Electrocatalytic effect of phenanthroline iron complexes on oxygen reduction in sulfuric acid media

The study of oxygen reduction on a platinum rotating disk was performed at different pHs in 1 M H₂SO₄. An increase in the velocity of this reaction with the addition of 2×10^–3M Fe(II) and 0.1 M 1,10-phenanthroline was observed. This increase depends on the solution pH, i.e. at pH<0.5, it is about 100-fold, whereas for pH>0.5, it is greater than by a factor of 600. This change at pH=0.5 can be explained by a change in the coordination sphere of electrogenerated Fe(II). The complex species Fe(II)–SO₄ at pH<0.5 changes to [Fephen₃]²⁺ at pH>0.5.

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pH 1M H₂SO₄. 2·10^–3M Fe(II) 0,1M 1,10- . pH , pH<0,5 100, pH>0,5 600 . pH=0,5 Fe(II). Fe(II)–SO₄ pH<0,5 [Fephen₃]²⁺ pH>0,5.

     

Electrochemical impedance of passive iron in sulfuric acid water-organic solutions

The passive state of iron in sulfuric acid solutions in dimethylformamide and dimethyl sulfoxide containing different amounts of water is studied by the impedance method in a wide range of ac frequencies and also by the methods of polarization curves and open-circuit potential transients. In the studied systems, the metal passivation potential is shown to shift in the positive direction with a decrease in the water content in the solvent. The open-circuit potential of the destruction of the passive layer (Flade potential) is independent both of the nature of the solvents and the water amount in them. The impedance characteristics of passive iron can adequately be modeled by an equivalent circuit consisting of two parallelR-C circuits, i.e. similarly to a circuit used earlier for modeling the impedance of a passive Fe electrode in neutral aqueous solutions. The physical meaning of the equivalent-circuit elements calculated from the impedance measurements is analyzed. The effects the electrode potential, the organic-solvent type, the water content in the latter, etc. have on the elements are discussed. The obtained results suggest that the potential difference applied to the interface between passive iron and studied solutions is located mainly in the Helmholtz layer. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.     

H~2S对硫酸溶液中铁腐蚀作用的CNDO/2研究

动电位扫描得出工业纯铁在含H~2S的H~2SO~4溶液中腐蚀的电化学行为。应用CNDO/2法确定了阴、阳极电位下H~2S,HS^-在金属Fe晶面上的稳定吸附取向与最佳吸附间距,通过对吸附物总能量、结合能、净电荷分布的计算,得出H~2S体系阴、阳极反应被加速的微观机制。阳极电位下,大量HS^-为S原子的平行吸附方式,HS^-负电荷大部分向Fe转移,促进铁的溶解。阴极电位下,少量H~2S则为H原子的平行吸附方式,Fe表面负电荷向H~2S分子中与Fe作用的H转移,促进析氢。在CNDO/2法计算的基础上,圆满地解释了实验结果。     

Inhibitive action of some dibenzofuran derivatives on corrosion of iron in sulphuric acid media

The inhibitive properties of Dibenzofuran (D.B.F.) and some derivatives (3-NH₂-, 2-NH₂-, 2,3-NH₂-, 3-NHCOCH₃-, 2-SH-, 3-SH-, 3-NO₂) against the corrosion of iron in H₂SO₄ 1N at 25°C and 50°C have been investigated.Experimental data of electrochemical, colorimetric and weight loss measurements are reported.The results show that these molecules act as quite effective inhibitors at 25°C. They do show instead not a same effectiveness at 50°C.     

Conditions for the onset of current oscillations at the limiting current of the iron electrodissolution in sulfuric acid solutions

The experimental conditions and parameters that control the transition from a steady to an nonsteady limiting current and vice versa in the anodic Fe dissolution are studied in sulfuric acid solutions by using a downward-facing Fe electrode. Periodic and chaotic current oscillations are observed at the beginning of the limiting current region within a fixed potential region by decreasing the sulfuric acid concentration, by increasing the Fe-disk rotation rate and by increasing a series external resistance. It is found that current oscillations emerge when theIR drop exceeds a critical value (IR)_crit. The latter depends on the hydrodynamic conditions pertaining to the system. This is realized by the differences appeared in the value of (IR)_crit on using a stationary or a rotating Fe electrode. The effect of hydrodynamic conditions is shown by additional experimental results obtained by using an upward-facing Fe electrode, by increasing the density and viscosity of the solution on addition of glycerol, and by altering the solution properties near the Fe surface on addition of halide ions. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the authors in English.     

Electrochemical studies of mild steel corrosion inhibition in sulfuric acid chloride by aniline

The corrosion behavior of mild steel in dilute hydrochloric acid under the inhibiting action of various concentrations of aniline was studied using the weight loss and linear polarization resistance technique. The efficiency of the inhibitor increased with the increase in the inhibitor concentration. The results obtained reveal that aniline performed effectively as a corrosion inhibitor. The adsorption mechanism indicates mixed molecular interaction from values of Gibbs free energy. The values of the inhibition efficiency calculated from the two techniques are in reasonably good agreement. The adsorption of the inhibiting compound was found to obey Langmuir, Frumkin and Freudlich adsorption isotherms. The mechanism of inhibition was discussed in the light of the chemical structure of the inhibiting compound and their adsorption on steel surfaces in relation to the potentiodynamic parameters.     

An evaluation of the analytical performance of collinear multi-pulse laser induced breakdown spectroscopy

A detailed study of the relevant analytical figures of merit for time- and spatially integrated multi-pulse laser induced breakdown spectroscopy (MP-LIBS) was performed. Laser bursts containing up to 6, ns-range duration collinear pulses, separated by 20–40 μs interpulse gaps were used in the experiments, and the effect of the number of pulses within the burst on the analytical parameters was investigated. Signal enhancement, repeatability, matrix effects, background signals, sensitivity, linear dynamic range and limits of detection were studied for 20 lines of 11 elements in different solid matrices. It was established that all analytical figures of merit significantly improved with respect to those of single- or double-pulse LIBS as a result of the use of multiple laser pulses. For example, six-pulse limits of detection values were found to be with a factor of 4.2–16.7 lower than for double-pulses and calibration plots were found to be linear up to several tens of percents concentrations in some alloys.     

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.     

Oxidation of benzyl alcohols by nitrous and nitric acids in strong sulfuric acid media

We have studied the oxidation of benzyl alcohols by nitrous and nitric acid in sulfuric acid media. The oxidation by nitrous acid is rapid and has an activation energy of 10.6 ± 0.8 kcal mol^?1. A Hammett plot of logk₂ vs. σ⁺ is linear with a ρ value of ?1.4. The oxidation by nitric acid in sulfuric acid media is autocatalytic. From the kinetic and product analyses, it is concluded that a common oxidant, the nitrosonium ion is involved when either nitrous or nitric acid is used. A mechanism is proposed which involves the abstraction of hydride from the alcohols as the rate determining step. It is demonstrated that the autoxidation of the alcohols is catalyzed by nitrous acid or nitric oxide.     

Effect of Sn content on the properties of passive film on PbSn alloy in sulfuric acid solution

The effect of Sn content on properties of anodic film formed on PbSn alloys in sulfuric acid solution was investigated using linear sweeping voltage (LSV), cyclic voltammetry (CV), and a.c. voltammetry (ACV), based on the Mott-Schottky analysis. The results revealed that the addition of Sn into lead alloys can promote the corrosion resistance property and could decrease the impedance of anodic film; these results were more remarkable with enhancing the Sn content. The over potential of oxygen evolution on lead alloys enhanced with the increase of Sn content. The Mott-Schottky analysis indicated that the passive film appeared an n-type semiconductor, and the donor density of passive film increased with increasing Sn content. The increased vacancies in the passive film with Sn content increasing could illustrate this trend.     

Inhibition effect of butan-1-ol on the corrosion behavior of austenitic stainless steel (Type 304) in dilute sulfuric acid

The electrochemical behavior of austenitic stainless steel (Type 304) in 3 M sulfuric acid with 3.5% recrystallized sodium chloride at specific concentrations of butan-1-ol was investigated with the aid of potentiodynamic polarization, open circuit measurement and weight loss technique. Butan-1-ol effectively inhibited the steel corrosion with a maximum inhibition efficiency of 78.7% from weight-loss analysis and 80.9% from potentiodynamic polarization test at highest concentration studied. Adsorption of the compound obeyed the Freundlich isotherm. Thermodynamic calculations reveal physiochemical interactions and spontaneous adsorption mechanism. Surface characterizations showed the absence of corrosion products and topographic modifications of the steel. Statistical analysis depicts the overwhelming influence and statistical significance of inhibitor concentration on the inhibition performance.     

EIS study on passive films of AISI 304 stainless steel in oxygenous sulfuric acid solution

Electrochemical impedance spectroscopy (EIS) and Kramers–Kronig (K–K) transforms were made on American Iron and Steel Institute (AISI) 304 stainless steel (SS) in naturally aerated sulfuric acid solution at room temperature. The K–K relations testify that the systems under investigation comply with the linearity, causality, and stability constraints of linear system theory (LST) and thereby validate the EIS data. The polarization resistance decreased with removing of passive film and pitting formed in the passive layer, due to layer thinning or pitting caused by chloride. The impedance data for 304 SS with passive films can be accurately modeled using individual components of the equivalent circuits. The polarization resistances (Rp) of the 304 SS can be confirmed by Nyquist plots and estimated from the anodic polarization curves. The reaction model of the dissolution‐passivation process of 304 SS in acid solution is proposed. Copyright © 2009 John Wiley & Sons, Ltd.     

A study of the effect of metal corrosion inhibitors on the hydrogenation of steel and changes in its plasticity upon etching in sulfuric acid solutions

Effect of metal corrosion inhibitors, N-acetylmethylpyridium salts, on the hydrogen charging of 08 KP steel and changes in its plasticity upon its etching in solutions of 3 M sulfuric acid. Inhibitors more strongly diminishing the fraction of hydrogen atoms diffusing into the steel and preserving or raising its plasticity as compared with the shipment level were found.     

The effect of temperature oscillation on the passive corrosion properties of Alloy 22

A temperature-oscillating heated electrode technique (TOHET) was developed for investigating the temperature effect on the passive corrosion properties of Alloy 22 (UNS N06022, Ni–22Cr–13Mo–3W–3Fe), which has been selected as the corrosion-resistant material (CRM) of the waste package outer barrier for the high level nuclear waste (HLNW) repository at Yucca Mountain, NV, USA. Cyclic and potentiostatic polarization tests were conducted on a temperature-controlled hot surface of Alloy 22, which was immersed in simulated Yucca Mountain ground waters. The current recorded during cyclic polarization tests was sensitive to temperature changes when the temperature amplitude was greater than 2 °C. Corrosion potential increased from −293 mV to −256 mV (Ag/AgCl) when temperature was decreased from 102 °C to 72 °C. Current variation was also observed during a potentiostatic test at −150 mV over which temperature oscillated between 65 °C and 95 °C. The log–linear plot of passive current density vs. temperature exhibited a linear relationship. In summary, the TOHET method is a valuable technique for studying the effects of temperature on the corrosion rate of passive alloys.     

Inhibition of copper corrosion in acidic sulphate media by eco-friendly amino acid compound

This investigation aimed to study a “green” non-toxic biodegradable copper corrosion inhibitor in an acidic sodium sulphate solution. The methods used in the investigation of cysteine as a copper corrosion inhibitor in an acidic sodium sulphate solution were: potentiodynamic measurements, open circuit potential measurements, and chronoamperometric measurements. Optical microscopy was used in addition to electrochemical methods. Potentiodynamic measurements show that cysteine has good inhibitory properties in an acidic medium. Polarisation curves indicate that the presence of cysteine in a sulphate solution decreases the current density and that using various cysteine concentrations results in the formation of a protective film on the surface of the electrode due to the formation of the Cu(I)-cys complex. These results are confirmed by chronoamperometric measurements. Furthermore, it is clear from microphotographs that a protective film does form on copper electrode in the presence of cysteine. The Langmuir adsorption isotherm indicates that cysteine is chemisorbed on the surface of the electrode.     

Influence of some thiophene derivatives on the corrosion of iron in nitric acid solution

Corrosion of iron in 2MHNO₃ has been studied by the electrochemical polarization and weight loss measurements. The effect of some thiophene derivatives has been investigated. The results show that the inhibitors under consideration, influencing both the cathodic and anodic process, are adsorbed on the metal surface in molecular form. They do not change the mechanism of the reaction between iron and nitric acid, but decrease its rate. This effect is controlled by the values of their dipole moments. The weight loss technique also gave the same order of inhibition efficiency of the tested inhibitors.

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Der Einflu einiger Thiophen-Derivate auf die Korrosion von Eisen in salpetersauren Lösungen

Zusammenfassung Es wurde die Korrosion von Eisen in 2M HNO₃ mittels Messungen der elektrochemischen Polarisation und des Gewichtsverlustes untersucht. Dabei wurde der Einfluß einiger Thiophenderivate überprüft. Die Ergebnisse zeigen, daß die Inhibitoren, die den kathodischen und den anodischen Prozeß beeinflussen, an der Metalloberfläche in molekularer Form adsorbiert werden. Dabei wird der Reaktionsmechanismus der Reaktion zwischen Eisen und Salpetersäure nicht geändert, es wird jedoch die Geschwindigkeit herabgesetzt. Dieser Effekt ist mit den Dipolmomenten korrelierbar. Die Gewichtsverlustmessungen ergaben übereinstimmende Resultate.

     

Thin-layer chromatography of inorganic ions on polyethyleneimine cellulose in sulfuric acid and acid-ammonium sulfate media

Summary The thin-layer chromatographic behavior of 49 inorganic ions on polyethyleneimine (PEI) cellulose, a weakly basic anion-exchanger, has been systematically studied in sulfuric acid and ammonium sulfate media (both 0.01–1.0 moldm⁻³). The sorption on the cellulose decreases with increasing concentration of the acid or sulfate for most of the ions and to a lesser extent for Hg(II), Bi(III), Th(IV), Nb(V), and U(VI). The R_f values of Pd(II), Ru(III), Au(III), Pt(IV), and Ta(V) are extremely low in both systems. Ba(II), Pb(II), Sb(III), Mo(VI), and W(VI) are also strongly retained on the layer. Oxy-anions such as As(III) and Se(VI) are not adsorbed on the cellulose to any great extent, but Re(VII) distributes on the plate with a R_f value of about 0.5. The characteristic retention on PEI-cellulose layer of several polyvalent ions, which form anionic sulfato complexes, can be observed in ammonium sulfate media. Possibilities for separations of analytical interest are also demonstrated in both systems.     

Adsorption behavior of various metals on a weakly basic anion-exchange resin in sulfuric acid media

A systematic study is presented on the adsorption behavior of some 20 metals on a weakly basic condensed phenol resin, Amberlite CG-4B, in sulfuric acid media. The distribution coefficients were determined over a sulfuric acid concentration range of 0.005 M to 2 M. The metals adsorbed are similar to those which exhibit strong adsorption on a strongly basic resin, but the magnitudes of the distribution coefficients and the adsorption sequences differ considerably between the two types of the resin. Several two- and three-component separations of analytical interest are possible. A new method for the separation of titanium(IV) is described; this is based on its high adsorption on CG-4B from sulfuric acid media containing hydrogen peroxide.     

Electrochemical study of the degradation kinetics of polyaniline powder in sulfuric and hydrochloric acid media

Investigation of the degradation kinetics of polyaniline (PANi) powder has been performed with a cavity microelectrode in sulfuric and hydrochloric acid electrolytes using cyclic voltammetry. It was shown that the overall degradation mechanism is limited by first-order reaction kinetics. The rate constant of the polymer hydrolysis was found to be lower than the one determined for thin films. The influence of the electrolyte concentration was also investigated and compared with our previous work on the use of PANi as a battery material. Electronic Publication