INQUIMAE   12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
Sorption Isotherms of Water in Nanopores: Relationship Between Hydropohobicity, Adsorption Pressure, and Hysteresis
Autor/es:
MATIAS H. FACTOROVICH; ESTEFANÍA GONZALEZ SOLVEYRA; VALERIA MOLINERO; DAMIAN A. SCHERLIS
Revista:
JOURNAL OF PHYSICAL CHEMISTRY C
Editorial:
AMER CHEMICAL SOC
Referencias:
Lugar: Washington; Año: 2014 vol. 118 p. 16290 - 16290
ISSN:
1932-7447
Resumen:
The motivation of this study is to elucidate how the condensation and desorption pressures in water sorption isotherms depend on the contact angle. This question is investigated for cylindrical pores of 2.8 nm diameter by means of molecular dynamics simulations in the grand canonical ensemble, in combination with the mW coarse-grained model for water. The contact angle is characterized for different sets of water?surface interactions. First, we show that desorption in open-ended pores with moderate or low water affinity, with contact angles greater or equal than 24°, is a nonactivated process in which pressure is accurately described by the Kelvin equation. Then, we explore the influence of hydrophobicity on the capillary condensation and on the width of the hysteresis loop. We find that a small increase in the contact angle may have a significant impact on the surface density and consequently on the nucleation free energy barrier. This produces a separation of the adsorption and desorption branches, exacerbating the emerging hysteresis. These results suggest that the contact angle is not as relevant as the adsorption energy in determining condensation pressure and hysteresis. Finally, we consider nonequilibrium desorption in pores with no open ends and describe how homogeneous and heterogeneous cavitation mechanisms depend on hydrophilicity.