Infrared spectroscopy and phase behavior of n-butane aerosols and thin films at cryogenic temperatures.

Autor: Lang EK; Department of Chemistry, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia, V6T 1Z1, Canada., Knox KJ, Momose T, Signorell R
Jazyk: angličtina
Zdroj: The journal of physical chemistry. A [J Phys Chem A] 2013 Nov 21; Vol. 117 (46), pp. 11745-59. Date of Electronic Publication: 2013 May 29.
DOI: 10.1021/jp402483m
Abstrakt: Spectroscopic studies of two phase transitions of solid n-butane aerosol droplets performed under conditions representative of those in the lower atmosphere of Titan are presented. Pure n-butane aerosols and mixed ensembles of n-butane/acetylene, n-butane/carbon dioxide and n-butane/water aerosols were generated in a bath gas cooling cell at 78 K and their phase transition dynamics monitored using infrared extinction spectroscopy. For pure n-butane aerosols the volume and surface nucleation constants were found to range from JV = 10(12) -10(14) cm(-3) s(-1) and JS = 10(13) -10(15) cm(-2) s(-1), respectively, for the first observed transition, and JV = 10(9) -10(11) cm(-3) s(-1) and JS = 10(11) -10(13) cm(-2) s(-1) for the second observed transition. The phases of the n-butane aerosols were determined by comparing their spectroscopic signatures with spectra collected from thin films of liquid and solid n-butane. The first observed transition was from an amorphous-annealed phase into the metastable crystalline phase II of n-butane. The second transition was from the metastable crystalline phase II into the crystalline phase III. The effect of the presence of a second aerosol substance (acetylene, carbon dioxide or water) was examined; while this accelerated the first phase transition, it did not directly influence the rate of the second phase transition. The kinetic studies might be important for the understanding of cloud formation on Titan, while the spectral data provided, which include the first reported spectrum of liquid n-butane close to the melting point, are expected to be of use for remote sensing applications.
Databáze: MEDLINE