The kinetics of the thermal degradation of calcium carbonate

The decomposition of calcium carbonate fine powder in a flowing nitrogen atmosphere has been investigated by non-isothermal thermogravimetry at heating rates in the range, 10–50 deg min^–1. The analog percentage weight change record was digitized at 1 deg intervals. The resulting data, transformed into dimensionless extents of reaction and calculated rates of reaction, was then subjected to the Arrhenius, Friedman and Generalized Kissinger analyses, using a recently developed FORTRAN program system. The value ofn namely 0.39 ±0.04, resulting when the data is analyzed assuming an nth order reaction, strongly indicates that the most probable rate controlling step is a three-dimensional diffusion process (D4 mechanism), withE=172.4 kJ·mol^–1 andA=1.97·10⁴ K^–1·min^–1. Reasons for the wide disparity in previously reported kinetic data are discussed.

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Zusammenfassung Die Zersetzung von feinpulvrigem Calciumcarbonat im Stickstoffstrom wurde durch nicht-isotherme Thermogravimetrie bei Aufheizgeschwindigkeiten von 10–50 °C/min untersucht. Die analoge prozentuale Gewichtsverlustregistrierung wurde in Intervallen von einem Grad digitalisiert. Die erhaltenen, in solche eines dimensionslosen Reaktionsgradcs überführten Daten und berechnete Reaktionsgeschwindigkeiten wurden der Arrhenius-, der Friedmann- und einer verallgemeinerten Kissinger-Analyse unterzogen, wobei ein kürzlich aufgestelltes FORTRAN-Programm benutzt wurde. Der unter der Annahme einer Reaktion n-ter Ordnung fürn erhaltene Wert von 0.39 ±0.04 ist ein nachdrücklicher Hinweis darauf, daß der geschwindigkeitsbestimmende Schritt höchstwahrscheinlich ein dreidimensionaler Diffusionsprozeß (D4-Mechanismus) mitE=172.4 kJ·mol^–1 undA=1.97·10⁴ K^–1·min^–1 ist. Gründe für die weitreichende Verschiedenheit der bisher mitgeteilten kinetischen Daten werden diskutirt.

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10–50° . , , 1. , , , , , . n- , =0,39 ±0,04 , , e (4 ) E=172, 4 · ^–1 =1,97·10^{4 –1}·^–1. .

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To be presented at the 14th North American Thermal Analysis Society Conference, San Francisco, CA, September 15–18, 1985.     

Coadsorption of ethylene and oxygen on an iridium surface

It is established that the hydrocarbon coverage (0<1) formed at T<400 K on the Ir surface is oxidized upon oxygen exposures to CO and H₂O by an adsorption mechanism. Complete oxidation to CO₂ and H₂O is achieved at T350 K after C₂H₄ exposures of the oxygen coverage.

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, (<1), T<400 K Ir, CO H₂O . CO₂ H₂O T350 K C₂H₄ .

     

Thermal research of montmorillonite synthetized from the oxides SiO2-Al2O3-MgO-CaO

The thermal behaviour of synthetic montmorillonite of relatively simple chemical composition has been studied and interpreted. Montmorillonite was prepared by hydrothermal synthesis at 300° and 8.8 MPa during 165 hours. With the methods of DTA, DTG, TG, X-ray diffraction analysis, infrared spectroscopy and electron microscopy it was proved that the synthetic montmorillonite is a monomineral sample and no differences from natural montmorillonite were observed.

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Zusammenfassung Das thermische Verhalten synthetischer Montmorillonite verhältnismässig einfacher chemischer Zusammensetzung wurde untersucht und gedeutet. Montmorillonit wurde durch hydrothermische Synthese bei 300°C und 8.8 MPa in 165 Stunden hergestellt. Durch die Methoden der DTA, DTG, TG, Röntgendiffraktionsanalyse, Infrarotspektroskopie und Elektronenmikroskopie wurde erwiesen, daß synthetische Montmorillonit eine monominerale Probe ist und keine Abweichungen von natürlichem Montmorillonit beobachtet werden konnten.

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. 165 300° 8.8 . , , , , , .

     

Catalytic desulfurization of ethanethiol over zinc-forms of NaX zeolites

Zinc exchanged zeolite X was found to catalyze effectively the dehydrosulfurization of ethanethiol. The catalytic activity correlated linearly with the degree of ion exchange and increased with the reaction temperature. The role of zinc cations in the reaction examined is discussed and suggestions concerning the reaction mechanism are put forward.

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X, Zn, . . .

     

Calculation of the rate of SO2 oxidation to SO3

Approximate equation to calculate the effectiveness factor of catalyst for SO₂ oxidation to SO₃ has been derived. Calculated data agree well with those predicted by a quasi-homogeneous model.

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. .

     

Coke deposition on naphtha reforming catalysts: II. Influence of the addition of a second metal to platinum

The nature and rate of coke deposited on mono-and bimetallic reforming catalysts have been studied for normal heptane reforming. For bimetallic catalysts it has been shown that coke deposition is less extensive than on monometallic catalyst, depending on the degree of polymerization and the type of bimetallic catalyst.

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-. , , , .

     

Photooxygenation of 9-methyl-1,2,3,4-tetrahydrocarbazole: A kinetic study

The reaction of the singlet oxygen with 9-methyl-1,2,3,4-tetrahydrocarbazole has been undertaken to give a benzazonine derivative in good yield. Rose-bengal supported on an anionic resin was used as heterogeneous photosensitizing agent. Kinetic evaluation has been made for the additon of singlet oxygen to the indole ring at room temperature.

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9--1,2,3,4- . , , . .

     

Catalytic properties of V?Mo?O systems in acrolein oxidation

Catalytic properties of V–Mo–O systems have been studied in acrolein oxidation. When catalysts are activated in reaction mixtures at 673 K, then a solid solution of molybdenum oxides in reduced vanadium oxides is formed, which is responsible for deep oxidation. Also, several compounds are produced, which by their activity and selectivity to acrylic acid formation are arranged in the sequences VMo₃O₁₁VMo₂O_8+x>V₆Mo₄O₂₅, and VMo₃O₁₁>VMo₂O_8+xV₆Mo₄O₂₅, respectively.

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V–Mo–O . 673 K , , , : VMo₃O₁₁VMo₂O_8+x>V₆Mo₄O₂₅, : VMo₃O₁₁>VMo₂O_8+xV₆Mo₄O₂₅.

     

Gasification in steam of a bituminous coal from Peñarroya (Cordoba,Spain) and of different samples prepared from it

The gasification with steam of a bituminous coal from Peñarroya (Cordoba, Spain) (H—O) and of several samples prepared from either by acid treatment (H—H, H—N, H—F and H—F(3)) or by thermal treatment (H—O—C) was studied under both dynamic and isothermal conditions (10 deg/min and 40 min at 1000°).It was found that only for the samples prepared by hydrofluoric acid treatment, H-F and H—F(3), did the gasification effected under such experimental conditions take place in a complete manner.

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Zusammenfassung Die Dampfvergasung von bituminöser Kohle (H—O) (Penarroya, Cordoba, Spanien) und von daraus durch Säurebehandlungen (H—H, H—N, H—F und H-F(3)) oder thermische Behandlung (H—O—C) hergestellten Proben wurde unter dynamischen und isothermen Bedingungen (10 °/min und 40 min bei 1000°) untersucht. Es wurde festgestellt, daß nur die durch Flußsäurebehandlung hergestellten Proben (H—F und H—F(3)) unter den experimentellen Bedingungen vollständig vergasbar sind.

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(10°/ 40 1000°) () , . , , , .

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The authors are grateful to the CAICYT of Spain for the financial support on Project No. 0794/82.     

Kinetics of alkane oxidation by chromic acid in aqueous solutions of Ir(IV) chloride complexes

The kinetics of propane and isobutane oxidation by aqueous solutions of chromic acid in the presence of Ir(IV) chloride complexes has been studied. Reaction rate decreases with increasing Cl ion concentration and decreasing acidity. Ir(H₂O)Cl ₅ ^– complexes are by an order of magnitude more active than IrCl ₆ ^2– .

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Ir(IV). Cl- . Ir(H₂O)Cl ₅ ^– , IrCl ₆ ^2– .

     

Kinetic and mechanistic studies on the oxidation of arginine and histidine by chloramine-T in hydrochloric acid medium

The oxidation of amino acids by chloramine-T (CAT) in HCl medium at 30°C indicates simultaneous catalysis by H⁺ and Cl^– ions in the HCl concentration range of 0.04–0.12 M. The reaction is first order with respect to concentrations [CAT], [H⁺] and [arginine], but zero order with respect to [histidine]. The rate depends also on Cl^– concentration following 0.7th order. At HCl concentrations >0.12 M, the rate equation is:w=k[CAT] [amino acid]^0.6 and is independent of the [Cl^–]. A suitable mechanism has been suggested.

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-T (CAT) HCl (30°C) H⁺, Cl^– [HCl]=0,04–0,12M. [CAT], [H⁺] [] []. [Cl^–]^0,7. [HCl]>0,12M =k · [CAT][]^0,6 [Cl^–]. .

     

The role of excited states in the photolysis of n-butyraldehyde, II. Intersystem crossing quantum yields

Singlet triplet intersystem crossing quantum yields were determined for n-butyraldehyde, using the photosensitized cis-trans isomerization of piperylene to monitor the process. At room temperature and 313 nm, 0.58±0.05 and 0.72±0.05 were obtained for the triplet yield in the vapor phase and in isooctane, respectively.

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- - - . 0,58±0,05 0,72±0,05 313 .

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For Part I, see Ref. /1/     

Catalytic properties and phase composition of multicomponent catalysts for oxidative ammonolysis of propane

Studies of the phase composition and catalytic properties of several complex oxide catalysts for oxidative ammonolysis of propane indicate that the active phases of these catalysts are antimonates of the respective metals. Phosphorus and tungsten additives to the catalysts promote the formation of such phase compositions, i.e. the formation of antimonates and the binding of excess antimony oxide.

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. , ; , .

     

Effect of reductant adsorption on the ESR parameters of O

The change in the ESR parameters of O ₂ ^– ion-radicals under the effect of adsorption of reducing molecules on zinc oxide consists in the increase of the Z-component of the g-tensor. This change is assumed to be due to the transition of O ₂ ^– coordination from -to the -type.

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- O ₂ ^– , Z- g-. , O ₂ ^– - -.

     

Diffusion-controlled recombination of peroxide radicals in polyatomic esters

Pulse photolysis measurements of rate constants for the decay of peroxide radicals of seven polyatomic esters show that the reaction is diffusion-controlled for esters with 2 cP. The Smoluchowsky equation is suggested to calculate 2k_t for esters with short alkyl radicals.

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. , - , 2 . 2k_t .

     

Catalysts for selective hydrogenation of conjugated dienes into olefins in the presence of PdCl2 complexes

Complexes of PdCl₂ with amines or pyridine reduced by (iso-Bu)₂ AlH are shown to be catalytically active in the selective hydrogenation of conjugated dienes into olefins in aromatic media. The promoting effect of H₂O and O₂ has been established.

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PdCl₂ , (-Bu)₂ AlH, . H₂O O₂.

     

Effect of the partial pressure of reactants on the selectivity of methylcyclopentane hydrogenolysis over a platinum catalyst

The kinetics of methylcyclopentane hydrogenolysis on a Pt/Al₂O₃ catalyst (10% Pt) has been studied at 230°C. The selectivity to 2-methyl- and methylpentane formation depends on the partial pressures of the starting reactants (methylcyclopentane and hydrogen); the surface coverage by these reactants must be taken into account in selectivity studies.

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Pt/Al₂O₃ (10% Pt) 230°C. 2-- 3- ( ). .

     

Oxidation of ethylene to ethylene oxide: A tpr study on fresh and aged catalysts

The deactivation of a silver catalyst was investigated after six years of industrial production of ethylene oxide. Temperature-programmed reduction was used to characterize the chemical nature of the silver and its reactivity towards oxygen. The fresh and some aged catalysts were examined, also after different thermal treatments.During the industrial run, the surface species were modified and some oxygen diffused into the bulk of the metal. Aging caused permanent changes in the characteristics of the silver, resulting in a different interaction with oxygen. The TPR spectra exhibited a trend along the reactor axis, suggesting a correlation with the degree of deactivation of the catalyst.

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Zusammenfassung Die Desaktivierung eines Silberkatalysators wurde nach 6-jährigem Einsatz zur industriellen Produktion untersucht. Temperaturprogrammierte Reduktion wurde angewandt, um die chemische Natur des Silbers und dessen Reaktivität gegenüber Sauerstoff zu charakterisieren. Frische und einige gealterte Katalysatoren wurden nach verschiedenen thermischen Vorbehandlungen untersucht. Die Alterung verursachte bleibende Veränderungen in charakteristischen Eigenschaften des Silbers, was in der unterschiedlichen Wechselwirkung mit Sauerstoff zum Ausdruck kommt. Die TPR-Resultate zeigen einen Trend entlang der Reaktorachse, was auf eine Korrelation mit dem Grad der Desaktivierung des Katalysators hindeutet.

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. () . , , . . , , . , .

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The experimental contributions by F. Genoni and G. Valassina are gratefully acknowledged.     

Catalytic hydrogenation of olefins with the VCl4?Mg?H2 system in tetrahydrofuran

The hydrogenation of olefins with the VCl₄–Mg–H₂ system in tetrahydrofuran was examined. The yield was found to depend on the Mg: VCl₄ mole ratio. The maximum yield of cyclohexene hydrogenation is achieved at C₆H₁₀/VCl₄=4. Addition of AlCl₃ or triphenylphosphine increases the yield of hydrogenation to a mole ratio C₆H₁₂/VCl₄=7.

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: VCl₄–Mg–H₂ . , Mg:VCl₄. C₆H₁₀/VCl₄=4. AlCl₃ C₆H₁₂/VCl₄=7.