The thermal decomposition of alkali metal formates

The thermal decompositions of lithium, sodium, potassium, rubidium and caesium formates were investigated by a complex dynamic thermoanalytical method. The ratio of the products in reactions resulting in alkali metal carbonates and oxalates depended variously on the atmosphere used. Differences were found compared to isothermal investigations, in that the catalytic effects of bases could not be observed and the oxalate-conversion was lower. The formation of oxalate did not occur in the cases of lithium and caesium formates; the order for the other salts was sodium formate < potassium formate > rubidium formate.     

Thermal decompositions of formates. Part VII. Thermal decomposition of yttrium formate dihydrate

The thermal dehydration of yttrium formate dihydrate and decomposition of yttrium formate anhydride were studied in flowing nitrogen and carbon dioxide atmospheres by means of TG and DTA.The dehydration reaction was not affected by the atmospheric condition and took place successively without any intermediate hydrate. The mechanism of the dehydration reaction was found to be a phase boundary controlled interface reaction.The decomposition of yttrium formate occurred in three stages, and yttrium oxyformate and yttrium oxycarbonate were formed as the intermediate products.In a carbon dioxide atmosphere, the decomposition took place at a higher temperature than in a nitrogen atmosphere.The anhydrous salt melted during the main stage of the decomposition and the kinetic behaviour of this stage was characteristic of a homogeneous first order reaction.     

Solid state decomposition studies on metal salicylates. Thermal decomposition of some lanthanide salicylato complexes

The thermal stability and mechanism of thermal decomposition in air of the four lanthanide complexes of 2-hydroxybenzoic acid have been studied by TG, DSC, IR and MS techniques. An analysis of the prepared compounds show that Pr(III), Nd(III) and Tb(III) form anhydrous salicylato (Hsal)⁻ complexes while the corresponding holmium compound contains four water molecules. The TG curves show two (praseodymium, terbium), three (neodymium) or four (holmium) main stages of thermal decomposition. The most unstable among the complexes studied is Ho(Hsal)₃·4H₂O which releases four water molecules in an endothermic dehydration step. Ligand molecules decompose mainly in two stages of which the first is endothermic and is attributed to the release of the ligand acid and the second is a strongly exothermic decarboxylation process. The final decomposition product is the corresponding lanthanide(III) oxide, except in the case of terbium which decomposes to Tb₄O₇.     

Thermal decompositions of formates. Part VI. Thermal dehydration reaction of copper(II) formate dihydrate

The thermal dehydration reactions of two kinds of copper(II) formate dihydrate, which differ in origin and preparation history, have been investigated by means of TG, DTA and DSC. The kinetics of isothermal dehydration were studied by weight loss, and the difference in kinetic behavior between these two samples was related to the difference in origin and preparation history. On the whole, the dehydration mechanisms of these two samples were found to be phase boundary controlled contracting interface reactions.     

The thermal decomposition of oxalates Part 14. Dehydration of magnesium oxalate dihydrate

The isothermal dehydration of magnesium oxalate dihydrate has been studied under various pressures of water vapour by use of a thermogravimetric balance. The rate of dehydration was found to be dependent upon the water vapour pressure.The reaction rate at temperatures below 124°C decreases sharply with an increase in water vapour pressure up to 0.5 mm Hg. With further increase in pressure an increase in rates is observed; this rises to a maximum and then falls again as the pressure is increased. The limitation of this phenomena to a limited temperature range is shown in the case of magnesium oxalate dihydrate. Above 124°C the initial fall in rate is not observed, the rate rises with increasing pressure from vacuum to a maximum and the falls. X-ray diffraction studies indicated that the anhydrous product prepared in the second region where a decrease of rate of dehydration occurred was crystalline but the sample dehydrated under vacuum or in the first region produced an amorphous anhydrous salt. A compensation effect is demonstrated with plots of the activation energy against the logarithm of the pre-exponential term in the Arrhenius equation.     

The thermal decomposition of alkaline earth formates

The thermal decomposition of alkaline earth formates has been studied. Experiments with single crystals, compacts and powders of strontium formate demonstrate that the method of sample presentation can affect the rate of decomposition.For anhydrous calcuim, strontium and barium formates, isothermal kinetic runs show that the decompositions follow the Erofeev law, In(l-α) = ktⁿ; the measured activation energies were 199.4, 228 and 270 kJ/mol respectively.     

Solid state decomposition studies on metal salicylates: Kinetics of iso-thermal dehydration of some transition metal salicylato complexes

The dehydration of cadmium(II ) , copper(II), manganese(II), nickel(II) and zinc(II) salicylato complexes were investigated by means of isothermal TG measurements. The Cd, Mn and Zn complexes were dihydrates. Ni complex was a tetrahydrate while Cu formed both dihydrate and tetrahydrate complexes. Thermal decomposition of the studied complexes synthesized using a pure salicylic acid as a ligand occurs in three stages, the oxides finally being formed. The first step being associated to the dehydration of the complexes obeys a phase boundary reaction mechanism. The ΔH values for hydration of Cd, Cu, Mn and Zn dihydrate complexes are 116.5, 76.0, 86.8, 113.3 kJ mol⁻¹ and for Cu and Ni tetrahydrates 117.1 and 108.9 kJ mol⁻¹, respectively.     

The effect of water vapour pressure on the thermal dehydration of yttrium formate dihydrate

The kinetics of the thermal dehydration of yttrium formate dihydrate was studied by means of isothermal gravimetry under various water vapour pressures from 5×10^–4 to 8 torr. On the whole, the dehydration was described as the three dimensional phase boundary reaction, R₃. An unusual dependence of the rate of dehydration on the atmospheric water vapour pressure was observed: with increasing water vapour pressure, the rate increased at first, passed through a maximum, and then decreased gradually to a constant value. These phenomena were similar to the Smith-Topley effect. The mechanism of the phenomena can be described on the basis of the crystallinity of the dehydrated product phase.The authors wish to thank Mr. H. Minagawa of the Analytical Instrument Laboratory of Niigata University, for the X-ray diffraction measurements at high temperatures, and Mr. K. Hirata for help in the experimental work.     

Mössbauer studies of thermal decomposition of metal(II) hexacyanoferrates(II)

The thermal decompositions of metal(II) hexacyanoferrates(II) (Co, Ni and Zn) were studied in air with Mössbauer, infrared, thermal analysis and magnetic susceptibility techniques. Dehydration is almost complete at 200° and decomposition starts at 250° in the cases of cobalt and nickel hexacyanoferrates(II), and at 300° for zinc hexacyanoferrates (II). Finally, ferrites are formed as decomposition products.     

The effect of the water vapor pressure on the kinetics of thermal dehydration of manganese(II) formate dihydrate

The effect of the water vapor pressure on the thermal dehydration of manganese(II) formate dihydrate was studied by means of isothermal gravimetry under various water vapor pressure, ranging from 4.6 to 24.4 torr. The kinetics of dehydration was described by a two-dimensional phase-boundary model,R ₂. The rate of dehydration decreased with increasing atmospheric water vapor pressure, but the Smith-Topley phenomenon was not observed for the present dehydration. The activation energy and the frequency factor for the dehydration were 110–170 kJ·mol⁻¹ and 10¹⁰–10¹⁶ cm·s⁻¹, respectively. These values increased with increasing water vapor pressure, and were much larger than those reported for the dehydration in vacuum.     

Thermal decomposition reactions of metal carboxylato complexes in the solid state: II. Thermographic and differential thermal studies of metal oxalato,malonato and succinato complexes

The thermal investigations of metal carboxylato complexes of the first transition metals, Mn(II), Fe(II), Fe(III), Co(II), Ni(II) and Cu(II) and non transition metals like Zn(II) and Cd(II) in solid state were carried out under non-isothermal condition in nitrogen atmopshere by thermogravimetric (TG) and differential thermal analyses (DTA) methods. The results of DTA curves inferred that the thermal stability of the complex decreased approximately with the increase of standard potential of the central metal ion. The thermal parameters like activation energy (E_a¹), enthalpy change (ΔH) and entropy change (ΔS) corresponding to deaquation, deammoniation and decomposition processes occurred simultaneously or separately were determined from TG and DTA curves by the standard methods. A linear correlation has been found in the plots of ΔH vs. ΔS and E_a¹ vs. ΔS in deaquation, deammoniation and decomposition processes. An irreversible phase transition was noticed for H₂[Mn(suc)₂] and H₂[Co(suc)₂] complexes in DTA curves. The residual pyrolysed products were metal carbonates.     

Some studies on thallium oxalates. II. Thermal decomposition of potassium bisoxalato diaquothallate(III) dihydrate

Potassium bisoxalato diaquothallate(III) dihydrate is obtained by precipitating thallium(III) with oxalic acid from slightly acidic (HNO₃ or H₂SO₄) solutions in the presence of potassium ions. The thermal decomposition behaviour of the complex is studied using the techniques of TG, DTA and DTG. The solid complex salt and the intermediate products of its thermal decomposition are characterised using IR absorption spectra, microscopic observations, electrical conductivity measurements and X-ray diffraction data.     

Thermodynamic properties and thermal stability of the synthetic zinc formate dihydrate

Zinc formate dihydrate has been synthesized and characterized by powder X-ray diffraction, elemental analysis, FTIR spectra and thermal analysis. The molar heat capacity of the coordination compound was measured by a temperature modulated differential scanning calorimetry (TMDSC) over the temperature range from 200 to 330 K for the first time. The thermodynamic parameters such as entropy and enthalpy vs. 298.15 K based on the above molar heat capacity were calculated. The thermal decomposition characteristics of this compound were investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG curve showed that the thermal decomposition occurred in two stages. The first step was the dehydration process of the coordination compound, and the second step corresponded to the decomposition of the anhydrous zinc formate. The apparent activation energy of the dehydration step of the compound was calculated by the Kissinger method using experimental data of TG analysis. There are three sharply endothermic peaks in the temperature range from 300 to 650 K in DSC curve.     

Origin of organic gaseous products formed in the thermal decomposition of formates

The gaseous products of the thermal decomposition of formates have been investigated and compared with the products of formaldehyde and synthesis gas transformation under analogous conditions in the presence of the solids formed in the thermal decomposition of particular formates. It was found that formaldehyde transformation leads to organic compounds identical to those obtained in the thermal decomposition of the respective formates, while synthesis gas does not react under such conditions. This fact substantiates the hypothesis that formaldehyde is a precursor of the organic compounds identified in the thermal decomposition of formates. The nature of the organic componds obtained in the thermal decomposition of formates indicates that the formaldehyde formed in the initial stages is then transformed in the Cannizzaro or Tishchenko reactions.

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Zusammenfassung Die gasförmigen Produkte der thermischen Zersetzung von Formiaten wurden untersucht und mit den Produkten verglichen, die bei der Umwandlung von Formaldehyd und Synthesegas unter analogen Bedingungen in Gegenwart von bei der thermischen Zersetzung von speziellen Formiaten gebildeten Feststoffen entstehen. Formaldehydumwandlungen führen zu organischen Verbindungen, die identisch mit denen sind, die bei der thermischen Zersetzung des betreffenden Formiats gebildet werden, während Synthesegas unter solchen Bedingungen nicht reagiert. Dies erhärtet die Hypothese, daß Formaldehyd eine Vorstufe der bei der thermischen Zersetzung von Formiaten identifizierten organischen Verbindungen ist. Die Natur der bei der thermischen Zersetzung von Formiaten auftretenden organischen Verbindungen weist darauf hin, daß das in den ersten Reaktionsschritten gebildete Formaldehyd nach der Cannizzaro-oder Tishchenko-Reaktion weiterreagiert.

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, , . , i , . . , , . , , , .

     

Mössbauer studies of thermal decomposition of metal(III) hexacyanoferrates(II)

The thermal decomposition of metal(III) hexacyanoferrates(II) (Al, As, Sb, Bi) was studied up to 700° in air by employing Mössbauer, infrared spectroscopy and thermal analysis techniques. With the exception of the bismuth compound, the isomer shift of these hexacyanoferrates(II) increases on dehydration at 200°. Dehydration is complete at 200°, decomposition into the ferrite at 300°, and formation of-Fe₂O₃ from aluminium and bismuth hexacyanoferrates(II) and Fe₃O₄ from antimony and arsenic hexacyanoferrates(II) at 700°.

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Zusammenfassung Die thermische Zersetzung von Metall(III)ferrocyaniden (Al, As, Sb, Bi) wurde bis zu 700° in Luft unter Anwendung der Mössbauer und Infrarotspektroskopie, sowie thermoanalytischer Techniken untersucht. Die Isomerverschiebung dieser Ferrocyanide nimmt mit der Dehydratisierung bei 200° zu, mit Ausnahme des Wismuts. Die Dehydratisierung ist bei 200° abgeschlossen, die Zersetzung zum Ferrit bei 300° und die Bildung von-Fe₂O₃ aus Aluminium- und Wismutferrocyanid, von Fe₃O₄ aus Antimon- und Arsenferrocyanid bei 700°.

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Résumé On a étudié dans l'air jusqu'à 700°, la décomposition thermique des ferrocyanures de métaux trivalents (Al, As, Sb, Bi), par spectroscopies Mössbauer et infrarouge, ainsi que par les techniques d'analyse thermique. Le déplacement des isomères de ces ferrocyanures augmente lors de la déshydratation à 200°, à l'exception du bismuth. La déshydratation est complète à 200°, la décomposition en ferrite à 300°, la formation d'-Fe₂O₃ à partir des ferrocyanures d'aluminium et de bismuth ainsi que du Fe₃O₄ à partir des ferrocyanures de l'antimoine et de l'arsenic à 700°

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-, , — Al, As, Sb, Bi- 700° . , , 200°. 200°, 300° -Fe₂O₃. 700° Fe₃O₄.

     

Kinetic studies on the decomposition of cyano complexes. I. the thermal decomposition of cyanoferrate(II) acids

The formation of HCN from solid iron(II) cyano complex acids is studied by a non-isothermal kinetic method. A derivatograph is used for the measurements and the kinetic parameters are calculated by different methods using the Horowitz—Metzger, Coats—Redfern and Zsako equations. The results are discussed and the kinetic parameters (energy and entropy of activation) are compared with IR and Mössbauer spectroscopic data.     

Kinetics of thermal decomposition of the solid state II. Delimiting the homogeneous-reaction model

Present evidence shows that many thermal processes can be described by the generalized rate equation

−dx/dt = Z exp(E*/RT)f(x) but many others cannot. Still others may be adequately describable by a modified equation. A small set of tests will enable the experimenter to determine whether or not the equation applies. These include change of sample size, change of sample geometry, and extended time of reaction.     

Kinetics and thermodynamics of thermal dehydration of magnesium oxalate dihydrate

The kinetics and thermodynamics of the thermal dehydration of crystalline powders of MgC₂O₄ · 2 H₂O were studied by means of thermal analyses both at constant temperatures and at linearly increasing temperatures. The dehydration of the dihydrate is regulated by one of the Avrami-Erofeyev laws. The kinetic parameters from TG at constant temperatures are in good agreement with those from TG at the lowest rate of rising temperatures. The dynamic dehydration kinetics was also examined, using DSC recorded simultaneously with TG at linearly increasing temperatures. The validity of the estimated mechanism and kinetic parameters is briefly discussed.     

Kinetics of thermal decomposition of nickel oxalate dihydrate in air

Thermal decomposition taking place in solid state complex, NiC₂O₄·2H₂O, has been investigated in air by means of TG–DTG/DTA, DSC, XRD. TG–DTG/DTA curves showed that the decomposition proceeds through two well-defined steps with DTA peaks closely corresponding to the weight loss obtained. XRD showed that the final decomposition product of NiC₂O₄·2H₂O was NiO. Kinetics analysis of NiC₂O₄·2H₂O decomposition steps was performed under non-isothermal conditions. The activation energies were calculated through Friedman and Flynn–Wall–Ozawa (FWO) methods, and the most possible kinetic model function has been estimated through the multiple-linear regression method. The activation energies for the two decomposition steps of NiC₂O₄·2H₂O were 171.1 ± 4.2 and 174.4 ± 8.1 kJ/mol, respectively.