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Secondary aerosol formation from atmospheric reactions of aliphatic amines

Murphy, S. M. and Sorooshian, A. and Kroll, J. H. and Ng, N. L. and Chhabra, P. and Tong, C. and Surratt, J. D. and Knipping, E. and Flagan, R. C. and Seinfeld, J. H. (2007) Secondary aerosol formation from atmospheric reactions of aliphatic amines. Atmospheric Chemistry and Physics Discussions, 7 (1). pp. 289-349. ISSN 1680-7367.

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Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

Item Type:Article
Related URLs:
URLURL TypeDescription
Murphy, S. M.0000-0002-6415-2607
Sorooshian, A.0000-0002-2243-2264
Ng, N. L.0000-0001-8460-4765
Surratt, J. D.0000-0002-6833-1450
Flagan, R. C.0000-0001-5690-770X
Seinfeld, J. H.0000-0003-1344-4068
Additional Information:© 2007 Author(s). This work is licensed under a Creative Commons License. Published by Copernicus GmbH on behalf of the European Geosciences Union. Received: 17 December 2006 – Accepted: 17 December 2006 – Published: 10 January 2007. This work was supported by the Electric Power Research Institute.
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Electric Power Research Institute (EPRI)UNSPECIFIED
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ID Code:7326
Deposited By: Archive Administrator
Deposited On:31 Jan 2007
Last Modified:02 Oct 2019 23:41

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