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A series of molecular dynamics simulations were performed using the ReaxFF reactive force field to investigate the pyrolysis of Longkou oil shale kerogen in the presence of methanol. The roles of methanol in kerogen pyrolysis were deeply explored to reveal the microscopic mechanism of methanolysis by analyzing the distribution of products, the consumption of methanol, and the formation processes of typical products at different temperatures. The results demonstrate that the yield of shale oil in the presence of methanol is consistently higher than that of kerogen direct pyrolysis at the same temperature, which is consistent with the trend of oil yield with temperature reported by previous methanolysis experiments. Methanol supplies a large number of small radicals under the pyrolysis condition, which can facilitate the breakage of weak bonds and take part in the formation of products through combining with the radical fragments generated by the pyrolysis of kerogen. This study will provide theoretical guidance for understanding the methanolysis process of oil shale. [ABSTRACT FROM AUTHOR]

The product distribution and reaction mechanism of steam pyrolysis of Longkou oil shale kerogen was researched by molecular dynamics simulation. Molecule structural model used in the simulation was constructed according to the analysis results of a series of detection about kerogen extracted from Longkou oil shale. Reactive force field molecular dynamics (ReaxFF MD) was used to simulate both steam pyrolysis and direct pyrolysis process of the kerogen at the temperature of 1600, 2000, 2400 and 2800 K. The results show that temperature is a critical factor affecting product distribution in steam pyrolysis, and 2000 K is a proper set temperature for studying steam pyrolysis via molecular simulation method. Besides that, adding the H2O molecules during steam pyrolysis can form complexes with heterogeneous atoms, thus destroying the intermolecular interactions in kerogen. Moreover, as the hydrogen radicals come from H2O molecules can inhibit cross-linking reactions between small fractions, it can reduce the average molecular weight of organic molecules product. These conclusions could be helpful for rational use of oil shale. [ABSTRACT FROM AUTHOR]

The reaction of N (2D) radical with NO2 molecule has been studied theoretically using density functional theory and ab initio quantum chemistry method. Singlet electronic state [N2O2] potential energy surfaces (PES) are calculated at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311+G(d) + ZPE and G3B3 levels of theory. All the involved transition states for generation of (2NO) and (O2 + N2) lie much lower than the reactants. Thus, the novel reaction N + NO2 can proceed effectively even at low temperatures and it is expected to play a role in both combustion and interstellar processes. On the basis of the analysis of the kinetics of all pathways through which the reactions proceed, we expect that the competitive power of reaction pathways may vary with experimental conditions for the title reaction. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [ABSTRACT FROM AUTHOR]

Abstract: The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition–elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition–elimination reactions, the halogen atoms approach C2H2, perpendicular to the Cbond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C2H2F/C2H2Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry. [Copyright &y& Elsevier]