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利用355nm激光闪光光解技术研究了无氧和氧饱和两种条件下三丁基锡与亚硝酸水溶液的紫外光解反应.实验表明,·OH自由基攻击三丁基锡阳离子(SnBu3+)的正丁基生成SnBu3+·OH加合物,其二级生成速率常数为(1.05±0.07)×1010L·mol-1·s-1.SnBu3+·OH加合物在无氧时发生一级衰减,其衰减速率常数为(3.50±0.32)×105s-1;氧饱和时,SnBu3+·OH加合物衰减速率比无氧时要快很多,表明SnBu3+·OH加合物能迅速与O2发生反应,生成SnBu3+·OHO2加合物.根据实验结果和动力学推导得到其二级生成速率常数为(6.4±1.3)×108L·mol-1·s-1.
The photolysis of tributyltin with nitrous acid solution under both oxygen-free and oxygen-saturated conditions was studied by 355nm laser flash photolysis technique. The experimental results show that · OH radical attacks n-butyl group of SnBu3 + to generate SnBu3 + · OH adduct, the second order formation rate constant is (1.05 ± 0.07) × 1010L · mol-1 · s-1.SnBu3 + · OH adduct undergoes first order decay without oxygen and the decay rate constant is ( 3.50 ± 0.32) × 105s-1. At the time of oxygen saturation, the decay rate of SnBu3 + · OH adduct is much faster than that of anaerobic, indicating that SnBu3 + · OH adduct can react with O2 rapidly to form SnBu3 + · OHO2 adduct According to the experimental results and kinetics, the second order formation rate constant was (6.4 ± 1.3) × 108L · mol-1 · s-1.