The electrochemical reduction and determination of reduced nicotinamide adenine dinucleotide in acidic media

The apparent reduction of reduced nicotinamide adenine dinucleotide (NADH) in acidic media at a static mercury drop electrode was investigated. A simple, quick pretreatment procedure was developed to convert the NADH to its acid-hydrated form. This adsorbs on the mercury surface during a film deposition time and the film is then reduced. The adsorption is diffusion-controlled and hence the peak currents for square-wave and linear-scan voltammetry are proportional to Ct^1/2_pAf and Ct^1/2_pAv, respectively, where t_p is the effective film deposition time, C the concentration of NADH, A the electrode area, f the square-wave frequency, and ν the linear scan rate. Several electrochemical techniques were compared for the determination of NADH; the method of choice is square-wave voltammetry, although staircase or linear scan voltammetry can also be used. The detection limit is less than 7 nM, and the range of linear response covers 2–3 orders of magnitude of NADH concentration.     

An electrochemical investigation of the redox properties of lumiflavin in acidic media

The electrochemistry of lumiflavin in acidic media (1% to 40% sulfuric acid) has been investigated using cyclic voltammetry and bulk electrolysis in conjunction with UV—Vis absorption spectroscopy. The observed stabilization of flavin radicals in strongly acidic media has been explained on the basis of differences in medium effects on fully reduced flavin cations (FH⁺₄) as compared with protonated oxidized (FH⁺₂) and radical (FH^∓+₃) species. The equilibrium constant for the comproportionation reaction between protonated lumiflavin species (FH⁺₂ + FH⁺₄ → 2 FH^∓+₃) has been determined. Acid dissociation constants for FH⁺₂ and FH⁺₄ have also been evaluated. These data are used in conjunction with the pK_a reported for FH^∓+₃ to estimate the value of the comproportionation constant for the neutral lumiflavin species.     

In situ quantification of electrochemical dissolution of hafnium-tantalum alloys in acidic media

A thin film hafnium-tantalum combinatorial library with a compositional spread of over 70 at.% was used for electrochemical dissolution experiments in nitric acid. Surface microstructure analysis and crystallographic characterization of individual Hf–Ta alloys confirmed a hexagonal to tetragonal transition from pure Hf to pure Ta accompanied by a change in the surface grain structure. A flow-type scanning droplet cell microscope coupled to downstream analytics was used for the quantification of Hf and Ta dissolution rates along the entire compositional spread. Potentiostatically applying 3 V vs. SHE for 120 s for an electrolyte flow of 0.46 ml min^− 1 resulted in dissolution rates of pure Hf and pure Ta in the ng s^− 1 cm^− 2 and pg s^− 1 cm^− 2 range, respectively. For both species, the average dissolution rate was independent of the compositional gradient, indicating a dissolution enhancement of minor species. A decrease in their activation energy for dissolution triggered by a surface energy modification was the reason for the observed behavior.     

Study of corrosion inhibition phenomena in acidic media by electrochemical and surface analysis techniques

The kinetics of iron dissolution in sulfuric acid solutions is investigated by polarization measurements in the presence of halide ions and/or organic additives. Both the inhibition action and additive interactions are investigated during polarization measurements as a function of inhibitor concentration. The Armco iron surface is studied by scanning electron microscopy, Fourier transform infrared reflection-absorption spectroscopy, and X-ray photoelectron spectroscopy techniques. Anodically pre-polarized and non-polarized specimens are investigated. The non-polarized specimens were immersed in the aggressive solution for different time periods. It is found that the inhibition efficiency of different aminophosphonic acids can be increased by halide ions. In the presence of aminophosphonic acids, the anomalous behavior of halide ions can be eliminated during anodic polarization. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the authors in English.     

Extraction of technetium(vii) by calix[4]arene tetraketones and tetraesters from acidic and basic media

Tetrasubstituted on the lower rim calix[4]arenes, containing carbonyl and ester groups, and existing in a cone conformation are selective and efficient extracting agents for Tc^VII extraction from both acidic and basic solutions.     

Evaluation of the dissolved oxygen-related electrochemical behavior of pure titanium in acidic fluoride-containing solutions

Journal of Solid State Electrochemistry - The effects of dissolved oxygen (DO) on the corrosion behavior of pure titanium in acidic fluoride-containing acids (pH = 0.6–2.0) were...     

Sorbents based on calix[4]arenes for extraction of technetium(vii) from acidic and alkaline media

Sorption of Tc^VII from solutions of various compositions with new sorbents prepared by the noncovalent immobilization of (thia)calix[4]arenes on the Amberlite XAD-7™ support was studied. The sorbents studied efficiently extract technetium(vii) from both acidic and alkaline media. The sorption capacity of the sorbent with thiacalix[4]arene groups is superior to that of the sorbents with calix[4]arene groups and several times higher than that of the sorbents previously proposed for the sorption of Tc^VII. Technetium(vii) is sorbed by this sorbent as 1: 1 and 1: 2 thiacalix[4]arene—NH₄TcO₄ and 1: 1 and 1: 2 thiacalix[4]arene—NaTcO₄ complexes.     

Chemical and electrochemical behavior of titanium, silicon, and boron oxides in molten carbonates

The process of dissolution of titanium, silicon, and boron oxides in carbonate melts is studied. Voltammetric studies are used to show that the most electropositive electrochemical process in molten carbonates is discharge of carbon dioxide dissolved in the melt to elementary carbon. Electrochemical synthesis of carbides in carbonate melts is possible at the potentials more positive by their value than the potential of carbonate decomposition. Interaction of titanium and silicon carbides with carbonate solutions is studied.     

Baylis-Hillman reactions in aqueous acidic media

The Baylis-Hillman reaction has been successfully performed under aqueous acidic conditions at pH 1, using a range of substrates and tertiary amines as catalysts.     

Transformations of unsymmetrical N-hetarylformazans in acidic media

1-Aryl-3-phenyl-5-hetarylformazans undergo acid cleavage to give benzaldehyde hetarylhydrazones, whereas 1-hetaryl-3-phenyl-5-(4-nitrophenyl)formazans undergo acid cleavage to give benzaldehyde 4-nitrophenylhydrazones. 1-Aryl-3-phenyl-5-(6-oxo-4-methyl-2-pyrimidinyl)-formazans undergo cyclization to 1,2,4-triazolo[4,3-a]pyrimidine derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1268–1270, September, 1977.     

Effects of dissolved oxygen on the electrochemical corrosion behavior of pure titanium in fluoride-containing weakly acidic solutions

The effects of dissolved oxygen (DO) on the electrochemical behavior of titanium in fluoride-containing weakly acidic solutions (pH?=?5.0) were evaluated quantitatively by electrochemical methods, such as open circuit potential (OCP) measurements and potentiodynamic polarization tests, combined with corrosion morphology observation. The results showed that the electrochemical behavior changed from spontaneously passive to active-passive behavior with increasing the fluoride concentration irrespective of the DO content. DO was found to increase the critical fluoride concentration for the corrosion of titanium due to the increased limiting diffusion current density of oxygen reduction reaction and decreased maximum anodic current density caused by DO. But the corrosion rate of titanium would be accelerated by DO once the fluoride concentration exceeded the critical value. Moreover, corrosion products were observed on the surface when the fluoride concentrations were high enough and titanium was in the active state, which altered the electrochemical behavior of titanium further, such as facilitating the occurrence of OCP oscillation.

Open image in new window

Graphical abstract ?

     

Anoxic dissolution of troilite in acidic media

The anoxic dissolution of troilite (FeS) in acidic medium has been investigated at 50 degrees C using batch dissolution experiments. Two different progress variables were followed during solid dissolution, i.e., the amounts of dissolved iron (nFe) and formed hydrogen sulfide (n(H(2)S)). The experimental studies performed at hydrogen ion concentrations ([H+]) ranging from 0.04 to 0.2 mol L(-1) showed that anoxic dissolution of troilite is dependent on [H+]. The cumulative release of both Fe and H2S could be described by a diffusion-like rate law, with rate constants for Fe (k(p)(Fe) always greater than for H2S (k(p)(H2S). The surplus of dissolved iron over formed hydrogen sulfide was quantified by the n(Fe):n(H2S) ratio, and ranged from 1.21 to 1.46, higher than the specific n(Fe):n(H2S) ratio of troilite bulk, i.e., 1. Rate constants are linearly related to the pH with a slope of 0.66 +/- 0.23 (n(Fe)) or 0.63 +/- 0.13 (n(H2S)). The obtained results suggest that troilite anoxic dissolution is a process controlled by the diffusion of the reaction products across an obstructive layer, sulfur-rich layer (SRL), having a thickness that increases during reaction progress. The accumulation of H2S between the surface and the SRL, eventually leads to the mechanical destruction of this outer layer, a process that results an increased flux of reaction products.     

Heterogeneous reactions of epoxides in acidic media

Epoxides have recently been identified as important intermediates in the gas phase oxidation of hydrocarbons, and their hydrolysis products have been observed in ambient aerosols. To evaluate the role of epoxides in the formation of secondary organic aerosols (SOA), the kinetics and mechanism of heterogeneous reactions of two model epoxides, isoprene oxide and α-pinene oxide, with sulfuric acid, ammonium bisulfate, and ammonium sulfate have been investigated using complementary experimental techniques. Kinetic experiments using a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) show a fast irreversible loss of the epoxides with the uptake coefficients (γ) of (1.7 ± 0.1) × 10(-2) and (4.6 ± 0.3) × 10(-2) for isoprene oxide and α-pinene oxide, respectively, for 90 wt % H(2)SO(4) and at room temperature. Experiments using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) reveal that diols are the major products in ammonium bisulfate and dilute H(2)SO(4) (<25 wt %) solutions for both epoxides. In concentrated H(2)SO(4) (>65 wt %), acetals are formed from isoprene oxide, whereas organosulfates are produced from α-pinene oxide. The reaction of the epoxides with ammonium sulfate is slow and no products are observed. The epoxide reactions using bulk samples and Nuclear Magnetic Resonance (NMR) spectroscopy reveal the presence of diols as the major products for isoprene oxide, accompanied by aldehyde formation. For α-pinene oxide, organosulfate formation is observed with a yield increasing with the acidity. Large yields of organosulfates in all NMR experiments with α-pinene oxide are attributed to the kinetic isotope effect (KIE) from the use of deuterated sulfuric acid and water. Our results suggest that acid-catalyzed hydrolysis of epoxides results in the formation of a wide range of products, and some of the products have low volatility and contribute to SOA growth under ambient conditions prevailing in the urban atmosphere.     

Voltammetric study and electrochemical detection of hexavalent chromium at gold nanoparticle-electrodeposited indium tinoxide (ITO) electrodes in acidic media

The voltammetric behavior of hexavalent chromium species (Cr(VI)) was respectively studied at ITO, bulk Au, and Au-electrodeposited electrodes in 0.01 M NaCl aqueous solutions containing 0.01 M HCl. It was found that performance degradation of the ITO electrodes toward the reduction of Cr(VI) can be suppressed by modifying the electrode surface with gold nanoparticles (AuNPs), which were formed on ITO electrodes by potential-sweeping or potential-step electrodeposition in a 0.01 M Na(2)SO(4) solution containing 1 mM HAuCl(4) x 3 H(2)O and 0.01 M H(2)SO(4). After the modification, the surface of ITO electrodes turned to the characteristically red or blue color exhibited by AuNPs. The gold nanoparticle-electrodeposited indium-tinoxide electrode (AuNP-ITO) demonstrates unique catalytic behavior, higher sensitivity and stability in the reduction of Cr(VI). Cr(VI) species was detected by either cyclic voltammetry or hydrodynamic amperometry. By cyclic voltammetry, the dependence of cathodic peak current on concentration was linear from 5 to 100 microM with a detection limit of 2 microM (sigma=3), and linearity was obtained from 0.5 to 50 microM by hydrodynamic amperometry where a constant potential of +0.2V (vs. Ag/AgCl) was applied and a batch-injection cell was employed. For hydrodynamic amperometry, the detection limit was 0.1 microM (sigma=3).     

Modification of hydrolyzed lignin in acidic and basic media

The content of reactive groups such as OH, CO, and COOH was increased by modifying hydrolyzed lignin with sulfuric acid and sodium hydroxide. The increase was confirmed by IR spectral analysis. The sorptive capacity of the resulting hydrolyzed lignin derivatives was increased sharply by base activation. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 70–72, January–February, 2006.     

The behavior of technetium in technetium-scrubbing stage of PUREX process

Technetium decontamination factor as a function of the acidity, flow ratio, scrubbing stage number was investigated by counter-current cascade experiments or mixer-settler batch tests. Results showed that the acidity of the scrubbing acid has little influence on the decontamination factor of technetium when the acidity was kept in the range of 4.5–6 M. The most effective method to increase the decontamination factor is to lower the feed-to-acid flow ratio. Keeping other condition same the factor increased to 10.3 from 3.1 when feed-to-acid ratio changed to 4 from 5.6. The loss of uranium and plutonium can be recovered through a re-extraction technology.     

5,8-isoquinolinediones. II. Chemical and electrochemical behavior of the 5,8-isoquinolinedione system

We have devised two general synthetic schemes to 5,8-isoquinolinediones and have investigated the chemical and electrochemical behavior of these compounds. The 1,4-addition reactions of these quinones with amines was shown to occur at the 7-position and a number of 7-amino-5,8-isoquinolinediones. were synthesized. The 1,4-addition of hydrogen bromide was also studied. The ethylenic double bond of the 5,8-quinone system underwent Diels-Alder additions to yield the oxidized forms of the adducts. The nucleophilic displacement of the methoxy group in 7-methoxy-5,8-isoquinoline was accomplished with both potassium hydroxide and morpholine. A Polarographic study of the half-wave potentials of substituted 5,8-isoquinolinediones showed a linear correlation between the change in the half-wave potential of the quinone system (ΔE° 1/2) resulting from the introduction of different substituents, and the substituent constants (σ_p-x).     

Hydrogen-bubble-propelled zinc-based microrockets in strongly acidic media

Tubular polyaniline (PANI)/Zn microrockets are described that display effective autonomous motion in extreme acidic environments, without any additional chemical fuel. These acid-driven hydrogen-bubble-propelled microrockets have been electrosynthesized using the conical polycarbonate template. The effective propulsion in acidic media reflects the continuous thrust of hydrogen bubbles generated by the spontaneous redox reaction occurring at the inner Zn surface. The propulsion characteristics of PANI/Zn microrockets in different acids and in human serum are described. The observed speed-pH dependence holds promise for sensitive pH measurements in extreme acidic environments. The new microrockets display an ultrafast propulsion (as high as 100 body lengths/s) along with attractive capabilities including guided movement and directed cargo transport. Such acid-driven microtubular rockets offer considerable potential for diverse biomedical and industrial applications.     

Fabrication of metallic nanoparticles by electrochemical discharges

A method for the fabrication of metallic nanoparticles in large quantities by electrochemical discharges is presented. In an aqueous electrolyte, large current density (∼1 A/mm² at ∼20 V) leads to the formation of a ‘gas film’ around the electrode through which discharges occur. When metal ions are additionally present in the electrolyte and when the applied potential is cathodic, metal nanoparticles (typically 10–150 nm) are produced. The nanoparticles are formed in the solution and the gas film prevents them from depositing on the electrode. To control the size of the particles a method based on ‘rotating electrode’ is developed. Rotating the cathode rotates the fluid around it, which provides centrifugal force to the particles to move away from the electrode where they cannot grow. This method has been successfully used for fabrication of nanoparticles from several metal salts.