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GEOPHYSICAL RESEARCH LETTERS, VOL. 32, L16805, doi:10.1029/2005GL022893, 2005

Competitive oxidation in atmospheric aerosols: The case for relative kinetics

N. M. Donahue

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA
Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


A. L. Robinson

Department of Mechanical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA
Department of Engineering and Public Policy, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


K. E. Huff Hartz

Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


A. M. Sage

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


E. A. Weitkamp

Department of Mechanical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


Abstract

We develop relative kinetics for heterogeneous oxidation of multi-component organic aerosols. Common accommodation, diffusion, and deposition terms cancel in this formulation, and rate constants may be determined for many compounds simultaneously within an aerosol with a realistic composition. Finally, cross-phase relative rate constants with a gas-phase reference compound and a condensed-phase target compound provide effective rate constants for use in atmospheric models.

Received 8 March 2005; accepted 18 July 2005; published 18 August 2005.

Index Terms: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801, 4906); 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0345 Atmospheric Composition and Structure: Pollution: urban and regional (0305, 0478, 4251); 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry.

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Citation: Donahue, N. M., A. L. Robinson, K. E. H. Hartz, A. M. Sage, and E. A. Weitkamp (2005), Competitive oxidation in atmospheric aerosols: The case for relative kinetics, Geophys. Res. Lett., 32, L16805, doi:10.1029/2005GL022893.