Trace analysis of volatile polar organics by direct aqueous injection gas chromatography

Summary Procedures for the quantitative analysis of industrial effluents which involve concentration by solvent extraction or the purge-and-trap method are time-consuming, labor-intensive, and prone to error. Direct aqueous injection gas chromatography using an electron-capture detector for the analysis of volatile halocarbons at the ppb level is in routine use in many laboratories. We now discuss the development of a similar protocol for the analysis of volatile polar organics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and tretrahydrofuran using a flame-ionization detector.     

Paradigms and paradoxes: patterns and estimation of the entropy of formation of aqueous hydrogen containing mono and polynuclear oxyanions

“Simple” energetic patterns, where simple means the use of parameters derived only from the stoichiometry of these species, are relatively rarely discussed in the literature. In addition, entropy studies have been dominated by derivation of the absolute quantity S° rather than the entropy of formation (TΔ_f S ^o). Relationships between the entropy of formation and different parameters such as negative value of the charge of the species, the number of oxygen atoms, the natural logarithm of the molecular weight, the total number of atoms and the number of central atoms that are gases were recently discussed by us for aqueous polynuclear oxyanions. As shown here hydrogen containing anions do not follow this pattern. In this study, new approaches for the estimation of the entropy of formation of aqueous hydrogen containing mono and polynuclear oxyanions are suggested, evaluated and recommended.     

The electrochemical interface between copper(111) and aqueous electrolytes

The electrochemical double layer between Cu(111) electrodes and aqueous electrolytes (F⁻ and SO²⁻₄ at various pH values) was studied by means of linear scan voltammetry and ac impedance measurements. It is found that electrochemisorption of oxygen species proceeds on the Cu(111) surface in the potential regions more negative than the electrodissolution potential of copper. The adsorption-desorption kinetics are analysed; the anodic and cathodic symmetry coefficients are found to be equal (α = β = 0.3), and the standard rate constant is k° = 4 × 10⁻¹⁰cm s⁻¹.     

Electrical conductivities of halide salts in aqueous formamide solutions

The electrical conductivities of sodium chloride and sodium iodide solutions in formamide-water mixtures of different composition have been measured at 25°C. From these data, the limiting equivalent conductances for these salts have been determined. The correspondingWalden products are compared together with the one reported for sodium bromide in the same solvent mixtures, and they are analysed as functions of the anion size. Further, the limiting ionic equivalent conductances are estimated for the different ions. The variation of the ionicWalden products with solvent composition is discussed in terms of ionic solvation and solvent structure.

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Elektrische Leitfähigkeit von Halogensalzen in wäßrigen Formamid-Lösungen

Zusammenfassung Es wurden die elektrischen Leitfähigkeiten von Natriumchlorid- und Natriumjodidlösungen in Formamid-Wasser-Mischungen verschiedener Zusammensetzung bei 25°C gemessen. Aus diesen Daten wurden die Grenzäquivalenzleitfähigkeiten für diese Salze bestimmt. Die entsprechendenWalden-Produkte wurden mit den für Natriumbromid in den gleichen Lösungsmittelgemischen berichteten verglichen und hinsichtlich der Anionengrößen analysiert. Außerdem wurden die ionischen Grenzäquivalenzleitfähigkeiten für die einzelnen Ionen abgeschätzt. Die Variation der ionischenWalden-Produkte mit der Lösungsmittelzusammensetzung wurde bezüglich Ionensolvatation und Lösungsmittelstruktur diskutiert.

     

Rhodium-catalyzed hydroformylation of C6 alkenes and alkene mixtures - a comparative study in homogeneous and aqueous-biphasic media using PPh3, TPPTS and TPPMS ligands

The complexes RhH(CO)L₃, where L = PPh₃, P(m-C₆H₄SO₃Na)₃ (TPPTS), and (C₆H₅)₂P(m-C₆H₄SO₃Na) (TPPMS) were used as catalyst precursors for a comparative study of the catalytic hydroformylation of several C6 alkenes and alkene mixtures under moderate reaction conditions in homogeneous (PPh₃) and aqueous-biphasic (TPPTS, TPPMS) media. The biphasic systems are efficient for the hydroformylation of hex-1-ene, 2,3-dimethyl-1-butene, styrene, cyclohexene, and mixtures thereof, in water/n-heptane at 80 °C. The main problem associated with these catalysts is their tendency to promote alkene isomerization if the effective syngas concentration in the liquid phases is low, but this side-reaction can be suppressed by using higher CO/H₂ pressures (54 atm). The selectivity of both water-soluble catalysts for linear products of hex-1-ene and for branched products of styrene is modest in comparison with the homogeneous system, which may limit their utility for classical oxo uses, but this is not a disadvantage for other interesting applications related to the hydroformylation of alkene mixtures and particularly to naphtha upgrading where linear and branched products are equally useful. The catalysts can be recycled without significant loss of activity and are resistant to the presence of benzothiophene in the mixture.     

缬沙坦类似物合成中间产物的捕获(Ⅱ)

In this article we mainly discuss the effect of anion of Lewis acid on the structure of the intermediate in synthesis of valsartan analogue. The crystal belongs to monoclinic system with space group P2₁/c, and a=1.099 9(3) nm, b=1.913 4(5) nm, c=0.977 8(3) nm, β=104.806(4)°, V=1.989 5(9) nm³, D_c=1.708 g·cm^-3, Z=18. CCDC: 629931.     

[{Zn(3-SBA)(2，2′-bipy)(H2O)2}·H2O]n的合成和晶体结构研究

A novel coordination ploymer [{Zn(3-SBA)(2,2′-bipy)(H₂O)₂}·H₂O]_n was synthesized by the hydrothermal reaction of 3-Na₂SBA, ZnSO₄·7H₂O and 2,2′-bipy. The structure was characterized by elemental analysis, IR and single crystal X-ray diffraction. The title coordination ploymer crystallized in monoclinic with space group P2₁, a=0.803 42(18) nm, b=1.501 8(3) nm, c=0.821 13(19) nm, β=109.350(4)°. The coordination polymer has an infinite chain structure and its luminescent property has also been studied. CCDC: 282746.     

微波衍生-离子对高效液相-磺化四苯基卟啉光度法同时测定痕量镍、铜、锰和锌

 用磺化四苯基卟啉 (TPPS4 )作柱前衍生试剂 ,在微波作用下进行衍生反应 ,研究了衍生和分离Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的最佳条件。在 75 0W的微波作用下衍生反应 3min ,在C18柱上采用乙腈 水 (体积比为 2 2 5∶77 5 )体系作流动相 ,四乙基溴化铵 (TEABr)作离子对试剂 ,在 415nm处检测 ,建立了微波衍生 离子对高效液相快速分离、光度检测Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的新方法。络合物和反应试剂在 15min内出峰完毕。Zn2 + ,Cu2 + ,Ni2 + 和Mn2 + 的检测限分别为 0 0 5 μg/L ,0 0 1μg/L ,0 10 μg/L和 0 40 μg/L。     

Complexation of Ni, Cu, Zn, and Cd by DOC in some metal-impacted freshwater lakes: a comparison of approaches using electrochemical determination of free-metal-ion and labile complexes and a computer speciation model, WHAM V and VI

Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V.     

Heat Capacities of Aqueous Solutions of Acetone; 2,5-Hexanedione; Diethyl Ether; 1,2-Dimethoxyethane; Benzyl Alcohol; and Cyclohexanol at Temperatures to 523 K

The heat capacities of aqueous solutions of acetone, 2,5-hexanedione, diethyl ether, 1,2-dimethoxyethane, benzyl alcohol and cyclohexanol at concentrations of 0.1 to 1.0 mol⋅kg⁻¹ were determined at temperatures of 298.15, 423.15, 473.15 and 523.15 K and pressures up to 28 MPa. The measurements were performed at ambient conditions using the commercial Picker differential flow calorimeter and at high temperatures and pressures with a customized Picker type calorimeter constructed at the Blaise Pascal University, Clermont-Ferrand. Standard molar heat capacities were obtained by weighted extrapolation to the infinite dilution limit. The contributions of –CO–, –O– and –OH groups to the standard molar volume and standard molar heat capacity were determined from the newly determined and literature data. The variation of the three oxygen-containing group contributions with temperature and molecular structure is examined qualitatively.