4.6 Article

Langmuir Adsorption Kinetics in Liquid Media: Interface Reaction Model

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ACS OMEGA
卷 6, 期 22, 页码 14481-14492

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AMER CHEMICAL SOC
DOI: 10.1021/acsomega.1c01449

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Adsorption kinetic equation was derived and converted to Langmuir isotherm, a working equation was developed, dimensionless numbers were used to distinguish kinetics, emphasizing the importance of well-defined chemical kinetics for accurate adsorption characterization.
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.

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