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首页> 外文期刊>RSC Advances >Pressure-dependent branching in initial decomposition of gamma-valerolactone: a quantum chemical/RRKM study
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Pressure-dependent branching in initial decomposition of gamma-valerolactone: a quantum chemical/RRKM study

机译：γ-戊酮初始分解中的压力依赖性分支：量子化学/ RRKM研究

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摘要

Recently, the potential of gamma-valerolactone (a cyclic ester, C5H8O2) as a bio-fuel and fuel additive has been highlighted. To unravel its chemical behavior in combustion, the reaction kinetics of initial decomposition of gamma-valerolactone (GVL) has been investigated theoretically by utilizing ab initio calculations and transition-state-theory based simulations. The effect of pressure on decomposition rates and, more importantly, on the branching fractions of major products has been explored. The potential energy surface was constructed at the CCSD(T)-F12/cc-pVDZ-f12 level based on B2PLYPD3/cc-pVTZ optimized geometries. Rate coefficients were obtained from the solution of RRKM/master-equations at a number of pressures (within the range of 7.6-76000 torr). The isomerization of GVL to 4-pentenoic acid (4PA) followed by C-C bond fission to form allyl plus CH2COOH is confirmed to be the most important route in the initial decomposition of GVL. Aside from isomerization to 4PA, several other routes also occur with significant contributions, during which pressure was found to take a great role in their branching. At pressures above 760 torr, the concerted reactions to form CO + ethene + acetaldehyde and propene + 2-oxiranone account for over 50% of the overall decomposition at the higher temperature end. On the other hand, the formally direct formation of allyl + CH2COOH, which occurs via directly skipping the 4PA well, has a non-ignorable branching above 1400 K at low pressures. As opposed to GVL, the effect of pressure on the branching of 4PA consumption routes is very minor. It is hoped that the present study will establish a firm foundation for more comprehensive kinetic studies on GVL combustion in the future.
机译：最近，γ-戊内酯（环状酯，C5H8O2）作为生物燃料和燃料添加剂的潜力已被突出显示。解开在燃烧其化学行为，γ-戊内酯（GVL）的初始分解的反应动力学已理论上通过利用从头计算和基于过渡态理论模拟研究。并且，更重要的是，在主要产品的分支比一直探索的压力分解率的影响。势能面以基于B2PLYPD3的CCSD（T）-F12 / CC-pVDZ-F12级构建/ CC-pVTZ优化的几何形状。率系数从RRKM /主方程在多个压力下的溶液（7.6-76000乇的范围内）得到。 GVL到随后的C-C键断裂4-戊烯酸（4PA）异构化以形成烯丙基加CH2COOH被确认是在GVL的初始分解的最重要的途径。除了异构化4PA，其他几个路线也与显著的贡献，在此期间，压力被发现能在其分支的巨大作用发生。在高于760托的压力下，协同反应，以形成用于在较高温度下端的整体分解超过50％的CO +乙烯+乙醛和丙烯+ 2-oxiranone帐户。在另一方面，在正式直接形成烯丙基+ CH2COOH，其中发生通过直接跳过4PA阱，具有高于1400 K A不可忽略分支在低压下。相对于GVL，压力对4PA消费路线的分支的影响是非常小的。我们希望，本研究将建立在未来GVL燃烧更全面的动力学研究打下坚实的基础。

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  • 来源
    《RSC Advances》 |2018年第23期|共9页
  • 作者

    Ye Lili; Li Wei; Qi Fei;

  • 作者单位

    Shanghai Jiao Tong Univ Key Lab Power Machinery &

    Engn MOE Shanghai 200240 Peoples R China;

    Shanghai Jiao Tong Univ Key Lab Power Machinery &

    Engn MOE Shanghai 200240 Peoples R China;

    Shanghai Jiao Tong Univ Key Lab Power Machinery &

    Engn MOE Shanghai 200240 Peoples R China;

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  • 正文语种 eng
  • 中图分类 化学;
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