Characterization of reaction kinetics in a porous electrode

A continuum-model approach, analogous to porous electrode theory, was applied to a thin-layer cell of rectangular and cylindrical geometry. A reversible redox couple is assumed, and the local reaction current density is related to the potential through the formula of Hubbard and Anson for a uniformily accessible thin-layer cell. The placement of the reference electrode is also accounted for in the analysis. Primary emphasis is placed on the effect of the solution-phase ohmic potential drop on the voltammogram characteristics. Correlation equations for the peak-potential displacement from E(sup 0 prime) and the peak current are presented in terms of two dimensionless parameters

Effect of Ohmic, Mass-Transfer, and Kinetic Resistances on Linear-Sweep Voltammetry in a Cylindrical-Pore Electrode

Extracting quantitative kinetic information from linear-sweep voltammograms (LSV) on porous electrodes is more difficult than on planar electrodes since the electrode surface is not uniformly accessible to the bulk supply of reactant or the counterelectrode. We present here a means to account for the effect of ohmic, mass-transfer, and kinetic resistances on LSV by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne– \u3c=\u3e R where both O and R are soluble species. Both analytical and numerical techniques are used to solve the governing equations. The calculated peak currents and potentials are correlated by simple-to-apply empirical formulas to the measurable parameters: sweep rate, concentration of the redox species, diffusion coefficient, conductivity of the electrolyte, and pore dimensions. Using the correlations, a methodology is established for determining if the redox reaction kinetics are irreversible or reversible (Nernstian). If the reaction is irreversible, it is shown how the standard rate constant and the transfer coefficient may be extracted from linear-sweep voltammetry data, or if the reaction is reversible, how the number of electrons transferred may be deduced

Self-Assembled Silica Nano-Composite Polymer Electrolytes: Synthesis, Rheology & Electrochemistry

The ultimate objectives of this research are to understand the principles underpinning nano-composite polymer electrolytes (CPEs) and facilitate development of novel CPEs that are low-cost, have high conductivities, large Li+ transference numbers, improved electrolyte-electrode interfacial stability, yield long cycle life, exhibit mechanical stability and are easily processable. Our approach is to use nanoparticulate silica fillers to formulate novel composite electrolytes consisting of surface-modified fumed silica nano-particles in polyethylene oxides (PEO) in the presence of lithium salts. We intend to design single-ion conducting silica nanoparticles which provide CPEs with high Li+ transference numbers. We also will develop low-Mw (molecular weight), high-Mw and crosslinked PEO electrolytes with tunable properties in terms of conductivity, transference number, interfacial stability, processability and mechanical strengt

MASS TRANSFER CONTROLLED REACTIONS IN PACKED BEDS AT LOW REYNOLDS NUMBERS

The a priori prediction and correlation of mass-transfer rates in transport limited, packed-bed reactors at low Reynolds numbers is examined. The solutions to the governing equations for a flow-through porous electrode reactor indicate that these devices must operate at a low space velocity to suppress a large ohmic potential drop. Packed-bed data for the mass-transfer rate at such low Reynolds numbers were examined and found to be sparse, especially in liquid systems. Prior models to simulate the solid-void structure in a bed are reviewed. Here the bed was envisioned as an array of sinusoidal periodically constricted tubes (PCT). Use of this model has not appeared in the literature. The velocity field in such a tube should be a good approximation to the converging-diverging character of the velocity field in an actual bed. The creeping flow velocity profiles were calculated. These results were used in the convective-diffusion equation to find mass transfer rates at high Peclet number for both deep and shallow beds, for low Peclet numbers in a deep bed. All calculations assumed that the reactant concentration at the tube surface is zero. Mass-transfer data were experimentally taken in a transport controlled, flow-through porous electrode to test the theoretical calculations and to provide data resently unavailable for deeper beds. It was found that the sinusoidal PCT model could not fit the data of this work or that available in the literature. However, all data could be adequately described by a model which incorporates a channelingeffect. The bed was successfully modeled as an array of dual sized straight tubes