Institut für Physikalische Chemie, Universität zu Köln, Germany.
J Chem Phys. 2010 Jan 14;132(2):024307. doi: 10.1063/1.3274629.
Homogeneous nucleation rates of the n-alkanes (C(i)H(2i+2); i=7-10) were determined by combining information from pressure trace measurements and small angle x-ray scattering (SAXS) experiments in a supersonic Laval nozzle. The condensible vapor pressure p(J max), the temperature T(J max), the characteristic time Deltat(J max), and supersaturation S(J max) corresponding to the peak nucleation rate J(max) were determined during the pressure trace measurements. These measurements also served as the basis for the subsequent SAXS experiments. Fitting the radially averaged SAXS spectrum yielded the mean droplet radius r, 5<r/nm<31, the width of the aerosol size distribution sigma, 2<sigma/nm<6, and the particle number density N, 7x10(10)<N/cm(-3)<2.2x10(12). The nucleation rates for the n-alkanes J(max), 4x10(15)<J(max)/cm(-3) s(-1)<2x10(18), vary by almost three orders of magnitude as the temperature T(Jmax) decreases from approximately 200 K to as low as 150 K. At the lowest temperatures, the supersaturations S(Jmax) are on the order of 10(5). In spite of these extreme operating conditions, we find good agreement between the current experimental results and those available in the literature using Hale's scaling formalism [Phys. Rev. A 33, 4156 (1986); Metall. Trans. A 23, 1863 (1992)] and the scaling parameters reported by Rusyniak and El-Shall [J. Phys. Chem. B 105, 11873 (2001)]. Comparing the experimental nucleation rates with the predictions of classical nucleation theory, we find that our experimental nucleation rates are 4.5-8 orders of magnitude higher than the predictions.
在超声速拉瓦尔喷嘴中,通过结合压力轨迹测量和小角 X 射线散射(SAXS)实验的信息,确定了正构烷烃(C(i)H(2i+2);i=7-10)的均相成核速率。在压力轨迹测量过程中,确定了相应于峰值成核速率 J(max)的可冷凝蒸气压力 p(J max)、温度 T(J max)、特征时间 Deltat(J max)和过饱和度 S(J max)。这些测量结果也为随后的 SAXS 实验提供了依据。拟合径向平均 SAXS 谱得出了平均液滴半径 r,5<r/nm<31,气溶胶粒径分布的宽度 sigma,2<sigma/nm<6,以及颗粒数密度 N,7x10(10)<N/cm(-3)<2.2x10(12)。正构烷烃的成核速率 J(max),4x10(15)<J(max)/cm(-3) s(-1)<2x10(18),随着温度 T(Jmax)从约 200 K 降低到低至 150 K,变化了近三个数量级。在最低温度下,过饱和度 S(Jmax)约为 10(5)。尽管这些极端操作条件,我们发现当前实验结果与使用 Hale 标度形式主义[Phys. Rev. A 33, 4156 (1986); Metall. Trans. A 23, 1863 (1992)]和 Rusyniak 和 El-Shall[J. Phys. Chem. B 105, 11873 (2001)]报告的标度参数的文献中可用的结果之间存在良好的一致性。将实验成核速率与经典成核理论的预测进行比较,我们发现我们的实验成核速率比预测值高 4.5-8 个数量级。