Electrochemical synthesis of lead fluoroborate by anodic dissolution of lead in fluoroboric acid solution

Lead fluoroborate solution was prepared by anodic dissolution of lead in fluoroboric acid solution. The optimal current density could reach 2 A/dm² with a current efficiency over 90%. The exchange current density of this system was found to be 0.649 A/dm² and to follow the Tafel Equation.Polarography shows that the cathodic reaction of lead fluoroborate involves only free lead ions with a charge transfer number equal to 2.     

Electrochemical synthesis of niobium compounds in anodic dissolution of ferroniobium in methanol

Anodic dissolution of ferroniobium in anhydrous methanol in the presence of sodium methylate was studied. The possibility of recovering pure hexamethoxyniobate from the electrolyzate and its conversion into niobium methylate with an iron content not exceeding 0.01% was analyzed.     

Electrochemical noise generated during the stress corrosion cracking of sensitized alloy 690

Electrochemical noise in current has been used to monitor the stress corrosion cracking (SCC) susceptibility of alloy 690 sensitized at 700 °C during 48 h in sodium thiosulfate at 90 °C. At 48 h of aging, the specimen failed by SCC and the corrosion current pulses had high intensity and low frequency, and were associated with the nucleation and propagation of stress corrosion cracks during slow strain rate tests. When the alloy was immune to SCC, the observed corrosion current pulses had a much higher frequency and lower intensity, indicating either uniform corrosion or passivation. The type of transients observed do not indicate the mechanism responsible for the observed embrittlement, but only the cracking initiation or propagation process.     

Regularities of gold anodic dissolution in thiocarbamide solutions

It is shown that the gold dissolution in thiocarbamide electrolytes containing sulfide ions in the pH range from 1 to 4 proceeds with a current efficiently of almost 100%, and a change in solution acidity has a weak effect on the process. The oxidation of thiocarbamide to formamidine disulfide proceeds at the potentials around 1.1 V and depends on the pH of solution. When the pH value is raised, the thiocarbamide oxidation potential shifts in the negative direction and approaches the potential of gold dissolution. It is found that, in the absence of catalytically active species, the gold dissolution rate in thiocarbamide solutions in the pH range from 6 to 10 is vary low. At these pH values, as well as in the acidic solutions, an addition of less than 10⁻⁴ M sulfide ions to thiocarbamide electrolyte accelerates the gold dissolution at the potentials about 0.6 V. It is shown that sulfide ions in the concentration above 10⁻⁴ M inhibit the process. At pH 11, the gold dissolution proceeds also with no special addition of sulfide ions. This is associated with the formation of sulfide ions as a result of accelerated decomposition of thiocarbamide and formamidine disulfide with increasing pH value. It is found that in the pH range from 12 to 13, the processes of gold dissolution and thiocarbamide oxidation are inhibited as a result of the formation of passive film on the electrode surface. Probably, the film consists of elemental sulfur.     

Complex surface dynamics during anodic dissolution of Ni

The evolution of the surface roughness during the anodic dissolution of polycrystalline Ni was investigated by means of ex situ AFM in acid phosphate solutions. To characterize the time and spatial scaling behavior of surface roughness, the interface width and the power spectral density of the surface at different dissolution stages were analyzed in terms of dynamic scaling theories. The time dependence of global surface roughness, W(L,t), shows an unstable behavior characterized by a continuous increase without saturation following the relation W approximately t(beta), where beta > 0.5. The unstable behavior results from the development of wide grooves that originates a surface consisting of mounds. Two scaling regimes at scales shorter and larger than the mound dimensions (l(c)) were observed. For l < l(c), we found alpha approximately 1 consistent with mounds exhibiting smooth (faceted) walls, whereas an anomalous scaling behavior with a proper local roughness exponents (alpha(loc) < 1) dominates at l > l(c). The introduction of nitrite in the solution, a common additive used in phosphating baths, leads to some changes in the scaling behavior as a consequence of different generated chemical surface conditions during dissolution. The different dissolution rates of the exposed crystal orientations and surface diffusion of adatoms were identified as the physical processes that govern the interface dynamic for this system.     

Kinetics of silver anodic dissolution in thiosulfate electrolytes

The regularities of silver anodic dissolution are studied by using the voltammetry (at the potential scan rates from 5 to 1000 mV/s) on the electrode, which was renewed immediately in the solution by cutting-off a thin surface metal layer, and quartz microgravimetry, for various concentrations of sodium thiosulfate (0.05–0.2 M). It is shown that, in the potential range from 0 to 0.4 V (normal hydrogen electrode), the polarization curves reflect the silver dissolution, whereas the contribution of oxidation of S₂O₃²⁻ ions is insignificant. At low potential scan rates, the process kinetics is of mixed nature. The kinetics and mechanism of anodic process are studied by using the measurements at high potential scan rates (100–200 mV/s) and the calculations of equilibrium composition of near-electrode layer. It is found that the exchange current in the electrolytes studied is 5 × 10⁻⁵ A/cm², the transfer coefficient α is approximately 0.5, and both parameters are virtually independent of the concentration of S₂O₃²⁻ ions. The reaction order of silver dissolution with respect to the ligand $ \left. {\frac{{\partial logi}} {{\partial logc}}} \right|_E $ \left. {\frac{{\partial logi}} {{\partial logc}}} \right|_E is close to unity and is independent of potential. With regard for the literature data on the adsorption of thiosulfate ions on silver, this result is interpreted as the evidence for the involvement of one S₂O₃²⁻ ion from bulk solution, along with adsorbed ligands, in the elementary act of metal dissolution.     

Electrochemical dissolution of chalcopyrite studied by voltammetry of immobilized microparticles

The characteristics of anodic electrochemical dissolution of chalcopyrite (CuFeS₂) powder in hydrochloric acid medium with sodium chloride have been studied. Cyclic voltammetry and chronopotentiometry of immobilized microparticles using paraffin-impregnated graphite electrode was employed. Present work is focused on electrochemical identification of chalcopyrite cathodic and anodic reaction products within the potential range of −0.7 to +0.8 V (vs. SCE) in hydrochloric acid solution containing sodium chloride and/or copper(II) chloride.     

Relaxation kinetics of the current of hydrophilic metal dissolution activated by anodic pulses

Relaxation kinetics of the metal dissolution current after pulsed anodic activation are analyzed using a model of spatial separation of the dissolution and passivation of hydrophilic metals. The current rise is contributed to mainly by the formation of new step sources resulting from the desorption of blocking oxygen atoms from vertexes of trihedral pyramids that are formed in excess quantities during the activation pulse.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1487–1493.Original Russian Text Copyright © 2004 by Lazorenko-Manevich, Sokolova.     

Alumina-based nanoparticles obtained by anodic dissolution of Al in electrolytes with alcohol solvents

In the present work, alumina-based nanoparticles were produced by an electrochemical method. Alcohols (methanol, ethanol, and propanol) containing 5 % of water and LiCl were applied as electrolytes. Sizes of the micelles in the obtained solution ranged from 200 nm to over 1 μm depending on the used alcohol. Measurements performed by ultraviolet and visible light (UV-VIS) spectroscopy indicated a presence of aluminum oxides and hydroxides in the solution. Studies using transmission electron microscopy (TEM) revealed that the obtained nanoparticles are in a form of flakes and membranes and their size is ~200 nm for methanol and ~50 nm for propanol. The composition of the product was characterized by the Fourier transform infrared spectroscopy (FTIR) and x-ray diffraction (XRD). It consists of amorphous Al oxides and hydroxides as well as poorly crystallized aluminates and metallic Al.     

Electrochemical symmetric stochastic diffusion

Symmetric stochastic diffusion in an equilibrium electrochemical ac circuit is studied theoretically. The electrochemical circuit included double layer capacitance and slow discharge resistance. Electrochemical analog of the stochastic Einstein formula is found. An equation is obtained for the excess of electrochemical stochastic diffusion. It is shown that an excess of electrochemical stochastic diffusion increases at high relaxation times in proportion to the observation time. It is found that excess is related to correlation between the phenomenon of electrochemical stochastic diffusion and the central limiting theorem.     

Modeling the environment influence on the anodic metal dissolution

The influence of the electrolyte composition on the anodic indium dissolution is studied by the RRDE method. A model is designed for the active dissolution of indium according to the hydroxide and anion mechanisms. The model is used for calculating polarization curves and the limiting current of the oxidation of intermediate ions of univalent indium on the ring electrode at different solution compositions and electrode rotation rates. The calculated curves agree well with the experimental ones, which confirms validity of the model. The paper illustrates the way one can analyze the active metal dissolution kinetics in the case of the hydroxide and anion mechanisms. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

The anodic dissolution of chalcocite in an ammoniacal environment

Presented is the proposed model for the mechanism of anodic oxidation of the semiconductor mineral chalcocite in an ammoniacal environment. The kinetic parameters of the process α_a, k_s, j₀⁰, the formal potential and the electrochemical order of the reaction in relation to ammonia are given.     

Kinetic calculations of the Ni anodic dissolution from EIS

Anodic nickel dissolution in acid media has been analyzed by means of electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy techniques. The experimental impedance spectra have been fitted to an equivalent circuit which is related to a mechanism of two consecutive electron transfers followed by a Ni²⁺ mass transfer step. That way, an estimation for values of rate constants and surface concentrations of the Ni(0), Ni(I) and Ni(II) species has been obtained.     

On nonlinear structure of electrical noise generated by slow discharge

Nonlinear structure of electrical noise of slow electrochemical discharge is analyzed within theory of integral random homogeneous fluxes with independent increments. It is shown that the degree of deviation of a flux of elementary acts from the Poissonian flux is defined by the magnitude of the factor of symmetry of slow discharge. An equation that links polyspectra of slow discharge of first, second, and third orders is derived.     

Electrochemical dissolution of aluminium in electrocoagulation experiments

Six experiments are presented to highlight important features of aluminium dissolution when used in electrocoagulation procedure employed to remove oily contaminations from water. First, using a common oil-in-water emulsion: diluted milk, we show that the electrochemically generated coagulant ions are active only in the first few seconds following their generation—hence, the electrocoagulation cells’ construction should promote the mixing of the nascent Al colloid with the water phase. For this reason, the use of the narrow-gap cells is suggested. Second, in experiments with Al-Al electrode pairs and dilute, neutral, unbuffered, aqueous solutions we (i) estimate the maximum amount of Al dissolution on the cathode and (ii) show how the rate of Al dissolution changes with frequency if the cell voltage polarity is alternating.     

Electrochemical dissolution of CrIII and CrIV oxides

Oxidative dissolution of Cr oxides can be easily performed using voltammetry of immobilised microparticles. A combined procedure based on the dependence of current on time and potential (chronoamperometry with potential jumps) is suitable for the determination of the sensitivity of the dissolution rate to electrochemical potential. Applying this procedure, it was found that the rate determining step is preceded by two-electron oxidation in the solid phase that probably proceeds as a reversible equilibration between surface sites of Cr^III, Cr^IV and Cr^V. Voltammetry is sensitive to the phase composition, and so the voltammetric peak potentials obtained under the same conditions increase in the order LaCrO₃<CrO₂<Me^IICr₂O₄<α-Cr₂O₃. The influence of Fe- and Ni-for-Fe substitution on dissolution reactivity is also discussed. Received: 20 February 1998 / Accepted: 31 March 1998     

Electrochemical dissolution of magnetite in acid solutions

The present paper deals with the electrochemical behavior of magnetite microcrystals in an acid medium. A voltammetric method employing a carbon-paste electroactive electrode (CPEE) with an organic binder was used. It was found that the cathodic voltammograms, which were recorded at different scan rates, formed a set bounded in the space of i–E parameters by a generalizing voltammetric curve corresponding to the effective potential scan rate _eff. In other words, all curves are situated under one enveloping curve, just as the smaller dolls sit in the largest doll of a Russian doll. Reverse currents (a cathodic current in the anodic direction of the potential scan) were observed on the cyclic voltammogram. Forward and reverse currents obey the same laws and have one and the same generalizing curve, which could be taken as the magnetite characteristic.     

Kinetics of anodic dissolution of Zr in acidic fluoride media

The kinetics of anodic dissolution of Zr in hydrofluoric acid (HF) was investigated using potentiodynamic polarization experiments. At lower potentials, an active region with a rapid increase in current with the potential was observed and at higher potentials, a large passivation current plateau was observed. The current decreased only slightly with potential in the passive region. Scanning electron micrographs confirmed that the passivation is incomplete in the region where current exhibits a plateau and x-ray photoelectron spectroscopic analysis showed that oxides and oxyfluorides are present on the surface. A four-step mechanism with two adsorbed intermediate species was evaluated and the model captures the essential characteristics of the polarization plots. The results suggest that \( {HF}_2^{-} \) species participates in the chemical dissolution step and actual HF participates in the electrochemical dissolution step.