Homogeneous water nucleation in carbon dioxide-nitrogen mixtures: Experimental study on pressure and carrier gas effects.

New homogeneous nucleation experiments are presented at 240 K for water in carrier gas mixtures of nitrogen with carbon dioxide molar fractions of 5%, 15%, and 25%. The pulse expansion wave tube is used to test three different pressure conditions, namely, 0.1, 1, and 2 MPa. In addition, a restricted series of nucleation experiments is presented for 25% carbon dioxide mixtures at temperatures of 234 and 236 K at 0.1 MPa. As pressure and carbon dioxide content are increased, the nucleation rate increases accordingly. This behavior is attributed to the reduction in the water surface tension by the adsorption of carrier gas molecules. The new data are compared with theoretical predictions based on the classical nucleation theory and on extrapolations of empirical surface tension data to the supercooled conditions at 240 K. The extrapolation is carried out on the basis of a theoretical adsorption/surface tension model, extended to multi-component mixtures. The theoretical model appears to strongly overestimate the pressure and composition dependence. At relatively low pressures of 0.1 MPa, a reduction in the nucleation rates is found due to an incomplete thermalization of colliding clusters and carrier gas molecules. The observed decrease in the nucleation rate is supported by the theoretical model of Barrett, generalized here for water in multi-component carrier gas mixtures. The temperature dependence of the nucleation rate at 0.1 MPa follows the scaling model proposed by Hale [J. Chem. Phys. 122, 204509 (2005)].

Homogeneous water nucleation: Experimental study on pressure and carrier gas effects.

Homogeneous nucleation of water is investigated in argon and in nitrogen at about 240 K and 0.1 MPa, 1 MPa, and 2 MPa by means of a pulse expansion wave tube. The surface tension reduction at high pressure qualitatively explains the observed enhancement of the nucleation rate of water in argon as well as in nitrogen. The differences in nucleation rates for the two mixtures at high pressure are consistent with the differences in adsorption behavior of the different carrier gas molecules. At low pressure, there is not enough carrier gas available to ensure the growing clusters are adequately thermalized by collisions with carrier gas molecules so that the nucleation rate is lower than under isothermal conditions. This reduction depends on the carrier gas, pressure, and temperature. A qualitative agreement between experiments and theory is found for argon and nitrogen as carrier gases. As expected, the reduction in the nucleation rates is more pronounced at higher temperatures. For helium as the carrier gas, non-isothermal effects appear to be substantially stronger than predicted by theory. The critical cluster sizes are determined experimentally and theoretically according to the Gibbs-Thomson equation, showing a reasonable agreement as documented in the literature. Finally, we propose an empirical correction of the classical nucleation theory for the nucleation rate calculation. The empirical expression is in agreement with the experimental data for the analyzed mixtures (water-helium, water-argon, and water-nitrogen) and thermodynamic conditions (0.06 MPa-2 MPa and 220 K-260 K).