State of cobalt and molybdenum in cobalt-molybdenum-containing zeolites

NaY and CaHY zeolites containing 7 wt.% Mo and 0.7 wt.% Co have been studied by means of IR and diffuse reflectance spectroscopy (DRS). It is shown that ammonium heptamolybdate (AHM) interacts with the zeolite forming a silicon molybdenum heteropoly complex (SiMo HPC). In contrast to NaY, along with SiMo HPC, MoO₃ is formed on CaHY after calcining.

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NaY CaY , 7 .% Mo 0,7 .% Co, . , , (SiMo HPC). NaY, CaHY SiMo HPC MoO₃.

     

Effect of the state of vanadium cations on the IR spectra of adsorbed carbon monoxide

ESR and IR-spectrosocpic studies of the effect of the state of vanadium ions on the IR-spectra of adsorbed CO have revealed complex formation of CO with V⁴⁺ (vCO at 2192 and 2205 cm^–1) and V³⁺ (vCO at 2178 and 2185 cm^–1) ions.

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-- - CO. CO V⁴⁺ (vCO 2192, 2205 cm^–1) V³⁺ (vCO 2178, 2185 cm^–1).

     

Proof of the kinetic reaction mechanism of PVC degradation using TA

The possibility of describing the kinetics of thermal degradation of PVC samples under both isothermal and nonisothermal conditions with a unique model and using the same set of parameters was investigated. Analysis of the experimental data revealed good agreement at higher temperatures (above 175 °C) when the catalytic action of generated HCl and its distribution in the sample were considered. At lower reaction temperatures, further experimental conditions and/or sample characteristics must be considered, and a modification of the model is necessary.

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Zusammenfassung Es wird die Möglichkeit untersucht, die Kinetik des thermischen Abbaus von PVC sowohl unter isothermen wie unter nichtisothermen Bedingungen durch ein einziges Modell und unter Verwendung des gleichen Parametersatzes zu beschreiben. Die Analyse der Messdaten zeigt gute Übereinstimmung bei hohen Temperaturen (über 175 °C), wenn die katalytische Aktivität des entwickelten HCL und seine Verteilung in der Probe berücksichtigt werden. Bei tieferen Temperaturen müssen weitere experimentelle Bedingungen und/oder Probeneigenschaften berücksichtigt werden, was eine Modifizierung des Modells erforderlich macht.

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. ( 175°), . , .

     

Behavior of CSTR upon fast external effects: Possibility of increasing average conversion

The objective of the work was to study the influence of external factors (changes in composition, load and temperature) on the regimes of heterogeneous catalytic reactors. As shown, a rather fast change in external parameters causes an internal reorganization of the CSTR thus leading to an increase in average conversion.

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( , , ). , , , .

     

An investigation of some homo- and heterobinuclear complexes of copper(II) and nickel(II) with pyridine-2-aldoxime

The reactions between copper(II) or nickel(II) with thecis-pyridine-2-aldoxime complexes of the same metal ions have been investigated by spectrophotometric measurements. The homo and heterobinuclear chelates involved have been isolated as the chlorides and characterized by spectroscopic and thermoanalytical techniques. The first decomposition step is not dependent on the furnace atmosphere (N₂ or O₂) and is accompanied by a large exothermic effect (DSC curves in N₂). TG curves show that binuclear complexes are generally slightly less stable than the respective mononuclear complexes but, in the case of [Cu(NiL₂)Cl₂(H₂O)₂], the complexation of copper(II) gives rise a drastic decrease of its thermal stability.

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Zusammenfassung Die Reaktionen zwischen Kupfer(II) und Nickel(II) mit den cis-Pyridin-2-aldoxim-Komplexen der gleichen Metallionen wurden spektrophotometrisch untersucht. Die homo- und heterobinuklearen Chelate wurden als Chloride isoliert und durch spektroskopische und thermoanalytische Methoden charakterisiert. Der erste Zersetzungsschritt ist unabhängig von der Ofenatmosphäre (N₂ oder O₂) und ist stark exotherm (s. DSC-Kurven in Abb. 1). Die TG-Kurven lassen erkennen, dass zweikernige Komplexe im allgemeinen etwas weniger stabil als die entsprechenden einkernigen Komplexe sind, im Falle von [Cu(NiL₂)Cl₂(H₂O)₂], aber die Anlagerung von Liganden an das Kupfer zu einer drastischen Verminderung der Stabilität führt.

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- -2- . - , . ( ) , -, . , , , , [Cu(NiL₂)Cl₂(H₂O)₂], .

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This work was carried out with financial support by MPI National Project.     

Kinetic investigations of the formation of carbonate sodalite

The kinetics of sodium carbonate formation within a sodalite matrix by an intracage reaction of hydrothermally grown basic nitrite sodalite and carbon dioxide has been studied. This heterogeneous reaction inside the sodalite cages was followed in the 773 K–1153 K temperature interval by thermogravimetry, IR-spectroscopy, as well as X-ray powder diffraction. The weight uptake during heating and the increase of the unit cell volume has been discussed to describe the imbibition of CO₂ and the resulting intra-cage carbonate formation.

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. 773–1153 , . CO₂, .

     

Kinetic studies of ozonation of polyhydric alcohols

Kinetic studies of the oxidation of polyhydric alcohols by ozone-oxygen mixtures in aqueous solutions at 284–302 K indicate that the second-order effective rate constantk decreases with increasing substrate concentration.

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- 284–302 . , .

     

The thermal behaviour of cis-1,4-polyisoprene in the presence of cobalt salt

The effects of synthetic fatty acids (Versatic 10, average formula C₁₁H₂₂O₂) and the cobalt salts of these acids (cobalt siccative) on the thermal properties of cis-1,4-polyisoprene were examined, using a rheometer and a derivatograph. It was found that both Versatic 10 and the cobalt siccative accelerate the peroxide vulcanization of the isoprene rubber considerably, simultaneously decreasing the cross-linking density and increasing the sol fraction content in the vulÇanizates. This is brought about by parallel radical and ionic decomposition of the peroxide initiator in the presence of these compounds. The addition of Versatic 10 or the cobalt siccative to the polyisoprene rubber does not alter the general character of its thermal changes, but decreases the temperatures of these processes and the degradation degree of the elastomer.

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Zusammenfassung Der Einfluss synthetischer Fettsäuren (Versatic 10, mittlere Summenformel C₁₁H₂₂O₂) und ihres Kobaltsalzes (Kobalt-Sikkativ) auf die thermischen Eigenschaften von cis-1,4-Polyisopren wurde mittels Rheometer und Derivatograph untersucht. Sowohl Versatic 10 als auch das Kobaltsikkativ beschleunigen die Peroxid-initiierte Vulkanisation des Isoprenkautschuk, gleichzeitig wird die Vernetzungsdichte verringert und der Gehalt an löslichen Stoffen in den Vulkanisaten erhöht. Ursache dafür ist der parallelle Ablauf der radikalischen und ionischen Zersetzung des Peroxids in Gegenwart der Zusätze. Die Beimengung von Versatic 10 oder Kobaltsikkativ zum Polyisoprenkautschuk ändert nicht den allgemeinen Charakter der thermischen Umwandlungen, aber die Temperatur dieser Reaktionen und der Abbau des Elastomeren werden verringert.

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, C₁₁H₂O₂ ( 10) -1,4-. , 10, , . . 10 , , .

     

Kinetics and mechanism of the oxidation of p-aminobenzoic acid by periodate ion in aqueous medium

Kinetic results of the oxidation of p-aminobenzoic acid by periodate ion in aqueous medium are discussed. A suitable mechanism based on kinetic evidence and product analysis is proposed.

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- . , .

     

Role of tin in a PtSb alloy and a Pt-Sn/Al2O3 reforming catalyst

The conversion of n-hexane was studied on a Pt-Sn/Al₂O₃ catalyst, a PtSn alloy and on the corresponding Pt catalysts. The results indicate the same catalytic effect of tin in supported and unsupported catalysts. It is concluded that the role of tin is connected with alloy formation.

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- Pt-Sn/Al₂O₃, PtSn Pt-. . , .

     

V2O5/TiO2 oxidation catalysts, III. Oxidation of CO on pure and sodium-doped systems

The activity of vanadia/titania catalysts in CO oxidation has been tested and found to be of the same order as that observed for unsupported vanadia; the simultaneous presence of vanadium-sodium compounds cancels the activity, probably because of the elimination of labile V=0 species at surface defects.

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V₂O₅/TiO₂ CO, V₂O₅; - , , V=0 .

     

Potassium addition to Fe/MgO, Ni/MgO and Ni/SiO2: Reducibility, dispersity and stabilization of the promoter by the support

The influence of potassium addition on the morphological properties of Fe/MgO and Ni/MgO has been investigated: KNO₃ addition to precursors results in a decrease of the reducibility and in a smaller dispersity of the metallic phase. A loss of potassium is observed at reduction temperatures in excess of 773 K. Silica-supported Ni behaves differently: silica inhibits the potassium volatilization and nickel reducibility is enhanced. This illustrates how promoter effects can be influenced by the nature of support.

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Fe/MgO Ni/MgO: KNO₃ . , 773 K. , : . .

     

Application of nitroxyl radicals to study mass transfer processes in porous materials

A method to determine rates for gaseous and liquid transfer of moisture in the process of mass transfer in porous materials is suggested. The data obtained agree well with the theoretical concepts about liquid transfer of moisture under contact of two porous bodies.

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. .

     

Kinetics and mechanism of isothermal dehydration of LiKC4H4O6 · H2O single-crystals

The kinetics of isothermal dehydration of LiKC₄H₄O₆.H₂O single-crystals was investigated in the [001] crystallographic direction under a dynamic vacuum of 6.7×10^–5 Pa with a quartz crystal microbalance. The removal of H₂O molecules may be described by a diffusion equation for a semi-infinite medium. The diffusion coefficients vary from 2.13×10^–11 cm² s^–1 at 391.7 K to 9.9×10^–9 cm² s^–1 at 453.2 K. The scanning electron microscope data provide some evidence that the dehydration is not a topochemical reaction. From the experimental data it is concluded that the anhydrous product is in the state of premelting. This explains the anomalous diffusion energyE _D=37±1 kcal mol^–1 and preexponential factorD ₀=5×10⁹ cm² s^–1.

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Zusammenfassung Die Kinetik der Entwässerung von LiKC₄H₄O₆.H₂O in [001] — Richtung unter dynamischem Vakuum wurde mit einer Quarzkristall-Mikrowaage verfolgt. Die Abgabe von Wasser kann mit einer Diffusionsgleichung für ein halb-unendliches Medium beschrieben werden, die Diffusionskoeffizienten variieren von 2, 13 · 10^–11 cm²s^–1 bei 391,7 K bis 9,9 · 10^–9 cm² s^–1 bei 453,2 K. Rasterelektronenmikroskopische Aufnahmen zeigen, daß die Entwässerung nicht topochemisch abläuft. Nach dem experimentellen Ergebnis befindet sich das entwässerte Produkt in einem Vorschmelz-Stadium. Daraus erklären sich die anomalen Werte für die DiffusionsenergieE _D=(37±1) kcal mol–1 und den präexponentiellen FaktorD ₀=5 · 10⁹ cm² s^–1.

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6,7 · 10. LiKC₄H₄O₆.H₂O [001]. . 2,13·10^{–11 2 –1} 391,7 9,9·10^{–9 2 –1} 453,2 . , . , «», E =37±1 ·^{– 1} ₀=5·10⁹²·^–1.

     

Kinetics of thermal decomposition of diacyl peroxides in the presence of aerosil

In the presence of aerosil the thermal decomposition of the polymeric peroxide of sebacic acid is enhanced proportionally to the filler weight fraction in the reaction system. This is attributed to the interaction of peroxide groups with acidic groups on the aerosil surface and their decomposition according to a nonradical mechanism unlike the homolytic radical decomposition in solution.

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, , . .

     

Heat capacity measurements by computer-interfaced DSC

A computer assisted heat capacity measuring system has been designed from commercial components. A differential scanning calorimeter of type Perkin-Elmer DSC-2 forms the basis for measurements from 100 to 1000 K. A Hewlett-Packard calculator (minicomputer) of type 9821 is the data handling system. The data are collected and permanently stored on teletape. The program has been written to govern measurement and final computation, tabulation, plotting, and curve fitting. Calibration is done by comparison with benzoic acid or aluminium oxide (sapphire). Zinc heat capacities have been measured as an example and for evaluation of accuracy. Accuracies of better than ± 0.5% have been achieved, an improvement of approximately a factor 3 to 5 over a similar system without computer assist. The system will be used mainly for heat capacities of linear macromolecules.

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Zusamenfassung Ein mit einem Komputer ausgestattetes Wärmekapazitäts-Mess-System wurde aus handelsüblichen Bestandteilen gebaut. Ein Differential-Scanning Kalorimeter vom Typ Perkin-Elmer DSC-2 bildet das Grundgerät für Messungen zwischen 100 und 1000 K. Ein Hewlett-Packard Kalkulator (Mini-Komputer) des Typs 9821 ist das Datenbehandlungssystem. Die Daten werden gesammelt und laufend am Tele-Band gespeichert. Das Programm eignet sich zur Steuerung der Messung und zur Endauswertung, Tabulierung, Berechnung von Zusammenhängen und Anpassung an Kurven. Geeicht wird mittels Vergleichen mit Benzoesäure oder Aluminiumoxid (Saphir). Die Wärmekapazitäten von Zink wurden als Beispiel und zur Bewertung der Genauigkeit gemessen. Die Genauigkeiten erwiesen sich besser als ± 5 %, also 3 bis 5-mal so gut wie bei einem ähnlichen System ohne Komputer. Das System wird hauptsächlich zur Messung der Wärmekapazitäten linearer Makromoleküle eingesetzt.

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Résumé Un dispositif a été conçu à partir de composants commerciaux pour la mesure des chaleurs spécifiques et a été associé à un calculateur. Un analyseur calorimétrique différentiel à compensation de puissance, de type Perkin-Elmer DSC-2, constitue l'élément de base pour les mesures entre 100 et 1000 K. Le traitement des données s'effectue avec un calculateur du type Hewlett-Packard 9821 (mini-ordinateur). Celui-ci assure l'acquisition des données et leur conservation permanente sur télé-bande. Le programme a été conçu pour contrôler la mesure et le calcul final, la mise en tableaux, le tracé des courbes et leur ajustement. L'étalonnage s'effectue par comparaison avec l'acide benzoïque ou l'oxyde d'aluminium (saphir). A titre d'exemple, la chaleur spécifique du zinc a été mesurée afin d'évaluer l'exactitude. Celle-ci est meilleure que ± 0,5% c'est-à-dire qu'elle est 3 à 5 fois supérieure à celle d'un système similaire sans calculateur. Le dispositif sera surtout utilisé pour la détermination des chaleurs spécifiques des macromolécules linéaires.

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. - -2 100 1000 . - (-) 9821. . , , . (). . +0.5%, 3 5 . .

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The authors wish to express their appreciation to Dr. A. P. Gray, Dr. R. C. Ryan and the Perkin-Elmer Corporation, Norwalk, Connecticut for their assistance in setting up the DSC-2 and providing us with the digital data recording facilities.This work was supported by a grant from the National Science Foundation (Grant Number GH42634X) and partially purchased with an equipment grant Number GH36965.     

Cumene hydroperoxide decomposition in the presence of metal complex catalysts supported on amorphous SiO2

By the method of molecular deposition, ions of CrO ₂ ²⁺ VO³⁺ and MoO ₂ ²⁺ were supported on a matrix of amorphous SiO₂. Different types of organic ligands were supported subsequently on the surface compounds so formed. The catalytic activity of the samples was studied in the decomposition of comene hydroperoxide.

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SiO₂ CrO ₂ ²⁺ , VO³⁺, MoO ₂ ²⁺ . . .

     

Kinetics and mechanism of the decomposition of pyrite under conventional and quasi-isothermal — quasi-isobaric thermoanalytical conditions

The kinetics and mechanism of the thermal decomposition of pyrite were examined by the method of quasi-isothermal and quasi-isobaric thermogravimetry (Q-TG). It emerged that by means of this technique the overlapping partial processes of the complicated oxidation and decomposition reactions of pyrite can be separated and studied independently from one another. It was found that the partial reactions FeS₂=FeS +S and Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ are endothermic processes taking place quasiisothermally and leading to equilibrium, while the oxidation FeS+O₂=Fe₂O_3–x(SO₄)_x is an exothermic process which takes place in an oscillating manner in a rather broad temperature interval.

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Zusammenfassung Autoren untersuchten die Kinetik und den Mechanismus der thermischen Zersetzung von Pyrit durch quasi-isotherme und quasi-isobare Thermogravimetrie (Q-TG). Es stellte sich heraus, daß sich überlagernde Teilprozesse der komplizierten Oxydations- und Zersetzungsprozesse von Pyrit mit Hilfe dieser Technik absondern und unabhängig voneinander untersuchen lassen. Es wurde festgestellt, daß die Teilreaktionen FeS₂=FeS+S und Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ endotherme Prozesse sind, die quasi-isotherm verlaufen und zu einem Gleichgewicht führen, während die Oxydation FeS+O₂=Fe₂O_3–x(SO₄)_x ein exothermer Prozeß ist, der oszillierend in einem ziemlich breiten Temperaturintervall verläuft.

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(Q-) . . , FeS₂=FeS+S Fe₂O_3–x(S₂O₄)_x=Fe₂O₃+SO₃ , . FeS+O₂ =Fe₂O_3–x(SO₄)_x , .

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The authors thank Prof. E. Pungor for valuable discussions, and Mrs. M. Kiss and Miss I. Fabian for their technical assistance.