Islam Md Akhtarul, Chowdhury Myisha Ahmed, Mozumder Md Salatul Islam, Uddin Md Tamez
Center for Environmental Process Engineering, Department of Chemical Engineering and Polymer Science, Shahjalal University of Science and Technology (SUST), Sylhet 3114, Bangladesh.
ACS Omega. 2021 May 26;6(22):14481-14492. doi: 10.1021/acsomega.1c01449. eCollection 2021 Jun 8.
Adsorption kinetic equation has been derived assuming that the process follows the behavior of a heterogeneous chemical reaction at the solid-liquid interface. This equation is converted into the Langmuir isotherm at equilibrium and describes well the unsteady-state adsorption process. Based on that, a working equation has been developed, which gives adsorption-rate-constant independent of operating parameters including concentration. Also, a kinetic model expressed as a sum of first- and second-order systems available in the literature has been applied (modified with the interface reaction concept) to determine the adsorption rate constant. Both methods gave similar results. Three dimensionless numbers have been developed to determine and distinguish pseudo-first-order and pseudo-second-order kinetics justified from the viewpoint of chemical kinetics. It is shown that curve-fitting with a high correlation coefficient could validate an empirical kinetic model, but the fitted model parameters could not automatically be related to chemical kinetic parameters if the model itself is not grounded on well-defined chemical kinetics. Finally, it is concluded that the currently applied empirical approach could not provide reliable data for comparison among similar systems, while the Langmuir kinetic equation developed based on the concept of heterogeneous reaction would be a good basis for standardization of the method for adsorption system characterization.
吸附动力学方程是在假设该过程遵循固液界面非均相化学反应行为的前提下推导出来的。该方程在平衡时可转化为朗缪尔等温线,并且能很好地描述非稳态吸附过程。在此基础上,开发了一个工作方程,该方程给出了与包括浓度在内的操作参数无关的吸附速率常数。此外,文献中可用的一阶和二阶系统之和表示的动力学模型(用界面反应概念进行了修正)已被用于确定吸附速率常数。两种方法得出了相似的结果。为了从化学动力学的角度确定和区分拟一级和拟二级动力学,已经开发了三个无量纲数。结果表明,具有高相关系数的曲线拟合可以验证经验动力学模型,但如果模型本身不是基于明确的化学动力学,则拟合的模型参数不能自动与化学动力学参数相关。最后得出结论,目前应用的经验方法不能为相似系统之间的比较提供可靠的数据,而基于非均相反应概念开发的朗缪尔动力学方程将是吸附系统表征方法标准化的良好基础。