激光诱导的亚硝酸与二苯醚的反应机理

355 nm光照下利用瞬态吸收光谱技术进行了有氧、无氧条件下二苯醚与亚硝酸体系的反应机理研究, 考察了其中瞬态物种的衰减行为, 并对其光解产物进行了GC-MS分析. 研究表明, HNO₂在355 nm紫外光的照射下产生的OH自由基和二苯醚反应生成C₁₂H₁₀O-OH 加合物, N₂条件下C₁₂H₁₀O-OH衰减的速率常数为(1.86±0.14)×10⁵ s^－1, 在有氧条件下, C₁₂H₁₀O-OH可转化为C₁₂H₁₀O-OHO₂, 衰减的速率常数为(6.6±0.4)×10⁶ s^－1. N₂条件下最终产物为苯酚、2-羟基二苯醚、4-羟基二苯醚、4-硝基二苯醚.

Reaction Mechanism of Diphenyl Ether with Nitrous Acid by Transient Absorption Spectrum Technique

The microscopic reaction mechanism of diphenyl ether with nitrous acid in the presence or absence of O₂ was studied by laser flash photolysis. The main characteristic peaks in these transient absorption spectra were attributed and the decay trends were investigated. The final photolysis products were analyzed by using GC-MS method. OH radical obtained by nitrous acid exposed to 355 nm laser beam reacts with diphenyl ether to produce C₁₂H₁₀O-OH adduct. In the absence of O₂ the decay constant of C₁₂H₁₀O-OH adduct was measured to be (1.86±0.14)×10⁵ s^－1 and the final photolysis products were phenol, o-hydroxydiphenyl ether, p-hydroxydiphenyl ether and p-nitrodiphenyl ether. While in the presence of O₂ the decay constant of C₁₂H₁₀O-OH adduct was measured to be (6.6±0.4)×10⁶ s^－1.