Dynamics of light-induced excited state quenching of ferrioxalate complexes by peroxides. Fast kinetic events and interaction with toxic pollutants

被引:41
作者
Nadtochenko, V
Kiwi, J
机构
[1] Institute of Physical Chemistry II, Swiss Fed. Institute of Technology
[2] Institute of Physical Chemistry, Russian Academy of Sciences
关键词
adduct formation; fast kinetics; Fe oxalate; laser photolysis; (OH)-O-. radicals; peroxides; phenol; quenching of complexes;
D O I
10.1016/S1010-6030(96)04377-8
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 behaviour of the trioxaloferrate (Fe(ox)(3)(3-)) complex on laser illumination and its quenching in the presence of H2O2 were investigated by laser photolysis. At neutral Ph, a short (approximately 30 mu s) sind a longer (approximately 1 ms) lifetime were observed for transient Fe(ox)(3)(3-). The lifetime decreases as the pH becomes more acidic. In light-induced processes, the intensity of the light used is one of the determining reaction parameters and this effect is reported in detail. The excited states of the Fe oxalate complexes induced by laser photolysis are quenched by H2O2. The decay observed can be fitted in a simplified way by a bi-exponential function. The transient species Fe(ox)(3)(3-*) observed on laser photolysis does not undergo excited state annihilation, but ground state collisional quenching. The fast formation of a hydroxylated phenol adduct is shown by kinetic laser spectroscopy. A detailed account of the kinetics and spectral characteristics of the transients is presented for these reactions. This allows a scheme to be suggested for the intervention of these radicals in agreement with the experimental observations. The results obtained implicate the (OH)-O-. radical in the degradation of pollutants involving Fe complexes in the presence of H2O2.
引用
收藏
页码:145 / 153
页数:9
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