Comparative study of solid state reactivity between ferrous oxalate dihydrate and unsubstituted/substituted aniline hydrochlorides

The solid state reactions between ferrous oxalate dihydrate i.e. FeC₂O₄.2H₂O and unsubstituted/ substituted aniline hydrochlorides have been studied. The products [FeCl/oxH/. AN-Cl] have been characterized by elemental analysis, infrared and Mössbauer spectroscopic techniques. The kinetic studies for the reactions have been performed at various temperatures for fixed particle sizes at constant compaction. The following order of reactivity has been observed: unsubstituted > p-substituted > m-substituted o-substituted.     

Physico-chemical studies on manganese soaps in solid state

The physico-chemical characteristics of manganese soaps (caproate, caprylate and caprate) in solid state were investigated by infrared (IR), x-ray diffraction, magnetic and TGA measurements. The IR results revealed that the fatty acids exist in dimeric state through hydrogen bonding and manganese soaps possess ionic character. The x-ray analysis showed that manganese soaps have single-layer structure with molecular axes slightly inclined to the basal plane. The magnetic results suggested the presence of five unpaired electrons with octahedral geometry and possesssp ³ d ² hybridization. The thermal decomposition of these soaps is kinetically of zero order and the energy of activation for the decomposition process lies in the range 9.2–12.8 K Cal mol^–1.     

Physico-chemical studies on samarium soaps in solid state

Summary The physico-chemical characteristics of samarium soaps (caproate and caprate) in solid state were investigated by IR, X-ray diffraction and TGA measurements. The IR results revealed that the fatty acids exist in dimeric state through hydrogen bonding and samarium soaps possess partial ionic character. The X-ray diffraction measurements were used to calculate the long spacings and the results confirmed the double layer structure of samarium soaps. The decomposition reaction was found kinetically of zero order and the values of energy of activation for the decomposition process for caproate and caprate were found to be 8.0 and 7.8 kcal mol^–1, respectively.

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Physikochemische Untersuchungen an Samariumseifen in festem Zustand

Zusammenfassung Die physikochemischen Charakteristika von Samariumseifen (Caproat und Caprat) wurden im festen Zustand mittels IR, Röntgendiffraktion und TGA-Messungen untersucht. Die IR-Ergebnisse zeigten, daß die Fettsäuren durch Wasserstoffbrücken dimer vorliegen und daß die Samariumseifen partiell ionischen Charakter besitzen. Die Röntgenuntersuchungen bestätigen die Doppelschichtstruktur der Seifen. Die Zersetzungsreaktion verlief nach nullter Ordnung, und die Aktivierungsenergien für den Zersetzungsprozeß für Caproat und Caprat waren 8.0 und 7.8 kcal mol^–1.

     

Thermal studies on oxalate complexes. IV. Potassium bis(oxalato)cuprate(II) dihydrate

The dehydration and decomposition of K₂[Cu(C₂O₄)₂] · 2 H₂O have been studied using TG. The dehydration reaction gave the best fit to a second-order rate equation and has an activation energy of 411.5 ± 41.1 kJ mole^?1. Three distinct decomposition patterns were observed for the anhydrous complex. In the first case, K₂[Cu(C₂O₄)₂] decomposes to K₂CO₃ and CuO by loss of CO₂ and 2 CO. In the second case, decomposition leads to K₂C₂O₄ and Cu by loss of 2 CO₂. In the third case, the basic carbonate K₂[Cu(CO₃)_3/2O_1/2] is produced by loss of 2 CO and 0.5 CO₂. In the last case additional loss of CO₂ leads to the formation of K₂CO₃ and CuO in a separate reaction. Kinetic parameters are reported and discussed for all these reactions.     

Phase composition and structure of nanocrystalline products of solid-phase oxidative thermolysis of iron oxalate dihydrate

X-ray diffraction studies of the ultradisperse products of the solid-phase oxidative thermolysis of iron oxalate dehydrate are performed. Models are considered and diffraction patterns are calculated for the nanopowders of different crystalline modifications of iron oxide. Calculations are performed for the particles of various shapes and sizes, starting from one unit cell. Despite that the final product is the hematite phase, the reaction is shown to pass through the formation of particles with the ferrihydrite structure.     

Thermal decomposition of hydrated iron(II) oxalate and manganese(II) oxalate in vacuum

The thermal decomposition of hydrated iron(II) oxalate and manganese(II) oxalate under high vacuum conditions (10^–5 mm Hg) has been studied by differential thermal analysis. The decomposition in vacuum of iron(II) oxalate is exothermic, while that of manganese(II) oxalate is endothermic. An explanation is offered for this behaviour.The financial support by National Bureau of Standards, U.S.A., through a PL-480 scheme is gratefully acknowledged.     

The thermal decomposition of metal formates. II. Solid state thermal decomposition studies on magnesium formate dihydrate

Magnesium formate dihydrate has been synthesized by the action of formic acid on anhydrous magnesium oxide. This product analysed as Mg(COOH)₂ · 2H₂O. Its mode of thermal decomposition has been studied by thermal methods of analysis including simultaneous DTA/mass spectrometry. Nitrogen adsorption surface area of the solid products at various stages of its decomposition have been obtained. X-Ray diffraction and scanning electron micrographs have also been used to interpret the results. The decomposition of magnesium formate took place in three stages, which includes a phase change, at 265°C. The endotherm at 430°C changed to an exotherm in the presence of air; it corresponded to the decomposition of a new anhydrous phase of magnesium formate. The effect of the sample holder and changing atmospheres on the DSC analysis has been investigated. A scheme is presented for the thermal decomposition.     

Physico-chemical studies on the thermal decompositions of iron(III) phthalates

The thermal decompositions of basic salts of iron(III)o-phthalate sesquihydrate, Fe(C₈H₄O₄)(OH)·1.5H₂O, iron(III)m-phthalate trihydrate, Fe(C₈H₄O₄)(OH)·3H₂O, and iron(III)p-phthalate monhydrate, Fe(C₈H₄O₄)(OH)·H₂O, have been investigated from ambient temperature up to 973 K in air using Mössbauer and infrared spectroscopy, derivatography (DTG-DTA-TG) and X-ray diffraction. The thermal decomposition proceeds without reduction to Iron(II) species in the cases of iron(III)o-phthalate and iron(III)p-phthalate, whereas iron(II) species have been detected in the case of basic iron(III)m-phthalate.-Fe₂O₃ is formed as the end-product. Increase in the particle size of the-Fe₂O₃ with increasing decomposition temperature has also been observed.

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Zusammenfassung Die thermische Zersetzung basischer Salze von Eisen(III)-o-phthalat-Sesquihydrat, Fe(C₈H₄O₄)(OH) · 1,5H₂O, Eisen(III)-m-phthalat-Trihydrat, Fe(C₈H₄O₄)(OH)·3H₂O, und Eisen(III)-p-phthalat-Monohydrat, Fe(C₈H₄O₄)(OH)·H₂O, wurden im Temperaturbereich von Raumtemperatur bis 973 K in Luft mittels Mössbauer- und IR-Spektroskopie, Derivatographie (DTG-DTA-TG) und Röntgendiffraktometrie untersucht. Im Gegensatz zu basischem Eisen(III)-m-phthalat erfolgt bei den entsprechendeno- undp-Phthalatverbindungen im Verlaufe der Zersetzung keine Reduktion zu Eisen(II)-Species.-Fe₂O₃ wird als Endprodukt erhalten. Mit steigender Zersetzungstemperatur nimmt die Größe der-Fe₂O₃-Partikel zu.

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c Fe(C₈H₄O₄)(OH)·vH₂O, x = 1.5,3 1, , -, - n-, 973 . , , ë . - n- , m- . -Fe₂O₃. -Fe₂O₃.

     

Thermal studies on oxalate complexes. II. Complexes of iron (III) and chromium (III)

The decomposition of solid K₃[Fe(C₂O₄)₃] · 2 H₂O and K₃[Cr(C₂O₄)₃] · 3 H₂O has been studied using TGA and DSC. After dehydration, the chromium compound was found to decompose by the loss of CO in two steps, the loss of CO₂ and additional CO, and finally the loss of CO₂. The final product appears to be either K₃CrO₃ or the mixed oxides of chromium and potassium. Kinetic parameters and enthalpy data are presented for these reactions. In the case of K₃[Fe(C₂O₄)₃] · 2 H₂O, dehydration is followed by the loss of CO₂ and CO, CO₂ alone, and finally CO. The final product appears to be a basic carbonate of the type K₃[FE(O)₂(CO₃)]. Kinetic and thermal data are presented for most of these decomposition reactions.     

Thermal-Dependent dehydration process and intramolecular cyclization of lisinopril dihydrate in the solid state

The pathway of dehydration and intramolecular cyclization of lisinopril dihydrate in the solid state was investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and a combination of thermal analyzer with Fourier transform infrared microspectroscopy (thermal FT-IR microscopic system). The results indicate that the dehydration from the solid-state lisinopril dihydrate had a two-step process from dihydrate to monohydrate at 76 degrees C and then from monohydrate to anhydrate at 99-101 approximately C, which could be clearly observed from the above three methods. Only the thermal FT-IR microscopic system could give vital information on diketopiperazine (DKP) formation via intramolecular cyclization in anhydrous lisinopril. A new peak at 1670 cm(-1) assigned to the carbonyl band of DKP formation was clearly evidenced. The water of reaction byproduct was liberated at a temperature >157 degrees C and appeared on the IR spectra near 3200-3400 cm(-1). Moreover, the peak at 1574 cm(-1) assigned to carboxylate shifted to 1552 cm(-1) due to the DKP formation. The peak at 1670 cm(-1) related to the DKP formation changed slightly in intensity from 147 degrees C and significantly near 157 degrees C. DSC and TGA methods were poor for use in supplying information on DKP formation in lisinopril. The thermal FT-IR microscopic system is useful from the view point that it can quickly and directly show the solid-state stability of drug.     

Thermal studies of Zn(II) hydrazine complexes in the solid state

The synthesis and characterization of ZnL_nX₂ · mH₂O, where L = N₂H₄; n = 3, 2 and 1.5; X = Cl^?, Br^? and $\text{1}\text{2}$SO^2?₄; and m = 0 or 1, have been done and their thermal studies have been carried out using a Shimadzu DT-30 Thermal Analyzer. ZnL₃SO₄, ZnL_2.75SO₄, ZnL₂SO₄, ZnLCl₂ and ZnL_0.5Cl₂ have been synthesized pyrolytically in the solid state from their parent complexes synthesized from solution. Two varieties of ZnL₂Cl₂ synthesized by us are indistinguishable by IR spectroscopy but possess appreciable differences in their thermal profiles. Two forms of ZnL₃SO₄ which are also indistinguishable by IR spectroscopy show noticeable differences in their thermal profiles.     

Carbohydrazone polychelates: Synthesis,physicochemical characterization,solid state conductance and biological studies

The polychelates of Ti(III), VO(IV), Cr(III), Mn(III), Fe(III), Zr(IV), MoO₂(VI) and UO₂(VI) with the chelating hydrazone derived from 2,4-dihydroxy-5-acetylacetophenone and carbohydrazide have been synthesized. The polychelates have been characterized on the basis of elemental analyses, IR, magnetic moment, electronic spectral data and thermal analysis. Various kinetic parameters have been determined from the thermal data and decomposition follows first order kinetics. The solid—state electrical conductivity has been measured over 40–130°C-temperature range and all the compounds showed semiconducting behavior as their conductivity increases with increase in temperature. The ligand and its polychelates have also been screened for their antimicrobial activities using various microorganisms and all of them were found to be active against the organisms.     

Synthesis and characterization of antimony mixed-valence compounds in view of solid state isotopic exchange studies

Several attempts have been made to synthesize mixed-valence compound of antimony at low temperature in view of studying the isotopic exchange in solids. The experimental procedure for the synthesis, at 263 K of Cs₄(Sb^IIICl₆)(Sb^VCl₆) has been established. This compound seems very promising for isotopic exchange studies in the solid state.     

Solid state synthesis and characterization of iron（Ⅱ） pyrophosphate Fe2P2O7

Offwhite pure Fe_2P_2O_7 was synthesized through solid phase reaction using Fe_2O_3 and NH_4H_2PO_4 in argon atmosphere.The reaction products of Fe_2O_3 and NH4_H_2PO_4 at a series of temperatures from 400 to 900℃were characterized by XRD.Comparison and analysis of XRD patterns of resultant products indicated well-crystallized Fe_2P_2O_7 could be obtained over 630℃and Fe_2P_2O_7 prepared at 700℃was triclinic in cell type.Comparison of the cell parameters proved that the as-prepared Fe_2P_2O_7 belonged toβ- Fe_2P_2O_7 in crystal phase and SEM showed its size distribution was 0.5-2μm.     

Solid state reactions between nickel(II) sulphide and oxides of manganese and iron

Thermogravimetry and differential thermal analysis have shown that, when nickel(II) sulphide and manganese or iron oxides are heated together, several reactions occur depending on the molar ratio of the reactants. Detailed examinations of these reactions have shown that there are a number of intermediate stages, including the formation of sulphates.

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Zusammenfassung Thermogravimetrie und Differentialthermoanalyse zeigen, daß bei gemeinsamer Erhitzen von Nickel(II)-Sulfid und Manganoder Eisenoxiden, in Abhängigkeit von dem Molarverhältnis der Reaktionspartner verschiedene Reaktionen stattfinden. Das eingehende Studium dieser Reaktionen zeigte das Auftreten einer Anzahl Zwischenstufen, darunter auch die Bildung von Sulfaten.

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Résumé On montre par thermogravimétrie et analyse thermique différentielle que plusieurs réactions peuvent se produire suivant les rapports molaires des constituants lorsque l'on chauffe du sulfure de nickel(II) avec des oxydes de manganèse ou de fer. L'étude détaillée de ces réactions a mis en évidence un certain nombre d'étapes intermédiaires, avec formation de sulfates.

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, (II) , . , , .

     

Synthesis and solid state characterization of two insoluble tetrathiometalates

The aqueous reaction of ammonium tetrathiometalates (NH₄)₂[MS₄] (M = Mo or W) with (dbtmen)Br₂ · 2H₂O (dbtmen = N,N′-dibenzyl-N,N,N ′, N′-tetramethylethylenediammonium dication) results in the formation of the highly insoluble compounds (dbtmen)[MoS₄] (1) and (dbtmen)[WS₄] (2) in near quantitative yields. Compounds (1) and (2) have been characterized by elemental analysis, spectroscopic methods, X-ray powder diffraction and TG–DTA. Both compounds exhibit nearly identical IR spectra and X-ray powder patterns. The compounds exhibit a single strong signal for the asymmetric M–S stretching vibration at 475 cm⁻¹ in (1) and at 457 cm⁻¹ in (2). Complex (2) is thermally more stable than the corresponding Mo analogue (1). Thermal decomposition products of (1) and (2) are carbon contaminated amorphous metal disulfides and are formulated as MoS_1.99C_2.06N_0.07 and WS_1.75C_3.02 based on elemental analysis of the residue.     

Spectroscopic studies of iron(III) complexes of D-saccharose and D-glucose in the solid state and in solution

Iron(III) complexes of D-saccharose and D-glucose were prepared. The compositions of the complexes were determined by standard analytical methods. The Mössbauer spectra reflected the presence of high-spin iron(III) in the polynuclear species. EPR spectroscopy demonstrated antiferromagnetically coupled iron(III) centers within the solid complexes. The¹³C NMR spectra indicated the presence of a mixture of coordination isomers of iron(III) complexes containing the sugar ligand in differently bound forms.This work is dedicated to the memory of Dr. L. Korecz.     

Physico-chemical studies on thermal analyses of sodium hexa/carboxylato/ferrates/III/

The thermolysis of sodium hexa/benzoato/ferrate/III/, i. e. Na₃[Fe/C₆H₅COO/₆].4.5H₂O has been investigated at different temperatures in air using Mössbauer, infrared spectroscopic and derivatographic techniques /DTG, DTA, TG/. The thermal decomposition proceeds without the reduction of iron/III/. An increase in particle size of -Fe₂O₃ formed during thermolysis has been observed with increasing temperature. The end product, -NaFeO₂ is formed as a result of the solid state reaction between -Fe₂O₃ and sodium carbonate.