L'ATD dans l'identification du polystyrene et de ses copolymeres a usage alimentaire et pharmaceutique

Polystyrene (PS) and its copolymers (SBR, ASA, SAN and ABS) have been studied by differential thermal analysis. These five families exhibit a large endothermic decomposition peak at about 380 °C. The curves exhibit also one exothermic peak (ASA, SAN, ABS) or two (PS, SBR) which are larger and nearer for SBR than for PS. ASA, SAN and ABS copolymers are characterized by an endothermic peak shape (the slope of the ascending part has been computed and expressed for one gramme of sample). This method was used for identification of alimentary package and some pharmaceutical disposables.

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Zusammenfassung Polystyren (PS) und dessen Copolymere (SBR, ASA, SAN und ABS) wurden mittels DTA untersucht. Diese 5 Systeme ergeben einen starken endothermen Zérsetzungspeak bei 380 °C. Die Kurven weisen auch einen (ASA, SAN, ABS) bzw. zwei (PS, SBR) exotherme Peaks auf, die bei SBR größer und näher bei einander sind als bei PS. Für ASA-, SAN- und ABS-Copolymere ist die Form des endothermen Peaks charakteristisch (die Steigung des Kurvenastes ansteigender Temperatur wurde berechnet und bezogen auf 1 g der Probe angegeben). Diese Methode wurde zur Identifizierung von Verpackungsmaterial von Lebensmitteln und Arzneimitteln herangezogen.

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(PS) (SBR, ASA, SAN ABS). 380° . ASA, SAN, ABS , PS, SBR , SBR , PS. ASA, SAN ABS ( ). .

     

Y (Grunwald-Winstein) parameters of aqueous solutions of sugars

The kinetics of solvolysis of t-butyl chloride in water-glucose and water-sucrose solutions have been studied. From the data obtained, Y Grunwald-Winstein parameters corresponding to these mixtures have been derived.

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- . Y - .

     

Selectivity of Fischer-Tropsch synthesis on supported nickel catalysts

Alumina supported Ni as well as Ni²⁺ exchanged CaNaX zeolites were used to study Fischer-Tropsch synthesis. Two significant selectivity effects can be distinguished, which are related to the different structures and acidities of the catalysts.

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CaNaX, Ni, Ni⁺² , -. , .

     

On the mechanism of auto-oscillations in CO hydrogenation on supported palladium catalysts

A mechanism accounting for the occurrence of auto-oscillations in the formation rates of CH₃Cl and (CH₃)₂O during CO hydrogenation on chlorine-containing supported palladium catalysts is proposed.

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, CH₃Cl (CH₃)₂O CO .

     

Diffusion of antioxidants in sheets and plates of isotactic polypropylene measured by isothermal differential-thermal-analysis

The diffusion of the phenolic antioxidant 1, 3, 5-tris (3,5-ditert. butyl-4-hydroxybenzyl)mesitylene (IRGANOX 1330) in compressed sheets of isotactic polypropylene (iPP) was investigated over the temperature range from 80°C to 120°C by isothermal differential-thermal-analysis (DTA).The measurements showed a clear relation between oxidation induction time and oxidation maximum time, (both determined by isothermal DTA) and the concentration of stabilizer.It was possible to calculate the diffusion co-efficients and the activation energy of diffusion of IRGANOX 1330 in iPP by measuring the oxidation maximum times across stacks of isotactic polypropylene sheets.The same method was employed to measure the diffusion coefficient of IRGANOX 1330 in compressionmolded plates of iPP.The influence of the morphological structure of iPP on the diffusion process was investigated by measuring the cristallinity degree of iPP-films and-plates and the determination of the dimensions of the spherulites.

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Zusammenfassung Die Diffusion des phenolischen Antioxidanten 1, 3, 5-Tris (3,5-ditert.butyl-4-hydroxybenzyl)mesitylen (IRGANOX 1330) in zusammengepreßten, isotaktischen Polypropylenfolien wurde mittels isothermer Differentialthermoanalyse (DTA) über einen Temperaturbereich von 80°C bis 120°C untersucht.Die isothermen DTA-Messungen zeigten einen klaren Zusammenhang zwischen Oxidationsinduktionszeit und Oxidationsmaximumszeit und der Konzentration des Antioxidanten.Über die Bestimmung der Oxidationsmaximumszeiten von Folienstapeln aus isotaktischem Polypropylen war es möglich, die Diffusionskonstanten und Aktivierungsenergie der Diffusion von IRGANOX 1330 in iPP zu bestimmen.Um den Einfluß der Kristallstruktur auf die Diffusion von Stabilisatoren zu ermitteln, wurdedie gleiche Methode bei gepreßten Platten angewendet. Die Gefügestruktur (Kristallinitätsgrad und Sphärolithgröße) der Platten und Folien wurde mittels dynamischer DTA und Polarisationsmikroskop untersucht.

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80–120° 1, 3, 5-- /3, 5--. -4- / / 1330/ / -/. / / . , -. 1330 - . - .

     

A general integral technique for kinetic analysis of temperature-programmed thermogravimetry

A general integral technique for analyzing the first-order kinetics of temperature-programmed thermogravimetry has been developed. The method has been successfully applied to calculate the kinetic parameters of the thermal decomposition reaction of poly(tetrafluoroethylene).

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Zusammenfassung Es wurde eine allgemeine Integraltechnik zur Analyse der Kinetik erster Ordnung bei temperaturprogrammierter Thermogravimetrie entwickelt. Diese Methode wurde zur Berechnung der kinetischen Parameter der thermischen Zersetzungsreaktion von Poly(tetrafluoräthylen) mit Erfolg eingesetzt.

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Résumé Mise au point d'une technique générale d'intégration pour l'analyse des phénomènes de cinétique du 1^er ordre par thermogravimétrie en température programmée. La méthode a été appliquée avec de bons résultats au calcul des paramètres cinétiques de la réaction de décomposition thermique du polytétrafluoroéthylène.

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- . $ .

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Comparative study of single-crystal dehydration of LiCOOH.H2O and Li2SO4·H2O

The kinetics of isothermal dehydration of two crystal hydrates with equivalent water molecule sublattices (LiCOOH.H₂O and LiSO₄.H₂O) was investigated in vacuum with a quartz crystal microbalance, and the dynamics of structural reorganization of the substances was studied by the synchrotron radiation method. Differences were found both in the nucleation stage and in the stage of reaction interface advance. The results indicate that the kinetic behaviour of isothermal decomposition of solids is determined by the structural reorganization of a metastable intermediate.

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Zusammenfassung Die Kinetik der isothermen Entwässerung zweier Kristallhydrate mit gleichartigen Teilgittern der Wassermoleküle wurde untersucht mittels isothermer TG im Vakuum und Synchrotron-Röntgenbeugung. Unterschiede zwischen beiden Materialien werden sowohl in der Keimbildungswie- wei in der Ausbreitungsphase gefunden. Die Ergebnisse zeigen, dass die Kinetik der isothermen Zersetzung fester Stoffe durch die strukturelle Reorganisation eines metastabilen Zwischenprodukts bestimmt wird.

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HCOOLi.H₂O Li₂SO₄.H₂O . , — . , . , .

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The authors would like to thank N. Kosova for experimental assistance.     

Effect of iron on the properties of supported Rh?Fe catalysts. Rh?Fe/SiO2 catalysts

The state of metals in Rh–Fe/SiO₂ catalysts has been examined. Iron is shown to form clusters with rhodium, whose size and composition depend on the metal ratio in the catalyst. The structure of active sites affects the amount and adsorption heat of hydrogen and carbon monoxide and their interaction mechanism.

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Rh–Fe/SiO₂-. , , . , CO .

     

Reduction of alkenes by hydrogen transfer over a Pd/sepiolite catalyst. Compensation effect

This paper shows the occurrence of a linear relationship between the activation energy (E_A) and the logarithm of the pre-exponential factor (ln A) in the Arrhenius equation, and between the enthalpy increment (H) and the entropy increment (S) in the Eyring equation for the reduction of olefinic double bonds by hydrogen transfer over a Pd/sepiolite catalyst. Such a relationship is known as the compensation effect or isokinetic relationship.

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Pd/ (E_a) (ln A) (H) (S) . .

     

State of copper ions, bond energy of oxygen and catalytic properties in hydrogen oxidation for a copper-magnesium system

The bond energy of surface oxygen in a copper-magnesium catalyst and its reactivity are shown to be greatly dependent on the structure of the nearer environment of copper ions. For catalysts prepared at low temperatures (773 K) this structure changes from a symmetrical square planar in CuO to an octahedral with various degrees of axial distortion depending on the copper content.

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, . , (773 ), CuO .

     

XPS and chemisorption studies of the surface layer of Pd?Ag catalysts for CO oxidation

XPS and chemisorption studies of the surface composition of a Pd–Ag alloy (5% Pd) before and after its application in CO oxidation have been performed. It is shown that in a freshly prepared sample the bulk and surface layer compositions are the same. High-temperature treatment of the catalyst in the reaction medium leads to a thermodynamic equilibrium between surface and bulk.

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Pd–Ag Pd 5% CO . , . .

     

Reactivity of oxidized substances and its correlation with catalyst properties in deep oxidation reactions

In terms of the donor-acceptor interaction concept /1/ the relative reactivity (RR) of organic and inorganic compounds and its correlation with catalyst properties in deep oxidation reactions are treated. RR and relative activity of the catalysts are shown to change depending on the predominant character (acceptor or donor) of reactant-catalyst interaction.

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- /1/ (OPC) . , OPC .

     

m-Xylene conversion over dealuminated Y zeolites studied by the pulse method

m-Xylene conversion was studied over dealuminated Y type zeolites in hydrogen forms, SiO₂ to Al₂O₃ ratios were varied from 4.86 to 12.95.

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- . SiO₂/Al₂O₃ 4,86 12,95.

     

Classification of physico-chemical transformations in thermal analysis

In the present classification the different types of physicochemical transformations are dealt with which may be useful in studying different substances by the methods of thermal analysis. Equations were derived for describing the correlation between the thermodynamic characteristics and the parameters of the differential thermal analytical (DTA) peaks for two classes of physicochemical transformations.All experiments were conducted on DTA-4 instruments constructed in the Baykov Institute of Metallurgy, the USSR Academy of Sciences.

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- , . , ( ), . — 4, . . . .

     

Partial hydrogenation of benzene over platinum supported catalysts

Partial hydrogenation of benzene to cyclohexene has been studied on Pt/Nylon 66, Pt/MgO and Pt/TiO₂. An effect of the support on the selectivity to cyclohexene was observed, Pt/Nylon showing the highest selectivity, followed by Pt/MgO and Pt/TiO₂. An interaction of platinum with the more basic supports (Nylon, MgO) and a pretreatment under oxidizing conditions, results in a higher selectivity to cyclohexene.

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Pt/ 66, Pt/MgO PtTiO₂. , Pt/, Pt/MgO Pt/T,O₂. (, MgO) .

     

A differential scanning calorimetric study of some phenol derivatives

Differential scanning calorimetry has been applied to derive the fusion enthalpies and entropies of series of mono and dimethylphenols, mono and dichlorophenols, and mono and dinitrophenols.

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Zusammenfassung DSC wurde verwendet zur Ermittlung der Schmelzenthalpie und Entropie der Reihen von Mono- und Dimethylphenolen, Mono- und Dichlorphenolen, Mono- und Dinitrophenolen.

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- , - , - .

     

Исследование роли фосфиновых комплексов никеля различных степеней окисления в каталитической димеризации олефинов

Ni(II), Ni(I) Ni(O) . , , , Ni(O) Ni(I) - Ni(I) Ni(II) Ni(O).

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The interaction of organoaluminium compounds with phosphine complexes of Ni(II), Ni(I) and Ni(0) has been studied under the conditions of catalytic propylene dimerization. The active complexes are formed from Ni(II) compounds, the regeneration of the latter is ensured by repeated reduction, oxidation of Ni(0) to Ni(I), and by disproportionation of Ni(I) into Ni(II) and Ni(0).

     

Novel evidence for the selective behaviour of tungsten carbide in liquid phase heterogeneous catalytic hydrogenation

Liquid (aqueous) phase catalytic hydrogenation of compounds containing two oxo-groups in -position (biacetyl, glyoxal, alloxan) was studied in the presence of tungsten carbide catalyst. It has been shown that only one of the oxo-groups is affected in the course of the process and is transformed into a >CH–OH group. Comparative studies carried out in the presence of platinum catalyst attest the selective behaviour of tungsten carbide.

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- - (, , ). , >C=O >CH–OH, . .

     

A gradientless flow microreactor

A simple flow microreactor can perform as a gradientless microreactor under suitable conditions so that, thanks to molecular diffusion, the reactant concentration is leveled out considerably. This was demonstrated on the basis of a mathematical analysis of the reactant concentration distribution in a flow reactor and the observation was confirmed experimentally. A simple flow microreactor was designed and its gradientless property was verified using carbon dioxide hydrogenation as a test reaction.

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. . , . , .

     

The general applicability of the Kissinger equation in thermal analysis

Computer modelling calculations will be presented which verify the fact that, if a single reaction follows either Arrhenius or transition state kinetic theory over its entire extent, then the maximum rate of reaction data obeys the modified Kissinger equation, irrespective of the applicable kinetic model. The magnitude of the Kissinger parameter correction term is dependent on the model, ranging from about 0.4% for n^th order and random nucleation, Avrami-Erofeev models to 17% for three dimensional diffusion controlled reactions. The consequences of selecting the incorrent kinetic model in interpreting experimental thermoanalytical data will be examined, thereby giving a rational explanation for the wide range of published kinetic parameters for a number of solid state decompositions.

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Zusammenfassung Computer-Modellberechnungen werden dargelegt, die die Tatsache bestätigen, daß die maximale Reaktionsgeschwindigkeit unabhängig vom angewandten Modell von der modifizierten Kissinger-Gleichung beschrieben wird, wenn eine einzelne Reaktion über den gesamten Verlauf hinweg entweder der kinetischen Arrhenius- oder der Übergangszustands-Theorie folgt. Die Größe der Kissinger-Parameter hängt vom Modell ab und liegt zwischen 0,4% für Avrami-Erofeev-Modelle mitn-ter Ordnung und ungeordneter Kristallkeimbildung und 17% für dreidimensionale diffusionskontrollierte Reaktionen. Die bei Wahl eines falschen kinetische Modells für die Interpretierung thermoanalytischer Daten eintretenden Folgen werden untersucht, wobei eine vernünftige Erklärung für die große Streuung von publizierten kinetischen Parametern einer Anzahl von Festkörperzersetzungsreaktionen gegeben wird.

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, , , , . 0,4% n- - 17% — - . , .

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Presented at the 13th North American Thermal Analysis Society Conference, Sept. 1984, Philadelphia, PA, paper 55.This work was conducted as a part of the Kentucky Energy Resource Utilization Program supported by the Commonwealth of Kentucky, Kentucky Energy Cabinet.