Applying Linear Forms of Pseudo-Second-Order Kinetic Model for Feasibly Identifying Errors in the Initial Periods of Time-Dependent Adsorption Datasets

Abstract

Initial periods of adsorption kinetics play an important role in estimating the initial adsorption rate and rate constant of an adsorption process. Several adsorption processes rapidly occur, and the experimental data of adsorption kinetics under the initial periods can contain potential errors. The pseudo-second-order (PSO) kinetic model has been popularly applied in the field of adsorption. The use of the nonlinear optimization method to obtain the parameters of the PSO model can minimize error functions during modelling compared to the linear method. However, the nonlinear method has limitations in that it cannot directly recognize potential errors in the experimental points of time-dependent adsorption, especially under the initial periods. In this study, for the first time, the different linear types (Types 1–6) of the PSO model are applied to discover the error points under the initial periods. Results indicated that the fitting method using its linear equations (Types 2–5) is really helpful for identifying the error (doubtful) experimental points from the initial periods of adsorption kinetics. The imprecise points lead to low adjusted R2 (adj-R2), high reduced χ2 (red-χ2), and high Bayesian information criterion (BIC) values. After removing these points, the experimental data were adequately fitted with the PSO model. Statistical analyses demonstrated that the nonlinear method must be used for modelling the PSO model because its red-χ2 and BIC were lower than the linear method. Type 1 has been extensively applied in the literature because of its very high adj-R2 value (0.9999) and its excellent fitting to experimental points. However, its application should be limited because the potential errors from experimental points are not identified by this type. For comparison, the other kinetic models (i.e., pseudo-first-order, pseudo-nth-order, Avrami, and Elovich) are applied. The modelling result using the nonlinear forms of these models indicated that the fault experimental points from the initial periods were not detected in this study.