Effects of high pressure and temperature on carbon isotope compositions of some acyclic alkanes and preservation of organic matter

The effects of high pressure and temperature on carbon isotopic compositions of acyclic alkanes and the stability of the acyclic alkanes were experimentally investigated. The pyrolysis of lignite with water in a closed system was conducted at 400–700°C and 1–3 GPa. The carbon isotope data, variations of peak carbon and evident odd–even predominance of acyclic alkanes indicated that: (1) the high pressure retarded the maturation of organic matter and destruction of hydrocarbons, (2) n-C₁₂₊ hydrocarbons from biogenic sources could be preserved in the cool slab subducted into the upper mantle, and (3) some organic compounds might preserve the carbon isotope signals inherited from biogenic sources. The results favor tracing the origins of organic matter in mantle rocks and extraterrestrial organic matter in meteorites and the process of deep carbon cycle.     

Mechanisms of the oxidation and combustion of normal alkanes: Transition from C<Subscript>1</Subscript>–C<Subscript>5</Subscript> to C<Subscript>6</Subscript>H<Subscript>14</Subscript>

A previously proposed algorithm of constructing optimal mechanisms of the low- and high-temperature oxidation and combustion of normal alkanes was applied to n-hexane. The proposed mechanism can be considered a nonempirical detailed mechanism, since all the constituent reactions have a solid kinetic substantiation. The mechanism features two main peculiarities: it contains no reactions of double oxygen addition (first to the peroxide radical and then to its isomerized form) and (2) involves no isomeric compounds and derivatives thereof. Application of the algorithm to n-hexane made it possible to create a new compact kinetic mechanism. The mechanism was demonstrated to correctly describe the multistage character of low-temperature self-ignition: the appearance of a cool and then a blue flame.     

Modeling of oxidative transformations of light alkanes over heterogeneous catalysts

An approach to modeling catalytic oxidative transformations of light alkanes (LAs) based on the use of thermochemical data is developed. The fact that LAs are virtually not adsorbed on the surface of oxidation catalysts seriously limits the possibility of experimentally studying the mechanisms of their transformations. In addition, LAs, the least reactive organic compounds, are oxidized at elevated temperatures even on the most active catalysts, a circumstance that makes the contribution from the homogeneous process to the overall conversion rate significant. For this reason, it is necessary to develop multilevel models capable of describing of the elementary reactions of LAs and intermediate products of their transformations (including free radicals of various types) with active sites of catalysts as well as the process as a whole. The proposed approach, based on the experimental data on the thermochemical properties of redox active sites, is applicable to describing processes occurring in the presence of an oxide catalyst. It makes it possible to estimate the kinetic parameters of the elementary interactions of molecules and radicals with active sites in reduced and oxidized states, that is, to solve the problem of the initial stage of modeling of a multistep process. A number of examples of applying this approach to studying oxidative transformations (partial oxidation and oxidative coupling) of methane, oxidative dehydrogenation of C₂–C₄ alkanes, and reoxidation of catalysts are considered. The prospects of modeling the heterogeneous-homogeneous oxidation of light alkanes are discussed.     

石油组分的拉曼位移特征统计分析Ⅰ: 链烷烃和芳香烃

烃类包裹体被用于含油气盆地中油气的生成、运移、聚集等研究中,确定其中的烃类分子类型具有重要意义。激光拉曼光谱技术作为单个流体包裹体非破坏性分析技术受到广泛重视,但在烃类包裹体研究方面受到两个方面的制约,一是油气烃类物质的复杂性导致不好识别;二是大部分烃类包裹体会发荧光而覆盖了拉曼信号。通过对大量石油组分常见的烃类分子拉曼光谱特征统计,总结了饱和链状烷烃和芳香烃的拉曼特征。结果显示,碳数大于10的正构烷烃可通过1 438,2 890和2 850 cm-1三个拉曼峰组合识别,而异构化烷烃(以C₈H₁₈为例)C—C(1 450 cm-1±)和C—H(2 875 cm-1±)的最强拉曼峰组合可作为识别含一个支链的异构烷烃的标志,含两个支链的异构烷烃有一个稳定的拉曼强峰在2 875 cm-1。含一个苯环的芳香烃可通过在1 600 cm-1附近的稳定双峰确定;以1 005 cm-1和3 060 cm-1两个特征峰组成的强拉曼组合峰可识别苯环上含单个支链的芳香烃;1 250 cm-1±和2 910～2 920 cm-1的拉曼强峰组合可识别苯环上含三个支链的芳香烃。含两个苯环的芳香烃不仅在1 600 cm-1处有稳定的拉曼双峰,而且在2 800～3 300 cm-1范围内具有一稳定的最强拉曼峰(3 060 cm-1)。本次总结的规律可以用于识别烃类包裹体中的链烷烃和芳香烃,而分析结果表明短波长光源(蓝光到紫外光)的拉曼光谱仪分析烃类包裹体可以有效避免荧光干扰。     

Correlation between drop vaporization and self-ignition

A parametric analysis of numerical solutions to problems of vaporization and self-ignition of liquid hydrocarbon drops was performed, and a new criterion determining the conditions of drop self-ignition was suggested. According to this criterion, self-ignition at a given reduced distance from the drop begins when the required reduced gas temperature and equivalence ratio are reached. A new model of heating and vaporization of drops in dense gas suspensions was suggested. The model was verified in multidimensional calculations of self-ignition and combustion of drop clouds. Calculations showed that the model correctly described the phenomenology of local formation and anisotropic propagation of self-ignition waves in suspensions of drops in gases.     

Complex microscopic effective interaction for (p,n) reactions

A simple recipe for generating a complex effective interaction for distorted wave Born approximation calculations from a real, microscopic charge-exchange form factor is investigated. The recipe is tested against angular distribution data for ²⁰⁸Pb(p, n) and ²⁰⁹Bi(p, n) from 25 to 50 MeV incident proton energy. The form factor resulting from the recipe is also compared qualitatively to complex effective coupling potentials, resulting from a charge-independent Lane-model formalism and from coupled-channion-channels calculations for a suggested multistep (p, d)—(d, n) reaction mechanism.     

Optical Spectroscopy and the Structure of Polyfunctional Hydrocarbon Compounds and Oil Products

The optical and physicochemical properties associated with the change (oxidation, thermolysis and photolysis), during the operation, of the spatial and electronic structures of the polyfunctional hydrocarbon compounds, oils, oil products, and N-, O-, and S-containing heteroaromatic compounds and additives, which comprise a variety of fuel and lubricant compositions involved in the structural and phase rearrangements, as well as in the formation of colloidal and micelle aggregates altering the structure with respect to their hydrocarbon, chemical, and fractional compositions, are investigated. The spectroscopic-luminescent properties of the compounds and their ion-radical forms were studied using optical and spectroscopic methods and quantum-chemical calculations when the excitation energy in the full spectra of singlet and triplet (for the ion, quartet and doublet) electronic excited states was deactivated. Intramolecular mechanisms of the hyperfine electron–nucleus interaction between the active groups of quasi-oscillators in the structure of polyfunctional compounds in the paramagnetic states of hydrocarbons, which form the electronic structure of the triplet–triplet transitions induced by pumping in the optical absorption spectra, are studied. It is shown that the mechanism of multistep ionization, fragmentation, and appearance of radicals and the electronic-vibrational mechanism of an increase in the vibration temperature up to T = 6000–7000 K are developed during the action of the ultraviolet (UV) pumping pulse of a nanosecond duration until the light emission, which gives rise to thermolysis and recombination that create the conditions for the combustion and explosion when the excitation energy is localized on a limited number of groups of quasi-oscillators in the structure.     

Experimental and kinetic modeling of the ignition delays of cyclohexane,cyclohexene, and cyclohexadienes: Effect of unsaturation

Cyclic and aromatic hydrocarbons are important components of usual commercial fuels, with C₆-rings being among the most abundant cyclic structures. The combustion chemistry of C₆-rings involves different levels of unsaturation, either as initial fuels (aromatics, naphtenes, …) or as intermediates formed during their combustion. In this work the ignition delays of cyclohexane, cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene are systematically studied using experiments and kinetic modeling. Shock tube experiments were performed at high-temperature (above 1200 K) and for mean pressures of 6 atm. A detailed chemical kinetic model was developed that includes the combustion chemistry of the four cyclo-C₆ fuels. Electronic structure calculations were performed at the CCSD(T)/CBS//B2PLYP-D3 level of theory on the pericyclic reactions of the unsaturated fuels. Pressure-dependent rate coefficients were computed by solving the master equation, and included in the mechanism. The model was validated against the new ignition data and against data of the literature. It was able to reproduce the experimental ranking of reactivity: cyclohexene > 14-CHD > cyclohexane > benzene ≈13-CHD. Kinetic analyses were performed to explain this difference of reactivity. It is shown that pericyclic reactions play a major role in the initial decomposition of the unsaturated fuels.     

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C–C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C–C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.     

A theoretical kinetics study on low-temperature oxidation of n-C4H9 radicals

The low-temperature oxidation mechanism of n?butyl radicals (n-C₄H₉) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO₂ elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes.     

Theoretical calculations of homogeneous catalysis in the gas phase: elimination kinetics of 2,2-dimethoxypropane in the presence of HCl,F3CCOOH and CH3COOH

The mechanisms of gas-phase elimination kinetics of 2,2-dimethoxypropane in the presence of hydrogen chloride, trifluoroacetic acid and acetic acid were studied using Moller Plesset, ab initio combined method Complete Basis Set (CBS)-QB3 and various density functional theory methods with 6-311G(d,p) and 6-311++G(d,p) basis sets. The M06-2X/6-311++G(d,p) method provided reasonable agreement with the experimental enthalpy and energy of activation. Formation of 2-methoxypropene and methanol products occurs through six-membered cyclic ring transition state (TS) structure. The TS was characterised by single imaginary frequency, and confirmed through intrinsic reaction coordinate (IRC) calculations. The IRC calculations suggest the development of a van der Waal complex between the 2, 2-dimethoxy propane and the acid catalyst, leading to the TS formation. The process of decomposition in the absence of the acid catalyst requires much higher temperature with an energy of activation above 200 kJ/mol. This fact appears to be a consequence of a four-membered cyclic TS-type of mechanism in the non-catalysed reaction. Structural parameters, analyses of natural bond orbital charges and bond orders of the acid-catalysed elimination reactions in this study suggest that the polarisation of the C–O bond, in the direction C^δ+—O^δ?, is rate-determining in the TS. These reactions are non-synchronous concerted polar in nature.     

Gas-phase spontaneous ignition of hydrocarbons

The ignition of hydrocarbons at low temperatures is experimentally studied in a rapid-mixture-injection static reactor. The ignition process was monitored using a high-speed color video camera. It was found that, at low temperatures, ignition starts in kernels, a feature also characteristic of methods for measuring the ignition delay time at high and medium temperatures (shock tube, rapid compression machine). Kernel-mode ignition is associated with gas-dynamic phenomena inherent in different techniques of heating the gas to the desired temperature. Ignition in the kernel is of chain-thermal nature. The emergence of a visible kernel can be considered the beginning of hot flame propagation. It is shown that, in the self-ignition mode, the propagation of the flame front from the initial kernel occurs by the induction mechanism, proposed by Ya.B. Zel’dovich, rather than by the diffusion-heat-conduction mechanism. Introduction of a platinum wire into the reactor produces a catalytic effect in the negative temperature coefficient region, while virtually unaffecting the ignition delay at lower temperatures.     

Multistep scattering in the 160 MeV208Pb(α, α′) reaction

New experimental data has been obtained for the²⁰⁸Pb(α, α′) reaction induced by 160 MeV alpha particles, for inelastic scattering to forward angles. We use these data to investigate the applicability of the multistep scattering theory of Feshbach, Kerman, and Koonin for describing this reaction. The mechanism we study, following the work of Gadioli et al. [1], is of the incident alpha particle remaining intact throughout the scattering process, exciting nucleon particle-hole pairs through multistep process. We conclude that this mechanism, combined with compound nucleus decay at low emission energies, can account for much of the observed data. However, there are indications that other processes also contribute at energies above the compound nucleus emission regime, and we outline future theoretical analyses that are needed.     

Nuclear Fermi Motion Effect on Pion Double Charge Exchange

The influence of nuclear Fermi motion on the conventional mechanism of pion double charge exchange (DCX) is examined.Concrete calculations of the 0° excitation function over the energy region 0—300MeV are performed for the double isobaric analog DCX transition on ¹⁴C.The calculated results coincide very well with the experimental data for the energies above 100MeV,but are about a factor of 2—3 smaller than the experimental data around 50MeV.It indicates that the pure conventional mechanism seems incapable to fully explain the anomalous behavior of the low energy DCX,and some new mechanisms are needed.     

The mechanisms of oxidation and combustion of normal alkane hydrocarbons: The transition from C1–C3 to C4H10

The known detailed mechanisms of oxidation of the higher hydrocarbons include hundreds of particles and thousands of reactions. In spite of their merits, the use of such mechanisms for solving applied problems of the gas dynamics of combustion is impeded at present because of great computational expenditures. We suggest a compact kinetic mechanism of the oxidation of n-butane including the main processes and intermediate and final reaction products. The mechanism can be classified as a nonempirical detailed mechanism, because all its elementary reactions are kinetically substantiated. The mechanism does not contain reactions of the double addition of oxygen and intermediate species in the form of isomeric compounds and their derivatives. The calculation results are compared with the experimental data on the oxidation, self-ignition, and combustion of n-butane.     

低成本吸附剂稻壳灰对Cr(Ⅵ)去除机制的谱学表征

以低成本稻壳灰作为吸附剂,使用FTIR,SEM,XPS,XRD,XRF等分析手段,研究稻壳灰对Cr(Ⅵ)的去除机制。FTIR研究表明酰胺Ⅱ带,Si—O—Si,O—Si—O等在Cr(Ⅵ)去除过程中有一定贡献。由SEM图片清晰可见：吸附Cr(Ⅵ)后,稻壳灰表面分布有众多的光亮沉积物。XPS图谱证明：稻壳灰的主要组成元素为C,N,O,P和Si;C元素的存在状态以醛酮类为主,含C官能团与Cr(Ⅵ)发生了配位反应;N元素以—NH₂形态为主,Cr(Ⅵ)可能以静电作用与含N基团结合,并以物理吸附为主;Si的存在以Si—O为主,含Si官能团可能与Cr(Ⅵ)发生了配位反应。XRD分析结果表明：谱图中出现的峰是典型的SiO2特征峰;稻壳灰的结晶度增加,表明稻壳灰与Cr(Ⅵ)形成了具有晶体结构的金属化合物。XRF研究发现,K,Na,Mg和Ca的元素含量在吸附前后有所变化,另有两种新元素出现,这说明吸附过程存在离子交换机制。所有这些皆表明：各种官能团在Cr(Ⅵ)去除过程中的角色各不相同,无机微沉淀机制、氧化还原机制、表面络合机制、离子交换机制等是稻壳灰去除Cr(Ⅵ)的主要途径。这可以为吸附技术的实际应用提供理论支持。     

Extraction of hydrocarbons from carbonaceous rock in supercritical carbon dioxide

Experiments on supercritical CO₂ extraction of organic matter from carbonaceous raw material show that, regardless of its geological origin, the process is characterized by selective extraction of hydrocarbons, especially alkanes and naphthenes. The composition of the supercritical extract makes it possible to use it for manufacturing lubricants.     

A flow visualization study on self-ignition of high pressure hydrogen gas released into a tube

Hydrogen is known as one of the green energy sources for fuel cells and hydrogen-fueled cars in the next generation. The storage of high-pressure hydrogen gas conditions is preferred to its storage in cryogenic liquid state. However, cases of unidentified self-ignitions were reported, notably when the high-pressure hydrogen gas suddenly leaked out. Only a few of numerical simulations have shown visually the processes of the self-ignition inside a tube. This paper presents a flow visualization study to investigate the self-ignition mechanism in a test tube i.e. how the ignition process is initiated and the flame propagates. In addition to visualization, measurement of a number of pressure and light sensors installed in the tube supported the analysis of the self-ignition and flame propagation. The test result showed that self-ignition takes place at the boundary layer behind the front center of mixing zone at first, and the flame propagates to the front of mixing zone and tail of the mixing zone along the boundary layer. It showed that self-ignition is accompanied with complex mixing induced by shock interaction with the mixing front. It is also suggested that the self-ignition boundary has a certain critical threshold of static pressure at the boundary layer, based on various burst pressures of hydrogen.     

The polaronic nature of intraband relaxation in InAs/GaAs self-assembled quantum dots

Polaron relaxation processes in a series of n-type InAs quantum dots (QDS) have been investigated using energy-dependent far-infrared pump–probe spectroscopy. For energies up to 53 meV, polarons decay to 2 longitudinal acoustic phonons; above this energy additional decay channels open resulting in a reduction of the decay time. Inter-state transfer has been observed between closely spaced p-like excited states, with the measured transfer times in good agreement with calculations assuming acoustic phonon assisted transfer. Finally, for QDs containing 2 electrons we observe evidence of a spin-flip process resulting in long (700 ps) relaxation times.     

Experimental investigation on the self-ignition of pressurized hydrogen released by the failure of a rupture disk through tubes

Hydrogen is expected to be used as a clean energy carrier. However, when high-pressure hydrogen is suddenly released into the air through tubes, self-ignition can occur by a diffusion ignition mechanism. In this paper, the phenomena of self-ignition and flame propagation during the sudden release of high-pressure hydrogen were investigated experimentally. Experimental results show that self-ignition can occur when bursting pressure is sufficiently high in spite of the shortness of the tube. For example, self-ignition was observed at a bursting pressure as high as 23.5 MPa with 50 mm long tube. When self-ignition successfully occurs, a hydrogen jet flame is produced by the ignition. The flame is then stabilized at the tube outlet. From photodiode signals and flame images, the propagation of a flame inside the tube is confirmed and the flame is detected near the rupture disk as the bursting pressure increases. When the tube length is not long enough to produce self-ignition, a hydrogen flame is observed in the only boundary layer at the end of tube and it quenches after the flame exits the tube. Consequently, the formation of a complete flame across the tube is important to initiate self-ignition, which sustains a diffusion flame after jetting out of the tube into the air. Also, in order to establish a complete flame across the tube, it is necessary to have sufficient length such that the mixing region is generated by multi-dimensional shock–shock interactions.