Portugaliae Electrochimica Acta

Professor Gennady Zaikov: 50 years in science

Electrochemical Determination and Removal of Pentachlorophenol at Diamond Electrodes

This work describes the determination of pentachlorophenol (PCP) in pure and polluted waters by square wave voltammetry (SWV) and the influence of the electrode potential on PCP oxidation on boron doped diamond (BDD) electrodes. Measurements carried out in solutions of the Britton-Robinson buffer with pH = 5.5 revealed a single oxidation peak at 0.80 V vs. Ag/AgCl for PCP in a process that is controlled by the adsorption of the species. The detection limits obtained were 5.5 mg L-1 in pure water and 15.5 mg L-1 for water taken from a local creek, respectively. Controlled potential electrolyses were carried at 0.9, 2.0 and 3.0 V vs. Ag/AgCl and the solutions analysed by SWV, HPLC, chloride ion selective electrode and UV-vis spectroscopy. At low positive potential (0.9 V), the formation of an adherent film on the electrode surface involving the transference of 1 electron per PCP molecule was observed. At potentials close to the onset of O2 evolution (2.0 V), the formation of the corresponding quinone was detected. Electrolyses carried out well into the region of oxygen evolution (3.0 V) lead to the total combustion of PCP to CO2 and H2O as well as to the release into solution of 5 Cl- ions per PCP molecule destroyed.

LiMg_y1Cr_y2Mn_2-y1-y2O4 (0.0 £ y₁ £ 0.30; y₂= 0.30 - y₁) as a Cathode Active Material for Lithium Batteries

LiMn2O4 is an attractive 4 V positive material in lithium rechargeable batteries owing to its favourable electrochemical characteristics besides its economic and environmental advantages. However, problems of limited cyclability, especially at elevated temperatures, have limited the utility and commercialization of this cathode material. Stabilization of the LiMn2O4 spinel structure has been sought to be realized by doping the spinel with suitable cations. In this paper, the results of an exploratory research on the capacity and cyclability of LiMn2O4 cathodes simultaneously doped with Cr3+ and Mg2+ are reported. LiMg y1Cr y2Mn2-y1-y2O4 spinels with y1 = 0.00, 0.05, 0.10, 0.20, 0.25 and 0.30 and y2 (0.3 - y1) were synthesized by a solid-state fusion method. While Mg2+ bestows a positive effect on cyclability, it leads to a considerable reduction in capacity due to the oxidation of Mn3+ to the inactive Mn4+ as a result of charge compensation. Cr3+ on the other hand, leads only to half as much reduction in capacity while according added stability to the structure. Any expectation of a synergistic effect by Cr3+ and Mg2+ ions was belied by these findings.

Ion Transfer Through DPPC Monolayers

The transfer of acetylcholine cation through a monolayer of a lipid, dipalmitoylphosphatidylcholine, formed at a polarized water | 1,2-dichloroethane interface has been studied using electrochemical impedance spectroscopy. The ion transfer process was characterized at different levels of interfacial coverage. From measurement of the cyclic voltammograms and double layer capacitance it was found that cation transfer through dipalmitoylphosphatidylcholine monolayers was cation and phospholipid concentration dependent. An increase on current intensity and capacitance values was observed at more positive potentials due to the transfer of acetylcholine across the interface in the absence or presence of lipid in the organic phase. The thermodynamic and kinetic parameters were also accessed from electrochemical impedance measurements.

Corrosion Inhibition of Electrodeposited Tellurium and Palladium in Nitric Acid Solution

Corrosion inhibition of 3-phenyl hydrazonoacetyl acetone derivatives on electrodeposited tellurium and palladium in nitric acid was measured by using electrochemical method. Polarization curves showed that these compounds are cathodic inhibitors. The inhibition appears to function through general adsorption following the Flory-Huggins adsorption isotherm. The rate of corrosion depends on the nature of the inhibitor and its concentration, mode of interaction with the metal surface, molecular size, formation of complexes and the active center in the molecules and its electron charge density. Also, ΔGºads. values were calculated. The reaction rate was found to be proportional to the absolute value of the Hammett constant (s).

Complex Formation Between Alkaline-Earth Cations and Anthraquinone Crown Ethers in Methanol and Acetonitrile

Formation of complexes of alkaline-earth cations with crown ethers containing an anthraquinone unit (AQ18C6 and AQ21C7) was investigated in methanol and acetonitrile solutions. Stability constants of the resulting complexes were estimated by means of potentiometric methods. The results obtained show the formation of complexes of the LM2+ type for all alkaline-earth ions; for the larger cations, (Sr2+ and Ba2+) and in excess of ligand, L2M2+ complexes were also detected. The most stable complexes were obtained with Ba2+ cation and for both ligands. The binding strength for the cations towards AQ18C6 and AQ21C7 ligands and in both solvents, increased in the order, Mg2+ < Ca2+ < Sr2+ < Ba2+. The results of this study suggest that on the 1:1 complexes, the size of the cation and its fit into the macrocyclic internal cavity of the ligand was a dominant factor on the coordination binding. The number of donor atoms in the ring of the macrocycle does not affect the binding strength and the AQ18C6 complexes have larger stability than the corresponding AQ21C7 complexes. The presence of an anthraquinone unit on the structure of the crown ether induced a decrease of the cation binding strength. The external carbonyl group of the ligand molecules was not involved on the coordination to the cation. Considering the two solvents, the complexes were more stable on acetonitrile, the solvent of weaker solvating capacity.

Evaluation of Corrosion Behavior of Copper in Chloride Media Using Electrochemical Impedance Spectroscopy (EIS)

The corrosion behavior of pure copper rotating cylinder electrode (RCE) exposed to 3% NaCl or artificial seawater prepared as Vätäänen nine salt solution (VNSS) has been studied using electrochemical impedance spectroscopy (EIS) and polarization techniques. EIS experiments for copper RCE were carried out at different rotation rate from 0 rpm to 1600 rpm. Polarization resistance (Rp) values were obtained from both EIS and polarization experiments. Excellent agreement between impedance and polarization data is observed. RCE experiments demonstrated that Ecorr and corrosion rate for copper depend linearly on rotation speed r0.7. The results obtained showed that EIS is a powerful electrochemical method to follow the change of corrosion mechanisms.

Organotin Dithiohydrazodicarbonamides as Corrosion Inhibitors for Mild Steel-Dimethyl Sulphoxide Containing HCl

A few 1-aryl-2,5-dithiohydrazodicarbonamides and their triphenyltin and dibutyltin complexes have been studied as corrosion inhibitors for mild steel in dimethyl sulphoxide containing HCl at 25 ºC using electrochemical polarisation technique. Among dithiohydrazodicarbonamides, ethoxyphenyl derivative exhibited maximum inhibition efficiency (IE) followed by benzyl and phenyl analogues. The same order of IE was observed in their corresponding organotin complexes; however, IE of a complex was found to be significantly higher than that of the constituents ligand. All organotin complexes behaved predominantly as cathodic inhibitors. Triphenyltin complexes proved to be better corrosion inhibitors than their dibutyltin analogues.

Trace Determination of Palladium in Environmental Samples by Adsorptive Voltammetry

The objective of the present work is the study and optimization of a voltammetric methodology to determine palladium traces and ultratraces, with the purpose of being able to establish the environmental levels of this element and to verify if a contamination takes place starting from the gases of escape of the vehicles equipped with catalytic converters. The voltammetric determination of palladium is based in the formation of a complex of palladium with dimethylglyoxime that adsorbes actively on the surface of a hanging mercury drop electrode, for then to be reduced when making the square wave potential sweep. The quantification is made by the method of standard additions. The study of interferences demonstrated that Na+, Mg2+, K+, Ca2+, Zn2+, Cu2+ and Al3+ are not even interferences at the level of 10 mg/L. The detection and quantification limits of the methodology are respectively 10 ng/L and 33 ng/L, with a sensibility of (4.3±0.8)*10² nA L/ng.

El objetivo del presente trabajo es el estudio y optimización de una metodologia voltamperométrica para determinar trazas y ultratrazas de paçadio, con el fin de poder establecer los niveles ambientales de este elemento y verificar si se produce una contaminación a partir de los gases de escape de los vehículos equipados con convertidores catalíticos. La determinación voltaperométrica de paladio se fundamenta en la formación de un complejo del paladio con dimetilglioxima, que se adsorbe activamente sobre la superficie de un electrodo de gota suspendida de mercurio, para luego ser reducido al efectuar el barrido de potencial con onda cuadrada. La cuantificación se efectúa por el método de las adiciones estándar. El estudio de interferencias demostró que Na+, Mg2+, K+, Ca2+, Zn2+, Cu2+ y Al3+ no son interferencias incluso al nivel de 10 mg/L. Los límites de detección y de cuantificación de la metodología son 10 ng/L y 33 ng/L respectivamente, con una sensibilidad (4.3±0.8)*10² nA L/ng.