In this paper, thermodynamic miscibility
in nanoconfined spaces
is quantified and evaluated. First, an analytical generalized equation
of state (EOS) is developed by considering the effects of pore radius,
molecule–molecule interaction, and molecule–wall interaction
at nanometer scale, on the basis of which four extended cubic EOS
are proposed. Second, the analytical formulations of the confined
fluid free energy of mixing and solubility parameter at nanometer
scale are developed thermodynamically. Third, the free energy of mixing
and solubility parameter are calculated under different conditions,
by means of which the conditions and characteristics of the fluid
miscibility at nanometer scale are specifically studied. Finally,
two important factors, the temperature and molecule–wall (m–w)
interaction, are specifically studied to evaluate and compare their
effects on miscibility. The fluid miscibility benefits from the reduction
of the pore radius, while the m–w interaction is detrimental
to the development of miscibility. Moreover, the molecular size of
the single largest molecule in the mixture along with the wall-effect
region radius is determined to be the bottom limit of the pore radius,
above which fluid miscibility can be achieved and improved by reducing
the pore radius. It is found that the solubility parameter is a better
quantitative indicator of fluid miscibility; the calculated results
from the extended van der Waals, Soave–Redlich–Kwong,
and Peng–Robinson EOS are better than those from the extended
Redlich–Kwong EOS. Furthermore, a more fluid miscible state
is found to be achieved by reducing the temperature and wall-effect
region radius. The extent of the effect of temperature on the fluid
miscibility of different mixtures can be different. More specifically,
the so-called lean gas (i.e., N2, CH4, and CO2)-induced miscibility through the vaporizing process is found
to be affected by the temperature to a larger extent in comparison
with the rich gas (i.e., C2H6, C3H8, and i- and n-C4H10)-induced miscibility through the condensing–vaporizing
process.