Chromatographic studies of corrosion sites in metallic materials

Many types of corrosion phenomena are controlled by the ionic composition of a small volume of solution at the surface. Localized corrosion and atmospheric corrosion are two examples in which < 1 μl of solution can cause dramatic damage. Ion chromatographic (IC) techniques have been used to analyze these solutions in order to gain a better understanding of the mechanisms which govern them. Two examples are presented. The presence of minor alloying elements at localized corrosion sites in two aluminum alloys has been demonstrated, indicating non-stoichiometric dissolution of the alloy during localized corrosion. In addition, IC analysis allowed the determination of the species responsible for the atmospheric corrosion failure of electrical connectors, including their likely origin.     

Simultane Ionen-Chromatographie von Kationen und Anionen mit Komplexonen als Elutionsmittel und selektiver UV-Detektion

Summary The complexones EDTA, DCTA and EGTA were investigated as eluting agents at various pH-values for the simultaneous separation of 9 cations and 6 anions using ion chromatography on a silica gel based anion exchanger (Nucleosil 10-Anion II). 1,2-Diaminocyclohexanetetraacetic acid (DCTA) proved to be the best eluting agent. UV spectrophotometry was used for both direct and indirect detection of the anions and anionic metal complexes and a detailed study was carried out with respect to selectivity of detection. This was facilitated by referring to the UV absorption spectra of the anions and metal complexes involved. By choice of a suitable wavelength between 203 and 270 nm and taking into account pH effects, a number of selective determinations were possible. Examples include Pb and Cu in the presence of excess of Ca and Mg as well as nitrate, nitrite and bromide in a large excess of chloride and sulphate. Some examples of detection limits are (g/l) nitrate 2, Fe(III) 3, Cu 9 and Pb 12 (sample volume 20 l, direct UV-detection). The Chromatographie behaviour of Fe(II) and Fe(III) was studied and discussed. Drinking water was analysed for chloride, nitrate and sulphate as well as Ca and Mg using DCTA in the eluent. Complete analyses can be carried out in less than 15 min.

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Herrn Prof. Dr. R. Neeb zum 60. Geburtstag gewidmet     

烟酸对酸性硫酸盐体系铜电沉积的影响

对溶液A: 0.8 mol•L－1硫酸铜,0.6 mol•L－1硫酸,5.0×10－5 mol•L－1氯离子,1.0×10－4 mol•L－1聚乙二醇的溶液,溶液B:在溶液A中加入2.0×10－2 mol•L－1烟酸,pH为0.5,运用循环伏安和计时安培法研究玻碳电极上铜的电沉积行为.结果表明,铜的电沉积过程经历了晶核形成过程,其电结晶按瞬时成核和三维生长方式进行.烟酸的加入对铜的电沉积具有阻化作用,但不改变铜的电结晶机理.沉积层的X射线衍射表明Cu为面心立方结构,在烟酸存在下沉积层出现(220)高择优取向,这可能是烟酸在Cu(220)晶面上发生强烈吸附作用的结果.     

The co-stacking of a planar metal complex and a novel 1,3-dithiole: The synthesis and crystal structure of [Pt(mnt)(CNMe)2]·(NC)2C2S2

The reaction of [NBu₄ⁿ]2Cu(mnt)₂] with [Pt(CNMe)₄][PF₆]₂ gives [Pt(mnt)(CNMe)₂]·(NC)₂C₂S₂CNMe, an X-ray study of which reveals co-stacking of neutral planar metal and organic molecules.     

Errors involved in the activation energy calculated by integral methods when the frequency factor depends on the temperature ( A = A 0 T m)

The dependence of the frequency factor on the temperature (A=A ₀ T ^m) has been examined and the errors involved in the activation energy calculated from some integral methods without considering such dependence have been estimated. Investigated integral methods are the Coats-Redfern method, the Gorbachev-Lee-Beck method, the Wanjun-Yuwen method and the Junmeng-Fusheng method. The results have shown that the error in the determination of the activation energy calculated ignoring the dependence of the frequency factor on the temperature can be rather large and it is dependent on x=E/RT and the exponent m.     

Temperature-programmed reduction and oxidation of bimetallic Pd?Ni/Al2O3 catalysts

Temperature-programmed reduction and oxidation of bimetallic catalysts Pd–Ni/Al₂O₃ seem to indicate phase segregation of palladium and nickel oxides and alloying of palladium and nickel in the process of reduction of oxidized catalysts.

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- Pd–Ni/Al₂O₃ , .

     

The pectin of ginseng. The structure of the poly-galacturonide

Conclusions The partial hydrolysis of the pectin ofPanax ginseng C. A. Mey gives a polygalacturonide which has a linear carbohydrate chain consisting of residues of D-galacturonic acid in the pyranose form linked by -(1 4)-bonds.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 201–203, 1969     

Ein Beitrag zur ?nologie und ?kologie von Selen

Summary Little is known about selenium contents in alcoholic beverages, especially in wine, because no reliable determination method was available so far. A procedure for the detection of selenium in the pg- and low ng-range was developed, which uses the hydride-generation-condensation-AAS (HGC-AAS). Selenium contents in 103 German wines of the year vintages 1950 until 1985 were determined. In mean they range between 0.29 and 0.79 g/l Se and show a certain dependence from the geological soil formation and the wine species. Corresponding vineyard soils from Ingelheim (Rheinhessen, FRG) contain 0.18–0.44 mg/kg Se, mean 0.24 mg/kg Se, 10% of it is available for plants. The distribution of selenium in grape berries shows selenium-rich seeds and — with red wine species — selenium-rich skins. Higher selenium contents by contamination were observed near an industrial location. The behaviour of selenium in the vegetation cycle is pursued. The selenium depletion during fermentation may amount to 60%. All results are summarized in the so-called trace element vinogram. Selenium hence is a regular and natural constituent part of wine.

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Herrn Prof. Dr. R. Neeb zum 60. Geburtstag gewidmet     

New diterpenoid components of the oleoresin ofPinus koraiensis

Summary 1. The following compounds have been isolated from the oleoresin ofPinus koraiensis Sieb. et Zucc., in addition to those described previously: cis-abienol, labd-8(20),13-dien-15-ol, (+)-manoyl oxide, epimanoyl oxide, and 7-hydroxydehydroabietinol (in the form of the diacetate). The structure of the last-mentioned, previously unknown, diterpenoid has been shown by chemical transformations and by spectroscopy.2. It has been established that the cembrene, isocembrene, pinacenes, neoabienol isolated previously and the 18-norcembra-2,7,11-trien-4-one now isolated for the first time are secondary products formed in the storage and treatment of the oleoresin.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–179. March–April, 1976.