Limiting temperatures of the thermal decomposition of polymers and their determination by rapid thermal analysis

Experimental and theoretical foundations are established for the limiting temperatures of thermal decomposition of thermoplastic polymers. The correlation between the limiting temperatures and the intermolecular interactions of the polymers investigated is reported.

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Zusammenfassung Experimentelle und theoretische Grundlagen der Grenztemperaturen der thermischen Zersetzung von thermoplastischen Polymeren werden behandelt. Es besteht eine Korrelation zwischen den Grenztemperaturen und den intermolekularen Wechselwirkungen der untersuchten Polymere.

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Decomposition of benzenediazonium fluoborate in esters of α,β-unsaturated acids

Summary It was shown that In contrast to the Meerwein-Koelsch reaction, the decomposition of benzenediazonlum fluoborate In esters of ,-unsaturated acids proceeds by a heterolytlc mechanism with the phenyl attacking the -carbon and the carbalkoxyl group of these esters. The reaction with ethyl crotonate gave -methylatropic acid (after hydrolysis) and a small amount of a dibasic acid, C₁₄H₁₆O₄ (or C₁₄H₁₄O₄). With methyl acrylate it gave atropic acid, phenyl acrylate, and a smaller amount of -methyl--phenylglutaric acid. With methyl methacrylate It formed benzylacrylic acid and the product of further conversions of phenyl methacrylate, namely the keto phenol 2-methyl-5-hydroxyindan-1-one.     

Effect of the central metal ion on the inhibiting properties of metal dithiocarbamates in oxidation processes

The dependence of inhibiting properties of M(dtc) on M for the complexes of M(II) and n M(III) has been studied. Inhibition is due to the interaction of M(dtc)_n with RO₂.

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M(dtc)_n M M(II) M(III). M(dtc)_n RO₂.

     

Synthesis and properties of composite catalysts containing Pd and Ho2O3 particles in pores of carbon carrier

Specific activity (TOF) of the catalysts prepared through the interaction of C₃H₅PdC₅H₅ with the surface of evacuated Ho₂O₃/C is two orders of magnitude higher compared to that of Pd/C in the synthesis of both CH₃OH and CH₄. Deactivation data suggest that CH₃OH and CH₄ are formed on different active sites.

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, C₃H₅PdC₅H₅ Ho₂O₃/C, Pd/C CH₃OH, CH₄. CH₃OH CH₄ .

     

Chemical conversion of various celluloses to glucose and its derivatives in supercritical water

The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques.     

Active coke formation in oxydehydrogenation of ethylbenzene to styrene

In oxydehydrogenation of ethylbenzene to styrene catalytic active centers are created by coke formed during the reaction. Formation of active coke can be made evident by product analysis in the first minutes of operation and by analysis of the carbonaceous resisdues by temperature programmed oxidation (TPO) and EPR.

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. , , , .

     

Le systeme EAU-phenobarbital

The binary system water-phenobarbital is presented as a new example of systems with non-negligible vapour pressure. It is explained on the basis of aT- V- x diagram. Two invariant equilibria occur at very close temperatures: a peritectic equilibrium at 123 °C and a monotectic equilibrium at 125 °C.The two endotherms could not be separated and only the total area was calculated. Using theoretical diagramS _tot=f(V/m), the theoretical invariant planes were first set up. Then, the corroborating experimental results made it possible to determine the vapour composition at the invariant equilibrium.The compositions of the two saturated solutions at the monotectic equilibrium were fixed at 99 and 70 mol % H₂O. This means that phenobarbital is about forty times more soluble in the latter.

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Zusammenfassung Das binäre System Wasser/Phenobarbital wird als ein neues Beispiel für Systeme mit nicht zu vernachlässigendem Dampfdruck vorgestellt. Es wird auf der Grundlage einesT-V-x-Diagramms erklärt. Zwei nichtvariante Gleichgewichte liegen bei nahe beieinanderliegenden Temperaturen vor; ein peritektisches Gleichgewicht bei 123 °C und ein monotektisches bei 125 °C. Die zwei entsprechenden endothermen Peaks sind nicht aufgetrennt und nur die Gesamtfläche konnte ausgewertet werden. Zunächst wurden die theoretischen invarianten Flächen unter Anwendung des theoretischen DiagrammsS _tot=f(V/m) errechnet. Die diese Berechnungen bekräftigenden experimentellen Ergebnisse ermöglichten dann, die Dampfzusammensetzung beim invarianten Gleichgewicht zu bestimmen. Die Zusammensetzung der zwei gesättigten Lösungen beim monotektischen Gleichgewicht wurden mit 99 und 70 mol-% festgelegt. Das heißt, daß Phenobarbital in der letzteren um das 40-fache löslicher ist.

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— . -V-. : 123 ° — 125 °. . S =f(V/m), . , . 99 70 . , .

     

Thermal analysis of some complexes LH[Cr(NCS)4L2].xH2O (L=NH3 or organic base)

Data obtained by thermal analysis of K₃[Cr(NCS)₆].4H₂O and some derivatives, LH[Cr(NCS)₄L₂].xH₂O, where L=NH₃ or an organic base, are reported. The TG, DTG and DTA curves show common behaviour (SCN^– ligand decomposition) as well as specific behaviour for each complex due to the base L, which complicates the thermal decomposition of the complexes. Some weak bases with low boiling points are easily eliminated, which determines the common thermal behaviour of the complexes.A general mechanism of thermal decomposition is advanced involving dehydration and decomposition processes for both LH⁺ and [Cr(NCS)₄L₂]^–. The apparent activation energies of different processes confirm the thermal decomposition mechanisms of the complexes under study.

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Zusammenfassung Die thermische Analyse von K₃[Cr(NCS)₆].4H₂O und einigen Derivaten der allgemeinen Formel LH[Cr(NCS)₄L₂].xH₂O (L=NH₃ oder eine organische Base) betreffende Daten werden angegeben. Die TG-, DTG- und DTA-Kurven zeigen sowohl gemeinsame Charakteristika (Zersetzung des Liganden SCN^–) als auch für jeden Komplex spezifische, durch die Base L bedingte Züge, die die thermische Zersetzung der Komplexe komplizieren. Einige schwache Basen mit niedrigen Siedepunkten werden leicht eliminiert, was ein gleiches thermisches Verhalten dieser Komplexe zur Folge hat. Ein allgemeiner Mechanismus der thermischen Zersetzung wird angegeben, der die Dehydratisierung und die Zersetzungsprozesse sowohl für LH⁺ als auch für [Cr(NCS)₄L₂]^– in sich einschließt. Die scheinbaren Aktivierungsenergien der verschiedenen Prozesse sind mit dem Mechanismus der thermischen Zersetzung der Untersuchten Komplexe im Einklang.

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K₃[Cr(NCS)₆].4H₂O LH[Cr(NCS)₄L₂].x₂, L=NH₃ - . , - , , . , . , LH⁺ [Cr(NCS)₄L₂]^–. .

     

Studies of molybdenum in Mo?Ti oxide catalysts

ESR studies indicate that in Mo–Ti oxide catalysts prepared via the addition of ammonium paramolybdate to pasted titanium hydroxide, Mo⁵⁺ ions are observed in three states: in heteropoly blue, disperse MoO₃ and a solid substitutional solution in TiO₂.

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, , - , - Mo⁵⁺— , MoO₃ TiO₂.

     

On the structure and activity of a Pt/C catalyst subjected to repeated deactivation and regeneration cycles

Electron microscopic studies reveal that repeated air/hydrogen regeneration cycles cause irreversible structural changes of a Pt/C catalyst involving sintering and migration of the platinum over the support. This is reflected by a serious decrease of the catalytic activity. With hydrogen treatment only, these effects are less significant.

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, / Pt/C, . . .