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Isothermal Nucleation Rates of n-Propanol, n-Butanol, and n-Pentanol in Supersonic Nozzles: Critical Cluster Sizes and the Role of Coagulation B

Author:
Mullick, K., Bhabhe, A., Manka, A., Wölk, J., Strey, R., Wyslouzil, B. E.
Source:
The Journal of physical chemistry 2015 v.119 no.29 pp. 9009-9019
ISSN:
1520-5207
Subject:
1-propanol, X-radiation, butanol, byproducts, coagulation, droplets, nozzles, pentanols, physical chemistry
Abstract:
We follow the nucleation of n-alcohols, n-propanol through n-pentanol, in two sets of supersonic nozzles having differing linear expansion rates. Combining the data from static pressure trace measurements with small-angle X-ray scattering we report the experimental nucleation rates and critical cluster sizes. For n-propanol, position resolved measurements clearly confirm that coagulation of the 2–10 nm size (radius) droplets occurs on the time scale of the experiment but that the effect of coagulation on the results is minimal. Under the conditions of the current experiments, our results suggest that alcohols have critical clusters that range from the dimer (n-pentanol) to the hexamer (n-propanol). We then compare the experimental results with classical nucleation theory (CNT), the Girshick-Chiu variant of CNT (GC), and the mean field kinetic nucleation theory (MKNT). Both CNT and MKNT underestimate the nucleation rates by up to 5 and 7 orders of magnitude, respectively, while GC theory predicts rates within 2 orders of magnitude. Correspondingly, the critical cluster size for all alcohols is overpredicted by factors of 2–9 with agreement improving with increasing chain length. An interesting byproduct of our experiments is that we find that the coagulation rate is enhanced by a factor of 3 over the value one would calculate for the free molecule regime.
Agid:
5606514