Hamilton Varela

Temperature (Over)Compensation in an Oscillatory Surface Reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 °C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 °C and at T) < 1 is found in most cases, except that temperature compensation with q(10) ≈ 1 predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than from a weak temperature dependence of the individual steps.

Comparisons of charge compensation process in aqueous media of polyaniline and self-doped polyanilines

Abstract This work describes comparisons between the redox behavior of electrochemically formed polyaniline (PANI) and two chemically obtained self-doped polyanilines: sulfonated polyaniline (SPAN) and poly-(aniline-co-N-propanesulfonic acid-aniline) (PAPSAH). The charge compensation processes in HCl and camphorsulfonic acid (HCSA) aqueous solutions were studied using simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance techniques. Film electroactivity decreases in the PANI⪢SPAN>PAPSAH sequence in HCl solution. Charge compensation is carried out mainly with proton participation in SPAN modified electrode in both HCl and HCSA solutions. In contrast, for PANI and PAPSAH, the participation of anions also occurs, with a contribution strongly dependent on anion size. These results were analyzed in terms of the acid/base equilibrium of the polymer chains.

Electrodeposition of PbO2 onto Au and Ti substrates

The electrodeposition of lead dioxide (PbO2) onto Au and Ti substrates was anodically executed at 65°C and the electrochemical characteristics and the mechanism in the PbO2 films deposition were investigated by the using an in-situ electrochemical quartz crystal microbalance, cyclic voltammogram, and chronoamperometry experiments. An X-ray diffractometer and scanning electron microscope were also used for investigation of the formed lead dioxide films onto both substrates. Considering the experimental and theoretical mass/charge ratios, PbO2 deposition on Au by applying constant potential was in excellent agreement with the theoretical value, while relatively higher values of the mass/charge ratio due to film hydration were found when Ti was used as substrate. Analysis of X-ray diffractometer and scanning electron microscope show different film structures on each substrate, especially the additional hydration of the lead dioxide film deposited on Ti leads to some structural effects, identified as Sky-Lotus PbO2.

Catalytic oxidation of ethanol on gold electrode in alkaline media

This work presents a study of the catalytic oxidation of ethanol on polycrystalline gold electrode in alkaline media. The investigation was carried out by means of chronoamperometry, cyclic voltammetry, andin situ FTIR spectroscopy. The main goal was to investigate the early stages of ethanol electrooxidation, namely at fairly low potentials (E = 600 mV vs. RHE) and for moderate reaction times (t < 300 s). Chronoamperometric experiments show a current increase accompanying the increasing in the ethanol concentration up to about 2 M and then a slight decrease at 3 M. Adsorbed CO has been observed as early as about 200 mV vs. RHE and indicates that the cleavage of the C-C bond might occur, probably to a small extent, at very low overpotentials during ethanol adsorption on gold surface. The amount of dissolved acetate ions produced during the chronoamperomentry was followed by the asymmetric stretching band at 1558 cm−1 as a function of time, and found to increase linearly with time up to 300 s. This allowed estimating the reaction order of acetate formation with respect to ethanol concentration.

Complex Oscillatory Response of a PEM Fuel Cell Fed with H2 / CO and Oxygen

Oscillatory kinetics is commonly observed in the electrocatalytic oxidation of most species that can be used in fuel cell devices. Examples include formic acid, methanol, ethanol, ethylene glycol, and hydrogen/carbon monoxide mixtures, and most papers refer to half-cell experiments. We report in this paper the experimental investigation of the oscillatory dynamics in a proton exchange membrane (PEM) fuel cell at 30°C. The system consists of a Pt/C cathode fed with oxygen and a PtRu (1:1)/C anode fed with H 2 mixed with 100 ppm of CO, and was studied at different cell currents and anode flow rates. Many different states including periodic and nonperiodic series were observed as a function of the cell current and the H 2 /CO flow rate. In general, aperiodic/ chaotic states were favored at high currents and low flow rates. The dynamics was further characterized in terms of the relationship between the oscillation amplitude and the subsequent time required for the anode to get poisoned by carbon monoxide. Results are discussed in terms of the mechanistic aspects of the carbon monoxide adsorption and oxidation.

Técnicas in situ de baixo custo em eletroquímica: a microbalança a cristal de quartzo

Among in situ techniques, the electrochemical quartz crystal microbalance (EQCM) is a powerful tool for the study of electrochemical reactions that produce mass changes in the electrode/solution interface. This review present some systems in which the EQCM combined with classical electrochemical techniques, gives relevant information for understanding the charge transport process at a molecular level. The aim of this review is to do a brief description of experimental arrangements, with emphasis on some special cares that must be considered by the users. Secondly, some chosen electrochemical systems where the technique was successfully applied are discussed. Finally, a brief analysis of electroacoustic impedance experiments was done in order to show when the Sauerbrey equation can be used.

Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q10 of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

Ionic transport in conducting polymers/nickel tetrasulfonated phthalocyanine modified electrodes

This work describes the study of the ionic transport in polyaniline (PANI) and polypyrrole (PPY) modified electrodes polymerized in presence of nickel tetrasulfonated phthalocyanine (NiTsPc). Elemental analysis and infrared spectroscopy were used to characterize the resulting composite films. The impact of the phthalocyanine incorporation was evaluated by electrochemical quartz crystal microbalance under potentiodynamic conditions. Results have shown that the presence of the negative charge (SO3 groups) modifies the nature of the ‘ionic exchange’ membranes, during the cycling. In the case of PANI/NiTsPc modified electrodes, the electroneutralization is mainly achieved by the participation of protons both in HCl and in camphorsulfonic acid (HCSA) electrolyte solutions. For PPY/NiTsPc composites, the cation contribution is dominant in the case of LiCl and NaCl solutions and the anion transport becomes important when CsCl and BaCl2 solutions are used. q 2003 Published by Elsevier Ltd.

Ionic Exchange Phenomena Related to the Redox Processes of Polyaniline in Nonaqueous Media

Polyaniline films in nonaqueous media, mainly propylene carbonate and acetonitrile, are studied by using simultaneous potentiodynamic experiments with the electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy. The role of ionic transport and solvent participation during redox reactions is emphasized to obtain information about all chemical species involved in the process occurring in the conducting polymer film. The contribution of each species (neutral and ionic) depends on both the chemical nature of the ionic salt and the solvent used. Quartz crystal microbalance results have shown that both cation and anion contribute to the electroneutralization process, and the participation of solvent molecules is related mainly to changes in the oxidation state of the polymer matrix. As propylene carbonate propylene (∈ = 66.1) is a more polar solvent than acetonitrile (∈ = 37.3), it produces a more pronounced swelling process.