Search results for "ELECTROCHEMISTRY"
showing 10 items of 1918 documents
Distribution potential in electrified microemulsions with potential determining salts
2018
Abstract The electrical polarization of lamellar and water-in-oil microemulsions composed of the aqueous solution of a potential determining salt (PDS), an organic solvent and a nonionic surfactant has been studied. The distribution of the PDS ions across the interface between two immiscible electrolyte solutions (ITIES) generates an electrical potential difference which can be used to control charge transfer processes. In macroscopic ITIES, this distribution potential is independent of the PDS concentration and can be determined from the electroneutrality condition far from the interface. In microemulsions, on the contrary, the distribution potential is smaller in magnitude and depends on …
The role of lithium, perchlorate and water during electrochemical processes in poly(3,4-ethylenedioxythiophene) films in LiClO4 aqueous solutions
2021
Abstract Thin films of poly(3,4-ethylendioxythiophene) (PEDOT) were electrochemically deposited on gold electrodes in aqueous media. The role of perchlorate, lithium, and water during the charge/discharge of PEDOT films was investigated by cyclic voltammetry together with EQCM, vis − NIR spectroscopy, and acoustic impedance, also by means of ac-electrogravimetry in a 0.1 M LiCl O 4 aqueous solutions. In this way, it has been possible to correlate the electrical, mass, color and electromechanical properties changes during the electrochemical reactions of this polymer. Both, hydrated lithium cations and perchlorate anions can act as counterions during the electrochemical reactions, however, a…
An electromechanical perspective on the metal/solution interfacial region during the metallic zinc electrodeposition
2009
The difficulty of studying the metal/solution interfacial region makes the use of non-conventional measurement techniques indispensable. In this way, a careful in situ study by means of acoustic impedance techniques coupled with nano-electrogravimetric techniques allowed this interface to be monitored during the metallic zinc electrodeposition process. This paper proves the formation of a viscoelastic layer consisting of ultra-hydrated Zn(II)/Zn(I) salts as a key step in the metallic zinc electrodeposition mechanism in sulfate aqueous solutions. Surprisingly, this layer is located in the metal/solution interfacial region and not on the reaction substrate. The chloride ions effect on the met…
Influence of the dissolution of MnS inclusions under free corrosion and potentiostatic conditions on the composition of passive films and the electro…
2006
Abstract The influence of the dissolution of MnS inclusions at the OCP value and 400 mV versus SCE on the chemical composition of passive films and the electrochemical behaviour of resulfurized austenitic stainless steel was studied in 1 M NaClO 4 , pH 3, solution using SIMS, XPS, electrochemical impedance spectroscopy and the electrochemical microcell technique. The electrochemical dissolution (at 400 mV versus SCE) of inclusions occurred uniformly along the interface and this process was almost complete after 25 min immersion. A small amount of sulfur was detected on the matrix that exhibited a wide passive range. By contrast, the dissolution process under free corrosion was not uniform a…
Application of the Generalized Molar-Ratio Method to the Determination of the Stoichiometry and Apparent Binding Constant of Nanoparticle-Organic Cap…
2015
A generalization of the molar-ratio method is applied to the determination of the stoichiometry and apparent binding constant of metal nanoparticle-organic capping complexes (MmLx) using voltammetric data for the oxygen reduction reaction (ORR) in air-saturated aqueous phosphate buffer solutions. The method is applied to the formation of binary nanohybrids consisting of gold nanoparticles (AuNPs) capped with a rigid spacer, cucurbit[7]uril (CB), termed AuNP@CB, as well as to the formation of their ternary complexes (MmLxBz) with methylene blue (MB), termed AuNP@CB@MB. The obtained stoichiometries correspond to binding of four Au surface atoms for each CB unit.
Estimation of free energies of anion transfer from solid-state electrochemistry of alkynyl-based Au(I) dinuclear and Au(I)–Cu(I) cluster complexes co…
2011
A method is presented to determine the free energy for anion transfer between two solvents. This is based on solid-state electrochemistry of alkynyl-based dinuclear Au(I) complexes (AuC2R)2PPh2C6H4PPh2 (L1: R=Fc; L2: R=C6H4Fc) and heterometallic Au(I)–Cu(I) [{Au3Cu2 (C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (L3: R=Fc; L4: R=C6H4Fc) complexes. These compounds exhibit a reversible ferrocenyl-centred solid-state oxidation processes involving anion insertion in contact with aqueous, MeOH and MeCN electrolytes. Voltammetric data can be used for a direct measurement of the free energy of ion transfer using midpeak potentials in solutions of suitable salts in the solvents separately or in mixtures of the s…
Kinetic and Mechanistic Aspects of a Poly(o-Toluidine)-Modified Gold Electrode. 2. Alternating Current Electrogravimetry Study in H2SO4 Solutions
2012
International audience; Electrodeposited poly(o-toluidine) (POT) on gold electrodes was investigated in 0.5 M H2SO4 aqueous solutions using alternating current electrogravimetry (simultaneous electrochemical impedance and mass transfer functions). The kinetic aspects of the three different redox transitions proposed for this polymer (leucoemeraldine-polaron transition, polaron-bipolaron transition, and bipolaron-pernigraniline transition) and the species involved, cation (hydrated proton), anion (bisulfate ion), and free solvent (water), are studied by means of the mass impedance technique. An ionic transfer model is proposed with coherent results where anion transfer is the fastest process…
Electrochemical molecular recognition of silver cation by electropolymerised thieno[3′,4′:5,6][1,4]dithiino[2,3-b]quinoxaline: a joint experimental a…
2000
The novel annelated monomer thieno[3′,4′:5,6][1,4]dithiino[2,3-b]quinoxaline 1 has been electropolymerised on a variety of electrodes, resulting in films which are electroactive in non-aqueous and aqueous solution. The polymer films exhibit a transformation in voltammetric response corresponding to a positive shift in redox potential in the presence of silver cation, the maximum shift being ca. 150 mV in acetonitrile and ca. 400 mV in aqueous LiClO4 solution. Mercury dication demonstrates a similar, but smaller (ca. 130 mV) shift in aqueous solution. Theoretical calculations clearly show the potential of poly(1) as a metal complexation agent. The Ag+ ion coordinates with 1 in two ways: (i) …
Enhanced ion transfer rate due to the presence of zwitterionic phospholipid monolayers at the ITIES
2000
Abstract The transfer of cations across phospholipid monolayers at ITIES is studied both experimentally and theoretically. Further evidence of the enhanced rate for cation transfer due to the presence of the monolayer is presented, and a theoretical model that can explain these observations is worked out. The system considered experimentally is Li + ion transfer across a hemispherical water ∣ 1,2-dichloroethane interface covered by distearoyl phosphatidylcholine. The theoretical description is based on the electrical double layer correction to the Butler–Volmer equation, coupled with a solution of the Poisson–Boltzmann equation across the interfacial region. The phospholipid monolayer is mo…
Extended Investigation of the Aqueous Self-Assembling Behavior of a Newly Designed Fluorinated Surfactant
2009
The physicochemical behavior of the newly synthesized fluorinated 5-hydroxyamino-3-perfluoroheptyl-1,2,4-oxadiazin-6-one (PFHO) surfactant was investigated. Thermal analysis showed that the pure surfactant is thermally stable under an inert atmosphere to 135 degrees C, which is several degrees higher than the melting point (99 degrees C). PFHO is rather active at the water/air interface where it assumes a standing up configuration. It exhibits an enhanced self-assembling behavior; accordingly, the critical micellar concentrations at some temperatures are 2 orders of magnitude lower than those of a similar surfactant having the same phobicity, such as sodium perfluorooctanoate. Even in the d…