scholarly journals Electrochemical Modeling of Iodide Oxidation in Metal-Halide Molten Salts

2021 ◽  
Vol 168 (12) ◽  
pp. 126511
Author(s):  
Rose Y. Lee ◽  
Stephen J. Percival ◽  
Leo J. Small
Keyword(s):  
Molten Salts ◽  
Equilibrium Constants ◽  
Oxidation Potential ◽  
Simulation Software ◽  
Metal Halide ◽  
Lewis Acidity ◽  
Oxidation Potentials ◽  
Iodide Oxidation ◽  
Electrochemically Active ◽  
Current Densities

The oxidation of iodide in NaI-AlBr3, NaI-AlCl3, and NaI-GaCl3 molten salts was analyzed using simulation software to extract relevant kinetic parameters. The experimental oxidation potentials were ordered AlCl3 < AlBr3 < GaCl3, with higher oxidation potentials correlating with softer Lewis acidity of the metal halide. An iodide oxidation and metal halide speciation model was developed and simulated to fit the electrochemical response, enabling determination of electrochemical charge transfer parameters and chemical equilibrium constants. NaI-AlBr3 displayed the fastest electron transfer rates yet showed the lowest current densities. All salts revealed smaller than expected current densities, explained by equilibrium between various species, where some are not electrochemically active at the studied potentials. These equilibrium reactions are due to the various metal halide species, controlling the reactant concentration of iodide and the resultant current. We hypothesize the electrochemically active iodide species, present as a metal halide monomer (MX3I−), is decreased dramatically from the expected concentration, sequestered as a more stable metal halide dimer species (M2X6I−) with a higher oxidation potential. Traditional Tafel analysis of the experimental data supports the validity of the simulations. These results increase understanding of iodide oxidation in low-temperature Lewis acidic molten salts and inform task-specific molten salt design.

Effects of Doping on the Electrochemical and Electrical Properties of Poly(2,5-di(2-thienyl)pyrrole)

1999 ◽  
Vol 64 (8) ◽  
pp. 1357-1368 ◽  
Author(s):  
Enric Brillas ◽  
José Carrasco ◽  
Ramon Oliver ◽  
Francesc Estrany ◽  
Víctor Ruiz
Keyword(s):  
Mass Spectrometry ◽  
Fast Atom Bombardment ◽  
Oxidation Potential ◽  
Ethanolic Solution ◽  
Pt Electrode ◽  
Reversible Process ◽  
Oxidation Potentials ◽  
Lower Productivity ◽  
Polymeric Chains ◽  
Linear Molecules

The electropolymerization of 2,5-di(2-(thienyl)pyrrole) (SNS) on a Pt electrode from ethanolic solution with LiClO4 or LiCl as electrolyte has been studied by cyclic voltammetry (CV) and chronoamperometry (CA). In both media, a quasi-reversible process has been indicated by CV, reversing the scan at low oxidation potentials. Under these conditions, reducible positive charges formed in both oxidized polymers are compensated by the entrance of anions from solution. Elemental analysis reveals that polymers generated at a low oxidation potential by CA contain a 21.03% (w/w) of ClO4- or a 9.56% (w/w) of Cl-. The poly(SNS) doped with Cl- presents higher proportion of reducible positive charges, higher polymerization charge and lower productivity. A much higher electrical conductivity, however, has been found for the poly(SNS) doped with ClO4-. Both polymers are soluble in DMSO, acetone and methanol. The dimer, trimer, tetramer and pentamer have been detected as soluble and neutral linear oligomers by mass spectrometry-fast atom bombardment. The analysis of polymers by infrared spectroscopy confirms the predominant formation of linear molecules with α-α linkages between monomeric units. A condensation mechanism involving one-electron oxidation of all electrogenerated linear and neutral polymeric chains is proposed to explain the SNS electropolymerization.

Polarization Studies of Aluminum Alloys In Water at 200 C and 300 C

CORROSION ◽  
1963 ◽  
Vol 19 (4) ◽  
pp. 146t-155t ◽  
Author(s):  
J. H. GREENBLATT ◽  
A. F. McMILLAN
Keyword(s):  
Anodic Polarization ◽  
Cathodic Polarization ◽  
Oxidation Potential ◽  
Electronic Conduction ◽  
Film Resistance ◽  
Applied Current ◽  
Weight Gain Data ◽  
Current Densities ◽  
Polarization Studies ◽  
Impressed Current

Abstract Specimens of commercial 2S aluminum and two special alloys containing iron and nickel were polarized anodically and cathodically at a number of different current densities at 200 C and 300 C. Weight gains were obtained and the potentials relative to the stainless steel autoclave were measured by an interrupter method. The weight gain data indicated that the polarizing current is being carried by electronic conduction. The potential-time curves for anodic polarization indicate differences between 2S aluminum and the alloys in that greater polarization is obtained with the latter. These curves also indicate that the impressed current decreases the film resistance. In all cases the potential reached a plateau value with time and this time was shorter for the alloys. The potential-time curves for cathodic polarization also show plateau values but the rise to a plateau value is in the opposite sense to the applied current. With increasing cathodic polarization the plateau values occur at more negative values of the potential. This latter trend is in the same direction as the applied polarizing current. This apparently is explained in terms of the build-up of the aluminum oxidation potential which acts in a sense opposite to the applied current. Again the time to reach plateau values was shorter for the alloys. Voltage current curves were also obtained on specimens left overnight (approximately 17 hours) at two different anodic polarizing currents. These curves indicated differences between 2S aluminum and the alloys; these differences are discussed in terms of the semi-conducting properties of the oxide film. The observations made on the differences in the properties of the oxide films on the materials examined as revealed by potential and polarization curves are discussed as to their significance in determining corrosion resistance.

1-Iodoacétylènes. IV. Relations structure–réactivité pour la complexation des 1-iodoacétylènes substitués avec des bases de Lewis

1983 ◽  
Vol 61 (1) ◽  
pp. 135-138 ◽  
Author(s):  
Christian Laurence ◽  
Michèle Queignec-Cabanetos ◽  
Bruno Wojtkowiak
Keyword(s):  
Complex Formation ◽  
Triple Bond ◽  
Vibrational Frequency ◽  
Chemical Shifts ◽  
Structural Parameters ◽  
Equilibrium Constants ◽  
Lewis Acidity ◽  
Frequency Shifts ◽  
Substituent Constants ◽  
Substituted 1

The equilibrium constants for complex formation between the substituted 1-iodoacetylènes 1–8 and the vibrational frequency shifts induced by complex formation are related to the electronic substituent constants. The 13C chemical shifts of the triple bond are also useful structural parameters for predicting the Lewis acidity of iodoalkynes.

Dynamics of the transient species generated upon photolysis of diarylmethanes within zeolites — Deprotonation and oxidation reactions

2005 ◽  
Vol 83 (9) ◽  
pp. 1637-1648 ◽  
Author(s):  
Suzanne Shea ◽  
Norman P Schepp ◽  
Amy E Keirstead ◽  
Frances L Cozens
Keyword(s):  
Radical Cation ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Radical Cations ◽  
Laser Flash ◽  
Oxidation Potential ◽  
Oxidation Reactions ◽  
Oxidation Potentials ◽  
Multistep Process ◽  
Acid Zeolites

The oxidation of diarylmethanes is a multistep process involving initial formation of a radical cation, deprotonation of the radical cation to the radical, and oxidation of the radical to the carbocation. The dynamics and efficiency of the last two steps in this process, namely deprotonation and oxidation, in acidic zeolites and non-acid zeolites are examined in the present work as a function of the acidity of the diarylmethane radical cations and the oxidation potential of the diarylmethyl radicals. Our results indicate that rate constants for deprotonation strongly depend on the acidity of the radical cations, but not on the composition of the zeolites. In addition, oxidation of the radicals to the diarylmethyl cations is strongly dependent on both the oxidation potential of the radicals and the oxidizing ability of the zeolite. This dependence allows oxidation potentials of the zeolites to be estimated.Key words: radical cations, carbocations, zeolites, laser flash photolysis.

Reactions of some substituted phenols with chromyl and vanadyl chlorides

1980 ◽  
Vol 58 (7) ◽  
pp. 686-693 ◽  
Author(s):  
John F. Harrod ◽  
Asha Pathak
Keyword(s):  
Metal Complexes ◽  
Oxidation Potential ◽  
Lewis Acidity ◽  
Substituted Phenols ◽  
Phenoxyl Radicals ◽  
Organic Group ◽  
Product Distributions ◽  
Carbenium Ion ◽  
Electron Withdrawal ◽  
Ligand Transfer

The oxidation of 2,4,6-tritertbutylphenol and several other alkyl and halophenols by CrO2Cl2 and VOCl3 was studied. The products of CrO2Cl2 oxidation are mostly quinones and diphenoquinones, whilst those of VOCL3 oxidation also include major amounts of dealkylated phenols and C—C coupled dimers. The product distributions are interpreted in terms of a mechanism involving phenoxyl radicals, ligand transfer from metal to radical, and either phenoxonium ions or metallate esters where there is sufficient electron withdrawal from the organic group for it to exhibit carbenium ion properties. The differences in behaviour between CrO2Cl2, VOCl3, and CuCl2 are attributed to different balances between the oxidation potential and Lewis acidity of the metal complexes. It is concluded that CrO2Cl2 is not a good model for proposed ferryl intermediate in heme oxidase systems since it induces 1 → 3 rather than 1 → 2 halogen shifts and an NIH shift that is best explained by carbenium ion-like intermediates.

Corrosion Properties of Plasma Oxidized Titanium Nitride for Biomedical Applications

2015 ◽  
Vol 227 ◽  
pp. 471-474 ◽  
Author(s):  
Jerzy Robert Sobiecki ◽  
Agnieszka Brojanowska ◽  
Konrad Kowalczyk
Keyword(s):  
Titanium Nitride ◽  
Calcium Ions ◽  
Biomedical Applications ◽  
Oxidation Potential ◽  
Plasma Oxidation ◽  
Corrosion Properties ◽  
Oxide Layers ◽  
Oxidation Processes ◽  
Oxidation Potentials ◽  
Electrolytic Plasma Oxidation

The article compares the corrosion properties of oxide layers formed on titanium nitride (obtained in glow-discharge nitriding) using electrolytic plasma oxidation. The corrosion properties are analysed in correlation with the surface morphology, microstructure and chemical composition of the layers. The oxidation processes were carried out in 10% and 25% phosphoric acid (V) solutions containing Ca2+ calcium ions. In each of these environments, oxide layers were formed using three oxidation potentials: 200V, 400V and 600 V. The oxidation potential and the concentration of acid and calcium ions in the oxidation solution was shown to affect the morphology of the surface and the corrosion properties of the oxide layers obtained.

scholarly journals On the control of coolant parameters in long-life facilities

2020 ◽  
Vol 6 (3) ◽  
pp. 137-141
Author(s):  
Yury G. Cherednichenko ◽  
Oleg E. Levin
Keyword(s):  
Oxygen Content ◽  
Temperature Region ◽  
Power Plants ◽  
Oxidation Potential ◽  
Oxygen Activity ◽  
Maximum Temperature ◽  
Pure Lead ◽  
Oxidation Potentials ◽  
Dissolved Oxygen Control ◽  
Long Life

When nuclear power plants with heavy coolants are brought to operating mode as well as during their operation, it is necessary to control and maintain the oxygen content in the coolant within the specified limits. As a rule, the oxygen content in metal melts is controlled by sensors based on solid oxygen-ionic electrolytes. The article presents an analysis of the methodological aspects of dissolved oxygen control in non-isothermal circulating loops with metal coolants, using such sensors. It is shown that in the presence of dissolved loop wall materials and suspensions of their various oxides in the coolant, control over the values of the oxygen activity and concentration calculated for a pure coolant is in general unjustified. The authors present the experimental results of the distribution of oxidation potentials along the loop depending on the coolant temperature, obtained during long-term tests of cladding samples in a lead melt in two circulation facilities – SM2-M and TsU1-M – which differ in principal methods for maintaining specified oxygen conditions. In the low temperature region, the experimental values of the oxidation potential in both facilities are lower than those calculated for pure lead, which leads to a difference by two or more times of the calculated oxygen concentrations for the regions of the loop with Тmin and Тmax, i.e., the so-called oxygen ‘non-isoconcentration’ is observed along the loop. In deoxidation mode during hydrogen ejection into the coolant, the oxidation potential in the loop changes in a complex way, and it makes no sense to talk about the oxygen concentration. It is concluded that in long-life facilities, the coolant parameters for oxygen must be controlled not by the calculated oxygen activity or concentration but by the oxidation potential in the maximum temperature region. To obtain the correct values of the oxidation potential, measurements should be carried out in temperature-stable modes of throughout the facility.

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