Kinetics and mechanism of gold dissolution in thiourea solutions: Effect of sulfide ions

Chronoamperograms for gold in solutions containing 0.1 M thiourea, 0.5 M H₂SO₄, and catalytically active sulfide ions at the concentration c ₁ from 1 × 10^?5 to 4 × 10^?5 M are obtained at different potentials with the aid of an automated setup intended for renewing the electrode surface directly in the solution by cutting off a thin surface layer of the metal. It is shown that the results of measurements of the current practically coincide at a constant value of the product c ₁ t, where t is the time period elapsed after the renewal of the electrode surface. Such a coincidence testifies to a diffusion nature of processes that hamper accumulation of sulfide ions at the gold surface. This fact permitted the use of a procedure developed previously for the calculation of polarization curves at constant values of surface coverage θ by catalytically active ions. At θ = const, the voltammetric curves for gold in sulfide-containing thiourea solutions are shown to correspond to the Tafel equation. With the surface coverage increasing, the effective values of the exchange current i ₀, transfer coefficient α, and anodic reaction order with respect to thiourea P _a increase from the values i }~ 10^?5 A cm^?2, α }~ 0.12, and P _a = 0.2, which are characteristic of pure solutions, to 2 × 10^?4 A cm^?2, α }~ 0.5, and P _a = 1.1 (at θ }~ 0.5). An interpretation to the established regularities is given.     

Determination of Diffusion Coefficients for Binary Nonelectrolyte Mixtures. A Free-Volume Predictive Approach

A diaphragm cell has been used to measure mutual diffusion coefficients at 25°C for four binary nonelectrolyte mixtures: ethylbenzene + n-hexane, carbon tetrachloride + ethylbenzene, cyclohexane + p-xylene, and 1,2-dichloroethane + cyclohexane. A free-volume predictive approach for binary mutual diffusion coefficients was developed and tested. Only infinite dilution diffusion coefficients, some readily available pure substance data, and UNIFAC group contribution parameters are used in the model. No binary equilibrium thermodynamic information is required. For 73 binary systems with an overall average absolute deviation of 5.2%, it has been shown that the developed method is better than two commonly available reference methods for the prediction of liquid diffusion coefficients.     

Electromagnetic interference shielding and radiation absorption in thin polypyrrole films

Results of permittivity measurements, electromagnetic interference shielding effectiveness, and heat generation due to microwave absorption in conducting polymer coated textiles are reported and discussed. The intrinsically conducting polymer, polypyrrole, doped with anthraquinone-2-sulfonic acid (AQSA) or para-toluene-2-sulfonic acid (pTSA) was applied on textile substrates and the resulting materials were investigated in the frequency range 1-18 GHz. The 0.54 mm thick conducting textile/polypyrrole composites absorbed up to 49.5% of the incident 30-35 W microwave radiation. A thermography station was used to monitor the temperature of these composites during the irradiation process, where absorption was confirmed via visible heat losses. Samples with lower conductivity showed larger temperature increases caused by microwave absorption compared to samples with higher conductivity. A sample with an average sheet resistivity of 150 Ω/sq. showed a maximum temperature increase of 5.27 °C, whilst a sample with a lower resistivity (105 Ω/sq.) rose by 3.85 °C.     

Characterization of CNS disorders and evaluation of therapy using structural and functional MRI

Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required.     

Mass transfer to horizontal gas-generating electrodes

Mass transfer to a horizontal electrode during electrolytic evolution of oxygen and hydrogen at current densities of 100 to 10 000 A/m² is studied. The mass transfer intensity is evaluated from the diffusion layer thickness, which varies from 60 to 5 μm at such current densities. Calculations show that the decrease in the diffusion layer thickness is due to bubbles with a stationary interphase surface crossing the diffusion layer. During the hydrogen evolution, the diffusion layer thickness is nearly the same for vertical and horizontal electrodes. During the oxygen evolution, the diffusion layer is much thinner for a horizontal electrode. Additional decrease of the diffusion layer thickness during the evolution of oxygen is associated with the lesser solution density in the near-electrode layer and with its transport away by means of natural convection.     

Measurement of diffusion coefficients in multicomponent gas mixtures by the reversed-flow technique

Summary The reversed-flow method for measurement of gas diffusion coefficients in binary mixtures is now extended to simultaneous determination of effective diffusion coefficients for each substance in a multicomponent gas mixture. The method is applied to six ternary mixtures, each consisting of two gaseous hydrocarbons and H₂, He or N₂. The results are in agreement with a limiting case of the Stefan-Maxwell equations.     

带电胶体离子扩散与交换动力学的比较

Taking soil colloid and hydrated silica (quartz sand) as the experimental material, the comparative study has been made on the kinetics of ion diffusion and ion exchange in charged colloid and charged coarse disperse systems. The results showed that ion exchange kinetics in the two systems conform to the kinetic law of ion diffusion. Besides, through this comparative study on the kinetics of ion exchange and ion diffusion, a method has been advanced theoretically to estimate the quantity of adsorbed ion that is located in the inner of the Helmholtz layer. As far as hydrated silica is concerned , there were about 33 per cent of the total adsorbed quantity of Mg2+that were located in the inner of the Helmholtz layer under the given experimental conditions, bu tfor soil colloid the percentage was only 7.5.     

Comparison of the Diffusion of Aqueous Glycine Hydrochloride and Aqueous Glycine

A Taylor dispersion tube has been used to measure mutual diffusion in aqueous solutions of glycine hydrochloride at 25°C and concentrations from 0.0005 to 0.5 M. Analysis of the dispersion profiles shows that the diffusion of glycine hydrochloride (GlyHCl) produces a subtantial additional flow of hydrochloric acid that is liberated by the dissociation: GlyH⁺ + Cl^- Gly + H⁺ + Cl^-. Diffusion in this system is, therefore, a ternary process described by the equations J ₁(GlyHCl) = – D ₁₁C ₁ – D ₁₂C ₂ and J ₂(HCl) = –D ₂₁C ₁ – D ₂₂C ₂ for the coupled fluxes of total glycine hydrochloride (1) and hydrochloric acid (2) components. The ratio D ₂₁/D ₁₁ of measured diffusion coefficients indicates that up to two moles of HCl are cotransported per mole of GlyHCl. Although protonated glycine diffuses with relatively mobile Cl^– counterions, the main diffusion coefficient of glycine hydrochloride, D ₁₁, is lower than or nearly identical to the diffusion coefficient of aqueous glycine. A model for the diffusion of protonated solutes is developed to interpret this result and the large coupled flows of HCl. Diffusion coefficients are also reported for the aqueous hydrochlorides of 3- and 4-aminobenzoic acids.     

Computational Modelling of the Behaviour of Potentiometric Membrane Biosensors

This paper presents a mathematical model of a potentiometric biosensor based on a potentiometric electrode covered with an enzyme membrane. The model is based on the reaction–diffusion equations containing a non-linear term related to theMichaelis–Menten kinetics of the enzymatic reaction. Using computer simulation the influence of the thickness of the enzyme membrane on the biosensor response was investigated. The digital simulation was performed using the finite difference technique. Results of the numerical simulation were compared with known analytical solutions.      

聚乙撑二氧噻吩膜在氧化态的充电过程及电容研究

In this paper, the chronoamperometry was used to study the charging processes of polyethylenedioxythiophene (PEDOT) modified electrodes in the potential range where PEDOT was in the oxidized state. The results show that the charging behaviors of the PEDOT films are well agreed with the exhausted finite diffusion model. The dependence of the capacitance values of the films on potential and concentration of solution was also studied in this potential range.