A study of the dependence of ferrocene diffusion on electrolyte concentration and size in a polymer medium using non-steady-state chronoamperometry

This article describes a quantitative study of the diffusion rate of ferrocene(Fc) dissolved in ploy(ethylene glycol)(PEG) medium containing MClO(4)(M = Li+, Na+, Bu(4)N(+), Hx(4)N(+)). The apparent diffusion coefficient D-app and the active concentration c(a) of Fc were simultaneously measured by using non-steady-state chronoamperometry. The D-app and c(a) of Fc have been estimated in PEG containing different concentrations and sizes of supporting electrolyte, and the dependence of D-app on ferrocene concentrations has been observed. The values of D-app decrease with increasing concentrations of Fc, increasing concentrations of LiClO4 or the ratio (O:Li) and also with 4 decreasing cation radius of the electrolyte. The temperature dependencies conform to a simple free volume model. The concentration and size of the counterion dependencies of the diffusion rate are similar to the behavior of their dependencies of ionic conductivity in polyelectrolyte.

THEORY OF STEADY-STATE CURRENT AT MULTIPLE MICROCYLINDER ELECTRODES COUPLED WITH A PARALLEL PLANAR ELECTRODE

A novel device of multiple cylinder microelectrodes coupled with a parallel planar electrode was proposed. The feedback diffusion current at this device was studied using bilinear transformation of coordinates in the diffusion space, where lines of mass flux and equiconcentration are represented by orthogonal circular functions. The derived expression for the steady-state current shows that as the gap between cylindrical microelectrodes and planar electrode diminishes, greatly enhanced currents can be obtained with high signal-to-noise ratio. Other important geometrical parameters such as distance between adjacent microcylinders, cylinder radius, and number of microcylinders were also discussed in detail.

STUDY ON MASS-TRANSPORT IN EASTMAN-AQ POLYMER FILM BY USING NON-STEADY-STATE CHRONOAMPEROMETRY AT AN ULTRAMICRODISK ELECTRODE

Non-steady-state chronoamperometry of ultramicroelectrodes is a powerful method for the study of mass transport in polymer films. This method has many advantages over the conventional methods at a macroelectrode and the steady state method at an ultramicroelectrode, which yield the most information. The apparent diffusion coefficient, D(app), and the concentration of reactant in the film, c(f), can be determined from a single experiment without knowing the thickness of the film. We studied the transport of several species such as Ru(NH3)63+, Ru(bpy)3(2+), NR and MV2+ in Eastman-AQ polymer film coated ultramicroelectrodes by using this method.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .3. THE CONDITION FOR QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS AT ULTRAMICRODISK ELECTRODES IN THE STEADY-STATE

The conditions for quasi-first and second order homogeneous catalytic reactions and their variation with each other at an ultramicrodisk electrode in the steady state are discussed in this paper. The order of reaction can be controlled by changing the dimension of the ultramicroelectrode: the second order reaction can be changed to quasi-first by decreasing the dimension of the ultramicroelectrode. An example of this is given. The main factor effect on the reaction order is the dimension of the ultramicroelectrode. The K4Fe(CN)6-aminopyrine system is selected to confirm the theory, the experiments showing that the system is a second order reaction at a 432 mum microelectrode, and a quasi-first order reaction at a 19 mum ultramicroelectrode. The kinetic constant of the system can be determined by applying the previous theory of homogeneous catalytic reaction.

THE APPLICATION OF AN ULTRAMICROELECTRODE IN HOMOGENEOUS CATALYTIC REACTION .1. GENERAL CHARACTERISTIC OF A HOMOGENEOUS CATALYTIC REACTION AT AN ULTRAMICROELECTRODE WITH ARBITRARY GEOMETRY UNDER STEADY-STATE

A general characteristic of the electrochemical process coupling with a homogeneous catalytic reaction at an ultramicroelectrode under steady state is described. It was found that the electrochemical process coupling with homogeneous catalytic reaction has a similar steady state voltammetric wave at an ultramicroelectrode with arbitrary geometry. A method of determination for the kinetic constant of homogeneous catalytic reaction at an ultramicroelectrode with arbitrary geometry is proposed.

A 3-min all-out test to determine peak oxygen uptake and the maximal steady state

Burnley, M., Doust, J., Vanhatalo, A., A 3-min all-out test to determine peak oxygen uptake and the maximal steady state, Medicine & Science in Sports & Exercise. 38(11):1995-2003, November 2006. RAE2008

Steady-state motion of a Mode-III crack on imperfect interfaces

Mishuris, Gennady; Movchan, N.V.; Movchan, A.B., (2006) 'Steady-state motion of a Mode-III crack on imperfect interfaces', Quarterly Journal of Mechanics and Applied Mathematics 59(4) pp.487-516 RAE2008

Speaker Normalization Using Cortical Strip Maps: A Neural Model for Steady State Vowel Identification

Auditory signals of speech are speaker-dependent, but representations of language meaning are speaker-independent. Such a transformation enables speech to be understood from different speakers. A neural model is presented that performs speaker normalization to generate a pitchindependent representation of speech sounds, while also preserving information about speaker identity. This speaker-invariant representation is categorized into unitized speech items, which input to sequential working memories whose distributed patterns can be categorized, or chunked, into syllable and word representations. The proposed model fits into an emerging model of auditory streaming and speech categorization. The auditory streaming and speaker normalization parts of the model both use multiple strip representations and asymmetric competitive circuits, thereby suggesting that these two circuits arose from similar neural designs. The normalized speech items are rapidly categorized and stably remembered by Adaptive Resonance Theory circuits. Simulations use synthesized steady-state vowels from the Peterson and Barney [J. Acoust. Soc. Am. 24, 175-184 (1952)] vowel database and achieve accuracy rates similar to those achieved by human listeners. These results are compared to behavioral data and other speaker normalization models.

The steady-state visual evoked potential in vision research: A review.

Periodic visual stimulation and analysis of the resulting steady-state visual evoked potentials were first introduced over 80 years ago as a means to study visual sensation and perception. From the first single-channel recording of responses to modulated light to the present use of sophisticated digital displays composed of complex visual stimuli and high-density recording arrays, steady-state methods have been applied in a broad range of scientific and applied settings.The purpose of this article is to describe the fundamental stimulation paradigms for steady-state visual evoked potentials and to illustrate these principles through research findings across a range of applications in vision science.

Fundamentals of steady state, non-Newtonian rimming flow

Rimming flow on the inner surface of a horizontal rotating cylinder is investigated. Using a scale analysis, a theoretical description is obtained for steady-state non-Newtonian flow. Simple lubrication theory is applied since the Reynolds number is small and the liquid film is thin. Since the Deborah number is very small the flow is viscometric. The shear-thinning number, which characterizes the shear-thinning effect, may be small or large. A general constitutive law for this kind of flow requires only a single function relating shear stress and shear rate that corresponds to a generalized Newtonian liquid. For this case the run-off condition for rimming flow is derived. Provided the run-off condition is satisfied, the existence of a continuous steady-state solution is proved. The rheological models, which show Newtonian behavior at low shear rates with transition to power-law shear thinning at moderate shear rates, are considered. Numerical results are carried out for the Carreau and Ellis models, which exhibit Newtonian behavior near the free surface and power-law behavior near the wall of the rotating cylinder.

On the importance of steady-state isotopic techniques for the investigation of the mechanism of the reverse water-gas-shift reaction

The formation and reactivity of surface intermediates in the reverse water-gas-shift reaction on a Pt/CeO2 catalyst are critically dependent on the reaction conditions so that conclusionsregarding the reaction mechanism cannot be inferred using ex operando conditions.