Vapor–Liquid Equilibria of Nitrogen + Diethyl Ether and Nitrogen + 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone by Experiment, Peng–Robinson and PC-SAFT Equations of State

The saturated liquid line of the systems nitrogen (N2) + diethyl ether and N2 + 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (Novec 649) is measured along three isotherms, that is, 390, 420, and 450 K and 360, 390, and 420 K, respectively. The employed gas solubility apparatus, based on the synthetic method, allows to measure points up to the critical region of these mixtures. The experimental data are used to correlate the Peng–Robinson and PC-SAFT equations of state (EOS). For the parametrization of the system, N2 + diethyl ether the Peng–Robinson EOS is combined with the Huron–Vidal mixing rule and the non-random two-liquid (NRTL) excess Gibbs energy model; for the system N2 + Novec 649 the quadratic mixing rule is used

The air pressure effect on the homogeneous nucleation of carbon dioxide by molecular simulation

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

Comparison of macro- and microscopic solutions of the Riemann problem I. Supercritical shock tube and expansion into vacuum

The Riemann problem is a fundamental concept in the development of numerical methods for the macroscopic flow equations. It allows the resolution of discontinuities in the solution, such as shock waves, and provides a powerful tool for the construction of numerical flux functions. A natural extension of the Riemann problem involves two phases, a liquid and a vapour phase which undergo phase change at the material boundary. For this problem, we aim at a comparison with the macroscopic solution from molecular dynamics simulations. In this work, as a first step, the macroscopic solution of two important Riemann problem scenarios, the supercritical shock tube and the expansion into vacuum, were compared to microscopic solutions produced by molecular dynamics simulations. High fidelity equations of state were used to accurately approximate the material behaviour of the model fluid. The results of both scenarios compare almost perfect with each other. During the vacuum expansion, the fluid obtained a state of non-equilibrium, where the microscopic and macroscopic solutions start to diverge. A limiting case was shown, where liquid droplets appeared in the expansion fan, which was approximated by the macroscopic solution, assuming an undercooled vapour.DFG, 84292822, TRR 75: Tropfendynamische Prozesse unter extremen Umgebungsbedingunge