Advanced oxidation processes (AOPs) based on formation of free radicals at ambient temperature and pressure are effective for treating endocrine disrupting chemicals (EDCs) in waters. In this study, we systematically investigated the degradation kinetics of bisphenol A (BPA), a representative EDC by hydroxyl radical (OH) with a combination of experimental and theoretical approaches. The second–order rate constant (k) of BPA with OH was experimentally determined to be 7.2 ± 0.34 × 10⁹ M⁻¹ s⁻¹ at pH 7.55. We also calculated the thermodynamic and kinetic behaviors for the bimolecular reactions by density functional theory (DFT) using the M05–2X method with 6–311++G** basis set and solvation model based on density (SMD). The results revealed that H–abstraction on the phenol group is the most favorable pathway for OH. The theoretical k value corrected by the Collins–Kimball approach was determined to be 1.03 × 10¹⁰ M⁻¹ s⁻¹, which is in reasonable agreement with the experimental observation. These results are of fundamental and practical importance in understanding the chemical interactions between OH and BPA, and aid further AOPs design in treating EDCs during wastewater treatment processes.

基于在环境温度和压力下自由基形成的高级氧化工艺（AOP）可有效治疗水中的内分泌干扰化学物质（EDC）。在这项研究中，我们结合实验和理论方法，系统地研究了双酚A（BPA）的降解动力学，该双酚A是具有代表性的羟基自由基（OH）。通过实验确定BPA与OH的二阶速率常数（k）为7.2±0.34×10 ⁹  M ^-1  s ^-1在pH 7.55下。我们还根据密度泛函理论（DFT），使用具有6–311 ++ G **基集的M05–2X方法和基于密度的溶剂化模型（SMD），通过密度泛函理论（DFT）计算了双分子反应的热力学和动力学行为。结果表明，苯酚基团上的H吸收是OH最有利的途径。经柯林斯–金伯尔法校正的理论k值确定为1.03×10 ¹⁰  M ^-1  s ^-1，与实验观察值合理地吻合。这些结果对于理解OH和BPA之间的化学相互作用具有重要的现实意义，并有助于进一步设计AOP设计废水处理过程中的EDC。