The Henderson Approximation and the Mass Action Law of Guldberg and Waage

Using contemporary accounts, we describe the scope of the Henderson approximation, and its relationship to the mass action law of Guldberg & Waage. The Henderson approximation, apparently written in logarithmic form by Hasselbalch, has the same form as the mass action law, but has a completely different meaning and a much more restricted range of applicability. The Guldberg-Waage law is the fundamental mass action relationship valid for all chemical equilibria, whereas the Henderson approximation is useful only within a limited range of a sufficiently concentrated two-component buffer mixture.     

The semi‐iterative method applied to the hyper‐power iteration

The semi‐iterative method (SIM) is applied to the hyper‐power (HP) iteration, and necessary and sufficient conditions are given for the convergence of the semi‐iterative–hyper‐power (SIM–HP) iteration. The root convergence rate is computed for both the HP and SIM–HP methods, and the quotient convergence rate is given for the HP iteration. Copyright © 2005 John Wiley & Sons, Ltd.     

Alien limit cycles near a Hamiltonian 2-saddle cycle

It is known that perturbations from a Hamiltonian 2-saddle cycle Γ can produce limit cycles that are not covered by the Abelian integral, even when it is generic. These limit cycles are called alien limit cycles. This phenomenon cannot appear in the case that Γ is a periodic orbit, a non-degenerate singularity, or a saddle loop. In this Note, we present a way to study this phenomenon in a particular unfolding of a Hamiltonian 2-saddle cycle, keeping one connection unbroken at the bifurcation. To cite this article: M. Caubergh et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

Ein Doppelaspirator

Ohne Zusammenfassung     

Local Minimizers of the Ginzburg-Landau Energy with Magnetic Field in Three Dimensions

We establish the existence of locally minimizing vortex solutions to the full Ginzburg-Landau energy in three dimensional simply-connected domains with or without the presence of an applied magnetic field. The approach is based upon the theory of weak Jacobians and applies to nonconvex sample geometries for which there exists a configuration of locally shortest line segments with endpoints on the boundary.Research partially supported by NSERC grant number 261955     

Collisional parameters of H2O lines: effects of vibration

A complex semiclassical model for the calculation of line widths and shifts of H₂O broadened by N₂, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v₂=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration.     

Synthesis of optically active 6-substituted 2-(aminomethyl)chromans

Three novel, optically active, 6-substituted 2-(aminomethyl)chromans were synthesized from readily available chroman 2-carboxylic acid precursors. These chroman-containing primary amines are useful building blocks for the synthesis of chroman-derived pharmaceutical agents.     

Hollow latex particles as submicrometer reactors for polymerization in confined geometries

A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004