Mass transport in gas channels of electrochemical cells with a solid-oxide electrolyte: Allowing for the electrode reaction rates in numerical calculations

The concentration fields, Nusselt number distributions along the electrode, and ratios of concentrations of electrochemically active components at the entrance into and exit out of an electrochemical cell are determined by numerical integration of the convective-diffusion equation for a broad range of rate constants of electrode reactions, Peclet numbers, and geometrical parameters of channels. Three regions of parameter values are revealed. At low reaction rates (K _l < 0.5), mass transfer is completely determined by electrode kinetics; at high rates (K _l > 20), it is completely determined by the diffusion in the gas phase; and in the intermediate region of values of K _l it is necessary to allow for both the diffusion processes and the electrode reactions.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 317–324.Original Russian Text Copyright © 2005 by Ezin, Somov.     

电化学氟化的新进展

电化学氟化是利用电极反应将氟直接引入有机或无机物的一种重要方法。有机物的电化学氟化方法有两种: 一是Simons于1941年发明的, 用镍作阳极, 在无水氟化氢溶液中, 电解制备全氟化合物的方法。此方法在近年来有不少改进。另一是1970年Rozhkov提出的, 以有机溶剂(如含Et3N.3HF的MeCN)为介质, 在铂阳极上,氧化得到单氟化产物的方法。本文全面地综述了这两种方法, 并着重于最新民发展。     

Application of Nafion／Cobalt Hexacyanoferrate Chemically Modified Electrodes for the Determination of Electroinactive Cations by Ion Chromatography

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｉｏｎｃｈｒｏｍａｔｏｇｒａｐｈｙ (ＩＣ)ｈａｓｂｅｅｎｒｅｃｏｇｎｉｚｅｄａｓａｕｓｅｆｕｌｍｅｔｈｏｄｆｏｒｔｈｅｓｅｐａｒａｔｉｏｎｏｆｉｎｏｒｇａｎｉｃａｎｉｏｎｓａｎｄｃａｔｉｏｎｓｓｉｎｃｅｉｔｓｉｎｔｒｏｄｕｃｔｉｏｎｂｙＳｍａｌｌｅｔａｌ .ｉｎ 1975 .1ＡｓｉｇｎｉｆｉｃａｎｔｔｒｅｎｄｉｎｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆＩＣｍｅｔｈｏｄｉｓｓｅａｒｃｈｆｏｒｓｅｎｓｉｔｉｖｅａｎｄｕｎｉｖｅｒｓａｌｄｅｔｅｃｔｉｏｎｍｅｔｈｏｄｓ .Ｔｈｅｍａｉｎｄｅｔ…     

Electrochemical detector with a 20 nl volume for micro-columns liquid chromatography

Summary A flow-through two electrode wall-jet cell with a platinum measuring electrode and a cell volume of 20 nl has been designed and evaluated. It has been used to detect phenols by reversed phase liquid chromatography using short micro bore columns. The linear dynamic range between the measured current and the concentration is greater than 10³ (1.5×10^–7–5×10^–4 mol/l) and the minimum analyzable amount was found to be 10 pg for pyrocatechol. A negligible broadening in the detector permits the use of micro columns down to 0.5 mm internal diameter, packed with 5 m particles, without any substantial distortion of eluted zones.Presented at the 14th International Symposium on Chromatography London, September, 1982     

壳聚糖作用下一步法合成具有高电活性的AgCl@聚苯胺核壳结构

在壳聚糖的作用下，采用简单的一步法合成了具有星状结构的氯化银/聚苯胺核壳型复合材料。当壳聚糖的浓度为1%时，所制备的氯化银/聚苯胺复合材料具有高度的分散性，壳层厚度为30～80 nm、核的直径在25～60 nm范围内。通过透射电镜、红外光谱和X-射线衍射对样品的形态和组成进行了表征。循环伏安实验结果表明这种复合材料在中性条件下具有很好的电化学活性。     

主族元素取代的11-钨铜杂多配合物的合成、表征及性质研究

合成了ⅡA,ⅣA,ⅤA族元素为取代原子的3个系列钨铜杂多配合物.经ICP,TG曲线确定其化学式为K8[CuZ(OH2)W11O39].xH2O和K17,18[Z′(CuW11O39)2].xH2O(Z=Mg,Ca;Z′=Sr,Ba,Sn,Pb,Sb,Bi).通过TG-DTA,IR,XRD,XPS,183W-NMR等手段对合成配合物结构进行了表征,并对其进行了讨论.结果表明,新配合物具有典型的Keggin结构,且主族元素进入到配合物的骨架中.由于新配合物中CuⅡ具有顺磁性,导致XPS,183W-NMR的测试结果表现出特殊性;用循环伏安法测定了新配合物的电化学性质,表明均为可逆氧化还原过程,还对导电性和热稳定性进行了研究.     

New organic metals: Radical cation salts of bis(ethylenedioxo)tetrathiafulvalene with halide mercurate anions

Radical cation salts with halide mercurate anions were obtained by the electrochemical oxidation of bis(ethylenedioxo)tetrathiafulvalene (BEDO-TTF), and their conductivity was studied. The compounds (BEDO-TTF)₄Hg₃X₈ (X = Cl or Br), (BEDO-TTF)₄Hg_3.5I₉, and (BEDO-TTF)₂HgBr₃ possess the conductivity of the metallic type down to helium temperatures.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1167–1170, May, 1996.     

Study on the anodic reaction of Ni in an alkaline solution by transient pH detection based on scanning electrochemical microscopy (SECM)

The anodic reaction of Ni in an alkaline solution was studied by the tip–substrate voltammetry mode of scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). A platinum microdisc electrode was selected as the tip electrode, which functioned as a pH sensor with transient response capability. The pH value of the solution near the Ni electrode surface varied while the Ni substrate oxidation reaction occurred, and the pH variation could be detected by the tip faradic current. The cyclic voltammogram results showed that two types of hydroxides: i.e. α‐Ni(OH)₂ and β‐Ni(OH)₂ were formed during Ni oxidation in the lower potential region. In the proceedings of α‐Ni(OH)₂ → γ‐NiOOH and β‐Ni(OH)₂ → β‐NiOOH, the process of OH^? concentration decrease in the solution was ahead and behind of electron transfer in the solid phase, respectively. These results indicate that the OH^? adsorption process occurs as an elementary step in the former reaction and the H⁺ diffusion process from the inner to the outer layer of the solid phase occurs as a subsequent step in the latter reaction. The results also revealed that the oxide film on the Ni surface has a two‐layer structure. The real potential of the oxygen evolution reaction (OER) on the Ni surface with different cycles is also analyzed in the paper. Copyright © 2007 John Wiley & Sons, Ltd.     

Studies on the Electrochemical Characteristics of K2FeO4 Electrode

Discharge performance of K2FeO4 electrode under different conditions was studied by the constant electric current discharge method. The electrochemical characteristics of K2FeO4 electrode were investigated for the first time by means of cyclic voltammetry. The results show that the K2FeO4 electrode made at moderate pressure (20MPa) and discharged at lower current has better discharge performance. It is also found that K2FeO4 electrode is significantly rechargeable.     

The influence of the sacrificial anode nature on the mechanism of electrochemical arylation and alkylation of white phosphorus

The material of the sacrificial anode has a substantial effect on the nature and yield of the target products of electrochemical phosphorylation of organic halides by white phosphorus in the presence of the nickel complexes with 2,2"-bipyridine. The use of the zinc anode results in the products with tricoordinated phosphorus, viz., triorganylphosphines, the reaction on the aluminum anode affords triorganylphosphine oxides, and the presence of Mg²⁺ ions in the reaction mixture provides the transformation of white phosphorus into cyclic phosphines (PhP)₅.