DESCRIPTION OF INITIAL REACTIONS IN KINETIC MODELING OF LOW-TEMPERATURE OXIDATION OF N-ALKANES

Mild Oxidation of Cyclic C6-C10 Hydrocarbons in Liquid Phase at Room Temperature by Heterogeneous Photocatalysis

The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems.

The formation of cyclic ethers is a major product in the oxidation of hydrocarbons, and the oxidation of biomass derived alcohols. Cyclic ethers are formed in the initial reactions of alkyl radicals with dioxygen in combustion and precombustion processes that occur at moderate temperatures. They represent a significant part of the oxygenated pollutants found in the exhaust gases of engines. Cyclic ethers can also be formed from atmospheric reactions of olefins. Additionally, cyclic ethers have been linked to the formation of the secondary organic aerosol (SOA) in the atmosphere. In combustion and thermal oxidation processes these cyclic ethers will form radicals that react with (3)O2 to form peroxy radicals. Density functional theory and higher level ab initio calculations are used to calculate thermochemical properties and bond dissociation enthalpies of 3 to 5 member ring cyclic ethers (oxirane, yC2O, oxetane, yC3O, and oxolane, yC4O), corresponding hydroperoxides, alcohols, hydroperoxy alkyl, and alkyl radicals which are formed in these oxidation reaction systems. Trends in carbon-hydrogen bond dissociation energies for the ring and hydroperoxide group relative to ring size and to distance from the ether group are determined. Bond dissociation energies are calculated for use in understanding effects of the ether oxygen in the cyclic ethers, their stability, and kinetic properties. Geometries, vibration frequencies, and enthalpies of formation, ΔH°f,298, are calculated at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), the composite CBS-QB3, and G3MP2B3 methods. Entropy and heat capacities, S°(T) and Cp°(T) (5 K ≤ T ≤ 5000), are determined using geometric parameters and frequencies from the B3LYP/6-31G(d,p) calculations. The strong effects of ring strain on the bond dissociation energies in these peroxy systems are also of fundamental interest. Oxetane and oxolane exhibit a significant stabilization, 10 kcal mol(-1), lower ΔfH°298 when an oxygen group is on the ether carbon relative to the isomer with the oxygen group on a secondary carbon. Relative to alkane systems the ether oxygen decreases bond dissociation energies (BDEs) on carbon sites adjacent to the ether by ∼5 kcal mol(-1), and increases BDEs on nonether carbons ∼1 kcal mol(-1). The cyclic structures have significant effects on the C-H, CO-OH, COO-H, and CO-H bond dissociation enthalpies. These values can be used to help calibrate calculations of larger more complex bicyclic and tricyclic hydrocarbon and ether species.

Low temperature oxidation chemistry of n-butylbenzene in n-decane/n-butylbenzene mixture: Product characterization and kinetic modeling study

Abstract. Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partition coefficients between the gas phase, an aqueous phase and a water-insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualisation and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM-phase polarity, organic aerosol load, and liquid water content) and chemical properties (such as oxidation state, molecular size, functionalisation, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile α-pinene oxidation products will contribute to aqueous SOA under the conditions of high liquid water content encountered in clouds but would remain vapours in wet aerosol. It is conceivable to develop parameterisations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

Monosaccharide formation resulting from hydrocarbon oxidation by Candida rugosa was determined. C. rugosa was grown in a mineral medium containing 1% alkane (C10-C17) as sole carbon source. Monosaccharide formation was found on all hydrocarbon substrates tested. A similar result was obtained from fatty acids as intermediate oxidation product of hydrocarbon. An interrelationship between cell growth and formation of monosaccharide was observed in all cases. The amount of monosaccharide with n-alkane was greater than with 1-alkene. Also, n-alkanes of even-carbon numbers yield approximately 50% more monosaccharide as compared with n-alkanes of odd-carbon numbers. The optimal substrates for monosaccharide formation were n-dodecane and tetradecane. These yields were 170.7 and 181 μg/ml culture broth, respectively. The monosaccharide formed from n-alkane oxidation was D-glucose as determined by thin-layer chromatography, infrared spectroscopy, and nuclear magnetic resonance analyses. No extrapolysaccharide was detected in C. rugosa. The biosynthesis of extracellular saccharide is discussed.

Cyclic ethers are an important product from the gas-phase reactions of hydrocarbon radicals with molecular oxygen in the atmospheric chemistry of diolefins and in low to moderate temperature combustion and oxidation reaction systems. They are also important in organic synthesis. Structures, and fundamental thermochemical parameters-enthalpy (ΔH°(f,298)), entropy (S°(298)), and heat capacity (C(p)(T))-have been calculated for a series of cyclic alkyl ethers and their carbon centered radicals. Enthalpies of formation (ΔH°(f,298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p), and CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contributions from the internal methyl rotors are substituted for torsion frequencies. Calculated enthalpies of formation for a series of 12 cyclic ethers and methyl substituted cyclic ethers are in good agreement with available literature values. C-H bond dissociation enthalpies are reported for 28 carbon sites of 3 to 5 member ring cyclic ethers for use in understanding effects of the ring and the ether oxygen on kinetics and stability. Trends in carbon-hydrogen bond energies for the ring and methyl substituents relative to ring size and to distance from the ether group are described.

Over 20 new strains of methane-utilizing bacteria were isolated from lake water and soil samples. Cell suspensions of these and of other known strains of methane-utilizing bacteria oxidized n-alkanes (propane, butane, pentane, hexane) to their corresponding secondary alcohols (2-propanol, 2-butanol, 2-pentanol, 2-hexanol). The product secondary alcohols accumulated extracellularly. The rate of production of secondary alcohols varied with the organism used for oxidation. The average rate of 2-propanol, 2-butanol, 2-pentanol, and 2-hexanol production was 1.5, 1.0, 0.15, and 0.08 mumol/h per 5.0 mg of protein in cell suspensions, respectively. Secondary alcohols were slowly oxidized further to the corresponding methylketones. Primary alcohols and aldehydes were also detected in low amounts (rate of production were 0.05 to 0.08 mumol/h per 5.0 mg of protein in cell suspensions) as products of n-alkane (propane and butane) oxidation. However, primary alcohols and aldehydes were rapidly metabolized further by cell suspensions. Methanol-grown cells of methane-utilizing bacteria did not oxidize n-alkanes to their corresponding secondary alcohols, indicating that the enzymatic system required for oxidation of n-alkanes was induced only during growth on methane. The optimal conditions for in vivo secondary alcohol formation from n-alkanes were investigated in Methylosinus sp. (CRL-15). The rate of 2-propanol and 2-butanol production was linear for the 40-min incubation period and increased directly with cell protein concentration up to 12 mg/ml. The optimal temperature and pH for the production of 2-propanol and 2-butanol were 40 degrees C and pH 7.0. Metalchelating agents inhibited the production of secondary alcohols. The activities for the hydroxylation of n-alkanes in various methylotrophic bacteria were localized in the cell-free particulate fractions precipitated by centrifugation between 10,000 and 40,000 x g. Both oxygen and reduced nicotinamide adenine dinucleotide were required for hydroxylation activity. The metal-chelating agents inhibited hydroxylation of n-alkanes by the particulate fraction, indicating the involvement of a metal-containing enzyme system in the oxidation of n-alkanes. The production of 2-propanol from the corresponding n-alkane by the particulate fraction was inhibited in the presence of methane, suggesting that the subterminal hydroxylation of n-alkanes may be catalyzed by methane monooxygenase.

Neogene eolian successions are one of the most important terrestrial palaeoenvironmental archives in East Asia. However, they have received far less attention than Quaternary loess deposits, especially in the case of lipid biomarker analysis. In order to obtain a better insight into the early-middle Miocene palaeoenvironment, we conducted a study of n-alkane biomarkers from sediments of the QA-I section (Qinan) in the western Chinese Loess Plateau, and compared the results with those of previous n-alkane analyses of eolian and aquatic sediments of varying age. Our principal results are as follows: (1) All QA-I samples contain n-alkanes ranging from C14 to C35, among which the relative content of short-chain n-alkanes (C14–C20) from microorganisms is significantly greater than that of long-chain n-alkanes (C26–C35) from the waxes of terrestrial higher plants; the main peak is at C16–C18. All samples have a relatively lower abundance of medium-chain n-alkanes (C21–C25) than that of long- and short-chain n-alkanes, similar to strongly weathered palaeosols in Quaternary loess and Late Miocene-Pliocene Hipparion Red-Earth; however, this distribution is significantly different from that in weakly-weathered loess of Quaternary loess and Late Miocene-Pliocene Hipparion Red-Earth, as well as from aquatic sediments. (2) Despite some odd-over-even carbon predominance of long-chain n-alkanes in the QA-I samples, the carbon preference index (CPI) values are significantly lower than those of most of the weakly-weathered sediments. Our results show that strong weathering and microbial processes have significantly altered the n-alkanes in the Miocene eolian deposits in Qinan, and led to a significant oxidation and degradation of long-chain n-alkanes and the predominance of short-chain n-alkanes from bacteria. Therefore, the contribution of microorganism to total organic carbon (TOC) and its resulting in carbon isotopic composition should be carefully assessed in future studies.

Model for the origin of carboxylic acids in basinal brines

Fragmentation mechanisms from electron-impact of complex cyclic ethers formed in combustion

The oxidizing activity of cobaltic acetate in acetic acid is enhanced by strong organic or inorganic acids to such an extent that n-alkanes can be significantly oxidized at low temperature. The kinetics of cobalt(III) consumption in the presence of n-heptane as substrate and trifluoroacetic acid as activator under a nitrogen atmosphere has been studied: the process appears to be of the second order with respect to cobalt(III) and it is markedly retarded by cobalt(II). The products of the oxidation of n-alkanes by acid-activated cobaltic acetate in acetic acid are different according to whether oxygen is present or not. Acetic esters of alcohols are formed under nitrogen while ketones are mainly produced if oxygen is present; when trichloroacetic acid is used as activator under nitrogen, alkyl chlorides are the principal products. In each case, the products consist of a mixture of position isomers with a marked predominance of the isomer resulting from attack of the alkane on the second carbon atom of the chain. These results are consistent with a mechanism wherein the n-alkanes are attacked by cobalt(III) to afford reversibly cobalt(II) and an alkyl free radical. The selectivities observed are discussed.

The influence of molecular structure on the oxidation reactivity of long-chain ethers: Experimental observation and theoretical analysis

1. A study has been made of the oxidation of ethylene and propene in presence of various catalysts (V2O5 V2O4 MgCr2O4. 2. By observations on the oxidation of ethylene and propene with heavy oxygen in presence of oxidative catalysts, the varying extents to which the oxygen,of the catalyst participates in the process have been demonstrated. 3. A relation has been established between the formation of products of the partial oxidation of the hydrocarbons (aldehydes) and the extent to which the oxygen of the catalyst participates in the oxidation reaction. 4. The application of the mass spectrometer method of analysis to the reaction products from the catalytic oxidation of hydrocarbons has enabled us to explain the diffferent mechanisms of the oxidation reactions at dffferent catalysts.

Microbial oxidation of gaseous hydrocarbons: Oxidation of lower n-alkanes and n-alkanes by resting cell suspensions of various methylotrophic bacteria and the effect of methane metabolites Hou, C.T., Patel, R.N., Laskin, A.I. and Barnable, N. FEMS microbiology letters, 9 (1980) 267–270