NMR evidence of pentaoxo organosilicon complexes in dilute neutral aqueous silicate solutions

Silicon-29 NMR spectra of a neutral, dilute aqueous silicic acid solution, with a pH and Si concentration typical of soil solutions, reveal that a significant fraction of the silicon is incorporated in two five-coordinated organosilicon complexes when sodium gluconate is present.     

Stoichiometries and stability constants for the cerium(IV) carbonate complexes in dilute aqueous solution

Complexation between cerium(IV) and carbonate ions in aqueous solution has been studied by UV/Visible absorption spectroscopy, ¹⁷O NMR spectroscopy and potentiometric titration, and it is shown that in dilute solutions at pH 8.8 and 10, both 1?:?1 and 1?:?2 (metal?:?ligand) complexes are formed. This contrasts with the behaviour of the corresponding Th(IV) complex, where the dominant species is the pentacarbonato complex. From the NMR spectra, it is suggested that these species involve bidentate binding of carbonate ion by the metal, while potentiometric data provided accurate formation constants and indicated the dominant species to be the 1?:?2 complex.     

利用微生物本身的PHAs解聚酶生产羟基丁酸单体

金黄芽孢杆菌Bacillus aureus JMα5先在糖蜜上发酵积累聚羟基丁酸酯（PHB）,然后在限氧条件下降解生成手性羟基丁酸（HB）分子。研究各种培养条件如pH值、温度、时间等对该菌降解生产手性HB分子的影响。结果表明,37℃下,当pH=6时,10h内,HB单体的产量可达3．04g/L,降解率为75％,说明采用酶降解法生产HB单体具有一定的实际应用价值。在各种影响因素（包括降解体系的pH值、降解的温度和降解时间等）中,pH值对降解率的影响最大。     

Global non-ideality effects in adsorption of organic substances from dilute aqueous solutions on activated carbon

Summary A method for the quantitative estimation of the global non-ideality of the adsorption of weak organic electrolytes on activated carbon from dilute aqueous solutions is presented. The method is based on the analysis of aGraham plot which reflects the adsorption isotherm deviations from ideality. Averaging these deviations over the whole range of adsorption, one gets a single value representing the global non-ideality of a system. The method also allows to estimate the contributions of heterogeneity and interactions in the adsorbed phase to the global non-ideality effect. The theoretical considerations are illustrated by some model calculations. The usefulness of the method is tested for experimental data of benzoic and salicyclic acid adsorption over a wide range ofpH and concentrations.

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Globaler Effekt der Nicht-Idealität bei der Adsorption organischer Substanzen aus verdünnten wässerigen Lösungen an Aktivkohle

Zusammenfassung Es wird eine Methode zur quantitativen Abschätzung der globalen Nicht-Idealität für die Adsorption schwacher organischer Elektrolyte aus verdünnten wässerigen Lösungen an Aktivkohle vorgestellt. Diese Methode basiert auf der Analyse der bekanntenGraham-Abhängigkeit, die die Abweichung der Adsorptionsisotherme von der Idealität zeigt. Bei Errechnung des Durchschnittwertes dieser Abweichung über den ganzen Asorptionsbereich erhält man einen Wert, der die globale Nicht-Idealität für ein Adsorptionssystem charakterisiert. Die Methode erlaubt auch, den Beitrag der Heterogenität und der Wechselwirkungen in der Adsorptionsphase zum globalen Effekt der Nicht-Idealität abzuschätzen. Die theoretischen Erörterungen werden an Hand von Modellberechnungen illustriert. Die Nutzbarkeit der Methode wurde mit experimentellen Daten der Benzoe- und Salicylsäureadsorption in einem weiten Bereich vonpH und Konzentration getestet.

     

Structural properties of dilute aqueous solutions of dimethylformamide and acetone based on computer simulation

The Monte Carlo simulation of molecular configurations for aqueous solutions ofN,N-dimethylformamide and acetone was carried out. The atom-atom radial distribution functions were determined. The topological properties of the H-bond system were investigated. The concentrations of closed H-bond cycles and the radial distribution functions of their geometric centers were found. It was shown that the local arrangement of molecules and supermolecular assemblies typical of the H-bond network in neat water is retained in the solutions studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 592–599, April, 1998.     

Activity coefficients and diffusion coefficients of dilute aqueous solutions of lithium,sodium, and potassium hydroxides

A simplified version of Harned's conductimetric technique has been used to measure binary diffusion coefficients of aqueous lithium, sodium, and potassium hydroxides at 25°C from 0.002 to 0.14 mol-dm^–3. Because of the large difference in mobility between OH^– and the cations, the electrophoretic effect tends to reduce the rate of diffusion of the alkali metal hydroxides; the largest effect is observed for LiOH solutions. The measured diffusion coefficients are in excellent agreement with predictions of the Onsager-Fuoss theory of ion transport. Precise activity coefficients determined from the diffusion measurements are compared with activity coefficients obtained previously by emf methods.     

Liquid-vapor equilibrium of dilute aqueous solutions of ethanol and 2-propanol

An automated vapor pressure apparatus has been used to obtain highly precise values of the total pressure and composition of aqueous solutions of ethanol and of 2-propanol in the water-rich region at 25 and 35°C. From these results, values of the partial pressures and fugacities of the components and osmotic coefficients have been inferred. Interaction virial coefficients derived from the present results are compared with interaction parameters previously reported for alcohol molecules in dilute aqueous solution. A discussion is given of the relative importance of hydrophobic effects and hydrogen-bonding in producing the unusual thermodynamic properties of aqueous alcohol solutions.     

Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation

The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's⁽¹⁾ equations as well as the Chen and Evans⁽²⁾ model were used to correlate the new data. Results are reported and compared to literature data and correlations.     

Synthesis of polymers in aqueous solutions: Polyaddition of bis(oxazolines) with dithiol in aqueous solutions

Polyaddition of bis(4-mercaptophenyl) sulfide ( BMPS ) with m-phenylenebis(2-oxazoline) ( MPBO ) proceeded very smoothly in the mixtures of aprotic ploar solvents such as N-methyl-2-pyrrolidone ( NMP ) with water to produce the corresponding poly(amide–sulfide) with high molecular weights at 90°C under nitrogen. The reaction of BMPS with MPBO , p-phenylenebis(2-oxazoline), and 1,4-butylenebis(2-oxazoline) was also examined in water under the same conditions, and it was found that the reaction proceeds successfully to give the corresponding poly(amide–sulfide)s with high molecular weights. These results mean that water along as well as the mixed solvents of aprotic polar solvents such as NMP with water can be uses as suitable reaction media for the polyaddition of bis(oxazolines) with dithiol to synthesize poly(amide—sulfide)s with high molecular weights. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2711–2717, 1997     

The influence of pressure on ionization equilibria in aqueous solutions

A comparison is made of the abilities of two simple relationships to describe the influence of pressure on ionization constants in aqueous solutions.     

Thermodynamics of bolaform electrolytes. V. Enthalpies and heat capacities in aqueous urea solutions

The partial molal heats of solution at infinite dilution of 1,4-bis(triethylammonium)butane dibromide and 1,10-bis(triethylammonium)decane dibromide in aqueous urea (up to 8m urea) have been determined calorimetrically in the temperature range 18–33°C. These data have been used to derive the partial molal heat capacities at infinite dilution, the enthalpies of transfer, and heat capacities of transfer at infinite dilution from water to urea-water solutions. The results show that the enthalpies of transfer are negative and decrease with increasing urea concentrations. The heat capacities of transfer are negative at low urea concentrations and increase in magnitude at higher urea concentrations. In the case of the smaller cation the partial molal heat capacity in 8m aqueous urea solution is greater than in pure water. The results are discussed in terms of structural changes in the solvents on dissolution.     

Viscometric study of gelatin in dilute aqueous solutions

The viscosities of aqueous solutions of gelatin at different temperatures were carefully measured in a common glass‐capillary Ubbelohde viscometer at dilute to extremely dilute concentrations. The adsorption effect that occurred in the viscosity measurements was theoretically analyzed and discussed. A theory based on Langmuir isotherms could adequately describe the existing data. Some structural information was obtained by the use of an iterative fitting procedure to treat the reduced viscosity data, which disclosed that individual gelatin chains underwent a coil‐to‐helix transition as the solution cooled from 40 to 15 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1804–1812, 2006     

Volumetric properties of dilute aqueous solutions of cobalt-amine-type salts. Part I. Densities at 25°C

The densities of dilute aqueous solutions of [CoL₃]X₃ [L=1,2-diaminoethane(en), 1,2-diaminopropane(pn), 1,3-diaminopropane(tn) X=Cl^–, Br^– and (ClO₄)^–] have been measured at 25°C from 0 to 5×10^–2m. The apparent molar volumes were calculated and extrapolated to infinite dilution. Ion-solvent interactions were detected from the change of the ionic partial molar volumes with concentration. These interactions depend both on the properties of the ion (polarization charge density at the surface, hydrophobic groups, etc.) and the characteristics and structure of the solvent.     

Complexation of the potassium ion by diaza crown compounds in aqueous solutions

The conductance behavior of potassium nitrate in water with and without 1,7,10,16-tetraoxa-4,13-diazacyclooctandecane[2.2] and 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-8.8.8-exacosane[2.2.2] macrocyclic ligands have been studied in order to analyze the complexation behavior of potassium cations in water. The absence of the complexation found in the [2.2] system is discussed in terms of the ligand structural features (presence of hydrogen bond donor and acceptor sites). The ion pair association constant of potassium cryptate as obtained from conductance measurements is also reported and discussed.     

壳聚糖硫酸酯稀溶液的粘度特性

通过毛细管粘度法考察了壳聚糖硫酸酯(Sulfated Chitosan,SCM)稀溶液的粘度特性。在非电解质溶液中,SCM比浓粘度随浓度的变化符合Fouss-Strauss经验关系式:ηsp/C=316.45×(1+79.88C1/2)-1。通过外加强电解质,SCM表现出正常的粘度行为,并且[η]随着外加强电解质离子强度的增加而减小。     

Enthalpies of mixing of some nitriles aqueous solutions with dodecylsurfactants micellar solutions

The enthalpies of mixing of some n-nitriles (from acetonitrile to valeronitrile) aqueous solutions with dodecyltzimethylammonium bromide, sodium dodecylsulfate and dodecyltzimethylammonium oxide micellar solutions were determined. The measurements were performed by systematically changing the surfactant concentration at a given solute concentration. The experimental enthalpies were rationalized in terms of the standard enthalpy of transfer of solute from the aqueous to the micellar phase and of the distribution constant between the two phase. Information on the effect of the nature of the surfactant on the standard thermodynamic quantities of transfer(G _t ^o , H _t ^o , TS _t ^o ) is reported. The present data are compared to those previously reported for primary alcohols and the solubilizing properties shown by the different types of micelles are discussed.     

Variations of activity coefficients in concentrated electrolyte solutions at constant lonic strength

Measurements of different types on various (trace) electrolytes in HClO₄–Na(Li)ClO₄ solutions at several (constant) values of the ionic strength have been used to determine the variation of their activity coefficients with changing amount of perchloric acid in the solution. These variations (with respect to the hydrogen ion) differ considerably among different cations and anions. The results for the alkali metal ions and the anions are interpreted in the light of the recent work of Pitzer on short-range ionic interactions. The results for the cations with outerd-electrons and the alkaline earth metal ions are interpreted in terms of ion-solvent interactions. It is concluded that the use of HClO₄–NaClO₄ solutions of high ionic strength (rather than the use of HClO₄–LiClO₄ solutions) is advisable in studies where the variation in activity coefficients must be accounted for. Finally, it is shown that the usual interpretation of the influence of the salt medium in studies of complex equilibria and reaction kinetics is sometimes questionable.