Journal ArticleDOI
Kinetic and theoretical studies of the reactions acetylperoxy + nitrogen dioxide + M .dblarw. acetyl peroxynitrate + M between 248 and 393 K and between 30 and 760 torr
Isabelle Bridier,Françoise Caralp,Helene Loirat,Robert Lesclaux,Bernard Veyret,Karl H. Becker,A. Reimer,F. Zabel +7 more
TLDR
In this paper, the thermal decomposition and formation reactions of PAN were studied as a function of temperature and pressure, and the equilibrium constant was calculated to be 0.9{plus minus}0.Abstract:
The kinetics of the thermal decomposition and formation reactions of acetyl peroxynitrate (PAN) CH{sub 3}C(O)O{sub 2} + NO{sub 2} + M {leftrightarrow} CH{sub 3}C(O)O{sub 2}NO{sub 2} + M (1, {minus}1) was studied as a function of temperature and pressure by two groups. In one set of experiments, the decomposition of the peroxynitrate formed in the photolysis of CH{sub 3}CHO/Cl{sub 2}/O{sub 2}/N{sub 2}/NO{sub 2} mixtures was followed by in situ FTIR spectrometry. In the second set of experiments, the decay of the acetylperoxy radical formed in the flash photolysis of Cl{sub 2}/CH{sub 3}CHO/NO{sub 2}/air mixtures was monitored by UV absorption. From the two independent kinetic determinations of k{sub 1} and k{sup {minus}1}, the equilibrium constant K{sub 1}(T) was calculated to be 0.9 {times} 10{sup {minus}28} exp((14,000 {plus minus} 200)/T) cm{sup 3} molecule{sup {minus}1}. Quantum chemical and RRKM calculations were performed to obtain accurate and predictive representations of the data. In Troe's notation, the RRKM curves corresponding to the experimental results are represented by the following expressions for the limiting low- and high-pressure rate constants, with F{sub c} = 0.30: k{sub 0}({minus}1) = 4.9 {times} 10{sup {minus}3} exp({minus}(12,100 {plus minus} 500)/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}; k{sub {infinity}}({minus}1) = 4.0 {times}more » 10{sup 16} exp({minus}(13,600 {plus minus} 350)/T) s{sup {minus}1}; k{sub 0}(1) = 2.7 {times} 10{sup {minus}28}(T/298){sup {minus}7.1{plus minus}1.7} cm{sup 6} molecule{sup {minus}2} s{sup {minus}1}; k{sub {infinity}}(1) = (12.1 {plus minus} 0.5) {times} 10{sup {minus}12}(T/298){sup {minus}0.9{plus minus}0.15} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The thermochemistry of reactions 1 and {minus}1 and the atmospheric implications of the thermal stability of PAN are briefly discussed.« lessread more
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Journal ArticleDOI
Carboxylic acids in the troposphere, occurrence, sources, and sinks: A review
A. Chebbi,P. Carlier +1 more
TL;DR: In this paper, a synthesis of low molecular weight carboxylic acids in tropospheric aqueous and gaseous phases and in aerosol particles for different environments is presented.
Journal ArticleDOI
Organic peroxy radicals: Kinetics, spectroscopy and tropospheric chemistry
P.D Lightfoot,Richard A. Cox,John Crowley,M Destriau,G. D. Hayman,Michael E. Jenkin,Geert K. Moortgat,F Zabel +7 more
TL;DR: A review of the state of the art in peroxy radical detection can be found in this article, where a number of experimental techniques have been used for the generation and detection of peroxy radicals and products of their reactions.
Journal ArticleDOI
Atmospheric chemistry of small organic peroxy radicals
Geoffrey S. Tyndall,Richard A. Cox,Claire Granier,Robert Lesclaux,Geert K. Moortgat,Michael J. Pilling,A. R. Ravishankara,Timothy J. Wallington +7 more
TL;DR: In this paper, the atmospheric chemistry of the four most abundant organic peroxy radicals (CH3O2, C2H5O2 and CH3C(O)O2) was evaluated.
Journal ArticleDOI
Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution
Emily V. Fischer,Daniel J. Jacob,Robert M. Yantosca,Melissa P. Sulprizio,Dylan B. Millet,Jingqiu Mao,Fabien Paulot,Hanwant B. Singh,Anke-Elisabeth Roiger,L. Ries,Robert W. Talbot,Katja Dzepina,S. Pandey Deolal +12 more
TL;DR: An improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) is used and it is shown that it can simulate PAN observations from aircraft campaigns worldwide and is very sensitive to plume chemistry and plume rise.
Journal ArticleDOI
A thermal dissociation–chemical ionization mass spectrometry (TD‐CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide
TL;DR: In this article, a thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) technique was developed for fast measurements of a series of peroxyacyl nitrates and dinitrogen pentoxide.
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