Oxide reduction and oxygen removal in water-atomized iron powder: a kinetic study

Journal of Thermal Analysis and Calorimetry - The purpose of the present work is to investigate humidification–dehumidification desalination system and to explore the effect of pertinent...     

Immunoassay detection in a perfluorocarbon emulsion oxygen therapeutic

The effect of a perfluorocarbon emulsion oxygen therapeutic (PEOT) on detecting theophylline was explored using a commercial EMIT® (enzyme multiplied immunoassay technique) immunoassay. The EMIT technique is based on a colorimetric reaction, the product of which can be measured spectrophotometrically. The intent was to determine whether the presence of PEOT interferes with this detection. We found that the immunoassay yields excellent quantitative data in the therapeutic range (10–20 ppm theophylline) in 2–10% PEOT, but as the amount of PEOT in the sample increases, the accuracy of the detection method decreases.     

Electrochemical study of oxygen interaction with lapachol and its radical anions

Cyclovoltammetric studies were performed with lapachol [2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone], in the absence and presence of oxygen, which aimed to investigate possible oxygen interaction with lapachol and its radical anion. The obtained results clearly indicate the consumption of the semiquinone anion-radicals by oxygen in an EC type reaction, generating the deprotonated form of lapachol and HOO*. The observed generation of reactive oxygen species (ROS) after electron transfer can be related to the mechanism of biological action of lapachol.     

Electrochemical kinetic analysis of a 1,4-hydroxynaphthoquinone self-assembled monolayer

Electroactive 5-hydroxy-3-hexanedithiol-1,4-naphthoquinone (JUG_thio) has been self-assembled on gold. Electrochemical results show the surface coverage is 2.2 × 10⁻¹⁰ mol cm⁻², which is consistent with a dense monolayer. The JUG_thio shows one quasi-reversible and stable voltametric wave in aqueous buffered solution. A kinetic analysis of the redox reactions involving both electron and proton transfer has revealed an unusual behaviour of this molecule due to the presence of the hydroxyl function in the vicinity of the quinone group. The apparent kinetic rate constant and the anodic coefficient transfer of this reaction depend on the pH. In acid medium, a classical concerted 2e⁻/2H⁺ mechanism is obtained. In basic medium (pH > 7), strong intramolecular hydrogen interactions between the quinone and the hydroxyl function have a strong influence on the redox kinetics. These results show that JUG_thio electroactivity is very sensitive to hydrogen interactions in neutral and basic pH solution and is able to act as sensitive layer for electrochemical biosensing.     

Electrochemical kinetic study of surface layer growth on natural pyrite in acid medium

This paper presents electrochemical experiments on natural pyrite that combine potentiostatic and voltammetric techniques. X-ray microanalysis is used as an auxiliary technique. The layer growth on pyrite surface is conducted in a wide range of pH and potential range: 3.4 ≤ pH ≤ 5.9 with E = 0.80 V (versus SHE), and 0.80 V ≤ E ≤ 1.00 V with pH 4.5 (versus SHE) in acetic acid–acetate buffer. This work is unique for two reasons: (1) phenomenological model about layer growth is applied and mathematical-physic consistence is verified and (2) Meyer's hypotheses of chemical mechanism are used to explain kinetic parameters of the phenomenological model.     

19F, 13C NMR analysis of an oxygen carrier,perfluorotributylamine, and perfluoropentanoic acid

NMR relaxation measurement of perfluorocarbons (PFCs), such as perfluorotributylamine (FTBA), is a convenient method for the determination of oxygen concentrations in tissues and tumors. Previous relaxation studies of FTBA used different ¹⁹F NMR assignments causing some confusion. Fluorine‐detected ¹⁹F, ¹³C HMQC and HMBC and selectively ¹⁹F‐decoupled ¹³C NMR provided unequivocal ¹⁹F and ¹³C assignments for FTBA and perfluoropentanoic acid (FPA). Based on those assignments, ¹³C spin–lattice relaxation time constants (T₁) and effective correlation times for FTBA and FPA are reported and discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Electrochemical reduction of oxygen at a porous flow-through electrode

The electrochemical reduction of oxygen at a porous flow-through electrode is described with emphasis on the effects of concentration, flow speed and surface area. On a packed bed copper electrode in sulfuric acid, it was found that oxygen undergoes a two electron reduction process giving rise to H₂O₂.     

Electrochemical study on determination of diffusivity,activity and solubility of oxygen in liquid bismuth

Diffusivity of oxygen in liquid bismuth was measured by potentiostatic method and is given by$\lg (D_{\mathrm{O}}^{\mathrm{Bi}}/{\mathrm{cm}}^2·{\mathrm{s}}^{-1})(\pm 0.042)=-3.706-1377/(T{\mathrm{K}}^{-1})(804<T/\mathrm{K}<1090)\text{.}$Activityof oxygen in bismuth was determined by coulometric titrations and using the measured data standard free energy of dissolution of oxygen in liquid bismuth was derived for the reaction:$1/2{\mathrm{O}}_2(\mathrm{g})=[\mathrm{O}{]}_{\mathrm{Bi}}(\mathrm{at}\text{.}\%)$and is given by$\mathrm{\Delta }{G}_{\mathrm{O}(\mathrm{Bi})}^{\circ }/(\mathrm{J}·\mathrm{g}\text{-}\mathrm{atom}{\mathrm{O}}^{-1})(\pm 720)=-108784+20.356T{\mathrm{K}}^{-1}(753<T/\mathrm{K}<1020)\text{.}$Using the above data and Gibbs free energy of formation of Bi₂O₃ (s), solubility of oxygen in liquid bismuth was derived as a function of temperature and is given by the following expressions:$\begin{array}{cc}\hfill & \lg (S/\mathrm{at}\%\mathrm{O})(\pm 0.05)=-4476/T{\mathrm{K}}^{-1}+4.05(753<T/\mathrm{K}<988)\text{;}\hfill \\ \hfill & \lg (S/\mathrm{at}\text{.}\%\mathrm{O})(\pm 0.04)=-3786/T{\mathrm{K}}^{-1}+3.36(988<T/\mathrm{K}<1020)\text{.}\hfill \end{array}$The present data on solubility of oxygen in liquid bismuth is compared with the literature data.     

Membrane-entrapped cytochrome c: Electrochemical and kinetic studies

The redox kinetics and the electrochemical behaviour of cytochrome c entrapped in a cellulose triacetate membrane have been investigated with reference to the behaviour in solution. The results suggest that the membrane plays an important role in controlling the redox properties of the immobilized protein; diffusion of the reagents into the membrane is rate-limiting, and the nature of the working electrode has no effect on the observed electrochemical behaviour.     

Electrochemical and kinetic study of the coupling reaction between 4-nitroso and 4-hydroxylaminopyridine-1-oxide

The study of the reduction process of nitrosopyridine-1-oxide at platinum electrodes in aqueous solution by controlled potential coulometry is reported. The results obtained are consistent with the hypothesis that a pH dependent reaction takes place between the depolarizer and the reduction product. Such results have been confirmed by conventional kinetic experiments. The pH dependence of the rate constant can be accounted for in terms of a base catalyzed mechanism.     

Particle formation mechanism and kinetic model of ultrasonically initiated emulsion polymerization

A general kinetic model of particle formation in an ultrasonically initiated emulsion polymerization system is presented. This model takes into account homogeneous, micelle entry, and monomer droplet nucleation mechanism. The effects of the ultrasound in producing free radical, degrading free radical and influencing the fashion of the nucleation are also considered. Moreover, chain transfer to monomer and termination in the aqueous phase, capture of oligomer radicals by particles, and coagulation of particles are also considered. An analytical solution is obtained for the initial particle stage consideration. This model predicts that, if the desorption of radical from particles can be neglected, the concentration of the total radical in the aqueous phase is directly proportional to the cavitation concentration. Model predictions are in good agreement with experimental data obtained from the literature.     

Electrochemical kinetic study about cobalt electrodeposition onto GCE and HOPG substrates from sulfate sodium solutions

In the present work, we analyze the electrodeposition of cobalt by electrochemical techniques onto GCE (system I) and HOPG (system II) electrodes from sulfate solutions. Cyclic voltammetry and current transient measurements were used to obtain the nucleation and growth mechanism. The results clearly showed that electrodeposition of cobalt is a diffusion-controlled process with a typical 3D nucleation mechanism in both substrates. The average ΔG calculated for the stable nucleus formation was 1.97 × 10⁻²⁰ J nuclei⁻¹ and 3.58 × 10⁻²⁰ J nuclei⁻¹ for system I and system II, respectively. The scanning electron microscope (SEM) images indicated similar nucleation and growth processes on GCE and HOPG substrates at same overpotential with a homogeneous disperse cobalt clusters. X-ray energy-dispersive spectroscopy (EDS) was performed in order to ensure that the clusters formed are cobalt. The nuclei’s size obtained was dependent of the overpotential applied; at lower overpotentials, the growth rate of the cobalt clusters diminishes when their number increases due to the strongly reduced concentration of cobalt ions because of their consumption by a larger number of growing particles. A theoretical quantum study employing PM6 method suggests that Na⁺ adsorbed deactivate the local surface occasionating the formation of disperse cobalt clusters on carbon electrodes.     

Polyaniline-based electrocatalysts through emulsion polymerization:Electrochemical and electrocatalytic performances

One of the major challenges associated with fuel cells is the design of highly efficient electrocatalysts to reduce the high overpotential of the oxygen reduction reaction(ORR). Here we report Polyaniline(PANI)based micro/nanomaterials with or without transition metals, prepared by the emulsion polymerization and subsequent heat treatment. PANI microspheres with the diameter of about 0.7 μm have been prepared in basic(NH3solution) condition, using two different types of surfactant(CTAB, SDS) as the stabilizer, ammonium persulphate(APS) as oxidant with aniline/surfactants molar ratio at 1/1 under the hydrothermal treatment. PANI nanorods, Fe–PANI, and Fe–Co–PANI have been synthesized in acidic(HCl)medium with aniline/surfactants molar ratio at 1/2 and polymerization carried out without stirring for24 h. Products mainly Fe–Co–PANI have shown high current density with increasing sweep rate and excellent specific capacitance 1753 F/g at the scan rate of 1 m V/s. Additionally, it has shown high thermal stability by thermogravimetric analysis(TGA). Fe–PANI has been investigated for excellent performance toward ORR with four electron selectivity in the basic electrolyte. The PANI-based catalysts from emulsion polymerization demonstrate that the method is valuable for making non-precious metal heterogeneous electrocatalysts for ORR or energy storage and conversion technology.     

Amperometric homogeneous competitive immunoassay in a perfluorocarbon emulsion oxygen therapeutic (PEOT)

The effect of a perfluorocarbon emulsion oxygen therapeutic (PEOT) on the detection of the drugs theophylline and phenytoin was explored using a commercial enzyme multiplied immunoassay technique (EMIT®). The EMIT technique is based on the enzymatic production of NADH, which is typically detected in serum samples spectrophotometrically. Here, amperometry using the rotating disk electrode on a single drop of solution is demonstrated to detect theophylline and phenytoin in the presence of PEOT. In the study, 2,6-dichloroindophenol (DCIP) added to the immunoassay mixture is reduced by the NADH to DCIPH₂. Oxidation of DCIPH₂ is monitored electrochemically at +200 mV using a glassy carbon rotating disk electrode. Slopes of amperograms are proportional to the concentration of drug in the immunoassay sample. This technique yields excellent quantitative data in the therapeutic range for both drugs in 2–20 % PEOT.     

Synthesis and kinetic studies of PMMA nanoparticles by non-conventionally initiated emulsion polymerization

The aqueous emulsifier-free emulsion polymerization of methyl methacrylate (MMA) was studied under the catalytic effect of in situ developed bivalent transition metal-EDTA complex with ammonium persulfate (APS, (NH₄)₂S₂O₈) as initiator. Out of these, Cu(II)-EDTA system was selected for detailed kinetic and spectrometric study of polymerization. The apparent activation energy E_a, 34.5 kJ/mol, activation energy of initiator decomposition E_d, 26.9 kJ/mol, energy of propagation E_p, 29 kJ/mol and energy of termination E_t, 16 kJ/mol were reported. The emulsion polymer (PMMA) latex was characterized through the determination of the size and morphology by scanning electron microscopy, the average molecular weight by GPC and viscosity methods and the sound velocity by ultrasonic interferometer. From the kinetic results, the rate of polymerization, R_p at 50 °C was expressed by

     

Electrochemical synthesis of poly(3‐methylthiophene): A kinetic study

Poly(3‐methylthiophene) (P3MT) films were electrogenerated on both platinum and carbon‐felt working electrodes. The kinetic equation was determined by the monomer and electrolyte concentrations being changed for different reaction times. For each sample, the weight of the polymer obtained was measured along with the polymerization charge, the oxidation charge, the ratio (R) between the two magnitudes, the charge storage efficiency (SE), and the doping level. The results obtained from the kinetic study indicate significant electrolyte participation in the electropolymerization process. The SE and the doping level decreased inversely proportionately to both the reaction time and the concentrations of the monomer and electrolyte. The ratio R increased with reaction time as well as with monomer or electrolyte concentrations for all P3MTs generated on the carbon‐felt electrodes, whereas for those films generated on platinum electrodes, the highest values were obtained for the lowest monomer and electrolyte concentrations. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1258–1266, 2000     

Mechanistic and kinetic aspects of photosensitization in the presence of oxygen

Determining whether the first step of photooxygenation is Type I or Type II is a necessary prerequisite in order to establish the mechanism of photodynamic action. But this distinction is not sufficient, because other processes, both consecutive and competitive, commonly participate in the overall mechanism. Thus, in both Type I and Type II reactions, the initial products are often peroxides that can break down and induce free radical reactions. These aspects of photosensitization are discussed and illustrated by sensitizer/substrate systems involving (1) only radical reactions (decatungstate/alkane) and (2) reactions of singlet oxygen occurring in competitive and consecutive processes and possibly followed by radical reactions (methylene blue/2'-deoxyguanosine). Two other previously investigated systems involving, respectively, a Type II interaction followed by radical processes (methylene blue/alkene) and Type II reactions, some of which being competitive or consecutive (rose bengal/alkene), are briefly reconsidered.     

Electrochemical oxygen transfer reactions: electrode materials,surface processes,kinetic models,linear free energy correlations,and perspectives

This work summarizes progresses achieved in electrochemical oxygen transfer reactions from water to organic pollutant molecules on metal oxide electrodes during the past two decades. Fundamental understanding of the dynamics of the electrochemical oxygen transfer reaction is of crucial importance for the development of key concepts of electrocatalytic processes, leading to the implementation of environmental electrochemistry wastewater treatment schemes with rational design of the suitable electrocatalytic systems. We discuss the current knowledge on the electrochemical oxygen transfer reaction, emphasizing the importance of surface processes in order to generalize mechanistically the experimental results obtained on different electrode materials, describing also the practical kinetic models developed and their implications. From the information gathered in this review, it is apparent that explanations for the kinetics of the reactions in relation to the structure of the organic compounds involved is lacking, hence that new information about structure-reactivity relationships is needed. We show in particular that the open circuit decay of the concentration of radical cations, obtained from spectroelectrochemical data, allows correlating the structure of adsorbed states with reactivity during oxygen transfer reactions, pointing as well to research efforts required to understand the catalytic performance of metal oxide electrodes in decomposing organic compounds strongly adsorbed on their surfaces. Finally, some perspectives for future research in this area are briefly commented.     

Iron(II) sulfate oxidation with oxygen on a Pt/C catalyst: A kinetic study

The kinetics of iron(II) sulfate oxidation with molecular oxygen on the 2% Pt/Sibunit catalyst was studied by a volumetric method at atmospheric pressure, T = 303 K, pH 0.33–2.4, [FeSO₄] = 0.06?0.48 mol/l, and [Fe₂(SO₄)₃] = 0?0.36 mol/l in the absence of diffusion limitations. Relationships were established between the reaction rate and the concentrations of Fe²⁺, Fe³⁺, H⁺, and Cl^? ions in the reaction solution. The kinetic isotope effect caused by the replacement of H₂O with D₂O and of H⁺ with D⁺ was measured. The dependence of Fe²⁺ and Fe³⁺ adsorption on the catalyst pretreatment conditions was studied. A reaction scheme is suggested, which includes oxygen adsorption, the formation of a Fe(II) complex with surface oxygen, and the one-electron reduction of oxygen. The last step can proceed via two pathways, namely, electron transfer with H⁺ addition and hydrogen atom transfer from the coordination sphere of the iron(II) aqua complex. A kinetic equation providing a satisfactory fit to experimental data is set up. Numerical values are determined for the rate constants of the individual steps of the scheme suggested.