World Library  


Add to Book Shelf
Flag as Inappropriate
Email this Book

H2O and Hcl Trace Gas Kinetics on Crystalline Hcl Hydrates and Amorphous Hcl / H2O in the Range 170 to 205 K: the Hcl / H2O Phase Diagram Revisited : Volume 14, Issue 10 (27/05/2014)

By Iannarelli, R.

Click here to view

Book Id: WPLBN0003993862
Format Type: PDF Article :
File Size: Pages 22
Reproduction Date: 2015

Title: H2O and Hcl Trace Gas Kinetics on Crystalline Hcl Hydrates and Amorphous Hcl / H2O in the Range 170 to 205 K: the Hcl / H2O Phase Diagram Revisited : Volume 14, Issue 10 (27/05/2014)  
Author: Iannarelli, R.
Volume: Vol. 14, Issue 10
Language: English
Subject: Science, Atmospheric, Chemistry
Collections: Periodicals: Journal and Magazine Collection, Copernicus GmbH
Historic
Publication Date:
2014
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications

Citation

APA MLA Chicago

Iannarelli, R., & Rossi, M. J. (2014). H2O and Hcl Trace Gas Kinetics on Crystalline Hcl Hydrates and Amorphous Hcl / H2O in the Range 170 to 205 K: the Hcl / H2O Phase Diagram Revisited : Volume 14, Issue 10 (27/05/2014). Retrieved from http://comicbooklibrary.org/


Description
Description: Laboratory of Atmospheric Chemistry (LAC), Paul Scherrer Institute (PSI), PSI Villigen, 5232, Switzerland. In this laboratory study, H2O ice films of 1 to 2 μm thickness have been used as surrogates for ice particles at atmospherically relevant conditions in a stirred flow reactor (SFR) to measure the kinetics of evaporation and condensation of HCl and H2O on crystalline and amorphous HCl hydrates. A multidiagnostic approach has been employed using Fourier transform infrared spectroscopy (FTIR) absorption in transmission to monitor the condensed phase and residual gas mass spectrometry (MS) for the gas phase. An average stoichiometric ratio of H2O : HCl = 5.8 ± 0.7 has been measured for HCl · 6H2O, and a mass balance ratio between HCl adsorbed onto ice and the quantity of HCl measured using FTIR absorption (NinNescNads) / NFTIR = 1.18 ± 0.12 has been obtained. The rate of evaporation Rev(HCl) for crystalline HCl hexahydrate (HCl · 6H2O) films and amorphous HCl / H2O mixtures has been found to be lower by a factor of 10 to 250 compared to Rev(H2O) in the overlapping temperature range 175 to 190 K. Variations of the accommodation coefficient α(HCl) on pure HCl · 6H2O up to a factor of 10 at nominally identical conditions have been observed. The kinetics (α, Rev) are thermochemically consistent with the corresponding equilibrium vapour pressure. In addition, we propose an extension of the HCl / H2O phase diagram of crystalline HCl · 6H2O based on the analysis of deconvoluted FTIR spectra of samples outside its known existence area. A brief evaluation of the atmospheric importance of both condensed phases – amorphous HCl / H2O and crystalline HCl · 6H2O – is performed in favour of the amorphous phase.

Summary
H2O and HCl trace gas kinetics on crystalline HCl hydrates and amorphous HCl / H2O in the range 170 to 205 K: the HCl / H2O phase diagram revisited

Excerpt
Abbatt J. P. D., Beyer, K. D., Fucaloro, A. F., McMahon, J. R., Wooldridge, P. J., Zhang, R., and Molina, M. J.: Interaction of HCl Vapor with Water-ice: Implications for the Stratosphere, J. Geophys. Res. 97, 15819–15826, 1992.; Ammann, M., Cox, R. A., Crowley, J. N., Jenkin, M. E., Mellouki, A., Rossi, M. J., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates, Atmos. Chem. Phys., 13, 8045–8228, doi:10.5194/acp-13-8045-2013, 2013.; Broker, W. and Mossman, A. L.: Matheson Gas Data Book, 6th ed., Matheson Gas Products Inc., Lyndhurst, NJ, 1980.; Banham, S. F., Sodeau, J. R., Horn, A. B., McCoustra, M. R. S., and Chesters, M. A.: Adsorption and ionization of HCl on an ice surface, J. Vac. Sci. Technol. A, 14, 1620–1626, 1996.; Carslaw, K. S., Peter, Th., and Clegg, S. L.: Modeling the composition of liquid stratospheric aerosols, Rev. Geophys. 35, 125–154, 1997.; Chiesa, S. and Rossi, M. J.: The metastable HCl · 6H2O phase – IR spectroscopy, phase transitions and kinetic/thermodynamic properties in the range 170–205 K, Atmos. Chem. Phys., 13, 11905–11923, doi:10.5194/acp-13-11905-2013, 2013.; Chu, L. T., Leu, M.-T., and Keyser, L. F.: Uptake of HCl in water ice and nitric acid ice films, J. Phys. Chem. 97, 7779–7785, 1993.; Crowley, J. N., Ammann, M., Cox, R. A., Hynes, R. G., Jenkin, M. E., Mellouki, A., Rossi, M. J., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates, Atmos. Chem. Phys. 10, 9059-9223, doi:10.5194/acp-10-9059-2010, 2010.; Deitz, V. R. and Turner, N. H.: Introduction of water vapor into vacuum systems and the adsorption by the walls, J. Vac. Sci. Technol., 7, 577–580, 1970.; Delval, C., Flückiger, B., and Rossi, M. J.: The rate of water vapor evaporation from ice substrates in the presence of HCl and HBr: implications for the lifetime of atmospheric ice particles, Atmos. Chem. Phys. 3, 1131–1145, doi:10.5194/acp-3-1131-2003, 2003.; Delval, C: Study of the kinetics of Condensation and Evaporation of Water Vapor over Atmospherically relevant Pure and Doped Ice Films: A Multidiagnostic Approach, Thèse EPFL (Ecole Polytechnique Fédérale de Lausanne) no. 3159, 2005.; Kuhs, W. F., Sippel, Ch., Falenty, A., and Hansen, Th. C.: Extent and relevance of stacking disorder in ice Ic, PNAS 109, 21259–21264, 2012.; Delzeit, L., Rowland, B., and Devlin, J. P.: Infrared spectra of HCl complexed/ionized in amorphous hydrates and at ice surfaces in the 15–90 K range, J. Phys. Chem. 97, 10312–10318, 1993.; Dushman, S. and Lafferty, J. M.: Scientific Foundations of Vacuum Technique, 2nd ed., John Wiley & Sons, New York, 1, p. 58, 1962.; Flückiger, B., Thielmann, A., Gutzwiller, L., and Rossi, M. J.: Real time kinetics and thermochemistry of the uptake of HCl, HBr and HI on water in the temperature range 190 to 210 K, Ber. Bunsenges. Phys. Chem. 102, 915–928, 1998.; Flückiger, B. and Rossi, M. J.: Common precursor mechanism for the heterogeneous reaction of D2O, HCl, HBr and HOBr with Water Ice in the range 170–230 K: Mass accommodation coefficients on ice, J. Phys. Chem. A 107, 4103–4115, 2003.; Friedl, R. R., Goble, J. H., and Sander, S. P.: A kinetic study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction, Geophys. Res. Lett. 13, 1351–1354, 1986.; Graham, J. D. and Roberts, J. T.: Formation of HCl · 6H2O from ice and HCl under ultrahigh vacuum, Chemometrics and intelligent laboratory systems 37, 139–148, 199

 
 



Copyright © World Library Foundation. All rights reserved. eBooks from Comic eBook Library are sponsored by the World Library Foundation,
a 501c(4) Member's Support Non-Profit Organization, and is NOT affiliated with any governmental agency or department.