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31.
The acid dissociation constants of 1,2-bis(cis-aminophenoxy)ethane-N,N,N′,N′;-tetraacetic acid (H4BAPAT or H4Z), and the stability constants of its chelates with tripositive rare-earth metal ions have been determined by the potentiometric titration and mercury indicator electrode methods at 15°, 25′ and 35°C and an ionic strength of 0.1 (KNO3). The existence of a monohydrogen chelate species, LnHZ, and the normal chelate, LnZ?, is illustrated. Enthalpy and entropy changes characterizing the formation of the normal chelates and the dissociation of the last two protons of chelating acid have been calculated at 25°C. These functions have been compared with corresponding values for related chelating agents. 相似文献
32.
Elena V. Frolova M. Ivanovskaya V. Sadykov G. Alikina A. Lukashevich S. Neophytides 《Progress in Solid State Chemistry》2005,33(2-4):317-325
Structural peculiarities of Ce–Zr–La–O and Ce–Zr–La–O/Ru samples in mean of catalytic properties are compared. The samples (Ce:Zr = 1:1, La = 10÷30 mol.%, Ru = 1.5 wt.%) were obtained by sol–gel method (X-samples) and co-precipitation (P-samples). It is shown that Ce0.45Zr0.45La0.1O2−δ/Ru X-samples are characterized by high thermal stability and the highest catalytic activity in partial methane oxidation reaction. According to XRD, BET, FTIR, EPR and XPS data it is concluded that the difference in the samples catalytic activity is caused by various disposition of Ru-containing phase on the support surface. The distinction in the dimension of Ru-containing particles (3D or 2D) is conditioned by structural peculiarities of Ce0.45Zr0.45La0.1O2−δ and Ce0.35Zr0.35La0.3O2−δ P- and X-samples. 相似文献
33.
Stefan?DiethelmEmail author Joseph?Sfeir Frank?Clemens Jan?Van herle Daniel?Favrat 《Journal of Solid State Electrochemistry》2004,8(9):611-617
Dense planar and tubular oxygen separation membranes of La0.6Ca0.4Fe0.75Co0.25O3– were investigated as reactors for the partial oxidation (POX) of methane to syngas. Their permeation properties were measured in an air/argon
pO2 gradient as a function of temperature. At 900 °C, the oxygen flux through a 1.26-mm-thick membrane was 0.075 mol/cm2·s and through a 0.25-mm-thick tube, 0.24 mol/cm2·s.For the POX measurements, a catalyst was added to the membrane and methane was introduced on the argon side. This resulted in a gradual increase of the oxygen flux with increasing concentration of methane, reaching 2 mol/cm2·s at 900 °C with pure methane. For the planar reactor, the CO selectivity reached 99% and the CH4 conversion 75% at 918 °C with pure methane. For the tubular reactor, the CO selectivity and CH4 conversion were 83 and 99%, respectively, under the same conditions. After 1,400 h of operation in a tubular POX reactor, the membrane was examined revealing phase demixing and local decomposition.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
34.
The silver iodate(VII), Ag5IO6, was obtained by reacting a stoichiometric mixture of Ag2O and KIO3, at elevated oxygen pressure, adding a small portion of distilled water. The synthesis was done at 673 K and 270 MPa of oxygen pressure. The crystal structure was solved by direct methods based on single crystal diffraction data ( , Z = 6, a = 5.9366(1), c = 32.1471(6) Å, 323 independent reflections, R1 = 2.31 %). According to conductivity measurements, Ag5IO6 is semiconducting with a specific resistance of 0.08 Ωcm at 300 K. The activation energy was determined as 7.4(1) meV in the temperature range of 220 – 300 K, and 4.3(1) meV in the temperature range of 90 – 180 K. The optical band gap for Ag5IO6 is 1.4 eV. Ag5IO6 is diamagnetic with a magnetic susceptibility of ?4.4×10?4 emu/mol. 相似文献
35.
纳米碳管电极上氧的电催化还原 总被引:5,自引:0,他引:5
以聚四氟乙烯为粘结剂制成了多壁纳米碳管(MWNT)电极.采用恒电位阶跃法和循环伏安法研究了MWNT电极在碱性溶液中的电化学行为,并对碱性溶液中溶解氧在该电极上的电化学还原行为进行了研究.实验结果表明: MWNT电极具有比石墨电极更高的孔隙率和电化学表面积;MWNT电极上O2还原成的反应为准可逆过程;在5~50 mV•s-1的扫描速率范围内,阴极峰电流与扫描速度成线性关系,表明MWNT电极上O2还原成的反应受吸附控制;对碱性溶液中的氧还原反应, MWNT比石墨具有更高的催化活性. 相似文献
36.
Capillary zone electrophoresis with UV detection was used for determination of dissociation constants of alkaloids sanguinarine and chelerythrine. Despite the limited solubility of the uncharged forms of the alkaloids resulting in insufficient analytical signal at higher pH the reliable dissociation constants were obtained when acidified samples containing low amount of the alkaloid were injected into the capillary. The precipitation of the alkaloid in the capillary induced by injecting sample of low pH into the background electrolyte of higher pH does not affect the mobility of the alkaloid if its concentration injected exceeds the solubility only to a small extent. Dissociation constants (pK(R+)) of sanguinarine and chelerythrine calculated to 8.3 +/- 0.1 and 9.2 +/- 0.1, respectively, are relevant to Good buffers of ionic strength of 30 mM. 相似文献
37.
Jorge Pavez Maritza Páez Armelle Ringuedé Fethi Bedioui José H. Zagal 《Journal of Solid State Electrochemistry》2005,9(1):21-29
We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O2) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O2 reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O2 to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy. 相似文献
38.
E Gaudin 《Journal of solid state chemistry》2003,175(1):124-131
The compound La2Ca2MnO6(O2) has been synthesized from La2Ca2MnO7 heated at 1123 K under high pressure (4 GPa) with KClO3 as oxygen source. The crystal structure has been refined from X-ray powder data in the space group. The unit-cell parameters are a=5.6335(2) Å and c=17.4879(8) Å. Perpendicular to the c-axis, the structure is built up by the periodic stacking of two close packed [LaO3] layers separated by a layer of composition [Ca2O2] containing (O2)2− peroxide ions. This oxide belongs to the family of compounds formulated as [A′2O2−δ][AnBn−1O3n] for n=2 and δ=0. It is the first member of the series where the thickness of the perovskite slab corresponds to one [BO6] (B=Mn) octahedron. The structural relationships with La2Ca2MnO7 are discussed and the magnetic properties show that in both phases manganese is tetravalent. 相似文献
39.
40.