Kinetic Equations for Thermal Dissociation Processes. Part I. KEKAM equation

Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetic equations for thermal dissociation processes

Relationships between average degree of transformation and time of dissociation were derived for polydisperse granular materials with account to the type of grain size distribution. It has been checked, under what conditions the kinetic curves obtained by numeric solution of those relationships may be described in terms of equations D1 α²=kt , F2 [1/(1 - α) - 1 =kt] and F3 [1/(1 - α)² - 1=kt]. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of Gas Atmosphere on Removal of Sulphate Groups From Titanium Oxide

The studies were devoted to determination of the effect of gas atmosphere and its pressure on the second step of decomposition of hydrated titanium dioxide (HTD) promoted by sulfate groups. It has been found that thermal decomposition of HTD at temperatures above 300°C consists of a number of processes such as dehydroxylation, desulfuration, recrystallization and sintering of solid grains, photochemical processes (if the decomposition proceeds in the presence of light) and adsorption of gas phase components (in the presence of air or SO₂). Kinetic parameters characterizing this step of decomposition have been determined for processes carried out in vacuum and in argon or air atmospheres (at a pressure of 13.33hPa). The kinetic curves of decomposition carried out in the presence of gases capable of being adsorbed on the surface of partly dehydrated HTD are featured by local extrema due to simultaneous processes of decomposition and adsorption of gas components. This revised version was published online in August 2006 with corrections to the Cover Date.     

Compensation effect and isokinetic temperature in thermal dissociation reactions of the type Asolid ⇌ Bsolid + Cgas

It is shown that the Zawadzki — Bretsznajder rule, compensation effect, and isokinetic temperature are simple consequences of interpretation of the Arrhenius equation as a projection correlation. It is established that such an interpretation of the Arrhenius equation allows the discrimination of the deviation factors which impart a definite (although not always simple and recognized) physical sense, to the known empirical correlation. A possibility of deriving new correlation relationships by this method of reasoning is presented.     

Investigation of thermal decomposition of solids

Practical aspects of the studies of stages of thermal dissociation of solids, of the kinetics of the stages, and of utilization of general regularities of the process for verification of kinetic studies are discussed.

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Zusammenfassung Die praktischen Aspekte der Untersuchungen über die Stufen der thermischen Dissoziation von Festkörpern und ihrer Kinetik weiterhin über die Anwendungsmöglichkeiten der RegelmÄssigkeiten der Verifikation der kinetischen Untersuchungen werden erörtert.

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Thermal dissociation of basic aluminium ammonium sulfate in vacuum

A mathematical model of the thermal decomposition of basic aluminium ammonium sulfate has been developed. The construction of the model consisted in simulation of TG and DTG curves, with the use of kinetic parameters identified on the basis of results obtained in measurements of the rate of thermal dissociation of the compound under isothermal and non-isothermal conditions.

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Zusammenfassung Es wurde das mathematische Modell fur thermische Zersetzung des basischen Ammoniumaluminiumsulfats bearbeitet. Die Struktur des Modells bestand in der Nachbildung von thermogravimetrischen Kurven TG, DTG mittels der kinetischen Parameter, die auf Grund der isothermen und der nichtisothermen Ergebnisse der Untersuchungen nach der Dissoziationsgeschwindigkeit von Verbindungen identifiziert wurden.

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Résumé Un modèle mathématique décrivant la décomposition thermique du sulfate basique d'aluminium et d'ammonium est présenté.La méthode consiste à simuler les courbes thermogravimétriques TG et TGD à l'aide des paramètres cinétiques identifiés sur la base des résultats des déterminations isothermes et nonisothermes de la vitesse de la dissociation du composé.

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Thermal Transformations of CuNH4PO4⋅H2O

The isothermal and non-isothermal transformations of polycrystalline CuNH₄PO₄⋅H₂O in vacuum and in various gas atmospheres (in open air and in gaseous ammonia atmosphere) were studied at 20–800°C by means of differential thermal analysis, thermogravimetry, X-ray diffraction, paper chromatography, optical microscopy and chemical analyses. The effects of the gas phase composition on the kinetic peculiarities of total gas evolution and on the partial processes of dehydration, ammonia removal and rearrangement of the anionic sub-lattice were considered. This revised version was published online in August 2006 with corrections to the Cover Date.     

Noncommutative Dynamics of Random Operators

We continue our program of unifying general relativity and quantum mechanics in terms of a noncommutative algebra А on a transformation groupoid Γ = E × G where E is the total space of a principal fibre bundle over spacetime, and G a suitable group acting on Γ . We show that every a ∊ А defines a random operator, and we study the dynamics of such operators. In the noncommutative regime, there is no usual time but, on the strength of the Tomita–Takesaki theorem, there exists a one-parameter group of automorphisms of the algebra А which can be used to define a state dependent dynamics; i.e., the pair (А, ϕ), where ϕ is a state on А, is a “dynamic object.” Only if certain additional conditions are satisfied, the Connes–Nikodym–Radon theorem can be applied and the dependence on ϕ disappears. In these cases, the usual unitary quantum mechanical evolution is recovered. We also notice that the same pair (А, ϕ) defines the so-called free probability calculus, as developed by Voiculescu and others, with the state ϕ playing the role of the noncommutative probability measure. This shows that in the noncommutative regime dynamics and probability are unified. This also explains probabilistic properties of the usual quantum mechanics.     

Fundamental Problems in the Unification of Physics

We discuss the following problems, plaguing the present search for the “final theory”: (1) How to find a mathematical structure rich enough to be suitably approximated by the mathematical structures of general relativity and quantum mechanics? (2) How to reconcile nonlocal phenomena of quantum mechanics with time honored causality and reality postulates? (3) Does the collapse of the wave function contain some hints concerning the future quantum gravity theory? (4) It seems that the final theory cannot avoid the problem of dynamics, and consequently the problem of time. What kind of time, if this theory is supposed to be background free? (5) Will the dynamics of the “final theory” be probabilistic? Quantum probability exhibits some essential differences as compared with classical probability; are they but variations of some more general probabilistic measure theory? (6) Do we need a radically new interpretation of quantum mechanics, or rather an entirely new theory of which the present quantum mechanics is an approximation? (7) If the final theory is to be background free, it should provide a mechanism of space-time generation. Should we try to explain not only the generation of space-time, but also the generation of its material content? (8) As far as the existence of the initial singularity is concerned, one usually expects either “yes” or “not” answers from the final theory. However, if the mathematical structure of the future theory is supposed to be truly more general that the mathematical structures of the present general relativity and quantum mechanics, is a “third answer“ possible? Could this third answer be related to the probabilistic character of the final theory? We discuss these questions in the framework of a working model unifying gravity and quanta. The analysis reveals unexpected aspects of these rather wildly discussed issues.     

Thermal decomposition of basic aluminium potassium sulfate. Part II. Kinetics of the reaction

The kinetics of individual stages of thermal dissociation of basic aluminium potassium sulfate (BAPS) were studied thermogravimetrically under isobaric and isothermal conditions at a reduced pressure of the order of 10^?3 hPa and in the atmosphere of gaseous products of the reaction (H₂O, SO₂).The kinetic parameters of all the reaction stages have been identified and the nature of the stages and the effect of changes of the reaction of conditions on the course of the processes have been determined.