1,4-dioxane as a solvent in spectroscopy and photochemistry

Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented.     

Controlled Rate Thermal Analysis of Hydrated Borates

Quasi-isothermal-isobaric analysis was applied as a main method for investigation of thermal decomposition of borates. The structural mechanism of the dehydration and dehydroxylation of selected borates is considered. It has been found that they consist of two independent stages: formation of gaseous water molecules localized into the structural framework and their release. The internal pressure of gaseous water molecules is the factor influencing the course of these processes. The strengths of the chemical bonds of the components and the freedom of their displacement also determine thermal stability of hydrated borates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies

The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.     

Crystallization kinetics of polyamide 6 containing pigments

In terms of the Avrami equation, the effects of selected organic pigments on the kinetic parameters of the isothermal crystallization of coloured polyamide 6 were examined in the temperature range 468–478 K. It was found that B Blue and BB Red are active nucleating agents, which is acribed to their crystalline structure. G Orange slightly accelerates the crystallization of PA 6 at lower temperatures and concentrations, whereas in other conditions its effect is the opposite.The isothermal data were confirmed by the results of non-isothermal crystallization. The degree of supercooling corresponding to the peak of the DSC curve was the measured feature in this case.It was found that B Blue and BB Red reduce the free energy of formation of criticalsize nuclei by 20 and 12%, respectively, which is reflected in the rates of crystallization.

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Zusammenfassung Mit Hilfe der Avrami Gleichung wurde der Einfluß einiger ausgewählter organischer Pigmente auf die kinetischen Parameter der isothermen Kristallisation gefärbter Polyamide 6 im Temperaturbereich 468–478 K untersucht. B Blue und BB Red erwiesen sich als aktive Keimbilder, was mit Hilfe ihrer kristallinen Struktur erklärt werden kann. Bei niedrigeren Temperaturen und geringeren Konzentrationen wird die Kristallisation von PA 6 durch G Orange leicht beschleunigt, unter anderen Bedingungen kann das Gegenteil beobachtet werden. Die isothermen Daten wurden durch die Ergebnisse bei nichtisothermer Kristallisation bekräftigt. In diesem Falle wurde das dem DSC Peak entsprechende Maß an Unterkühlung untersucht. Es wurde gefunden, daß B Blue und BB Red die freie Energie zur Bildung von Keimen kritischer Größe um 20 bzw. 12% herabsetzen, was sich in den Kristallisationsgeschwindigkeiten widerspiegelt.

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, -6 468–478 . , , . , . . . , , , 20 12%, .

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This work was supported by the Polish Academy of Science, goal 01.14.     

Long-range interaction in the D and D′ states of H2

The interaction energy between two hydrogen atoms in the D and D′ ¹Π_u states of the hydrogen molecule has been calculated for large internuclear distances (12 ? R ? 25 bohr). The variational method and a very flexible trial wave-function were used. The results indicate that for the states under consideration the Rayleigh-Schrödinger perturbation theory with the multipole expansion of the interaction hamiltonian gives reliable results only for R > 25 bohr i.e. in the region where the interaction energies are practically negligible.     

The mechanism of thermal decomposition of Co(NO3)2 · 2H2O

The mechanism of thermal decomposition of Co(NO₃)₂ · 2H₂O was found to involve stages in which Co(NO₃)₃ and Co₂O₃ · H₂O are formed both of which decompose to Co₃O₄. During the process, the total cobalt enters the +3 oxidation state, which is consistent with the results reported by Mehandjiev [2].

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Zusammenfassung Es wurde gefunden, daß der Zersetzungsmechanismus von Co(NO₃)₂ · 2H₂O Schritte umfaßt, bei denen Co(NO₃)₃ sowie Co₂O₃ · H₂O gebildet werden, beides weiterzerfallend zu Co₃O₄. Während des Vorganges erreicht das Gesamtkobalt die Oxidationsstufe +3, was mit Ergebnissen von Mehandjiev übereinstimmt [2].

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, , CO₃O₄. , .

     

Causal logic of Minkowski space

It is shown that double-orthogonal sets (diamonds) in Minkowski space form an orthomodular complete lattice. Connection with empirical logic of Randall and Foulis is discussed.     

Triplet losses in dye lasers

The expression for losses due to triplet states in dye laser considered as a six-level system is given. It is shown that triplet losses depend on pumping parameters and photon number. Depending on molecular and cavity parameters two different behaviours of dye lasers are expected. Physical conditions are discussed in which triplet losses as well as photon number undergo a jump at the threshold.