...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Combustion and Flame >Global uncertainty analysis for RRKM/master equation based kinetic predictions: A case study of ethanol decomposition
【24h】

Global uncertainty analysis for RRKM/master equation based kinetic predictions: A case study of ethanol decomposition

机译：基于RRKM /主方程的动力学预测的全局不确定性分析：以乙醇分解为例

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

A precise understanding of the accuracy of reaction rate constants, whether determined experimentally or theoretically, is of considerable importance to kinetic modelers. While the uncertainties of experimentally measured rate constants are commonly provided, the "error bars" of computed (temperature- and pressure-dependent) rate constants are rarely evaluated rigorously. In this work, global uncertainty and sensitivity analysis is applied to the propagation of the uncertainties in the input parameters (e.g. barrier heights, frequencies and collisional energy transfer parameters et al.) to those in the rate constants computed by the RRKM/master equation method for the decomposition of ethanol. This case study provides a systematic exploration of the effect of temperature and pressure on the parametric uncertainties in RRKM/master equation calculations for a prototypical single-well multiple-channel dissociation. In the high pressure limit, the uncertainties in the theoretical predictions are controlled by the uncertainties in the input parameters involved in the transition state theory calculations, with the most important ones being those describing the energetics of the decomposition. At lower pressures, where fall-off is important, the uncertainties in the collisional energy transfer parameters play a significant role, particularly for the higher energy of the two channels. Remarkably, the competition between dissociation and collisional excitation leads to uncertainties of more than a factor of 100 in the predictions for the higher energy channel. These large uncertainties are related to the need for large-scale single-collision-induced transitions in energy in order to produce the higher energy products in the low pressure limit. The present study illustrates the value of detailed qualitative and quantitative studies of the uncertainties in theoretical kinetics predictions. (C) 2015 The Combustion Institute.. Published by Elsevier Inc. All rights reserved.
机译：精确地理解反应速率常数的准确性，无论是通过实验还是从理论上确定，对于动力学建模者而言都具有相当重要的意义。虽然通常提供实验测量的速率常数的不确定性，但很少严格评估计算的（取决于温度和压力的）速率常数的“误差线”。在这项工作中，将全局不确定性和敏感性分析应用于输入参数（例如势垒高度，频率和碰撞能量传递参数等）中不确定性的传播，以及由RRKM /主方程法计算出的速率常数中的不确定性的传播。用于乙醇的分解。该案例研究为典型的单井多通道解离提供了对RRKM /主方程计算中温度和压力对参数不确定性影响的系统研究。在高压极限下，理论预测中的不确定性由过渡态理论计算中涉及的输入参数的不确定性控制，其中最重要的是描述分解能的参数。在较低的压力下（下降非常重要），碰撞能量传递参数的不确定性起着重要作用，特别是对于两个通道的较高能量而言。值得注意的是，在较高能量通道的预测中，解离和碰撞激发之间的竞争导致不确定性超过100倍。这些巨大的不确定性与需要大规模的单碰撞诱发的能量跃迁有关，以便在低压极限下产生更高的能量产物。本研究说明了详细的定性和定量研究不确定性在理论动力学预测中的价值。 （C）2015 The Combustion Institute。由Elsevier Inc.出版。保留所有权利。

著录项

  • 来源
    《Combustion and Flame》 |2015年第9期|3427-3436|共10页
  • 作者

    Xing Lili; Li Shuang; Wang Zhaohui; Yang Bin; Klippenstein Stephen J.; Zhang Feng;

  • 作者单位

    Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China;

    Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China|Tsinghua Univ, Ctr Combust Energy, Beijing 100084, Peoples R China|Tsinghua Univ, Dept Thermal Engn, Beijing 100084, Peoples R China;

    Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China;

    Tsinghua Univ, Ctr Combust Energy, Beijing 100084, Peoples R China|Tsinghua Univ, Dept Thermal Engn, Beijing 100084, Peoples R China;

    Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA;

    Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Anhui, Peoples R China;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    Transition state theory; RRKM/master equation method; Uncertainty analysis; Sensitivity analysis; Collisional energy transfer model;

    机译：过渡态理论RRKM /主方程法不确定度分析灵敏度分析碰撞能量传递模型;

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号