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355 nm光照下液相中甲苯与亚硝酸的交叉反应
  • ISSN号:0254-6108
  • 期刊名称:《环境化学》
  • 时间:0
  • 分类:TQ241.12[化学工程—有机化工]
  • 作者机构:[1]合肥工业大学资源与环境工程学院,合肥230009, [2]合肥工业大学分析测试中心,合肥230009, [3]合肥工业大学大气环境与污染控制研究所,合肥230009
  • 相关基金:国家自然科学基金(21177034)资助
中文摘要:

利用激光闪光光解技术研究了在355 nm激光作用下甲苯与亚硝酸的交叉反应机理,考察了反应瞬态物种的生长和衰减行为,对产物进行了GC-MS分析.结果表明,HNO_2在355 nm的紫外光照下产生的OH自由基和甲苯有两种反应途径,其一是加成反应,甲苯与OH自由基反应生成CH_3C_6H_5-OH加合物,反应速率常数为(4.1±0.4)×10~9L·mol^-1·s^-1,该反应途径在对流层大气中占主导地位;其二是发生在侧链甲基上的提氢反应,反应生成苄基自由基.有氧条件下,CH_3C_6H_5-OH可与O_2反应,氧化为CH_3C_6H_5-OHO_2,反应速率常数为(6.8±0.2)×10~8L·mol^-1·s^-1.

英文摘要:

Reaction mechanism of aqueous solution of toluene with nitrous acid in the presence of O_2 and absence of O_2 were studied by laser flash photolysis. The main characteristic peaks in these transient absorbance spectra were assigned and the build-up/decay processes of several transient species were investigated. Results illustrated ·OH was produced in aqueous solution of nitrous acid exposed to 355 nm laser beam. There are two possible pathways of the reaction between ·OH and toluene. The first is radical adduct formation,especially the addition of ·OH to aromatic ring. The bimolecular rate constant was measured to be( 4.1±0.4) ×109L·mol^-1·s^-1,and it was considered as a dominated way of the reaction between ·OH and toluene in troposphere system. In addition,·OH could also abstract a hydrogen atom from side chain methyl group to form benzyl radicals. The transient product CH_3C_6H_5-OH reacted with O_2 to form CH_3C_6H_5-OHO_2 with a rate constant of( 6.8±0.2) ×10~8L·mol^-1·s^-1. The photo products were analyzed by GC/MS and the possible reaction pathways were discussed.

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期刊信息
  • 《环境化学》
  • 北大核心期刊(2011版)
  • 主管单位:中国科学院
  • 主办单位:中国科学院生态环境研究中心
  • 主编:郭良宏
  • 地址:北京2871信箱
  • 邮编:100085
  • 邮箱:hjhx@rcees.ac.cn
  • 电话:010-62923569
  • 国际标准刊号:ISSN:0254-6108
  • 国内统一刊号:ISSN:11-1844/X
  • 邮发代号:82-394
  • 获奖情况:
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),美国剑桥科学文摘,日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:27127