Vapor-liquid equilibria for the nitrogen-isobutane system

Vapor-liquid equilibria have been investigated experimentally for the nitrogen-isobutane system at temperatures from 120 K to 220 K and at pressures up to 150 bar. Below 126.5 K, two liquid phases were observed as pressure was increased to near the vapor pressure of pure nitrogen. The equilibrium ratio of nitrogen in the binary system and the Henry’s law constants for nitrogen in isobutane were determined from experimental data. The experimental phase equilibrium data were correlated by means of the Peng-Robinson equation of state.     

Some Aspects of the Solubility of Gases in Liquids

Summary.  Henry’s law constants may usually be used to calculate solubilities of gases at low pressures. If experimental measurements are unavailable values of Henry’s law constants may be estimated by various methods. Several of these methods depend upon quantitative structure-property relationships. A method developed by Hine and Mookerjee depends on the assumption that each bond of a particular type makes approximately the same contribution to the molar free energy change when different organic gases are dissolved in water. The solubility of gases and also the rate at which gases dissolve in cloud droplets is important for the understanding of processes which occur in the atmosphere. A simple model for the uptake of gases by water is based on an analogy with the behaviour of an electric circuit containing resistances in series and in parallel. This model is important for the interpretation of experimental measurements of rates of gas uptake. E-mail: pfogg@compuserve.com Dedicated to Prof. Heinz Gamsj?ger Received September 21, 2002; accepted September 30, 2002 Published online April 3, 2003     

Determination of Selenium Species in Environmental Samples

 The essential nature of selenium as well as its toxicity depend on the concentration and the chemical forms in which this element is present in a given sample. Dissolved inorganic selenium can be found in natural water and soil as selenides, selenite and selenate. Organoselenium compounds present in air, soil and plants are volatile methylselenides, trimethylselenonium ion and several selenoamino acids. This review is a summary of recent research on the determination of selenium species in environmental samples such as water, air, soil and plants. Stability of selenium species in solutions and their storage is also discussed. In the metabolic pathway in the body selenide could act as the common intermediate for inorganic and organic Se sources as well as the checkpoint between further utilisation and excretion of selenium. Received May 30, 2001; accepted October 19, 2001; published online July 15, 2002     

The Legacy of Raimond Castaing

 In April 1998 Raimond Castaing left the world of electrons, of ions and others particles, his wife and his family, his numerous students, for the world of stars. Raimond Castaing (Fig. 1) had a very strong personality. No one will forget their first meeting with him and all his students remember how brilliant he was as a teacher. A lot of anecdotes about his famous hot temper are still circulating among his friends and his former students. But in this paper, we would like to evoke Castaing’s memory through his achievements in Instrumental Physics, from the time of his doctoral thesis to later developments with his students, which were all centred on the imaging of the microstructures of materials and their quantitative chemical analysis.     

Analytical Potential of EDS at low Voltages

 This paper addresses some of the principles underpinning chemical microanalysis of bulk specimens in the scanning electron microscope using low beam voltages ( ≤5 kV) and energy dispersive x-ray spectrometry. The advantages of this relatively new method lie primarily in the strong dependence of the sample penetration range on the electron beam energy (∼10x from 5 kV to 20 kV). This directly yields superior spatial resolution and sensitivity for the analysis of sub-micron particles, surface films and at interfaces. The correspondingly shorter x-ray escape range reduces the importance of the complex matrix absorption and fluorescence terms; the parameters for which may not always be known accurately. A useful x-ray signal can only be generated with a beam energy which is at least 1.3x the excitation energy for the relevant characteristic x-rays. Low voltage fluorescent yields are relatively low and depend strongly on overvoltage (U < 3) and low voltage x-ray signals are relatively weak. These considerations lead to the development of a radical new instrument which produces 9000 counts per second from an Aluminium target with a < 2 nm probe containing 0.2 nA of current at 5 kV, fast submicron resolution x-ray maps ( < 0.1 μm is possible), and close to 1 nm electron image resolution at 1 kV. The greatly improved (15x) EDS sensitivity and superior electron and x-ray imaging are being used to extend, to explore and to exploit more fully the superior performance envelope of the SEM with EDS at low voltages.     

Flow Injection Spectrophotometric Determination of Iodide in Environmental Samples

 An alternative and simple flow injection spectrophotometric analysis method for the determination of iodide in environmental samples is reported. The method is based on the catalytic destruction of the colour of the Fe(III)–SCN⁻–CP⁺–_nBP_y quarternary complex. The complex shows maximum absorption at 495 nm. The apparent molar absorptivity of the complex in terms of iodide is (6.22) × 10⁵ l mol⁻¹ cm⁻¹. The detection limit of the method is 0.1 ng ml⁻¹ of iodide. The method obeys Beer’s law up to 120 μg l⁻¹ with slope, intercept and correlation coefficient of 0.11, − 0.52 and + 0.99, respectively. Various flow injection analysis parameters for the determination of iodide in the environmental samples were optimized. The sample throughput of the method is 60 samples h⁻¹. The method was successfully useful for the determination of trace level of iodide in environmental samples i.e. ground, surface water. Received November 12, 2001; accepted April 2, 2002; published online July 22, 2002     

Uncertainties in Determination of pH

 A statistical analysis of multi-point calibration procedure for practical measurement of pH under laboratory conditions is given. The procedure is shown to provide the necessary elements for simple assignment of an uncertainty to a pH measurement – an essential element of quality control. Performance of ordinary least squares regression for prediction of confidence limits is compared to orthogonal regression, inverse regression and Monte Carlo simulations. In case of pH measurement by multi-point calibration procedure, methods considering uncertainties in both axes are found to be statistically more satisfactory than ordinary least squares regression. By analysis of 50 pH calibration data, randomly selected from 250 5-point glass electrode calibrations, it is found that the practical differences, however, are of minor importance. The significance of uncertainty in pH is demonstrated for an example from metal ion speciation in aqueous solution. Received September 20, 1999. Revision April 19, 2000.     

New Experimental Cross-Section Measurements for Cr and Cu and Comparison with Model Predictions

 In order to obtain more accurate experimental values of X-ray emission cross sections, resulting from the interaction of ion with atoms, we have measured them for the K-inner-shell of Cr and Cu elements using a proton beam of energy range 1–2.3 MeV. The experimental data obtained in the present work are compared with the theoretical calculations given by the two models BEA (binary encounter approximation) and ECPSSR (energy coulombian perturbed stationary state relativistic). Also, the present experimental results are compared with those obtained by Paul and Sachert. The comparison shows a good agreement between the previous and the present data with a slight improvement in the measurement accuracy for Cr. From the theoretical point of view, agreement with the experimental data is observed only for the ECPSSR predictions, while the BEA’s cross section calculations at higher energies are approximately 20% lower than the present experimental values.     

Study on the Catalytic Determination of Vanadium (V) Using the Rhodamine 6G-Periodate Redox Reaction and its Analytical Application

 A fluorescence quenching method for the determination of vanadium (V) based on the vanadium- catalyzed oxidation of rhodamine 6G (R6G) with periodate in the presence of ethylenediaminetetraacetic acid disodium salt (EDTA) in sulfuric acid medium is described. The fluorescence was measured with excitation and emission wavelengths of 525 and 555 nm, respectively. The calibration graph for vanadium (V) had linear ranges of 3.0 × 10⁻⁹–1.5 × 10⁻⁸ mol/l and 1.5 × 10⁻⁸–4.0 × 10⁻⁸ mol/l, respectively. The detection limit was 1.7 × 10⁻⁹ mol/l. The proposed method was successfully applied to the determination of vanadium (V) in river water, rain water and cast iron samples. Received June 29, 2001 Revision October 9, 2001     

Analytical Techniques Applied in Optimization of Electrophoretic Deposition of Thin Film YBCO Superconductors

 YBa₂Cu₃O _7−x (x = 0.1–0.2) compounds (YBCO) were produced by the oxalate coprecipitation and the solid state reaction methods. The powders obtained were used for the production of YBCO superconducting coatings on Pt/Si wafers, by the electrophoretic deposition technique. The optimum process conditions for the production of both powders and coatings were found by using a combination of modern analytical techniques. The thermal treatment of the samples was followed by thermogravimetry (TG) and differential scanning calorimetry (DSC). The optimization and characterization of the superconducting properties of the powders and coatings were achieved by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), optical microscopy, magnetic susceptibility and electrical resistivity measurements.     

Exploring the use of a structural alphabet for structural prediction of protein loops

 The prediction of loop conformations is one of the challenging problems of homology modeling, owing to the large sequence variability associated with these parts of protein structures. In the present study, we introduce a search procedure that evolves in a structural alphabet space deduced from a hidden Markov model to simplify the structural information. It uses a Bayesian criterion to predict, from the amino acid sequence of a loop region, its corresponding word in the structural alphabet space. The results show that our approach ranks 30% of the target words with the best score, 50% within the five best scores. Interestingly, our approach is also suited to accept or not the prediction performed. This allows the ranking of 57% of the target words with the best score, 67% within the five best scores, accepting 16% of learned words and rejecting 93% of unknown words. Received: 17 July 2000 / Accepted: 5 January 2001 / Published online: 3 April 2001     

Micellar Enhanced Analytical Application of Bismuthiol-II for the Spectrophotometric Determination of Trace Copper in Nutritional Matrices

 A simple spectrophotometric method for the determination of copper is described herewith, based on the formation of colored species of Cu (II) with 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thione (Bismuthiol II) in the presence of a neutral surfactant, Triton X-114. The yellow colored complex of Cu (II)–Bismuthiol-II–Triton X-114 shows maximum absorbance at 395 nm in water. The detection limit of the method is 0.03 mg/l while the Beer’s law is obeyed up to 1.2 mg/l of the analyte in an aqueous medium. The validity of the method has been examined for the determination of copper in wines, food supplements and raisins. The results obtained were in good agreement with those obtained using flame atomic absorption spectrometry (FAAS). The method thus constitutes a handy alternative for the determination of copper (II) in nutritional samples. Received May 16, 2001; accepted December 10, 2001; published online June 24, 2002     

Construction and Analytical Applications of Plastic Membrane Electrodes for Oxytetracycline Hydrochloride

 Oxytetracycline hydrochloride-selective electrodes of both the coated wire and the conventional polymer membrane types based on oxytetracyclinium phosphotungstate and phosphomolybdate have been prepared. A Nernstian response is shown by these electrodes within 1.0×10⁻⁶–1.0×10⁻² M concentration ranges depending on the type of electrode. The response is unaffected by the change of pH over the range 4–11. The standard electrode potentials, E°, were determined at different temperatures and used to calculate the isothermal temperature coefficients of the electrodes. The electrodes show good selectivity to oxytetracycline hydrochloride with respect to many inorganic cations, sugars and amino-acids. Oxytetracycline hydrochloride is determined successfully in pure solutions and in pharmaceutical preparations using calibration by standard addition and potentiometric titration. A regeneration process for the exhausted electrodes has been developed. Received February 2, 2000. Revision April 7, 2000.     

Asymmetric Synthesis of a Structurally Simplified Analogue of the Antibiotic Heptelidic Acid

Summary.  A structurally simplified analogue of the antibiotic (+)-heptelidic acid was synthesized in ten steps with an overall yield of 9%. Key step was a conjugate addition of a silyl protected vinylcuprate to an asymmetrically shielded enoate, which gave an adduct as a single diastereomer. Transesterification in the presence of triethylamine allowed a selective cleavage of the chiral auxiliary and afforded an enantiomerically pure methyl ester. This easily enolizable β-ketoester was transformed to the trans configurated methylene derivative using a four-step reaction sequence. Finally, the desired epoxylactone was accessible from the methylene derivative by lactone ring formation and successive oxidation in four steps. Received July 13, 2001. Accepted August 16, 2001     

Analytical X-Ray Microscopy on Psaronius sp. – A Contribution to Permineralization Process Studies

 290 Million years old petrifactions from the Lower Permian Rotliegend of Chemnitz were examined by analytical X-ray microscopy to determine their chemical composition. Mappings show the inhomogeneous distribution of the involved elements, which may reflect the former plant anatomy, as well as some contemporaneous processes of permineralization (with silica and fluorite) and agate-formation. Most prominent advantages of the analytical X-ray microscopy are the low preparation expense of the museum samples, the analysis scanning range and the X-ray spot diameter suitable with the dimension of the fossil plants.     

A HREM and Analytical STEM Study of Precipitates in an AZ91 Magnesium Alloy

 The paper focuses on the microstructural characterisation of secondary phases in an AZ91 magnesium alloy. The orientation relationship and atomic structure of semi-coherent Mg/Mg₁₇Al₁₂ interfaces are studied by means of selected area diffraction, EDS and high resolution TEM. Besides the common Mg₁₇Al₁₂ semi-coherent platelets of high density and coarser incoherent Mg₁₇Al₁₂ particles, other, less frequent precipitates were found, rich in Al and Mn. The quasicrystalline nature of these precipitates was detected by means of electron diffraction.     

A Novel Catalytic Procedure for the Determination of Ultratrace Zirconium

 A novel catalytic procedure for zirconium was proposed based on Zr(IV) catalyzed oxidation of gallocyanine by hydrogen peroxide in hexamethylene tetramine-hydrochloric acid buffer medium. The calibration graph is linear for 0–110 ngċml⁻¹, and the detection limit is 0.4 ngċml⁻¹ Zr(IV). Most foreign ions do not interfere with the determination, except for Cu²⁺, Fe³⁺ and Cr(VI). The interferences of Cu²⁺ and Fe³⁺ could be eliminated by masking with EDTA and mannitol, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for zirconium, and the determination could be carried out at room temperature. It had been used to the determination of zirconium in zirconium bronze, simulated samples and a certified reference material. The recoveries were 98.6 ∼ 102%, and relative standard deviations (R.S.D.) were 0.9 ∼ 1.5%, respectively. Received September 12, 1999. Revision April 10, 2000.     

Analytical Electron Microscopy Study of a ZnO-NiO Solid Solution

 Results of an analytical electron microscopy study of a binary ZnO-NiO system are reported and discussed. Emphasis was placed on the determination of Ni concentration (solubility) in the ZnO grains using quantitative TEM-EDXS. The influence on the results of beam diameter, foil thickness and corrections used are described and discussed. During the study small precipitates, presumably NiO, were found in the ZnO grains of the ZnO-NiO samples with different ZnO/NiO ratios. In TEM, the precipitates exhibited image contrast only at certain orientations and were normally invisible during the EDXS analysis. The presence of the precipitates too small to be seen using scanning electron microscopy could explain erroneous results for the Ni concentration in a ZnO solid-solution phase obtained previously using SEM-EDXS. Quantitative EDXS analyses were performed on ZnO grains using different electron beam diameters. In each sample, the spread of the results was correlated to the beam diameter (analysed volume). It was found that when the average number of precipitates was less than one per analysed volume the measured points that included precipitates could easily be identified on the basis of their deviation from the mean value of the Ni content.     

Adsorptive Stripping Voltammetric Behavior of Probucole. Experimental and Theoretical Treatment

 Adsorptive stripping voltammetric behavior of probucole has been studied by means of cyclic staircase and square-wave voltammetry. It was found that the redox reaction of probucole in an aqueous medium exhibits properties of a surface process involving significant repulsion interactions between adsorbed molecules. A theoretical model was developed to explain the experimentally observed phenomena. Analytical application of the adsorptive stripping square-wave voltammetry for quantitative determination of probucole has been discussed. Received December 15, 2000. Revision June 20, 2001.     

A new Fluorimetric Reagent for Highly Selective and Sensitive Determination of Terbium Ion

 In this work, a new ligand, 2,9-bis[N,N-bis(carboxymethyl)-aminomethyl]-1,10-phenanthroline (BBCAP), was synthesized and used to establish a novel fluorimetric method for the determination of trace amounts of terbium in a binary system. Its luminescence mechanism was studied. The excitation and emission wavelengths are 284 nm and 547 nm, respectively. Other rare-earth metal ions in 100-fold excess caused no interference. The fluorescence intensity was a linear function of the concentration of terbium in the range of 5.0 × 10⁻¹⁰–1.0 × 10⁻⁶ mol/L. The detection limit was 2.0 × 10⁻¹¹ mol/L (n = 12). The standard addition method was used to determine the terbium in a synthetic rare-earth sample with satisfactory results. This method represents a direct, rapid, selective and sensitive analytical procedure with a widely linear range. Received November 29, 2001 Revision February 9, 2002