摘要
利用瞬态吸收光谱技术进行了有氧、无氧条件下氯苯与亚硝酸水溶液的交叉反应机理研究,初步考察了这些瞬态物种的生长与衰减等行为,并对其光解产物进行了GC/MS分析.研究表明,HNO2在355nm紫外光的照射下可产生·OH自由基,·OH和氯苯反应生成C6H5Cl···OH,反应速率常数为(6.6～7.0)×109L·mol-1·s-1;在有氧条件下C6H5Cl···OH可氧化为C6H5Cl···OHO2,反应速率常数为(1.6±0.2)×109L·mol-1·s-1,然后进一步分解;C6H5Cl···OH衰减或与亚硝酸等作用可形成多种含硝基的化合物或醌类物质.
The reaction microscopic mecbunism of aqueous solution of chlorobenzene with nitrous acid in-the presence of O-2 and absence of O-2 was studied by laser flash photolysis. The main characteristic peaks in these transient absorbance spectra were attributed and the build-up/decay trends of several transient species were investigated. center dot OH radical can be produced in aqueous solution of nitrous acid exposed to 355nm laser beam. The rate constant of the reaction between center dot OH radical and chlorobenzene was measured to be (6.6-7.0)x10(9) L . mol(-1) . s(-1). The transient product C6H5Cl-OH reacted with O-2 to form C6H5Cl-OHO2 with a rate constant of (1.6 +/- 0.2) x10(9) L . mol(-1) . s(-1). The photolysis products were analyzed by GUMS method and the possible reaction pathways were discussed.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2005年第4期367-371,共5页
Acta Physico-Chimica Sinica
基金
国家自然科学基金(29777003)
上海市科技发展基金(022312116)资助项目~~
关键词
激光闪光光解
氯苯
HNO2
瞬态吸收光谱
·OH自由基
laser flash photolysis
chlorobenzene
nitrous acid
transient absorption spectra
center dot OH radical
