Some aspects of approach to equilibrium in classical and quantum systems

Investigations of general properties of time evolution of both classical and quantum systems show that the evolution (on a microscopic level) is reversible, and, if there is an approach to equilibrium, it exists only in the sense of weak convergence and necessarily in both directions of time. In this connection attempts to derive irreversibility and the approach to equilibrium in the sense of strong convergence and without any loss of information (using the so-called Lyapunov converters) are discussed. After demonstrating their drawbacks, an alternative approach is proposed based on the spectral properties of the generator of the group. The relevant spectral criteria for the approach of both classical and quantum ensembles to equilibrium are given, and the decisive role of loss of information in obtaining stronger variants of convergence is emphasized. The asymmetry between initial and any other state —consisting of different levels of information needed to prepare the states—is proposed as an adequate explanation of irreversibility. The importance of the method of complex scaling in this context is discussed, and its application in proving some spectral properties in the quantal Hamiltonian formulation is stressed.     

Interlayer inclusion of tetracyanonickelate anion and water molecules: The crystal and molecular structure of [-ZN(en)2-μ-(NC)2-NI-μ -(CN)2-ZN(en) -] n 2n+ ·n[NI(CN)4]2− · 3n H2O

The crystal structure of [Zn(en)₂- (NC)₂Ni(CN)₂ Zn(en)][Ni(CN)₄]· 3 H₂O consists of infinite positively charged wave-shaped layers of composition [Zn(en)₂-(NC)₂Ni(CN)₂- Zn(en)] _n ²ⁿ⁺ with the [Ni(CN)₄]^2– anions and water molecules included between them. Both Ni atoms exhibit square-planar coordination. The chelate bonded en (=ethylenediamine) and N-bonded cyano ligands around two independent zinc atoms form a deformed tetrahedron and a deformed octahedron, respectively. Yellow needles of the complex belong to the orthorhombic space groupPbcm witha = 6.977(1),b = 25.407(4),c = 14.876(2)Å,Z = 4,D _m = 1.74(1) g cm^–3 andD _c = 1.739 g cm^–3. The structure was refined toR = 6.31 %.     

Trialkyltin Compounds as Neutral Carriers for Anions in PVC Liquid Membranes and Complex Formation with Oxoanions

Under the influence of an electric field, trialkyltin compounds of the type R₃SnX behave as electrically neutral carriers for anions in poly(vinyl chloride) liquid membranes. The interaction of tinorganic compounds with oxoanions was studied in organic phase by means of ¹¹⁹Sn-NMR-monitored titrations. In the case of tributyltin chloride, no appreciable amount of complex was formed with hydrogensulfate, whereas dihydrogenphosphate gave rise to a new species. Dioctyltin dichloride and dioctyltin dioctyltin diacetate formed a 1:2 (salt/ligand) complex with hydrogenphosphate.     

Влияние переменного магнитного поля на остаточное состоя ние магнитно — Мягких материалов

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The influence of an alternating magnetic field on the remanent state of magnetically soft materials

A study is made of the influence of an alternating magnetic field of varying maximum amplitude on the remanent state, or rather, apparent remanent state of toroidal and open samples of metallic and non-metallic magnetically soft ferromagnetics. An interpretation of the corresponding dependences is given on the basis of Kondorski's conception of the composition of a polycrystalline jerromagnetic material.

     

(E)-2-Benzylidenebenzocyclanones, part VIII: spectrophotometric determination of pKa values of some natural and synthetic chalcones and their cyclic analogues

Abstract  

UV–Vis spectrophotometry was used to determine acid dissociation constant (pK _a) values of the natural flavonoids phloretin, phlorizin, naringenin, and naringin, as well as 4′-hydroxychalcone, 4′-(dimethylamino)chalcone, and their cyclic analogues. Comparison of the results with those previously reported for the natural flavonoids showed the applied method is a relatively straightforward and easy-to-perform technique for the determination of pK _a values of compounds with relatively low solubility. Comparative analysis of the pK _a values of the synthetic chalcones showed a strong correlation between the degree of conjugation and the acid strength of the respective compounds with different geometry. Our results provide further evidence that modification of the three-dimensional structure of open-chain bioactive compounds is the method of choice to modify not only their stereochemistry but also their physicochemical properties.     

Modelling of the High-Impact Polystyrene Morphogenesis

Summary: High-impact polystyrene (HIPS) is a hetero-phase polymer with the so-called salami morphology. Salami morphology is formed by a continuous PS phase containing micron-sized PB domains. PB domains contain submicron-sized irregular PS occlusions. In our modeling work we addressed several weak points of Cahn-Hilliard model of HIPS salami morphology evolution. The weakest point of Cahn-Hilliard model is the inherently present Ostwald ripening destabilizing or competing with graft-stabilized domains. Two mechanism of formation of HIPS morphology are supported by the model: (i) encapsulation of graft-stabilized PS-rich domains in PB particles, and (ii) polymerization of styrene dissolved in PB-rich phase and subsequent phase separation leading to PS occlusions in PB domains.     

Diffusion Transport in Reconstructed Semi-Crystalline Structure of Polyolefins

Summary: Diffusion of penetrants (e.g., monomers) in polyolefins is important not only in their manufacturing and down-stream processing, but also in packaging and separation applications. We propose a general methodology linking the semi-crystalline structure of polyolefins to their application properties. This methodology comprises of AFM imaging of semi-crystalline structure, reconstruction of 3D replica of semi-crystalline polymer and calculation of application properties (e.g., diffusivity) depending on 3D morphology. Our algorithm is capable to achieve realistic crystallinities of reconstructed samples up to 70% and to reconstruct spherulites with preferential orientation of lamellae. We demonstrate and discuss difficulties experienced during AFM imaging of HDPE morphology, particularly the dependence of resulting AFM image representing the distribution of crystalline domains on the sample preparation including etching.