  Vapour-liquid equilibria (VLE) and the influence of an inert carrier gas on
homogeneous vapour to liquid nucleation are investigated by molecular
simulation for quaternary mixtures of carbon dioxide, nitrogen, oxygen, and
argon. Canonical ensemble molecular dynamics simulation using the
Yasuoka-Matsumoto method is applied to nucleation in supersaturated vapours
that contain more carbon dioxide than in the saturated state at the dew line.
Established molecular models are employed that are known to accurately
reproduce the VLE of the pure fluids as well as their binary and ternary
mixtures. On the basis of these models, also the quaternary VLE properties of
the bulk fluid are determined with the Grand Equilibrium method.
  Simulation results for the carrier gas influence on the nucleation rate are
compared with the classical nucleation theory (CNT) considering the "pressure
effect" [Phys. Rev. Lett. 101: 125703 (2008)]. It is found that the presence of
air as a carrier gas decreases the nucleation rate only slightly and, in
particular, to a significantly lower extent than predicted by CNT. The
nucleation rate of carbon dioxide is generally underestimated by CNT, leading
to a deviation between one and two orders of magnitude for pure carbon dioxide
in the vicinity of the spinodal line and up to three orders of magnitude in
presence of air as a carrier gas. Furthermore, CNT predicts a temperature
dependence of the nucleation rate in the spinodal limit, which cannot be
confirmed by molecular simulation.
