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用于有机染料吸附的分数动力学策略:摆脱与伪一级和伪二级速率定律相关的困境

Fractional Kinetic Strategy toward the Adsorption of Organic Dyes: Finding a Way Out of the Dilemma Relating to Pseudo-First- and Pseudo-Second-Order Rate Laws.

作者信息

Tawfik Ashraf M, Eltabey Rania M

机构信息

Theoretical Physics Research Group, Physics Department, Faculty of Science, Mansoura University, 35516 Mansoura, Egypt.

Department of Chemistry, Faculty of Science, Mansoura University, 35516 Mansoura, Egypt.

出版信息

J Phys Chem A. 2024 Feb 15;128(6):1063-1073. doi: 10.1021/acs.jpca.3c07615. Epub 2024 Jan 31.

Abstract

Recently, there has been debate about using a pseudo-second-order model in adsorption kinetics and its ability to fit experimental data, especially at the initial stages. This paper introduces a generalized fractional kinetic model obtained via a fractional reaction-diffusion equation with a time-dependent reaction rate. This model is presented as a dependable approach to understanding chemical adsorption kinetics. It offers insights into the adsorbate history and extends classical kinetic models, such as pseudo-first-order and pseudo-second-order models. The generalized fractional kinetic model accounts for memory effects with long-range interactions, heterogeneity, and nonequilibrium dynamics, leading to more accurate predictions of adsorption rates, capacities, and equilibrium values. As an applied context, we use the fractional kinetic model to analyze experimental data on the adsorption of anionic acid yellow-17 and cationic brilliant green dyes in single and binary systems. The fractional kinetic model is employed to fit the data by incorporating waiting times into the adsorption process and correlating macroscopic properties, such as the pH, with adsorption dynamics.

摘要

最近,关于在吸附动力学中使用伪二级模型及其拟合实验数据的能力,尤其是在初始阶段,一直存在争论。本文介绍了一种通过具有时间依赖性反应速率的分数反应扩散方程获得的广义分数动力学模型。该模型被提出作为理解化学吸附动力学的可靠方法。它提供了对吸附质历史的见解,并扩展了经典动力学模型,如伪一级和伪二级模型。广义分数动力学模型考虑了具有长程相互作用、非均质性和非平衡动力学的记忆效应,从而能够更准确地预测吸附速率、容量和平衡值。作为一个应用实例,我们使用分数动力学模型来分析单体系和双体系中阴离子酸性黄-17和阳离子亮绿染料吸附的实验数据。分数动力学模型通过将等待时间纳入吸附过程并将宏观性质(如pH值)与吸附动力学相关联来拟合数据。

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