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J. E. Dykstra

Publications and source records attributed to J. E. Dykstra.

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A concise tutorial review of reverse osmosis and electrodialysis

Reverse osmosis (RO) and electrodialysis (ED) are the two most important membrane technologies for water desalination and treatment. Their modes of operation and transport mechanisms are very different, but on a closer look also have many similarities. In this concise version of our tutorial review, we describe state-of-the-art theory for both processes, focusing on simple examples that are helpful for the non-specialist and useful for classroom teaching. Both processes are described by solution-friction (SF) theory which combines ion and water transport across membranes with chemical and mechanical equilibrium at membrane/solution interfaces. We present a derivation of SF theory based on force balances on water and ions and show how the various terms, convection, diffusion, and electromigration, are derived, and how solute partitioning is implemented. Finally, we demonstrate how SF theory accurately describes the osmosis experiment where water and ions are transported in opposite directions across a membrane.

physics.chem-ph

The difference between Faradaic and non-Faradaic electrode processes

Both Faradaic and non-Faradaic processes can take place at an electrode. The difference between the two processes is clearly discussed in several classical sources, starting with Grahame (1952). However, later reference to charge transfer across the metal-solution interface as a defining feature of a Faradaic process, has led to ambiguities. Following Grahame, in a Faradaic process, charged particles transfer across the electrode, from one bulk phase to another. Thus, in a Faradaic process, after applying a constant current, the electrode charge, voltage and composition go to constant values. Instead, in a non-Faradaic (capacitive) process, charge is progressively stored. We characterize the intercalation material nickel hexacyanoferrate by two electrochemical methods and compare with theory. Data for the capacitance of this material is well described by the extended Frumkin isotherm. This data, and the correspondence with theory, demonstrates that this is a capacitive material and ion and charge storage in this material a non-Faradaic electrode process. Cyclic Voltammetry (CV) diagrams for this material have broad peaks for certain potential windows, and rectangular shapes for other conditions, both experimentally and in theoretical calculations based on a RC network model that includes how capacitance is a function of charge. Measured and predicted CV diagrams are in perfect agreement with one another. This shows that (broad) peaks in CV diagrams do not establish whether an electrode material is Faradaic or not.

physics.chem-ph

Theory of Ion and Electron Transport Coupled with Biochemical Conversions in an Electroactive Biofilm

Bioelectrochemical systems are electrochemical cells that rely on conductive biofilms covering an electrode. We consider the example of a microbial fuel cell, and we derive a dynamic model of ion transport, biochemical reactions and electron transport inside such a biofilm. After validating the model against data, we evaluate model output to obtain an understanding of the transport of ions and electrons through a current-producing biofilm. For a system fed with a typical wastewater stream containing organic molecules and producing 5 A/m$^{2}$, our model predicts that transport of the organic molecules is not a limiting factor. However, the pH deep within the biofilm drops significantly, which can inhibit current production of such biofilms. Our results suggest that the electronic conductivity of the biofilm does not limit charge transport significantly, even for a biofilm as thick as 100 $μ\mathrm{m}$. Our study provides an example of how physics-based modelling helps to understand complex coupled processes in bioelectrochemical systems.

physics.chem-ph