ABSTRACT
We present homogeneous vapor-liquid nucleation rates of the 1-alcohols (C(n)H(2n+1)OH, n = 2-4) measured in the well-established two-valve nucleation pulse chamber as well as in a novel one-piston nucleation pulse chamber at temperatures between 235 and 265 K. The nucleation rates and critical cluster sizes show a very systematic behavior with respect to the hydrocarbon chain length of the alcohol, just as their thermo-physical parameters such as surface tension, vapor pressure, and density would suggest. For all alcohols, except ethanol, predictions of classical nucleation theory lie several orders of magnitude below the experimental results and show a strong temperature-dependence typically found in nucleation experiments. The more recent Reguera-Reiss theory [J. Phys. Chem. B 108(51), 19831 (2004)] achieves reasonably good predictions for 1-propanol, 1-butanol, and 1-pentanol, and independent of the temperature. Ethanol, however, clearly shows the influence of strong association between molecules even in the vapor phase. We also scaled all experimental results with classic nucleation theory to compare our data with other data from the literature. We find the same overall temperature trend for all measurement series together but inverted and inconsistent temperature trends for individual 1-propanol and 1-butanol measurements in other devices. Overall, our data establishe a comprehensive and reliable data set that forms an ideal basis for comparison with nucleation theory.
ABSTRACT
Homogeneous nucleation rates of water at temperatures between 240 and 270 K were measured in a laminar flow diffusion chamber at ambient pressure and helium as carrier gas. Being in the range of 10(2)-10(6) cm(-3) s(-1), the experimental results extend the nucleation rate data from literature consistently and fill a pre-existing gap. Using the macroscopic vapor pressure, density, and surface tension for water we calculate the nucleation rates predicted by classic nucleation theory (CNT) and by the empirical correction function of CNT by Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)]. As in the case of other systems (e.g., alcohols), CNT predicts a stronger temperature dependence than experimentally observed, whereas the agreement with the empirical correction function is good for all data sets. Furthermore, the isothermal nucleation rate curves allow us to determine the experimental critical cluster sizes by use of the nucleation theorem. A comparison with the critical cluster sizes calculated by use of the Gibbs-Thomson equation is remarkably good for small cluster sizes, for bigger ones the Gibbs-Thomson equation overestimates the cluster sizes.
