Kinetics of nonisothermal reduction and carburization of WO3─NiO nano-composite powders by CO─CO2

The kinetics of simultaneous reduction and carburization of WO₃─NiO nanocomposite powders by CO/CO₂ was studied using a nonisothermal thermogravimetric analysis. The experiments were carried out at heating rates between 5 and 15°C/min, showing that the thermochemical processes can be divided into four steps, each dominated by a reaction, as following: NiO → Ni, WO₃ → WO₂, WO₂ → W, and W → WC. The apparent activation energy for each step was obtained based on the Flynn-Wall-Ozawa isoconversional method for the individual steps, and the kinetic model was assessed by fitting master plots of various kinetic models for these steps at different heating rates. The Avrami-Erofeev kinetic model was found to fit to the third and fourth steps and main part of the first, and the geometric contracting model fitted the best for the second step. Changing the heating rate did not affect the master plots of the third step. However, for the first step, increasing the heating rate made the Avrami-Erofeev model the best-fitting correlation and also for the second step the matching model changed at the highest heating rate (15°C/min) from a two-dimensional contracting model (cylindrical particles) to a three-dimensional contracting model (spherical particles).     

Formation and decomposition of Lanthanum Monoxocarbonate

Amorphous lanthanum carbonate was prepared by hydrolysis of lanthanum isopropoxide using ammonia water in the atmosphere. Lanthanum monoxocarbonate, La₂O(CO₃)₂ · H₂O, crystallizes when this amorphous material was washed with hot water. The crystallization and thermal behavior of the crystalline material are studied by X-ray diffraction, thermal analysis, and infrared spectroscopy. The decomposition of La₂O(CO₃)₂ · H₂O into type-IA (LaO)₂CO₃ is observed at 440 to 540°C. Decomposition isotherms are described by the contracting cube equation, the activation energy being 42.6 kcal mol^?1. Type-IA (LaO)₂CO₃ subsequently decomposes to A-type La₂O₃ at 750 to 870°C. The kinetics is also interpreted in terms of the contracting cube equation, the activation energy being 58.3 kcal mol^?1.     

Thermal transformations of titanium slag of high titania content

Titanium raw materials play important role as a source of titanium and titanium dioxide. The investigation of the rate of oxidation and phase transformation of titanium slag in static air atmosphere by use of thermogravimetry (TG) and X-ray diffractometry (XRD) were presented. The investigation were carried out for three different particle size fractions to determine influence of this parameter on rate of reaction. To estimate kinetic parameters was used the kinetic model of contracting volume. The value of kinetic parameters show that influence of heating rate and particle size on rate of reaction is not so large. The thermogravimetric investigations of the oxidation of titanium slag in air atmosphere shown that reaction proceeds in two stages. The XRD investigation shown that titanium slag has the pseudobrookite structure and its diffraction pattern is very close to the diffractogram of magnesium titanate MgTi₂O₅ and iron magnesium titanium oxide (Fe-Mg-Ti-O). At elevated temperature the structure of slag transforms to the ferric pseudobrookite structure and excess titanium dioxide forms the rutile phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal stability and structural deformation of rutile SnO2 nanoparticles

Nanoparticles of rutile SnO₂ were synthesized by precipitation at room temperature. Samples were characterized with X-ray diffraction, transmission electron microscopy, thermoanalysis and nitrogen physisorption by BET method. The rutile crystalline structure was refined by Rietveld method. Crystallites had spherical morphology with crystallite sizes growing with the annealing temperature. The spherical crystallites aggregate to form grains composed of a number of crystallites defining the specific surface area and porosity. The crystallites contained hydroxyls in their structure and on their surface generating considerable amount of tin vacancy sites in the structure. These hydroxyls modify the Sn-O bonds, increase the lattice parameters and produce asymmetry in the representative rutile tin-oxygen octahedron. As the dehydroxylation was done with the annealing temperature, the atomic bond length between the oxygen atoms shared by adjacent octahedra decreased, contracting the lattice and increasing the symmetry.     

Effect of sample mass on the kinetics of thermal decomposition of a solid

Effects of sample mass on the kinetics of isothermal dehydration of crushed crystals of Li₂SO₄·H₂O were investigated using conventional TG. The process was characterized by a combination of Avrami-Erofeyev and contracting geometry models. Distribution of the fractional reaction, α, in particles within the sample assembly as well as the change in the rate of gross diffusion of the evolved water vapour appear responsible for the sample-mass-dependent kinetic parameters obtained for the system.     

Thermal decomposition of zinc hydroxy azide

The isothermal decomposition of zinc hydroxy azides, Zn(OH)_2-x(N₃)_x: follows deceleratory kinetics throughout the temperature range studied. The initial part of the decomposition fits into unimolecular decay law, log (1-a) = -kt. The contracting volume law satisfactorily describes the data at higher degrees of decomposition. The maximum value ofa upto which the slow decomposition could be recorded was 0.75. The aged form of zinc hydroxy azide decomposes with much lower rates and slightly different topochemical characteristics. The decrease in the rate of decomposition on ageing has been attributed to the formation of carbonate on the surface of the compound during storage. The change in topochemical behaviour is traced to the reported layer structure of zinc hydroxy azide. The effect of pre-heating on subsequent thermal decomposition has also been discussed.     

TG study on the chlorination of MoO2 by CCl4

Molybdenum-dioxide samples were produced by reduction of MoO₃ in flowing H₂. The chlorination kinetics of the pure crystalline MoO₂ and samples containing a mixture of Mo-oxides were studied by thermogravimetry, using gaseous CCl₄ as chlorinating agent. The initial samples and the chlorinated residues were investigated by XRD and BET methods, as well. The pure molybdenum-dioxide sample was remarkably less reactive than the partially reduced non-stoichiometric molybdenum-oxides or MoO₃. The characteristic sigmoid shape of the TG curves were explained by the difference in the reactivity of molybdenum-oxides and by the change of the specific surface area during chlorination. The observed reaction order ofn=0.5 suggests a fast, reversible dissociative adsorption of CCl₄ before the volatilization step. For samples of low specific surface area activation energies of 123 and 97 kJ·mol^?1 were obtained, and the kinetic curves could be well fitted by an Avrami-Erofeev equation. For sample of much higher specific surface area a diffusion controlled reaction (E _a=52 kJ·mol^?1) was supposed, and the kinetic model of contracting spheres could be applied.     

The synthesis of manganese-zinc ferrite through the transformation of polynuclear coordination compounds

The authors analyse the possibility of obtaining manganese-zinc ferrite through the transformations of polynuclear coordination compounds (pcc), either in the solid state or in a reaction medium. Polynuclear coordination compound precursors with the general molecular formula: [Fe(II)_xFe(III)_y(Mn_0.5Zn_0.5)(C₂O₄)₂(OH)_y+2(H₂O)₂] with 0.2相似文献   

Kinetics of Thermal Dissociation of Ammonium Metavanadate

The solid products of thermal decomposition of ammonium metavanadate can be used as catalysts in many important processes, and a knowledge of the dynamics of these processes is therefore essential. The thermal dissociation of ammonium metavanadate was studied under non-isothermal conditions in air atmosphere. This process occurred in three steps under the applied experimental conditions, and was associated with the elimination of ammonia and water below 330°C and with the formation of nitrogen oxides above 330°C. The kinetics of particular stages of (NH₄)₂OV₂0₅ decomposition was evaluated from the dynamic mass loss data by means of the integral method, with applycation of the Coats and Redfern approximation. The first stage of decomposition to ammonium hexavanadate is governed by a random nucleation model, the second step by a three-dimensional diffusion or contracting volume model, and the last stage again by a random nucleation model. The apparent activation energies found for the particular stages were 144.97, 378.31 or 184.40 and 260.65 kJ mol^?1, respectively.     

Chain-backbone motion in glassy polycarbonate studied by polarized infrared spectroscopy

Chain-backbone motion in glassy polycarbonate has been investigated both under isothermal stress, and also under zero stress during isothermal annealing of freely contracting film specimens. In both types of experiment, backbone motion was detected by measuring the change in infrared dichroism. The dichroism of absorption bands at 1364 and 2971 cm^?1, which have transition moment vectors directly related to the chain-backbone orientation, was studied. Under tensile stress in the homogeneous region of deformation, changes of up to 2.2° in the mean chain-backbone orientation angle were measured at 23°C. With the onset of cold drawing a total orientation change of some 8° was observed. For the isothermal annealing experiments, a film specimen holder employing conductive heating with radiative losses was employed. It enables infrared measurements to be made while the temperature of the contracting specimen is maintained constant to ± 0.5°C. Oriented specimens were prepared by isothermal stretching of polycarbonate films to strains of the order of 100%. Changes in the mean chain-backbone orientation angle were observed during annealing of these oriented films at temperatures between 80°C and the glass transition (149°C). Chain motion proceeded during annealing, and chain segments were observed to move cooperatively. The temperature at which the polymer is prestretched has a pronounced effect on its subsequent relaxation during annealing: when the sample was stretched at 23°C. motions were detected during annealing at temperatures as low as 81°C, while, if it was stretched at 154°C, no motion was detected at annealing temperatures below 127°C. The data are discussed in comparison with theories of the glassy state that predict the absence of chain-backbone motion at temperatures significantly below the glass transition. A shift in frequency of the ν_a (CH₃) absorption peak in stretched polycarbonate was measured by using polarized radiation. The effect was interpreted in terms of changes in the intermolecular bonding structure of the oriented polymer.     

Effect of thermal dehydration and rehydration on Na-magadiite structure

The effect caused by dehydration and rehydration of the synthetic Na-magadiite was investigated by TGA, XRD, SEM, and ²⁹Si NMR. Thermal analysis of Na-magadiite presented two well-defined loss mass stages between 20 and 150 °C and another between 270 and 310 °C, both related to the removal of interlayer water. The swelling behavior of Na-magadiite was studied by thermal dehydration data obtained at 150 and 300 °C, and respective rehydration by water addition. X-ray patterns showed that the dehydration of Na-magadiite at 150 and 300 °C provoked the basal spacing decrease. The XRD also showed that only the material treated at 150 °C returned to the original structure with the rehydration. ²⁹Si NMR spectra showed that after rehydration, the Q₃/Q₄ relationship presented the same value for Na-magadiite treated at 150 °C. However, this Q₃/Q₄ value decreased when the treatment was done at 300 °C. Kinetic studies of thermal decomposition showed that the dehydration of magadiite is based on a phase boundary-controlled reaction, caused by contracting areas. The exfoliation of lamellas with thermal treatment can explain this behavior, as observed in SEM images.     

Synthesis of thromboxane A2 analog dl-(9,11),(11,12)-dideoxa-(9,11),(11,12)-dimethylene thromboxane A2

The thromboxane A₂ analog, dl-(9,11),(11,12)-dideoxa-(9,11),(11,12)-dimethylene thromboxane A₂ (TX A₂) has been synthesized; the compound showed high agonist activities on platelet aggregation and the aorta contracting activities.     

Thermal decomposition kinetics of potassium iodate

The thermal decomposition of potassium iodate (KIO₃) has been studied by both non-isothermal and isothermal thermogravimetry (TG). The non-isothermal simultaneous TG–differential thermal analysis (DTA) of the thermal decomposition of KIO₃ was carried out in nitrogen atmosphere at different heating rates. The isothermal decomposition of KIO₃ was studied using TG at different temperatures in the range 790–805 K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of KIO₃. The non-isothermal decomposition of KIO₃ was subjected to kinetic analyses by model-free approach, which is based on the isoconversional principle. The isothermal decomposition of KIO₃ was subjected to both conventional (model fitting) and model-free (isoconversional) methods. It has been observed that the activation energy values obtained from all these methods agree well. Isothermal model fitting analysis shows that the thermal decomposition kinetics of KIO₃ can be best described by the contracting cube equation.     

Thermal decomposition kinetics of potassium iodate

The rate and kinetics of the thermal decomposition of potassium iodate (KIO₃) has been studied as a function of particle size, in the range 63?C150???m, by isothermal thermogravimetry at different temperatures, 790, 795, 800 and 805?K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of all samples of KIO₃ at all temperatures studied. The isothermal decomposition of all samples of KIO₃ was subjected to both model-fitting and model-free (isoconversional) kinetic methods of analysis. It has been observed that the activation energy values are independent of the particle size. Isothermal model-fitting analysis shows that the thermal decomposition kinetics of all the samples of KIO₃ studied can be best described by the contracting cube equation.     

The effects of sample size and heating rate on the kinetics of the thermal decomposition of CaCO3

Isothermal and dynamic methods were used to study the rate of weight loss of CaCO₃. Sample sizes were controlled in the range of 1–32 mg. The contracting area rate law proved universally applicable. A pronounced dependence of the activation enthalpy, pre-exponential term, and rate constant upon sample weight and heating rate was observed. This dependence is discussed primarily in terms of the effects of self-cooling and sample geometry. The concept of a unique activation energy is questioned.     

Kinetics of γ-alumina chlorination by carbon tetrachloride

The kinetics of the reaction between γ-Al₂O₃ and gaseous CCl₄ has been studied by isothermal TG measurements in the temperature range 700—1123 K. The reaction starts with a weight gain which can be attributed to the chemisorption of the reactive gas. The weight loss vs. time curves at relatively high temperatures can be described by the contracting cylinder equation and at relatively low temperatures by first-order kinetics. The dependence of the initial reaction rate on the CCl₄ partial pressure follows the Langmuir—Hinshelwood rate expression. At 700—723 K, chemical control is thought to be predominant and an apparent activation energy of 212 kJ mole^?1 is found for the chlorination process.     

The effect of particle size on the thermal decomposition kinetics of potassium bromate

The thermal decomposition of potassium bromate (KBrO₃) has been studied as a function of particle size, in the range 53?C150???m, by isothermal thermogravimetry at different temperatures, viz. 668, 673, 678, and 683?K in static air atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of all samples of KBrO₃ at all temperatures studied. The isothermal decomposition of all samples of KBrO₃ was subjected to both model fitting and model-free (isoconversional) kinetic methods of analysis. Isothermal model fitting analysis shows that the thermal decomposition kinetics of all the samples of KBrO₃ studied can be best described by the contracting square equation. Contrary to the expected increase in rate followed by a decrease with decrease in particle size, KBrO₃ shows a regular increase in rate with reduction in particle size, which, we suggest, is an impact of melting of this solid during decomposition.     

Kinetic studies on the thermal decomposition of phosphate-doped sodium oxalate

The thermal decomposition kinetics of sodium oxalate (Na₂C₂O₄) has been studied as a function of concentration of dopant, phosphate, at five different temperatures in the range 783–803 K under isothermal conditions by thermogravimetry (TG). The TG data were subjected to both model-fitting and model-free kinetic methods of analysis. The model-fitting analysis of the TG data of all the samples shows that no single kinetic model describes the whole α versus t curve with a single rate constant throughout the decomposition reaction. Separate kinetic analysis shows that Prout–Tompkins model best describes the acceleratory stage of the decomposition, while the decay region is best fitted with the contracting cylinder model. Activation energy values were evaluated by both model-fitting and model-free kinetic methods. The observed results favour a diffusion-controlled mechanism for the thermal decomposition of sodium oxalate.     

Isothermal decomposition of K2C2O4

The effect of semiconducting metal oxide (CuO and TiO₂) additives on the kinetics of thermal decomposition of potassium oxalate (K₂C₂O₄) to potassium carbonate has been studied at five different temperatures in the range 793–813 K under isothermal conditions by thermogravimetry (TG). The decomposition is enhanced by CuO (p-type) and suppressed by TiO₂ (n-type). The diverse behaviour of K₂C₂O₄ in the presence of different types of oxides in contrast with the like behaviour of K₂C₂O₄ suggests the involvement of different rate determining steps in the decomposition of these solids. The TG data of 2 mass% oxide mixed samples of K₂C₂O₄ were subjected to both model fitting and model-free (isoconversional) kinetic methods of analysis. The model fitting method of analysis shows that the rate law for the decomposition of K₂C₂O₄ (Prout–Tompkins and contracting cylinder models, respectively, for the acceleratory and decay stages) remained unaffected by the additives.     

Thermal decomposition kinetics of potassium iodate

The effect of gamma ray irradiation on the rate and kinetics of thermal decomposition of potassium iodate (KIO₃) has been studied by thermogravimetry (TG) under non-isothermal conditions at different heating rates (3, 5, 7, and 10 K min^?1). The thermal decomposition data were analyzed using isoconversional methods of Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, and Friedman. Irradiation with gamma rays increases the rate of the decomposition and is dependent on the irradiation dose. The activation energy decreases on irradiation. The enhancement of the rate of the thermal decomposition of KIO₃ upon irradiation is due to the combined effect of the production of displacements and extended lattice defects and chemical damage in KIO₃. Non-isothermal model fitting method of analysis showed that the thermal decomposition of irradiated KIO₃ is best described by the contracting sphere model equation, with an activation energy value of ~340 kJ mol^?1.