Proposal and application of a novel isothermal model for the thermodynamic study of ion exchange reactions

Abstract

Ion exchange is a separation and purification technique widely employed in chemistry, environment and metallurgy. Commonly, the isotherm models used for thermodynamic study are the Langmuir model and the Freundlich model. However, these two models are initially used to study the adsorption of gas molecules onto solids, and there are some limitations if they are applied to ion exchange reactions. In this paper, a novel isotherm model (NIM) for ion exchange reactions was derived based on the process of ion exchange, the principle of electroneutrality and the law of conservation of mass. The NIM was utilized to study the reactions of anions (F-, WO42-, MoO42-, PO43-, AsO43-, MoS2O22-, MoS42-) with chloride-form strongly basic anion exchange resins. Moreover, the reactions of cations (K+, Ca2+) with sodium-form cation exchange resins were also explored. The results indicated that the calculation data based on the NIM matched up well with the experiments, even though the ions have various valences and different affinities for the resin, which proved the reliability of the model. In addition, the compatibility of the NIM with the Langmuir and Freundlich models was theoretically analyzed, and the conclusions were also verified by the experimental data. By contrast, the physical meaning of the parameters involved in the NIM was clear and had a good generality, which can be applicable to various situations of ion exchange reactions. Therefore, the NIM proposed in this work can effectively obtain the thermodynamic parameters of ion exchange reactions, and is expected to provide theoretical basis for the design, optimization and control of ion exchange processes.