计时安培法测定镧在汞中的扩散系数

计时安培法测定镧在汞中的扩散系数徐逸心，牟兰，张长庚（贵州大学化学系，贵阳，５５００２５）关键词镧，镧汞齐，扩散系数，计时安培法金属在汞中的扩散系数与离子在溶液中的扩散系数一样，是电化学研究中的重要基础数据。目前已用各种方法测定过３２种金属元素和１种...     

铁、钴、镍在汞中扩散系数的测定

用恒电位球形汞齐电极伏安法可测定金属在汞中的扩散系数^[1,2].本文报导了用这个方法测定的铁、钴、镍在汞中的扩散系数值.     

金属在汞中的扩散系数及其扩散规律

扩散系数是研究扩散动力学的一个重要参数。金属在汞中的扩散系数不仅对研究汞齐电极的电极过程是必不可少的,而且对在汞中形成的金属间化合物的研究也是重要的。因此,     

锂和钙在汞中的扩散系数测定

用汞阴极电解法制备锂汞齐和钙汞齐。用毛细管取－小滴汞齐挂洋电极上，以悬汞电极作荼电极，用计时安培法在－０．２Ｖ下测定了锂、钙在汞中的扩散系数。在２５℃下其值为ＤＬｉ＝（８．６５±０．１７）×１０＾－６ｃｍ＾２／ｓ；ＤＣａ＝（７．４３±０．１６）×１０＾－６ｃｍ＾２／ｓ。用Ｓｕｔｈｅｒｌａｎｄ－Ｅｉｎｓｔｅｉｎ扩散方程式计算了汞中扩散粒子半径，其值分别２４７ｐｍ和２８８ｐｍ。这些数值说明锂和钙都是以     

密闭溶样两次金汞齐冷原子吸收光谱法测定煤中微量汞

建立了密闭溶样两次金汞齐冷原子吸收光谱法测定煤样中微量汞的方法，该法具有试剂空白低的特点，适合于测定煤样中的微量汞。研究表明，该法最低检出限为２５×１０－９，精密度为７３％，回收率平均为９９８１％。     

密闭溶样两次金泵齐冷原子吸收光谱法测定煤中微量汞

建立了密闭溶样两次金汞齐冷原子吸收光谱法测定煤样中微量汞的方法，该法具有试剂空白低的特点，适合于测定煤样中的微量汞。研究表明，该法最低检出限为２．５×１０＾－９，精密度为７．３％，回收率平均为９９．８１％。     

极谱分析中物质的富集

极谱分析中若采用物质在电极上的富集,能更进一步地提高测定灵敏度,目前,对此已引起相当的重视。物质在电极上的富集方法,大致可以分为两大类: 第一类方法是物质以形成汞齐的方式富集于汞电极上。第二类方法是物质以形成难溶解膜状物的形式富集于液态或固态电极上。适合用第一类富集方法的仅限于那些能与汞形成汞齐的金属离子。阴离子、贵金属离子、不能在汞电极上还原成金属的离子和不能生成汞齐的金属就必须以第二类方法进行富集。     

固体进样一直接测汞仪法测定金精矿粉中微量汞

将金精矿粉样品直接置于石英舟中,在高纯氧气氛中燃烧,释放出汞,与齐化管中的金形成金汞齐,于900℃热释放出汞蒸汽,用直接测汞仪法测定汞的含量。测定结果的相对标准偏差为0．28％～1．57％（n=6）,方法检出限为1．0pg／kg,加标回收率为95．7％～117．4％。用该法对4种土壤标准样品进行了测定,测定结果与标准值相符。该方法适合于金精矿粉中微量汞的测定。     

钾汞齐的标准电极电位与平衡电位

仿照前文^[1],选定汞齐中钾的标准态并规定钾汞齐的标准电极电位。本文利用前人数据,采用一般化学热力学方法计算在25°钾汞齐的标准电极电位ε°的数值,并以图表示该温度下不同浓度的钾汞齐与不同浓度的氢氧化钾溶液的平衡电位ε的数值。Armbruster等、Bent等和柴田荣一等曾用电动势法测定汞齐中钾的活度。     

典型表面活性物质在汞、镉汞齐和铅汞齐电极上的吸附行为

本文采用DD-1型电镀参数测试仪,测定了汞、镉汞齐和铅汞齐电极在1MKCl的基底溶液中,四下基碘化铵等十二种典型有机表面活性物质在三种电极上的脱附电位。由于镉汞齐和铅汞齐电极的阳极溶解电位比较负,未观测到F^-、Cl^-、Br^-离子的吸附现象。I^-离子及同一有机表面活性物质在三种电极上的吸附活性顺序为:Hg>Pb(Hg)>Cd(Hg)。测试结果表明:同浓度的同一种表面活性物质,在三种电极上的脱附峰电位值之差小于10mV。反映了镉汞齐和铅汞齐电极在脱附峰电位时的表面性质接近于纯汞。     

用单次电化学实验求电极邻近区域三维扩散方程的通解

电化学问题中的三维扩散方程一般都很难求解,即使是微园盘电极,也多采用数值计算或近似方法来处理。若电极形状不规则,严格求解将更困难,即便借助计算机也是件耗时而麻烦的工作。为解决这一困难,本文提出用单次电化学实验求电极邻近区域三维扩散方程通解的设想:     

Metal Exchange Reactions in Metallothioneins Explored by Electrochemical Methods

Metallothioneins (MTs) are widely occurring, small, cysteine‐rich proteins, important for essential metal (Zn, Cu) homeostasis and transport and for heavy metal (Cd, Hg) detoxification. In buffered solutions of mammalian MT, voltammetry and potentiometric striping analysis (PSA) can distinguish different coordination of bound metals or follow their exchange, especially that of zinc and cadmium for copper, silver, and cobalt. The examples of different electrode applications as of hanging mercury drop electrode (HMDE), of silver solid amalgam (AgSAE) electrode, and of silica gel modified carbon paste electrode (SiO₂‐CPE) are given.     

Electrodes of Nontoxic Solid Amalgams for Electrochemical Measurements

The preparation, activation and electrochemical pretreatment of electrodes based on nontoxic solid amalgams were described. Testing of metal solid amalgam electrodes (MeSAEs) proved their broad applicability in many respects, e.g., as to the range of working potentials and the level of background currents, well comparable with those of the hanging mercury drop electrode (HMDE). A regeneration of their surfaces before each measurements could be simply automatized using a PC‐controlled system providing a reasonable repeatability of voltammetric measurements down to 3% RSD. Combination with stripping techniques at accumulation times t_ac=300 s the detection limit amounted to the concentration level of 1 ppb Cu(II), Pb(II), Cd(II), Zn(II), etc. Best electrochemical properties were exhibited by the silver solid amalgam electrode (AgSAE). For example, polished AgSAE (p‐AgSAE), completely free of liquid mercury, proved satisfactory even at more negative potentials enabling the determination of Zn(II), Mn(II), IO , etc. Moreover, even better repeatability of mercury meniscus modified AgSAE (m‐AgSAE) was due to better quality and renewability of its surface. In many cases further testing confirmed that under appropriate conditions MeSAEs represent good, often cheaper and more users‐friendly alternatives to HMDE.     

Comparison of constant-current stripping chronopotentiometry and anodic stripping voltammetry in metal speciation studies using mercury drop and film electrodes

Capabilities for heavy metal speciation of anodic stripping voltammetry (ASV) and constant-current stripping chronopotentiometry (SCP) in both mercury drop (HMDE) and mercury film rotating disk (MFE-RDE) electrodes are compared. For this purpose, the Cd(II)–glycine and Cd(II)–polymethacrylate (PMA) systems are used as models of simple labile and macromolecular labile complexes adsorbing onto the electrode, respectively. The results suggest that SCP could be a valuable alternative to the more widespread ASV in this kind of study. Concerning the electrode, the MFE-RDE is less user-friendly than the HMDE, but presents a better definition of both the hydrodynamic conditions during the deposition step and the stripping regime during the oxidation. An important interference in SCP is the dissolved oxygen, which can be minimised by combining relatively large oxidation currents and low stirring rates. Moreover, for Cd–PMA, double peaks have been observed in both ASV and SCP, which seems to be due to the lack of enough ligand excess to complex the metal ions released by the amalgam oxidation. Anyway, this problem can be minimised by optimising the rotation rate of the electrode and ensuring enough ligand excess.     

离子型碳氟与碳氢表面活性剂在胶团及吸附层中的分子间相互作用

本工作研究了二元表面活性剂溶液的热力学, 考虑了反离子对表面活性离子在表面相和胶团中的相互作用的影响, 得出计算分子相互作用参数β_m和β_σ的将遍公式(β_m和β_σ分别代表胶团和吸附层中的分子相互作用参数):β_m=ln[((cmc_1)/(cmc_1~0x_(1m)))(c″_1/c′_1)~(K_1)]/x_(2m)~2=ln[((cmc_2)/(cmc_2~0x_(2m)))(c″_2/c′_2)~(K_2)]/x_(1m)~2β_σ=ln[((c_1(π))/(c_1~0(π)x_(1σ)))(c″_1/c′_1)~(K_1)]/x_(2σ)~2=ln[((c_2(π))/(c_2~0(π)x_(2σ)))(c″_2/c′_1)~(K_2)]/x_(1σ)~2作为极限情况, 此式对于非离子型表而活性剂或有过量无机电解质时可简化为:β_m=ln[(cmc_1)/(cmc_1~0x_(1m)]/x_2m~2=ln[(cmc_2)/(cmc_2~0x_(2m)]/x_(1m)~2β_σ=ln[(c_1(π))/(c_1~0(π)x_(1σ)]/x_2σ~2=ln[(c_2(π))/(c_2~0(π)x_(2σ)]/x_(1σ)~2应用公式于各类型碳氟、碳氢表面活性剂二元混合溶液, 包括正离子-负离子、负离子-负离子、负离子-非离子混合体系。自表、界面张力-浓度关系计算各体系的β_m及β_σ。结果表明：(1)碳氟、碳氢正离子-负离子表面活性剂混合体系的β_m及β_σ有很大的负值, 表示有强烈的分子相互作用；(2)碳氟链与碳氢键间存在“互憎性”。这种“互憎性”在负离子-负离子混合体系及非离子-负离子混合体系中皆有明显表现；(3)表面压维持恒定时, 不论表面或溶液内部的表面活性剂的摩尔分数如何变化, β_σ值一般近于常数；(4)表面压越高则分子相互作用越强, 表现为β_σ绝对值变大。     

Wax-impregnated carbon paste electrode modified with mercuric oxalate for the simultaneous determination of heavy metal ions in medicinal plants and Ayurvedic tablets.

A wax-impregnated carbon paste electrode with mercury oxalate as the bulk modifier is found to be suitable for the determination of heavy metal ions by differential pulse anodic stripping voltammetry. The contents of binder and modifier have been optimized, until they showed low background current and easy renewability. The bulk-modified electrode is applied for the simultaneous determination of Zn, Cd, Pb and Cu in medicinal plants and Ayurvedic tablets (Liv 52). The results obtained have been validated with HMDE and AAS and are found to be comparable.     

Voltammetric determination of heavy metals leached from ceramics

Anodic stripping voltammetry using a mercury film electrode (MFE) and hanging mercury drop electrode (HMDE) was applied for the determination of trace amounts of lead, cadmium, zinc and copper leached from plates by 4% acetic acid standard solution. The use of a MFE, the fast scan rate (1000 mV/s) by DC voltammetry with subtraction of background current allowed to determine low concentrations of heavy metals. The amounts of metals leached from ware were Pb: 0.1 to 25, Cd: 0.015 to 0.44, Zn: 0.07 to 1.06, Cu: 0.14 to 0.40 μg/mL, depending on the kind of plate and manufacture. Determinations of copper and zinc were carried out using the HMDE electrode in the leachate, determination of tin after medium exchange, and thallium after complexing of lead by EDTA. A significant decrease of metals leached during the second leaching and after washing with detergent solution was found for plates with overglaze decoration. Received: 5 November 1997 / Revised: 24 February 1998 / Accepted: 26 February 1998     

Anodic stripping voltammetry of germanium at the hanging mercury drop electrode

The Ge(IV)—Ge(0) system was investigated by cyclic and stripping voltammetry at HMDE in acidic pyrogallol medium and in phosphate, borate and carbonate buffers. It was found that germanium electrodeposited from dilute Ge(IV) solutions dissolved anodically forming two peaks corresponding to the oxidation of the unstable homogeneous and stable heterogeneous amalgams. Both peaks can be exploited analytically for the determination of traces of germanium but due to the complex nature of the germanium amalgam the sensitivity and reproducibility of the determinations are lower compared to the results obtained for metals well-soluble in mercury.     

Trace determination of Cd, Cu, Pb and Zn in annual growth rings by differential pulse anodic stripping voltammetry

Summary A new voltammetric procedure has been developed for the determination of toxic heavy metals in annual growth rings. The method is based on a wet digestion of minute quantities of wood material of 10–25 mg with an acid mixture of HNO₃ and HClO₄ in a quartz cup and the subsequent simultaneous determination of Cd, Pb, Cu and Zn by differential pulse anodic stripping voltammetry (DPASV) at the hanging mercury drop electrode (HMDE). The accuracy of the method has been proved by using electrothermal atomic absorption spectrometry as an independent procedure. The problems of the contamination by ubiquitous heavy metals during the wet digestion were investigated and their influence on the results was effectively diminished. Losses of the studied metals have not been observed. The high sensitivity of the method enables the determination of the toxic metals Pb and Cd in the analyte of the wet digestion with a relative standard deviation of less than 20% in the low level range 0.1–4 g/l.The potentialities of the method have been shown in the determination of Cd, Pb, Cu and Zn in cores of oak (Quercus petraea) from Königstein (Taunus, FRG). The high sensitivity made it possible to analyze individual growth rings and thus to avoid damages on trees using an excessive quantity of material. In two samples taken as example a distinct increase of the concentration of Cd and Pb during the last decade indicates metal pollution of the region by atmospheric precipitates.

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Spurenbestimmung von Cd, Cu, Pb und Zn in Jahresringen mit Hilfe der Differentialpuls-ASV

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Attached from the Institute of Chemistry, Universidad del Norte, Antofagasta, Chile. Taken in part from the Ph.D. Thesis, University in Bonn     

以衣康酸-BrO-3-Mn2+为体系的化学振荡研究

本文研究了BrO_3~--Br~--H~+-Mn~(2+)-衣康酸体系的振荡行为, 利用电位法及分光光度计对体系做了一系列测定, 根据FKN机理, 提出了本体系可能的反应进程, 同时测定了各种反应条件对振荡的诱导期及周期影响, 并根据机理分析把诱导期分成两个部分, 得到1/τ_(i1), 1/τ_(i2), 1/τ_p对各种反应物起始浓度的关系式。还发观葡萄糖能促进振荡进行。