The PVT and thermal properties of HF

The PVT and thermal properties of pure HF have been revised. The available data,which cover two distinct regions, one at low and one at high pressure, have been organized in a consistent set of data; volume properties and enthalpy have been plotted in the temperature range between 0°C and 300°C, for pressures up to 300 atm.Some experimental work has also been done to test the volume properties of HF in the presence of an inert gas at moderate temperatures and pressures. At these conditions the association factor, which for pure HF is a function of temperature and molar volume, appears to be strongly affected by the presence of inerts.     

Investigations of azimuthal asymmetry in semi-inclusive leptoproduction

We consider the azimuthal asymmetries in semi-inclusive deep inelastic leptoproduction arising due to both perturbative and nonperturbative effects at HERMES energies and show that the order corrections to and are significant. We also reconsider the results of perturbative effects for at large momentum transfers [1] using the more recent sets of scale-dependent distribution and fragmentation functions, which bring up to 18% difference in . In the same approach we calculate the as well. Received: 24 October 1997 / Revised version: 10 February 1998 / Published online: 30 March 1998     

First-order kinetic approximation for a reactive gas mixture

A multicomponent reacting gas with an arbitrary number of chemical species and one reversible reaction is studied at a kinetic level in the frame of discrete velocity models of the Boltzmann equation, with the main objective of deriving the reactive Navier Stokes equations of the model, and characterizing the dissipative terms related to shear viscosity, thermal conductivity and thermal diffusion. The closure of the system formed by conservation and chemical rate equations is based on a first-order Chapman-Enskog method, to be applied in the strong reaction regime, and on a convenient representation of the density vector space in terms of the macroscopic variables. A mathematical procedure is proposed which leads to identification of the transport coefficients, and may be applied to a quite large variety of reactive gas flows. Moreover, it allows characterization of the functional form of the transport coefficients in dependence on the local gas concentrations, once the model is specified.Received: 4 October 2004, Accepted: 3 December 2004, Published online: 18 March 2005PACS: 51.10. + y, 51.20. + d, 47.70.Fw Correspondence to: A.J. Soares     

Kinetic and equilibrium studies on the polyazamacrocycle neotetren: metal-complex formation and DNA interaction

The macrocyclic polyamine 2,5,8,11,14-pentaaza[15]-[15](2,9)[1,10]phenanthrolinophane (neotetren) is studied in its ability to coordinate Cu(ii) even at very low pH values and to interact, as a metal complex, with DNA. The kinetics and equilibria for 1 : 1 and 2 : 1 metal-ligand complexes formation are studied by the stopped-flow method and UV spectrophotometry. Differently protonated complexes are formed, with rate constants much lower than that of water exchange at copper(II) and other Cu(II)/amine systems, this behaviour being ascribed to ring effects and intra-molecular hydrogen bonds. Concerning the DNA/copper(II)-neotetren complexes interaction, analysis of data suggests an intercalative mode of binding. The kinetic results for both DNA/CuL and DNA/Cu(2)L systems agree with the sequence D + S <-->D,S <-->DS where the metal complexes (D) react with the DNA sites (S) leading to fast formation of an externally bound form (D,S) which is converted into an intercalated complex (DS). A very slow process is also detected and ascribed to a conformational change in the polynucleotide secondary structure where the metal centre plays a crucial role. Chromatographic experiments demonstrate that both the investigated Cu(II)/L complexes are able to cleave DNA, but only in the presence of hydrogen peroxide.     

Solution phase synthesis of a library of tetrasubstituted pyrrole amides

An efficient strategy for the solution-phase parallel synthesis of a library of pyrrole-amides is described. Key reactions include functional homologation of beta-ketoesters with a set of aldehydes followed by oxidation to produce a series of differently substituted 1,4-dicarbonyl compounds. Rapid cyclization using a microwave-assisted Paal-Knorr reaction provided a set of 24 pyrrole esters that were further functionalized through a trimethylaluminum-mediated aminolysis to obtain a larger library of 288 diverse pyrrole-3-amides. The tetrasubstitution allows a good exploration of the chemical space around the central pyrrole core. The last step was entirely automated with a Bohdan Myriad personal synthesizer.     

Experimental microkinetic approach of the photocatalytic oxidation of isopropyl alcohol on TiO2. Part 1. Surface elementary steps involving gaseous and adsorbed C3H(x)O species

The present study concerns an experimental microkinetic approach of the photocatalytic oxidation (PCO) of isopropyl alcohol (IPA) into acetone on a pure anatase TiO2 solid according to a procedure previously developed. Mainly, the kinetic parameters of each surface elementary step of a plausible kinetic model of PCO of IPA are experimentally determined: natures and amounts of the adsorbed species and rate constants (preexponential factor and activation energy). The kinetics parameters are obtained by using experiments in the transient regime with either a FTIR or a mass spectrometer as a detector. The deep oxidation (CO2 and H2O formation) of low concentrations of organic pollutants in air is one of the interests of the PCO. For IPA, literature data strongly suggest that acetone is the single route to CO2 and H2O and this explains that the present study is dedicated to the elementary steps involving gaseous and adsorbed C3H(x)O species. The microkinetic study shows that strongly adsorbed IPA species (two species denoted nd-IPA(sads) and d-IPA(sads) due to non- and dissociative chemisorption of IPA, respectively) are involved in the PCO of IPA. A strong competitive chemisorption between IPA(sads) and a strongly adsorbed acetone species controls the high selectivity in acetone of the PCO at a high coverage of the surface by IPA(sads). The kinetic parameters of the elementary steps determined in the present study are used in part 2 to provide a modeling of macroscopic kinetic data such as the turnover frequency (TOF in s(-1)) of the PCO using IPA/O2 gas mixtures.     

Well-posed equilibrium problems

In this paper we introduce some notions of well-posedness for scalar equilibrium problems in complete metric spaces or in Banach spaces. As equilibrium problem is a common extension of optimization, saddle point and variational inequality problems, our definitions originates from the well-posedness concepts already introduced for these problems.We give sufficient conditions for two different kinds of well-posedness and show by means of counterexamples that these have no relationship in the general case. However, together with some additional assumptions, we show via Ekeland’s principle for bifunctions a link between them.Finally we discuss a parametric form of the equilibrium problem and introduce a well-posedness concept for it, which unifies the two different notions of well-posedness introduced in the first part.