Formaldehyde, acetaldehyde, ozone and nitrogen dioxide in ambient air are simultaneously collected on silica gel cartridges coated with 1-methyl-1-(2,4-dinitrophenyl)hydrazine (MDNPH), where the two aldehydes are derivatized to their respective hydrazones, while the two oxidants are converted into N-methyl-2,4-dinitroaniline (MDNA). The three products are then separated and quantified by HPLC with UV detection at 360 nm. The stoichiometric factors of the MDNPH reactions with O3 and NO2 in laboratory tests correspond to 2.0 +/- 0.1 moles of MDNA per mole of O(x) (O3 + NO2). The limits of detection (LOD) are 0.7 ppbv HCHO, 0.8 ppbv CH3CHO and 1.6 ppbv O(x) for 30 L (1 h) air sampled. The sampling performance is insensitive to relative humidities encountered in real atmospheres. When compared with Sep-Pak DNPH silica cartridges as well as with ozone photometric and nitrogen dioxide chemiluminescent analyzers, the proposed chromatographic method demonstrates a very good accuracy (12% for HCHO, 14% for CH3CHO and 7% for O(x), on the average) under field sampling conditions at concentrations lower than 3 and 1 ppbv, for HCHO and CH3CHO, respectively and ranging from 28 to 62 ppbv for O(x).
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J Phys Chem A
September 2024
Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States.
Criegee intermediates, formed by alkene ozonolysis in the troposphere, can react with volatile organic compounds (VOCs). The temperature-dependent kinetics of the reactions between the Criegee intermediate CHOO and three aliphatic aldehydes, RCHO where R = H, CH, and CH (formaldehyde, acetaldehyde, and propionaldehyde, respectively), have been studied using a laser flash-photolysis transient absorption spectroscopy technique. The experimental measurements are supported by calculations at various composite levels of theory that characterize stationary points on the reaction potential and free energy surfaces.
View Article and Find Full Text PDFEnviron Pollut
March 2024
Department of Environmental Science and Engineering, Beijing University of Technology, Beijing, 100124, China; Key Laboratory of Beijing on Regional Air Pollution Control, Beijing, 100124, China.
Large petrochemical complex (PC) widely exists in both developing and developed countries, and is expected to have a special photochemical pollution in local scale due to huge VOCs emissions. Here, a typical large-scale PC in North China was selected as the study case, to explore the character, formation and influence of local photochemical pollution regarding PCs based on an improved 0-D chemical model. In the study PC, VOCs-rich character was apparent with THCs level of 90.
View Article and Find Full Text PDFAtmospheric carbonyl compounds play significant roles in the cycling of radicals and have exhibited surprisingly high levels in winter that were well correlated to particulate matter, for which the reason have not been clearly elucidated. Here we measured carbonyl compounds and other trace gasses together with PM over urban Jinan in North China Plain during the winter. Markedly higher carbonyl concentrations (average: 14.
View Article and Find Full Text PDFJ Phys Chem A
July 2023
Department of Chemistry, Indian Institute of Science Education and Research Pune, Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411008, India.
n → π* interaction is analogous to the hydrogen bond in terms of the delocalization of the electron density between the two orbitals. Studies on the intermolecular complexes stabilized by the n → π* interaction are scarce in the literature. Herein, we have studied intermolecular N···C═O n → π* interactions in the complexes of -substituted pyridines (-R-Py) with formaldehyde (HCHO), formyl chloride (HCOCl), and acetaldehyde (CHCHO) using quantum chemistry calculations.
View Article and Find Full Text PDFJ Am Chem Soc
November 2022
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota55455-0431, United States.
Kinetics provides the fundamental parameters for elucidating sources and sinks of key atmospheric species and for atmospheric modeling more generally. Obtaining quantitative kinetics in the laboratory for the full range of atmospheric temperatures and pressures is quite difficult. Here, we use computational chemistry to obtain quantitative rate constants for the reactions of HO with HCHO, CHCHO, and CFCHO.
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