Mechanism of thermal decomposition of hydrogenphosphities

Evolution of hydrogen during thermal decomposition of some M^IIHPO₃ (M= Mg, Ca, Zn, Sr, Cd, Ba) phosphities under nitrogen atmosphere was investigated. Step mechanism of thermal decomposition has been proposed.

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Zusammenfassung Es wurde die Wasserstoffentwicklung während der thermischen Zersetzung einiger Phosphite M^II)HPO₃ (mitM=Mg, Ca, Zn, Sr, Cd, Ba) in einer Stickstoffatmosphäre untersucht. Es wurde ein schematischer Mechanismus für die thermische Zersetzungsreaktion gegeben.

     

Thermal expansion of ternary oxides in the M<Stack><Subscript>2</Subscript><Superscript>I</Superscript></Stack>O-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> system

Compounds formed in the M₂^IO-Cr₂O₃-TiO₂. system were synthesized by solid-state reactions. These compounds crystallize in hollandite- and spinel-type structures. The features of themal decomposition of the compounds with the compositions M₂^ICr₂Ti₆O₁₆(M^I = Na, K, Cs) and LiCrTiO₄ were revealed, and their thermal expansion coefficients were determined with the use of high-temperature X-ray diffraction analysis.     

Thermodynamic exploitation of the liquidus curves in the MIPO3–Pb(PO3)2, MIPO3–Cu(PO3)2 and MIPO3–Ce(PO3)3 systems (M I=Li, Na, K, Rb, Cs, Ag, Tl)

The thermodynamic exploitation of the solid–liquid equilibria in the M^IPO₃–Pb(PO₃)₂, M^IPO₃–Cu(PO₃)₂ and M^IPO₃–Ce(PO₃)₃ systems (with M ^I=Li, Na, K, Rb, Cs, Ag, Tl) is carried out using a semi-empirical equation of the liquidus curves already used with success for similar binary systems. The enthalpy of fusion is calculated for each pure polyphosphate on the assumption that the liquid solution is ideal and only formed by M^IPO₃ and M(PO₃)_q entities (q=2 for Pb and Cu, q=3 for M=Ce). In the most binary systems, a wide difference between the calculated values of the melting enthalpies of these polyphosphates and the measured ones determined from the DTA curves, was observed. This difference is probably due to the existence of some molecular associations in the liquid phase.     

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.     

Electronegativity force of cations and thermal decomposition of complex fluorides

The thermal decomposition of anhydrous fluoroborates MBF₄ (M=Li, Na, K, Rb, Cs) and M(BF₄)₂ (M=Ca, Sr, Ba) was investigated. The decomposition proceeds according to a simple acid-base mechanism with evolution of BF₃. The influence of the acidity of cationic counterions, expressed by the electronegativity force on the course of thermal decomposition was estimated quantitatively.     

A study on the thermal decomposition of iron-cobalt mixed hydroxides

Thermal decomposition of pure Fe(OH)₃ and mixed with Co(OH)₂ were studied using TG, DTA, kinetics of isothermal decomposition and electrical conductivity measurements. The thermal products were characterized by X-ray diffraction and IR spectroscopy. The TG and DTA analysis revealed the presence of Co²⁺ retards the decomposition of ferric hydroxide and the formation of -Fe₂O₃. The kinetics of decomposition showed that the mixed samples need higher energy to achieve thermolysis. The investigation of thermal products of mixed samples indicated the formation of cobalt ferrite on addition ofx=1 or 1.5 cobalt hydroxide. The electrical conductivity accompanying the thermal decomposition decreases in presence of low ratio of Co²⁺ (x=0.2) via the consumption of holes created during thermal analysis. The continuous increase in values on increasing of Co²⁺ concentration corresponded to the electron hopping between Fe²⁺ and Co³⁺.

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Zusammenfassung Mittels TG, DTA und der Kinetik von Messungen der isothermen Zersetzung und der elektrischen Leitfähigkeit wurde die Zersetzung von Fe(OH)₃ in reinem Zustand und vermengt mit Co(OH)₂ untersucht. Die thermischen Produkte wurden mittels Röntgendiffraktion und IR-Spektroskopie charakterisiert. TG und DTA zeigen, daß die Zersetzung von Eisen(III)-hydroxid und die Bildung von -Fe₂O₃ durch Gegenwart von Co²⁺ verzögert wird. Die Zersetzungskinetik zeigt, daß die Mischproben mehr Energie für die Thermolyse benötigen. Die Untersuchung der thermischen Produkte zeigt die Bildung von Cobaltferrit bei Zusatz vonx=1 oder 1,5 Cobalthydroxid. Die elektrische Leitfähigkeit nimmt bei der thermischen Zersetzung in Gegenwart von niedrigen Co²⁺-Konzentrationen (x=0.2) durch Verbrauch der bei der Thermoanalyse geschaffenen Löcher ab. Das monotone Ansteigen der -Werte bei steigender Co²⁺-Konzentration stimmt mit dem Überspringen von Elektronen zwischen Fe²⁺ und Co³⁺ überein.

     

Mise au point d'un dispositif d'analyse thermique haute pression (2 GPa) application a l'etude des systemes quaternaires SiO2-Al2O3-M2O-H2O (M=Li,Na, K)

An apparatus for thermal analysis operating up to 500°C temperature and up to 2 GPa, pressure using a conventional piston-cylinder device, is described.A few results concerning solid phases of the quaternary systems SiO₂-Al₂O₃-M₂O-H₂O (M=Li, Na, K) studied under 2.10⁸ Pa pressure, are discussed.

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Zusammenfassung Es wird eine Apparatur für die Thermoanalyse bis 500°C und bis zum Druck von 2 GPa beschrieben. Dabei wird ein herkömmliches Kolben-Zylinder-Gerät verwendet. Einige Ergebnisse bezüglich der Festphasen des quaternären Systemes SiO₂-Al₂O₃-M₂O-H₂O (M=Li, Na, K) bei einem Druck von 2·10⁸ Pa wurden beschrieben.

     

The relationship between the structures of Cu(II) complexes and their chemical transformations

The thermal dehydration of the compounds M ₂ ^I [M^II(H₂O)₆](SeO₄)₂, where M^I=NH₄, K, Rb, Cs and Tl, and M=Cu and Ni, was studied in order to correlate the course of the decomposition with the known crystal structures. It was found that the stoichiometry of the reactions is the same as that established for the analogous sulphato compounds of Cu(II) and Ni(II), respectively. Because of the discrepancies between the room-temperature crystal structures and the observed decomposition stoichiometries, high-temperature powder diffractograms were taken. These indicated structural changes of the copper(II) compounds during heating. The powder patterns for different structure changes were calculated and compared with the experimental ones. It was shown that during the heating two axial CuH₂O bonds are shortened and two equatorial bonds are lengthened. The observed decomposition stoichiometry is compatible with the formation of four nearly equal Cu-H₂O bonds. The activation energies (E^*) and pre-exponential factors (log A) for the first dehydration reaction of the Cu(II) compounds display the following sequence of M^I: Tl > Rb > NH₄ > K, and they are the higher, the shorter the split equatorial Cu(II) bonds. For the compounds of Ni(II) the sequence of E^* and log A values is K > Tl > NH₄ > Rb > Cs.

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Zusammenfassung Zur Aufklärung des Zusammenhanges zwischen dem Zersetzungsweg und der bekannten Kristallstruktur wurde die thermische Dehydration der Verbindungen M ₂ ^I [M^II(H₂O)₆](SeO₄)₂ mit M^I=NH₄, K, Rb, Cs and Tl sowie mit m^II=Cu und Ni untersucht. Man fand für diese Reaktion die gleiche Stöchiometrie wie für die analogen Sulfatverbindungen von Cu(II) bzw. Ni(II). Wegen des Widerspruches zwischen der Kristallstruktur bei Raumtemperatur und der festgestellten Stöchiometrie der Zersetzungsreaktion wurden auch Pulverdiffraktionsaufnahmen bei höheren Temperaturen angefertigt. Bei Cu(II)-Verbindungen konnte während des Erhitzens eine Strukturänderung festgestellt werden. Für verschiedene Strukturänderungen wurden Pulveraufnahmen berechnet und mit den experimentellen verglichen. Es konnte gezeigt werden, da sich während des Erhitzens zwei axiale Cu-H₂O-Bindungen verkürzen und zwei äquatoriale Bindungen strecken. Die beobachtete Zersetzungsstöchiometrie entspricht der Bildung von vier anänhernd gleichen Cu-H₂O-Bindungen. Die Aktivierrungsenergie (E^*) und der präexponentielle Faktor (log A) und der ersten Dehydratationsreaktion der Cu(II)-Verbindungen sinken in folgender Reihenfolge für M^I:Tl, Rb, NH₄, K und sind umso größer, je kürzer die gespaltenen äquatorialen Cu(II)-Bindungen sind. Für Ni(II)-Verbindungen nehmen E^* und log A in folgenden Reichenfolge ab: K, Tl, NH₄, Rb, Cs.

     

Diagrammes d'equilibre des systemes d'halogenures CuY-MYn

Phase diagrams for the series of CuY-M^IY and CuY-M^IIY systems (whereM ^I=Li, Na, K, Rb, Cs, Tl,M ^II=Zn, Cd, Hg, Sn, Pb andY=Cl, Br, I) were compared. Changes and trends accompanying the increase of charge of the second cation were discussed.

     

The thermal dehydration,decomposition and kinetics of Mn(NO3)2 · 6H2O and its deuterated analogue

The processes of thermal dehydration and decomposition of Mn(NO₃)2 ·.6H₂O and its deuterated analogue were studied by DTA, TG and DSC. Comparisons were made between the data obtained for the two compounds. The following phase transitions were observed: melting of the compound; dehydration to monohydrate; dehydration of the monohydrate, accompanied by its partial decomposition to MnO₂; and decomposition of the anhydrous nitrate to MnO₂.The DSC data were used to determine the enthalpies of the phase transitions, and those corresponding to the partial dehydration were compared with the calculated ones. The formal kinetic parameters (E ^* andA) for the three stages (without the melting stage) were calculated from the TG curves, and the corresponding kinetic equations are reported.

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Zusammenfassung Mittels DTA, TG und DSC wurde der Verlauf der thermischen Dehydratation und Zersetzung von deuteriertem und undeuteriertem Mn(NO₃)₂·6H₂O untersucht und die erhaltenen Ergebnisse beider Verbindungen miteinander verglichen. Folgende Phasenumwandlungen konnten beobachtet werden: Schmelzen der Verbindung; Dehydratation bis zum Monohydrat; Dehydratation des Monohydrates unter teilweiser Zersetzung zu MnO₂; Zersetzung von wasserfreiem Nitrat zu MnO₂. DSC-Daten wurden zur Bestimmung der Enthalpien für die Phasenumwandlungen benutzt, die so ermittelten Ergebnisse für die partielle Dehydratation wurden mit den berechneten verglichen. Anhand der TG-Kurven wurden die formellen kinetischen Parameter (E ^* undA) der drei Schritte (ohne Schmelzvorgang) berechnet und die entsprechenden kinetischen Gleichungen beschrieben.

     

High-temperature X-ray diffraction studies of compounds in the M 2 I O-Ga2O3-TiO2 system

Compounds that are formed in the M ₂ ^I O-Ga₂O₃-TiO₂ system and crystallize in three structural types were prepared by solid-phase reactions. The M ₂ ^I Ga₂Ti₆O₁₆ (M^I = Na, K, Rb, Cs) compounds were prepared for the first time. The thermal expansion coefficients of LiGaTiO₄, Na₂Ga₂Ti₆O₁₆, K₂Ga₂Ti₆O₁₆, Rb₂Ga₂Ti₆O₁₆, and Cs₂Ga₂Ti₆O₁₆ were determined by high-temperature X-ray diffraction. Some tendencies of thermal distortions in M ₂ ^I A ₂ ^III Ti₆O₁₆ and LiA^IIITiO₄ (M^I = Na, K, Rb, Cs; A^III = Al, Cr, Fe, Ga) were disclosed.     

Darstellung,Schwingungsspektren und Struktur von Oxotetrafluorovanadaten MIVOF4 (MI = Na,K, Rb,Cs, Tl, (CH3)4N)

Preparation, Vibrational Spectra, and Structure of Oxotetrafluorovanadates M^IVOF₄ (M^I = Na, K, Rb, Cs, Tl, (CH₃)₄N) The compounds M^IVOF₄ (M^I = K, Rb, Cs, Tl) and M^IVOF₄ · H₂O (M^I = Na, (CH₃)₄N) have been prepared. The crystal structure of KVOF₄ has been determined by single crystal X-ray diffraction. The VOF-ions form endless chains by fluorine bridges. The lengths of the bridge bonds are 1.875(7) and 2.333(7) Å. The terminal V? O- and V? F-distances are 1.572(8) and 1.793 Å (mean value), respectively. The vibrational spectra have been registered and assigned.     

Chemie der Seltenerdmetalle, 24. Mitt.: Komplexverbindungen des dreiwertigen Cers mit Malonsäure

Zusammenfassung Durch Auflösen von Ce₂ Mal ₃·6H₂O^** in wäßr. Malonsäure wurde die Dimalonato-Ce(III)-säure in zwei Hydratformen hergestellt: HCeMal ₂·2 H₂O und HCeMal ₂·3 H₂O.Durch Auflösen von Ce₂ Mal ₃·6H₂O in konz. Malonatlösungen vom TypusM ₂ ^I Mal (M ^I=Li, Na, K, NH₄) wurden nachstehende Komplexalze gewonnen: LiCeMal ₂·3H₂O, NaCeMal ₂·2 H₂O, KCeMal ₂·2 H₂O und NH₄CeMal ₂·3 H₂O. Die Verbindungen wurden auf Grund der quantit. Analysen, Debyeogramme und IR-Spektren identifiziert. Der thermische Zerfall wurde mit Hilfe derDTA undGTA verfolgt.In neutralen und schwach sauren Lösungen kommt es bei allen Verbindungen zur hydrolytischen Spaltung unter Ausscheidung des neutralen Ce(III)-Malonates. Bei der Dimalonato-Ce(III)-säure wurde an Hand der Löslichkeitsmethode ihre Dissoziation verfolgt.

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Chemistry of the rare earth metals, XXIV: Complex Ce(III)-malonates

By dissolving Ce₂ Mal ₃·6 H₂O^** in aqueous malonic acid, the Ce(III)-dimalonic acid was prepared in two forms: HCeMal ₂·2 H₂O and HCeMal ₂·3 H₂O.When Ce₂ Mal ₃·6 H₂O is dissolved in concd. malonate solutions of the typM ₂ ^I Mal (M ^I=Li, Na, K, NH₄), the following complex salts can be isolated: LiCeMal ₂·3H₂O, NaCeMal ₂·2 H₂O, KCeMal ₂·2 H₂O and NH₄CeMal ₂·3 H₂O. The compounds where identified by quantitative analysis, X-ray powder photographs and IR spectra. The thermal decomposition was followed byDTA andGTA.In neutral and weakly acidic solutions, all these compounds are hydrolyzed with the simultaneous precipitation of the neutral Ce(III)-malonates. The dissociation of Ce(III)-dimalonic acid was followed by means of a precipitation method.

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23. Mitt.:F. Bezina, Mh. Chem.100, 1684 (1969).     

离子对生成反应的LCAC-SW量子散射理论研究＊

LCAC-SW method has been extended to study the reaction dynamics for ion-pair formation processes.M+X₂M⁺+X^-₂ reaction system involves two potential energy surfaces,i.e.,the covalence state(M+X₂) and the ionic state(M⁺+X^-₂) and their crossing effect.The working equations for calculating state-to-state probability have been derived based on the above two-state model.The selected-state reaction probabilities of collinear ion-pair formation process M+I₂M⁺+I^-₂(M=Na,K,Cs) on Aten-Lanting-Los two-state potential energy surface have been calculated.The results show that the reaction probabilities are of resonance effect.     

Thermal decompostion studies on nickel(II) bis(oxalato)nickelate(II) pentahydrate

The paper describes the synthesis and thermal decomposition of nickel(II)bis(oxalato)nickelate(II)pentahydrate, Ni[Ni(C₂O₄)2].5H₂O. The complex was characterized by elemental analysis, infrared, electronic, e.s.r., magnetic moment measurement and X-ray powder diffraction studies. The thermal decompostion of the complex led to NiO in air at about 338° and in nitrogen at about 720°. The activation energies (E ^*) for the dehydration and decompostion reactions in air and nitrogen were evaluated. Tentative reaction mechanisms have been suggested for the termal decompostion of the complex in air and nitrogen.

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Zusammenfassung Es wird die Synthese und thermische Zersetzung von Nickel(II) -bis(oxalato)- nickelat(II) - pentahydrat beschrieben: Ni[Ni(C₂O₄)2].5H₂O. Dieser Komplex wurde mittels Elementaranalyse, IR-Spektroskopie, ESR-Spektroskopie, der Messung des magnetischen Momentes sowie mittels Pulverdiffraktionsuntersuchungen charakterisiert. Im Ergebnis der thermischen Zersetzung entsteht NiO, in Luft bei etwa 338°, in Stickstoffatmosphäre bei ca. 720°. Die Aktivierungsenergien (E^*) der Dehydratations- und Zersetzungsreaktionen in Luft und in Stickstoff wurden ermittelt. Für die thermische Zersetzung des Komplexes in Luft bzw. in Stickstoff wurde ein Reaktionsmechanismus entwickelt.

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The authors thank the RSIC, CDRI, Lucknow for microanalysis, RSIC, NEHU, Shillong for i.r. spectra, RSIC, IIT, Madras for far i.r. spectra, RSIC, Nagpur University for thermal analysis, Dr. S. K. Datta for Forensic Science Laboratory, Guwahati, Assam for DSC and Dr. K. L. Deori of Dibrugarh University for X-ray powder diffraction photographs.     

Thermoanalytical investigations on the decomposition of double salts

The melting and decomposition behaviour of the double salts MBr·MgBr2·6H₂O (M=K, NH₄, Rb, Cs) has been investigated in a closed system under dynamic and quasi-isothermal and quasi-isobaric conditions between 20°C and 300°C or 600°C, respectively. DTA heating and cooling cycles illustrate the melting behaviour of the double salts and give information on the melting point of these substances.The thermal decomposition of double salts under quasi-isothermal and quasi-isobaric conditions takes place in the melt (with the exception of RbBr·MgBr2·6H₂O) and under reduced pressure in the solid phase. A double salt of the type MBr·MgBr2·6H₂O is formed as a stable intermediate. The final product of all types of thermal decomposition are basic products with different hydroxide or oxide contents, respectively.

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Zusammenfassung In einem abgeschlossenem System wurde unter dynamischen und quasiisothermen und quasiisobaren Bedingungen im Temperaturbereich zwischen 20°C und 300°C oder 600°C das Schmelz- und Zersetzungsverhalten der Doppelsalze MBrMgBr2·6H₂O (mitM=K, NH₄, Rb, Cs) untersucht. DTA-Heiz- und Kühlzyklen zeigen das Schmelzverhalten der Doppelsalze und geben gleichzeitig Auskunft über den Schmelzpunkt dieser Verbindungen.Die thermische Zersetzung der Doppelsalze unter quasiisothermen und quasiisobaren Bedingungen erfolgt ausgehend von der Schmelze (mit Ausnahme von RbBrMgBr2·6H₂O) und unter vermindertem Druck ausgehend vom Feststoff. Ein Doppelsalz des Typs MBrMgBr2·2H₂O wird als Zwischenprodukt gebildet. Das Endprodukt bei allen Zersetzungstypen sind basische Produkte mit unterschiedlichem Hydroxidoder Oxidgehalt.

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Dedicated to Prof. Dr. H. J. Seifert on the occasion of his 60^th birthday     

Univalent metal uranyl carbonates

Optimal procedures were developed for the synthesis of A _4?m ^I B _m ^I [UO₂(CO₃)₃]·nH₂O (A^I = Li, Na, K, Rb, Cs, NH₄, Ag, Tl; B^I = Na; m = 0?1; n = 0?6) compounds. The structure and thermal decomposition of these compounds were studied by X-ray diffraction, precision IR spectroscopy, and thermal analysis. The IR bands were assigned using mathematical simulation based on small-vibration theory. The standard enthalpies of formation of the compounds at 298.15 K were determined for the first time by reaction calorimetry.     

Precise Conductance Measurements on Dilute Aqueous Solutions of Sodium and Potassium Hydrogenphosphate and Dihydrogenphosphate

Precise conductance measurements are reported on dilute aqueous solutions of the sodium and potassium salts of orthophosphoric acid at 25 ^∘C. Conductance measurements on solutions of electrolytes such as these phosphate salts that exist in solution as complicated mixtures of ions have previously proved difficult to interpret. To overcome this, a mathematical method has been developed to calculate the concentrations of all the species in the aqueous system M₃PO₄/M₂HPO₄/M₂HPO₄/H₃PO₄ (M = Na or K) over a continuous range of stoichiometries. The Lee–Wheaton conductance equation has been used to interpret the conductance of these multicomponent solutions in terms of the limiting ionic conductances and concentrations of all the ions in the solution. The limiting molar conductances of the ions H₂PO₄ ⁻ and HPO₄ ²⁻ and the ion-pair formation constants of these ions with sodium and potassium ions were determine This work has enabled the accurate determination of solution parameters for the important hydrogenphosphate ions in water and provides an excellent example of the use of an advanced conductance theory in the analysis of the conductance of multicomponent electrolyte systems.     

On the relationship between the structures of CuII complexes and their chemical transformations

The thermal decomposition of the complexes M ₂ ^I Cu(SO₄)₂ · 6 H₂O and M₂Ni(SO₄)₂ · · 6 H₂O (M^I=NH₄, K, Rb, Tl) containing the complex cation M^II(H₂O)₆ ²+ (M^Il = =Cu, Ni) was studied. The values of the experimental activation energyE obtained for the dehydration reactions of both complex cations were found to be influenced in different ways by the outer-sphere cations present. It was therefore concluded that the activation energy of the decomposition of Cu(H₂O)₆ ²⁺ depends on the degree of tetragonal distortion of this cation, which increases with the ionic radius of cation M^I. TheΔH values of the studied reactions depend less on the structures of the coordination polyhedra.     

IR-Spektren einiger hydratisierter Fluoro-aluminate,-gallate und-indate

Zusammenfassung Die Analyse der IR-Spektren einer Auswahl der Verbindungen des TypsM ₂ ^I M ^IIIF₅·H₂O bzw.M ^I M ^IIIF₄·2 H₂O und der entsprechenden Deuterohydrate führt zum Ergebnis, daß das Wasser nicht koordinativ gebunden, sondern als Gitterwasser auftritt. Bei den hydratisierten Fluorogallaten ist die Wasserstoffbindung stärker ausgeprägt als bei den entsprechenden Fluoro-aluminaten und-indaten.

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Fluoro metallates (III), IV: IR-Spectra of some hydrated fluoro-aluminates,-gallates, and-indates

Interpretation of the IR spectra of several compounds of the stoichiometryM ₂ ^I M ^IIIF₅·H₂O,M ^I M ^IIIF₄·2H₂O and their deuterated analogs proves the presence of the lattice water. Hydrogen bond is stronger in the case of fluorogallates in comparision to the similar fluoroaluminates and indates.

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3. Mitt.: Mh. Chem.102, 885 (1971).