A thermodynamic description of nano-porous media must handle the size- and shape-dependence of the media properties. Such dependencies are typically due to the presence of immiscible phases, contact areas and contact lines. We propose a way to obtain average densities suitable for integration on the course grained scale, applying Hill's thermodynamics for small systems to the subsystems. we argue that the average densities of the porous medium, when defined in a proper way, obey the Gibbs equation. All contributions are additive or weakly coupled. From the Gibbs equation and the balance equations, we derive the entropy production in the standard way, for transport of multi-phase fluids in a non-deformable, porous medium exposed to di¤erences in boundary pressures, temperatures, and chemical potentials. Linear relations between thermodynamic fluxes and forces follow for the control volume. Fluctuation- dissipation theorems are formulated for the first time, for the fluctuating contributions to fluxes in the porous medium. These give an added possibility for determination of porous media permeabilities. Practical possibilities are further discussed.

We discuss a central concept of nanothermdynamics; the subdivision potential. We explain how it can be measured or calculated for some typical ensembles, as this has been disputed in the literature. We proceed to discuss its meaning for particular systems, and predict scaling laws for three ensembles. The laws depend on the small system geometry in a predictable way for an ideal gas model with surface adsorption. We provide new equations which relate the subdivision potential to experimental investigations, and give expressions for grand canonical ensembles of spheres, cylinders, slit pores and fluids confined in porous media. The subdivision potential is not compatible with the popular Hadwiger theorem in geometry, and can therefore not be described by a Minkowski set of variables. It is equivalent to Gibbs descriptions when shape- and size variables are defined.