Reduction of HOCl to Cl⁻ by in-situ electrochemical synthesis or ex-situ addition of H₂O₂ is a feasible method to minimize Cl-DBPs and ClO_x⁻ (x = 2, 3, and 4) formation in electrochemical oxidative water treatment systems. This work has investigated the kinetics and mechanism of the reaction between H₂O₂ and HOCl. The kinetics study showed the species-specific second order rate constants for HOCl with H₂O₂ (k₁), HOCl with HO₂⁻ (k₂) and OCl⁻ with H₂O₂ (k₃) are 195.5 ± 3.3 M⁻¹s⁻¹, 4.0 × 10⁷ M⁻¹s⁻¹ and 3.5 × 10³ M⁻¹s⁻¹, respectively. The density functional theory calculation showed k₂ is the most advantageous thermodynamically pathway because it does not need to overcome a high energy barrier. The yields of ¹O₂ generation from the reaction of H₂O₂ with HOCl were reinvestigated by using furfuryl alcohol (FFA) as a probe, and an average of 92.3% of ¹O₂ yields was obtained at pH 7–12. The second order rate constants of the reaction of ¹O₂ with 13 phenolates were determined by using the H₂O₂/HOCl system as a quantitative ¹O₂ production source. To establish a quantitative structure activity relationship, quantum chemical descriptors were more satisfactory than empirical Hammett constants. The potential implications in electrochemical oxidative water treatment were discussed at the end.

通过原位电化学合成或异位添加 H ₂ O ₂将 HOCl 还原为 Cl ^{-是减少电化学氧化水中 Cl-DBP 和 ClO} _x ^- (x = 2、3 和 4) 形成的可行方法治疗系统。本工作研究了H ₂ O ₂与HOCl 反应的动力学和机理。_{动力学研究表明 HOCl 与 H 2} O ₂ (k ₁ )、HOCl 与 HO ₂ ^- (k ₂ ) 和 OCl ^-与 H ₂ O ₂ (k )的物种特异性二级速率常数₃ )分别为195.5 ± 3.3 M ^-1 s ^-1、4.0 × 10 ⁷ M ^-1 s ^-1和3.5 × 10 ³ M ^-1 s ^-1。密度泛函理论计算表明，k ₂是最有利的热力学途径，因为它不需要克服高能垒。以糠醇（FFA）为探针，重新研究了H ₂ O _{2与HOCl反应生成}¹ O ₂的产率，平均¹ O _{2产率为92.3%。}在 pH 7-12 下获得产率。¹ O ₂与13 种酚盐反应的二级速率常数是通过使用H ₂ O ₂ /HOCl 体系作为定量¹ O ₂生产源来确定的。为了建立定量的结构活性关系，量子化学描述符比经验哈米特常数更令人满意。最后讨论了电化学氧化水处理的潜在影响。