Thermal decomposition of alkali metal perchlorates

The effect of past mechanical history on the subsequent thermal decomposition kinetics of sodium, potassium, rubidium and caesium perchlorates, has been investigated. At low temperatures the decomposition of all these salts is significantly sensitized by pre-compression. At high temperatures, however, prior compression results in a lowered decomposition rate in the case of potassium, rubidium and caesium perchlorates and in an increase in the thermal reactivity of sodium perchlorate. The high temperature behaviour is shown to be an indirect consequence of the low temperature behaviour. The difference in behaviour between sodium perchlorate and the other alkali metal perchlorates is explained on the basis of the stability of the respective chlorates, formed during the low temperature decomposition. This is substantiated by experiments which show that the addition of sodium chlorate to sodium perchlorate brings about a sensitization while potassium perchlorate admixed with potassium chlorate results in a desensitization at high temperatures.     

Thermal decomposition of aluminium hydroxides

The thermal decompositions of the crystalline aluminium hydroxides hydrargillite, bayerite and nordstrandite were investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. It was found that these aluminium hydroxides undergo thermal decomposition in the following sequences: hydrargillite-1

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Zusammenfassung Die thermische Zersetzung von kristallinen Aluminiumhydroxiden, wie Hydrargillit, Bayerit und Nordstrandit, wurde thermogravimetrisch, differentialthermoanalytisch, röntgendiffraktometrisch und IR-spektrophotometrisch untersucht. Es wurde festgestellt, da\ diese Aluminiumhydroxide in der folgenden Reihenfolge zersetzt werden: Hydrargillit-I

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Thermal decomposition of silylated layered double hydroxides

Anionic surfactant and silane modified layered double hydroxides (LDHs) were synthesized through an in situ coprecipitation method. The structure and morphology were characterized by XRD and TEM techniques, and their thermal decomposition processes were investigated using infrared emission spectroscopy (IES) combined with thermogravimetry (TG). The surfactant modified LDHs (H-DS) shows three diffractions located at 1–7° (2θ), while there is only one broad reflection for silane grafted LDHs (H–Si) in this region. The morphologies of the H-DS and H–Si show fibrous exfoliated layers and curved sheets, respectively. The IES spectra and TG curves indicate that alkyl chain combustion and dehydroxylation are overlapped with each other during heating from 373 to 723 K in H-DS and to 873 K in H–Si. Sulfate anion transformation process occurs at 473 K in H-DS and 523 K in H–Si. The derivant of sulfate can exist even above 1073 K. After further decomposition, the metal oxides and the new type of Si–O compounds are formed beginning at around 923 K in silane modified sample.     

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO⁺₂, CO⁺, H₂O⁺, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.     

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 stability of alkali metal bifluorides

The thermal stability and non-isothermal kinetics of the decomposition of alkali metal bifluorides were studied using a derivatograph. The removal of hydrogen fluoride from LiF · HF and NaF · HF takes place before melting and their decomposition occurs in a single stage; however, potassium, rubidium and cesium bifluorides at first undergo polymorphous transformation and melting on heating, and their decomposition proceeds stepwise. The thermal stability of alkali metal bifluorides has been found to increase with increasing ionic radius of the cation, reflecting its correlation with the hydrogen bond strength in these compounds.

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Zusammenfassung Es wurde die thermische Stabilität und die nichtisotherme Kinetik der Zersetzung der Alkalibifluoride thermogravimetrisch untersucht. HF entweicht aus LiF · HF und NaF · HF vor dem Schmelzen in einer Stufe. Bei den entsprechenden Salzen des Kaliums, Rubidiums und Cäsiums erfolgt zuerst eine polymorphe Umwandlung, danach das Schmelzen, wobei die Zersetzung in mehreren Stufen vor sich geht. Die thermische Stabilität der Verbindungen wächst mit zunehmenden Ionenradien, was auf die entsprechende Stärke der Wasserstoffbindung zurückgeführt werden kann.

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Résumé Etude thermogravimétrique de la stabilité thermique de fluorhydrates de métaux alcalins et de la cinétique de leur décomposition en conditions non isothermes. Dans le cas de LiF · HF et de NaF · HF, le départ de l'acide fluorhydrique se produit avant la fusion et la décomposition s'effectue en une seule étape. Par contre, les fluorhydrates de potassium, rubidium et césium subissent une transition cristalline et une fusion avant de se décomposer. On observe que la stabilité thermique des fluorhydrates de métaux alcalins augmente avec le rayon ionique du cation et l'on montre qu'elle peut être reliée à la force de la liaison hydrogène dans ces composés.

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. LiF · HF NaF · HF , , , . , , .

     

Thermal decomposition of metal polyacrylates

Results of thermal and pyrolysis-GC/MS analyses of Na, Ca and Mg polyacrylates are presented. It was confirmed that the main decomposition reactions of the Na salt take place in the temperature range 420 – 470 and those of the other two polymers in the range 450–490. It was found that the solid residue after decomposition was the metal carbonate or oxide, while the volatile products consisted of H₂, CO, CO₂, saturated and unsaturated hydrocarbons (including cycloolefins and aromatic hydrocarbons) and aliphatic ketones. This suggests that the thermal decomposition of the metal polyacrylates proceeds via side-chain splitting and breaking of the main chain of the polymer, without retropolymerization.

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Zusammenfassung Die Ergebnisse der Thermo- und Pyrolyse-GC/MS-analysen von Na-, Ca- und Mg-Polyacrylaten werden beschrieben. Es wurde bestÄtigt, dass die Hauptzersetzungsreaktionen des Natriumsalzes im Temperaturbereich von 420 bis 470, jene der anderen zwei Polymeren im Bereich von 450 bis 490 ablaufen. Es wurde nach der Zersetzung ein fester Rückstand von Metallkarbonat oder -oxid gefunden, wÄhrend die flüchtigen Produkte aus N₂, CO, CO₂, gesÄttigten und ungesÄttigten Kohlenwasserstoffen (darunter Zykloolefinen und aromatischen Kohlenwasserstoffen) und aliphatischen Ketonen bestanden. Dies lÄsst darauf schliessen, dass sich die thermische Zersetzung der Metallpolyacrylate über die Abspaltung der Seitenkette und der Spaltung der Hauptkette des Polymers ohne Retropolymerisation vollzieht.

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Résumé On présente les résultats des analyses thermiques et des produits de décomposition pyrolytique par chromatographie en phase gazeuse et spectrométrie de masse (GC/MS) des polyacrylates de Na, Ca et Mg. On confirme que la réaction de décomposition principale du sel de sodium a lieu entre 420 et 470 et celle des deux autres polymères entre 450 et 490. On trouve que le résidu solide après décomposition est le carbonate ou l'oxyde du métal, tandis que les produits volatils consistent en N₂, CO, CO₂, en hydrocarbures saturés et non-saturés (y compris les cyclooléfines et hydrocarbures aromatiques) et en cétones aliphatiques. Cela permet de supposer que la décomposition thermique des polyacrylates métalliques s'effectue par coupure de la chaÎne latérale et par rupture de la chaÎne principale du polymère, sans rétropolymérisation.

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-- -- Na, Ca Mg. , 420–470, — 450–490. , . H₂, CO, CO₂, , , . , .

     

Thermal decomposition of metal nitrates

The paper presents a study regarding the preparation of 40 %M^IIFe₂O₄/60 %SiO₂ nanocomposites (M = Ni, Zn, Cu) by thermal decomposition of metal nitrates—poly(vinyl alcohol)–tetraethyl orthosilicate gels. Thermal analysis and FT-IR spectroscopy have evidenced that a redox reaction takes place between PVA and NO ₃ ^? ions in the pores of the formed hybrid gels. The result of this redox reaction is the formation of carboxylate-type coordination compounds that have the role of a precursor of the ferrite nanoparticles. By thermal decomposition of these precursors inside the silica matrix, the corresponding MFe₂O₄/SiO₂ nanocomposites are obtained starting with 600 °C, as resulting from XRD analysis. Elemental maps of the corresponding involved elements M (Ni, Zn, Cu), Fe, and Si have confirmed the homogenous distribution of the ferrite nanoparticles within the silica matrix. TEM images have shown that the nanocomposites were obtained as fine nanoparticles, with diameter up to 20 nm. All nanocomposites 40 %M^IIFe₂O₄/60 %SiO₂ obtained at 1000 °C presented magnetic properties characteristic to this type of nanocomposite.     

Thermal decomposition of iron(II) sulphate heptahydrate in the presence of alkali metal carbonates

The thermal decomposition of iron(II) sulphate heptahydrate was carried out in air under dynamic conditions in the presence of lithium, sodium, potassium and rubidium carbonates. The decomposition path in the presence of lithium carbonate differs from that in the presence of the other carbonates. In the presence of lithium carbonate, the heptahydrate loses all the water molecules before entering into reaction with the carbonate. The anhydrous sulphate then reacts with the carbonate, presumably to form iron(II) carbonate, which in turn undergoes decomposition — oxidation via magnetic oxide to ferric oxide. In the case of the other carbonates, iron(II) sulphate enters into reaction with the carbonate in question even before dehydration is complete, to form ferrous carbonate, which in turn reacts with the moisture still present to form green iron(II) hydroxide. This compound then undergoes decomposition — oxidation reactions via magnetic oxide to ferric oxide.

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Zusammenfassung Die thermische Zersetzung von Eisen(II)-sulfat-Heptahydrat wurde in Luft unter dynamischen Bedingungen in Gegenwart von Lithium-, Natrium-, Kalium und Rubidiumcarbonat ausgeführt. In Gegenwart von Lithiumcarbonat verläuft die Zersetzung auf einem anderen Wege als in Gegenwart der anderen untersuchten Carbonate. In Gegenwart von Lithiumcarbonat verliert das Heptahydrat alle Wassermoleküle, bevor es mit dem Carbonat in Reaktion tritt. Das wasserfreie Sulfat reagiert mit dem Carbonat vermutlich unter Bildung von Eisen(II)-carbonat, das oxydativ über Magnetit zu Eisen(III)-oxid zersetzt wird. Im Falle der anderen Carbonate tritt Eisen(II)-sulfat mit dem betreffenden Carbonat noch vor der völligen Beendigung der Dehydratation unter Bildung von Eisen(II)-carbonat in Reaktion, das daraufhin mit noch vorhandenem Wasser zu grünem Eisen(II)-hydroxid weiterreagiert. Diese Verbindung zersetzt sich oxydativ über Magnetit zu Eisen(III)-oxid

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The authors express their sincere thanks to Dr. B. R. Sant for his keen interest in this work and for his valuable suggestions. They also express their gratitude to Professor P. K. Jena, Director, for his permission to publish the results. One of us (MSRS) also thanks the Director for a Senior Fellowship.     

Thermal decomposition of some metal sulphates

The thermal decomposition temperatures of some metal sulphates (iron, copper, cobalt, nickel, zinc and lead sulphates) have been investigated by TG and DTA. The mechanism of decomposition of these sulphates is discussed, making use of additional information obtained from isothermal studies and X-ray diffraction measurements. The activation energies of these reactions were calculated and found to increase, with almost the same increments, in the order Zn<Fe<Co<Ni<Cu.     

Thermal decomposition temperatures of metal sulfates

The thermal decomposition of sixteen metal sulfates was studied by thermogravimetry at heating rates of 2 and 5°C min^?1 in flowing air and high-purity nitrogen. Their decomposition behaviors, especially the initial decomposition temperatures, were examined with relation to the thermodynamic functions for decomposition. Of the factors possibly influencing the decomposition temperature, the equilibrium SO₃ pressures over the sulfates were evaluated: the equilibrium pressures at the initial temperatures for sulfates of metals, of which the oxidation state was unchanged during decomposition, were nearly equal to 1×10^?4 atm at 2°C min^?1 in flowing nitrogen.     

Thermal decomposition of transition metal carboxylates

Thermal decomposition of anhydrous Cu(HCOO)₂ (1) affords H₂, CO, CO₂, H₂O, HCuOOH, CuHCOO, Cu, and the polymeric product, which contains -CH₂O,-C(O)OH-, and -RCH-0- groups. Dccomposition of1 proceeds in stages with formation of copper(I) formate as an intermediate. Possible pathways of decomposition ofI, including isomeric forms of the HCO₂ radical as intermediates, were analyzed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1406–1412, June, 1996.     

Thermal decomposition of transition metal dithiocarbamates

Transition metal dithiocarbamate complexes, [M(S₂CN(C₂H₅)(CH₂CH₂OH)] (M=Co, Ni, Cu, Zn and Cd) have been prepared and characterized by elemental analysis and infrared spectra. Thermal decomposition of all the complexes occurs in two or three stages. The first stage in all the complexes is always fast with 65-70% mass loss. In all cases the end product is metal oxide except in the case of cobalt complex which gives Co metal as an end product. During decomposition of copper complex, first CuS is formed at ~300°C which is converted into CuSO₄ and finally CuO is formed. However, decomposition in helium atmosphere yields CuS. SEM studies of transition metal dithiocarbamates reveal needle shape crystalline phase at room temperature and formation of metal sulphide/oxide at higher temperatures. The activation energy varies in a large range of 33.8-188.3 kJ mol^-1, being minimum for the Cu complex and maximum for the Zn complex possibly due to d ¹⁰ configuration. In the case of Ni, Zn and Cd complexes the order of reaction is two suggesting bimolecular process involving intermolecular rearrangement. However, in other cases it is a unimolecular process. Large negative values of ΔS ^# for all the complexes suggest that the decomposition process involves rearrangement. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal decomposition of transition metal carboxylates

Thermal solid-phase decomposition of anhydrous copper(ii) formate has been studied at 120–180 ° The rate of gas evolution during the decomposition depends on the depth of conversion and can be presented as the sum of first-order reaction rates and the rate of the autocatalytic process (a second-order reaction). The evolution of the solid phase during thermolysis has been observed by optical microscopy. The decomposition of copper formate is a complex topochemical process, a combination of homogeneous and heterogeneous transformations and dispersion of large crystals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. l, pp. 72–76, January, 1996.     

Thermal decomposition of transition metal carboxylates

Dynamics of changes in microstresses during thermal decomposition of Cu(HCOO)₂ crystals and their effect on the thermal decomposition kinetics were studied by IR spectroscopy at 105 to 120 °C. The formation of solid intermediate HCOOCu was observed, and the dynamics of its accumulation was followed. Kinetic regularities of transformation of HCOO groups were compared with those for gas evolution.For Communication 1, see Ref. 1.Translated from Izvestiya va Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–354, February, 1996.     

Studies on double selenates. I. Thermal decomposition of lanthanum and alkali metal double selenates

Thermogravimetry, differential thermal analysis and other methods of analysis have been used to study the decomposition of hydrated lanthanum and alkali metal double selenates up to 1300°C. The results showed slight variations in the initial temperature of the various intermediate decomposition stages of the double selenates, as compared with the initial temperature of the corresponding decomposition of the simple selenates. The results also permitted the suggestion of mechanisms of thermal decomposition of these compounds.