Ruthenium(III)‐catalyzed oxidation of cyclopentanol and cyclohexanol by N‐bromoacetamide

Kinetic investigations on Ru(III)‐catalyzed oxidation of cyclopentanol and cyclohexanol by acidic solution of N‐bromoacetamide (NBA) in the presence of mercury(II) acetate as a scavenger have been carried out in the temperature range of 30–45°C. Similar kinetics was followed by both the cyclic alcohols. First‐order kinetics in the lower concentration range of NBA was observed to tend to zero order at its higher concentrations. The reaction exhibits a zero‐order rate dependence with respect to each cyclic alcohol, while it is first order in Ru^III. Increase in [H⁺] and [Cl^?] showed positive effect, while successive addition of acetamide exhibited negative effect on the reaction rate. Insignificant effect of sodium perchlorate, D₂O, and mercury(II) acetate on the reaction velocity was observed. Cationic bromine has been proposed as the real oxidizing species. Various thermodynamic parameters have been computed. A suitable mechanism in agreement with the kinetic observations has been proposed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 275–281, 2005     

Fast intersections on nested tetrahedrons (FINT): An algorithm for adaptive finite element based distributed parameter estimation

A variety of biomedical imaging techniques such as optical and fluorescence tomography, electrical impedance tomography, and ultrasound imaging can be cast as inverse problems, wherein image reconstruction involves the estimation of spatially distributed parameter(s) of the PDE system describing the physics of the imaging process. Finite element discretization of imaged domain with tetrahedral elements is a popular way of solving the forward and inverse imaging problems on complicated geometries. A dual-adaptive mesh-based approach wherein, one mesh is used for solving the forward imaging problem and the other mesh used for iteratively estimating the unknown distributed parameter, can result in high resolution image reconstruction at minimum computation effort, if both the meshes are allowed to adapt independently. Till date, no efficient method has been reported to identify and resolve intersection between tetrahedrons in independently refined or coarsened dual meshes. Herein, we report a fast and robust algorithm to identify and resolve intersection of tetrahedrons within nested dual meshes generated by 8-similar subtetrahedron subdivision scheme. The algorithm exploits finite element weight functions and gives rise to a set of weight functions on each vertex of disjoint tetrahedron pieces that completely cover up the intersection region of two tetrahedrons. The procedure enables fully adaptive tetrahedral finite elements by supporting independent refinement and coarsening of each individual mesh while preserving fast identification and resolution of intersection. The computational efficiency of the algorithm is demonstrated by diffuse photon density wave solutions obtained from a single- and a dual-mesh, and by reconstructing a fluorescent inclusion in simulated phantom from boundary frequency domain fluorescence measurements.     

Kinetics and mechanism of the ruthenium(III)-catalysed oxidation of aminoalcohols by cerium(IV) in a sulphuric acid medium

Summary The kinetics of the ruthenium(III)-catalysed oxidation of primary (viz. 2-aminoethanol and 3-aminopropanol) secondary (diethanolamine) and tertiary aminoalcohols (triethanolamine) by cerium(IV) in a sulphuric acid medium have been studied spectrophotometrically. The reactions exhibit a zero-order rate-dependence with respect to the oxidant and first-order rate-dependence with respect to each of the substrate and catalyst. First order dependence of rate in sulphuric acid is found for primary aminoalcohols. A suitable mechanism, consistent with the observed kinetic data, is proposed.     

Phase transition in triglycine family of hydrogen bonded ferroelectrics: An interpretation based on structural studies

Using the crystal structure, a comprehensive interpretation of the origin of ferroelectricity in the hydrogen bonded triglycine family of crystals is given. Our detailed analysis showed that the instability of nitrogen double well potential plays a driving role in the mechanism of the ferroelectric transitions in these crystals.     

The electrical properties of semiconductor/metal,semiconductor/liquid,and semiconductor/conducting polymer contacts

Critical comparisons are drawn between the basic electrical properties of semiconductor/metal, semiconductor/liquid, and semiconductor/conducting polymer junctions. A theoretical model is developed to describe the basic current-voltage properties of semiconductor contacts, with emphasis on the contrasts between ideal and observed behavior. Using the concepts from this model, the characteristics of a variety of semiconductor contacts are evaluated. The discussion focuses on the following semiconductors: Si, GaAs, InP, and II-VI compounds based on the Cd-(chalcogenide) materials.     

Electron interactions and the electrical resistivity of alkali metals at low temperatures

The contribution of the electron-electron umklapp scattering processes to the electrical resistivity of sodium, potassium, rubidium and cesium at low temperatures has been evaluated using a simplified spherical Fermi-surface model with an isotropic transition probability. Our values of the electrical resistivity so obtained compare fairly well with the recent experimental values for sodium, potassium and rubidium. Our theoretical results have also been compared with the other available data in the literature due to Lawrence and Wilkins and MacDonald and Geldart.     

Ultrasonic attenuation in potassium at low temperatures

The contribution of the electron-electron interactions to the ultrasonic attenuation in potassium at low temperatures has been evaluated using a simplified spherical Fermi-surface model with an isotropic umklapp transition probability. Our results show that the e-e scattering processes contribute very little to the ultrasonic attenuation in K at low temperatures as compared to the electron-photon interactions.     

Temperatures of Tesla discharges from OH A → X intensity measurements

The OH A²Σ⁺ → X²Π system is used as a diagnostic tool for temperature measurements of Tesla discharges in Ar and He seeded with 0.5 torr H₂O. From relative intensities of low-N′ lines in the 0-0 band we obtain temperatures which are independent of pressure for the range 100–650 torr and which are only a few degrees higher than the estimated wall temperatures. A check on the theoretical line strengths for OH A → X shows 1% agreement for main-branch transitions but only 5% agreement for satellite lines. Self-absorption problems are encountered and corrected for in the He discharge work; from the ≈10% magnitude of the correction, there are significant amounts (8 mtorr) of ground-state OH produced in the He Tesla discharge.     

The complete finitely axiomatized theories of order are dense

We prove a conjecture of Lauchli and Leonard that every sentence of the theory of linear order which has a model, has a model with a finitely axiomatized theory.