caa a22 4500 475823591 CHVBK 20180406123825.0 cr unu---uuuuu 170329e20000301xx s 000 0 eng 10.1023/A:1006278410328 doi (NATIONALLICENCE)springer-10.1023/A:1006278410328 Neeb Peter Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, PO Box 3060, 55020, Mainz, Germany aut Structure-Reactivity Based Estimation of the Rate Constants for Hydroxyl Radical Reactions with Hydrocarbons [Elektronische Daten] [Peter Neeb] The reaction with the OH radical constitutes the singlemost important removal process for most organiccompounds found in the atmosphere. Efforts to measurethe OH radical rate constants of all troposphericconstituents remain incomplete due to the largevariety of primary emitted compounds and theirtropospheric degradation products.Based on the measured rate constants of ≈250molecules with the OH radical, a structure-activityrelationship (SAR) for OH reactions has beendeveloped. The molecules used in the dataset includemost classes of tropospheric compounds (includingalkanes, alkenes, and oxygenated hydrocarbons), withthe exception of aromatic and halogen-containingcompounds. Using a new parameterization of themolecular structure, the overall agreement betweenmeasured values and those estimated using the SARdeveloped in this study is usually very good, with10% of the molecules showing deviations larger than50%. In particular, the estimated rate constants ofethers and ketones are in better agreement withexperimental data than with previous SARs (Kwok andAtkinson, Atmos. Environ. 29, 1685-1695,1995). Rate constants of organic nitrates werenot well described by the SAR used in thisstudy. The basic assumption that the additive rateconstant for a chemical group is only influenced byneighbouring functional groups did not allow a goodparameterization for the rate constants of organicnitrates. The use of a second parameter to alter thereactivity of C-H bonds in β-position to thefunctional group resulted in markedly better agreementbetween calculated and measured rate constants, butwas not extended due to the limited set of data. This indicates that strong electron withdrawing groups(e.g., nitrate groups) might influence the reactivityof C-H bonds that are not directly adjacent. Kluwer Academic Publishers, 2000 chemical mechanism development nationallicence structure activity relationship nationallicence tropospheric oxidation nationallicence organic nitrates nationallicence ethers nationallicence Journal of Atmospheric Chemistry Kluwer Academic Publishers 35/3(2000-03-01), 295-315 0167-7764 35:3<295 2000 35 10874 https://doi.org/10.1023/A:1006278410328 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1023/A:1006278410328 text/html Onlinezugriff via DOI NATIONALLICENCE 100 1- Neeb Peter Division of Atmospheric Chemistry, Max-Planck-Institut für Chemie, PO Box 3060, 55020, Mainz, Germany aut NATIONALLICENCE 773 0- Journal of Atmospheric Chemistry Kluwer Academic Publishers 35/3(2000-03-01), 295-315 0167-7764 35:3<295 2000 35 10874 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer