The oxidation of decane in the liquid and gaseous phases

Cullis, C. F.; Hirschler, Marcelo M.; Rogers, R. L.

doi:10.1098/rspa.1981.0067

Cited by 11 publications

(3 citation statements)

References 22 publications

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“…Similarly, all ketone isomers of C ini are formed and also all 2-ketones (from C 3 to C ini ). According to our results, the 2-ketones with C ini–1 are disfavored, in line with literature. , C ini ketones are qualitatively more produced than lighter ones. All aldehydes from C 1 to C ini are formed during n -alkanes autoxidation as well.…”

Section: Resultssupporting

confidence: 92%

Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact onn-Alkanes Autoxidation

Chatelain¹,

Nicolle²,

Amara³

et al. 2016

Energy Fuels

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The control of deposit precursors formation resulting from the oxidative degradation of alternative fuels relies strongly on the understanding of the underlying chemical pathways. Although C8–C16 n-alkanes are major constituents of commercial fuels and well-documented solvents, their respective reactivities and selectivities in autoxidation are poorly understood. This study experimentally investigates the influence of chain length, temperature (393–433 K), purity, and blending on n-alkanes autoxidation kinetics under concentrated oxygen conditions, using both Induction Period (IP) and speciation analysis. It also numerically constructs new detailed liquid-phase chemical mechanisms for n-C8–C14 obtained with an automated mechanism generator. Macroscopic reactivity descriptors such as IP, combined to microscopic ones, obtained from GC-MS analyses, are herein used to emphasize similarities and discrepancies in n-alkanes autoxidation processes. Experimental results highlight a nonlinear IP evolution with n-alkanes chain length, a linear IP variation for two component paraffinic blends, and similarities among oxidation product families. Experimental data from the present study and from the literature are used to evaluate n-C8–C14 mechanisms on IP and on monohydroperoxides (ROOH) concentrations. Under pure O2 conditions, mechanisms generally predict IPs within a factor of 3 for intermediate and high temperature and even lower when air is used instead of pure oxygen. In addition, the chain length impact is also well reproduced, with a reactivity increase from C8 to C12 and a plateau for higher chain length. Rate of Consumption (RoC) analyses of n-C8 and n-C12 mechanisms evidenced the main role of peroxy radicals in autoxidation through fuel consumption, and ROOH and polyhydroperoxides (R(OOH)2) formation.

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Section: Resultssupporting

confidence: 92%

Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact onn-Alkanes Autoxidation

Chatelain¹,

Nicolle²,

Amara³

et al. 2016

Energy Fuels

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“…Table presents products identified by chemical family for all C 8 alkanes studied in the present work. These identifications are also confirmed with previous work. ,,−, Except for the TMP, similar oxidation products were identified over the temperature range 373–433 K. TMP analyses did not reveal a significant amount of oxygenated species for the low temperature range (≤393 K), while both C 8 ketones and alcohols where observed at higher temperature (≥403 K). This tends to demonstrate two oxidation regimes of TMP respectively below 400 K and above 400 K in the absence of possible experimental bias for long IP measurements.…”

Section: Resultssupporting

confidence: 90%

Structure–Reactivity Relationships in Fuel Stability: Experimental and Kinetic Modeling Study of Isoparaffin Autoxidation

et al. 2018

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Liquid phase stability is a major concern in the transportation and the energy field where fuels, lubricants and additives have to be stable from their production site to their application (engine, combustors). Although alkanes are major constituents of commercial fuels and well-documented solvents, their respective reactivities and selectivities in autoxidation are poorly understood. This experimental and modeling study aims at (i) enhancing the current knowledge on alkane autoxidation and (ii) reviewing and correcting the previously established structure reactivity relationships in alkane autoxidation. Experimentally, this study investigates the influence of branching [0-3] and temperature [373-433 K] on the autoxidation of alkanes using four octane isomers: n-octane (C8), 2-methylheptane (MH), 2,5-dimethylhexane (DMH) and the 2,2,4-trimethylpentane(TMP). Induction Period (IP) and qualitative species identification are used to characterize the autoxidation processes of alkanes. The present study also presents new detailed liquid-phase chemical mechanisms obtained with an automated reaction mechanism generator. Experimental results highlight a non-linear effect of the paraffins branching on IP according to compound structure and similar oxidation products for both normal and branched paraffins. The four iso-octanes mechanisms reproduce fairly well the temperature and the branching effects on IP within a factor of 4 for high temperature range (T>403 K). From rate-of-reaction and sensibility analyses, similarities in alkane autoxidation have been evidenced with notably the key role of peroxy radicals in both normal and branched alkane autoxidation. The origin of the structure-reactivity relations was confirmed from a kinetic point of view with the main role of the hydrogen type on the molecule. Finally, based on experimental results available in literature, an empirical relation involving simple descriptors (number of carbons, type of carbons, temperature) is proposed to estimate alkane stability.

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“…There is a possibility that, instead of increased production from lipid peroxidation, oxidative stress resulted in autoxidation of these alkanes. This remains a relatively improbable reaction at body temperature, however, and would require free radical chain initiators or other catalysts [ 29 , 30 ]. Interestingly, studies with healthy volunteers have consistently found an association of oxygen exposure with an increase in various alkanes, methyl alkanes and aldehydes, although they remain heterogeneous in terms of specific VOCs found [ 8 , 11 , 12 ].…”

Section: Discussionmentioning

confidence: 99%

HS-GC–MS analysis of volatile organic compounds after hyperoxia-induced oxidative stress: a validation study

Lilien,

Fenn,

Brinkman

et al. 2024

ICMx

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Background Exhaled volatile organic compounds (VOCs), particularly hydrocarbons from oxidative stress-induced lipid peroxidation, are associated with hyperoxia exposure. However, important heterogeneity amongst identified VOCs and concerns about their precise pathophysiological origins warrant translational studies assessing their validity as a marker of hyperoxia-induced oxidative stress. Therefore, this study sought to examine changes in VOCs previously associated with the oxidative stress response in hyperoxia-exposed lung epithelial cells. Methods A549 alveolar epithelial cells were exposed to hyperoxia for 24 h, or to room air as normoxia controls, or hydrogen peroxide as oxidative-stress positive controls. VOCs were sampled from the headspace, analysed by gas chromatography coupled with mass spectrometry and compared by targeted and untargeted analyses. A secondary analysis of breath samples from a large cohort of critically ill adult patients assessed the association of identified VOCs with clinical oxygen exposure. Results Following cellular hyperoxia exposure, none of the targeted VOCs, previously proposed as breath markers of oxidative stress, were increased, and decane was significantly decreased. Untargeted analysis did not reveal novel identifiable hyperoxia-associated VOCs. Within the clinical cohort, three previously proposed breath markers of oxidative stress, hexane, octane, and decane had no real diagnostic value in discriminating patients exposed to hyperoxia. Conclusions Hyperoxia exposure of alveolar epithelial cells did not result in an increase in identifiable VOCs, whilst VOCs previously linked to oxidative stress were not associated with oxygen exposure in a cohort of critically ill patients. These findings suggest that the pathophysiological origin of previously proposed breath markers of oxidative stress is more complex than just oxidative stress from hyperoxia at the lung epithelial cellular level.

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The oxidation of decane in the liquid and gaseous phases

Cited by 11 publications

References 22 publications

Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact onn-Alkanes Autoxidation

Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact onn-Alkanes Autoxidation

Structure–Reactivity Relationships in Fuel Stability: Experimental and Kinetic Modeling Study of Isoparaffin Autoxidation

HS-GC–MS analysis of volatile organic compounds after hyperoxia-induced oxidative stress: a validation study

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