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We describe the thermodynamic state of a highly confined single-phase andsingle-component fluid in a slit pore using Hill's thermodynamics of smallsystems. This theory was more recently named nanothermodynamics. We start byconstructing an ensemble of slit pores for controlled temperature, volume,surface area, and chemical potential. We present the integral and differentialproperties according to Hill, and use them to define the disjoining pressure.We identify all thermodynamic pressures by their mechanical counterparts in aconsistent manner, and investigate the identification by molecular dynamicssimulations. We define and compute the disjoining pressure, and show that itcontains the standard definition. We compute the entropy and energy densities,and find in agreement with the literature, that the forces at the wall are ofan energetic, not entropic nature. The subdivision potential is zero for thisslit pore with large walls, but unequal to zero for related sets of controlvariables. We show how Hill's method can be used to find new Maxwell relationsof a confined fluid, in addition to a scaling relation, which applies when thewalls are separated far enough. By this expansion of nanothermodynamics, we setthe stage for further developments of the thermodynamics of confined fluids, afield that is central in nanotechnology.

Nanothermodynamic description and molecular simulation of a single-phase fluid in a slit pore