Vibrational frequencies and force constants of N2O4 in complexes with molecules of different solvents determined by Raman spectra andAb initio calculation

The Raman spectra of N₂O₄ solutions in organic solvents have been recorded. The frequencies ofv ₁,v ₂, andv ₃ bands of N₂O₄ increase with increasing solvent electron-donor properties. Especially large changes ofv ₃ N-N stretching band have been observed (254.5 cm^–1 in n-hexane, 276.5 cm^–1 in 1,4-dioxane). The ab initio calculations have shown that the interaction between N₂O₄ and electron-donor molecules causes an increase of N-N and N-O stretching and O-N-O bending force constants of N₂O₄ in agreement with the results of Raman study.     

Quantum theory of dye lasers

A quantum model of dye laser is given. To account for triplet losses a six levels model for the molecular system is assumed. The solution of generalized von Neumann equation in thermodynamical limit leads to a system of kinetic equations. Stationary solutions of this system are discussed. There are two distinct types of dependence of photon number versus pumping parameter. Beside a usual one, a new dependence characteristic for dye lasers only is present. In this case the definition of threshold should be revised.     

Thermal decompositions of Y,La and lanthanide 3-hydroxybenzoates in air and nitrogen atmospheres

When heated, the 3-hydroxybenzoates of Y, Sm and Eu(III) decompose in two steps. The hydrates first lose crystallization water and the anhydrous complexes are then transformed to oxides in air, and to mixtures of oxide and C in nitrogen atmosphere. When heated in air, the pentahydrates of La, Pr and Nd are dehydrated in two stages and the anhydrous complexes are then transformed to oxides; when heated in nitrogen, they are dehydrated in one step and then decomposed to mixtures of oxides and C.

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Zusammenfassung Die 3-Hydroxybenzoate von Y, Sm und Eu(III) zersetzen sich beim Erhitzen in zwei Schritten. Die Hydrate verlieren zunächst Kristallwasser und die wasserfreien Komplexe werden in Luft in die Oxide und in Stickstoffatmosphäre in ein Gemisch des betreffenden Oxids und Kohlenstoff überführt. Beim Erhitzen in Luft werden die Pentahydrate von La, Pr und Nd in zwei Schritten dehydratisiert und die wasserfreien Komplexe in die Oxide überführt; beim Erhitzen in Stickstoff erfolgt dagegen die Dehydratisierung in nur einem Schritt und Endprodukt der Zersetzung ist ein Gemisch von Kohlenstoff und dem entsprechenden Oxid.

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Application of a bilayer adsorption model for explaining the adsorption of esters fromn-heptane and benzene on silica gel

The adsorption isotherms of methyl, ethyl,n-propyl andn-butyl acetates from benzene andn-heptane on silica gel have been measured at 298 K. A bilayer model of surface phase has been used to interpret these experimental data. It has been shown that the chain length of the hydrocarbon part of the ester and the solvent affinity to the adsorbent influence the structure of the surface phase. Moreover, this structure is also determined by energetic heterogeneity of the adsorbent surface.

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Die Anwendung eines Zweischicht-Adsorptionsmodells zum Verständnis der Adsorption von Estern ausn-Heptan- und Benzollösungen auf Kieselgel

Zusammenfassung Es wurden die Adsorptionsisothermen der Methyl-, Ethyl-,n-Propyl undn-Butylacetate in Benzol undn-Heptanlösungen auf Kieselgel bei 298 K gemessen. Zur Interpretation der experimentellen Daten ist ein Zweischicht-Modell für die Oberflächenphase benutzt worden. Es wurde gezeigt, daß die Länge der Esterkohlenwasserstoffkette und die Aktivität des Lösungsmittels Einfluß auf die Struktur der Oberflächenform haben. Außerdem ist diese Struktur durch energetische Inhomogenität der Adsorbensoberfläche bestimmt.

     

Thermal investigations of dehydration of lanthanide(iii) 5-nitroanthranilates

The 5-nitro-2-anthranilates of lanthanum(III), samarium(III), terbium(III), erbium(III) and lutetium(III) were obtained as hydrates having 2.5 mol of water molecules per 1 mol of compound. The compounds are isostructural. The processes of dehydration and rehydration were investigated. The first step of dehydration does not cause the change of crystal structure. The entire dehydration gives anhydrous compounds with different structure than the structure of hydrates. However, the dehydration of La, Sm, Tb and Er is reversible - the rehydration process gives the complexes having the same crystal structure as the initial compounds. Only the anhydrous lutetium complex under the influence of moisture does not give the starting compound. This revised version was published online in July 2006 with corrections to the Cover Date.     

A spontaneously broken quintet Baryon model for strong interactions

A gauge type model of quantum field theory for strong interactions based on a quinted of observed fields, namely the proton, neutron, , _c and _b baryon fields is proposed. Gauging the resulting global symmetry groupK= SU(3)×¹ U(1)ײ U(1)׳ U(1) for matter fields, one obtains boson-fermion field theory with eleven gauge bosons. The analysis of admissible Higgs sector indicates that the Higgs multiple consists of one adjoint and two fundamental representationsSU(3) and three scalar representations of¹ U(1),² U(1) and³ U(1). The structure of the Higgs sector implies that the original symmetry group extends to the groupK×U(2). Breaking spontaneously the obtained field theory, one converts gauge bosons into the eleven massive vector bosons which can be identified with the observed , K^*, ¯K^*, , , J/ and Y vector mesons. The surviving global symmetry is isomorphic with the symmetry groupSU(2)× ⁰ U(1)× ×¹ U(1)ײ U(1)׳ U(1) corresponding to the isospin, strangeness, baryon number, charm and beauty conservation observed in strong interactions. The surviving Higgs scalars have the same quantum numbers as , K, ¯K, , S, , , and _b mesons. The model gives a newSU(3) classification scheme for baryons without charm and beauty in terms of triplets, sextets and 15-plets. These multiplets can be identified with the observed baryons; the scheme also includes the observed Z₀ and Z₁ baryons (the experimental evidence of which is, nevertheless, still weak). The model predicts the existence and the specific quantum numbers of new mesons and baryons with charm and beauty, and provides a very simple framework for the dibaryon analysis. Since all final physical fields are massive, this model is free from infrared divergences.Invited talk presented at the International Conference Selected Topics in Quantum Field Theory and Mathematical Physics, Bechyn, Czechoslovakia, June 23–27, 1986.     

One-dimensional random walk with self-interaction

A standard random walk on a one-dimensional integer lattice is considered where the probability ofk self-intersections of a path =(0, (1),..., (n) is proportional toe ^–k . It is proven that for <0,n ^–1/3(n) converges to a certain continuous random variable. For >0 the formulas are given for the asymptotic Westerwater velocity of a generic path and for the variance of the fluctuations about the asymptotic motion.     

Potential of average force between two ions in a solvent of polarizable hard spheres

A method of obtaining the potential of average force between two ions immersed in a polarizable hard sphere fluid is described. The ions and the solvent particles may have different hard sphere diameters. For large values of the reduced polarizability of the solvent particles, ^*, the potential of average force rises near contact much more steeply than the primitive model would permit and also has maxima and minima vanishing at larger distances, in semiquantitative agreement with the similar results of Patey and Valleau. The oscillating character of the potential of average force is due above all to the oscillations of the radial distribution function between the ion and polarizable hard sphere.     

Synthesis and properties of lanthanide(III) complexes with 4-hydroxy-3,5-dimethoxybenzoic acid

Complexes of yttrium(III) and lanthanides(III) with 4-hydroxy-3,5-dimethoxybenzoic (syringic) acid were obtained as solids with metal to ligand mole ratio of 1: 3. The compounds were characterized by elemental analysis, IR spectroscopy, X-ray diffraction patterns, solubility, and thermal studies. The complexes are sparingly soluble in water and stable at room temperature. Compounds of light lanthanides (from La to Nd) are hydrated and they crystallize in a triclinic system. When heated, they lose water molecules in one step and in the next step they decompose to oxides. Complexes of yttrium and other lanthanides are anhydrous and crystallize in a monoclinic system. They are stable up to 300°C and then decompose to oxides. As the coordination number of lanthanide ions is usually equal to 9 or 8, one can suppose that hydroxy or methoxy groups take part in the coordination of these metal ions.     

Oxidation kinetics study of the iron-based steel for solid oxide fuel cell application

Kinetics of oxidation of Fe-Cr steel containing 25 wt.-percent Cr was studied as a function of temperature (1023–1173 K) for up to 480 h in flowing air, which corresponds to SOFC cathode environment operating conditions. The oxidation process was found to be a parabolic, suggesting that the diffusion of ionic defects in the scale is the slowest, rate determining step and it occurs predominantly by short-circuit diffusion paths. Comparison of the determined activation energy of oxidation of the studied steel with literature data indicates that at 1098–1173 K the chromia scale grows by the outward solid-state diffusion of chromium interstitials, whereas at 1023–1098 K — through a significant contribution of counter-current oxygen/chromium diffusion along Cr₂O₃ grain boundaries. The oxide scales were composed mainly of Cr₂O₃ with a continuous thin Mn_1.5Cr_1.5O₄ spinel layer on top of the chromia scale. The oxidation test results on Fe-25Cr steel demonstrate the applicability of the commercial type DIN 50049 stainless steel as interconnect for SOFC. This revised version was published online in July 2006 with corrections to the Cover Date.