Alkali-metal trifluoromonosulphatomanganates (III) A2[MnF3(SO4)] (A = NH4, Li,Na or K)

Pink-brown crystalline alkali-metal trifluoromonosulphatomanganates(III), A₂[MnF₃(SO₄)] (A = NH₄, Li, Na or K), have been synthesised in high yields by reacting KMnO₄ or MnO(OH) with 40% HF and A₂SO₄ or by the reaction of MnO(OH) with 40% HF and A₂S₂O₈ (A = NH₄ or K). The chemicallly estimated oxidation state of manganese occurs between 2.9 and 3.1, and the room temperature magnetic moments lie in the range 4.0–4.2 BM. (NH₄)₂[MnF₃(SO₄)] on being pyrolysed at 340°C yields MnSO₄.     

Solid–liquid phase equilibria in the system K2SO4–MnSO4–H2O at 298 K and 313 K

Phase equilibria studies of the system K₂SO₄–MnSO₄–H₂O published revealed discrepancies between the data presented in the literature regarding the solid phases formed at ambient temperatures. The solubility in the system at 298 K and 313 K was determined. At 298 K, the existence of the double salt K₂SO₄·3MnSO₄·5H₂O and of MnSO₄·H₂O was confirmed. The examinations at 313 K showed the formation of the stable solid phases MnSO₄·H₂O, K₂SO₄·2MnSO₄, K₂SO₄·MnSO₄·1.5H₂O, K₂SO₄ and the formation of a metastable phase K₂SO₄·MnSO₄·2H₂O.     

Abtrennung von Submikrogramm-Mengen Arsen aus Ammomumfluoridlösungen

Arsenic has been separated from NH₄F solutions by coprecipitation with MnO(OH)₂, which is formed within the solution by addition of stoichiometric amounts of MnSO₄ and KMnO₄. The precipitate is dissolved in HC1 and As determined by known methods.     

Formation and decomposition of the rutile-type compound FeSbO4

The reaction between Fe₂O₃ (hematite) and Sb₂O₃ leading to the formation of the rutile-type compound FeSbO₄ was analysed by means of DTA and TG, performed under various O₂ partial pressures up to 1673 K. The reaction products were identified by means of XRD analysis. Three transformations occur in the analysed temperature range: 1. oxidation of Sb₂O₃ to Sb₂O₄ between 745 and 768 K; 2. formation of FeSbO₄ between 1226 and 1246 K; 3. decomposition of FeSbO₄ without melting above 1543-1591 K. The TG-DTA and XRD analysis results indicate that deviations from perfect stoichiometry are likely to exist inside FeSbO₄. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal and X-ray diffraction investigations of some lanthanum(III) and neodymium(III) oxide-alkali persulfate binary systems

Different molar ratios of La₂O₃ or Nd₂O₃:Na₂/K₂S₂O₈ have been prepared, and the results of their TG and DTA investigations, under an atmosphere of static air, are reported. The effects of either La₂O₃ or Nd₂O₃ on the thermal decomposition of the persulfates from ambient to 1050°C, using a derivatograph, have been studied. It has been found that La₂O₃ lowers the initial decomposition temperatures of these alkali persulfates through catalytic activity. Nd₂O₃ shows little or no catalytic effect and therefore it acts as an insulator. Intermediate and final products are identified by X-ray diffraction analysis. The stoichiometric molar ratios of the solid state reactions are 1:3::R₂O₃:M₂S₂O₈. (R = La or Nd. M = Na or K), which give double salts of formulae: NaLa(So₄)₂, KLa(SO₄)₂, NaNd(SO₄)₂, and KNd(SO₄)₂. No sulfates or oxysulfates of lanthanum or neodymium have been identified.     

TG/DTA/MS Study of the thermal decomposition of FeSO4·6H2O

The thermal decomposition of FeSO₄·6H₂O was studied by mass spectroscopy coupled with DTA/TG thermal analysis under inert atmosphere. On the ground of TG measurements, the mechanism of decomposition of FeSO₄·6H₂O is: i) three dehydration steps FeSO₄·6H₂O FeSO₄·4H₂O+2H₂O FeSO₄·4H₂O FeSO₄·H₂O+3H₂O FeSO₄·H₂O FeSO4+H₂O ii) two decomposition steps 6FeSO₄ Fe₂(SO₄)₃+2Fe₂O₃+2SO₂ Fe₂(SO₄)3 Fe₂O₃+3SO₂+3/2O₂ The intermediate compound was identified as Fe₂(SO₄)₃ and the final product as the hematite Fe₂O₃.     

An Exploratory Flow Reactor Study of H2S Oxidation at 30–100 Bar

Hydrogen sulfide oxidation experiments were conducted in O₂/N₂ at high pressure (30 and 100 bar) under oxidizing and stoichiometric conditions. Temperatures ranged from 450 to 925 K, with residence times of 3–20 s. Under stoichiometric conditions, the oxidation of H₂S was initiated at 600 K and almost completed at 900 K. Under oxidizing conditions, the onset temperature for reaction was 500–550 K, depending on pressure and residence time, with full oxidization to SO₂ at 550–600 K. Similar results were obtained in quartz and alumina tubes, indicating little influence of surface chemistry. The data were interpreted in terms of a detailed chemical kinetic model. The rate constants for selected reactions, including SH + O₂ ⇄ SO₂ + H, were determined from ab initio calculations. Modeling predictions generally overpredicted the temperature for onset of reaction. Calculations were sensitive to reactions of the comparatively unreactive SH radical. Under stoichiometric conditions, the oxidation rate was mostly controlled by the SH + SH branching ratio to form H₂S + S (promoting reaction) and HSSH (terminating). Further work is desirable on the SH + SH recombination and on subsequent reactions in the S₂ subset of the mechanism. Under oxidizing conditions, a high O₂ concentration (augmented by the high pressure) causes the termolecular reaction SH + O₂ + O₂ → HSO + O₃ to become the major consumption step for SH, according to the model. Consequently, calculations become very sensitive to the rate constant and product channels for the H₂S + O₃ reaction, which are currently not well established.     

A DSC study of benzoic acid: a suggested calibrant compound

It has been found that cobalt(II, III) oxide, Co₃O₄, lowers the thermal decomposition temperature of Na₂S₂O₈ and K₂S₂O₈ by about 25°C by catalysis, and it therefore acts as a P-type semiconductor at high temperature and atmospheric (air) pressure. Also, this oxide reacts at high temperature with sodium or potassium pyrosulfates to form thermally stable sodium cobalt disulfate, Na₂Co(SO₄)₂ and potassium cobalt trisulfate, K₂Co₂(SO₄)₃, respectively. Binary systems, consisting of a 1 : 3 mole ratio (oxide : persulfate), are established as representing the solid state stoichiometric reaction. X-Ray diffractometry is employed to identify intermediate and final reaction products in general. All calculations are based on data obtained from TG, DTG and DTA curves.     

Reaction Mechanisms of Strontium Ferrites Synthesis

The reactions between strontium and iron nitrates have been studied in an open atmosphere system using three different molar ratios, 1:1 (I), 1:2 (II) and 2:1 (III) at different temperatures as pointed out from the DTA data. The reaction mechanism was discussed based on the chemical composition characterized by means of thermal analysis, X‐ray diffraction patterns, infrared spectra and magnetic susceptibility. It was found that the reaction products depend on both temperature of reaction and the ratio between reactants. The reaction products were found to be composed of a variety of iron compounds that possess different valences: SrFeO_2.86, SrFeO_2.97, SrFe₂O₄, SrFe₁₂O₁₉, Sr₂Fe₂O₅ and Sr₇Fe₁₀O₂₂ in addition to some accessory reaction products namely α‐Fe₂O₃ and FeO(OH).     

Influence of temperatures and starting materials used to prepare α-Fe2O3 on its catalytic activity at the thermal decomposition of KClO4

In order to elucidate the influence of preparative history of α-Fe₂O₃ on its reactivity, the catalytic thermal decomposition of KClO₄ by α-Fe₂O₃ was studied by means of DTA and X-ray techniques. The catalysts were prepared by the calcination of three iron salts, Fe(OH)(CH₃COO)₂, FeSO₄ ? 7H₂O and Fe₂(SO₄)₃ ? αH₂O, at temperatures of 500–1200°C in air. The lower the preparation temperature of αFe₂O₃, the larger the specific surface area and reversely the smaller the crystalline size. KClO₄ without α-Fe₂O₃ was found to begin fusion and decomposition simultaneously at about 530°C. The addition of αFe₂O₃ resulted in promotion of the decomposition reaction of KClO₄; a lowering of 30–110°C in the initial decomposition temperature and a solid-phase decomposition before fusion of KClO₄. The influence of preparative history of α-Fe₂O₃ on the decomposition mainly depended on the preparation temperature rather than the starting material. The initial decomposition temperature of KClO₄ increased with an increase of the preparation temperature of α-Fe₂O₃. The effect of α-Fe₂O₃ was discussed on the basis of the charge transfer and the oxygen abstraction models.     

Sulfation of CuO,Fe2O3, MnO2, and NiO with (NH4)2SO4

An attempt has been made to calculate the free energy values for possible reactions utilising the available thermodynamic data in order to study the sulfation of CuO, Fe₂O₃, MnO₂ and NiO with (NH₄SO₄, and further trials have been made to determine the exact reaction through differential thermal analysis. There is no real correlation between the theoretical value of ΔH° and that calculated from the DTA peak, which may be due to some uncertainty in the thermodynamic values and the possibility of some side reactions.     

可回收Fe3O4@SiO2-Ag磁性纳米微球对染料污染物的快速脱色处理

介绍了一种采用无毒廉价的前驱物制备Fe₃O₄@SiO₂-Ag磁性纳米微球的快捷方法,制备的Fe₃O₄@SiO₂-Ag纳米微球在NaBH₄存在下可以催化还原染料污染物.实验结果表明,Fe₃O₄@SiO₂-Ag磁性纳米粒子保持了Ag纳米粒子和Fe₃O₄纳米粒子的双重优点,不仅对染料罗丹明B和曙红Y具有良好的催化还原效率,而且可以在外加磁场作用下从溶液中快速有效的分离.催化还原反应速率与反应温度及Fe₃O₄@SiO₂-Ag催化剂用量有关,反应体系中表面活性剂和无机盐(Na₂SO₄)的存在也会影响催化剂的催化活性.该Fe₃O₄@SiO₂-Ag磁性纳米粒子在工业染料污染物处理方面具有应用前景.     

Influence of mechanical activation time,annealing, and Fe/O ratio on Fe3O4/Fe composites formation from Fe2O3 and Fe powders mixture

Commercially, iron (α-Fe) and hematite (α-Fe₂O₃) powders were used for the synthesis of composite powders of Fe₂O₃/Fe type by mechanical milling. Several ratios of Fe₂O₃/Fe were chosen for the composite synthesis; the atomic percent of oxygen in the starting mixtures ranged from 21 to 46 %. The Fe₂O₃/Fe composite samples with various Fe/O ratios were milled for different milling times. The milled composite samples were subjected to the heat treatments in argon up to 900 °C. During the heat treatment at temperatures that do not exceed 550 °C, Fe₃O₄/Fe composite particles are formed by the reaction between the Fe₂O₃ and Fe. Further increase of the heat treatment up to 700 °C leads to the reaction of the Fe₃O₄/Fe composite component phases, resulting thus in the formation of FeO/Fe composite. The heat treatment up to 900 °C of the Fe₂O₃/Fe leads to the formation of a composite of FeO/Fe₃O₄/Fe independent of the milling time and Fe₂O₃/Fe ratios. The onset temperatures of the Fe₃O₄ and FeO formations decrease upon increasing the milling time. Another important aspect is that, in the case of the same milling time but with a large amount of iron into the composite powder the formations temperatures of Fe₃O₄ and FeO are also decreasing. The influence of the mechanical activation time, heat treatment temperature, and Fe/O ratio on the formation of the (Fe₃O₄, FeO)/Fe composite from Fe₂O₃+Fe precursor mixtures was studied by differential scanning calorimetry and X-ray diffraction techniques.     

Kinetic diagrams of Ln2O2SO4 phase transformations in a H2 flow (Ln = La, Pr, Nd, Sm)

Kinetic diagrams of Ln₂O₂SO₄ (Ln = La, Pr, Nd, Sm) systems reduction in a H₂ flow are plotted for the first time in temperature-duration of treatment coordinates in which there are five areas of phase states. The temperatures of formation are established for products of the Ln₂O₂SO₄ + 4H₂ = Ln₂O₂S + 4H₂O reaction in the temperature range of 880–900 K and products of the Ln₂O₂SO₄ + H₂ = Ln₂O₃ + SO₂+ H₂O reaction in the temperature range of 1090–1220 K. The ranges of the temperature of formation of the homo-geneous Ln₂O₂S phase were found to decrease: 880–1220, 900–1200, 900–1180, and 900–1090 K in the sequence La-Pr-Nd-Sm.     

Zum System V2O5?K2SO4

The phase diagram of the system V₂O₅? K₂SO₄ was established by means of X-ray diffraction and DTA. An endothermal reaction leads to the compound 5V₂O₅·3K₂SO₄ which melts at 510°C, crystallizes needle-shaped and forms hydrates. Eutectics occur at 31 (505°) and 55 mole-% K₂SO₄ (455°C).     

Mercury forms and their transformation in pyrite under weathering

Pyrite is considered to be the major carrier of mercury in coal. Here, the chemical characteristics of two natural pyrite samples of different weathering degrees were characterized by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Thermal stability of Hg was also analyzed via temperature programmed desorption experiment (TPD). Characteristic ions such as S⁻, Fe⁺, FeS⁻, and FeS₂⁻ were detected on the surface of fresh pyrite. The release temperature of Hg ranged between 180°C and 300°C, and the characteristic peak of black HgS was recorded. In addition, abundant Fe₂O₃⁻, FeSO⁻, SO₄⁻, and HSO₄⁻ were detected on the surface of weathered pyrite, and the release temperature of Hg therein was mainly distributed at 260°C to 380°C and 520°C to 600°C, corresponding to the characteristic peaks of red HgS and HgSO₄, respectively. The results show that pyrite is acidified during weathering and that Hg forms in pyrite are transformed from the original state (HgS) to HgSO₄.     

Solid-state reactions between alkali persulfates and oxides of corundum structure

The effects of three corundum structure oxides, α-Al₂O₃, α-Cr₂O₃, and α-Fe₂O₃, on the thermal decomposition of sodium and potassium peroxodisulfates (persulfates) under non-isothermal static air conditions and using various oxide/persulfate molar ratios, have been thermoanalytically investigated. Compounds such as Na₃Al(SO₄)₃, K₃Al(SO₄)₃, Cr₂(SO₄)₃, K₃Cr(SO₄₃, and Na₃Fe(SO₄)₃ are identified by X-ray diffractometry and conventional chemical analysis. The molar ratios as well as temperatures of the stoichiometric formation for these compounds have been established. At higher temperatures, α-Al₂O₃ acts as a promoter catalyst for the decomposition of pyrosulfate to sulfate, whereas α-Cr₂O₃ behaves as a retarder for the decomposition of persulfate. A eutectic mixture is formed between K₃Al(SO₄) and K₂SO₄ at 675°C. Also, K₃Fe(SO₄)₃ is identified as two crystalline phases.     

Synthesis,Crystal Structure and Magnetic Properties of Rb2Mn3O4

Rb₂Mn₃O₄, which is the first rubidium oxomanganates(II), has been synthesized via the azide/nitrate route from a stoichiometric mixture of the precursors RbN₃, RbNO₃, and MnO, as well as from Rb₂O and MnO, through an all solid state reaction. Its crystal structure (C2/c, Z = 4, a = 1546.9(2) pm, b = 666.22(7) pm, c = 588.06(6) pm) consists of a 3D arrangement of edge‐ and corner‐sharing MnO₄ tetrahedra with rubidium filling the space between. Magnetic susceptibility measurements indicate a magnetic phase transition at 126 K. The magnetic response as a function of temperature is complex, indicating strong, partly frustrated magnetic exchange interactions.     

XPS and ISS analysis of Fischer-Tropsch catalysts

Summary The surface compositions of K and Cu containing Fe/Mn oxide catalysts for Fischer-Tropsch synthesis were investigated by XPS and ISS. The surface species after calcination are identified as Fe₂O₃, Mn₂O₃, MnO₂, CuO and most likely KO₂, and after in situ reduction at 723 K Fe⁰, Cu⁰, Fe²⁺ and Fe³⁺ oxides, MnO and KOH. Mn and K are enriched on the surfaces after calcination and reduction; the Cu surface content is approximately equal to the bulk concentration. The K enrichment is especially strong and ISS indicates that potassium is mainly confined to the uppermost layers. The degree of reduction of Fe is strongly dependent on the amount of Cu or K. The change in surface composition during Fischer-Tropsch reaction in the XPS equipment can be correlated to the activity of the catalysts. The pure and Cu containing samples show a constant activity and only a small increase in carbon surface concentration. The K containing catalysts deactivate after a short time and are then totally covered by carbon. On all catalyst surfaces a small amount of carbonate is formed.

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XPS- and ISS-Analyse von Fischer-Tropsch-Katalysatoren

     

Activities of the components in a spinel solid solution of the Fe-Al-O system

The conditions of the equilibrium between the Fe₃O₄-FeAl₂O₄ solution and wustite are determined by measuring the EMF of galvanic cells containing a solid electrolyte, and the activities of the components in the Fe₃O₄-FeAl₂O₄ solution are calculated by treating the results of the experiment on the equilibrium between the spinel solution and wustite. Their properties are found to be different from those of ideal solutions at temperatures of 1000–1300 K. A significant positive deviation from the Raoult’s law is believed to indicate the tendency of the solution to decompose. The experimental data are treated in terms of the theory of regular solutions, assuming the energy of mixing to be a function of temperature only. The critical temperature of decomposition for the Fe₃O₄-FeAl₂O₄ solution is found to be 1084 K.