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In this two-part study we investigate the phase behaviour of a fluidspatially confined in a semi-infinite rectangular pore formed by threeorthogonal walls and connected to a reservoir maintaining constant values ofpressure and temperature in the fluid. Far from the capping wall thisprototypical two-dimensional system reduces to a one-dimensional slit pore.However, the broken translational symmetry leads to a wetting behaviorstrikingly different from that of a slit pore. Using a realistic model of anatomic fluid with long-ranged Lennard-Jones fluid-fluid and fluid-substrateinteractions, we present for the first time detailed computations of full phasediagrams of two-dimensional capped capillaries. Our analysis is based on thestatistical mechanics of fluids, in particular density functional theory. Weshow the existence of capillary wetting temperature, which is a property of thepore, and relatively to the fluid temperature determines whether capillarycondensation is a first-order or a continuous phase transition. We also reportfor the first time a first-order capillary wetting transition, which can bepreceded by a first-order capillary prewetting. A full parametric study isundertaken and we support our findings with exhaustive examples of densityprofiles, adsorption and free energy isotherms, as well as full phase diagrams.

Wetting in a two-dimensional capped capillary. Part I: Wetting temperature and capillary prewetting