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.     

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.     

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.     

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.     

Direct thermal decomposition of metal nitrates in octadecylamine to metal oxide nanocrystals

We have developed a method for the synthesis of metal oxide nanocrystals with controllable shape and size, which is based on the direct thermal decomposition of metal nitrates in octadecylamine. Mn3O4 nanoparticles and nanorods with different lengths were synthesized by using manganese nitrate as the decomposition material. Other metal oxide nanocrystals such as NiO, ZnO, CeO2, CoO, and Co3O4 were also prepared by this method. These nanocrystals were then assembled into 3D colloidal spheres by a surfactant-assisted self-assembly process. Subsequently, calcination was carried out to remove the surfactants to obtain mesoporous metal oxides, which show large pores, good crystallization, thermally stable pore mesostructures, and potential applications in various fields, especially in catalysis and lithium-ion batteries.     

Accurate rate constants for decomposition of aqueous nitrous acid

Decomposition of nitrous acid in aqueous solution has been studied by stopped flow spectrophotometry to resolve discrepancies in literature values for the rate constants of the decomposition reactions. Under the conditions employed, the rate-limiting reaction step comprises the hydrolysis of NO(2). A simplified rate law based on the known elementary reaction mechanism provides an excellent fit to the experimental data. The rate constant, 1.34 × 10(-6) M(-1) s(-1), is thought to be of higher accuracy than those in the literature as it does not depend on the rate of parallel reaction pathways or on the rate of interphase mass transfer of gaseous reaction products. The activation energy for the simplified rate law was established to be 107 kJ mol(-1). Quantum chemistry calculations indicate that the majority of the large activation energy results from the endothermic nature of the equilibrium 2HNO(2) ? NO + NO(2) + H(2)O. The rate constant for the reaction between nitrate ions and nitrous acid, which inhibits HNO(2) decomposition, was also determined.     

Gamma-ray induced decomposition of some divalent and trivalent nitrates

Gamma-ray induced decomposition of some divalent nitrates, viz. Mg(NO₃)₂·6H₂O, Ca(NO₃)₂·4H₂O, Sr(NO₃)₂, Ba(NO₃)₂, Zn(NO₃)₂·6H₂O, Cd(NO₃)₂·4H₂O, Hg(NO₃)₂·2H₂O, Mn(NO₃)₂·4H₂O, Cu(NO₃)₂·3H₂O and trivalent nitrates, viz. Al(NO₃)₃·9H₂O, Fe(NO₃)₃·9H₂O, Cr(NO₃)₃·9H₂O, Y(NO₃)₃·6H₂O, In(NO₃)₃·3H₂O, La(NO₃)₃·6H₂O, Ce(NO₃)₃·6H₂O, Pr(NO₃)₃·6H₂O, Bi(NO₃)₃·5H₂O has been studied in solid state at room temperature. G(NO ₂ ^– ) values (after applying appropriate dose correction) have been found to vary in the range 0.12–3.16 and 0.069–2.15 for divalent and trivalent nitrates respectively. G'-values were calculated by dividing G by the ratio of number of electrons in nitrate ion to the total number of electrons in the nitrate salt. Cation size, its polarizing power, available free space in the crystal lattice and the number and location of water molecules seem to play a dominant role in radiolytic decomposition. For Zn, Sr, In, La and Ce nitrates dose variation studies have been carried out.     

Thermal decomposition of mineral zircon by alkali metal hydroxides

Thermal decomposition of zircon mineral was studied in the presence of sodium and potassium hydroxides and in the presence of a waste mixture of hydroxides containing NaOH and KOH in a weight ratio of 23. The process was controlled in such a way that the decomposition products might contain the minimum possible amount of alkali and could thus be applied for the syntheses of zircon pigments without any further exacting treatment.

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Zusammenfassung Es wurde die thermische Zersetzung eines Zirkonminerals in Gegenwart von Natrium- und Kaliumhydroxid-sowie in Gegenwart einer Altlauge mit einem Gehalt an NaOH und KOH im Verhältnis zwei zu drei untersucht. Der Prozeß wird derart gesteuert, daß die Zersetzungsprodukte einen möglichst geringen Anteil an Lauge besitzen und so ohne weitere arbeitsaufwändige Behandlungen zur Synthese von Zirkonpigmenten verwendet werden können.

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, 23. , , , - .

     

Synthesis and thermal decomposition of acid alkali metal hexafluoroaluminates

Acid alkali hexafluoroaluminates of K and Rb were prepared by precipitation of alkali fluoride containing H₃AlF₆ solutions with ethanol. Compounds were characterized by X-ray diffraction, IR spectroscopy,¹H-NMR and chemical analysis. The constitution is M^I(H₃O)₂AlF₆. Lattice parameters were determined.Dehydration and thermal decomposition were investigated by thermal analysis (TG, DTG, DTA) on a derivatograph-Q and by high temperature X-ray diffraction. Thermal decomposition is accompanied by liberation of H₂O and HF and a condensation of [AlF₆]^3– octahedra forming layer structures. Stable intermediate products are M^IAlF₄·0.5H₂O and M^IAlF₄. At higher temperatures hydrolysis occurs.

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Zusammenfassung Es wurden saure Kalium- und Rubidiumhexafluoroaluminate durch Fällung aus Alkalifluorid enthaltenden H₃AlF₆-Lösungen mit Ethanol dargestellt. Die erhaltenen Verbindungen wurden chemisch, röntgenographisch, IR- sowie¹H-NMR-spektroskopisch charakterisiert. Die Konstitution der Verbindungen ist M^I(H₃O)₂AlF₆. Die Gitterkonstanten wurden aus Röntgendiffraktionsdaten bestimmt. Entwässerung und thermische Zersetzung wurden mittels Heizguiniertechnik und Thermoanalyse (TG, DTG, DTA) an einem Derivatograph-Q untersucht. Bei der thermischen Zersetzung erfolgt eine HF- und H₂O-Abgabe sowie eine Kondensation von AlF ₆ ^3– -Oktaedern unter Ausbildung von Schichtstrukturen. Als stabile Zwischenprodukte wurden M^IAlF₄·0.5H₂O und M^IAlF₄ nachgewiesen. Bei höheren Temperaturen werden Hydrolysereaktionen beobachtet.

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, H₃AlF₆, . M¹(H₃O)₂AlF₆ , - - . . (, , ) Q- , . [AlF₆]^3– . M¹AlF₄·0.5H₂O M¹AlF₄. .

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Presented at the Microsymposium on Halogen Chemistry held in Budapest, 1987.     

Mechanism and rate constants for the decomposition of 1-pentenyl radicals

This paper is concerned with the mechanisms and rate constants for the decomposition of 1-penten-3-yl, 1-penten-4-yl, and 1-penten-5-yl radicals. They are formed from radical attack on 1-pentene, which is an important decomposition product of normal alkyl radicals with more than 6 carbon atoms in combustion systems. This work is based on related data in the literature. These involve rate constants for the reverse radical addition process under high-pressure conditions, chemical activation experiments, and more recent direct studies. The high-pressure rate constants are based on detailed balance. The energy transfer effects and the pressure dependences of the rate constants are determined through the solution of the master equation and are projected to cover combustion conditions. The low barriers to these reactions make it necessary to treat these thermal reactions as open systems, as in chemical activation studies. The multiple reaction channels make the nature of the pressure effects different from those usually described in standard texts. The order of stability is 1-penten-3-yl approximately 1-penten-4-yl > 1-penten-5-yl and straddles those for the n-alkyl radicals. A key feature in these reactions is the effects traceable to allylic resonance. However, the 50 kJ/mol allylic resonance energy is not fully manifested. The important unsaturated products are 1,3-butadiene, the pentadienes, allyl radicals, and vinyl radicals. The results are compared with the recommendations in the literature, and significant differences are noted. Extensions to larger radicals with similar structures are discussed.     

The salting out action of alkali metal nitrates on the water-diethylamine binary system

The results of a polythermal study of the salting out action of alkali metal (Na, K, and Cs) nitrates on the water-diethylamine binary system characterized by stratification with a lower critical solution point (LCSP) were comparatively analyzed. Alkali metal nitrates experiencing homoselective solvation in aqueousorganic solvents were found to decrease the LCSP of this binary system, that is, have a salting out action. A decrease in the radius of the cation in the series CsNO₃-KNO₃-NaNO₃ decreased the temperature of critical tie line formation in the monotectic state of salt-water-diethylamine ternary systems (69.3, 48.1, and 22.9°C, respectively). In all ternary systems, first and foremost in the system with potassium nitrate, the effect of diethylamine salting out from aqueous solutions grew stronger as the temperature increased. The conclusion was drawn that, among the salts studied, sodium nitrate had the strongest salting out effect at 22.9–88.4°C, and potassium nitrate, at 88.4–150.0°C.     

Simultaneous dynamic thermogravimetry and mass spectrometry of the evaporation of alkali metal nitrates and nitrites

Six alkali metal nitrates and nitrites were evaporated in vacuum at a constant heating rate in a combined mass spectrometric and thermogravimetric apparatus. Time resolved profiles of decomposition gases and kinetics were obtained for LiNO₃, NaNO₃, KNO₃, Na/KNO₃, NaNO₂ and KNO₂. Activation energies for the evaporation of these salts were calculated and compared to previous results of isothermal experiments. In the temperature range 650–850 K, the decomposing nitrates released NO, N₂ and O₂ while the nitrites released only NO and N₂.

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Zusammenfassung Sechs Alkalimetallnitrate und -nitrite wurden in Vakuum, bei konstanter Erwärmungsgeschwindigkeit in einer kombinierten massenspektroskopischen und thermogravimetrischen Vorrichtung verdampft. Für LiNO₃, NaNO₃, KNO₃, Na/KNO₃, NaNO₂ und KNO₂ wurden die zeitzerlegten Profile der Zersetzungsgase, sowie die Kinetik erhalten. Für die Verdampfung dieser Salze wurden die Aktivationsenergien berechnet, und mit früheren Ergebnissen der isothermischen Versuche verglichen. In dem Temperaturbereich 650 bis 850 K wird von den zerfallenden Nitraten NO, N₂ und O₂ befreit, die Nitrite entwickeln dagegen nur NO und N₂.

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- . - LiNO₃, NaNO₃, KNO₃, Na/KNO₃, NaNO₂ KNO₂. . 650–850 , , — .

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This work is based in part on a thesis submitted by C. M. Kramer in partial fulfillment of the requirements for the degree of Doctor of Philosophy to the Division of Materials Science and Engineering, College of Engineering, University of California at Davis. The work was performed at the Sandia National Laboratories, Livermore, CA.     

Determination of stability constants for alkaline-earth and alkali metal ion complexes of glycine by spectrophotometry

The complex equilibria between alkaline-earth and alkali metal ions with glycine were studied by a spectrophotometric method. The following stability constant (concentration) values valid at 25 degrees and ionic strength 1.0M were found: K(HL) = 10(9.57), K(LiL) = 10(-1.2), K(BaL) = 10(-0.40), K(SrL) = 10(0.14), K(CaL) = 10(0.55), K(MgL) = 10(1.17).     

Gamma-ray induced decomposition of double nitrates of lanthanides with univalent and divalent cations

Double nitrates of Na and K having the composition 2M^INO₃·Ln^III(NO₃)₃·2H₂O(Ln^III=Pr, Nd, Sm, Eu, Gd, Tb and Dy) and of Ni and Cu with the composition 3M^II(NO₃)₂·2Ln^III(NO₃)₃·24H₂O (Ln^III=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy) have been prepared and their -radiolytic decomposition studied up to 500 kGy. G(NO ₂ ^– ) values of K double nitrates at 230 kGy follow the order Dy³⁺>Pr³⁺=Nd³⁺=Sm³⁺>Tb³⁺>Eu³⁺> Gd³⁺·G(NO ₂ ³⁺ ) for NI double nitrates are higher than those of Cu double nitrates. Variation of G(NO ₂ ^– ) with cationic radii and the number of f electrons in lanthanide ion show a minimum at Eu. Thermal decomposition studies of double nitrates were also carried out.     

The evaluation of rate constants in rate laws containing two terms

A simple computerized method using APL is described which gives the rate constants for systems obeying the rate law –d[A]/dt = k₁[A][B] + k₂[A] ^m [B]^l from sets of concentrations and times. Applications are discussed.     

Studies on the thermal decomposition of alkali metal thiosulphatobismuthates(III)

The thermal decomposition of thiosulphatobismuthates(III) of alkali metals was investigated. The general formulae of the thiosulphatobismuthates are M₃[Bi(S₂O₃)₃]·H₂O where M = Na, K, Rb or Cs, and M₂Na[Bi(S₂O₃)₃]·H₂O where M = K or Cs.Typical thermal curves for thiosulphatobismuthates(III) and the results obtained in thermal, X-ray, chemical and spectrophotometrical analyses of the decomposition products are shown. The results were used to determine three stages of the thermal decomposition. At the first stage, at about 200°C, hydrated compounds are dehydrated. At the second stage, above 200°C, there is a rapid decrease in mass which is caused by evolving sulphur dioxide; bismuth sulphide and an intermediate decomposition product are formed. At about 320°C the thermal decomposition products are bismuth sulphide and alkali metal sulphate.