Disilberoxotellurat(VI), Ag2TeO4

Disilver Oxotellurate(VI), Ag₂TeO₄ Ag₂TeO₄ was synthesised by reaction of Ag₂O and TeO₂ applying an elevated oxygen pressure. According to a single crystal structure determination (C2/c, a = 9.0588(9), b = 9.2456(8), c = 13.623(1) Å, β = 91.758(8)°, Z = 12, 1289 independent reflections, R1 = 2.32 %, wR2 = 5.51 %), Ag₂TeO₄ contains a novel chain‐like polyanion with tellurium in an octahedral coordination. The TeO₆ octahedra are connected via common edges and vertices in a way that the resulting polyanion represents a section of the rutile structure type. Ag₂TeO₄ shows diamagnetic and insulating behaviour, it decomposes at 560 °C into Ag₂TeO₃ and oxygen.     

Structural and conductivity studies of CsKSO4Te(OH)6 and Rb1.25K0.75SO4Te(OH)6 materials

The crystal structures of the title compounds were solved using the single-crystal X-ray diffraction technique. At room temperature CsKSO₄Te(OH)₆ was found to crystallize in the monoclinic system with Pn space group and lattice parameters: ; ; ; β=106.53(2)°; ; Z=4 and . The structural refinement has led to a reliability factor of R₁=0.0284 (wR₂=0.064) for 7577 independent reflections. Rb_1.25K_0.75SO₄Te(OH)₆ material possesses a monoclinic structure with space group P2₁/a and cell parameters: ; ; ; β=106.860(10)°; ; Z=4 and . The residuals are R₁=0.0297 and wR₂=0.0776 for 3336 independent reflections. The main interest of these structures is the presence of two different and independent anionic groups (TeO₆⁶⁻ and SO₄²⁻) in the same crystal.Complex impedance measurements (Z^*=Z^′—iZ^″) have been undertaken in the frequency and temperature ranges 20-10⁶ Hz and 400-600 K, respectively. The dielectric relaxation is studied in the complex modulus formalism M^*.     

Die Reaktion von Tellurhexafluorid mit Trimethylamin,Strukturen der TeF5−- und SeF5−-Anionen

Reaction of Telluriumhexafluoride and Trimethylamine, Structures of the TeF₅^? and SeF₅^? Anions The reaction of TeF₆ and (CH₃)₃N is of the redox kind, resulting in reduction of tellurium: X-ray single crystal analysis reveals the compounds (CH₃)₂N? CH₂? N(CH₃)₂⁺TeF₅^? and [(CH₃)₃NH⁺]₅(TeF₅^?)₃(HF₂^?)₂. By comparison with published data it can be shown that this mixture is identical to previously published [(CH₃)₃N]₂TeF₆. The latter was supposed to be one of the few examples of tellurium in a coordination state of eight. (CH₃)₄N⁺TeF₅^? and (CH₃)₄N⁴SeF₅^? are obtained and their structure is investigated by single crystal x-ray methods also. The anions SF₅^?, SeF₅^? and TeF₅^? are discussed in terms of weak interactions.     

The local structure of gadolinium vanadate–tellurate glasses and glass ceramics: Te2V2O9 crystalline phase

Glasses in the system xGd₂O₃ · (100 − x)[0.7TeO₂ · 0.3V₂O₅] with 0 ≤ x ≤20 mol% have been prepared from melt quenching method. Influence of gadolinium ions on structural behavior in vanadate–tellurate glasses has been investigated using FTIR spectroscopy, X-ray diffraction (XRD), and magnetic susceptibility measurements. The structural changes have been analyzed with increasing rare earth concentration. The structural changes, as recognized by analyzing band shapes of XRD and FTIR spectra, revealed that Gd₂O₃ causes a higher extent of network polymerization as far as 20 mol%. The structure of the heat-treated glasses was found to consist mainly of the Te₂V₂O₉ crystalline phase. These vitreous systems were investigated by magnetic susceptibility measurements. From the paramagnetic susceptibility χ was calculated at different temperature and from the 1/χ(T) graph, the Curie temperature of the glass has been evaluated. Magnetic susceptibility data show the presence of small antiferromagnetic interactions between the Gd⁺³ ions.     

A linear bridging angle in the pyrovanadate group within the crystal structure of Hg2V2Te2O11

The title compound, dimercury(II) divanadium(V) ditellurium(IV) undecaoxide, Hg₂V₂Te₂O₁₁, is a new representative within the family of divalent oxovanadato(V)tellurates(IV). The anionic framework is made up of disphenoidal [TeO₄] polyhedra that are linked by corner‐sharing to two neighbouring pyrovanadate units, resulting in chains of six‐membered rings propagating parallel to [10]. The bridging O atom of the pyrovanadate unit is located on an inversion centre, leading to a staggered conformation and a linear V—O—V angle between the two [VO₄] tetrahedra. The anionic chains are connected by interjacent six‐coordinate Hg²⁺ cations into a three‐dimensional framework. The 5s² lone electron pair of the Te^IV atom is stereochemically active and protrudes into the free space of the chain links.     

Temperature and Concentration Dependence of the Electrical Conductance,Diffusion, and Kinetics Parameters of the Ions in Aqueous Solutions of Sulfuric Acid,Selenic Acid,and Potassium Tellurate

The temperature and concentration dependences of the electrical conductance of aqueous solutions of sulfuric acid, selenic acid, and potassium tellurate were studied. The coefficients of the corresponding empirical equations were determined, and the values of equivalent conductances of the anions were evaluated at infinite dilution at the experimental temperatures. The values of the coefficients in the Fuoss and Onsager equation were evaluated for the three electrolytes at 298 K. The values of the molecular and ionic coefficients of self-diffusion at infinite dilution were calculated in the temperature range 288–318 K. The change of the translational energy Δ E∘_tr. of water molecules in the ionic hydration sphere was determined. The number of water molecules participating in the ionic hydration sphere at 298 K and the changes of Gibbs free energy, enthalpy, and entropy of activation of ionic conductance were calculated. The results obtained were interpreted according to the Samoylov’s theory of positive and negative hydration of ions. The differences observed in the temperature dependences of the mentioned parameters were explained in terms of the different radii and hydration numbers of the ions.     

Activation Energy for Electroconduction of Aqueous Solutions of Sulfuric and Selenic Acids and Potassium Tellurate

The temperature and concentration dependences of the electroconductivity of aqueous solutions of sulfuric and selenic acids and potassium tellurate are studied. Coefficients of empirical equations that describe these dependences are determined. Activation energies for electroconduction of these solutions as a function of concentration are calculated and it is assumed that these are linked with the hydration degree of ions and the destruction of the quasi-crystalline tetrahedral water cage.     

Why should transition metal chalcogenides be investigated as water splitting precatalysts even though they transform into (oxyhydr)oxides?

The extensive investigation of 3d transition metal chalcogenide (sulphides, selenides, tellurides) precatalysts has shown that they transform into (oxyhydr)oxides during the oxygen evolution reaction (OER) and likely during industrial hydrogen evolution reaction (HER) conditions, as predicted by their Pourbaix diagrams. The phases formed from chalcogenide precatalysts are often more active, due to anion leaching induced effects. But are chalcogenides suitable to be used sacrificially, are they abundant, cheap, and non-toxic enough? Is their unique chemical nature really required? This review answers these questions by discussing the role of chalcogenides in the reconstruction/transformation process. Furthermore, it examines the role of remaining traces of chalcogenates (sulphate, selenate) that were recently shown to improve the OER activity and can break the 1OH/1OOH scaling relations.     

过渡金属氧化物对阻燃剂聚磷酸铵热分解的影响机制

过渡金属氧化物(MO)可以显著影响聚磷酸铵(APP)的热分解过程,进而改善APP复配膨胀阻燃聚合物材料的阻燃效率。将ZnO、Fe2O3、TiO2掺入到APP中,采用热失重分析(TGA)、X射线光电子能谱(XPS)和X射线衍射分析(XRD),考察了3种MO对APP热分解行为的影响,分析了相互作用过程中金属原子和磷原子化学结合状态的变化以及高温热分解产物的物相结构。TGA和XPS图谱分析结果表明,MO可降低APP的起始热分解温度,并催化APP释放NH3和H2O,而在热分解后期由于金属磷酸盐的形成可显著增加APP的高温残留量。3种MO催化APP热分解脱NH3和H2O的活性由大到小的顺序是:ZnO>Fe2O3>TiO2,而对APP凝聚相热分解P-O产物的交联能力从大到小的顺序为:Fe2O3>ZnO>TiO2。XRD结果显示,ZnO在高温下与APP反应生成了Zn(PO3)2晶体,而Fe2O3和TiO2与APP反应分别生成了Fe4(P2O7)3和TiP2O7晶体。     

Study of the pyrolysis of H2O2 in the presence of H2and CO by use of UV absorption of HO2

In dissociation experiments of H₂O₂ under shock wave conditions, the spectra of H₂O₂ and HO₂ have been observed in the UV at 2200 ≤ 2800 Å. By the use of these spectra the H₂O₂ decomposition in the presence of H₂ and CO at 870 ≤ T ≤ 1000°K has been analyzed. It was found that in this temperature range, in contrast to low temperature behavior, reactions of H atoms with H₂O₂ and with HO₂ are equally important. The rate of the reaction H + H₂O₂ ← HO₂ + H₂ was estimated in comparison with the rate of the reaction between H and HO₂. Good agreement between calculated and measured concentration profiles of HO₂ and H₂O₂ was obtained.     

A study of the selenites of cerium

The solubilities of the systems CeO₂-SeO₂-H₂O and Ce₂O₃-SeO₂-H₂O were studied at 100°C. The field of crystallization of Ce(SeO₃)₂ was established in the system CeO₂-SeO₂-H₂O, and fields of crystallization of Ce₂(SeO₃)₃ and Ce₂(SeO₃)₃H₂SeO₃ were established in the system Ce₂O₃-SeO₂-H₂O. The compound obtained were identified by means of chemical, X-ray and derivatograph analysis. The mechanism of thermal dissociation of Ce(SeO₃)₂, Ce₂(SeO₃)₃ and Ce₂(SeO₃)₃·H₂SeO₃ was studied. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal decomposition of rhombohedral double carbonates of dolomite type

DTA and TG studies in air were carried out for hydrothermally prepared rhombohedral double carbonates of dolomite type, CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ and CdZn(CO₃)₂. The solid decomposition products in air have been compared to those obtained under hydrothermal conditions with CO₂ pressure. The dolomite [CaMg(CO₃)₂] decomposes in two stages both in air as well as under high CO₂ pressure. The other carbonates studied, follow a single stage decomposition in air and a two stage decomposition under hydrothermal condition. In air, the manganese containing carbonates CaMn(CO₃)₂ and CdMn(CO₃)₂, decompose to form mixed oxides of CaMnO₃ and CdMnO₃ respectively, while CdMg(CO₃)₂ and CdZn(CO₃)₂ decompose to their respective two mono oxides.

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Zusammenfassung Mittels DTA und TG in Luft werden die hydrothermisch hergestellten rhomboedrischen Doppelkarbonate (Dolomittyp) CaMg(CO₃)₂, CaMn(CO₃)₂, CdMg(CO₃)₂, CdMn(CO₃)₂ und CdZn(CO₃)₂ untersucht. Die in Luft erhaltenen festen Zersetzungsprodukte wurden mit denen verglichen, die unter hydrothermischen Bedingungen mit CO₂-Druck entstehen. Dolomit zersetzt sich sowohl in Luft als auch unter hohem CO₂-Druck in zwei Schritten. Die übrigen untersuchten Karbonate zersetzen sich in Luft in einem, unter hydrothermischen Bedingungen in zwei Schritten. In Luft zersetzen sich die magnesiumhaltigen Karbonate CaMn(CO₃)₂ und CdMn(CO₃)₂ unter Bildung der Mischoxide CaMnO₃ und CdMnO₃, während aus CdMg(CO₃)₂ und CdZn(CO₃)₂ jeweils die entsprechenden beiden Monoxide entstehen.

     

Calorimetric study of the component steps of oscillating chemical reactions

An influence of inorganic compounds (Fe₂O₃, ZnO, PbO, CaCO₃ and K₂CO₃) on the blast furnace coke thermal oxidation in the air and in the CO₂atmosphere was investigated by means of thermal analysis. A catalytic effect showed itself at the oxidation in the air, especially with PbO and K₂CO₃. These compounds bring the oxidation starting temperature and activation energy down and increase the reaction rate constant most distinctly. The PbO and K₂CO₃ actions differ in their mechanisms. K₂CO₃ accelerates particularly the amorphous coke fractions oxidation. In the CO₂ atmosphere an important catalytic effect occurred only with K₂CO₃. The PbO catalytic influence is less distinct. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic effects of six inorganic compounds on pyrolysis of three kinds of biomass

Six inorganic compounds, i.e., Na₂CO₃, NaOH, NaCl, Na₂SiO₃, TiO₂ and HZSM-5, have been investigated with regard to their catalytic effects on pyrolysis of three biomass species, i.e., pine wood, cotton stalk and fir wood by thermal analysis experiments. The results show that Na₂CO₃, NaOH, Na₂SiO₃ and NaCl made devolatilization occur at lower temperature regions in the pyrolysis of the three kinds of biomass, whereas TiO₂ and HZSM-5 made that occur at higher temperature regions in the pyrolysis of cotton stalk and had no obvious effects on pyrolysis temperatures of pine wood and fir wood. The basic catalysts NaOH, Na₂CO₃ and Na₂SiO₃ decreased the maximum weight loss rates while NaCl and HZSM-5 increased them and TiO₂ had no obvious effects on them. The four sodium compounds made pyrolysis of the three kinds of biomass more exothermic, which might be due to more char formation, whereas TiO₂ and HZSM-5 had minor effects on reaction heat. The catalytic effects in all aspects were roughly correlated with one another and their relationship with the basicity and acidity of the catalysts were preliminarily described and analyzed.     

Kinetics of the thermal decomposition of dinitramide

The kinetic regularities of the heat release during the thermal decomposition of liquid NH₄N(NO₂)₂ at 102.4–138.9 °C were studied. Kinetic data for decomposition of different forms of dinitramide and the influence of water on the rate of decomposition of NH₄N(NO₂)₂ show that the contributions of the decomposition of N(NO₂)₂ ⁻ and HN(NO₂)₂ to the initial decomposition rate of the reaction at temperatures about 100 °C are approximately equal. The decomposition has an autocatalytic character. The analysis of the effect of additives of HNO₃ solutions and the dependence of the autocatalytic reaction rate constant on the gas volume in the system shows that the self-acceleration is due to an increase in the acidity of the NH₄N(NO₂)₂ melt owing to the accumulation of HNO₃ and the corresponding increase in the contribution of the HN(NO₂)₂ decomposition to the overall rate. The self-acceleration ceases due to the accumulation of NO₃ ⁻ ions decreasing the equilibrium concentration of HN(NO₂)₂ in the melt. For Part 2, see Ref. 1. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 395–401 March 1998.     

通过阳离子的部分氯化和氟化提高离子液体的憎水性

报道了一类咪唑环阳离子上同时含有氯和氟元素的新型离子液体,即 和 。这类离子液体是将其前驱体甲基丁基咪唑氯盐或甲基丁基咪唑六氟磷酸盐经过氯化取代和氟化取代反应来制备的。采用氢核磁共振谱（1H-NMR）确定了氯化反应过程中氯取代氢的位置,结果表明,氯主要取代咪唑环上的氢以及部分丁基侧链上甲基基团中的氢。考察了这类离子液体的水溶性,热稳定性以及黏度。结果表明,离子液体经氯化和氟化处理可以显著提高其憎水性。     

过渡金属氧化物对阻燃剂聚磷酸铵热分解的影响机制

过渡金属氧化物(MO)可以显著影响聚磷酸铵(APP)的热分解过程, 进而改善APP复配膨胀阻燃聚合物材料的阻燃效率。将ZnO、Fe₂O₃、TiO₂掺入到APP中, 采用热失重分析(TGA)、X射线光电子能谱(XPS)和X射线衍射分析(XRD), 考察了3种MO对APP热分解行为的影响, 分析了相互作用过程中金属原子和磷原子化学结合状态的变化以及高温热分解产物的物相结构。TGA和XPS图谱分析结果表明, MO可降低APP的起始热分解温度, 并催化APP释放NH₃和H₂O, 而在热分解后期由于金属磷酸盐的形成可显著增加APP的高温残留量。3种MO催化APP热分解脱NH₃和H₂O的活性由大到小的顺序是:ZnO>Fe₂O₃>TiO₂, 而对APP凝聚相热分解P-O产物的交联能力从大到小的顺序为:Fe₂O₃>ZnO>TiO₂。XRD结果显示, ZnO在高温下与APP反应生成了Zn(PO₃)₂晶体, 而Fe₂O₃和TiO₂与APP反应分别生成了Fe₄(P₂O₇)₃和TiP₂O₇晶体。     

Kinetics of decomposition of alkylammonium salts

The thermogravimetric curves of di-n-propylammonium, di-iso-propylammonium, di-n-butylammonium and di-iso-butylammonium chlorides showed similar profiles, characterized by mass loss in only one stage, corresponding to decomposition of compounds. The following thermal stability order was obtained: [Bu₂ ⁿNH₂]Cl>[Pr₂ ⁿNH₂]Cl>[Pr₂ ⁱNH₂]Cl>[Bu₂ ⁱNH₂]Cl. The values of activation energy for non-isothermal data obtained by Ozawa and Coats-Redfern integral methods were in agreement and stability order obtained by thermogravimetry were reproduced in both methods. The decomposition reactions of [Pr₂ ⁿNH₂]Cl, [Pr₂ ⁱNH₂]Cl and [Bu₂ ⁱNH₂]Cl were better described by A3 model and [Bu₂ ⁿNH₂]Cl by A2 model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Laser flash photolysis of fullerols of C60 and of C70 in aqueous solutions

Fullerols of C₆₀ and of C₇₀ [C₆₀(OH)_n, C₇₀(OH)_m], water-soluble fullerene derivatives, unlike some other fullerene derivatives (such as C₆₀ (C₄H₆O), C₆₀ (C₃H₇N) and C₆₀ [C(COOEt)₂]_x), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser. The quantum yields of formation of hydrated electron (Φ_e ⁻) are determined to be 0.08 and 0.11 for fullerols of C₆₀ and of C₇₀ respectively at room temperature (ca. 15°C) with KI solution used as reference. By laser flash photolysis and oxidation of sulfate radical anion SO₄ ⁻, the fullerol radical cation or neutral radical of C₆₀ is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C₇₀ are observed for the first time. Project supported by the National Natural Science Foundation of China     

非晶态镍硼酸盐结构的EXAFS研究

由摩尔比分别为1:2和1:8的NiCl₂·6H₂O和Na₂B₄O₇·10H₂O作为反应物, 合成两种非晶态镍硼酸盐, 同时通过水热法合成β-Ni(OH)₂. 化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B₂O₃·4.5H₂O和NiO·B₂O₃·3H₂O. 激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B₃O₃(OH)₅^2-和B₂O(OH)₆^2-. 同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析, 通过数据拟合给出样品中Ni 原子周围近邻配位原子种类、配位数以及原子间距离. 用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明, 样品中Ni 原子周围局域结构与Ni₃B₂O₆晶体(ICSD No.31387)中的吻合较好. Ni 原子周围配位原子为O、B和Ni, 对于NiO·0.8B₂O₃·4.5H₂O, 配位数分别为5.7、3.8和3.8, 配位距离分别为0.208、0.263 和0.311 nm; 对于NiO·B₂O₃·3H₂O, 配位数分别为6.0、4.0 和4.0, 配位距离分别为0.207、0.262和0.310 nm.