Derjaguin-corrected Kelvin equation for finite open slits

Abstract

We formulate a Derjaguin-corrected Kelvin equation for phase transitions in finite open slits. In such pores, capillary condensation is modified by the finite wall length because the condensed phase is bounded by two terminal menisci pinned at the slit ends. Starting from the macroscopic generalized Kelvin equation, we introduce a scaling approximation which replaces the implicit edge-contact-angle condition by a closed analytic expression while preserving the exact limiting behaviours. We then incorporate mesoscopic wetting-layer contributions into the finite-slit free-energy balance. The single-wall contribution naturally separates into a planar Derjaguin term and a residual finite-length correction controlled by the competition between the wall length $H$ and the parallel correlation length $ξ_\parallel$. The resulting equation reduces to the standard Derjaguin-Kelvin equation for infinitely long slits and to the macroscopic finite-slit Kelvin equation when adsorbed layers are absent. Explicit forms are derived for long-ranged dispersion forces and for short-ranged forces. The theory is tested using classical density functional theory for finite slits with attractive Lennard-Jones walls and hard walls, corresponding respectively to capillary condensation and its drying analogue, capillary evaporation. The Derjaguin-corrected theory substantially improves on the purely macroscopic prediction, capturing both the correct infinite-slit limit and the observed dependence on wall length. For the short-ranged hard-wall system, the agreement with DFT remains nearly quantitative even for very narrow slits.