铁(Ⅱ,Ⅲ)-邻苯二酚紫-表面活性剂双峰双波长分光光度法测定铁

在pH＝12.6的KCl-NaOH缓冲介质中，研究了铁(Ⅱ,Ⅲ)与邻苯二酚紫及表面活性剂的反应．结果表明，该配合物的最大吸收波长为570nm，对试剂空白的最大负吸收波长为480nm，两波长处吸光度之差ΔA与铁量在0～8μｇ/25mL范围内成线性，ε为76×104L·mol－1·cm－1，方法用于水样中铁(Ⅱ,Ⅲ)的测定，结果令人满意.

Synthesis and luminescence characteristics of LiMgAlF6:Ln(3+) (Ln = Ce, Eu, Tb)

By solid state reaction, LiMgAlF6 and LiMgAlF6:Ln(3+) are synthetized with the ratio 120/100/110 of LiF/MgF2/AlF3, at 1008 K, in high-purity Ar stream. Their crystal structure which belongs to hexagonal system are determined by X-Ray-Diffraction (XRD). Luminescence characteristics of Ce3+, Eu3+, Tb3+ and sensitization of Ce3+ to Tb3+ in LiMgAlF6 are studied. It is shown that the sensitization of Ce3+ to Tb3+ is efficient and a bright green emission is observed.

Study of cupric hexacyanoferrate-modified platinum electrodes using probe beam deflection and electrochemical quartz crystal microbalance techniques

The ion exchange mechanism accompanying the oxidation/reduction processes of cupric hexacyanoferrate-modified platinum electrodes in different aqueous electrolyte solutions has been studied by means of in situ probe beam deflection and the electrochemical quartz crystal microbalance technique. The results demonstrate that the charge neutrality of the film during the reoxidation/reduction process is accomplished predominantly by the movement of cations, but anions and/or solvent are also participator(s). Moreover, in KHC8H4O4 (potassium biphthalate) solution, the EQCM data obtained from chronoamperometry experiment are more complicated than those in KCl and K2SO4 solutions. (C) 1997 Elsevier Science Ltd.

The fabrication and performance of an Ag/AgCl reference electrode in human serum

A simple set of electric circuits was used to assemble a pulse generator. With pulse potentials and under galvanostatical control, a clean silver wire was anodized electrochemically for 0.2-0.5 min in 1.0 moll(-1) HCl with a pulse current density of 20 mA cm(-2), and the pulse wave parameters of t(a)/t(c) = 1 and a cycle of 4 s forming an Ag/AgCl reference electrode. Even though the AgCl layer was consumed during the working period when the Ag/AgCl electrode was used as a cathode, the AgCl layer could be in situ recovered electrochemically in serum used when a reversed potential was applied to the electrode system immediately after the measuring program was finished. The current response curve of the anode indicated that an AgCl layer in high density was basically accomplished during the first 6 pulse cycles in human serum. In order to keep a stable and uniform AgCl layer on the reference electrode after each measuring cycle, the ratio of the recovery time (t(r)) to the working time (t(w)) was measured and the smallest value was obtained at 0.03. The open-circuit potential of the Ag/AgCl electrode with respect to a SCE in 0.1 moll(-1) KCl was monitored over a period of 14 days and the mean value was 40.09 mV vs SCE with a standard deviation of 2.55 mV. The potential of the Ag/AgCl reference electrode did remain constant when the measurements were repeated more than 600 times in undiluted human serum with a standard deviation of 1.89 mV. This study indicated that the Ag/AgCl reference electrode could been rapidly fabricated with a pulse potential and could be used as a reference electrode with long-term stable properties in human serum samples.

Probe beam deflection study of the ion exchange between Prussian blue film or indium hexacyanoferrate film and electrolyte solutions

Probe beam deflection(PBD) technique together with electrochemical techniques such as cyclic voltammetry was used to study the ion exchange in prussian blue(PB) film and its analogue indium hexacyanoferrate (InHCF) chemically modified electrodes, The ion exchange mechanism of PB was verified as following: K2Fe2+FeI(CN)(6)(-e--K+)reversible arrow(+e-+K+)KFe(3+)Fe(I)(CN)(6)(-xe--xK+)reversible arrow(+xe-+xK+) [Fe3+FeI(CN)(6)](x)[KFe3+FeI(CN)(6)](1-x) where on reduction in contact with an acidic KCl electrolyte, H+ enter PB film before K+. Both the cations and anions participate concurrently in the redox process of InHCF, meanwhile K+ ion plays a major role in the whole charge transfer process of this film with increasing radii of anions.

EFFECTS OF ANODIC-OXIDATION ON THE SURFACE-STRUCTURE OF HIGHLY ORIENTED PYROLYTIC-GRAPHITE REVEALED BY IN-SITU ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY IN H2SO4 SOLUTION

Effects of the potential of anodic oxidation and of potential cycling on the surface structure of a highly oriented pyrolytic graphite (HOPG) electrode were observed by in situ electrochemical scanning tunnelling microscopy (ECSTM) in dilute H2SO4 solution with atomic resolution. With potential cycling between -0.1 V and 1.8 V vs. Ag/AgCl (sat. KCI), some atoms on the top layer of HOPG protrude out of the base plane, and the graphite lattice of these protrusions is still intact but is strained and expanded. With further potential cycling, some protrusions coalesced and some grew larger, and an anomalous superperiodic feature was observed (spacing 90 Angstrom with a rotation 30 degrees relative to atomic corrugations) which superimposed on the atomic corrugation of HOPG. On the topmost of these protrusions, some atoms form oxides and others are still resolved by the ECSTM image. With potential cycling between -0.1 V and + 2.0 V vs. Ag/AgCl (sat. KCl), damage to freshly cleaved HOPG surface is more serious and fast, some ridges are observed, the atomic structure of the HOPG surface is partially and then completely damaged due to the formation of oxide. We also found that anodic oxidation occurred nonuniformly on the surface of HOPG near defects during potential cycling.

A novel in-situ spectroelectrochemical technique with probe beam deflection: For study of the ion exchange between films on electrode surface and solutions

A novel in-situ spectroelectrochemical technique, the combination of probe beam deflection (PBD) with cyclic voltammetry (CV), was used to study the ion exchange process of prussian blue(PB) modified film electrode in contact with various electrolyte solutions. The ion exchange mechanism was verified as following: (K2Fe2+FeII)(CN)(6) -e(-)-k(+)reversible arrow +e(-)+k(+) (KFe3+FeII)(CN)(6) -ke(-)-xk(+)reversible arrow +xe(-)+kk(+) [(Fe3+FeIII)(CN)(6)](x)[(KFe3+FeII)(CN)(6)](1-x) where on reduction PB film in contact with an acidic KCl electrolyte, it was confirmed that protons enter into the PB film before K+ cations.

ELECTROCHEMICAL FORMATION OF NI-Y INTERMETALLIC COMPOUND LAYER IN MOLTEN CHLORIDE

The reduction of Y(III) ions in molten chloride is known to be a one-step three electron reaction [1, 2, 3], but a voltammogram of YCl3 in molten LiCl-KCl-NaCl at a nickel electrode shows at least two reduction peaks of Y(III) ions, indicating the possibility of formation of Ni-Y intermetallic compounds. Using a galvanostatic electrolysis method, samples were prepared at several current densities at 450, 500, 600 and 700-degrees-C, respectively, and were identified with X-ray diffraction (XRD) and electron probe microanalysis (EPMA) methods. The results show that Ni2Y, Ni2Y3 and NiY can be produced by electrolysis and Ni2Y is found to be the predominant Ni-Y intermetallic compound under the experimental conditions. Nickel appears to diffuse in Ni2Y faster than yttrium, and the diffusion process is the rate determining step during Ni2Y formation.

熔盐电解制备Ga-Nd合金的研究

Ga-Nd合金对磁性材料及半导体材料的研制是非常有用的。本文详细地研究了采用低熔点的镓作为阴极,从KCl-NdCl_3熔盐中电解制备廉价Ga-Nd合金的工艺条件。 本研究采用KCl-NdCl_3熔盐体系进行电解。KCl为分析纯。NdCl_3由Nd_2O_3(>99.99％)加过量NH_4Cl混合后,在大瓷蒸发皿中于350℃进行搅拌反应,直至产物完全溶于水。用滴定法确定原料中NdCl_3的含量。以金属镓作阴极(纯度为99.99wt％),阴

STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

用透明电解槽研究镧、钕在氯化物熔盐中的溶解过程

采用透明电解槽技术首次观察了金属镧、钕分别在LaCl_3_KCl、NdCl_3+KCl以及KCl+NaCl熔盐中的溶解过程。实验发现镧、钕在各自熔盐中溶解时均产生黑色的金属雾。在电解条件下,镧、钕的溶解扩散受到很小的抑制。金属钕的溶解扩散明显快于金属镧的溶解扩散。形成的镧、钕金属雾主要由低价离子和部分金屈粒子(或原子)组成。

衬钽管石墨炉中分子背景的调查

调查了钾、钠、钙的化合物在热解管(PGT)和衬钽管(TaT)中的分子背景。结果表明,衬钽管对NaCl、KCl、CaCl_2、Ca(NO_3)_2的背景吸收均具有明显抑制作用。

二元氯化物熔体中锂和钠离子析出电位的测定及去极化作用的研究

本文利用Ⅰ-Ⅴ曲线法测定了锂和钠离子在二元混合氯化物体系(LiCl-KCl;NaCl-KCl)中的析出电位,为利用熔盐电解法制备低钠高纯铝-锂合金提供了理论依据.根据锂离子在铝阴极上产生的去极化值求出铝和锂发生合金化反应的热力学意义,提出二元合金类型与极化类型之间的经验关系.首次通过研究锂离子在铝合金电极上的去极化行为,发现某些第三合金元素的存在可以加强锂离子的去极化作用,为进一步制取低钠高纯三元铝-锂-M合金系列提供了参考.还研究了在氯化钾-氯化锂体系中,氯化锂浓度对锂离子在铝阴极上析出电位的影响,求出了氯化锂的平均活度系数.

氯化物熔盐中钕离子在铂电极上的电化学还原

利用极谱,Ⅲ利用电位阶跃研究了轻稀土离子在碱金属氯化物熔盐中的阴极还原。本文作者研究过Sm~(3+)在NaCl-KCl熔盐中的电还原。上述工作分别提出了稀土离子一步还原和分步还原的结论。本文采用线性扫描伏安法和恒电位电解,并配以扫描电子显微镜X射线能谱分析,对Nd~(3+)在Pt电极上的阴极还原过程进行了研究,利

石墨炉原子吸收光谱法测铝时氯化物的干扰及硝酸钙的增感作用

本文研究了石墨炉原子吸收光谱法测铝时各种氯化物的干扰及硝酸钙的增感作用。NaCl、KCl、FeCl_3、CuCl_2对铝的测定产生负干扰,这种干扰来自气相中铝和氯的结合;MgCl_2和CaCl_2对铝产生正干扰,其干扰来自它们分解出的氧物化对铝的增感作用。硝酸钙不仅对铝产生增感作用,而且也提高铝的最高允许灰化温度,降低原子化温度,同时也增强抗干扰能力。本文还利用钙的增感作用直接测定了河水及地下水中的痕量铝,结果满意。