Double potential step chronoamperometry at microdisk electrodes: simulating the case of unequal diffusion coefficients

An efficient approach to the simulation of the double potential step chronoamperometry at a microdisk electrode based on an exponentially expanding time grid and conformal mapping of the space is presented. The dimensionless second potential step flux data are included as a function of the first potential step duration and the ratio of the diffusion coefficients of the reacting species allowing instant analysis of the experimental double potential step chronoamperograms without a need for simulation. The values of the diffusion coefficients are determined for several test systems and found to be in good agreement with existing literature data. (C) 2004 Elsevier B.V. All rights reserved.

Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

Nonisothermal moisture transport in hygroscopic building materials: modeling for the determination of moisture transport coefficients

A mathematical model for calculating the nonisothermal moisture transfer in building materials is presented in the article. The coupled heat and moisture transfer problem was modeled. Vapor content and temperature were chosen as principal driving potentials. The coupled equations were solved by an analytical method, which consists of applying the Laplace transform technique and the Transfer Function Method. A new experimental methodology for determining the temperature gradient coefficient for building materials was also proposed. Both the moisture diffusion coefficient and the temperature gradient coefficient for building material were experimentally evaluated. Using the measured moisture transport coefficients, the temperature and vapor content distribution inside building materials were predicted by the new model. The results were compared with experimental data. A good agreement was obtained.

Vortex shedding and drag in dilute Bose-Einstein condensates

Above a critical velocity, the dominant mechanism of energy transfer between a moving object and a dilute Bose-Einstein condensate is vortex formation. In this paper, we discuss the critical velocity for vortex formation and the link between vortex shedding and drag in both homogeneous and inhomogeneous condensates. We find that at supersonic velocities sound radiation also contributes significantly to the drag force.

Alternative method to evaluate discharge coefficients. Part 2: case study

The purpose of this article is to apply an alternative method whereby discharge coefficients can be estimated for the flow through a poppet valve at various lifts. Presented is the development of an operational quasi-steady flow rig. An engine cylinder head poppet valve was used as the case study. The requirement to directly measure mass flowrates using a standard conventional steady flow apparatus has been eliminated. Transient mass flowrates, pressures and temperatures of air during an inflow test for a poppet valve at various lifts were measured. Mass flowrates were also calculated from measured cylinder gas pressures and corrected for heat transfer. Using both methods to determine the mass flowrates, isentropic discharge coefficients were calculated and shown to compare within +/- 4.0 per cent of steady flow data. A computational fluid dynamics (CFD) validation of the quasi-steady flow rig is also presented.

GAS-PHASE REACTIONS AND RATE COEFFICIENTS FOR USE IN ASTROCHEMISTRY - THE UMIST RATEFILE

We present the rate coefficients of 2880 gas-phase reactions among 313 species involving 12 elements for use in astrochemical models. We describe the motivation behind this work and the caveats which attach to the data in general as well as to specific reactions. We give the permanent electric dipole moments of nearly all the 112 neutral molecules contained in the data set, so that rate coefficients can be calculated at the low temperatures of dark interstellar dust clouds. We have used the data to calculate the pseudo-time-dependent chemical evolution of a dark, dense interstellar cloud and present both early time and steady-state abundances for all 313 species.

High-performance liquid chromatographic determination of 17 beta-estradiol and 17 beta-estradiol-3-acetate solubilities and diffusion coefficients in silicone elastomeric intravaginal rings

A rapid, sensitive reversed-phase high-performance liquid chromatographic method has been developed for the determination of in vitro release of 17 beta-estradiol and its ester prodrug, 17 beta-estradiol-3-acetate, from silicone intravaginal rings. Partial hydrolysis of the acetate under the aqueous conditions provided by the 1% benzalkonium chloride release medium necessitates its conversion to 17 beta-estradiol prior to HPLC analysis. Both steroid peaks have been fully resolved from the benzalkonium chloride peaks by the reported chromatographic method,which employs a C-18 bonded reversed-phase column, an acetonitrile-water (50:50, v/v) mobile phase and a UV detection wavelength of 281 nm. The peak area versus 17 beta-estradiol concentration was found to be linear over the range of 0.0137-1347 mu g ml(-1) The HPLC method has also been used to determine the silicone solubilities and diffusion coefficients of the two related steroids. The almost 100-fold increase in 17 beta-estradiol-3-acetate release from the silicone core-type intravaginal rings compared to 17 beta-estradiol is shown to be due to a 60-fold increase in silicone solubility and a one and a half-fold increase in diffusitivity. The results demonstrate that an effective estrogen replacement therapy dose of 17 beta-estradiol may be administered from a silicone intravaginal reservoir device containing the labile 17 beta-estradiol-3-acetate prodrug. (C) 2000 Elsevier Science B.V. All rights reserved.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.