QSAR study on the removal efficiency of organic pollutants in supercritical water based on degradation temperature.

Abstract

This paper aims to study temperature-dependent quantitative structure activity relationship (QSAR) models of supercritical water oxidation (SCWO) process which were developed based on Arrhenius equation between oxidation reaction rate and temperature. Through exploring SCWO process, each kinetic rate constant was studied for 21 organic substances, including azo dyes, heterocyclic compounds and ionic compounds. We propose the concept of T_R95, which is defined as the temperature at removal ratio of 95%, it is a key indicator to evaluate compounds' complete oxidation. By using Gaussian 09 and Material Studio 7.0, quantum chemical parameters were conducted for each organic compound. The optimum model is T_R95 = 654.775 + 1761.910f(+)_n - 177.211qH with squared regression coefficient R² = 0.620 and standard error SE = 35.1. Nearly all the compounds could obtain accurate predictions of their degradation rate. Effective QSAR model exactly reveals three determinant factors, which are directly related to degradation rules. Specifically, the lowest f(+) value of main-chain atoms (f(+)_n) indicates the degree of affinity for nucleophilic attack. qH shows the ease or complexity of valence-bond breakage of organic molecules. BO_x refers to the stability of a bond. Coincidentally, the degradation mechanism could reasonably be illustrated from each perspective, providing a deeper insight of universal and propagable oxidation rules. Besides, the satisfactory results of internal and external validations suggest the stability, reliability and predictive ability of optimum model.