Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Thermogravimetric studies of decomposition kinetics of six different IAC Hevea rubber clones using Flynn-Wall-Ozawa approach

The thermal degradation behaviour of rubber from six new Hevea brasiliensis clones (IAC 40, 56, 300, 301, 302 and 303) from São Paulo State, Brazil was studied by thermogravimetry using the Flynn-Wall-Ozawa approach to assess the kinetic parameters ( reaction order, activation energy and pre-exponential factor) of the decomposition process. This study indicated that the thermal behaviour is a complex multiple step process, which depends on the type of rubber Hevea clones studied. The rubber from these clones can be classified, following the order of decreasing thermal stability, as IAC 303 > 302 > 56 > 40 > 300 > 301.

Kinetic energy sum spectra in nonmesonic weak decay of hypernuclei

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange - an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.

Real-time monitoring and kinetic parameter estimation of the affinity interaction of jArtinM and rArtinM with peroxidase glycoprotein by the electrogravimetric technique

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Capacitance Spectroscopy: A Versatile Approach To Resolving the Redox Density of States and Kinetics in Redox-Active Self-Assembled Monolayers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Model approach for estimating potato pesticide bioconcentration factor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Transient stability indices from a hybrid approach

This paper deals with hybrid method for transient stability analysis combining time domain simulation and a direct method. Nowadays, the step-by-step simulation is the best available tool for allowing the uses of detailed models and for providing reliable results. The main limitation of this approach involves the large time of computational simulations and the absence of stability margin. On the other hand, direct methods, that demand less CPU time, did not show ample reliability and applicability yet. The best way seems to be using hybrid solutions, in which a direct method is incorporated in a time domain simulation tool. This work has studied a direct method using the transient potential and kinetic energy of the critical machine only. In this paper the critical machine is identified by a fast and efficient method, and the proposal is new for using to get stability margins from hybrid approaches. Results from systems, like 16-machine, show stability indices to dynamic security assessment. © 2001 IEEE.

Thermogravimetric studies of the decomposition kinetics of four different Hevea rubber clones using Ozawa's approach

Thermal degradation of natural rubber extracted from four different rubber clones of the Hevea brasiliensis species was investigated by thermogravimetry using Ozawa's approach to assess the kinetic parameters of the decomposition process. The results are discussed in terms of the order of reaction, kinetic parameters such as activation energy as a function of conversion degree, and thermal stability for each of the clones.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

Approach toward an efficient inoculum preparation stage for suspension BHK-21 cell culture

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)