...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Environmental Science & Technology >New Mechanistic Insights into Atmospheric Oxidation of Aniline Initiated by OH Radicals
【24h】

New Mechanistic Insights into Atmospheric Oxidation of Aniline Initiated by OH Radicals

机译：由oh自由基发起苯胺的大气氧化的新机制见解

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

This study theoretically reports the comprehensive kinetic mechanism of the aniline + OH reaction in the range of 200-2000 K and 0.76-7600 Torr. The temperature- and pressure-dependent behaviors, including time-resolved species profiles and rate coefficients, were studied within the stochastic RRKM-based master equation framework with the reaction energy profile, together with molecular properties of the species involved, characterized at the M06-2X/aug-cc-pVTZ level. Hindered internal rotation and Eckart tunneling treatments were included. The H-abstraction from the -NH_2 moiety (to form C_6H_5NH (P1)) is found to prevail over the OH-addition on the C atom at the ortho site of aniline (to form 6-hydroxy-1-methylcyclohexa-2,4-dien-1-yl (I2)) with the atmospheric rate expressions (in cm~3/molecule/s) as k~(abstraction)(P1) = 3.41 × 10~1 × T~(-4.56) × exp (-255.2 K/T) for 200-2000 K and k~(addition)(I2) = 3.68 × 10~9 × T~(-7.39) × exp (-1163.9 K/T) for 200-800 K. The U-shaped temperature-dependent characteristics and weakly positive pressure dependence at low temperatures (e.g., T ≤ 800 K and P = 760 Torr) of k_(total)(T) are also observed. The disagreement in k_(total)(T) between the previous calculations and experimental studies is also resolved, and atmospheric aniline is found to be primarily removed by OH radicals (τ_(OH) ～ 1.1 h) in the daytime. Also, via TD-DFT simulations, it is recommended to include P1 and I2 in any atmospheric photolysis-related model.
机译：本研究从理论上报告了200-2000 k和0.76-7600托的苯胺+ OH反应的综合动力机制。在基于随机RRKM的总方程框架内研究了温度和压力依赖性的行为，包括时间分辨物种谱和速率系数，与反应能曲线一起，以及涉及物种的分子特性，其特征在于M06- 2x / 8月/乌克CC-PVTZ水平。包括阻碍内部旋转和Eckart隧道处理。来自-NH_2部分的H-抽象（形成C_6H_5NH（P1））在苯胺的邻位点上的C原子上占OH-加法（形成6-羟基-1-甲基环己岛-2,4 - 用大气速率表达（在Cm〜3 /分子/ s中）为k〜（抽象）（p1）= 3.41×10〜1×t〜（-4.56）×exp（ -255.2 k / t）200-2000 k和k〜（另外）（i2）= 3.68×10〜9×t〜（-7.39）×exp（-1163.9 k / t）200-800 K.U在k_（总计）（t）的低温下 - 在低温下（例如，t≤800k和p = 760托）的清晰度依赖性特征和弱阳性压力依赖性。先前计算和实验研究之间的K_（总）（T）的分歧也得到了解决，发现大气苯胺在白天在白天（τ_（OH）〜1.1h）中主要被除去。此外，通过TD-DFT模拟，建议在任何大气光解相关模型中包括P1和I2。

著录项

  • 来源
    《Environmental Science & Technology》 |2021年第12期|7858-7868|共11页
  • 作者

    Tam V.-T. Mai; Thi T.-D. Nguyen; Hieu T. Nguyen; Trang T. Nguyen; Lam K. Huynh;

  • 作者单位

    Institute for Computational Science and Technology Ho Chi Minh City 700000 Vietnam University of Science Ho Chi Minh City 700000 Vietnam Vietnam National University Ho Chi Minh City 700000 Vietnam;

    Vietnam National University Ho Chi Minh City 700000 Vietnam International University Ho Chi Minh City 700000 Vietnam Department of Chemical Engineering The University of Melbourne Parkville Victoria 3010 Australia;

    Institute for Computational Science and Technology Ho Chi Minh City 700000 Vietnam;

    Vietnam National University Ho Chi Minh City 700000 Vietnam International University Ho Chi Minh City 700000 Vietnam;

    Vietnam National University Ho Chi Minh City 700000 Vietnam International University Ho Chi Minh City 700000 Vietnam;

  • 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);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

    aniline; OH-initiated oxidation; atmospheric degradation; thermodynamics; ab initio kinetics;

    机译：苯胺;OH-发起的氧化;大气降解;热力学;AB Initio Kinetics.;

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