Solvation of Cobalt(II) Ion in N,N-Dimethylformamide–Methanol Mixed Solvent: Calorimetry and VIS Spectroscopy Studies

The enthalpies of solution of Co(II) and Na(I) trifluoromethanesulfonates (triflates) in N,N-dimethylformamide (DMF)–methanol (MeOH) mixtures have been measured over the whole range of solvent composition. From these data the enthalpies of transfer of Co(II) and triflate ions from methanol to the mixed solvent have been determined usingliterature values of the enthalpies of transfer of the Na⁺ ion. The results have been analyzed by means of the theory of preferential solvation. The analysis revealed the preference of DMF for solvating the Co(II) ion in the MeOH-rich region of solvent composition and the lack of preference of any component in the DMF-rich region. Visible absorption spectra of the Co(II) ion in DMF–MeOH mixtures have been also measured in the whole range of solvent composition and analyzed using the partial least-squares method. The mean composition of the solvation sphere of the Co(II) ion versus solvent composition has been determined on the basis of both analyses. The results were found to be consistent with each other and with those obtained previously from FT-IR spectra.     

Fourier transform Raman spectral measurements of powdered quaternary mixtures of organic compounds: Exceptional pure component spectral reconstruction using band-target entropy minimization (BTEM)

Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures.     

Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.     

Radio-frequency induction plasmas at atmospheric pressure: Mixtures of hydrogen,nitrogen, and oxygen with argon

Numerical calculations are reported which simulate atmospheric-pressure radiofrequency induction plasmas consisting of either pure argon or mixtures of argon with hydrogen, nitrogen, or oxygen. These calculations are compared to observations of laboratory plasmas generated with the same geometry and run conditions. The major features of the laboratory plasmas are predicted well by the calculations: the pure argon plasma is the largest, with the argon-oxygen plasma slightly smaller. The argon-nitrogen plasma is considerably smaller and the argon-hydrogen plasma is the shortest, although somewhat fatter than the argon-nitrogen case. The calculations are not entirely successful in predicting the exact location of the plasmas relative to the coils. A likely explanation is that there is significant uncertainty regarding the actual power coupled to the laboratory plasmas.     

外加盐作用形成的正负离子表面活性剂双水相

癸基三乙基溴化铵-癸基磺酸钠（C10NE-C10SO3）等摩尔混合均相体系（即使在表面活性剂总浓度高达0.2 mol•L－1时仍然可形成稳定的均相溶液）在外加盐NaF、Na2SO4和Na3PO4的作用下可自发分离成两个水相（双水相）.研究了该类双水相体系的形成、相行为及其对牛血清蛋白（BSA）的分配，并与普通的正负离子表面活性剂混合双水相体系进行了比较.结果表明，该类双水相体系克服了普通的正负离子表面活性剂混合双水相体系的一些不足，具有一些独特的优点.该类双水相体系的相行为可以通过外加盐进行调控,通过外加盐的种类来调控和优化BSA的分配行为.图1表2参8     

ViscosityB-coefficients for lithium perchlorate in ethylene glycol-water mixtures

Viscosities and densities of lithium perchlorate solutions in different ethylene glycol-water compositions have been measured at 25.0 and 35.0 °C. From these data, the correspondingB-coefficients of theJones-Dole equation have been determined. TheB-value depends on the solvent composition and it reaches a maximum in the water-rich region. This behaviour is analysed in terms of ionic solvation and solvent structure.

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Viskositäts-B-Koeffizienten für Lösungen von Lithiumperchlorat in Ethylenglykol-Wasser-Mischungen

Zusammenfassung Es wurden die Dichten und Viskositäten für Lösungen von Lithiumperchlorat in verschieden zusammengesetzten Ethylenglykol-Wasser-Mischungen bei 25 °C und 35 °C gemessen. Auf Grund der erhaltenen Daten wurden dieB-Koeffizienten in den entsprechendenJones-Dole-Gleichungen für die relative Viskosität bestimmt. DieB-Werte hängen von der Zusammensetzung des Lösungsmittels ab und erreichen im wasserreichen Konzentrationsgebiet ein Maximum. Dieses Verhalten wird in Hinblick auf die Ionensolvatation und die Struktur des Lösungsmittels analysiert.

     

Influence of inhibitory compounds and minor sugars on xylitol production by <Emphasis Type="Italic">Debaryomyces hansenii</Emphasis>

To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose (60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0 g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic materials.     

Electrochemical study of 18-crown-6-Tl+ complexes in binary solvent mixtures

Summary The formation constants,K _S, of the 18-crown-6 complex with thallium(I) ion were studied by polarographic measurements in binary mixtures of acetonitrile, acetone, tetrahydrofuran, and dimethylsulfoxide with water, as a function of the solvent mole fraction. In all the cases, the variation of the stability constant can be described by the empirical relation logK _S=a[(–1)/(2+1)]+b where stands for relative permittivity of a given mixture anda andb mark the regression coefficients. The values ofa calculated for four series of binary mixtures showed correlation with the Gutmann donor numbers of the neat organic solvents which form the mixture.On leave from the Department of Chemistry, Jingzhou Teacher's College, Jingzhou, Hubei, China     

Quantitative volatilization of tin as mixed halides and its application in metal analysis

Proposed in this paper is an improved method for removal of tin as the matrix element by volatilization in an anhydrous medium as mixed halides of different composition. Any one of them boils at a lower temperature than SnBr₄. This ternary system enhances the eventual recombination of temporarily dissociated species to volatile ones, thus making the process quicker and more efficient. The presence of 2 mg of Pb(II) suffices to prevent Bi(III) from loss due to volatilization.     

Thermodynamic excess properties of alkanol + amine mixtures and application of the ERAS model

New experimental data of the molar excess volume V ^E of the mixtures ethanol/n-butylamine, heptanol/n-butylamine, n-propanol/dibutylamine have been obtained using the technique of the vibrating tube densitometer. Together with the data for the molar excess enthalpy H ^E from the literature, the V ^E data have been used for testing the applicability of the socalled ERAS model which accounts for hydrogen bonding effects as well as for free volume effects in associating mixtures. The results obtained by adjusting the model parameters reveal a strong cross association between the unlike molecules in the mixture resulting from strong negative values for the hydrogen bonding energy and the hydrogen bonding volume.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.