Kinetics and Thermodynamics of Limonene Ozonolysis

Abstract

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, ΔG(‡), indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 × 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 × 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.

Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

“…The oxidation of VOCs by the primary atmospheric oxidants, O 3 and q OH, C. Faxon et al: Characterization of organic nitrate constituents of secondary organic aerosol et al, 2016; Ng et al, 2017). Significant concentrations of these nitrates have been detected in the gas and condensed phases in both field and laboratory studies (Ayres et al, 2015;Beaver et al, 2012;Boyd et al, 2017;Bruns et al, 2010;Day et al, 2010;Fry et al, 2014;Lee et al, 2016;Nah et al, 2016;Paulot et al, 2009;Rindelaub et al, 2014Rindelaub et al, , 2015Rollins et al, 2012Rollins et al, , 2013Xu et al, 2016;Kiendler-Scharr et al, 2016). Organic nitrates (RONO 2 ) and organic peroxy nitrates (RO 2 NO 2 ), such as peroxy acetyl nitrate (PAN), may also form in the atmosphere (Roberts, 1990;Singh and Hanst, 1981;Temple and Taylor, 1983).…”

“…Several studies have focused on the ozonolysis of limonene and SOA formation from limonene (Leungsakul et al, 2005;Jonsson et al, 2006Jonsson et al, , 2008aZhang et al, 2006;Baptista et al, 2011;Sun et al, 2011;Pathak et al, 2012;Jiang et al, 2013;Youssefi and Waring, 2014;). NO q 3 oxidation of limonene and the resulting organic nitrates that may contribute to SOA formation have, however, rarely been investigated ( Hallquist et al, 1999;Spittler et al, 2006;Fry et al, 2011Fry et al, , 2014Boyd et al, 2017).…”

“…Moreover, although mechanistic models and molecular identities of these products have been proposed, direct measurement and identification thereof have yet to be reported. Further elucidation of the mechanisms governing the reactions of limonene and NO q 3 and the resultant products generated is warranted, since organic nitrates from BVOCs (including limonene) have been consistently observed in field studies (Perring et al, 2009;Ayres et al, 2015;Beaver et al, 2012;Lee et al, 2016Lee et al, , 2014b).…”

Schnelle Autoxidation bildet hochoxidierte RO2‐Radikale in der Atmosphäre

“…Die strukturell ähnlichen Substanzen Limonen und a-Pinen ergaben identische Signale mit derselben Elementzusammensetzung. Bei Limonen findet der Ozonangriff vorherrschend an der endocyclischen Doppelbindung statt, [7,8] bei a-Pinen nur dort. Geschlossenschalige C 10 -und C 20 -Produkte (genannt Monomere bzw.…”

Expanding the regioselective enzymatic repertoire: oxidative mono-cleavage of dialkenes catalyzed by Trametes hirsuta

“…One remarkable exception was described by Neumann and co-workers using a ruthenium catalyst in the presence of hydrogen peroxide, showing 45 that a terminal alkene group was regioselectively oxidized in the presence of other more sterically hindered internal (or cyclic) C=C double bonds in different aliphatic polyalkenes, displaying high to excellent selectivities. 12 The lack of more regioselective methods could be due to the fact that oxidative alkene cleavage is 50 highly exothermic (e.g., 47-64 kcal mol -1 for ozonolysis), 13 therefore hampering an easy control of the regioselectivity. To the best of our knowledge, alkene cleaving biocatalysts have not yet been investigated for their ability to differentiate between two alkene groups within the same molecule.…”