Kinetic analysis of reversible thermal decomposition of solids

The isoconversional method was used to elucidate the kinetics of reversible solid-state reactions occurring under nonisothermal linear heating. The characteristic dependencies of the effective activation energy (E) on the extent of conversion (W) were established for two model processes: a reversible first-order reaction and a reversible reaction followed by an irreversible one. For the first process, E is almost independent of W and varies between the activation energy of the direct and inverse reaction. For the second, process with an endothermic reversible step, the dependence of E on W is of decreasing shape. The effective activation energy is limited by the sum of the activation energy of the irreversible reaction and the enthalpy of the reversible reaction, at low conversions, and by the activation energy of the irreversible reaction at high conversions. Analyses of the kinetic data for the dehydration of crystalhydrates, as well as other processes proceeding through a reversible step, show the dependencies of E on W characteristic of a reversible reaction followed by an irreversible one. © 1995 John Wiley & Sons, Inc.     

Role of vapour oversaturation in the thermal decomposition of solids

Elementary thermochemical calculations show that in all cases of formation of solid product in the process of the congruent dissociative vaporization of reactants, the equilibrium partial pressure of the main product greatly exceeds its saturation vapour pressure, and therefore causes the appearance of vapour oversaturation. The oversaturation is responsible for the formation and growth of nuclei, their shape and position, the transfer of condensation energy to the reactant, the existence of induction and acceleration decomposition periods, the reaction localization, the epitaxial/topotaxy effects and the nanocrystal structure of the solid product. Variations in the energy transfer explain an increase of the molar enthalpy with temperature and the decelerating influence of melting on the rate of decomposition.     

Study on the thermal decomposition of solids in fluidized bed

Reliable thermodynamic parameters for the thermal decomposition of diammonium hydrogenphosphate [(NH₄)₂HPO₄] may be obtained using a fluidized bed. For the same size of particle, at the same temperature, but for different carrier gases, the rate constant and activation energy increase in the following order: air, methane, hydrogen. For the same carrier gas (air) the rate constant increases when the particle size decreases.     

Investigation of thermal decomposition of phosphonic acids

The paper compares building and decomposition pathways of two phosphonic acids, amino trimethylene phosphonic acid (ATMP) and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP).The theoretical formation reactions were composed using elementary reactions and compared to reaction routes published in literature. As result, summary reaction pathways for both phosphonic acids are proposed which only vary in the number of reaction steps required. These reaction steps include carbonyl reactions, S_N2-reactions, and ionic reactions. The synthesis of ATMP proceeds in three reaction steps, whereas HEDP is formed in one reaction. The thermal decomposition of both phosphonic acids in solid state was examined by combination of thermogravimetry coupled with infrared spectroscopy as well as pyrolysis gas chromatography coupled with mass spectrometry. Decomposition mechanisms were deduced and compared to the theoretical findings resulting in the conclusion that the decomposition processes of ATMP and HEDP follows the formation mechanism.Thus, the suitability of theoretical considerations for the understanding of thermal decomposition processes is shown.     

Investigation of thermal decomposition of rice husk

Studies on the thermal decomposition of untreated rice husk and that treated with HCl and H₂SO₄ of various concentrations were carried out by TG, DTG and DTA. The mass loss occurred in three distinct stages, namely, removal of moisture, release of volatile matter and burning of combustible material. The corresponding temperature ranges for untreated husk were 40–150, 215–350 and 350–690°C. The final temperature of combustion decreased with acid-treatment of the husk. The thermal decomposition of the husk was found to be an exothermic process.     

Investigation of thermal decomposition kinetics of taurine

The non-isothermal thermal decomposition of taurine was investigated by means of thermogravimetric analysis (TG) and differential thermal analysis (DTA). The experimental data were treated using Flynn–Wall–Ozawa, Doyle, Kissinger, and ?atava–?esták methods, respectively. The results show that the non-isothermal thermal decomposition mechanism of taurine is classified as phase boundary reaction, and the mechanism function is the Mampel Power law with n = 1. The forms of both integral and differential for the mechanism function are $ G(\alpha ) = \alpha $ and $ f(\alpha ) = 1 $ , respectively. The activation energy and the pre-exponential factor are 167.88 kJ mol^?1 and 1.82 × 10¹³min^?1, respectively.     

Investigation of thermal decomposition of hydrated aluminium oxide

The composition of a hydrated aluminium oxide was determined and the course of its thermal decomposition was investigated. The stages of the dissociation were established and all the solid and gaseous intermediates of the decomposition were identified. A correlation was observed between the peak temperatures for boehmite and the particle size and degree of crystallinity.

---

Zusammenfassung Die Zusammensetzung eines hydratisierten Aluminiumoxids wurde bestimmt und der Verlauf der thermischen Zersetzung dieses Oxids untersucht. Die Dissoziationsstufen wurden ermittelt und alle gasförmigen und festen Zwischenprodukte der Zersetzung identifiziert. Es wurde eine Korrelation zwischen den Peak-Temperaturen für Böhmit und der Partikelgrö\e und dem Kristallisationsgrad beobachtet.

---

. . , .

     

Study of the thermal decomposition of solids in a fluidized bed, III

The influence of the air humidity upon the thermal decomposition of diammonium hydrogen phosphate was studied in a fluidized bed, under isothermal conditions. It was found that the increase of the decomposition rate is influenced directly by the partial pressure of the water vapour in the air, and indirectly by the working temperature. The moisture effect is explained by the salt hydrolysis in the water condensed on the grain surface. The energy of activation of the thermal decomposition decreases when the air humidity increases.

---

Zusammenfassung Der Einfluß der Luftfeuchtigkeit auf die thermische Zersetzung des Diammoniumhydrogenphosphats wurde in fluidisiertem Bett unter isothermen Verhältnissen studiert. Die Zunahme der Zersetzungsgeschwindigkeit war direkt proportional dem partialen Wasserdampfdruck in der Luft und indirekt proportional der Arbeitstemperatur. Diese Wirkung wird durch Salzhydrolyse in dem kondensierten Wasser an der Kernoberfläche erklärt. Die Aktivierungsenergie der thermischen Zersetzung nimmt mit zunehmendem Feuchtigkeitsgehalt ab.

---

Résumé On a étudié l'influence de l'humidité atmosphérique sur la décomposition thermique de (NH₄)₂HPO₄ en lit fluidisé, en conditions isothermes. La pression partielle de la vapeur d'eau dans l'air intervient directement sur l'augmentation de la vitesse de décomposition et exerce une action indirecte sur la température de travail. On a expliqué l'effet de l'humidité par l'hydrolyse du sel dans l'eau condensée à la surface des grains. La valeur de l'énergie d'activation de la décomposition thermique diminue quand l'humidité atmosphérique augmente.

---

. , , , , . , .

     

Study of the thermal decomposition of solids in a fluidized bed,II

In order to eliminate the errors of the TG method with a static layer, and to determine the influence of the heating rate, the composition of the carrier gas and the particle size of the solids, a method of thermal gas evolution from a fluidized bed (FTGE) with continuous and linear increase of temperature was worked out and the thermal decomposition of diammonium hydrogen phosphate was followed. This method gives reproducible results and makes possible the determination of the apparent activation energies and kinetic parameters.

---

Zusammenfassung Um die Fehler der TG Methode unter fixierten Verhältnissen zu eliminieren, den Einfluß der Temperaturerhöhung, der Zusammensetzung des Trägergases und des Ausmaßes der Festkörper zu klären, wurde eine thermogasanalytische Methode im fluidisierten Bett (FTGE) mit kontinuierlichem und linearem Temperaturanstieg entwickelt und die thermische Zersetzung des Diammonium-biphosphates verfolgt. Man erhielt mit dieser Methode reproduzierbare Ergebnisse. Sie ist zur Bestimmung der scheinbaren Aktivierungsenergien und kinetischer Parameter geeignet.

---

Résumé Dans le but d'éliminer les erreurs des procédés thermogravimétriques avec couches fixes, et de mettre en évidence l'influence de la vitesse d'échauffement de la composition du gaz porteur et de la dimension des solides, on a développé une méthode d'analyse des gaz dégagés, avec lit fluidifié et élévation de la température continue et linéaire. On a suivi ainsi la décomposition thermique de (NH₄)₂HPO₄. Cette méthode donne des résultats reproductibles et rend possible la détermination des énergies d'activation apparentes et des paramètres cinétiques.

---

, , . . , .

---

---

Some parts presented at the IIIrd Analytical Conference, Budapest, 1970     

Study of the thermal decomposition of solids in a fluidized bed,III

The influence of the air humidity upon the thermal decomposition of diammonium hydrogen phosphate was studied in a fluidized bed, under isothermal conditions. It was found that the increase of the decomposition rate is influenced directly by the partial pressure of the water vapour in the air, and indirectly by the working temperature. The moisture effect is explained by the salt hydrolysis in the water condensed on the grain surface. The energy of activation of the thermal decomposition decreases when the air humidity increases.     

Investigation of thermal decomposition of anthranilates of alkali metals

The thermal properties of the anthranilates of the alkali metals Li, Na, K, Rb and Cs were studied. Thermal, chemical and X-ray analyses and infrared spectroscopy were used to determine the reactions of decomposition of these compounds. The thermal properties of the anthranilates of the alkali metals were compared with those of other metals.This work was done within Project 01.17: New Methods in Analytical Chemistry and Their Application in the National Economy.     

Use of the quartz crystal microbalance for kinetic studies of thermal decomposition of solids

A quartz crystal microbalance has been proposed for studies on the temperature dependence of the linear rate of a reaction interface advance in topochemical reactions of the thermal decomposition of solids. A quartz crystal microbalance has been used in investigations of the CuSO₄ · 5H₂O dehydration. The data agree fairly well with those available in the literature. Advantages and disadvantages of the method proposed are discussed.     

On the possibilities of theoretical analysis of kinetics of the thermal decomposition of solids

The main reasons for changes in the environment surrounding us are discussed on the basis of thermodynamics of irreversible processes. Subsequently, relations between thermodynamics of irreversible processes and chemical kinetics are shown, then the possibilities of theoretical determination of rate constants on the framework of the modified RRKM theory are presented. These latter considerations are supplemented by a discussion concerning the possibilities of determining the activation barriers and structural changes (necessary to account for entropy changes upon reaction) in molecules kept on the surface of crystalline phases by combination of quantum chemistry methods for isolated molecules with those reflecting the influence of the environment (i.e. interaction within the lattice). Finally, the future of theoretical methods in examining the reactivity of solid state systems is briefly discussed.     

Investigation of thermal decomposition of anthranilates of alkaline earth metals

The thermal properties of calcium, strontium and barium anthranilates (general formula MA₂·n H₂O, whsre M='metal, and) were studied. Thermal, chemical and X-ray analysis, as well as infrared spectra, were used to determine the mechanism of decomposition for these compounds. Calcium anthranilate is decomposed in four stages; the final reaction product is calcium oxide. The other anthranilates are decomposed in three stages; the final reaction products are strontium carbonate and barium carbonate.

---

Zusammenfassung Die thermischen Eigenschaften von Kalzium-, Strontium- und Bariumanthranilat (mit der allgemeinen Zusammensetzung MA₂·n H₂O, M=Metall, wurden untersucht.Die Zersetzungsmechanismen dieser Verbindungen wurden durch thermische, chemische- und Röntgenanalyse und mit Infrarotspektroskopie ermittelt. Kalziumanthranilat zersetzt sich in vier Stufen. Das Endprodukt ist Kalziumoxyd. Die anderen Anthranilate zersetzen sich in drei Stufen und geben Strontiumkarbonat und Bariumkarbonat als Endprodukt.

---

, MA₂·nH₂O, =, , , . . . .

     

Comparison of methods concerning the selection of a function describing the thermal decomposition of solids

Determination of the kinetic parameters of the thermal decomposition of solids usually requires a knowledge of the function describing the mechanism of decomposition. Research was made to obtain a method that enables the selection of one of the 16 functions used in the literature in such a way that it best describes experimental data in the isothermal measurements. The results obtained indicate that the best fit of experimental and calculated data is gained by using the weighted least-squares method with the equation g(α) = kt + b and using criteria based on the minimization of the difference between α_exp and α_calc     

Controlled rate thermal analysis commanded by mass spectrometry for studying the kinetics of thermal decomposition of very stable solids

A quadrupole mass spectrometer coupled to a thermobalance has been used to develop a controlled rate thermal analysis (CRTA) equipment. This instrument maintains constant the partial pressure of the gas generated in a solid–gas reaction during the entire process while recording the weight loss along the process. This system permits to perform the kinetic analysis of the thermal decomposition of very stable compounds with a very low equilibrium pressure in the temperature range at which the reaction takes place. The performance of the equipment was checked by studying the kinetics of the thermal decomposition of BaCO₃ using for the control the CO₂ partial pressure. Both the activation energy and the reaction kinetic model has been calculated. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 184–192, 2002; DOI 10.1002/kin.10042     

Theory of Emanation Thermal Analysis IX. Inert gas release during thermal decomposition of solids

In the Emanation Thermal Analysis the release of inert gas atoms previously incorporated in the sample is measured. Results of the statistical modelling of the inert gas release during thermal decomposition of solids are presented. The updated model supposing three components in the solid-state reaction system including the formation of an intermediate metastable component on the surface of the newly formed component was proposed for the modelling of the ETA curves. The release of inert gas atoms previously incorporated into the sample is used as a probe of microstructure changes. The random nucleation mechanism was considered in the modelling. The model can be used in modelling ETA curves of solid-solid, solid-gas and solid-liquid interactions where the existence of metastable intermediate component is supposed. This revised version was published online in August 2006 with corrections to the Cover Date.