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1.
The effect of the mechanoactivation on UO3 and U3O8 in agate or stainless steel vessels in air or in toluene is studied. UO2(OH)2 is the main product of UO3·H2O activation in steel vessel in air. The presence of toluene leads to strong amorphization and dispersity increase and, probably, to the formation of U2O5. The activation of U3O8 leads to its reduction to U3O7 which relative content in the reaction mixture depends on the mechanoactivation conditions.  相似文献   

2.
The reaction of MoO3 with various oxides of manganese (MnO, Mn2O3, Mn3O4 and MnO2) and with MnCO3 has been studied in air and nitrogen atmospheres employing DTA, TG and X-ray diffraction methods, with a view to elucidating the conditions for the formation of MnMoO4. Thermal decomposition of MnCO3 has also been studied in air and nitrogen atmospheres to help understand the mechanism of the reaction between MnCO3 and MoO3. The studies reveal that, whereas MnO, Mn2O3 and MnO2 react smoothly with MoO3 to form MnMoO4, Mn3O4 does not react with MoO3 in the temperature range investigated (48O–6OO°C). An equimolar mixture of MnCO3 and MoO3 reacts in air to yield MnMoO4, while only a mixture of Mn3O4 and MoO3 remains as final product when the same reaction is carried out in nitrogen. Marker studies reveal that manganese ions are the main diffusing species in the reaction between MoO3 and manganese oxides that result in MnMoO4.  相似文献   

3.
为研究重铬酸钠(Na2Cr2O7)对CO2溶解的影响, 本文在带有搅拌的气液相高压平衡釜内, 采用静态法测定了温度在313.2-333.2 K, 压力在0.1-1.9 MPa 范围内, 重铬酸钠浓度分别为0、0.361、0.650、0.901 mol·kg-1 时, CO2 在Na2Cr2O7溶液中的溶解度. 结果表明: (1) Na2Cr2O7对CO2 的溶解有盐析效应; (2) CO2 在Na2Cr2O7溶液中的溶解符合亨利定律, 并且CO2溶解度是温度和Na2Cr2O7浓度的函数, 且用改进的Setschenow方程和Peng-Robinson-Pitzer (PR-Pitzer)方程拟合了在此温度、压力及重铬酸钠浓度范围内的实验数据, 拟合效果较好, 并且其平均相对误差分别为4.24%和3.32%.  相似文献   

4.
The effects on the thermal properties and bioactivity of the substitution of CaO by La2O3, Y2O3 and Al2O3 in a glass of composition CaO·SiO2 were studied and compared. The trivalent metal oxides were all effective in raising the glass transformation and softening temperatures when they replaced CaO in the glass of composition CaO·SiO2. The experimental results suggest that Al2O3 plays the role of a glass-former, while La2O3 and Y2O3 behave as glass-modifiers. The tendency to devitrify appears to be the lower, the farther the glass composition is from those of the crystalline phases, owing to the need for diffusion over longer distances, the greater the composition difference. The substitution with the trivalent metal oxides is detrimental to the bioactivity, which is preserved only in the event of very small degrees of substitution. The most negative role appears to be played by Al2O3. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

5.
The method of laser photoelectron emission from metals in electrolyte solutions has been used to measure the rate constants w3 for the electrochemical reduction of simple organic radicals R to carbanions R. The following empirical rule has been established: the changes in the standard redox potential E° for R/R in series of organic radicals are equal to the changes in the potential corresponding to individual values of w3. On the basis of this rule and the value of E° for CH3 /CH3 E° values were obtained for C2H5, n-C3H7, n-C4H9, CH2OH, CH3CHOH, (CH3)2COH, CH2Cl, CHF2, CHFCl, CHCl2, CF2Cl, CFCl2, CF3, CCl3, C6H5, C6Cl5, and a scale of pK for the CH acids conjugate to R. Consideration is given to the nature of the changes in E° and pK on passing from aqueous solutions to solutions in water-dioxane mixtures and in acetonitrile.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1508–1514, July, 1990.  相似文献   

6.
The discovery of the unusual ability of Ca- and Mg-containing silicates in certain grinding regimes to absorb carbon dioxide from the environment in amounts comparable to the mass of the ground sample has stimulated interest in the study of mechanochemical effects. The range of objects for studying natural minerals, such as labradorite (CaAl2Si2O8)0.562(NaAlSi3O8)0.438, oligoclase (CaAl2Si2O8)0.148(NaAlSi3O8)0.852, diopside CaMgSi2O6, and akermanite Ca2MgSi2O7, as well as synthetic minerals gehlenite Ca2Al2SiO7 and wollastonite CaSiO3, is expanded to develop the model of deep mechanosorption of CO2 and to derive equations that allow the kinetic analysis of the absorption of carbon dioxide by silicates in the course of mechanochemical activation to be performed. Regularities revealed previously and analogies to the processes that occur upon the dissolution of carbon dioxide in silicate melts, are generalized. Data on the absorption of carbon dioxide by Ca- and Mgcontaining silicates and alumosilicates, depending on the duration of mechanochemical activation in an AGO-2 centrifugal planetary mill in the atmosphere of CO2 at a pressure of 105 Pa, are obtained. Based on the data of X-ray phase analysis and IR spectroscopy, structural chemical changes in minerals and the forms of carbon dioxide in mechanochemically activated samples are discussed. It is shown that the intense penetration of gas molecules in particle bulk and their “dissolution” in structurally disordered silicate matrix in the form of distorted CO 3 2? ions occurs upon mechanosorption.  相似文献   

7.
Ortho-phenylene-bridged phosphinoborane (2,6-Cl2Ph)2B-C6H4-PCy2 1 was synthesized in three steps from commercially available starting materials. 1 reacts with H2 or H2O under mild conditions to form corresponding zwitterionic phosphonium borates 1-H2 or 1-H2O . NMR studies revealed both reactions to be remarkably reversible. Thus, when exposed to H2, 1-H2O partially converts to 1-H2 even in the presence of multiple equivalents of water in the solution. The addition of parahydrogen to 1 leads to nuclear spin hyperpolarization both in dry and hydrous solvents, confirming the dissociation of 1-H2O to free 1 . These observations were supported by computational studies indicating that the formation of 1-H2 and 1-H2O from 1 are thermodynamically favored. Unexpectedly, 1-H2O can release molecular hydrogen to form phosphine oxide 1-O . Kinetic, mechanistic, and computational (DFT) studies were used to elucidate the unique “umpolung” water reduction mechanism.  相似文献   

8.
Non-precious metal bifunctional catalysts are of great interest for metal–air batteries, electrolysis, and regenerative fuel cell systems due to their performance and cost benefits compared to the Pt group metals (PGM). In this work, metal oxides of La0.1Ca0.9MnO3 and nano Co3O47 catalyst as bifunctional catalysts were used in oxygen reduction and evolution reactions (ORER). The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption isotherms. The electrocatalytic activity of the perovskite-type La0.1Ca0.9MnO3 and Co3O4 catalysts both as single and mixtures of both were assessed in alkaline solutions at room temperature. Electrocatalyst activity, stability, and electrode kinetics were studied using cyclic voltammetry (CV) and rotating disk electrode (RDE). This study shows that the bifunctional performance of the mixed La0.1Ca0.9MnO3 and nano Co3O4 was superior in comparison to either La0.1Ca0.9MnO3 or nano Co3O4 alone for ORER. The improved activity is due to the synergistic effect between the La0.1Ca0.9MnO3 and nano Co3O4 structural and surface properties. This work illustrates that hybridization between these two metal oxides results in the excellent bifunctional oxygen redox activity, stability, and cyclability, leading to a cost-effective application in energy conversion and storage, albeit to the cost of higher catalyst loadings.  相似文献   

9.
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.  相似文献   

10.

Spectrophotometric method was used to study the kinetics of the process in which aqueous solutions of selenurea of various compositions are oxidized. Significant differences between the stabilities of selenurea solutions were revealed in relation to the selenurea concentration and also to the acidity, or alkalinity of a medium. It was shown that the stability of selenurea solutions is affected by additives of various antioxidants: sodium sulfite Na2SO3, ascorbic acid C6H8O6, hydroxylamine chloride NH2OH·HCl, hydrazine hydrate N2H4·H2O, and tin chloride SnCl2·2H2O. It was found that using a 1 : 1 mixture of antioxidants Na2SO3 and C6H8O6 substantially raises their antioxidant activity and stabilizes the aqueous solutions of selenurea during up to five days. A hydro-chemical precipitation in the acetate—ethylenediamine reaction system in the presence of the antioxidants under study was used to obtain lead selenide films of stoichiometric composition with thicknesses of 230?670 nm. With the Na2SO3 + C6H8O6, Na2SO3, C6H8O6, and SnCl2 antioxidants used to stabilize selenurea solutions, a tendency is observed toward a decrease in the lattice constants of PbSe films from 6.1531 ± 0.0003 to 6.1367 ± 0.0002 Å, an increase in the share of nanosize particles, and rise in the PbSe energy gap width from 0.78 to 1.0 e V.

  相似文献   

11.
采用晶种法直接合成了硅铝比(SiO_2/Al_2O_3物质的量比)为137、224和309的三种Al-ITQ-13分子筛,并采用粉末X射线衍射(XRD)、扫描电镜(SEM)、N_2吸附-脱附、固体核磁共振(MAS NMR)和NH_3-程序升温脱附(NH_3-TPD)等分析方法对不同硅铝比分子筛进行了表征,并在固定床微型反应评价装置上,考察了硅铝比对甲醇转化制丙烯反应性能的影响。结果表明,不同硅铝比Al-ITQ-13分子筛呈现出相似的织构性质,酸量及酸强度随着硅铝比的升高逐渐下降。硅铝比对甲醇转化反应的产物分布存在较大的影响;随着硅铝比的升高,氢转移反应和芳构化反应活性降低,使得乙烯选择性下降,而丙烯和丁烯的选择性升高。硅铝比由137提高到309,丙烯的选择性(质量分数)由46.04%增加到55.52%,而丙烯/乙烯比由3.39提高到6.57。  相似文献   

12.
The crystallisation kinetics of experimental glasses in 3 different systems: (A) Li2O–SiO2, (B) Li2O–Al2O3–SiO2 and (C) Li2O–K2O–Al2O3–SiO2 were studied under non-isothermal conditions. The DTA results revealed a stronger tendency to crystallisation of binary compositions in comparison to the ternary and quaternary compositions comprising Al2O3 and K2O which present the lower crystallisation, i.e. the crystallisation propensity follows the trend A > B > C. The devitrification process in the Li2O–SiO2 and Li2O–Al2O3–SiO2 systems began earlier and the rate was higher in comparison to that of glasses in the quaternary Li2O–K2O–Al2O3–SiO2 system. Thus, addition of Al2O3 and K2O to glasses of Li2O–SiO2 system was demonstrated to promote glass stability against crystallisation. However, the activation energy for crystallisation was shown to depend also on the SiO2/Li2O ratio with the binary system showing a decreasing trend with increasing SiO2/Li2O ratio, while the opposite tendency was being observed for compositions with added Al2O3 and K2O.  相似文献   

13.
A series of mono-bipy and -phen complexes (bipy = bipyridine, phen = phenanthroline) of the perhalodisilanes, Si2F6, Si2Cl6 and Si2Br6, mixed methylhalodisilanes (Si2MenX6?n, X = Cl, I; n = 2,3) and Si3Cl8 · bipy have been prepared by reaction of the components, and have been characterized. 11 complexes are obtained exclusively.The structures of all complexes involve coordination of the base to the more acidic silicon and perpendicular alignment of the SiSi axis on the plane of the ligand. This may be rationalised in terms of steric requirements of the different groups, the more demanding groups occupying the sterically more favorable positions vertical to the plane of the ligand. For Si3Cl8 · bipy, spectroscopic and chemical evidence suggests bipy-coordination to the center silicon. PMR investigations of the dissociation equilibria of the complexes in solution led to determination of the heats of formation of four of the complexes and to a qualitative estimation of the relative acceptor strengths of several disilanes. Contrary to expectation, silyl groups increase the acceptor strength of silicon considerably and in the order SiMe3 < SiMe2Cl < SiMeCl2 < SiCl3. The effect of a SiMe3, substituent group may be compared to that of Cl. Methylchlorosilyl groups may exceed the effect of Cl as indicated by the increase in acceptor strength in the sequence (R =) Me < Ci < SiMe2Cl < SiMeCl2 for the acceptor RSiCl2Me. Si3Cl8 is the strongest acceptor in the series. Assuming the structural suggestion for Si3Cl8 · bipy (center coordination) to be correct an increase in acceptor strength is indicated in the sequence SiCl3(Si2Cl5) < SiCl2(SiCl3)2 (Si = coordinating center). This may be interpreted mainly in terms of charge accepting capacity of the polarisable silyl groups. Another interesting sequence of acceptor strengths measured in this work is 1,1,2-Si2Me3F3, 1,2-Si2Me2F4 < Si2Me3Cl3 < 1,2-Si2Me2Cl4, showing fluorodisilanes to be weaker acceptors than chlorodisilanes. This result is compared to the heats of formation of SiX4 · 2py complexes.  相似文献   

14.
Extraction of plutonium(IV) from aqueous sulfuric and sulfuric-nitric acid into di-2-ethylhexyl phosphoric acid (HY) in the diluents n-dodecane, toluene or chloroform has been investigated. The composition of the Pu(IV) species extracted from H2SO4 was found to be PuH2Y6, which changed to Pu(NO3)H2Y5 and Pu(NO3)2H2Y4 with increasing concentration of nitrate ion in the aqueous medium. These three species can be represented as PuY2(HY2)2, Pu(NO3)Y(HY2)2 and Pu(NO3)2(HY2)2, respectively, where Y represents the anion of monomeric HY, and HY2 the anion of dimeric H2Y2. Synergism in the extraction of Pu(IV) by the addition of thenoyltrifluoroacetone (HTTA) to HY was also investigated and attributed to extraction of the additional species, Pu(TTA)Y(HY2)2 and Pu(TTA)2(HY2)2. The addition of the neutral extractant tri-n-octylphosphine oxide (TOPO) to HY did not result in synergism in the extraction of Pu(IV) from aqueous sulfuric acid. With aqueous nitric acid under similar conditions, however, synergism was observed. The possible equilibria in these systems were identified and the corresponding equilibrium constants were determined.  相似文献   

15.
Benzene, toluene, and nitrobenzene interact rapidly with NF4BF4 in anhydrous HF to give, almost exclusively, fluorine substituted aromatic derivatives. Up to four hydrogens can be replaced in a rapid reaction, before a much slower addition reaction takes over. The direction of the substitution in C6H6, C6H5CH3 and C6H5NO2 and the lack of side chain fluorination in C6H5CH3 support an electrophillic substituion mechanism. These rapid substitution reactions are followed by much slower fluorine addition reactions to give the corresponding cyclo-hexadienes and -hexenes. These addition reactions were also studied separately using tetra-, penta- and hexa- fluorobenzene as the starting materials. In these addition reactions, almost no hydrogen substitution occured. The addition of the first pair of fluorines always gave 1,4-cyclohexadienes in which CF2 group was adjacent to hydrogen on the ring. The addition of the second pair of fluorines resulted in the formation of cyclohexenes. These reactions occured in high yield and offer a controlled, high yield path to dienes. All products were characterized spectroscopically and by comparison to literature data.  相似文献   

16.
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。  相似文献   

17.
Gaseous products evolved from (NH4)2SO4, NH4HSO4 and NH4NH2SO3 during successive heating and cooling cycles were flushed with inert gas into analyzer Dräger tubes hooked tightly to the terminal port of the DSC cell base. This simple procedure allowed the starting temperature of the decomposition to be determined and the amount of the individual gases in the mixture to be identified and even estimated. NH4NH2SO3 at 523 K in humid air produced HNH2SO3 initially and, on further cycling, (NH4)2SO4 and NH4HSO4 also appeared. The ΔHf values for NH4HSO4 were (kJ mole?1): in an airtight sample holder 12.67, in a dry argon atmosphere 11.93, and in a static air atmosphere 10.92. Endothermic peaks for (NH4)2SO4 and 498 and 411 K represented the incongruent melting point and the polymorphic transition of (NH4)2SO4·NH4HSO4. After the first heating in air to 530 K, (NH4)2SO4 and NH4HSO4 exhibited closely similar cyclic DSC curves. The endothermic peaks at about 393–420 K may be assigned to different combinations of (NH4)2SO4 and NH4HSO4.  相似文献   

18.
Although oxygenated fuel additives are effective in reducing soot emissions, the extent to which molecular structure of the oxygenate plays a role in soot reduction has remained unclear and controversial. To gain a deeper insight in this field, a detailed chemical kinetic modeling approach was used to examine the phenomenon of suppression of sooting by the addition of oxygenated hydrocarbon species to the fuel. For this task, the PREMIX code in conjunction with Chemkin II and models resulting from the merging of validated kinetic schemes describing the oxidation of the components of the n-butanol-benzene mixtures were used to investigate the effect of n-butanol addition on the formation?depletion of acetylene recognized as soot precursor in flames under fuel-rich conditions. The first part of this study treats the dependence of the soot precursor amounts on n-butanol percentage in the fuel mixture, whereas the second part defines the key reaction mechanisms responsible for the observed reduction in C2H2 and consequently in polycyclic aromatic hydrocarbons and soot amounts induced by the oxygenate additive. The principal objective of the current study was to obtain fundamental understanding of the mechanisms through which the oxygenate compound affects the soot precursor amounts. The modeling results indicated that there was a dramatic decrease in the acetylene peak height with the addition of the oxygenated addtitive. This finding was found to be due to the increase in the C2H2 consumption rates induced by n-butanol addition. Finally, the modeling results provided evidence that n-butanol played a role in changing acetylene formation mechanism by enhancing the role of C3H4P, C3H4 and aC3H5 and by eliminating the role of C6H4, C5H5, C5H6, H2CCCCH, C4H2, C5H4O, C2H, CHCHCHO, H2C4O and C4H4.  相似文献   

19.
Pseudo-first-order rate constants, kobs, for the alkaline hydrolysis of N-hydroxyphthalimide, 1, at 0.02 M NaOH and 30°C remain essentially independent of the total concentration of C12E23, [C12E23]T, at ≤0.005 M C12E23. The increase in [C12 E23]T from 0.005 to 0.015 M causes a nonlinear decrease in kobs. The rate of hydrolysis becomes either too slow or the change in absorbance values becomes significantly small to allow a reliable observed data fit to a first-order kinetic equation at ≥0.020 M C12E23 in the absence and presence of total concentration of cetyltrimethylammonium bromide, [CTABr]T ranging from 0.003 to 0.020 M. The values of fraction of nonionized 1, FSH, obtained at reaction time t = 0 and 0.02 M NaOH, remain ~0 at ≤0.010 M C12E23 while they increase from 0.39 to 0.89 with the increase of [C12E23]T from 0.015 to 0.10 M. The values of kobs show a nonlinear decrease of ~5-fold with the increase of [C12E23]T from 0.0 to 0.010 M in the presence of 0.02 M NaOH and [CTABr]T range of 0.003 to 0.020 M. The values of FSH remain ≤~0.10 at ≤0.015 M C12E23 while they vary between 0.40 and 0.90 within a [C12E23]T range 0.02 to 0.05 M in the presence of 0.02 M NaOH and [CTABr]T ranging from 0.003 to 0.020 M. The values of FSH represent the fraction of nonionized 1 trapped almost irreversibly by pure C12E23, and mixed C12E23–CTABr micelles.  相似文献   

20.
富氧条件下乙炔选择催化还原NOx   总被引:1,自引:0,他引:1  
于姗姗  王新平  王崇  徐岩 《中国化学》2006,24(5):598-602
Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 (C2H2-SCR) was investigated over a series 08% C2H2, and 9.95% O2 (volume percent) in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.  相似文献   

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