We thank Howard Johnsen and the staff at the Chemical Dynamics Beamline for technical support of the MPIMS experiments. Sandia authors and the development and maintenance of the MPIMS experiment, were funded by the Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences (BES), United States Department of Energy (DOE). Development of the time-resolved broadband cavity-enhanced absorption spectrometer was supported by the Laboratory Directed Research and Development program at Sandia National Laboratories. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration, under contract DE-AC04-94AL85000. The Advanced Light Source is supported by the Director, Office of Science, BES/DOE, under contract DE-AC02-05CH11231 between Lawrence Berkeley National Laboratory and the DOE. C.J.P. and D.E.S. thank NERC under whose auspices some aspects of this work were carried out.
Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications†
Article first published online: 25 MAR 2014
© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited
Volume 126, Issue 18, pages 4635–4638, April 25, 2014
How to Cite
Welz, O., Eskola, A. J., Sheps, L., Rotavera, B., Savee, J. D., Scheer, A. M., Osborn, D. L., Lowe, D., Murray Booth, A., Xiao, P., Anwar H. Khan, M., Percival, C. J., Shallcross, D. E. and Taatjes, C. A. (2014), Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications. Angew. Chem., 126: 4635–4638. doi: 10.1002/ange.201400964
- Issue published online: 25 APR 2014
- Article first published online: 25 MAR 2014
- Manuscript Received: 28 JAN 2014
- Funded Access
- Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences (BES), United States Department of Energy (DOE)
- Sandia Corporation. Grant Number: DE-AC04-94AL85000
- Director, Office of Science, BES/DOE. Grant Number: DE-AC02-05CH11231
- Organische Säuren;
Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.