Photooxidation of CF₃CF₂C(O)Cl in the presence of NO₂. Synthesis and characterization of pentafluoroethyl peroxynitrate, CF₃CF₂OONO₂

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• 作者：Adriana G. Bossolasco ; Fabio E. Malanca ; ^{fmalanca@fcq.unc.edu.ar} ; Gustavo A. Argü ; ello
• 关键词：Peroxynitrates ; Fluorinated peroxynitrates ; CF3CF2OONO2 ; CF3CF2C(O)Cl ; Photooxidation
• 刊名：Journal of Photochemistry and Photobiology A ; Chemistry
• 出版年：2012
• 期刊代码：66_10106030
• 类别：ch
• 出版时间：1 March, 2012
• 卷：231
• 期：1
• 页码：45-50
• 文件大小：574 K

摘要

The photolysis of CF₃CF₂C(O)Cl in the presence of NO₂ and O₂ at 254 nm leads initially to the formation of CF₃CF₂OONO₂, CF₂O, and CO as the main carbonaceous products. The NO₂ concentration governs the identity of the products. As photolysis continues the NO₂ concentration gradually decreases until new channels open up and the mechanism leads to the formation of CF₂O, CO₂ and CF₃OC(O)OONO₂.

In addition to the study of the mechanism, we present in this paper some characteristics of the pentafluoroethyl peroxynitrate, CF₃CF₂OONO₂ such as the infrared spectrum with the associated absorption cross-sections for the main peaks and kinetic parameters for its thermal decomposition at total pressures of 9.0 and 250 mbar (E_a = 87.7 kJ/mol, A = 3.8 脳 10¹³; and E_a = 96.7 kJ/mol, A = 2.37 脳 10¹⁵, respectively) which show that they are dependent both on the temperature and on the total pressure.