Classical binary nucleation theory applied to the real mixture <i>n</i>-nonane/methane at high pressures

Abstract

A thermodynamic model of the formation free energy of a droplet, based on a real equation of state, has been implemented in the binary classical nucleation theory to analyze homogeneous nucleation of mixtures of n-nonane and methane in the coexistence region at high pressures. The composition of the critical nucleus is computed by solving the Kelvin equations, the chemical potentials, and molar volumes being evaluated from the Redlich–Kwong–Soave equation of state. Real gas behavior appears to have a strong effect on nucleation due to mutual interactions between methane and nonane molecules. Numerical calculations show an increasing concentration of methane in critical clusters with increasing pressure at fixed temperature and supersaturation. As a consequence, the surface tension of the critical droplets, which is evaluated by means of the Parachor method, is lowered, having a strong increasing effect on the nucleation rate; a 10 bar increase of total pressure leads to an increase of the nucleation rate of several orders of magnitude.