The evaluation of the polarization resistance in a tubular electrode and its application to the hydrogen electrode reaction

An alternative method for the determination of the kinetic parameters involved in the elementary steps of the reaction mechanism of the hydrogen electrode reaction is proposed. It is based on the determination of the variation of the polarization resistance in a tubular platinum electrode with a laminar flow of electrolyte as a function of the activity of protons of the electrolyte solution. A theoretical expression that relates the experimental variables and the equilibrium polarization resistance is developed, which takes into account the current distribution along the electrode surface. The results are compared with others obtained previously, contributing to the verification of the kinetic mechanism through a completely different experimental procedure.     

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

Kinetics of the decomposition of total aliphatic waxes in olive oil during deodorization

Changes in the content of aliphatic waxes during industrial deodorization and/or physical refining of bleached olive oil were studied in an experimental discontinuous pilot plant of 250 kg deodorizer using nitrogen as stripping gas in place of steam. The kinetic constants for the decomposition of waxes during the deodorization process were determined. The reaction orders studied are zero (or can be considered zero) within the working interval. The values of rate constants, activation energy, frequency factor, increment of activation Gibbs free energy, activation enthalpy, and activation entropy are established.     

Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm⁻³ and varying H⁺ concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H⁺ concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO₂ and RTO. The expression of the kinetic current as a function of chlorine and H⁺ concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential.     

Ozonation of Selected Molecules Constituting Cellular Matter

Ozonation of purine and pyrimidine bases and of carbohydrates was studies in laboratory experiments. The results showed that nucleobases are much more reactive with molecular ozone in aqueous solution than carbohydrates. Second order rate constants for direct reaction of ozone on purines (adenine and guanine) and on pyrimidines (cytosine, thymine and uracil) ranged from 0.76 × 10³ to 6.8 × 10³ M^-1s^-1at 2°C. The difference of reactivity between these solutes may be attributed to their substituents. As far as carbohydrates are concerned, direct reactions of ozone are very slow k₀₃ ? 0.1 – 0.3 M_-1s_-1 at 20°C, and the results indicated that free radical reactions are predominant in the degradation pathway of carbohydrates by ozone. Some ozonation by-products of monosaccharides (glucose, xylose) and disaccharides (cellobiose) also were identified in this study by means of GC/MS analyses.     

Homogeneous Catalyzed Ozone Decomposition in the Presence of Co(II).

The homogeneous decomposition of ozone in the presence of a Co(II) catalyst has been investigated in aqueous solution. Under the conditions investigated (Co(II) concentration: 0.0 – 2.0?ppm, pH: 1.6- 8.4, O₃ concentration: 5 10^?5 – 2.0 10⁴?M) the process can be assumed to follow pseudo first order kinetics with respect to ozone. Cobalt concentration dependency also obeys first order kinetics although it may be considered to reach a steady state concentration. pH exerts a positive influence on the decomposition rate from 1.6 to 7.1, the process leveling off at pH 8.4. An Arrhenius analysis of the temperature effect gave a moderate activation energy of the global reaction (E=10917?cal mol^?1). A more detailed radical mechanism than a simple pseudo first order reaction can be postulated for simulation purposes. By numerical optimization of some unknown kinetic constants the influence of several operating variables can be adequately predicted.     

Theoretical investigation on cyclic reciprocal derivative chronopotentiometry: Kinetic study of totally irreversible electrode processes

Theoretical expressions and mathematical analysis in cyclic reciprocal derivative chronopotentiometry (CRDCP) are presented for totally irreversible electrode processes corresponding to the application of symmetrical and unsymmetrical programmed currents. For two successive unsymmetrical programmed currents, the effect of the currents ratio b (b = |I₂(t)/I₁(t)|) on the (dt/dE)–E curves is discussed. The electrochemical behavior of totally irreversible electrode processes has been studied corresponding to the application of the unique unsymmetrical programmed Φ^m(I₀) proposed recently. CRDCP characteristic parameters obtained for totally irreversible electrode processes are different from those of reversible electrode processes. Therefore, a comparison of CRDCP between both mechanisms is presented. Based on the mathematical derivation, alternative methods for kinetic measuring are described. It is prospected that CRDCP is convenient and applicable for studying the reversibility of the electrode processes in form of CRDCP characteristic parameters.     

High temperature corrosion mechanisms and effect of alloying elements for materials used in waste incineration environment

Corrosion products on two typical materials, SA213-T12 steel and alloy 625 exposed to the actual combustion gas, were analyzed in addition to laboratory tests for penetration of corrosive matter. It has been clarified that corrosion products of oxides containing a little chlorides and sulphides show lamellar structures and that at the alloy-scale interface, chlorination, sulphidation, and oxidation occur under a low P_O2-high P_Cl2 condition. The formation of scale structures and the effect of corrosion-resistant alloying elements can be explained according to the stability tendencies of metals, chlorides, and oxides in the M-Cl-O equilibrium diagrams. The severity of corrosion environments at the interface is influenced by the penetration extent of corrosive matters through deposits and scales, and the protective effects of oxide films derived from alloying elements play an important role in preventing the corrosion. On the other hand, it has been shown that thermal fluctuation characterized in this kind of environment makes the lamellar scale structures and sometimes breaks and peels off the scale, and thus accelerates the corrosion. On the basis of the above mentioned knowledge, a new corrosion model is presented.     

A hybrid differential evolution algorithm integrated with an ant system and its application

A new hybrid differential evolution algorithm, in which an ant system is used to select the optimal base vector of mutation operation, named the ant system differential evolution (ASDE), is proposed. In ASDE, each dimension in the feasible solution space is divided into several subspaces evenly, and each subspace is marked with the same initial intensity of pheromone trails. The probability of choosing an individual as the base vector is influenced by the visibility and pheromone quantity of the individual. The trail of the selected base vector’s location subspaces will be reinforced with some pheromones, when the offspring is better than its parent. The experimental results show that the ASDE generally outperforms the other differential evolution algorithms for nine benchmark functions. Furthermore, the ASDE is applied to develop the global kinetic model for SO₂ oxidation on the Cs-Rb-V catalyst, and satisfactory results are obtained.     

On the mathematical theory of living systems II: The interplay between mathematics and system biology

This paper aims at showing how the so-called mathematical kinetic theory for active particles can be properly developed to propose a new system biology approach. The investigation begins with an analysis of complexity in biological systems, continues with reviewing a general methodology to reduce complexity and furnishes the mathematical tools to describe the time evolution of such systems by capturing all their features.