Uncovering the fundamental chemistry of alkyl + O2 reactions via measurements of product formation

The reactions of alkyl radicals (R) with molecular oxygen (O(2)) are critical components in chemical models of tropospheric chemistry, hydrocarbon flames, and autoignition phenomena. The fundamental kinetics of the R + O(2) reactions is governed by a rich interplay of elementary physical chemistry processes. At low temperatures and moderate pressures, the reactions form stabilized alkylperoxy radicals (RO(2)), which are key chain carriers in the atmospheric oxidation of hydrocarbons. At higher temperatures, thermal dissociation of the alkylperoxy radicals becomes more rapid and the formation of hydroperoxyl radicals (HO(2)) and the conjugate alkenes begins to dominate the reaction. Internal isomerization of the RO(2) radicals to produce hydroperoxyalkyl radicals, often denoted by QOOH, leads to the production of OH and cyclic ether products. More crucially for combustion chemistry, reactions of the ephemeral QOOH species are also thought to be the key to chain branching in autoignition chemistry. Over the past decade, the understanding of these important reactions has changed greatly. A recognition, arising from classical kinetics experiments but firmly established by recent high-level theoretical studies, that HO(2) elimination occurs directly from an alkylperoxy radical without intervening isomerization has helped resolve tenacious controversies regarding HO(2) formation in these reactions. Second, the importance of including formally direct chemical activation pathways, especially for the formation of products but also for the formation of the QOOH species, in kinetic modeling of R + O(2) chemistry has been demonstrated. In addition, it appears that the crucial rate coefficient for the isomerization of RO(2) radicals to QOOH may be significantly larger than previously thought. These reinterpretations of this class of reactions have been supported by comparison of detailed theoretical calculations to new experimental results that monitor the formation of products of hydrocarbon radical oxidation following a pulsed-photolytic initiation. In this article, these recent experiments are discussed and their contributions to improving general models of alkyl + O(2) reactions are highlighted. Finally, several prospects are discussed for extending the experimental investigations to the pivotal questions of QOOH radical chemistry.     

Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical: C6H5C•(═O)

Alkyl substituted aromatics are present in fuels and in the environment because they are major intermediates in the oxidation or combustion of gasoline, jet, and other engine fuels. The major reaction pathways for oxidation of this class of molecules is through loss of a benzyl hydrogen atom on the alkyl group via abstraction reactions. One of the major intermediates in the combustion and atmospheric oxidation of the benzyl radicals is benzaldehyde, which rapidly loses the weakly bound aldehydic hydrogen to form a resonance stabilized benzoyl radical (C6H5C(?)═O). A detailed study of the thermochemistry of intermediates and the oxidation reaction paths of the benzoyl radical with dioxygen is presented in this study. Structures and enthalpies of formation for important stable species, intermediate radicals, and transition state structures resulting from the benzoyl radical +O2 association reaction are reported along with reaction paths and barriers. Enthalpies, ΔfH298(0), are calculated using ab initio (G3MP2B3) and density functional (DFT at B3LYP/6-311G(d,p)) calculations, group additivity (GA), and literature data. Bond energies on the benzoyl and benzoyl-peroxy systems are also reported and compared to hydrocarbon systems. The reaction of benzoyl with O2 has a number of low energy reaction channels that are not currently considered in either atmospheric chemistry or combustion models. The reaction paths include exothermic, chain branching reactions to a number of unsaturated oxygenated hydrocarbon intermediates along with formation of CO2. The initial reaction of the C6H5C(?)═O radical with O2 forms a chemically activated benzoyl peroxy radical with 37 kcal mol(-1) internal energy; this is significantly more energy than the 21 kcal mol(-1) involved in the benzyl or allyl + O2 systems. This deeper well results in a number of chemical activation reaction paths, leading to highly exothermic reactions to phenoxy radical + CO2 products.     

Reactivity of quinones as alkyl radical acceptors

The enthalpies of the addition of 11 alkyl radicals to ortho-and para-benzoquinones and substituted para-benzoquinones and the enthalpies of formation of various alkoxyphenoxyl radicals have been calculated. Experimental data for the addition of alkyl radicals to quinones are analyzed in terms of the intersection of two parabolic potential curves, and parameters characterizing this class of reactions are calculated. The classical potential barrier of the thermally neutral reaction of alkyl radical addition to benzoquinone is E _e,0 = 82.1 kJ/mol. This class of reactions is compared to other classes of free-radical addition reactions. The interaction between the electrons of the reaction center and the π electrons of the aromatic ring is a significant factor in the activation energy. Activation energies, rate constants, and the geometric parameters of the transition state have been calculated for 40 reactions of alkyl radical addition to quinones. Strong polar interaction has been revealed in the addition of polar macroradicals to quinones, and its contribution to the activation energy has been estimated. Kinetic parameters, activation energies, and rate constants have been calculated for the reverse reactions of alkoxyphenoxyl radical decomposition to quinone and alkyl. The competition between chain termination and propagation reactions in alkoxyphenol-inhibited hydrocarbon oxidation is discussed.     

Alkylation of nitroaromatics with tetraalkylborate ion via electrochemical oxidation

Aromatic nucleophilic substitution reaction (S(N)Ar) is one of the most thoroughly studied reactions. Alkylation of nitroaromatics with Grignard reagents via chemical oxidation of the sigma(H)-complexes is the most general method to introduce an alkyl group into a nitroaromatic compound. This approach has considerable drawbacks, especially when more than one nitro group are present in the aromatic ring. In this article, we present an electrochemical approach, which offers a new very selective methodology for obtaining alkyl polynitroaromatic compounds. Different strategies based on the use of tetralkylborate anion as nucleophiles are used so as to increase efficiency and to reduce the drawbacks associated with this reaction. A wide list of dinitro- and trinitro-aromatic compounds are studied, the range of yields obtained being from fair (40%) to excellent (85%). The key to improvement in the process is the use of electrochemical techniques for the oxidation of the mixture sigma(H)-complexes/tetrabutylborate ion. The electroactive character of the nucleophile, which can be oxidized to an alkyl radical, means that the S(N)Ar of the hydrogen polar mechanism is not the only mechanism operating during the electroxidation process, since the hydrogen radical S(N)Ar mechanism is running at the same time. Electrochemical mechanistic studies allow the participation of each mechanism in the global product yield obtained to be quantified.     

Organoboranes for synthesis. 5: Stoichiometrically controlled reaction of organoboranes with oxygen under mild conditions to achieve quantitative conversion to alcohols

The reaction of organoboranes with oxygen under mild conditions can be controlled to give an essentially quantitative conversion of all three alkyl groups on boron to the corresponding alcohol. The controlled oxidation is a very clean reaction, with only minor amounts of carbonyl and hydrocarbon products formed. All organoboranes react quite rapidly in the initial stages, but vary considerably in the time required to achieve the desired uptake of oxygen. In contrast to oxidation by alkaline hydrogen peroxide, a portion of this reaction proceeds through alkyl radicals, thus resulting in some loss of stereospecificity. Oxidation of mixed organoboranes reveals that the relative rates of oxidation of alkyl groups on boron are consistent with a radical mechanism, with tertiary ⪢ secondary ⪢ primary in the rate of oxidation. The selective oxidation of one alkyl group in the presence of the other is not possible, due to small differences in relative rates of oxidation. However, thexyl and cyclohexyl groups can be selectively removed from boron in the presence of alkenyl groups. Thus, controlled oxidation of thexyldialkenylborane affords pure dialkenylborinic acid.     

Experimental investigation and kinetic modeling of the negative temperature coefficient of the reaction rate in rich propane—oxygen mixtures

The phenomenon of the negative temperature coefficient (NTC) of the reaction rate of the oxidation of rich propane—oxygen mixtures was experimentally studied. The NTC phenomenon is qualitatively described by a simple kinetic model containing a minimum set of reactions related to the oxidation of the starting hydrocarbon, propane, and the propyl C₃H₇ ^. radical formed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2120–2124, December, 1997.     

Combustion chemistry of enols: possible ethenol precursors in flames

Before the recent discovery that enols are intermediates in many flames, they appeared in no combustion models. Furthermore, little is known about enols' flame chemistry. Enol formation in low-pressure flames takes place in the preheat zone, and its precursors are most likely fuel species or the early products of fuel decomposition. The OH + ethene reaction has been shown to dominate ethenol production in ethene flames although this reaction has appeared insufficient to describe ethenol formation in all hydrocarbon oxidation systems. In this work, the mole fraction profiles of ethenol in several representative low-pressure flames are correlated with those of possible precursor species as a means for judging likely formation pathways in flames. These correlations and modeling suggest that the reaction of OH with ethene is in fact the dominant source of ethenol in many hydrocarbon flames, and that addition-elimination reactions of OH with other alkenes are also likely to be responsible for enol formation in flames. On this basis, enols are predicted to be minor intermediates in most flames and should be most prevalent in olefinic flames where reactions of the fuel with OH can produce enols directly.     

Ignition and oxidation of 1‐hexene/toluene mixtures in a shock tube and a jet‐stirred reactor: Experimental and kinetic modeling study

The oxidation of several binary mixtures 1‐hexene/toluene has been investigated both in a shock tube and in a jet‐stirred reactor (JSR). The self‐ignition behavior of binary mixtures was compared to that of neat hydrocarbons studied under the same conditions. Furthermore, molecular species concentration profiles were measured by probe‐sampling and GC/MS, FID, TCD analyses for the oxidation of the mixtures in a JSR. Experiments were carried out over the temperature range 750–1860 K. Mixtures were examined under two pressures 0.2 and 1 MPa, with 0.1% initial concentration of fuel. The equivalence ratio was varied from 0.5 to 1.5. The experiments were modeled using a detailed chemical kinetic reaction mechanism. The modeling study showed that interactions between hydrocarbons submechanisms were not limited to small reactive radicals. Other types of interactions involving hydrocarbon fragments derived from the oxidation of the fuel components must be considered. These interactions mainly consist of hydrogen abstraction reactions. For example, benzyl radical that is the major radical produced from the oxidation of toluene at high temperature can abstract hydrogen from 1‐hexene and their products such as hexenyl radicals. Similarly, propyl, allyl, and hexenyl radicals that are the major radicals produced during 1‐hexene oxidation at high temperature can abstract hydrogen from toluene. Improved modeling was achieved when such interaction reactions were included in the model. Good agreement between experimental and calculated data was obtained using the proposed detailed chemical kinetic scheme. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 518–538, 2007     

CH and C2 measurements imply a radical pool within a pool in acetylene flames

Measured CH and C2 profiles show a striking resemblance as a function of time in a series of seven well-characterized fuel-rich (phi=1.2-2.0) non-sooting acetylene flames. This implied commonality and interrelationship are unexpected as these radicals have dissimilar chemical kinetic natures. As a result, a rigorous examination was undertaken of the behavior of each of the hydrocarbon species known to be present, C, CH, CH2, CH3, CH4, CHO, CHOH, CH2O, CH2OH, CH3O, CH3OH, C2, C2H, C2H2, CHCO, CH2CO, and C2O. This emphasized the main region where CH and C2 are observed (50-600 micros) and reduced the kinetic reactions to only those that operate efficiently and are dominant. It was immediately apparent that this region of the flame reflects the nature of a hydrogen flame heavily doped with CO and CO2 and containing traces of hydrocarbons. The radical species, H, OH, O, along with H2, H2O, and O2, form an important controlling radical pool that is in partial equilibrium, and the concentrations of each of the hydrocarbon radicals are minor to this, playing secondary roles. As a result, the dominant fast reactions are those between the hydrocarbons and the basic hydrogen/oxygen radicals. Hydrocarbon-hydrocarbon reactions are unimportant here at these equivalence ratios. CH and C2 are formed and destroyed on a sub-microsecond time scale so that their flame profiles are the reflection of a complex kinetically dynamic system. This is found to be the case for all of the hydrocarbon species examined. As might be expected, these rapidly form steady-state distributions. However, with the exceptions of C, CHO, CHOH, and CH2O, which are irreversibly being oxidized, the others all form an interconnected hydrocarbon pool that is under the control of the larger hydrogen radical pool. The hydrocarbon pool can rapidly adjust, and the CH and C2 decay together as the pool is drained. This is either by continuing oxidation in less rich mixtures, or in richer flames where this is negligible by the onset of hydrocarbon-hydrocarbon reactions. The implications of such a hydrocarbon pool are significant. It introduces a buffering effect on their distribution and provides the indirect connection between CH and C2. Moreover, because they are members of this radical pool, flame studies alone cannot answer questions concerning their specific importance in combustion other than their contributing role to this pool. The presence of such a pool modifies the exactness that is needed for kinetic mechanisms, and knowledge of every species in the system no longer is necessary. Furthermore, as rate constants become refined, it will allow for the calculation of the relative concentrations of the hydrocarbon species and facilitate reduced kinetic mechanisms. It provides an explanation for previous isotopically labeled experiments and illustrates the difficulty of exactly identifying in flames the role of individual species. It resolves the fact that differing kinetic models can show similar levels of accuracy and has implications for sensitivity analyses. It finally unveils the mechanism of the flame ionization detector and has implications for the differing interpretations of diamond formation mechanisms.     

Accurate thermochemistry of hydrocarbon radicals via an extended generalized bond separation reaction scheme

Detailed knowledge of hydrocarbon radical thermochemistry is critical for understanding diverse chemical phenomena, ranging from combustion processes to organic reaction mechanisms. Unfortunately, experimental thermochemical data for many radical species tend to have large errors or are lacking entirely. Here we develop procedures for deriving high-quality thermochemical data for hydrocarbon radicals by extending Wheeler et al.'s "generalized bond separation reaction" (GBSR) scheme (J. Am. Chem. Soc., 2009, 131, 2547). Moreover, we show that the existing definition of hyperhomodesmotic reactions is flawed. This is because transformation reactions, in which one molecule each from the predefined sets of products and reactants can be converted to a different product and reactant molecule, are currently allowed. This problem is corrected via a refined definition of hyperhomodesmotic reactions in which there are equal numbers of carbon-carbon bond types inclusive of carbon hybridization and number of hydrogens attached. Ab initio and density functional theory (DFT) computations using the expanded GBSRs are applied to a newly derived test set of 27 hydrocarbon radicals (HCR27). Greatly reduced errors in computed reaction enthalpies are seen for hyperhomodesmotic and other highly balanced reactions classes, which benefit from increased matching of hybridization and bonding requirements. The best performing DFT methods for hyperhomodesmotic reactions, M06-2X and B97-dDsC, give average deviations from benchmark computations of only 0.31 and 0.44 (±0.90 and ±1.56 at the 95% confidence level) kcal/mol, respectively, over the test set. By exploiting the high degree of error cancellation provided by hyperhomodesmotic reactions, accurate thermochemical data for hydrocarbon radicals (e.g., enthalpies of formation) can be computed using relatively inexpensive computational methods.     

C1-C2燃料燃烧机理的框架简化

采用六种直接关系图类（DRG）方法对包含253个物种和1542个反应的AramcoMech 1.3机理进行简化,并通过对所得到的六种简化机理取交集,最终得到包含81个物种和497个反应的框架机理。所得81个物种框架机理的点火延迟时间最大误差与其简化方法得到的框架机理最大误差相比并没有显著增加;这表明从不同简化方法的框架机理结果取交集可以有效去除冗余物种。基于81个物种框架机理模拟的双组分混合燃料的点火延迟时间与详细机理机理结果吻合很好。同时该框架机理在不同反应器中的模拟结果验证了温度、物种浓度分布和火焰等燃烧特性。元素流动分析结果表明,81个物种框架机理精确地再现了详细机理的燃烧反应路径。保留了详细机理的所有重要反应路径和层级结构,能够很好地再现C₁-C₂燃料的各种燃烧特性。因此,基于该81个物种框架机理可作为核心机理用于发展大分子烃类或含氧燃料的燃烧机理。     

Electron and oxygen transfer in polyoxometalate, H(5)PV(2)Mo(10)O(40), catalyzed oxidation of aromatic and alkyl aromatic compounds: evidence for aerobic Mars-van Krevelen-type reactions in the liquid homogeneous phase

The mechanism of aerobic oxidation of aromatic and alkyl aromatic compounds using anthracene and xanthene, respectively, as a model compound was investigated using a phosphovanadomolybdate polyoxometalate, H(5)PV(2)Mo(10)O(40), as catalyst under mild, liquid-phase conditions. The polyoxometalate is a soluble analogue of insoluble mixed-metal oxides often used for high-temperature gas-phase heterogeneous oxidation which proceed by a Mars-van Krevelen mechanism. The general purpose of the present investigation was to prove that a Mars-van Krevelen mechanism is possible also in liquid-phase, homogeneous oxidation reactions. First, the oxygen transfer from H(5)PV(2)Mo(10)O(40) to the hydrocarbons was studied using various techniques to show that commonly observed liquid-phase oxidation mechanisms, autoxidation, and oxidative nucleophilic substitution were not occurring in this case. Techniques used included (a) use of (18)O-labeled molecular oxygen, polyoxometalate, and water; (b) carrying out reactions under anaerobic conditions; (c) performing the reaction with an alternative nucleophile (acetate) or under anhydrous conditions; and (d) determination of the reaction stoichiometry. All of the experiments pointed against autoxidation and oxidative nucleophilic substitution and toward a Mars-van Krevelen mechanism. Second, the mode of activation of the hydrocarbon was determined to be by electron transfer, as opposed to hydrogen atom transfer from the hydrocarbon to the polyoxometalate. Kinetic studies showed that an outer-sphere electron transfer was probable with formation of a donor-acceptor complex. Further studies enabled the isolation and observation of intermediates by ESR and NMR spectroscopy. For anthracene, the immediate result of electron transfer, that is formation of an anthracene radical cation and reduced polyoxometalate, was observed by ESR spectroscopy. The ESR spectrum, together with kinetics experiments, including kinetic isotope experiments and (1)H NMR, support a Mars-van Krevelen mechanism in which the rate-determining step is the oxygen-transfer reaction between the polyoxometalate and the intermediate radical cation. Anthraquinone is the only observable reaction product. For xanthene, the radical cation could not be observed. Instead, the initial radical cation undergoes fast additional proton and electron transfer (or hydrogen atom transfer) to yield a stable benzylic cation observable by (1)H NMR. Again, kinetics experiments support the notion of an oxygen-transfer rate-determining step between the xanthenyl cation and the polyoxometalate, with formation of xanthen-9-one as the only product. Schemes summarizing the proposed reaction mechanisms are presented.     

Ab initio study of chain branching reactions involving second generation products in hydrocarbon combustion mechanisms

sec-Alkyl radicals are key reactive intermediates in the hydrocarbon combustion and atmospheric decomposition mechanisms that are formed by the abstraction of hydrogen from an alkane, or as a second generation product of n-alkyl H-migrations, C-C bond scissions in branched alkyl radicals, or the bimolecular reaction between olefins and n-alkyl radicals. Since alkanes and branched alkanes, which the sec-alkyl radicals are derived from, make up roughly 40-50% of traditional fuels an understanding of their chemistry is essential to improving combustion systems. The present work investigates all H-migration reactions initiated from an sec-alkyl radical that involve the movement of a secondary hydrogen, for the 2-butyl through 4-octyl radicals, using the CBS-Q, G2, and G4 composite methods. The resulting thermodynamic and kinetic parameters are compared to similar reactions in n-alkyl radicals in order to determine underlying trends. Particular attention is paid to the effect of cis/trans and 1,3-diaxial interactions on activation energies and rate coefficients. When combined with our previous work on n-alkyl radical H-migrations, a complete picture of H-migrations in unbranched alkyl radicals is obtained. This full data set suggests that the directionality of the remaining branched chains has a minimal effect on the rate coefficients for all but the largest viable transition states, which is in stark contrast to the differences predicted by the structurally similar dimethylcycloalkanes. In fact the initial location of the secondary radical site has a greater effect on the rate than does the directionality of the remaining alkyl chains. The activation energies for secondary to secondary reactions are much closer to those of the secondary to primary H-migrations. However, the rate coefficients are found to be closer to the corresponding primary to primary reaction values. A significant ramification of these results is that there will be multiple viable reaction pathways for these reactions instead of only one dominant pathway as previously believed.     

High-pressure rate rules for alkyl + O2 reactions. 2. The isomerization, cyclic ether formation, and β-scission reactions of hydroperoxy alkyl radicals

The unimolecular reactions of hydroperoxy alkyl radicals (QOOH) play a central role in the low-temperature oxidation of hydrocarbons as they compete with the addition of a second O(2) molecule, which is known to provide chain-branching. In this work we present high-pressure rate estimation rules for the most important unimolecular reactions of the β-, γ-, and δ-QOOH radicals: isomerization to RO(2), cyclic ether formation, and selected β-scission reactions. These rate rules are derived from high-pressure rate constants for a series of reactions of a given reaction class. The individual rate expressions are determined from CBS-QB3 electronic structure calculations combined with canonical transition state theory calculations. Next we use the rate rules, along with previously published rate estimation rules for the reactions of alkyl peroxy radicals (RO(2)), to investigate the potential impact of falloff effects in combustion/ignition kinetic modeling. Pressure effects are examined for the reaction of n-butyl radical with O(2) by comparison of concentration versus time profiles that were obtained using two mechanisms at 10 atm: one that contains pressure-dependent rate constants that are obtained from a QRRK/MSC analysis and another that only contains high-pressure rate expressions. These simulations reveal that under most conditions relevant to combustion/ignition problems, the high-pressure rate rules can be used directly to describe the reactions of RO(2) and QOOH. For the same conditions, we also address whether the various isomers equilibrate during reaction. These results indicate that equilibrium is established between the alkyl, RO(2), and γ- and δ-QOOH radicals.     

Computational singular perturbation analysis of two-stage ignition of large hydrocarbons

Computational singular perturbation (CSP) analysis has been used to gain understanding of the complex kinetic behavior associated with two-stage ignition of large hydrocarbon molecules. To this end, available detailed and reduced chemical kinetics models commonly used in numerical simulations of n-heptane oxidation phenomena are directly analyzed to interpret the underlying fundamental steps leading to two-stage ignition. Unlike previous implementations of the CSP methodology, temperature is included as one of the state variables so that factors controlling ignition can be unambiguously determined. The analyzed models show differences in the factors contributing to the initial development and shutdown of the first ignition stage. However, during the second stage, both models show the importance of the degenerate branching decomposition of hydrogen peroxide, which contradicts some previous interpretations of this phenomenon.     

RP-3航空煤油高温骨架机理构建及验证

依据RP-3航空煤油的成分,考虑平均分子量及碳氢摩尔比等性质,本文提出其三组分替代燃料模型,其中正癸烷74.24%、1,3,5-三甲基环己烷14.11%和正丙基苯11.65%(质量分数)。采用机理生成程序ReaxGen得到详细化学反应机理;采用机理简化程序ReaxRed,运用直接关系图法与主成分分析法获得高温骨架机理(79物种,311反应)。该机理针对多个工况进行了点火延迟时间与层流火焰速度的验证,能较好地预测实验结果。路径分析结果表明高温下替代燃料通过氢提取反应、单分子裂解反应及β-断键反应消耗。敏感性分析表明高温点火过程由多种小分子自由基(H、CHO、C2H3等)的氧化及分解反应和大分子燃料的氢提取反应控制;影响火焰传播过程的关键反应来源于C0-C3的小分子核心机理。本文所提出的这个尺寸较小但精度较高的骨架机理可用于发动机燃烧过程的高保真数值模拟。     

Plasma Assisted Low Temperature Combustion

This paper presents recent kinetic and flame studies in plasma assisted low temperature combustion. First, the kinetic pathways of plasma chemistry to enhance low temperature fuel oxidation are discussed. The impacts of plasma chemistry on fuel oxidation pathways at low temperature conditions, substantially enhancing ignition and flame stabilization, are analyzed base on the ignition and extinction S-curve. Secondly, plasma assisted low temperature ignition, direct ignition to flame transition, diffusion cool flames, and premixed cool flames are demonstrated experimentally by using dimethyl ether and n-heptane as fuels. The results show that non-equilibrium plasma is an effective way to accelerate low temperature ignition and fuel oxidation, thus enabling the establishment of stable cool flames at atmospheric pressure. Finally, the experiments from both a non-equilibrium plasma reactor and a photolysis reactor are discussed, in which the direct measurements of intermediate species during the low temperature oxidations of methane/methanol and ethylene are performed, allowing the investigation of modified kinetic pathways by plasma-combustion chemistry interactions. Finally, the validity of kinetic mechanisms for plasma assisted low temperature combustion is investigated. Technical challenges for future research in plasma assisted low temperature combustion are then summarized.     

Catalytic Ignition of Light Hydrocarbons

Catalytic ignition refers to phenomenon where sufficient energy is released from a catalytic reaction to maintain further reaction without additional extemai heating. This phenomenon is important in the development of catalytic combustion and catalytic partial oxidation processes, both of which have received extensive attention in recent years. In addition, catalytic ignition studies provide experimental data which can be used to test theoretical hydrocarbon oxidation models. For these reasons, catalytic ignition has been frequently studied. This review summarizes the experimental methods used to study catalytic ignition of light hydrocarbons and describes the experimental and theoretical results obtained related to catalytic ignition. The role of catalyst metal, fuel and fuel concentration, and catalyst state in catalytic ignition are examined, and some conclusions are drawn on the mechanism of catalytic ignition.     

Intermediate Q from soluble methane monooxygenase hydroxylates the mechanistic substrate probe norcarane: evidence for a stepwise reaction.

Norcarane is a valuable mechanistic probe for enzyme-catalyzed hydrocarbon oxidation reactions because different products or product distributions result from concerted, radical, and cation based reactions. Soluble methane monooxygenase (sMMO) from Methylosinus trichosporium OB3b catalyzes the oxidation of norcarane to afford 3-hydroxymethylcyclohexene and 3-cycloheptenol, compounds characteristic of radical and cationic intermediates, respectively, in addition to 2- and 3-norcaranols. Past single turnover transient kinetic studies have identified several optically distinct intermediates from the catalytic cycle of the hydroxylase component of sMMO. Thus, the reaction between norcarane and key reaction intermediates can be directly monitored. The presence of norcarane increases the rate of decay of only one intermediate, the high-valent bis-mu-oxo Fe(IV)(2) cluster-containing species compound Q, showing that it is responsible for the majority of the oxidation chemistry. The observation of products from both radical and cationic intermediates from norcarane oxidation catalyzed by sMMO is consistent with a mechanism in which an initial substrate radical intermediate is formed by hydrogen atom abstraction. This intermediate then undergoes either oxygen rebound, intramolecular rearrangement followed by oxygen rebound, or loss of a second electron to yield a cationic intermediate to which OH(-) is transferred. The estimated lower limit of 20 ps for the lifetime of the putative radical intermediate is in accord with values determined from previous studies of sterically hindered sMMO probes.     

Acid‐Mediated Formation of Radicals or Baeyer–Villiger Oxidation from Criegee Adducts

The acid‐mediated reaction of ketones with hydroperoxides generates radicals, a process with reaction conditions similar to those of the Baeyer–Villiger oxidation but with an outcome resembling the formation of hydroxyl radicals via ozonolysis in the atmosphere. The Baeyer–Villiger oxidation forms esters from ketones, with the preferred use of peracids. In contrast, alkyl hydroperoxides and hydrogen peroxide react with ketones by condensation to form alkenyl peroxides, which rapidly undergo homolytic O? O bond cleavage to form radicals. Both reactions are believed to proceed via Criegee adducts, but the electronic nature of the peroxide residue determines the subsequent reaction pathways. DFT calculations and experimental results support the idea that, unlike previously assumed, the Baeyer–Villiger reaction is not intrinsically difficult with alkyl hydroperoxides and hydrogen peroxide but rather that the alternative radical formation is increasingly favored.