碱式碳酸锌非等温热分解动力学研究

采用TG-DTA曲线分析研究了碱式碳酸锌在氮气气氛中的热分解反应动力学,利用Doyle-Ozawa法和Kissinger法对碱式碳酸锌非等温热分解动力学数据进行了分析,同时运用Satava-Sestak法研究了碱式碳酸锌的热分解机理.结果表明,碱式碳酸锌的热分解反应服从随机成核和随后生长机理.     

Thermal decomposition of zinc carbonate hydroxide

This study is devoted to the thermal decomposition of two zinc carbonate hydroxide samples up to 400 °C. Thermogravimetric analysis (TGA), boat experiments and differential scanning calorimetry (DSC) measurements were used to follow the decomposition reactions. The initial samples and the solid decomposition products were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and laser particle size analyzer. Results showed that zinc carbonate hydroxide decomposition started at about 150 °C and the rate of decomposition became significant at temperatures higher than 200 °C. The apparent activation energies (E_a) in the temperature range 150–240 °C for these two samples were 132 and 153 kJ/mol. The XRD analyses of the intermediately decomposed samples and the DSC results up to 400 °C suggested a single-step decomposition of zinc carbonate hydroxide to zinc oxide with not much change in their overall morphologies.     

Thermal decomposition of copper(II) and zinc carbonate hydroxides by means of TG-MS

Summary For the quantitative analyses of evolved CO₂and H₂O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal decomposition of sodium hydrogencarbonate NaHCO₃. The accuracy and reliability of the quantitative analyses of the evolved CO₂and H₂O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO₂and H₂O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite, Cu₂CO₃(OH)₂, and hydrozincate, Zn₅(CO₃)₂(OH)₆, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured by TG.     

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.     

Thermal decomposition of basic lead carbonate

TG and DTA curves of the thermal decomposition of basic lead carbonate, 2PbCO₃ Pb(OH)₂, are presented and compared with the thermogram of normal lead carbonate PbCO₃. The appearance of different intermediate compounds at identical experimental conditions is ascribed to the degree of perfection of the carbonate crystals. Poorly developed basic lead carbonate crystals, formed in the presence of polyglutamic acid, give no recognizable intermediate compounds.     

Thermal decomposition of nicotinate complexes of cobalt and nickel in dynamic nitrogen atmosphere

Thermal decomposition of cobalt and nickel nicotinate was studied by TG, DTG and DSC. The mechanism of decomposition has been established from TG and DSC data. The kinetic parameters namelyE, A together with ΔH were calculated from DSC curves using mechanistic and non-mechanistic integral equations.

---

Zusammenfassung Mittels TG, DTG und DSC wurde die thermische Zersetzung von Cobaltund Nickelnikotinat untersucht. Der Zersetzungsmechanismus wurde anhand der TG-und DSC-Daten entwickelt. Die kinetischen ParameterE, A wurden zusammen mit ΔH anhand der DSC-Kurven mit Hilfe von mechanistischen und nichtmechanistischen Integrationsgleichungen berechnet.

     

Kinetics of the thermal decomposition of cadmium carbonate (CdCO3)

Cadmium carbonate used in the study was prepared from cadmium chloride, ammonium carbonate and ammonia. The X-ray powder diffraction, infrared spectral and chemical analysis conducted on the product show that the sample is of analytically acceptable purity. The thermal decomposition kinetics of cadmium carbonate was then studied by using the isothermal thermogravimetric method under a flow of dry nitrogen gas. The decomposition kinetics is best described by a two-dimensional phase boundary reaction mechanism (R ₂). An activation energy (E _a) of 135.006 kJ·mol^?1 and natural logarithm of the frequency factor (lnZ) of 16.754 were obtained in the range of 9 temperatures (400, 390, 380, 370, 360, 350, 340, 330 and 320°C).     

Influences of evolved gases on the thermal decomposition of zinc carbonate hydroxide evaluated by controlled rate evolved gas analysis coupled With TG

The influences of atmospheric CO₂ and H₂O on the kinetics of the thermal decomposition of zinc carbonate hydroxide, Zn₅(CO₃)₂(OH)₆, were investigated by means of controlled rate evolved gas analysis (CREGA) coupled with TG. Although CO₂ and H₂O were evolved simultaneously in a single mass-loss step of the thermal decomposition, different effects of those evolved gases on the kinetic rate behavior were observed. No distinguished effect of atmospheric CO₂ was detected within the possible range of self-generated CO₂ concentration. On the other hand, apparent acceleration effect by the increase in the concentration of atmospheric H₂O was observed as the reduction of reaction temperature during the course of constant rate thermal decomposition. The catalytic effect was characterized by the decrease in the apparent activation energy for the established reaction with increasing the concentration of atmospheric H₂O, accompanied by the partially compensating decrease in the pre-exponential factor.     

Electrosynthesis and thermal characterization of basic copper carbonate nanoparticles

The present study concerns the electrochemical synthesis of basic copper carbonate nanoparticles by oxidation of metallic copper on the anode in an aqueous bicarbonate solution. This simple and one-step preparation can be considered as green synthesis. The scanning electron microscopy (SEM) analysis indicates that average particle size of the product is in the range of about 70 nm. On the other hand, basic copper carbonate micro-powder has been prepared, by mixing solutions of copper(II) sulphate and sodiu bicarbonate. The SEM analysis showed that the size of particles prepared in the same way is in the range of about 1 μm. In another part of this study, the thermal decomposition of micro and nanoparticles of copper carbonate produced by various methods was studied in air using TG-DTA techniques. The results of thermal study show that the decomposition of both samples occurs in single step. Also, the TG-DTA analysis of the nanoparticles indicates that the main thermal degradation occurs in the temperature range of 245–315°C. However, microparticles of Cu(OH)₂ · CuCO₃ decomposed endothermally in the temperature range of 230–330°C.      

Thermal decomposition of basic aluminium-ammonium sulfate (BAAS) in hydrogen atmosphere

The stages of thermal decomposition of basic aluminium-ammonium sulfate (BAAS) in hydrogen atmosphere were studied with use of differential thermal analysis (DTA), thermogravimetric (TG), X-ray diffraction phase analysis (XRD), and chemical analyses. It has been found that hydrogen greatly influences the process of the desulfurization of the investigated compound: this process occurs at lower temperatures as compared to the desulfurization process in air. The final decomposition product of the basic salt at 1223 K is-Al₂O₃. The experimental part is preceded by the thermodynamic analysis of the desulfurization process of BAAS in hydrogen atmosphere, and its results have been correlated with experimental tests.

---

Zusammenfassung Die Stufen der thermischen Zersetzung von basischem Aluminium Ammonium Sulfat (BAAS) in WasserstoffatmosphÄre wurden unter Verwendung von Differenzthermoanalyse (DTA), Thermogravimetrie (TG), röntgenographischer Phasenanalytik (XRD) und chemischer Analytik untersucht. Es wurde festgestellt, dass Wasserstoff den Desulfurierungsprozess der untersuchten Verbindung stark beeinflusst, indem dieser bei tieferer Temperatur ablÄuft als die Desulfurierung in Luft. Das Endprodukt der Zersetzung des basischen Salzes bei 1223 K ist-Al₂O₃. Die experimentellen Resultate wurden mit den Ergebnissen einer vorgÄngig durchgeführten thermodynamischen Betrachtung der Desulfurierung von BAAS in WasserstoffatmosphÄre korreliert.

     

Influence of iron ion additions on the thermal decomposition of basic zinc carbonate

Thermal decomposition of pure basic zinc carbonate (BZC) and doped or mixed with iron ions were studied using TG, DTA and kinetics of isothermal decomposition. The TG and DTA investigations revealed that, the presence of iron ions retards the decomposition processes of (BZC). Also, the retardation effect increases on increasing of iron concentration up to 50 at.%. The curves of isothermal decomposition show the usual sigmoidal character. The decomposition velocity contsant (K) values are plotted vs. 1/T according to Arrhenius equation gave a plot of good straight lines with activation energies of 43.7, 48.2, 53.2 and 57.1 kJ mol^–1 for pure (BZC) and incorporated with 1, 10, 30 and 50 at.% Fe²⁺ respectively. The products of the thermal decomposition of pure BZC and mixed with iron ions are characterized using X-ray diffraction, IR spectroscopy, surface area determination and the surface porosity. These investigations showed that iron ions are effectively incorporated into zinc oxide lattice in the range of 30–50 at.%, which gave a ZnFe₂O₄ spinel.

---

Zusammenfassung Mittels TG, DTA und der Kinetik der isothermen Zersetzung wurde der thermische Abbau von reinem bzw. von mit Eisenionen versetztem basischen Zinkcarbonat (BZC) untersucht. TG- und DTA-Untersuchungen zeigen, da\ der Zersetzungsproze\ von BZC durch Eisenionen gehemmt wird. Dieser Hemmungseffekt wÄchst bis zu einer Eisenionenkonzentration von 50 mol%. Die Kurven der isothermen Zersetzung zeigen den üblichen sigmoiden Charakter. Aus dem Auftragen der Geschwindigkeitskonstantek des Zersetzungsprozesses (gemÄ\ der Arrhenius-Gleichung) gegen 1/T ergeben sich in guter NÄherung Geraden mit den Aktivierungsenergien 43.7, 48.2, 53.2 und 57.1 kJmol^–1 für BZC mit einem Fe⁺-Gehalt von 0, 1, 10, 30 bzw. 50 mol%. Die thermischen Zersetzungsprodukte von reinem bzw. von mit Eisenionen versetztem BZC wurden unter Zuhilfenahme von Röntgendiffraktion, IR-Spektroskopie, OberflÄchenbestimmung und OberflÄchenporositÄt charakterisiert. Diese Untersuchungen ergaben, da\ Eisenionen im Bereich 30–50 mol% in das Zinkoxidgitter eingebaut werden und dabei ein ZnFe₂O₄ Spinell entsteht.

     

Thermal decomposition of silver carbonate

Conflicting results have been reported by different workers on the thermal decomposition of silver carbonate, Ag₂CO₃. In the present study, the decomposition mechanism was elucidated by various analytical methods; gas analysis (differential thermal gas analyses) in helium, carbon dioxide and oxygen flows with and without a P₂O₅ trap or a KOH trap, DTA-TG in a carbon dioxide flow and high-temperature X-ray diffraction analysis in a carbon dioxide flow. The gas evolution at ca. 200?C consisted of carbon dioxide. A simultaneous evolution of carbon dioxide and oxygen occurred at ca. 400?C. Two endothermic peaks (ca. 189 and 197?C) without weight change during the heating in a carbon dioxide atmosphere were due to the phase transition of silver carbonate from the normal viaΒ toα phase. The reverse transition occurred during the cooling.     

Thermal decomposition of oxalates. Part 17. Thermal decomposition of manganese(II) oxalate in a nitrogen atmosphere

Comparative studies of the kinetics of the isothermal and nonisothermal dehydration and decomposition of manganese(II) oxalate in an atmosphere of nitrogen are reported. Agreement between the values of the energy of activation for the isothermal and the nonisothermal dehydration at high heating rates was obtained. At low heating rate, the value obtained for the energy of activation is comparable with the enthalpy of dehydration. Values of 143 and 242 kJ mole^?1 were obtained for the energy of activation of the isothermal and nonisothermal decomposition, respectively. The difference is attributed to the condition of the anhydrous salt used in both cases. The theory of absolute reaction rate is applied and the parameters obtained are discussed.     

Thermal decomposition of some silver(I) carboxylates under nitrogen atmosphere

The thermal decomposition reactions of CH₃CH₂C(CH₃)₂COOAg (1), (CH₃)₃SiCH₂COOAg (2), CF₃COOAg (3), (CH₃)₃CCOOAg (4), C₂H₅COOAg (5), C₃F₇COOAg (6), C₆F₁₃COOAg (7) and (CF₂)₃(COOAg)₂ (8) were studied in N₂ atmosphere using thermogravimetry (TG), derivative thermogravimetry and differential thermal analysis. Characterized compounds decomposed in one- or multi-step processes with metallic silver formation in the range 215–465 °C. TG-IR studies of gases evolved during thermolysis revealed products of decomposition, such as carboxylic acids, CO₂ and recombination reactions.     

The thermal decomposition of the carbonate reaction products

The complex thermal analysis was used in the investigations of the carbonate reaction products in the residue after Al leaching from calcium aluminate-12CaO·7Al₂O₃ and Selfdisintegrated Powder. The conversion of Al was calculated basing on a content of Al in the pregnant solution as well as in a residue obtained from the kinetic investigations. The third method of measurements of a conversion of Al was presented and discussed. Results show, that the proposed method can be used for conversion estimations with 95% of confidence level as well as for the detection of carbonate products and is useful for an interpretation of the new approach for kinetic mechanism of Al leaching.     

Thermal decomposition of ammonium cerous carbonate

The thermal decomposition of ammonium ceryl(III) carbonate (ACeC) [NH₄CeO(CO₃)] was investigated by thermogravimetry, differential thermal analysis and X-ray diffraction. The results showed three endothermic stages of decomposition, each involving a loss in weight. The first stage, at 65.5 °C, is characteristic of the removal of adsorbed water, the second stage, at 214.8 °C, is associated with ammonia release, and the third stage, at 263.6 °C, relates to the removal of carbon dioxide.     

The thermal decomposition of (NH4)4V2O11 in a nitrogen atmosphere and the kinetics of the first decomposition step

Although the reaction products are unstable at the reaction temperatures, at a heating rate of 2 deg·min^?1 ammonium peroxo vanadate, (NH₄)₄V₂O₁₁, decomposes to (NH₄)[VO (O₂)₂ (NH₃)] (above 93°C); this in turn decomposes to (NH₄) [VO₃ (NH₃)] (above 106°C) and then to ammonium metavanadate (above 145°C). On further heating vanadium pentoxide is formed above 320°C. The first decomposition reaction occurs in a single step and the Avrami-Erofeev equation withn=2 fits the decomposition data best. An activation energy of 148.8 kJ·mol^?1 and a ln(A) value of 42.2 are calculated for this reaction by the isothermal analysis method. An average value of 144 kJ·mol^?1 is calculated for the first decomposition reaction using the dynamic heating data and the transformation-degree dependence of temperature at different heating rates.     

Synthesis and study of basic zinc carbonate

Basic zinc carbonate was synthesized from zinc oxide and ammonium hydrogencarbonate in aqueous medium. The resulting precipitates were studied by thermogravimetry and X-ray diffraction analysis. Pentazinc hexahydroxydicarbonate (Zn₅(CO₃)₂(OH)₆) was shown to be the reaction product at experimental times longer than 60 min.     

Kinetics of thermal decomposition of dimethyldioxirane in oxygen atmosphere

Dimethyldioxirane decomposition in oxygen atmosphere follows a first-order kinetic law. Decomposition rate constant (k, s⁻¹) in acetone in the temperature range from 30 to 50°C has been determined as lgk=(7.1±0.9)−(16.0±1.4)/θ, θ=2.303RT kcal/mol.     

Dimethyl carbonate synthesis catalyzed by DABCO-derived basic ionic liquids via transesterification of ethylene carbonate with methanol

Easily prepared DABCO-derived (1,4-diazobicyclo[2.2.2]octane) basic ionic liquids were developed for an efficient synthesis of dimethyl carbonate (DMC) via the transesterification of ethylene carbonate (EC) with methanol. 1-Butyl-4-azo-1-azoniabicyclo[2.2.2]octane hydroxide ([C₄DABCO]OH) exhibited high catalytic activity and 81% DMC yield together with 90% EC conversion was obtained under mild reaction conditions. Notably, the catalyst could be recycled for four times without loss of catalytic activity. Moreover, a possible mechanism was also discussed.