Thermodynamic study of a series lithium β-diketonates

Thermal behaviour of a series of lithium β-diketonates: Li(dpm) (dpm=dipivaloylmethanate (2,2,6,6-tetramethylheptane-3,5- dionate)), Li(pta) (pta=pivaloyltrifluoracetonate (2,2-dimethyl-6,6,6-trifluoro-3,5-hexanedionate)), Li(tfa) (tfa=trifluoracetylacetonate (1,1,1-trifluoro-2,4-pentandionate)), Li(hfa) (hfa=hexafluoracetylacetonate (1,1,1,5,5,5-hexafluoro-2,4-pentandionate)) has been investigated. Gas phase composition of these complexes has been established. Temperature dependences of vapor pressure of lithium compounds were obtained by static and dynamic methods, and thermodynamic parameters were calculated. Dependence of compound volatility on ligand structure is shown. For Li(dpm) detailed investigation has been done by differential scanning calorimetry (DSC).     

The large-particle method in arbitrary nets and its application to the solution of problems in the aeroelasticity of a parachute

Modifications are introduced into the large-particle method to make it possible to use the method in arbitrary nonrectangular computing nets in the study of the flow of an ideal compressible gas over mobile thin permeable membranes. A problem in the aeroelasticity of a parachute is stated. An example is given of the solution of a problem in the stationary formulation for an axially symmetric parachute in the wake of a cylindrical leading body for supersonic flow.Translated fromDinamicheskie Sistemy, No. 6, 1987, pp. 16–22     

An analysis of the possible causes of apparent compensation effects when investigating a substance under varying experimental conditions

The major causes leading to the apparent compensation effect (lgA=aE+b) at the thermal decomposition of one and the same substance in a series of experimental conditions (varying of the mass of the sample, of the heating rate, of disperseness, and at different distances from the equilibrium) were discussed. It was found that the appearance of a compensation effect at the study of the thermal decomposition of one and the same substance demonstrates the incorrect setup of the experiment, resulting in erroneous values calculated for the kinetic parameters.

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Zusammenfassung Die Hauptursachen, welche zum scheinbaren Kompensationseffekt (lgA=aE+b) der thermischen Zersetzung ein und derselben Substanz führen, wurden unter verschiedenen Versuchsbedingungen untersucht: unter Änderung der Probenmasse, der Aufheizgeschwindigkeit, der Dispersität und der Entfernung vom Gleichgewicht. Es wurde festgestellt, daß das Auftreten eines Kompensationseffekts bei der Untersuchung der thermischen Zersetzung ein und derselben Substanz auf die unrichtige Durchführung des Experiments hinweist, die zur Berechnung falscher Werte der kinetischen Parameter führt.

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Résumé On a étudié les causes principales de l'effet de compensation apparent (lgA=aE+ +b) lors de la décomposition thermique de la même substance dans différentes conditions expérimentales, en faisant varier notamment la masse du prélèvement, la vitesse du chauffage, la dispersion et l'écart à l'équilibre. On a trouvé que l'apparition d'un effet de compensation lors de l'étude de la décomposition thermique de la même substance résultait de l'exécution incorrecte de l'expérience qui mène à des valeurs fausses lors du calcul des paramètres cinétiques.

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, (lg A=aE+b) : , , , . , , .

     

Reactions of 4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidines with α,β‐unsaturated carbonyl compounds

The reaction of 5,7‐diphenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 1 ) with α,β‐unsaturated carbonyl compounds 2a‐f led to the formation of the alkylated heterocycles 3a‐f (Figure 1). However, the reaction of 5‐methyl‐7‐phenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 5 ) with 2a‐c yielded under the same conditions the triazolo[5,1‐b]quinazolines 6a‐c (Figure 3). In this case, the alkylation is followed by a cyclocondensation. The structure elucidation of the products is based on ir, ms, ¹H and ¹³C nmr measurements and on an X‐ray diffraction study.     

Thermal Decomposition in Systems of Acid Zn(II), Co(II), and Ni(II) Maleates with the Formation of Metallic Nanoparticles

Russian Journal of Physical Chemistry A - Conditions of synthesis are optimized and XRD and thermoanalytical studies are performed for normal maleate [Zn(H2O)2(C4H2O4)] and acid maleate...     

Regularities of thermolysis for the Fe(II), Co(II), and Ni(II) salts of maleic and ortho-phthalic acids with the formation of metal/polymer composites

Russian Journal of Coordination Chemistry - Regularities of the thermolysis of acidic salts of unsaturated (maleic) [M(H2O)4(C4H3O4)2] and aromatic (ortho-phthalic) [M(H2O)6](C8H5O4)2 (M = Fe(II),...     

Bernstein-Type Theorems and Uniqueness Theorems

Let be an entire function of finite type with respect to finite order and let be a subset of an open cone in a certain n-dimensional subspace (the smaller , the sparser ). We assume that this cone contains a ray 0} \right\}$$ " align="middle" border="0"> . It is shown that the radial indicator of at any point may be evaluated in terms of function values at points of the discrete subset . Moreover, if tends to zero fast enough as over , then this function vanishes identically. To prove these results, a special approximation technique is developed. In the last part of the paper, it is proved that, under certain conditions on and , which are close to exact conditions, the function bounded on is bounded on the ray.     

The study of the thermal dissociation processes of compounds of the type MoO2(C6H5CONHO)2.nA

Thermal dissociation processes of compounds with the composition MoO₂(C₆H₅CONHO)₂.nA (A-polar organic solvent: alcohols, aldehydes, ketones, organic acids) were investigated. Kinetics of dissociation was studied in a flow reactor, the values of activation energy and preexponential factor were calculated. The influence of a solvent nature, of the length of included molecules and of the type of crystalline lattice was studied. The sequence of kinetic stability was obtained. It corresponds to the sequence of solvent activity with respect to H-binding up with the complex. For the series of alcohols nonmonotonous dependence of kinetic parameters on the length of chain (with the division into two groups: with even and oddn) was obtained. For all the compounds studied a compensation relationship is observed (lgA=aE+b).

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Zusammenfassung Es wurden thermische DissoziationsvorgÄnge von Verbindungen der Zusammensetzung MoO₂(C₆H₅CONHO)₂ nA (mitA=polares organisches Lösungsmittel: Alkohole, Aldehyde, Ketone, organische SÄuren) untersucht. Die Dissoziationskinetik wurde in einem Durchlaufreaktor untersucht, die Werte für Aktivierungsenergie und prÄexponentiellen Faktor berechnet. Es wurde weiterhin der Einflu\ von der Art des Lösungsmittels, von der LÄnge der beteiligten Moleküle und vom Kristallgittertyp untersucht sowie eine Reihenfolge bezüglich der kinetischen StabilitÄt ermittelt. Diese stimmt mit der Reihenfolge der LösungsmittelaktivitÄt bezüglich der H-Bindung zum Komplex überein. Für die Alkoholreihen (zwei Reihen: mit geradem bzw. ungerademn) wurde keine sich monoton mit der analogen Reihe verÄndernde AbhÄngigkeit der kinetischen Parameter von der KettenlÄnge beobachtet. Für alle untersuchten Verbindungen wurde eine Kompensationsgleichung (lgA=aE+b) beobachtet.