Van der waals-like isotherms in a confined electrolyte by spherical and cylindrical nanopores.
Electrolytes confined by spherical, cylindrical, and slit-like charged nanopores are studied. Results for ionic distribution profiles, pressures of the confined fluid, and absorption isotherms are obtained through the hypernetted chain/mean spherical approximation (HNC/MSA) integral equations theory. In spherical and cylindrical geometries, an inward, non-monotonic behavior of the pressure is found as confinement increases, implying a negative compressibility. The pressure vs volume isotherms resemble liquid-vapor van der Waals-like phase transition diagrams. This effect is correlated with a charge separation inside a spherical pore previously reported (Phys. Rev. Lett., 79, 3656, 1997). Here, the mechanism of charge separation and negative compressibility are explored in detail. When compared with the slit-like pore pressure, important qualitative differences are found.
Aguilar-Pineda
Gabriel E
GE
Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa Apartado Postal 55-534, 09340 México, D. F., México.
Jiménez-Angeles
Felipe
F
Yu
Jiang
J
Lozada-Cassou
Marcelo
M