Influence of the Type of a Ligand on the Intensity of Luminescence of Ln3+ Ions in Aqueous Solutions

The luminescence characteristics of hydrated Ln³⁺ ions and their complexes with some acidic ligands have been investigated. The possibility of determining the stability of the complexes of lanthanides in solutions from the intensity of luminescence bands is shown. The influence of the characteristic features of the f-electron shell of Ln³⁺ on the formation of the spectrochemical series is discussed.     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

Liquid-liquid phase equilibria of aqueous two-phase systems containing salts and polyethylene glycol

Liquid-liquid phase equilibria of the ternary systems: (a) polyethylene glycol - ammonium sulfate- water and (b) polyethylene glycol - sodium carbonate -water have been determined experimentally at 15°, 25°, 35° and 45°C and for two different molecular weights of the polymer (Avg. M.W. 1000 and 2000). Details of the glass cell and of the equilibration and analytical procedures used are described. Equilibrium data along with phase diagrams are presented. Finally the effect of temperature and of the molecular weight of the polymer are also discussed.     

Ag纳米颗粒的光吸收和透射电镜研究

用硼氢化钠作还原剂,制备出两种相对稳定的含银纳米颗粒的水溶胶,用透射电镜（TEM）和光学吸收谱对这些颗粒进行了表征.当被还原的银离子较少时,所形成的银纳米颗粒较小,吸收峰呈现二极等离子体共振吸收峰.当被还原的银离子较多时,银纳米颗粒尺寸变大,并出现二极和四极共振吸收峰.在Ag纳米颗粒形成后,对其溶液稀释,发现其峰形保持不变,而峰位会出现红移,最大红移量可达到10 nm.透射电镜研究表明,低浓度溶胶中的Ag纳米颗粒尺寸较为均匀,平均直径12 nm.高浓度溶胶中的纳米颗粒尺寸呈双尺寸分布特点,少量颗粒直径小于14 nm,大部分颗粒直径大于20 nm.     

Activity coefficients for NaBr in aqueous ternary solutions with sodium propionate and butyrate from EMF measurements

The activity coefficients of NaBr in the NaBr–NaPropionate–H₂O and NaBr–NaButyrate–H₂O systems were determined from EMF measurements at constant total ionic strength of 0.1 0.5 1.0 1.5 2.0 and 2.5 mol-kg^–1 and at 25° C. The activity coefficients were fitted using Scatchard, Pitzer and Lim equations. Finally the excess Gibbs free energy of these mixtures were also calculated.     

Study of intermediates formed in the oxidation of thiols

The oxidation of aminoethanethiol (1) was investigated in acid solutions on a glass carbon anode. It was shown that at relatively low anode potentials thiyl radicals RS^· are released into the solution, but this does not lead to binding of the oxygen in the solution. Raising the anode potential leads to binding of oxygen, which is probably due to the formation of the intermediate RS⁺. The oxidation of 1 was studied in Ce(SO₄)₂+H₂SO₄ solution. It was shown that under certain conditions the intermediate is RS⁺, which subsequently converts to a product that could not be identified as any previously described product of the oxidation of thiols. Proposals are made regarding its structure and conversion pathways.B. P. Konstantinov Institute of Nuclear Physics, Russian Academy of Sciences, 188350 Leningrad. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 278–288, February, 1992.     

Flaked capillary columns with crown ether complexes for gas-liquid chromatography

Flaked capillary columns with an OV-101/CE-Na{in3}PO{in4} hydrophobic-hydrophilic sorbent have been suggested. This sorbent provides for the analysis of polar and nonpolar substances, including amines and aminoalcohols, in aqueous and organic solvents. The efficiency of new columns was demonstrated for the analysis of 25 organic substances of various classes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2169–2173, December, 1994.The work was financially supported by the Russian Foundation for Basic Research, Project No. 93-03-4969.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

Dimerization of some substituted benzoic acids in aqueous solution from conductance measurements

Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion.