This work focused on estimating the rate constants for three ozone-based processes applied in the degradation of diclofenac. The ozonation (Oz) and its intensification with catalysis (COz) and photocatalysis (PCOz) were studied. Three mathematical models were evaluated with a genetic algorithm (GA) to find the optimal values for the kinetics constants. The Theil inequality coefficient (TIC) worked as a criterion to assess the models’ deviation. The diclofenac consumption followed a slow kinetic regime according to the Hatta number ($Ha<0.3$). However, it strongly contrasted with earlier studies. The obtained values for the volumetric rate of photon absorption (VRPA) corresponding to the PCOz process ($1.75\times {10}^{-6}$ & $6.54\times {10}^{-7} \mathrm{E}\mathrm{i}\mathrm{n}\mathrm{s}\mathrm{t}\mathrm{e}\mathrm{i}\mathrm{n} {\mathrm{L}}^{-1} \mathrm{m}\mathrm{i}{\mathrm{n}}^{-1}$) were significantly distant from the maximum ($2.59\times {10}^{-5} \mathrm{E}\mathrm{i}\mathrm{n}\mathrm{s}\mathrm{t}\mathrm{e}\mathrm{i}\mathrm{n} {\mathrm{L}}^{-1} \mathrm{m}\mathrm{i}{\mathrm{n}}^{-1}$). The computed profiles of chemical species proved that no significant amount of hydroxyl radicals was produced in the Oz, whereas the PCOz achieved the highest production rate. According to this, titanium dioxide significantly contributed to ozone decomposition, especially at low ozone doses. Although the models’ prediction described a good agreement with the experimental data ($\mathrm{T}\mathrm{I}\mathrm{C}<0.3$), the optimization algorithm was likely to have masked the rate constants as they had highly deviated from already reported values.

中文翻译：

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用于臭氧化过程强化的双氯芬酸降解动力学的机理模型和优化

这项工作的重点是估计用于降解双氯芬酸的三种基于臭氧的过程的速率常数。研究了臭氧化 (Oz) 及其通过催化 (COz) 和光催化 (PCOz) 的强化。使用遗传算法 (GA) 评估三个数学模型以找到动力学常数的最佳值。Theil 不等式系数 (TIC) 用作评估模型偏差的标准。根据哈达数（Hatta number），双氯芬酸的消耗遵循缓慢的动力学规律（$H\mathrm{一种}<0.3$）。然而，它与早期的研究形成鲜明对比。获得的对应于 PCOz 过程的体积光子吸收率 (VRPA) 值 ($1.75\times {10}^{-6}$ & $6.54\times {10}^{-7} \mathrm{乙}\mathrm{一世}\mathrm{n}\mathrm{秒}\mathrm{吨}\mathrm{电子}\mathrm{一世}\mathrm{n} {\mathrm{升}}^{-1} \mathrm{米}\mathrm{一世}{\mathrm{n}}^{-1}$) 与最大值 ($2.59\times {10}^{-5} \mathrm{乙}\mathrm{一世}\mathrm{n}\mathrm{秒}\mathrm{吨}\mathrm{电子}\mathrm{一世}\mathrm{n} {\mathrm{升}}^{-1} \mathrm{米}\mathrm{一世}{\mathrm{n}}^{-1}$）。化学物质的计算曲线证明，Oz 中没有产生大量的羟基自由基，而 PCOz 的产生率最高。据此，二氧化钛显着促进了臭氧分解，尤其是在低臭氧剂量下。尽管模型的预测描述了与实验数据的良好一致性（$\mathrm{吨}\mathrm{一世}\mathrm{C}<0.3$)，优化算法很可能掩盖了速率常数，因为它们与已经报告的值有很大的偏差。