Homogeneous nucleation of water between 200 and 240 K: New wave tube data and estimation of the Tolman length

Abstract

We have measured homogeneous nucleation rates of water at 200-240 K in the carrier gas helium, in the range of 10(13) - 10(17) m(-3) s(-1) using an expansion wave tube. The rates agree well with the results of Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)] in the range of overlap (220-240 K), and are summarized by the empirical fit J = S exp[4.6 + 0.244T-(906.8 - 2.914T)(ln S)(2)], with J the nucleation rate in m(-3) s(-1), S the supersaturation, and T the temperature in K. We find that the supersaturation dependence of both our rates and those of Wolk and Strey is lower than classical theory predicts, and that the critical cluster is smaller than the classical critical size. These deviations are explained in the framework of the Tolman theory for surface tension, and the "Tolman length" is estimated from our experimental results. We find a positive Tolman length that increases with decreasing temperature, from about 0.1 Angstrom at 260 K to (0.6 +/- 0.4) Angstroms at 200 K. We present a nucleation rate expression that takes the Tolman length into account and show that both the supersaturation and temperature dependence are improved, compared to the classical theory.