to define the disjoining pressure on the new basis. We identified all thermodynamic pressures by their mechanical counterparts in a consistent manner, and have given evidence that the identification holds true using molecular simulations. We computed the entropy and energy densities, and found in agreement with the literature, that the structures at the wall are of an energetic, not entropic nature. We have shown that the subdivision potential is unequal to zero for small wall surface areas. We have showed how Hill’s method can be used to find new Maxwell relations of a confined fluid, in addition to a scaling relation, which applies when the walls are far enough apart. By this expansion of nanothermodynamics, we have set the stage for further developments of the thermodynamics of confined fluids, a field that is central in nanotechnology.