Sol-gel-derived, polishable, 1 : 12-phosphomolybdic acid-modified ceramic-carbon electrode and its electrocatalytic oxidation of ascorbic acid

Novel ceramic-carbon electrodes (CCEs) containing 1:12-phosphomolybdic acid (PMo12) were constructed by homogeneously dispersing PMo12 and graphite powder into methyltrimethoxysilane-derived gel. Peak currents for the PMo12-doped CCE were surface-controlled at lower scan rates but diffusion-controlled at higher scan rates and peak potentials shifted to the negative potential direction with increasing pH. In addition, the electrode exhibited electrocatalytic activity toward the oxidation of ascorbic acid. The PMo12-modified CCE presented good chemical and mechanical stability and good surface renewability (ten successive polishing resulted in less than 5% relative standard deviation). (C) 2000 Elsevier Science B.V. All rights reserved.

Mass transfer of Er(III) between HBTMPTP dissolved in n-heptane and HAc-NaAc

The rate of extraction of Er(III) from aqueous acetate solutions at 0. 2 mol/L ionic strength by HBTMPTP in n-heptane was studied by using a constant interfacial area cell with laminar flow at (30+/- 0. 5)degrees C. The interfacial activity of HBTMPTP was investigated at n-heptane/0. 2 mol/L (H, Na)Ac (pH=5. 00) interface, The rate of Er(III) extraction was measured at different chemical compositions by varying hydrogen ion, HBTMPTP, Cyanex 302 and chlorine ion concentrations, The effect of stirring speed, temperature and special interfacial area on the rate of extraction was also studied. The results showed that, under the conditions of the experiments, the overall rate is diffusion controlled, that the impurities of Cyanex 302 have the effect of synergistic extraction.

Electrochemical and spectroscopic study of vitamin D-2 by in situ thin layer CD spectroelectrochemistry

The electrooxidation of vitamin D-2 (VD2) was studied by cyclic voltammetry and in situ circular dichroic (CD) spectroelectrochemistry for the first time, The mechanism of electrooxidation and some useful kinetic and adsorption parameters were obtained. The results showed that the oxidation of VD2 in ethanol solution is an irreversible diffusion controlled process following a weak adsorption of the electroinactive product at a glassy carbon electrode, which blocks the electrochemical reaction. The electrooxidation occurs mainly at the triene moieties of the VD2 molecule. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E-0 = 1.08 V, alphan = 0.245, the standard electrochemical rate constant k(0) = 4.30( +/- 0.58) x 10(-4) cm s(-1) and the adsorption constant beta = 1.77(+/- 0.25) were obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Electrochemical studies of a lanthanide heteropoly tungstate/molybdate complex in polypyrrole film electrode and its electrocatalytic reduction of bromate

An electrode modified with a polybasic lanthanide heteropoly tungstate/molybdate complex K10H3[Nd(SiMo7W4O39)(2)] entrapped into polypyrrole (PPy) film, denoted as Nd(SiMo7W4)(2)-PPy, exhibits three couples of two-electron redox waves in pH 1-5 buffer solutions. The redox waves are surface-controlled at lower scan rates and diffusion-controlled at higher scan rates. The effects of pH on the electrochemical behavior of Nd(SiMo7W4)(2) in PPy film were investigated in detail and compared with that of Nd(SiMo7W4)(2) in aqueous solution. The various charge states of PPy during its redox process have peculiar effects on the relationship between pH and formal potentials of Nd(SiMo7W4)(2)-PPy at different acidities. The Nd(SiMo7W4)(2)-PPy cme can remarkably catalyze the electrochemical reduction of bromate with good stability. (C) 1997 Elsevier Science Ltd.

Proton transfer across conducting polypyrrole membrane separated by two electrolyte solutions

Electrochemical behavior of the transfer of H+ across polypyrrole membrane (PPM) was studied. The transfer process was quasi-reversible and mainly diffusion-controlled. PPM electropolymerized in water solution has better reversibility than that in CH3CN solution for the transfer of H+. The transfer process of H+ across the two kinds of PPM indicated that the PPM electrochemically polymerized was of asymmetry.

Preparation of highly dispersed gold microparticles and their electrocatalytic activity for the oxidation of formaldehyde

The electrochemical preparation of highly dispersed Au microparticles on the surfaces of glassy carbon (GC) electrodes and their electrocatalytic activities for the oxidation of formaldehyde were studied. It was found that the reduction of Au3+ to Au is controlled by diffusion and the formation mechanism of Au microparticles on the GC surfaces corresponds to an instantaneous nucleation and diffusion-controlled three dimensional growth process. The particle size is about 80-90 nm in diameter after the electrochemical ageing treatment. These highly dispersed Au microparticles have high surface areas and exhibit better electrocatalytic activity than that of bulk-form Au toward the electrochemical oxidation of formaldehyde in alkaline media.

Electrochemical behavior of FAD at a gold electrode studied by electrochemical quartz crystal microbalance

The electrochemical behavior of flavine adenine dinucleotide (FAD) at a gold electrode involving adsorption of the reduced form FADH(2) and desorption of the oxidized form FAD has been studied by using electrochemical quartz crystal microbalance (EQCM). EQCM can present information not only about the electrochemical behavior but also about the mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in FAD solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed when pH<4.5 and irreversible voltammograms were found when pH greater than or equal to 4.5. It is found to be a diffusion controlled process when the concentration of FAD is lower than 2x10(-4) moll(-1) (pH 1.5). On the contrary, at concentrations higher than 2x10(-4) moll(-1) (pH 1.5), it is found to be an adsorption controlled process.

INVESTIGATIONS OF HYDROLYSIS KINETICS OF ATROPINE SULFATE BY ELECTROANALYSIS AT THE WATER NITROBENZENE INTERFACE

The hydrolysis kinetics of atropine sulphate has been investigated by cyclic voltammetry at the water/nitrobenzene interface. The transfer process is diffusion controlled and the transfer species is a 1:1 proton-atropine complex. Two main factors, pH and temperature, which have notable effects on the hydrolysis rate, are illustrated. The most suitable pH for atropine to be preserved in aqueous solution and related parameters were estimated.

ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

A study on the dependence of the micro-pore configurations on the volatilization and the burn processes of the organic compounds in the matrix of molten carbonate fuel cells

The micro-pore configurations on the matrix surface were studied by SEM. The matrix of molten carbonate fuel cell (MCFC) performance was also improved by the better coordination between the reasonable radius of the micro-pores and the higher porosity of the cell matrix. The many and complicated micro-pore configurations in the cell matrix promoted the volatilization of the organic additives and the burn of polyvinyl butyral (PVB). The smooth volatilization of the organic additives and the complete burn of PVB were the significant factors for the improved MCFC performance. Oxygen diffusion controlled-burn mechanism of PVB in the cell matrix was proposed. (C) 2002 Published by Elsevier Science Ltd.

Collector-metal behaviour in the recovery of platinum-group metals from catalytic converters

A commercial pyrometallurgical process for the extraction of platinum-group metals (PGM) from a feedstock slag was analysed with the use of a model based on computational fluid dynamics. The results of the modelling indicate that recovery depends on the behaviour of the collector phase. A possible method is proposed for estimation of the rate at which PGM particles in slag are absorbed into an iron collector droplet that falls through it. Nanoscale modelling techniques (for particle migration or capture) are combined with a diffusion-controlled mass-transfer model to determine the iron collector droplet size needed for >95% PGM recovery in a typical process bath (70 mm deep) in a realistic time-scale (<1 h). The results show that an iron droplet having a diameter in the range 0.1–0.3 mm gives good recovery (>90%) within a reasonable time. This finding is compatible with published experimental data. Pyrometallurgical processes similar to that investigated should be applicable to other types of waste that contain low levels of potentially valuable metals.

Effect of adding 0.3wt% Ni into the Sn-0.7wt% Cu solder - Part II: Growth of intermetallic layer with Cu during wetting and aging

The growth behavior of intermetallic layer with or without adding 0.3 wt% Ni into the Sn-0.7Cu solder was studied during the wetting reaction on Cu-substrate and thereafter in solid-state aging condition. The Cu-solder reaction couple was prepared at 255, 275 and 295 °C for 10 s. The samples reacted at 255 °C were then isothermally aged for 2-14 days at 150 °C. The reaction species formed for the Sn-0.7Cu/Cu and Sn-0.7Cu-0.3Ni/Cu soldering systems were Cu6Sn5 and (CuNi)6Sn5, respectively. The thickness of the intermetallic compounds formed at the solder/Cu interfaces and also in the bulk of both solders increased with the increase of reaction temperature. It was found that Ni-containing Sn-0.7Cu solder exhibited lower growth of intermetallic layer during wetting and in the early stage of aging and eventually exceeded the intermetallic layer thickness of Sn-0.7Cu/Cu soldering system after 6 days of aging. As the aging time proceeds, a non-uniform intermetallic layer growth tendency was observed for the case of Sn-0.7Cu-0.3Ni solder. The growth behavior of intermetallic layer during aging for both solders followed the diffusion-controlled mechanism. The intermetallic layer growth rate constants for Sn-0.7Cu and Sn-0.7Cu-0.3Ni solders were calculated as 1.41 × 10-17 and 1.89 × 10-17 m2/s, respectively which indicated that adding 0.3 wt% Ni with Sn-0.7Cu solder contributed to the higher growth of intermetallic layer during aging. © 2006 Elsevier B.V. All rights reserved.

Elucidation of the controlling steps of reactive dyes adsorption on activated carbon

In this work, the rate-limiting steps of reactive dye adsorption onto FS-400 activated carbon were elucidated through the investigation of adsorption kinetics. These studies initially revealed that only 20% of the available adsorption capacity was achieved during the first 6 h of mixing. Kinetic profiles showed that the adsorption process was mainly controlled by external diffusion during the first 30 min of the reaction, after which internal diffusion controlled the process. The interruption test method identified the rate-limiting steps; the results showed that sorption of reactive dyes onto FS-400 was mainly controlled by internal diffusion. Furthermore, the external and internal diffusion coefficients and the desorption rate decreased after the interruption period. The same parameters increased when the solution temperature was raised. The thermodynamic parameters studied showed that the adsorption of reactive dyes onto activated carbon was endothermic and is mainly controlled by internal diffusion with a minor effect of external diffusion.