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The strongly implicit procedure is used to model the diffusion-only chronoamperometric responses of microband electrode geometries which deviate from the ideal. Specifically, attention is focused on four electrode shapes: elevated microband electrodes (with conducting supporting sides), recessed microband electrodes (with insulating pit walls), platform electrodes (with insulating supporting sides) and, for the purposes of comparison, a hypothetical line electrode without any support which permits diffusional mass transport to both sides of the infinitesimally thin electrode. In all cases the short time transient is found to be described by simple analytical expressions in which the contributions from linear diffusion over the electrode area(s) and non-linear diffusion to the electrode perimeters are clearly distinguishable. © 1995 Elsevier Science S.A. All rights reserved.

Analytical theory is presented which allows rigorous mass transport-corrected Tafel analysis for the reversible electrode processes (1) 2B ⇄ A2 + 2e− and (2) B2 ⇄ 2A + 2e− occurring at electrodes in flowing systems. Predictions are compared with the conclusions of numerical finite-difference modelling for both wall-jet and channel flow cell geometries. Exceillent agreement is found.

The hydroxide-driven dissolution of the polymer hydroxypropyl methylcellulose phthalate (HPMCP) in aqueous solution is studied using atomic force microscopy. The novel technique of employing the surface-averaged z-piezo voltage as a direct measure of the mean absolute surface height is described, so as, after appropriate calibration, to permit the ready inference of dissolution fluxes. In the case of interest the following dissolution rate law was established: j/g·cm-2·s-1 = 105.0[OH-] over the pH range 8.0−9.2, where j is the flux of the dissolving polymer and [OH-] is measured in mol cm-3.

A quantitative study of the hydrolytic dissolution of solid p-chloranil at alkaline pH using a combination of the channel flow cell and in situ atomic force microscopy measurements shows that the dissolution is driven by reaction of the substrate with hydroxide ions at, or very close to, the dissolving surface. The dissolution rate equation, deduced from the channel flow cell for single crystals of p-chloranil, is rate/mol cm-2 s-1 = 3.8 × 10-7[OH-]0 where [OH-]0/M is the hydroxide ion concentration adjacent to the solid surface. An analogous rate law is derived for pressed pellet substrates. The novel application of the atomic force microscope to make absolute measurements of surface averaged dissolution rates is described. Comparison with the independent channel flow cell data reveals good mechanistic agreement and consistency of rate constants provided it is recognised that a thick stagnant diffusion layer can be present under the usual conditions employed for AFM. © 1997 Elsevier Science S.A.

Microfluidic systems are developing in application and importance in many aspects of chemistry. This short review aims to provide a simple introduction to some of the concepts and instrumentation involved in this field. In particular, a number of systems for reactions, detections and analysis that have arisen from the research of our group are illustrated.

The application of power ultrasound in electrochemistry may promote or usefully modify electrode reactions. In the work reported here the four-electron reduction of nitrobenzene in alkaline (pH 13) aqueous media was studied as a model system. The electrochemical reduction is known to follow a complex mechanism [E. Laviron, A. Vallat and R. Meunier-Prest, J. Electroanal. Chem., 379 (1994) 427], involving protonations as well as a dehydration step; both surface and solution pathways for this reduction may be observed [C. Nishihara and H. Shindo, J. Electroanal. Chem., 221 (1987) 245], depending on the nature and state of the electrode. Both under silent and ultrasonic conditions nitrobenzene is reduced on glassy carbon electrodes in a chemically reversible one-electron process followed by an irreversible three-electron reduction. At sufficiently negative potentials the reduction process remains overall four-electron, with phenylhydroxylamine as the major product even at the high current densities obtained with intense ultrasound. Glassy carbon electrodes are shown to be suitable for kinetic studies, although damage, as endorsed by an increase in roughness and capacitance and probably initiated by mechanical damage at very short electrode–horn distances, was detected by a.c. impedance, voltammetric and atomic force microscopy (AFM) methods. On gold electrodes a more complicated mechanism due to a surface reaction pathway arises. A comparison of sonovoltammetric and rotating disk voltammetric results gives evidence for the homogeneous pathway being dominant under applied ultrasound conditions. The transition between surface and solution pathways is mass flux as well as concentration dependent, and an estimate for the rate of the surface catalyzed reaction for a concentration of 1.44 mM nitrobenzene (k = 4±2 × 10−2 cms−1), attributed to protonation of the nitrobenzene radical anion, is obtained from combined rotating disk and sonovoltammetric data. Damage to the gold surface as monitored by various techniques is small, but manifests itself by an interesting decrease in double layer capacitance.

The effect of power ultrasound in the modification of voltammetric processes is investigated and the role of surface activation by means of electrode erosion/roughening characterized. The potential benefits of sonovoltammetry are illustrated with two examples. First, the Fladè potential for the passivation of nickel in air-saturated aqueous KOH solution is shown to be anodically shifted in the presence of ultrasound. Second, the voltammetric study of Cr(CO)6 in acetonitrile solution is shown to be feasible without the passivation observed under silent conditions where the electrolysis results in surface-active species the adsorption of which block further electron transfer. © 1994 American Chemical Society.

A novel liquid flow cell allows atomic force microscopy (AFM) images to be obtained under defined hydrodynamic flow conditions, enabling reaction fluxes calculated from proposed heterogeneous reaction mechanisms to be compared with those determined experimentally. The cell employs an inclined jet to direct a fluid flow at the sample surface to cover the area under investigation including the AFM scanning cantilever tip. The flow pattern and velocity were calculated by using the finite element fluid dynamics program FIDAP and confirmed by placing an electrode at the sample position and measuring the limiting current for the one-electron oxidation of potassium hexacyanoferrate(II) in water as a function of flow rate. The operation of the cell has been further confirmed by the direct measurement of the dissolution rate of calcite exposed to a flow of 0.98 mM aqueous HCl by deducing the rate of removal of the surface from the change of the z-piezo voltage. The rate constant k1 = 0.035 cm s-1 obtained for the dissolution step was in excellent agreement with the value (0.043 ± 0.015) cm s-1 found from independent channel flow cell experiments. The dissolution of the (110) and (110) faces of salicylic acid (SA) single crystals in water and in solutions of salicylic acid was studied as a function of flow rate and was found to be consistent with a model combining a constant rate of dissolution with a simultaneous reprecipitation having a first-order dependence on [SA]0, with the flux J = kd - kp[SA]0 where the parameters are kd110 = 3 × 10-9 mol cm-2 s-1 and kp110 = 1.74 × 10-4 cm s-1 for the (110) face and kd110 = 1.5 × 10-8 mol cm-2 s-1 and kp110 = 1.06 × 10-3 cm s-1 for the (110) face.

A novel liquid flow cell is developed which allows atomic force microscopy images to be obtained under defined and modelled hydrodynamic flow conditions, enabling measured reaction fluxes to be compared with those calculated from proposed heterogeneous reaction mechanisms.

Increased transformer winding losses are an important consideration in determining the overall impact of harmonic currents in a power system. Frequently, losses due to harmonic currents are assumed to vary with the square of frequency. The purpose of this paper is to compare winding loss calculations from a finite element method with measured losses in single phase distribution transformers and to test the principle of superposition of harmonic losses due to nonsinusoidal currents. The results confirm both the finite element method and the principle of superposition. Furthermore, it is shown that, due primarily to inaccuracy in measuring 60 Hz eddy current losses, application of the commonly accepted frequency squared rule can yield overly pessimistic loss predictions for typical power system harmonic frequencies.