Wang Hongfei, Zhao Lingxi, Hou Wanguo
Key Laboratory of Colloid and Interface Chemistry (Ministry of Education), Shandong University, Jinan 250100, P. R. China.
Qilu University of Technology (Shandong Academy of Sciences), Shandong Analysis and Test Center, Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Jinan 250014, P. R. China.
Langmuir. 2024 Feb 6. doi: 10.1021/acs.langmuir.3c03235.
The sorbent concentration () effect and sorbate initial concentration () effect are common phenomena observed in the study of adsorption kinetics at solid-liquid interfaces. That is, adsorption rate constants simulated with classical kinetic equations, such as the pseudo-second-order (PSO) model, for a given system vary with and . The classical kinetic equations cannot predict or describe the "-effect" and "-effect" (called "-effects" here). In the current work, the dynamic partition coefficient of sorbate between solid and liquid phases () was used to describe the adsorption kinetic processes. Based on the surface component activity (SCA) model, which assumes the activity coefficients of the surface components () are not equal to unity but rather a function of and the adsorption capacity (or ) and referring to the classical PSO model, a new kinetic equation was established, called the "SCA-PSO kinetic model", and its two parameters, the intrinsic equilibrium partition coefficient () and the intrinsic rate constant (), are independent of and . In addition, the new model relates and the rate constant () to and via , and can thus describe the -effects. The can be estimated from the change of equilibrium partition coefficient () with and . The new model predicts that with the increase of and , decreases while increases. Its rationality was confirmed by the literature-reported adsorption kinetic data of heavy metals on inorganic and biomass sorbents with the -effects.
吸附剂浓度()效应和吸附质初始浓度()效应是在固液界面吸附动力学研究中观察到的常见现象。也就是说,对于给定体系,用经典动力学方程(如伪二级(PSO)模型)模拟的吸附速率常数会随和变化。经典动力学方程无法预测或描述“-效应”和“-效应”(此处称为“-效应”)。在当前工作中,用吸附质在固液相间的动态分配系数()来描述吸附动力学过程。基于表面组分活度(SCA)模型,该模型假定表面组分的活度系数()不等于1,而是和吸附容量(或)的函数,并参照经典PSO模型,建立了一个新的动力学方程,称为“SCA - PSO动力学模型”,其两个参数,即本征平衡分配系数()和本征速率常数()与和无关。此外,新模型通过将和速率常数()与和联系起来,因此可以描述-效应。可以根据平衡分配系数()随的变化来估算。新模型预测,随着和的增加,减小而增加。文献报道的具有-效应的重金属在无机和生物质吸附剂上的吸附动力学数据证实了其合理性。