Electrode reaction of zinc ions at a dropping mercury electrode in ammonium sulphate solutions

The electrode reaction of Zn(II) at a DME in aqueous solutions of (NH₄)₂SO₄ has been studied by d.c. and square-wave polarography at 25.0±0.1°C. The electrochemical kinetic parameters for the reaction are determined. The appearance of the second wave in the square-wave polarogram has been attributed to the low values of the rate parameter and the transfer coefficient.     

Electrochemical study of the redox reaction Yb(III) + e ⇄ Yb(II) in a molten LiCl-KCl eutectic

Electrochemical process of reduction of Yb(III) ions and oxidation of Yb(II) ions in a molten LiCl-KCl eutectic in the range 723–973 K was studied by linear, cyclic, and square-wave voltammetry and zero-current potentiometry.     

Controlled potential coulometry: the application of a secondary reaction to the determination of plutonium and uranium at a solid electrode

A method is described for the simultaneous determination of plutonium and uranium in mixed oxides by controlled potential coulometry at a gold working electrode in two stages: first a coulometric oxidation, at 0.73 V vs. a silver/silver chloride electrode, of Pu(III) and U(IV) to Pu(IV) and U(VI) by a combination of a direct electrode reaction and a secondary chemical reaction proceeding concurrently, and secondly, a coulometric reduction at 0.33 V of Pu(IV) to Pu(III), leaving uranium as U(VI). The determination is carried out in a mixture of sulphuric and nitric acids, and Ti(III) is used to reduce plutonium and uranium to Pu(III) and U(IV) before electrolysis. The precision (3sigma) of Pu:U ratio results obtained from mixtures containing about 30% and 2% plutonium was 0.5% and 1-5% respectively. The effect of experimental variables on the time taken to complete the coulometric determination is discussed.     

Electrochemical reactions with protonations at equilibrium: Part X. The kinetics of the p-benzoquinone/hydroquinone couple on a platinum electrode

The kinetics of the p-benzoquinone/hydroquinone Q/QH₂ couple on a platinum electrode are analysed on the basis of the theory presented earlier (E. Laviron, J. Electroanal. Chem., 146 (1983) 15) for the nine-member square scheme when the protonations are assumed to be at equilibrium, using experimental data from the literature. The square scheme is of the NN type. The Tafel plots and the variations of the experimental apparent rate constants between pH 0 and 7 are in good agreement with the theoretical predictions. The heterogeneous rate constants found for the elemental electrochemical steps are as follow: Q Q^?, k_h3=1/6×10^?3 cm s^?1; QH^.QH^?, k_h5=0.11 cm s^?1; QH⁺QH^., k_h2?160 cm s^?1; k_h4 for the reaction QH₂^+.QH₂ is in the range 0.5–4 cm s^?1. Between pH 0 and 7, the reaction sequence during the reduction is, for the most part, successively H⁺e^?H⁺e^?, e^?H⁺H⁺e^?, and e^?H⁺e^?H⁺ (reverse sequence during the oxidation).     

Computational study of reaction pathways for the formation of indium nitride from trimethylindium with HN3: comparison of the reaction with NH3 and that on TiO2 rutile (110) surface

The reactions of trimethylindium (TMIn) with HN3 and NH3 are relevant to the chemical vapor deposition of indium nitride thin film. The mechanisms and energetics of these reactions in the gas phase have been investigated by density functional theory and ab initio calculations using the CCSD(T)/Lanl2dz//B3LYP/Lanl2dz and CCSD(T)/Lanl2dz//MP2/Lanl2dz methods. The results of both methods are in good agreement for the optimized geometries and relative energies. These results suggest that the reaction with HN3 forms a new stable product, dimethylindiumnitride, CH3-In=N-CH3 via another stable In(CH3)2N3 (dimethylindium azide, DMInA) intermediate. DMInA may undergo unimolecular decomposition to form CH3InNCH3 by two main possible pathways: (1) a stepwise decomposition process through N2 elimination followed by CH3 migration from In to the remaining N atom and (2) a concerted process involving the concurrent CH3 migration and N2 elimination directly giving N2+CH3InNCH3. The reaction of TMIn with NH3 forms a most stable product DMInNH2 following the initial association and CH4-elimination reaction. The required energy barrier for the elimination of the second CH4 molecule from DMInNH2 is 74.2 kcal/mol. Using these reactions, we predict the heats of formation at 0 K for all the products and finally for InN which is 123+/-1 kcal/mol predicted by the two methods. The gas-phase reaction of HN3 with TMIn is compared with that occurring on rutile TiO2 (110). The most noticeable difference is the high endothermicity of the gas-phase reaction for InN production (53 kcal/mol) and the contrasting large exothermicity (195 kcal/mol) released by the low-barrier Langmuir-Hinshelwood type processes following the adsorption of TMIn and HN3 on the surface producing a horizontally adsorbed InN(a), Ti-NIn-O(a), and other products, CH4(g)+N2(g)+2CH3O(a) [J. Phys. Chem. B 2006, 110, 2263].     

Cation exchange at the mineral-water interface: H3O+/K+ competition at the surface of nano-muscovite

This article describes a (39)K nuclear magnetic resonance (NMR) spectroscopic study of K (+) displacement at the muscovite/water interface as a function of aqueous phase pH. (39)K NMR spectra and T 2 relaxation data for nanocrystalline muscovite wet with a solid/solution weight ratio of 1 at pH 1, 3, and 5.5 show substantial liquid-like K (+) only at pH 1. At pH 3 and 5.5, all K (+) appears to be associated with muscovite as inner- or outer-sphere complexes, indicating that H 3O (+) does not displace basal surface K (+) beyond the (39)K detection limit under these conditions. In our pH 1 mixture, only approximately 1/3 of the initial basal surface K (+) population is located more than 3-4 A from the surface. (29)Si and (27)Al MAS NMR spectra and SEM images show no evidence of dissolution during the (39)K experiments, consistent with the liquid-like (39)K fraction originating from displaced basal surface K (+). Assuming no muscovite dissolution or interlayer exchange, the K (+)/H 3O (+) ratio relevant to the solution/surface exchange equilibrium is controlled by the total amount of K (+) on the surface and H 3O (+) in solution (K (+) surf/H 3O (+) aq). These parameters, in turn, depend on the basal surface area, solution pH, and the solid/solution ratio. The results here are consistent with significant displacement of surface K (+) only under conditions where the initial K (+) surf/H 3O (+) aq ratio is less than approximately 1. Computational molecular models of the muscovite/water interface should account for both K (+) and H 3O (+) in the near-surface region.     

Mechanism and reaction rate of the karl-fischer titration reaction: Part III. Rotating ring-disk electrode measurements— comparison with the aqueous system

A platinum disk-platinum ring electrode was used to investigate the oxidation of sulfur dioxide by iodine and triiodide in aqueous solutions. Contrary to methanolic solutions, where the monomethyl sulfite ion is the only oxidizable species, in aqueous solutions both the hydrogen sulfite ion and the sulfite ion can be oxidized. The reaction rate was generally so high, that the method for measurements of homogeneous second order reactions had to be used. At pH values >5, the reaction proceeded too fast to be measured reliably. In a solution “diluted” with ethanol (50% of weight), however, the reaction rate was within the range where a rotating ring-disk electrode can be applied to measure fast homogeneous reactions. At very low pH values both the first order calculation technique and the second order method could be used. The results with both methods were in fair agreement.     

Application of differential electrochemical mass spectrometry to the electrocatalytic oxidation of formic acid at a modified Bi/Pt electrode surface

Ohne Zusammenfassung     

Electrochemical activity of solid solutions La1 -x Sr x CoO3 in the oxygen electroreduction reaction in carbonate melts

Solid solutions Lad_1-xSr_xCoO₃ are synthesized. An X-ray diffraction study reveals the formation of a rhombohedrically distorted perovskite-like phase. The kinetics and mechanism of the electroreduction of oxygen at the synthesized compounds in Li₂CO₃-K₂CO₃ (62: 38 mol %) and Na₂CO₃-Cs₂CO₃ (39:61 mol %) melts are studied by static coulometry and chronoamperometry. The exchange current grows with the strontium content in samples. The obtained apparent reaction orders of 0 and 0.14 by O₂ and CO₂ contradict all mechanisms offered earlier for the oxygen electroreduction at a gold electrode. A new mechanism is offered, in which the limiting step is the transfer of oxygen ions from the solid phase into the melt with corresponding changes in the electron subsystem of the electrode material. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

Cyclic voltammetry at microdroplet modified electrodes. A comparison of the reaction of vicinal dibromides with vitamin B12s at the liquid/liquid interface with the corresponding homogeneous process: evidence for polar-solvent effects at the liquid/liquid interface

The electrocatalytic reactions of vitamin B_12s with three vicinal dibromides (cis-1,2-dibromocyclohexane, trans-1,2-dibromocyclohexane and 1,2-dibromobutane) are investigated in homogeneous and heterogeneous media. In the latter, cyclic voltammetry with basal plane pyrolytic graphite electrodes modified with microdroplets of dodecane + dibromide is employed to obtain kinetic parameters for the liquid/liquid reaction. The homogeneous and interfacial reactions exhibit marked differences in reactivity and the contrasting behaviour of the two systems suggests the liquid/liquid interface has a major role in the B_12s/RBr₂ reaction, consistent with a polar solvent effect.     

Kinetics of the hydrogen electrode of a fuel cell with eutectic molten electrolyte (Li, K)2CO3 at 923 K in a coulostatic experiment

The anodic process on the hydrogen electrode in eutectic melt (Li, K)₂CO₃ is studied at 923 K by the coulostatic method. The experiment is performed at a relatively high electrode charge which makes its potential deviate from equilibrium by up to 50–100 mV. The relaxation dependence η vs.t is analyzed theoretically within the Ang-Sammels reaction scheme taking into consideration the charge-transfer and adsorption steps. Exchange currents (fluxes) of corresponding processes and the Au, Pt, Ni, and Pd electrode coverages with hydrogen adatoms are estimated. The adsorption step is shown to significantly contribute to the polarization resistance on the hydrogen electrode in a carbonate melt. This should be taken into account when estimating exchange currents of the charge-transfer step by the coulostatic method.     

Coating of Y2O3:Eu3+ particles with alumina by a humid solid state reaction at room temperature

Humid solid state reaction at room temperature was utilized for the first time to coat Y(2)O(3):Eu(3+) particles with alumina. The particles were studied with an X-ray photoelectron spectrometer (XPS), a scanning electron microscope (SEM), and an energy dispersive spectrometer (EDS). XPS results show that the yttrium and europium contents are decreased and that the aluminum content is the highest except for that of oxygen after coating. SEM and EDS results show that particles are coated with a thin shell of alumina.     

A first-principles study of molecular oxygen dissociation at an electrode surface: a comparison of potential variation and coadsorption effects

Influences of coadsorbed sodium and water, aqueous solvent, and electrode potential on the kinetics of O(2) dissociation over Pt(111) are systematically investigated using density functional theory models of vacuum and electrochemical interfaces. Na coadsorption alters the electronic states of Pt to stabilize the reactant (O(2)*), transition, and product (2O*) states by facilitating electron donation to oxygen, causing a more exothermic reaction energy (-0.84 eV for Na and O(2), -0.81 eV for isolated O(2)) and a decrease in dissociation barrier (0.39 eV for Na and O(2), 0.57 eV for isolated O(2)). Solvation decreases the reaction energy (-0.67 eV) due to enhanced hydrogen bond stabilization of O(2)* compared to 2O*. The influence of Na is less pronounced at the solvated interface (barrier decreases by only 0.11 eV) because H(2)O screens Na charge-donation. In the electrochemical model system, the dissociation energy becomes more exothermic and the barrier decreases toward more positive potentials. Potential-dependent behavior results from changes in interfacial dipole moment and polarizability between O(2)*, the dissociation transition state, and 2O*; each are influenced by changes in adsorption and hydrogen bonding. Coadsorption of Na in the solvated system dampens the dipole moment change between O(2)* and 2O* and significantly increases the polarizability at the dissociation transition state and for 2O*; the combination causes little change in the reaction energy but reduces the activation barrier by 0.08 eV at 0 V versus NHE. The potential-dependent behavior contrasts that determined at a constant surface charge or from an applied electric field, illustrating the importance of considering the electrochemical potential at the fully-solvated interface in determining reaction energetics, even for non-redox reactions.     

The interaction at the solid/liquid interface of 2,4-dichlorophenoxyacetic acid with silica modified by reaction with ammonia gas

A method for the attachment of ammonia to modified silica gel has been developed. In the first step, tetraethylorthosilicate and (3-glycidoxypropyl)trimethoxysilane were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified mesoporous silica. The epoxy group incorporated into the mesoporous silica was opened by ammonia gas thus introducing amine chelate groups covalently bound to the inorganic surface. The modified material contained 1.13+/-0.06 mmol of amine per gram of silica, exhibited a surface area of 831+/-29 m(2)g(-1) and a porous diameter of 1.95 nm. Infrared, 29Si and 13C NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. This ordered organic-inorganic hybrid presented a high capacity for the removal of the agrochemical 2,4-dichlorophenoxyacetic acid from water: the DeltaH and DeltaG values for the interaction were determined to be -110.61 and -9.37 kJ mol(-1), respectively.     

Supramolecular phenomena in organic redox films at electrodes: Part I. The methylene blue/leucomethylene blue redox couple at the platinum electrode

It is possible to generate conductive multilayer structures by reduction of methylene blue cations at the interface: clean surface of a platinum electrode/1 M aqueous electrolyte solution.The characteristics of the multilayer ordered phase generated in fluoride and nitrate solutions are presented and the mechanism of a fast charge transfer between electrode/organic film and organic film/aqueous solution interfaces is discussed. The conductivity of the film is interpreted by postulating formation of a mixed valence structure with the generation of a cation radical intermediate which is favoured in the solid state at characteristic potentials.     

Electrode materials and reaction mechanisms in solid oxide fuel cells: a brief review. III. Recent trends and selected methodological aspects

Continuing previous reviews on mixed-conducting electrodes for intermediate-temperature solid oxide fuel cells (IT SOFCs), this work presents a short overview of novel cathode and anode materials, their electrochemical performance in contact with oxygen anion- and proton-conducting solid electrolytes, and specific features determining possible applications. Priority was given mainly to recent research reports published during the last 2–5 years. Particular emphasis is focused on the relevant methodological aspects, potential limitations and drawbacks, and factors affecting electrode polarization and durability. Typical ranges of the polarization resistances, overpotentials, power densities in the cells with various current collectors, and the electrode materials total conductivity and thermal expansion are compared. The electrode compositions appraised in single-chamber and micro-SOFCs, hydrocarbon- and carbon-fueled cells, high-temperature electrolyzers, and other solid-electrolyte appliances are briefly covered in light of their similarity to the common SOFC materials discussed in the previous parts.     

The role of capillary and surface forces in the crossover behavior of solid nanoparticles at liquid interfaces

We investigate the interaction between a nanoparticle and an oil-water interface with particular emphasis on the particle crossing through the interface. The formation of a three-phase contact line is investigated in two cases, namely in the presence and in the absence of surface forces. We carefully examine the interplay between capillary and surface forces in such systems. Two instabilities of the interface (snap-in/snap-out) as the particle is moved through the interface are identified and quantitatively described. While the snap-in instability was observed in some AFM studies, the precise interface position and configuration relative to the particle at the instability depends on the nature of the surface forces present in the system. After the snap-in, the particle is adsorbed and must overcome an energy barrier due to the interface deformation in order to cross-over to the other liquid. We make quantitative predictions on the interface configuration at the instabilities and the free energy barrier height. The roles of particle size and different interaction parameters characterizing the system in determining the magnitude of the energy barrier for crossing and in the formation of a three-phase contact line are discussed. Ultimately, this study will enable us to make quantitative predictions on capillary effects in nanoparticle-microemulsions mixtures and other colloidal systems. For particles in the micrometer range and larger the capillary forces dominate over the surface forces and dictate how the snap-in occurs. However, the situation becomes different for particle sizes smaller than about 100 nm. The presence of surface forces modifies the interface configuration and the free energy jump at the snap-in instability.