Investigations of reactions of selected azaarenes with radicals in water. 1. Hydroxyl and sulfate radicals

被引:21
作者
Beitz, T [1 ]
Bechmann, R [1 ]
Mitzner, R [1 ]
机构
[1] Univ Potsdam, Inst Phys Chem & Theoret Chem, Potsdam, Germany
关键词
D O I
10.1021/jp980654i
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The oxidative degradation of binuclear azaarenes is studied in a number of environmentally relevant radical reactions. The comparison between oxidation mechanisms of hydroxyl and sulfate radicals, as well as between dark and photoreactions, is done. Most of the products formed are identified. With the change from dark to photoreactions of quinoline and isoquinoline, a shift of the oxidation center from the benzene to the pyridine rings is observed. The reaction behavior of the benzodiazines can be derived from the reaction patterns of quinoline and isoquinoline. The rate constants of second order are determined for the reactions of the azaarenes with carbonate radicals. The rate constants and the differences in the products formed conformably prove the importance of the inclusion of excited states in the reaction mechanism. The application of the frontier orbital concept allows an easy interpretation. Electron transfer reactions resulting in radical oxygen species are shown to be product determining in direct photolysis, too.
引用
收藏
页码:6760 / 6765
页数:6
相关论文
共 22 条
[1]  
BEITZ T, 1996, PHOTOCHEMISCHE REAKT
[2]   Probing the TiO2 photocatalytic mechanisms in water purification by use of quinoline, photo-fenton generated OH. radicals and superoxide dismutase [J].
Cermenati, L ;
Pichat, P ;
Guillard, C ;
Albini, A .
JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (14) :2650-2658
[3]   BEHAVIOR OF CO3-RADICALS GENERATED IN FLASH-PHOTOLYSIS OF CARBONATOAMINE COMPLEXES OF COBALT(III) IN AQUEOUS-SOLUTION [J].
CHEN, S ;
COPE, VW ;
HOFFMAN, MZ .
JOURNAL OF PHYSICAL CHEMISTRY, 1973, 77 (09) :1111-1116
[4]   REACTIVITY OF CARBONATE RADICAL TOWARD AROMATIC-COMPOUNDS IN AQUEOUS-SOLUTION [J].
CHEN, SN ;
HOFFMAN, MZ ;
PARSONS, GH .
JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (18) :1911-1912
[5]  
FAUST BC, 1994, AQUATIC AND SURFACE PHOTOCHEMISTRY, P3
[6]  
FAUST BC, 1994, ENVIRON SCI TECHNOL, V28, pA217, DOI 10.1021/es00054a712
[7]   PHOTOCHEMISTRY OF AQUEOUS IRON(III) POLYCARBOXYLATE COMPLEXES - ROLES IN THE CHEMISTRY OF ATMOSPHERIC AND SURFACE WATERS [J].
FAUST, BC ;
ZEPP, RG .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1993, 27 (12) :2517-2522
[8]  
Grimmer G., 1983, Environmental Carcinogens: Polycyclic Aromatic Hydrocarbons
[9]   Laboratory studies of atmospheric aqueous-phase free-radical chemistry: Kinetic and spectroscopic studies of reactions of NO3 and SO4- radicals with aromatic compounds [J].
Herrmann, H ;
Exner, M ;
Jacobi, HW ;
Raabe, G ;
Reese, A ;
Zellner, R .
FARADAY DISCUSSIONS, 1995, 100 :129-153
[10]   PHOTOREACTIVITY OF HUMIC ACIDS IN NATURAL-WATERS [J].
HERRMANN, M ;
KOTZIAS, D ;
KORTE, F .
CHEMOSPHERE, 1987, 16 (2-3) :523-525