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苯酚的O3/H2O2化学氧化反应动力学研究

     

摘要

应用 Stopped-flow 光谱仪研究苯酚在288~308K和 pH=3.2~9.8 的O3/H2O2 氧化反应动力学。通过实验及分析认为:在不同酸度的实验条件下苯酚 O3/H2O2 氧化降解的途径及动力学不同。在酸性及弱酸性(pH=6.5) 下苯酚 O3/H2O2 氧化反应机理是苯酚直接为O3氧化,在碱性(pH=9.8)时为自由基机理。%The reaction kinetics of phenol chemical oxidation by the O3/H2O2 process was investigated in the pH values ranging from 3.2~9.8 at temperatures varying from 288 to 308 K utilizing the stopped-flow spectrophometer. The conclusion coming from experiments and analyses is that the pathways and the reaction kinetics of phenol peroxone oxidation are different in various acidity. The reaction mechanism is direct oxidation of phenol with ozone molecules in acidic (pH=3.2) and weak acidic (pH=6.5) conditions, the overall kinetics of the peroxone ozonation of phenol is 0.35 order with respect to the concentration of phenol and independent of the concentrations of the ozone and H2O2 at pH3.2, and the overall kinetics of the peroxone ozonation of phenol is 1.3 order with 0.3 order in the concentration of phenol and first order in the concentrations of the ozone and independent of the concentrations of H2O2 at pH6.5. The hydroxyl radical mechanism is dominating in alkaline solutions (pH=9.8), and the overall kinetics of the peroxone ozonation of phenol is 1.35 order with first order in the concentration of in the concentration of ozone and 0.35 order in the concentration of H2O2 and independent of the concentrations of phenol. The rate constant increases with temperature, and the activation energy of 17.2kJ/mol at pH3.2 was obtained

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