Thermal decomposition of chromium(III) nitrate(V) nanohydrate

Thermal decomposition of Cr(NO₃)₃·9H₂O in helium and in synthetic air was studied by means of TG, DTA, EGA and XRD analysis. The dehydration occurs together with decomposition of nitrate(V) groups. Eight distinct stages of reaction were found. Intermediate products of decomposition are hydroxy- and oxynitrates containing chromium in hexa- and trivalent states. The process carried out in helium leads to at about 260°C and in air is formed at about 200°C. The final product of decomposition (>450°C) is Cr₂O₃, both in helium and in air. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polythermic decomposition of Co(COO)2 · 2H2O compound synthesized within pores of photonic crystals based on SiO2

Polythermic decomposition of Co(COO)₂ · 2H₂O synthesized within pores of photonic crystals based on SiO2 was studied by thermogravimetry and differential scanning calorimetry techniques in helium and air in flow and under static conditions. Efficient activation energies and dehydratation enthalpies of the photonic crystals based on SiO₂ both in the absence and in the presence of Co(COO)₂ · 2H₂O phase (23.6, 41.5 and 77.6, 49.8 kJ mol^-1, respectively) were calculated. Polythermic Co(COO)₂ · 2H2O decomposition within pores of the photonic crystallites was found to yield CoO and Co₃O₄ nanoparticles in helium and air, respectively, exhibiting higher catalytic activity in CO oxidation by molecular oxygen. A conclusion was drawn that exothermic effect in the temperature range covering dehydrated oxalate decomposition is due to heterogeneously catalytic CO oxidation on the CoO and Co₃O₄ phases.     

热分析与气相色谱联用研究一水合草酸氢钾

用热分析与气相色谱联用技术(TA-GC)研究KHC₂O₄·H₂O的热分解表明,在空气和氦气当中,开始时缓慢分解,放出结晶水。接着KHC₂O₄快速分解成K₂C₂O₄,并释放出一些气体产物：O₂(分解初期)、CO、CO₂和H₂O。讨论了KHC₂O₄的分解机理。     

Thermal decomposition of Cd(CH3COO)2·2H2O studied by a coupled TG-DTA-MS method

The thermal decomposition of cadmium acetate dihydrate in helium and in air atmosphere has been investigated by means of a coupled TG-DTA-MS method combined with X-ray diffraction analysis. Dehydration of Cd(CH₃COO)₂·2H₂O is a two-stage process with Cd(CH₃COO)₂·H₂O as intermediate. The way of Cd(CH₃COO)₂ decomposition strongly depends on the surrounding gas atmosphere and the rate of heating. CdO, acetone and CO₂ are the primary products of decomposition in air. In helium decomposition goes by two parallel and consecutive reactions in which intermediates, Cd and CdCO₃, are formed. Metallic cadmium oxidizes and cadmium carbonate decomposes giving CdO. Some of the metallic cadmium, depending on the heating rate and the concentration of oxygen, evaporates. Acetone is partially oxidized in secondary reactions with oxygen. This revised version was published online in July 2006 with corrections to the Cover Date.     

Humidity controlled thermal analysis

The low temperature formation of crystalline zinc oxide via thermal decomposition of zinc acetylacetonate monohydrate C₁₀H₁₄O₄Zn·H₂O was studied by humidity controlled thermal analysis. The thermal decomposition was investigated by sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis by mass spectrometry (TG-MS) and simultaneous differential scanning calorimetry and X-ray diffractometry (XRD-DSC). Decomposition of C₁₀H₁₄O₄Zn·H₂O in dry gas by linear heating began with dehydration around 60°C, followed by sublimation and decomposition above 100°C. SCTG was useful because the high-temperature parallel decompositions were inhibited. The decomposition changed with water vapor in the atmosphere. Formation of ZnO was promoted by increasing water vapor and could be synthesized at temperatures below 100°C. XRD-DSC equipped with a humidity generator revealed that C₁₀H₁₄O₄Zn·H₂O decomposed directly to the crystalline ZnO by reacting with water vapor.     

Rare earth trisoxalatocobaltates(III) a precursor for rare earth cobaltites(III)

Rare earth cobalties, LnCoO₃, can be conveniently prepared by the thermal decomposition of the precursor LnCo(C₂O₄)₃·nH₂O (La, Ce, n=9; Pr, Nd, n=8). CeCo(C₂O₄)₃·8H₂O, unlike the other oxalato compounds thermally decompose to a mixture of CeO₂ and Co₃O₄. Although LnCoO₃are formed from the precursors at a temperature lower than 800°C, thermal analysis of a mixture of La₂(C₂O₄)₃·10H₂O and CoC₂O₄·2H₂O at 900·C shows the residue containing mainly La₂O₃ and Co₃O₄ with a small amount of LaCoO₃.     

Thermal decomposition behaviour of lanthanum(III) tris-tartrato lanthanate(III) decahydrate

Lanthanum(III) tris-tartrato lanthanate(III) decahydrate, La[La(C₄H₄O₆)₃]·10H₂O has been synthesized and characterized by elemental analysis, IR, electronic spectral and X-ray powder diffraction studies. Thermal studies (TG, DTG and DTA) in air showed a complex decomposition pattern with the generation of an anhydrous species at ~170°C. The end product was found to be mainly a mixture of La₂O₃ and carbides at ~970°C through the formation of several intermediates at different temperature. The residual product in DSC study in nitrogen at 670°C is assumed to be a similar mixture generated at 500°C in TG in air. Kinetic parameters, such as, E*, ΔH, ΔS, etc. obtained from DSC are discussed. IR and X-ray powder diffraction studies identified some of the decomposition products. The tentative mechanism for the thermal decomposition in air of the compound is proposed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal dehydration and decomposition of M[M(C2O4)2]·xH2O (x=3 forM=Sr(II) andx=6 forM=Hg(II))

Strontium(II) bis (oxalato) strontium(II) trihydrate, Sr[Sr(C₂O₄)₂]·3H₂O and mercury(II) bis (oxalato) mercurate(II) hexahydrate, Hg[Hg(C₂O₄)₂]·6H₂O have been synthesized and characterized by elemental analysis, reflectance and IR spectral studies. Thermal decomposition studies (TG, DTG and DTA) in air showed SrCO₃ was formed at ca. 500°C through the formation of transient intermediate of a mixture of SrCO₃ and SrC₂O₄ around 455°C. Sharp phase transition from γ-SrCO₃ to β-SrCO₃ indicated by a distinct endothermic peak at 900°C in DTA. Mercury(II) bis (oxalato) mercurate(II) hexahydrate showed an inclined slope followed by surprisingly steep slope in TG at 178°C and finally 98.66% of weight loss at 300°C. The activation energies (E ^*) of the dehydration and decomposition steps have been calculated by Freeman and Carroll and Flynn and Wall's method and compared with the values found by DSC in nitrogen. A tentative reaction mechanism for the thermal decomposition of Sr[Sr(C₂O₄)₂]·3H₂O has been proposed.     

Solvothermal synthesis and characterization of coordination polymers of cobalt(II) and zinc(II) with succinic acid

The complexes [Co(C₄H₄O₄)]_n (1) and [Zn(im)₂(C₄H₄O₄)]_n (2) (C₄H₄O₄ = succinate dianion, suc; im = imidazole) have been synthesized solvothermally and characterized by elemental analysis, IR, TG–DTA, and single-crystal X-ray diffraction techniques. Complex 1 is the first anhydrous member of the cobalt succinate family and has high thermal stability under a static air atmosphere, up to 425 °C, and complex 2 is a 1D coordination polymer. In addition, a new synthesis method and some properties of the known [Co(HCOO)₂·2H₂O]_n (3) complex are reported. After in situ synthesis of 3 via decomposition of DMF at 140 °C, it was found that complex 3 can adsorb some solvents repeatedly and is selective for H₂O.     

CoC2O4·2H2O在空气中的热分解动力学研究

纳米Co3O4具有尖晶石结构,Co3 占据八面体位,具有较高的晶体场稳定化能,在空气中低于800℃时十分稳定,是优良的催化材料[1]。Co3O4还可以作为高比能锂离子电池负极材料具有非常好的电化学活性,充放电容量高达960m A h·g-1。纳米Co3O4在紫外、可见及近红外区域都有良好的吸收效果,因此,在隐身技术、保温节能技术等领域具有潜在的应用前景。所以,Co3O4超细粉体的制备和应用研究具有十分重要的意义。我们合成了草酸盐先驱物制备纳米Co3O4用作隐身材料,因此对先驱物的热分解过程研究是十分必要的。热分析方法在了解先驱物热分解反应的物理…     

Dielectric differential thermal analysis

Dithionates (CaS₂O₆·4H₂O, SrS₂O₆·4H₂O, BaS₂O₆·2H₂O, MnS₂O₆·4H₂O, MgS₂O₆·6H₂O, CoS₂O₆·6H₂O, NiS₂O₆·6H₂O, ZnS₂O₆·6H₂O and CuS₂O₆·4H₂O) were subjected to thermodielectric analysis. The thermoanalytical curves show low temperature effects from 60 to 350°. These are related with the dehydration and decomposition of the dithionates, which could be fully correlated with the knowledge of the thermal behavior of these compouds obtained with other thermal methods.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.     

Preparation of nanocrystalline BiFeO3 and kinetics of thermal process of precursor

The Bi₂Fe₂(C₂O₄)₅·5H₂O was synthesized by solid-state reaction at low heat using Bi(NO₃)₃·5H₂O, FeSO₄·7H₂O, and Na₂C₂O₄ as raw materials. The nanocrystalline BiFeO₃ was obtained by calcining Bi₂Fe₂(C₂O₄)₅·5H₂O at 600 °C in air. The precursor and its calcined products were characterized by thermogravimetry and differential scanning calorimetry, FT-IR, X-ray powder diffraction, and vibrating sample magnetometer. The data showed that highly crystallized BiFeO₃ with hexagonal structure [space group R3c(161)] was obtained when the precursor was calcined at 600 °C in air for 1.5 h. The thermal process of the precursor in air experienced five steps which involved, at first, the dehydration of an adsorption water molecule, then dehydration of four crystal water molecules, decomposition of FeC₂O₄ into Fe₂O₃, decomposition of Bi₂(C₂O₄)₃ into Bi₂O₃, and at last, reaction of Bi₂O₃ and Fe₂O₃ into hexagonal BiFeO₃. Based on Starink equation, the values of the activation energies associated with the thermal process of Bi₂Fe₂(C₂O₄)₅·5H₂O were determined. Besides, the most probable mechanism functions and thermodynamic functions (ΔS ^≠, ΔH ^≠, and ΔG ^≠) of thermal processes of Bi₂Fe₂(C₂O₄)₅·5H₂O were also determined.     

Study on thermal decomposition of copper(II) acetate monohydrate in air

The thermal decomposition of copper(II) acetate monohydrate (CuAc₂·H₂O) under 500 °C in air was studied by TG/DTG, DTA, in situ FTIR and XRD experiments. The experimental results showed that the thermal decomposition of CuAc₂·H₂O under 500 °C in air included three main steps. CuAc₂·H₂O was dehydrated under 168 °C; CuAc₂ decomposed to initial solid products and volatile products at 168–302 °C; the initial solid products Cu and Cu₂O were oxidized to CuO in air at 302–500 °C. The copper acetate peroxides were found to form between 100 and 150 °C, and the dehydration of these peroxides resulted in the presence of CuAc₂·H₂O above 168 °C. The initial solid products were found to be the admixture of Cu, Cu₂O, and CuO, not simply the single Cu₂O as reported before. Detailed reactions involved in these three steps were proposed to describe the complete mechanism and course of the thermal decomposition of CuAc₂·H₂O in air.     

Correction to: Multistage thermal decomposition in films of cadmium chloride-doped PVA–PVP polymeric blend

Core/shell composites of CuC₂O₄·2H₂O@AP and ZnC₂O₄·2H₂O@AP were prepared from metal oxalates on suspended AP particles in ethanol. CuO and ZnO nano-metal oxides as the nano-catalysts were made from CuC₂O₄·2H₂O and ZnC₂O₄·2H₂O simultaneously by thermal decomposition of AP. The particle size of CuO nano-particles was very finer, and the ZnO particles showed a considerable growth during formation. The kinetic triplet of activation energy, frequency factor, and model of thermal decomposition of pure AP, CuC₂O₄·2H₂O@AP, and ZnC₂O₄·2H₂O@AP composites were estimated by applying three model-free (FWO, KAS, and Starink) and model-fitting (Starink) methods. Based on the thermal analysis, the CuC₂O₄@AP composite has better catalytic performance and the thermal decomposition temperature of AP decreased to about 126.44 °C.     

Studies on lanthanoid sulphites: V. thermal decomposition of cerium and neodymium sulphites

The preparation and thermal behaviour of Ce₂(SO₃)₃· 3H₂O, Nd₂(SO₃)₃·6H₂O and Nd₂(SO₃)₃ have been studied. Cerium sulphite undergoes first dehydration which is followed by decomposition to CeO₂ in the temperature range 500 – 850 °C. The decomposition involves two intermediate phases both in air and nitrogen. According to the TG curves the phases in air are Ce₂(SO₃)₂SO₄ and Ce₂SO₃(SO₄)₂. In nitrogen, Ce₂O₂SO₄ was identified and this provides a synthetic route to cerium oxysulphate.Neodymium sulphite decomposes to Nd₂O₂SO₄ when heated in air or in nitrogen up to 950°C. The intermediate levels observed do not correspond to single phases, and the reaction mechanism depends strongly on the experimental conditions.     

Investigation of the thermal decomposition of some periodates by means of emanation thermal analysis (ETA) and DTA

Thermal decomposition of Be₃(IO₅)₂ · 12H₂O, Mg₂I₂O₉ · 11H₂O, Ca₂I₂O₉ · 9H₂O and Ba₂I₂O₉ · 9H₂O in the temperature interval of 20 to 600° was studied by means of emanation thermal analysis (ETA) and differential thermal analysis (DTA). The magnetic properties of decomposition intermediates of periodates studied are discussed.     

Synthesis and structural characterization of perovskite YFeO<Subscript>3</Subscript> by thermal decomposition of a cyano complex precursor,Y[Fe(CN)<Subscript>6</Subscript>]·4H<Subscript>2</Subscript>O

The thermal decomposition of Y[Fe(CN)₆]·4H₂O has been studied in order to investigate the formation of the multi-ferroic oxide YFeO₃. The starting material (Y[Fe(CN)₆]·4H₂O) and the decomposition products were characterized by IR spectroscopy, thermal analysis, X-ray powder diffraction (PXRD), and scanning electron microscopy. Metastable YFeO₃ with hexagonal structure, space group P6 ₃ /mmc, was obtained by thermal decomposition of Y[Fe(CN)₆]·4H₂O at 600 °C in air. Orthorhombic YFeO₃ was obtained by the same method at T ≥ 800 °C in air. The crystal structure of orthorhombic YFeO₃ was refined by Rietveld analysis using PXRD data. We found that it was slightly deficient in Y³⁺, which is in agreement with the small amount of Y₂O₃ found as impurity in the sample. The formula of the orthorhombic phase is Y_0.986FeO₃.     

Synthesis of micro- and nanosized manganese oxides from hydrated manganese oxalates and products of their chemical modification with ethylene glycol

The reactions of ethylene glycol with manganese oxalates MnC₂O₄ · 2 H₂O and MnC₂O₄ · 3H₂O on heating in air were studied. At temperature below 100°C, ethylene glycol was found to displace water from oxalates to give a new solvate compound according to the reaction MnC₂O₄ · nH₂O + HOCH₂CH₂OH = MnC₂O₄(HOCH₂CH₂OH) + nH₂O↑. The crystals of the solvates retain the morphology of the initial oxalates, which is then inherited by the products of their thermolysis. Thus, thermolysis of MnC₂O₄ · 3H₂O and MnC₂O₄(HOCH₂CH₂OH) having quasi-unidimensional structure gave Mn₃O₄ and Mn₂O₃ nanowhiskers in air and MnO in an inert gas environment. Heating of MnC₂O₄ · nH₂O in ethylene glycol at temperatures above 100°C results in anhydrous manganese oxalate.     

Synthesis and thermal decomposition of neodymium(III) peroxotitanate to Nd<Subscript>2</Subscript>TiO<Subscript>5</Subscript>

Neodymium(III) peroxotitanate is used as a precursor for obtaining Nd₂TiO₅. The last one possesses numerous valuable electrophysical properties. TiCl₄, Nd(NO₃)₃·6H₂O and H₂O₂ in mol ratio 1:2:10 were used as starting materials. The reaction ambience was alkalized to pH = 9 with a solution of NH₃. The obtained neodymium(III) peroxotitanate and intermediate compounds of the isothermal heating were proved by the help of quantitative analysis and infrared spectroscopy (IRS). It has Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O composition. The absorption band observed in IRS at 831 cm^?1 relates to a triangular bonding of the peroxo group of Ti, at 1062 cm^?1—terminal groups Ti–OH and at 1491 and 1384 cm^?1—the bridging OH^?-groups Ti–O(H)–Ti. Nd₂TiO₅ was obtained by thermal decomposition of neodymium(III) peroxotitanate. The isothermal conditions for decomposition were determined on the base of differential thermal analysis, thermogravimetric and differential scanning calorimetry results in the temperature range of 20–1000 °C. The mechanism of thermal decomposition of Nd₄[Ti₂(O₂)₄(OH)₁₂]·7H₂O to Nd₂TiO₅ was studied. In the temperature range of 20–208 °C, a simultaneous decomposition of the peroxo groups by the separation of oxygen and hydrate water is conducted and Nd₄[Ti₂O₄(OH)₁₂] is obtained. From 208 to 390 °C, the terminal OH^?-groups are separated and Nd₄[Ti₂O₇(OH)₆] is formed. In the range of 390–824 °C, the bridging OH^?-groups are completely decomposed to Nd₂TiO₅. The optimal conditions for obtaining nanocrystalline Nd₂TiO₅ are 900 °C for 6 h and 20–80 nm.