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The Decomposition Kinetics of Monocrotophos in Aqueous Solutions by the Hydrogen Peroxide--Ozone Process

机译:久效磷在水溶液中的过氧化氢-臭氧分解动力学

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Decomposition of monocrotophos in an aqueous solution by the hydrogen peroxide--ozone (H2O2--O3) process was studied under various solution pHs and H2O2--O3 molar ratios. Experimental results indicated that monocrotophos could be almost completely (>95) decomposed by the H2O2--O3 process within 20 minutes. Formation of carbon dioxide was observed, followed by the formation of nitrate and phosphate. A simplified kinetic model, consisting of three two-step consecutive reactions based on elemental mass balances, was found to accurately describe the temporal behaviors of reacting species during the decomposition of monocrotophos in aqueous solution by the H2O2--O3 process. In most experiments, acidic conditions favored the disappearance of monocrotophos, possibly because of breakage of the carbon--carbon double bond to form various organic intermediates, but mineralization of organic intermediates by free radical hydroxyl (OH.) attack was more favored in alkaline conditions. The decomposition of monocrotophos by the H2O2--O3 process was found to be significantly affected by the mode of H2O2 addition. For the batch mode of H2O2 addition, increased H2O2, dose reduced the decomposition rate, possibly because large amounts of H2O2 added initially served as a scavenger for OH. free radicals. For the continuous mode of H2O2 addition, increased H2O2 dose accelerated reaction rates of monocrotophos until an optimum H2O2--O3 molar ratio was reached, which was found to vary for different solution pHs.
机译:在各种溶液pH值和H2-O2--O3摩尔比下,研究了久效磷在水溶液中通过过氧化氢-臭氧(H2O2--O3)分解的过程。实验结果表明久效磷在20分钟内几乎可以被H2O2--O3分解(> 95)。观察到二氧化碳的形成,随后形成硝酸盐和磷酸盐。发现简化的动力学模型由基于元素质量平衡的三个两步连续反应组成,可以精确地描述久效磷在水溶液中通过H2O2--O3分解过程中反应物种的时间行为。在大多数实验中,酸性条件有利于久效磷的消失,这可能是因为碳-碳双键的断裂形成了各种有机中间体,但是在碱性条件下更倾向于通过自由基羟基(OH。)攻击使有机中间体矿化。发现久效磷通过H2O2--O3过程的分解受H2O2添加方式的影响很大。对于H2O2的分批添加方式,增加的H2O2剂量会降低分解速率,这可能是因为最初添加的大量H2O2可以用作OH的清除剂。自由基。对于连续添加H2O2的方式,增加H2O2剂量可加速久效磷的反应速率,直到达到最佳H2O2--O3摩尔比为止,发现该摩尔比随溶液pH的不同而变化。

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