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The low-temperature oxidation of a stoichiometric 2-methylhexane/O2/Ar mixture was examined in a jet-stirred reactor coupled with synchrotron vacuum UV photoionization molecular-beam MS. Low-temperature oxidation intermediates with two to five oxygen atoms were observed. The detection of C7H14O5 and C7H14O4 species implies that a third O2 addition process occurred in 2-methylhexane low-temperature oxidation. A detailed kinetic model was developed to describes the third O2 addition and subsequent reactions leading to C7H14O5 (keto-dihydroperoxide and dihydroperoxy cyclic ether) and C7H14O4 (diketo-hydroperoxide and keto-hydroperoxy cyclic ether) species. The kinetics of the third O2 addition reactions revealed that the addition reactions promoted 2-methylhexane auto-ignition at low temperatures.

This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the low-temperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [ J. Phys. Chem. A 2015 , 119 , 7361 - 7374 ] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450-1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH2OCH2O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this keto-hydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H2O2, HCOOH, CH3OCHO, and CH3OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C8H14O4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C8H16O5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C8H16O5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O2 addition, intramolecular isomerization, and OH release; C8H14O4 species are proposed to result from subsequent reactions of C8H16O5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. The results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.

This paper estimates the effect of the 2005 vending machine ban in French secondary schools on nutrient intakes and on the frequency of morning snacking at school. Using data before and after the ban, and exploiting the discontinuity associated with the age-dependent exposure to the ban, we specify a difference-in-differences regression discontinuity design. Since the relationship between age-at-interview and school level is not precise, we introduce fuzziness in the model. We find that the ban has generated a 10-gram reduction in sugar intakes from morning snacks at school, and a significant reduction in the frequency of these morning snacks. However, we find no evidence that the intervention affects total daily intakes, and our results are suggestive of compensation effects.