


Vol 52, No 10 (2016)
- Year: 2016
- Articles: 14
- URL: https://journal-vniispk.ru/1023-1935/issue/view/11790
Article
Determination of corrosion current density on bulk nickel and nickel powder by the rate of cathodic depolarizer consumption
Abstract
The method of “compensating additives” is used to determine the corrosion current of nickel and nickel powder in 0.5 M NaCl solution containing 0.01 M HCl. Comparing the corrosion currents measured on bulk nickel and nickel powder, the specific electrochemically active surface area of nickel powder is estimated.



Electroreduction of bromate anion on inactive RDE under steady-state conditions: Numerical study of ion transport processes and comproportionation reaction
Abstract
The study is devoted to analyzing the electroreduction of bromate anion BrO 3- on catalytically inactive (e.g., carbon) electrodes by numerical methods. This process is realized due to the combination of the reversible mediator pair Br2/Br- and the process of comproportionation (reaction of bromate and bromide anions) in solution phase. These reactions increase the concentration of bromine and bromide near the electrode surface; hence, this process is autocatalytic (EC″ mechanism). Within the framework of this study, a numerical algorithm which allows the system of diffusion-kinetic equations to be solved for this system is proposed for one-dimensional transport and the process under steady-state conditions. The results are compared with the conclusions of the approximate analytical theory published in Electrochim. Acta, 2015, vol. 173, p. 779, which allows inferring that both approaches are correct. The deviation between the latter is observed only in the cases of violation of approximations lying in the basis of the corresponding analytical relationships. Thus, the predictions of the analytical theory of practical interest can be considered as reliably confirmed by numerical calculations, particularly, the prediction on the nonmonotonous dependence of the maximum current on the diffusion layer thickness (or the RDE rotation rate) including the anomalous region of this dependence in which the current increases with the increase in the diffusion layer thickness.



Effect of thickness on the capacitive behavior and stability of ultrathin polyaniline for high speed super capacitors
Abstract
In this work four polyaniline (PANI) film electrode with different thickness were synthesized by electrochemical method on the surface of glassy carbon (GC) electrode. Four polymer films with various thicknesses from 0.5 to 11 μm were synthesized. Electropolymerization occurs in low monomer concentration. Morphology study of electrode shows that surface structure of polymers depends on film thickness. Capacitance of electrode was studied by CV and charge-discharge (CD) methods. Specific capacitance (SC) of electrodes using cyclic voltammetry were calculated 620, 247 F g–1 for thinnest and thickest polymer film, respectively. Stability of electrodes was studied during 1000 voltammogram cycles. Results show that with the increase of thickness the stability of electrodes enhanced and reach to a maximum and then decreased.



Simulation of differential pulse polarography of irreversible EC mechanism
Abstract
A reversible electrode reaction that is followed by totally irreversible chemical reaction is investigated theoretically. The influence of chemical reaction on two components of the net response of differential pulse polarogram is analyzed. It is demonstrated that this EC mechanism depends on two kinetic parameters and that their critical values can be used for the measurement of the rate constant of chemical reaction.



Experimental investigation and multiphysics simulation on the influence of micro tools with various end profiles on diametrical overcut of holes machined using electrochemical micromachining for a predetermined optimum combination of process parameters
Abstract
Electrochemical micromachining (EMM) process is generally applied to shaping of electrically conductive materials which has been gaining popularity in the production of biomedical, MEMS, aerospace and nuclear components. The dimensional accuracy is affected by various process parameters of EMM and by the end profile of the cathode (tool) used to machine the feature. In this study, it is proposed to investigate the EMM process to know the influence of various process parameters on the diametrical overcut of the machined hole and the optimum combination of process parameters to produce holes with minimum diametrical over cut. A bare electrode with flat end is used for this purpose. Later, insulated electrode with flat end and bare electrodes with various end profiles are used to drill holes at the optimum combination of process parameters on Titanium grade II sheet to identify the most suitable micro tool to produce holes with minimum diametrical overcut and minimum stray machined zone. The EMM process of drilling holes using insulated electrode with flat end and bare electrodes with various end profiles are simulated at the optimum combination of process parameters using COMSOL Multiphysics V4.2a software. Results justified the use of multiphysics simulation to understand the process before conducting experiments so that costly trial and error experiments can be reduced to a minimum.



Comparison of different carbon nanostructures influence on potentiometric performance of carbon paste electrode
Abstract
Recently, different carbon nanomaterials were introduced for construction of electrochemical sensors. In this study, the influence of carbon nanomaterial on performance of carbon paste potentiometric electrode was investigated. In this manner, different kinds of carbon nanomaterial, i.e., graphene, graphene oxide and carbon nanotube (CNT) were used as a conduction phase in carbon paste electrode. Then, potentiometric characteristics of the corresponding paste electrodes such as calibration slope, linear range, detection limit, response time and stability were compared with each other. The results appeared comprehensive findings about the role of electrode’s content in electrochemical performance.



Green synthesis of silver nanoparticles by pepper extracts reduction and its electocatalytic and antibacterial activity
Abstract
Stable silver nanoparticles were synthesized with the aid of a novel, non-toxic, eco-friendly biological material namely, green pepper extract. The aqueous pepper extract was used for reducing silver nitrate. The synthesized silver nanoparticles were analyzed with transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). TEM image shows the formation of silver nanoparticles with average particle size of 20 nm which agrees well with the XRD data. The main advantage of using pepper extract as a stabilizing agent is that it provides long-term stability for nanoparticles by preventing particles agglomeration. To investigate the electrocatalytic efficiency of silver nanoparticles, silver nanoparticles modified carbon-paste electrode (AgNPs–CPE) displayed excellent electrochemical catalytic activities towards hydrogen peroxide (H2O2) and hydrogen evolution reaction (HER). The reduction overpotential of H2O2 was decreased significantly compared with those obtained at the bare CPE. An abrupt increase of the cathodic current for HER was observed at modified electrode. Also, the antibacterial activity of silver nanoparticle was performed using Escherichia coli and Salmonellae. The approach of plant-mediated synthesis appears to be cost efficient, eco-friendly and easy methods.



Effect of electric field on lithium ion in silicene channel. Computer experiment
Abstract
The molecular dynamics method is used to study the drift of Li+ ions exposed to electric interactions in a planar channel formed by silicene sheets. The character of dynamics of the ion and also its effect on mechanical properties of silicene sheets are used to determine the optimum size of the planar channel clearance. Instability of the surface (4 × 4) structure of free bilayer silicene is demonstrated. Mobilities of Si atoms and distributions of the main stresses in silicene appearing in the course of lithium ion movement along the channel are calculated.



Determination of the stability constant and thermodynamic parameters between Tl+, Ag+ and Pb2+ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand
Abstract
The complexation reaction between Tl+, Ag+ and Pb2+ cations with 2,6-di(furyl-2yl)-4-(4-methoxy phenyl)pyridine as a new synthesis ligand in acetonitrile (ACN)–H2O and methanol (MeOH)–H2O binary solutions has been studied at different temperatures using conductometric method. The conductometric data show that the stoichiometry of the complexes is 1: 1 [M: L] and the stability constant of complexes changes with the binary solutions identity. Also, the structure of the resulting 1: 1 complexes was optimized using the LanL2dz basis set at the B3LYP level of theory using GAUSSIAN03 software. The results show that the change of logKf for (DFMP.Pb)2+ and (DFMP.Ag)+ complexes with the mole ratio of acetonitrile and for (DFMP.Ag)+ and (DFMP.Tl)+ complexes with the mole ratio of methanol have a linear behavior, while the change of logKf of (DFMP.Tl)+complex in ACN–H2O binary solutions (with a minimum in XACN = 0.5) and (DFMP.Ag)+ complex in MeOH–H2O binary solutions (with a minimum in XMeOH = 0.75) show a non-linear behavior. The selectivity order of DFMP ligand for these cations in mol % CAN = 25 and 75 obtain Tl+ > Pb2+ > Ag+ but in mol % CAN = 50, the selectivity order observe Pb2+ > Tl+ > Ag+. Also, this selectivity sequence of DFMP in MeOH–H2O (mol % MeOH = 75 and 100) and (mol % MeOH = 50) is obtained Pb2+ > Ag+ and Tl+ > Ag+ > Pb2+ respectively. The values of thermodynamic parameters show that these values are influenced by the nature and the composition of binary solution. In all cases, the resulting complexes are enthalpy stabilized and entropy destabilized. The TΔSC° versus ΔHC° plot of all obtained thermodynamic data shows a fairly good linear correlation which indicates the existence of enthalpy-entropy compensation in the complexation reactions.



Short Communications
Graphitized carbon materials for electrosynthesis of Н2О2 from О2 in gas-diffusion electrodes
Abstract
New graphitized carbon materials: technical carbon N220, С140, and СН85 (Omsktekhuglerod) were studied as catalysts of electrosynthesis of alkaline solutions of hydrogen peroxide from oxygen in gasdiffusion electrodes (GDEs). The kinetic parameters of oxygen reduction in alkaline solution and the capacity of gas-diffusion electrodes based on technical carbon N220, С140, and СН85 were determined. Data on the kinetics of hydrogen peroxide accumulation were obtained at different current densities. The fraction of current γ spent on the reduction of oxygen to hydrogen peroxide was determined. The rate constants of hydrogen peroxide decomposition under the given conditions were calculated.



Lithiation–delithiation of infinite nanofibers of the SinCm type—the possible promising anodic materials for lithium-ion batteries. Quantum-chemical modeling
Abstract
With the aim of finding the promising anodic materials for lithium-ion batteries, the quantumchemical simulation of the structure, stability, and electronic properties of loose infinite nanofibres such as [SinCm]k (k = ∞) with n = 12–16, m = 8–19 is carried out by the method of density functional with due regard to the gradient correction and periodic boundary conditions. It is shown that infinite nanofibres of the SinCm type can be used as the anodes in lithium-ion batteries because the cycling changes their volume by 6–8% starting from the third cycle. The anodes that passed more than 3–4 cycles of lithiation-delithiation are recommended for practical application.



Electrosynthesis and biological properties of persulfate–chloride solutions
Abstract
A method for electrochemical synthesis of medical solutions for oxidation of toxic substances in the human organism has been developed. The method is based on electrooxidation of sodium sulfate in the presence of chloride and NaOH microadditions (in amounts that provide рН 13) in a filter-press membrane electrolyzer. A diagram is presented for choosing the optimum ratio between the current density and the flow rate of electrolyte during the electrosynthesis of a medical solution. The use of an electrolyte of the suggested composition under the optimum electrosynthesis conditions leads to solutions with physiological рН values (7.2–7.4) and high oxidative ability with respect to Micrococcus sp. and Staphylococcus coag (–), but there was no injuring effect on blood cells.



Inclusion of the concentration dependence of the diffusion coefficient in the sand equation
Abstract
The applications of the Sand equation in potentiometry of electrode and membrane systems for precise measurements of the transition time (τ) have been determined. An approach was suggested for choosing the diffusion coefficient of electrolyte (D) in the case when the concentration changes from its value in the agitated solution (where D = Db) to the nearly zero value at the surface (D = D0 corresponds to an infinitely dilute solution), Db and D0 being substantially different. The Nernst–Planck–Poisson nonstationary equations were numerically solved in a one-dimensional system including an ion-exchange membrane and two adjacent diffusion layers (for the electrode–solution system, the result is a particular case). An effective value Def was found, whose substitution in the Sand equation gave τ identical to that obtained by numerical solution. The neglect of the concentration dependence D(с) can lead to a nonadequate determination of the ion transport numbers in the membrane.



Electrochemical noise spectroscopy: Method of secondary Chebyshev spectrum
Abstract
A new method of electrochemical noise diagnostics is presented: the method of the secondary Chebyshev spectrum based on the splitting of an individual spectral line in the primary Chebyshev spectrum with formation of a system of spectral lines of the secondary Chebyshev spectrum. Algorithm for calculation of the secondary Chebyshev spectrum is developed. The suggested method based on analysis of noises measured in a specific electrochemical system is tested. It is shown that the new method allows determining the differences in the state of the electrochemical system more reliably, than the method of primary Chebyshev noise spectra.


