Impedance and Photoadmittance of Passive Iron Electrodes in Different Solutions

Electric characteristics of the oxide film at the surface of an anodized iron electrode in 0.5 M Na₂SO₄, NaNO₃, and Na₂MoO₄ solutions are studied using the impedance and photoadmittance measurements and taking polarization curves. The impedance frequency spectra correspond to an equivalent circuit comprising two parallel (RC) chains connected in a series. The relaxation time of the high-frequency circuit approaches that of the photopotential; hence, it can be related to the impedance of the oxide film. The low-frequency component of the impedance describes the impedance of the film/solution interface. In the Na₂SO₄ solution, the oxide film resistance is significantly higher and the capacitance is lower than in two other solutions, which can be explained by the film thickening. The marked concurrent decrease in the resistance and increase in the capacitance of the film/solution interface at 1.2 V in all solutions is caused by oxygen adsorption, which precedes oxygen evolution.     

Study of ion adsorption at passive iron by using the impedance and photoadmittance methods

Intensity-modulated photocurrent (photoadmittance) and electrochemical impedance of anodicoxidized iron electrode in neutral nitrate solutions and in the presence of Ba²⁺, Ca²⁺, Cl^?, and C₆H₅COO^? (benzoate) are studied. It is shown that the ion adsorption at passive iron affects but slightly the system’s impedance; by contrast, it affects the photocurrent value significantly: when adsorbing, the anions increase the photoeffect, while the cations decrease it. These effects are associated with the potential drop redistribution in the Helmholtz layer and the film. The dissimilar changes of the generation current in the presence of similarly charged ions at their equal concentration evidence their different adsorption activity. The correlation between the generation current and surface-active ion concentration in solution is found. The photoelectrochemical spectroscopy allows evaluating qualitatively the surface-active ion adsorption at the passive iron and judging on the ion adsorption by the dependence of the generation current on the ion concentration.     

Determination of pH value of isoelectric solution and identification of passive iron surface phases using immersion method

Using the method of phase modeling, the pH values of solutions corresponding to the uncharged surface of passive iron and ferric oxide γ-Fe₂O₃ (pH₀) are compared. According to the theory of connected places, the charge of metal oxide surface is determined by the adsorption or desorption of hydrogen ions leading to a change in the potential drop at the oxide/solution interface. Preliminarily passivated iron electrode was washed with twice-distilled water and placed into 0.5 M NaNO₃ solution with various pH values; the variation in the potential (ΔE) with time was studied. The pH₀ value for passive electrode under the open-circuit conditions was determined by the dependence of ΔE on the pH value (pH₀ 6.2 ± 0.1). The pH₀ value was close to that for γ-Fe₂O₃ (pH₀ 6.2), which was determined by the method of potentiometrical titration of oxide suspension in the nitrate solution. The introduction of surface-active ions Ba²⁺ and Cl^? changes the charge of passive iron surface: Ba²⁺ ions increase the electrode potential, while Cl^? ions decrease it. Comparing the pH₀ values for passive electrode and metal oxides, one can identify the composition of passive electrode surface.     

Impedance and photoadmittance of a passive iron electrode in alkaline sodium sulfide solutions

The intensity-modulated photocurrents (photoadmittance) and the electrochemical impedance of an anodically oxidized iron electrode are studied in alkaline solutions containing the sulfide ion. The photooxidation of S^2- proceeds via a stage of their adsorption. The concentration of S^2- adsorbed on the surface decreases at a potential shift in the positive direction     

Effect of microenvironment on the potentiostatic-current oscillation of iron electrode in sulfuric acid solution

Potentiostatic current oscillation of iron electrode in 0.5 mol/l sulfuric acid solution in half open microenvironment is studied. Results show that the microenvironment at the vicinity of the electrode has an important effect on current oscillation. The rate of mass transport of the Fe²⁺ and H⁺ can influence the oscillation period: the more difficult the migration of the Fe²⁺ and H⁺ ions, the longer the oscillation period. Digital holography is used to study the dynamic changes at the electrode/solution interface during current oscillation. This new method offers a new approach to studying the influence of mass transport on current oscillation. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 551–556. The text was submitted by the authors in English.     

Comparative EIS study of a paste electrode containing zinc powder in neutral and near neutral solutions

The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na₂SO₄ and 5×10^–3 M Na₂HPO₄ solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some information about porous nature of zinc electrode could be extracted. Electronic Publication     

镍纳米线电极的交流阻抗研究

用交流阻抗法研究了一种新型电极－镍纳米线电极在碱性溶液中的电化学行为,给出了相应的等效电路和拟合效果。实验结果表明,外加电位对电极表面化学反应速度和类型有显著影响。在外加电位不高时,Ni（Ⅱ）氧化成Ni(Ⅲ)的电化学过程随着电位的升高而明显加速;当外加电位高于0．40V以后,电极表面同时发生电化学析氧反应。相同条件下,镍纳米线电极的表面电化学反应速度远远高于镍块体电极。     

Impedance of the copper electrode in isopotential solutions containing complexes of Cu(II) and glycolic acid

In the frequency interval from 0.01 Hz to 50 kHz, the impedance of copper electrodes is investigated in a series of isopotential solutions, which contain various amounts of ligands and of complexes of Cu(II) and glycolic acid, but a constant concentration of Cu²⁺ ions. An equivalent electrode scheme is analyzed, in which two successive one-electron steps and the diffusive flows of both the charged particles and the intermediate are taken into account, and the presence of a homogeneous chemical reaction is also considered. It is established that the exchange current density for the first electron in a series of solutions, which contain 5.3 mM Cu²⁺, is essentially independent of the concentration of free ligand and is equal to 0.1 mA/cm². This indicates that the electrically active particles are aqua complexes of Cu²⁺. It is proposed that the chemical step, which is suggested by the impedance data, is the dissociation of glycolic acid, which releases the active form of the ligand.     

Response of a copper(II) and iron(III) ion-selective electrode bielectrode array in saline media

A bielectrode array comprising a jalpaite membrane (i.e., Ag_1.5Cu_0.5S) copper(II) ion-selective electrode (ISE) and chalcogenide glass membrane (i.e., Fe_2.5(Se₆₀Ge₂₈Sb₁₂)_97.5) iron(III) ISE has been assembled by individually wiring each solid-state sensor into a single electrode body. Furthermore, a dual metal ion buffer calibration standard incorporating copper(II) and iron(III) coordinating ligands to regulate the levels of free copper(II) and iron(III) in the buffer has been developed to enable simultaneous calibration of the bielectrode ISE array. In this work, the bielectrode ISE array has been employed in the continuous flow analysis (CFA) of free copper(II) and iron(III) in seawater media. It is shown that the individual electrodes displayed Nernstian response in the metal ion buffer calibration standard over a wide dynamic range (viz., 10⁻¹⁵ to 10⁻⁵ M aCu²⁺ and 10⁻²¹ to 10⁻¹¹ M aFe³⁺), and the results of repetitive CFA analyses of free copper(II) and iron(III) in seawater are commensurate with the typical values found in coastal seawater samples. Clearly, the bielectrode ISE array may be used in the simultaneous analysis of free copper(II) and iron(III) in seawater without fear of cross-interference between the solid-state sensors.     

In situ monitoring of the rising of aqueous solution meniscus for a partially immersed silver electrode during electrochemical reduction of oxygen

Rising phenomena of aqueous solution meniscus were found for the silver electrode of a 5 MHz piezoelectric quartz crystal (PQC) partially immersed in Na₂SO₄, NaClO₄, HClO₄ and NaF aqueous solutions at oxygen reduction potentials, respectively. A detailed study revealed that a decrease in contact‐angle hysteresis (or a contact‐angle decrease) and a continued collection of the water product at the solid‐gas‐solution interface during oxygen reduction, rather than the electrocapillary effect and an agitation effect induced by the oscillation of PQC, are responsible for the meniscus‐rising phenomena. In addition, in situ determination of the immersed height of a partially immersed Ag electrode was studied on the basis of simultaneous measurements of the electroacoustic admittance and electrochemical impedance.     

Characterization of the passive films on electrodeposited Fe-Ni-Cr alloys in borate solution at pH 8.4

The corrosion properties of the passive layers formed on iron-nickel-chromium electrodeposits of Fe₂₉Ni₅₁Cr₂₀ were investigated in 0.3 M borate solution at a‘ pH of 8.4. On the basis of measurements by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy, a low passive dissolution/corrosion rate was identified for the electrodeposited Fe-Ni-Cr alloys due to the nature of the established corrosion layer. The stability of this passive layer was further enhanced after corrosion under oxidizing conditions. Mössbauer spectroscopic measurements confirmed the existence of a thin passive layer on the amorphous electrodeposits.      

Peculiarities of metal electrodeposition inside a flow-through porous electrode with low initial conductivity in oxidant containing solution

The earlier developed dynamic model of a flow-through electrode is used for studying how the variations in initial conductivity of a porous matrix κ_s,ini and a metal deposit affect the rate of metal deposition from an oxidant-containing solution for the direct-flow operation mode of the porous electrode. It is found that in contrast to an oxidant-free solution in which the decrease of κ_s,ini improves the uniformity of deposit distribution inside the porous cathode and increases the deposit final mass m _f, the opposite situation is observed in the presence of an oxidant, namely, a decrease in κ_s,ini, under otherwise similar conditions reduces the deposit mass and leads to its specific spatial distribution. The final metal deposit is divided into two separate fragments (rear and front) with a region of low conductivity of the initial porous matrix in between. Dynamics of the current and metal redistribution within the porous electrode, the reasons for the formation and stabilization of the rear fragment of coating, the correlation between the metal deposition rate and changes in the anodic zone position and intensity are discussed. It is shown that with the appearance of a specific profile of deposit distribution, the dependence of m _f on the metal conductivity develops a limit that differs considerably from the deposit final mass for an equipotential porous electrode.     

Impedance of solid electrolyte systems

The main regularities of studying electrode processes in the systems with solid electrolytes are described using the method of electrochemical impedance with the relationships of Ershler-Randles and Frumkin-Melik-Gaykazyan and analysis of results based on equivalent electric circuits.     

Analysis of Impedance Spectra of Vacuum-Annealed Undoped Polycrystalline Diamond Electrodes

Impedance spectra for a new electrode material, undoped polycrystalline diamond films vacuum-annealed at 1775 to 1915 K, taken in indifferent electrolytes are analyzed. Regular changing of parameters of the equivalent circuit (constant-phase element, ohmic and faradaic resistances) with increasing anneal temperature is demonstrated. It is concluded that both the amount of a nondiamond conducting phase in the electrode bulk increased and its properties (first and foremost, the conductivity) changed with increasing anneal temperature.     

Potentiodynamic and cyclic voltammetric behaviour of a lead electrode in NaOH solution

Summary The electrochemical behaviour of lead in NaOH solution was studied by potentiodynamic and cyclic voltammetric techniques in combination with X-ray diffraction analysis. The active dissolution of lead involves a small shoulderA1 followed by a peakA1 prior to a passive region. The shoulderA1 is assigned to the electroformation of a Pb(OH)₂ film, whereas peakA1 is due to the formation of PbO. Beyond the passive region, the current density increases again, forming a small shoulderA2 and a peakA2 prior to the oxygen evolution potential. The shoulderA2 and the peakA2 are correlated to the electrooxidation of PbO to Pb₃O₄ and PbO₂, respectively. The intensity of the anodic peaks increases with increasing alkali concentration, temperature and scan rate. In cyclic voltammetry, the reverse scan shows two cathodic peaksC1 andC2 which are correlated to the electroreduction of PbO and PbO₂ respectively, to Pb.

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Potentiodynamisches und cyclovoltammetrisches Verhalten einer Bleielektrode in NaOH-Lösung

Zusammenfassung Das elektrochemische Verhalten von Blei in NaOH wurde mittels potentiodynamischer und cyclovoltammetrischer Techniken unter Zuhilfenahme der Röntgenbeugungsanalyse untersucht. Die aktive Auflösung von Blei verläuft über eine SchulterA1, die von einem einer passiven Region vorgelagerten PeakA1 gefolgt wird. Die SchulterA1 wird der elektrochemischen Bildung eines Pb(OH)₂-Films, der PeakA1 der Bildung von PbO zugeschrieben. Jenseits der passiven Region steigt die Stromdichte wieder an, und vor Erreichen des Sauerstoffpotentials treten eine kleine SchulterA2 und ein PeakA2 auf, die mit der Elektrooxidation von PbO zu Pb₃O₄ und PbO₂ korrelieren. Analog dazu beobachtet man in der cyclischen Voltammetrie zwei kathodische PeaksC1 undC2, die der Elektroreduktion von PbO und PbO₂ zu Pb entsprechen. Die Intensität der anodischen Peaks steigt mit steigender Alkalikonzentration, Temperatur und Scangeschwindigkeit.

     

Impedance spectroscopy of lithium-carbon electrodes

The methods of coulometric titration and electrode impedance spectroscopy are used in studying the behavior of carbon film electrodes free of binding and conducting additives in the course of reversible lithium intercalation from nonaqueous electrolytes. The electrodes with the high and low degrees of graphitization are studied. The measurements are performed in the frequency range from 10⁵ to 10^?2 Hz with the lithium concentration in intercalate varied from 0.025 mol/cm³ (corresponds to LiC₆) to a state free of lithium. The factors responsible for the hysteresis in charge-discharge curves, the versions of equivalent circuits (EC) suitable for modeling the impedance spectra of Li _x C₆ electrodes, the dependence of EC parameters and the lithium diffusion coefficient on the concentration are discussed. It is shown that all experimental impedance spectra can be adequately modeled by a common general EC. The concentration dependences are consistent with the earlier data of pulse methods. The diffusion coefficient varies approximately from 10^?12 to 10^?13 cm²/s.     

Impedance of faradeic process with partial charge transfer

The electrochemical impedance of charge-transfer reaction involving the stages of adsorption and desorption of intermediate partially charged substance is analyzed theoretically in the frequency-potential plane in order to study the possibility for measuring the partial charge transfer. The simplest case of adsorption two-electron transfer, namely, the Langmuir adsorption with liner dependence of reaction rate on the coverage, is considered. It is assumed that the partial charge transfer is independent of the electrode potential.     

直接甲醇燃料电池的交流阻抗谱分析*

由于能够提供比直流测试方法更为丰富的信息,交流阻抗图谱近些年被广泛的用于直接甲醇燃料电池的研究中。同PEMFC相比,直接甲醇燃料电池具有更为复杂的电极体系。本文通过对交流阻抗技术在直接甲醇燃料电池领域应用的几个关键技术问题的分析,并按照阻抗分析过程的具体的实施步骤加以组织,结合具体的应用实例以阐述交流阻抗谱在直接甲醇燃料电池的各个应用方面,包括电池的原位极化分析,反应机理的剖析,材料性能评估等。     

Impedance spectroscopy of lithium-tin film electrodes

A method of electrochemical impedance spectroscopy was used to study the reversible lithium intercalation from nonaqueous electrolyte into tin films with the thickness of 0.1–1 μm. The impedance spectra of lithium-tin (Li _x Sn) electrodes have a complicated shape depending on the electrode state and prehistory; they reflect the occurrence of several consecutive and parallel processes, including the lithium migration, diffusion, and accumulation. The formation of a solid-electrolyte layer on the surface at Li intercalation into Sn is observed. Equivalent circuits are proposed that adequately model the experimental data on the Li _x Sn electrodes both freshly prepared and after prolonged cycling. Problems associated with the choice of equivalent circuits and determination of their parameters, the accuracy of the diffusion coefficient determination, the trends in the parameters’ variation with electrode potential (composition) are discussed.