Thermoanalytical study of the solid-state reactions in MgO-Cr2O3 and ZnO-Cr2O3 systems

The solid-state reactions in MgO-Cr₂O₃ and ZnO-Cr₂O₃ systems under atmospheres of oxygen, air and nitrogen were investigated by means of DTA and isothermal kinetic techniques. It was shown that the application of DTA to the solid-state reactions affords useful information with respect to the initial reaction stage: oxidation of Cr₂O₃ to CrO₃ in the presence of MgO or ZnO, followed by the formation of a thin layer of spinel, which consisted of an imperfect lattice, on the surface of the MgO or ZnO grains.     

Thermoanalytical study on the chlorination of hydrated aluminas and transition aluminas

The chlorination processes of four hydrated aluminas (bayerite, gibbsite, pseudoboehmite, boehmite) and four transition aluminas (η-,γ-,δ-,θ-Al₂O₃) were studied in the presence of active carbon by means of a gas-flow DTA apparatus. In the case of hydrated alumina systems three exothermic peaks appeared at about 230, 460 and 500°C or above, which corresponded to the formation of hydrogen chloride, white needle-like crystals and the chlorination of hydrated aluminas, respectively. On the other hand, in transition alumina systems, only one exothermic peak due to the chlorination of transition alumina appeared at 580–670°C. The relationship between the chlorination behavior and structure of transition aluminas was discussed.     

Thermoanalytical methods in detecting solid state photolysis reactions of [Co(NH3)5H2O]X*3

The solid state photolysis of [Co(NH₃)₅H₂O]X₃ compounds has been studied by reflectance spectroscopy and thermogravimetric analysis. The reflectance spectra have been transformed, in order to obtain a f(r) trend related to the absorbance exhibited by the compound, with the advantage of a more “significant” spectrum. The TG analysis of the compounds at different photolysis times shows that during the irradiation two different kinds of reactions take place: anation and/or photooxido-reduction. The extent of the two reactions is analysed and discussed.     

Bulk and surface analysis of Ti1–xFexO2/Fe2O3 composites prepared by solid state reaction for photocatalytic applications

Ti_1–xFe_xO₂ / Fe₂O₃ (x = 0.3, 0.6, and 0.7 wt%) composites were prepared by solid state reaction of the oxides TiO₂ (rutile phase) and Fe₂O₃ at 550 °C. The following techniques were applied for the characterization of the composites: X‐ray powder diffraction, Mössbauer spectroscopy, SEM, energy dispersive X‐ray spectroscopy and adsorption of nitrogen. The anatase/rutile/hematite ratio and the abundance of Fe³⁺ were quantified. The results indicate that Fe³⁺ substituted Ti⁴⁺ in the rutile structure and that the α‐Fe₂O₃ phase was predominantly on the surface of the crystalline Ti_1–xFe_xO₂ powders. A substantial increase of the materials density, with respect to rutile, favoured the application of the composites in photocatalytic experiments. The performance of the solids upon the photodegradation of aqueous solutions of carbofuran was evaluated. The Lewis sites created in the composites correlated directly with the photodegradation rate constant of carbofuran and the decrease of the total organic carbon content in the treated solutions. Copyright © 2011 John Wiley & Sons, Ltd.     

Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

The association reaction between silyl radical (SiH₃) and H₂O₂ has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH₃–H₂O₂ association in the temperature range 250–600 K, k(T) = 6.89 × 10^?13 T ^?0.163exp(?0.22/RT) cm³ molecule^?1 s^?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH₂(OH)₂ + H, is the major decomposition channel followed by secondary dissociation leading to SiO.     

Comparison of reduction behavior of Fe2O3, ZnO and ZnFe2O4 by TPR technique

Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature,regenerable,desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels.As a sort of effective desufurizer,such as Fe2O3,ZnO and ZnFe2O4,it will endure strong reducing atmosphere in desulfurization process.The reduced degree of desufurizer can have an effect on its desulfurization reactivity.In this paper,Fe2O3,ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH.After aging,washing and drying,the solids were calcined at 800℃.The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR).It is found that there are two reduction peaks for Fe203 in TPR,and whereas no reduction peaks for ZnO are found.The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3.ZnFe2O4 is easier to be reduced than Fe2O3.The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.     

用TiO2，ZnO及Fe2O3纳米粒子光催化氧化庚烷的反应

 制备了三种n－型半导体氧化物TiO2，ZnO和Fe2O3纳米粒子，用X射线衍射和N2吸附技术分别对它们的结构及比表面积进行了表征．考察了三种氧化物粒子对庚烷的气相光催化氧化反应的催化活性．研究表明，对于同种催化剂，随着焙烧温度的升高，催化剂的粒径增大，比表 面积减小，光催化活性下降．三种催化剂纳米粒子的光催化活性顺序为TiO2（锐钛矿）＞ZnO＞Fe2O3，金红石型TiO2粒子的催化活性低于ZnO粒子．结合能带理论探讨了三种催化剂光催化活性差异的原因．     

Synthesis of Fe3O4, Fe2O3, Ag/Fe3O4 and Ag/Fe2O3 nanoparticles and their electrocatalytic properties

Two important iron oxides:Fe3O4 and Fe2O3,as well as Fe3O4 and Fe2O3 nanoparticles mingling with Ag were successfully synthesized via a hydrothermal procedure.The samples were confirmed and characterized by X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).The morphology of the samples was observed by transmission electron microscopy(TEM).The results indicated Fe3O4,Fe2O3,Ag/Fe3O4 and Ag/Fe2O3 samples all were nanoparticles with smaller sizes.The samples were modified on a glassy carbon electrode and their elctrocatalytic properties for p-nitrophenol in a basic solution were investigated.The results revealed all the samples showed enhanced catalytic performances by comparison with a bare glassy carbon electrode.Furthermore,p-nitrophenol could be reduced at a lower peak potential or a higher peak current on a glassy carbon electrode modified with Ag/Fe3O4 or Ag/Fe2O3 composite nanoparticles.     

The effect of Fe2O3 dopants on electrophysical and sorption properties of ZnO

The effect of Fe₂O₃ dopants (0–0.8 mol.%) on ZnO conductivity and its chlorine chemisorption ability has been studied in the temperature range of 20–250 °C. Introduction of dopants increases the activation energy of ZnO conductivity and decreases the conductivity. The effective charge of the chemisorbed chlorine species as well as the strength of their bonding to the surface in samples containing Fe₂O₃ are considerably lower than in initial ZnO, which leads to a decrease of reactivity of the doped catalysts in chlorination.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1196–1199, July, 1993.     

Fe2O3/Al2O3氧载体制备方法的研究

采用溶胶-凝胶法、共沉淀法、水热合成法、低热固相合成法、机械混合法、燃烧合成法和冷冻成粒法制备铁基氧载体Fe₂O₃/Al₂O₃,并通过物理和化学表征手段来筛选和优化制备方法和制备工艺。对煅烧后的氧载体进行硬度测试,结果表明,溶胶-凝胶法、共沉淀法、机械混合法、燃烧合成法和冷冻成粒法制备的氧载体硬度较高;载体的X射线衍射(XRD)谱图表明,各种制备方法均能制得物相组成为Fe₂O₃/Al₂O₃的氧载体,且随着煅烧温度的提高、煅烧时间的延长,氧载体的结晶度、晶体粒径逐渐增大,煅烧温度1 200℃的氧载体的机械性能、晶体结构、晶相组成更稳定。借助化学吸附仪的程序升温还原(TPR)实验表征氧载体的反应活性,并计算氧载体活性度。综合物理和化学表征实验结果表明,最优制备方法为溶胶-凝胶法和冷冻成粒法。     

Kinetic study of the reaction between Fe2+-oxalate and 2,6-dichlorophenolindophenol

Ascorbic acid present in natural products is often analyzed by its reducing effect on 2,6-dichlorophenolindophenol (DCPI). In case of coexistence of Fe(II) in natural samples and if oxalic acid is used for their extraction and stabilization, a significant interference is observed. The reaction of Fe²⁺ with 2,6-dichlorophenolindophenol (DCPI) in acidic solutions in the presence or absence of oxalate ions was investigated. The reaction was studied with a Stopped-Flow Spectrophotometer (S.F.S) equiped with a data acquisition system, which allows the determination of initial rates and reaction rate constants. Results for the effect of the concentrations of all the reagents of the reaction are presented. During the experimental work all concentrations of the reagents were kept in such levels to make the reaction first-order in respect of DCPI. An interesting finding is, that, although Fe²⁺ and C₂O₄²⁻ ions do not react separately with DCPI (or react very slowly), they react very rapidly in mixtures and show a strong synergetic effect. The experimental data fit with the mechanism of the formation of intermediates FeC₂O₄ and [Fe(C₂O₄)₂]²⁻. The proposed rate law agrees with the above mechanism and the experimental results. The value k_c=(1.6±0.2)×10⁵ M⁻¹·s⁻¹ was calculated for the second-order rate constant of the reaction of FeC₂O₄ and DCPI. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 941–948, 1998     

A study of the formation of CuAl2O4 from CuO and Al2O3 by solid state reaction at 1000°C and 950°C

The formation of the spinel CuAl₂O₄ from the oxides CuO and Al₂O₃ has been studied at 1000 and 950°C in air by measuring the fraction reaction completed as a function of time. In the experiments the molar oxide ratios were CuO/Al₂O₃ = 0.5, 1.0 and 2.0 and the grain size for CuO was 1–3 μ throughout while for Al₂O₃ fractions of 40–60 μ, 71–100 μ and 100–125 μ, were used. The rate of reaction could be explained quite well assuming a three-dimensional diffusion mechanism.     

Anion influence on the hydrated oxides formed by Fe3+ and Fe2+ precipitation

The anion influence on the hydrated oxides formed by Fe³⁺ and Fe²⁺ precipitation simulating the aqueous radioactive waste treatment has been investigated by Mössbauer spectroscopy. Fe₃(SO₄)₂, Fe(NO₃)₃, FeCl₃, FeSO₄ and FeCl₂ were used as iron sources and neutralized by NaOH. The obtained products contain several kinds of amorphous and/or poorly crystallized hydrated oxides, depending on the anion type which exists in solution and on the initial iron valence. The pH influence on the final precipitate is taken into account.     

Thermoanalytical study of cyclization reaction of some thioureates

Thermal initiated conversion of N-aryl-N'-(2-benzylpyridinium)thioureates into 2-arylamino-4H-benzo[d][1,3]thiazines was studied by non-isothermal differential scanning calorimetry (DSC), thermogravimetry (TG) and differential thermal analysis (DTA) in the solid-state. The values of molar reaction ethalpies (DH _r) of six derivatives of thioureates and the melting parameters (T _f, DH _f, DS _f) of the obtained products - benzothiazines were determined by the DSC method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of the solid solution of MoO3 in Fe2V4O13

Differential thermal and phase X-ray analyses have shown that MoO₃ and Fe₂V₄O₁₃ form a solid substitution solution, in which Mo⁶⁺ ions are incorporate into the crystal lattice of Fe₂V₄O₁₃ in place of V⁵⁺ ions. The solubility limit of MoO₃ in Fe₂V₄O₁₃ at ambient temperature is 18 mole % of MoO₃. The phase equilibria in the system Fe₂V₄O₁₃-FeVMoO₇, were also studied. Results are presented in the form of a phase diagram.

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Zusammenfassung Durch DTA und Röntgenphasenanalyse wurde gezeigt, daß MoO₃ und Fe₂V₄O₁₃ Substitutionsmischkristalle bilden, in denen Mo⁶⁺-Ionen anstelle von V⁵⁺-Ionen in das Kristallgitter von Fe₂V₄O₁₃ eingebaut sind. Die Löslichkeitsgrenze von MoO₃ in Fe₂V₄O₁₃ beträgt bei Umgebungstemperatur 18 Mol-% MoO₃. Ebenfalls wurden die Phasengleichgewichte im System Fe₂V₄O₁₃-FeVMoO₇ untersucht. Die Ergebnisse sind in Form eines Phasendiagramms dargestellt.

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- , ₃ Fe₂V₄O₁₃ , o⁶⁺ V^5– Fe₂V₄O₁₃. ₃ Fe₂V₄O₁₃ 18 %. Fe₂V₄O₁₃-FeVMoO₇ .

     

Variational transition‐state theory study of the atmospheric reaction OH + O3 → HO2 + O2

We report variational transition‐state theory calculations for the OH + O₃→ HO₂ + O₂ reaction based on the recently reported double many‐body expansion potential energy surface for ground‐state HO₄ [Chem Phys Lett 2000, 331, 474]. The barrier height of 1.884 kcal mol^?1 is comparable to the value of 1.77–2.0 kcal mol^?1 suggested by experimental measurements, both much smaller than the value of 2.16–5.11 kcal mol^?1 predicted by previous ab initio calculations. The calculated rate constant shows good agreement with available experimental results and a previous theoretical dynamics prediction, thus implying that the previous ab initio calculations will significantly underestimate the rate constant. Variational and tunneling effects are found to be negligible over the temperature range 100–2000 K. The O₁? O₂ bond is shown to be spectator like during the reactive process, which confirms a previous theoretical dynamics prediction. © 2007 Wiley Periodicals, Inc. 39: 148–153, 2007     

Study on preparation of S2O8 2−/Fe2O3-SiO2 solid acid and its catalytic activity

The precursors of Fe₂O₃-SiO₂ mixed oxides prepared through co-precipitation method were modified by microwave hydrothermal treatment for the first time. S₂O₈ ²⁻/Fe₂O₃-SiO₂ solid acids were formed after being impregnated by (NH₄)₂S₂O₈ solution and calcined at high temperature. The samples were characterized by XRD, TEM, N₂ adsorption/desorption methods. It was found that the presence of SiO₂ obviously retarded the formation and growth of Fe₂O₃ crystals. Catalyst with appropriate specific surface area and narrow pore size distribution was obtained. The catalytic activities of the solid acids were evaluated by esterification of acetic acid and butanol and the results were compared with those catalysts prepared at normal conditions. The results showed that catalytic activity was extensively improved by microwave hydrothermal treatment. __________ Translated from Chinese Journal of Applied Chemistry, 2005, 22(8) (in Chinese)