Electron transfer between trans-dihydroxotetraoxoosmate(VIII) and thiosulfate. A kinetic study in aqueous alkaline media

The kinetics of oxidation of thiosulfate to tetrathionate by trans-dihydroxotetraoxoosmate(VIII) in aqueous alkaline media have been studied. The oxidation follows a rate expression where K_Os is the formation constant of trans-dihydroxotetraoxoosmate (VIII), and K₂ and k₃, respectively, represent the formation constants of the intermediate complex involving Os(VIII) and S₂O and its decomposition constant. The K_Os, K₂, and k₃ values have been computed to be (19.5 ± 3) dm³/mol, (6.12 ± 0.5) and (3.32 ± 0.3) × 10^?1 dm³/mol s at 303 K, and I = 0.32 mol/dm³, respectively. The rate law is consistent with a mechanism envisaging the equilibrium formation of an intermediate complex involving Os(VIII) and S₂O, followed by a rate-determining decomposition of the complex with concomitant electron transfer.     

The role of Fourier modes in extension theorems of Hartogs-Chirka type

We generalize Chirkas theorem on the extension of functions holomorphic in a neighbourhood of (F)(D×D) – where D is the open unit disc and (F) is the graph of a continuous D-valued function F – to the bidisc. We extend holomorphic functions by applying the Kontinuitätssatz to certain continuous families of analytic annuli, which is a procedure suited to configurations not covered by Chirkas theorem.Mathematics Subject classification (2000): 32D15Work supported by NSF Grant DMS-0072237.     

On L1 and Chebyshev estimation

The problem considered here is that of fitting a linear function to a set of points. The criterion normally used for this is least squares. We consider two alternatives, viz., least sum of absolute deviations (called the L₁ criterion) and the least maximum absolute deviation (called the Chebyshev criterion). Each of these criteria give rise to a linear program. We develop some theoretical properties of the solutions and in the light of these, examine the suitability of these criteria for linear estimation. Some of the estimates obtained by using them are shown to be counter-intuitive.     

Misassigned C-H...Cu agostic interaction in a copper(II) ephedrine derivative is actually a weak, multicentred hydrogen bond

Agostic interactions and weak hydrogen bonds to metal acceptors, M, are chemically and geometrically distinct, and this distinction must be maintained in the classification of new C-H...M interactions.     

On the repetitive operation of a self-switched transversely excited atmosphere CO<Subscript>2</Subscript> laser

The repetition rate capability of self-switched transversely excited atmosphere (TEA) CO₂ laser was studied for different gas flow configurations. For an optimized gas flow configuration, repetitive operation was achieved at a much smaller gas replenishment factor between two successive pulses when compared with repetitive systems energized by conventional pulsers.     

Phase Separation in the Advective Cahn–Hilliard Equation

The Cahn–Hilliard equation is a classic model of phase separation in binary mixtures that exhibits spontaneous coarsening of the phases. We study the Cahn–Hilliard equation with an imposed advection term in order to model the stirring and eventual mixing of the phases. The main result is that if the imposed advection is sufficiently mixing, then no phase separation occurs, and the solution instead converges exponentially to a homogeneous mixed state. The mixing effectiveness of the imposed drift is quantified in terms of the dissipation time of the associated advection–hyperdiffusion equation, and we produce examples of velocity fields with a small dissipation time. We also study the relationship between this quantity and the dissipation time of the standard advection–diffusion equation.

     

Polynomial approximation, local polynomial convexity, and degenerate CR singularities

We begin with the following question: given a closed disc and a complex-valued function , is the uniform algebra on generated by z and F equal to ? When F∈C¹(D), this question is complicated by the presence of points in the surface that have complex tangents. Such points are called CR singularities. Let p∈S be a CR singularity at which the order of contact of the tangent plane with S is greater than 2; i.e. a degenerate CR singularity. We provide sufficient conditions for S to be locally polynomially convex at the degenerate singularity p. This is useful because it is essential to know whether S is locally polynomially convex at a CR singularity in order to answer the initial question. To this end, we also present a general theorem on the uniform algebra generated by z and F, which we use in our investigations. This result may be of independent interest because it is applicable even to non-smooth, complex-valued F.     

A modified Brent’s method for finding zeros of functions

Brent’s method, also known as zeroin, has been the most popular method for finding zeros of functions since it was developed in 1972. This method usually converges very quickly to a zero; for the occasional difficult functions encountered in practice, it typically takes $O(n)$ iterations to converge, where $n$ is the number of steps required for the bisection method to find the zero to approximately the same accuracy. While it has long been known that in theory Brent’s method could require as many as $O(n^2)$ iterations to find a zero, such behavior had never been observed in practice. In this paper, we first show that Brent’s method can indeed take $O(n^2)$ iterations to converge, by explicitly constructing such worst case functions. In particular, for double precision accuracy, Brent’s method takes $2{,}914$ iterations to find the zero of our function, compared to the $77$ iterations required by bisection. Secondly, we present a modification of Brent’s method that places a stricter complexity bound of $O(n)$ on the search for a zero. In our extensive testing, this modification appears to behave very similarly to Brent’s method for all the common functions, yet it remains at worst five times slower than the bisection method for all difficult functions, in sharp contrast to Brent’s method.     

A Finite Deformation Microsphere Model for Magneto-Visco-Elastic Response in Magnetorheological Elastomers

In this work we present a novel approach to the modeling of magnetorheological elastomers (MREs) for finite deformations. Keeping in mind the composite nature at the microscale, we employ the microsphere model as an effective tool to capture the constitutive response of the material. The microsphere model has been successfully applied to the modelling of rubber-like materials. Here, we extend this approach by taking into account the effect of the magnetic dipole-dipole interactions on the orientation of the polymer chains. Thus, the presented microsphere model is directly motivated by considering the underlying phenomena at the microscale level. Finally the material model is embedded in a finite element framework and the results of a boundary value problems is presented. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)