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化学学报
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化学学报 ›› 2002, Vol. 60 ›› Issue (2): 251-255. 上一篇    下一篇

研究论文

乙烷/H2O/O2/N2体系中光致过氧化物的产生

胡敏;齐斌;陈忠明;张远航;唐孝炎   

  1. 北京大学环境科学中心.北京(100871);环境模拟与污染控制国家重点联合实验 室;陕西师范大学化学与材料科学学院
  • 发布日期:2002-02-15

Photo-induced peroxide formation in the ethane/H2O/O2/N2 system

Hu Min;Qi Bin;Chen Zhongming;Zhang Yuanhang;Tang Xiaoyan   

  1. Beijing Univ., Center of Environmental Sci..Beijing(100871)
  • Published:2002-02-15

PDF

527

被引次数

5

采用长光路Fourier红外光谱(LP-FTIR)和高压液相色谱(HPLC)技术研究了乙烷/H2O/O2/N2光化学体系中过氧化物的产生，证实乙烷降解产物中有过氧化氢、乙基过氧化氢(CH3CH2OOH,EHP)和过氧乙酸[CH3C(O)OOH,PAA]，并首次发现了甲基过氧化氢(CH3OOH,MHP)、羟甲基过氧化氢(HOCH2OOH,HMHP)和过氧甲醚(CH3OOCH3,DMP).H2O2,MHP和EHP的最大计算产率分别为6.8%，6.4%和6.7%，是乙烷降解生成的主要过氧化产物。MHP主要来自乙烷降解过程中的中间物乙醛的光解。HMHP的检出表明乙烷降解过程中可能有Criegee中间体.CH2OO.产生。OH自由基引发的乙烷降解反应可能是对流层大气H2O2，MHP及EHP的重要来源之一。

关键词: 乙烷, 高速液体色谱, 光化学烟雾, 红外分光光度法, 羟基, 自由基反应, 降解反应, 光化学反应, 过氧化物

Photochemical formation of peroxides in the ethane/H2O/O2/N2 system was studied with LP-FTIR and HPLC techniques. Hydrogen peroxide, ethyl hydroperoxide (CH3CH2OOH, EHP) and peroxyacetic acid [CH3(O)OOH, PAA] were proved to be the peroxide products in the degradation of ethane. Moreover, methyl hydroperoxide (CH3OOH, MHP) hydroxymethyl hydroperoxide (HOCH2OOH, HMHP) and dimethyl peroxide (CH3OOCH3, DMP) were identified for the first time in the system. The dominant peroxide products were H2O2, EHP and MHP with the maximum calculated yields of 6.8%, 6.4% and 6.7%, respectively. MHP was mainly generated from the photolysis of acet aldehyde formed in thee degradation of ethane. The identification of HMHP provide san evidence for the formation of Criegee intermediate.CH2OO. in the degradation of ethane. The OH radical initiated degradation of ethane was possibly one of the main sources of H2O2, MHP and EHP in the troposphere.

Key words: ETHANE, HIGH SPEED LIQUID CHROMATOGRAPHY, PHOTOCHEMICAL SMOG, INFRARED SPECTROPHOTOMETRY, HYDROXY GROUP, FREE RADICAL REACTION, DEGRADATION REACTION, PHOTOCHEMICAL REACTION, PEROXIDE

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