Substituted naphthalene reaction rates with peroxy-acid treatment: prediction of reactivity using PEST

Persistent organic contaminants in the environment pose an environmental risk due to widespread occurrence and toxic properties. Advanced oxidation processes (AOPs) are treatment methods that have been used to successfully degrade organic contaminants in water, soil, sediments and sludge. Reaction rate constants (<i>k</i>) for peroxy acid treatment of 10 substituted naphthalene compounds were determined. The treatment method utilized acetic acid, hydrogen peroxide and a sulphuric acid catalyst to degrade the polyaromatic structures found in the compounds. Molecular structures of the selected compounds were derived at the B3LYP/6-31G* level of theory. Property-encoded surface translator (PEST) descriptors were calculated from B3LYP/6-31G* optimized structures and were found to have significant levels of correlation with <i>k</i>. Models using minimum local ionization potential (PIP.MIN) and a histogram [bin] of the gradient of the K electronic kinetic energy normal to the isosurface (DKN) were evaluated and found to agree within 10% of experimentally derived values of <i>k</i> in most instances. Results show that a combination of PEST descriptors could be used to predict reactivity by the peroxy-acid process. The PEST technology could prove to be a valuable asset for effective remediation design by predicting reaction outcomes for substituted naphthalene compounds and possibly other hydrophobic organic compounds (HOCs).环境中的持久性有机污染物因分布广泛且具有毒性特性，故而构成环境风险。高级氧化工艺（Advanced Oxidation Processes, AOPs）是一类已被成功用于降解水、土壤、沉积物及污泥中有机污染物的处理技术。本研究测定了10种取代萘类化合物经过氧酸处理的反应速率常数（*k*）。该处理方法采用乙酸、过氧化氢与硫酸催化剂，降解化合物中的多环芳烃结构。所选化合物的分子结构基于B3LYP/6-31G*理论水平进行推导。从B3LYP/6-31G*优化后的结构中计算得到属性编码表面翻译器（Property-encoded surface translator, PEST）描述符，且发现其与*k*具有显著相关性。评估了基于最小局域电离势（PIP.MIN）与垂直于等值面的K电子动能梯度直方图[箱数]（DKN）构建的模型，结果显示在多数情况下，模型预测值与实验测得的*k*值偏差不超过10%。研究结果表明，PEST描述符的组合可用于预测过氧酸工艺下的反应活性。PEST技术有望通过预测取代萘类乃至其他疏水性有机化合物（Hydrophobic Organic Compounds, HOCs）的反应结果，为高效修复设计提供极具价值的支撑。