ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-3495-2010 Amine exchange into ammonium bisulfate and ammonium nitrate nuclei Bzdek B. R. 1 Ridge D. P. 1 Johnston M. V. 1 Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, USA 16 04 2010 10 8 3495 3503 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/10/3495/2010/acp-10-3495-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/3495/2010/acp-10-3495-2010.pdf

The exchange kinetics and thermodynamics of amines for ammonia in small (1–2 nm diameter) ammonium bisulfate and ammonium nitrate clusters were investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Ammonium salt clusters were reacted with amine gas at constant pressure to determine the kinetics of exchange. The reverse reactions, where aminium salt clusters reacted with ammonia gas, were also studied, and no substitution of ammonia for amine was observed. Gibbs free energy changes for these substitutions were determined to be highly exothermic, −7 kJ/mol or more negative in all cases. Uptake coefficients (reaction probabilities) were found to be near unity, implying that complete exchange of ammonia in small clusters by amine would be expected to occur within several seconds to minutes in the ambient atmosphere. These results suggest that if salt clusters are a component of the sub-3 nm cluster pool, they are likely to be aminium salts rather than ammonium salts, even if they were initially formed as ammonium salts.

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