Estimation of relative Autoxidation Rates of Normal Paraffins, secondary alcohols, and ketones by competitive reactions

Just, G.; Pritzkow, W.; Rudolf, Matthias; Tien, Tieu Dung; Voerckel, V.

doi:10.1002/prac.19863280402

Cited by 6 publications

(5 citation statements)

References 5 publications

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“…Figure 20 confirms these statements and presents that the kinetic rate increases by 2 orders of magnitude from primary to secondary or from secondary to tertiary hydrogen atoms. This second value is in agreement with literature 28,48 . Thus, the specific reactivity of TMP compared to others iC8 may be explained by the abundance of primary hydrogen atoms.…”

Section: Quantifying Structure-reactivity Relationssupporting

confidence: 94%

“…This second value is in agreement with literature. 28,48 Thus, the specific reactivity of TMP compared to others iC 8 may be explained by the abundance of primary hydrogen atoms.…”

Section: Energy and Fuelsmentioning

confidence: 99%

“…These preliminary studies are mandatory for the establishment of universal structure-reactivity or empirical relations, like the ones commonly used to estimate fuel properties [23][24][25] or gas phase combustion 26,27 . Several works evidenced the structure-reactivity relationship for n-paraffins presenting an increase of the oxidation rate with the chain length 12,15,17,28 . However, the effect of the branching was not widely studied 17,29 and the results available do not present the same conclusions.…”

Section: Introductionmentioning

confidence: 99%

“…All these studies aim at improving the comprehension of the autoxidation of each chemical family present in fuels. These preliminary studies are mandatory for the establishment of universal structure–reactivity or empirical relations, like the ones commonly used to estimate fuel properties − or gas phase combustion. , Several works evidenced the structure–reactivity relationship for n -paraffins presenting an increase of the oxidation rate with the chain length. ,,, However, the effect of the branching was not widely studied , and the results available do not present the same conclusions. The results from Stark et al tend to indicate an increase of the oxidation rate with the branching, while Skolniak et al evidenced a stability increase based on PetroOxy measurements.…”

Section: Introductionmentioning

confidence: 99%

“…26,27 Several works evidenced the structure−reactivity relationship for n-paraffins presenting an increase of the oxidation rate with the chain length. 12,15,17,28 However, the effect of the branching was not widely studied 17,29 and the results available do not present the same conclusions. The results from Stark et al tend to indicate an increase of the oxidation rate with the branching, while Skolniak et al evidenced a stability increase based on PetroOxy measurements.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Quantifying Structure-reactivity Relationssupporting

confidence: 94%

“…This second value is in agreement with literature. 28,48 Thus, the specific reactivity of TMP compared to others iC 8 may be explained by the abundance of primary hydrogen atoms.…”

Section: Energy and Fuelsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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Determination of the main products and intermediates of the Oxidation of Medium Normal Paraffins in dependence on the conversion indirect evidence for the importance of bifunctional intermediates

et al. 1986

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The mole numbers of the starting paraffins, of the intermediate alcohols and ketones with the same chain lengths, of the lower alkan‐2‐ones, of the carboxylic acids, and of the esters were determined at different reaction times for the oxidations of n‐tridecane, n‐tetradecane, and n‐pentadecane with molecular oxygen at 140°C in the presence of 0.1% Mn‐stearate. In the stationary region of the oxidation about 1.2 moles of acids and 0.7 moles of esters are formed from 1 mole of paraffin consumed. The relative oxidation rates of alcohols and of ketones with reference to the starting paraffins were estimated from the mole numbers of the starting paraffins, the alcohols and the ketones at the maxima of the alcohols and the ketones. These values are higher than those determined by competitive oxidations, and this discrepancy is an indirect evidence of the formation of bifunctional intermediates from the starting paraffins. The relative rates of the formation of alcohols, ketones, and bifunctional products from normal paraffins were estimated.

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Determination of the difunctional primary products in the Oxidates of Medium n‐Paraffins

et al. 1987

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The proportion of difunctional and monofunctional products with the original carbon skeleton was determined in the oxidates of n‐decane, n‐tridecane, n‐pentadecane, and n‐octadecane to about 0.32. This proportion does not significantly depend on the conversion of the starting paraffin. As well as mono‐ and difunctional products with the original carbon skeleton already at very low conversions of n‐tridecane, about 45% of lower oxygen‐containing compounds, for example aldehydes, alkan‐2‐ones, carboxylic acids and γ‐lactones, are also obtained. Obviously, a part of the difunctional primary products reacts very fast with scission of the carbon chain, forming lower oxygen‐containing compounds.

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Estimation of relative Autoxidation Rates of Normal Paraffins, secondary alcohols, and ketones by competitive reactions

Cited by 6 publications

References 5 publications

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

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

Determination of the main products and intermediates of the Oxidation of Medium Normal Paraffins in dependence on the conversion indirect evidence for the importance of bifunctional intermediates

Determination of the difunctional primary products in the Oxidates of Medium n‐Paraffins

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