Improved understanding of bimolecular reactions in deceptively simple homogeneous media: From laboratory experiments to Lagrangian quantification

摘要

Medium heterogeneity affects reaction kinetics by controlling the mixing of reactant particles, but the linkage between medium properties and reaction kinetics is difficult to build, even for simple, relatively homogeneous media. This study aims to explore the dynamics of bimolecular reactions, aniline + 1,2-naphthoquinone-4-sulfonic acid → 1,2-naphthoquinone-4-aminobenzene, in relatively homogeneous flow cells. Laboratory experiments were conducted to monitor the transport of both conservative and reactive tracers through columns packed with silica sand of specific diameters. The measured tracer breakthrough curves exhibit subdiffusive behavior with a late-time tail becoming more pronounced with decreasing sand size, probably due to the segregated flow regions formed more easily in columns packed with smaller size sand. Numerical analysis using a novel Lagrangian model shows that subdiffusion has a twofold effect on bimolecular reactions. While subdiffusion enhances the power-law growth rate of product mass by prolonging the exposure of reactant particles in the depletion zone, the global reaction rate is constrained because subdiffusion constrains the mobility of reactant particles. Reactive kinetics in deceptively simple homogeneous media is therefore controlled by subdiffusion, which is sensitive to the dimensions of packed sand.