Free energies of transfer of alkali halides from water to urea-water mixtures at 25°C from EMF measurements

The standard potentials_s E ^o of M/M⁺ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values of_s E ^o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G _t ^o (MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li⁺ to Na⁺ but fall from Na⁺ to K⁺ and rather sharply from K⁺ to Cs⁺ with a maximum at Na⁺ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G _t ^o (i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions.     

A conductance study of the association of alkali cations with 1,13-dibenzo-24-crown-8 in acetonitrile

A conductance study concerning the association of Na⁺, K⁺, Rb⁺, and Cs⁺ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity _C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb⁺>Cs⁺>K⁺>Na⁺. Values of H^o and S^o are reported and their significance is discussed.     

Uronic (hexenuronic) acid profile of ethanol–alkali delignification of giant reed Arundo donax L.

The effect of process variables on uronic acids (UAs) and hexenuronic acids (HexAs) in the annual crop Arundo donax L. during ethanol–alkali pulping has been examined. A substantial loss of UA moieties (up to 90%) was observed by the end of pulping (target kappa number 18) performed with 25% NaOH and 40% EtOH (by volume) within the temperature range of 130–150 °C. At the same time, the progressive formation of HexA in pulp was detected from the early phases of delignification. The proportion of HexA in the residual UA of the final pulp was found to be 84%, indicating almost complete conversion of 4-O-methylglucuronic acid side groups (MeGlcA) of heteroxylan into HexA. The kinetics of UA degradation and HexA formation has been described in terms of three consecutive first-order reaction stages. The overall rate of UA degradation was one order higher than the rate of UA conversion into HexA. The values of apparent activation energy were estimated as 68.6 and 94.7 kJ mol^–1, respectively. The reaction medium alkalinity was shown to be the controlling factor for UA and HexA stability during ethanol–alkali pulping. An increase in alkali charge from 5% to 35% (as NaOH) led to UA loss of 40%, but promoted HexA formation from 11.8 to 20.1 mol g^–1. The addition of organic solvent to the alkaline pulping solution had a similar effect, and about 10% of UA was lost and the content of HexA increased from 6.9 to 10.9 mol g^–1 with an increase in ethanol proportion in the liquor from 20% to 60%.     

Enthalpies of Phase Transitions and Heat Capacity of TbCl3 and Compounds Formed in TbCl3–MCl Systems (M=K, Rb, Cs)

The molar enthalpies of the solid–solid and solid–liquid phase transitions were determined by differential scanning calorimetry for pure TbCl₃ and KTb₂Cl₇, RbTb₂Cl₇, CsTb₂Cl₇, K₃TbCl₆, Rb₃TbCl₆ and Cs₃TbCl₆ compounds. Both types of compounds, i.e. M₃TbCl₆ and MTb₂Cl₇ (M=K, Rb, Cs) melt congruently and show additionally a solid–solid phase transition with a corresponding enthalpy Δ_trs H ⁰ of 6.1, 7.6 and 7.0 kJ mol^–1 for potassium, rubidium and caesium M₃TbCl₆ compounds andΔ_trs H ⁰ of 17.1 (rubidium) and of 12.1 and 10.9 kJ mol^–1 (caesium) for MTb₂Cl₇ compounds, respectively. The enthalpies of fusion were measured for all the above compounds with the exception of Rb₃TbCl₆ and Cs₃TbCl₆. The heat capacities of the solid and liquid compounds have been determined by differential scanning calorimetry (DSC) in the temperature range 300–1100 K. The experimental heat capacity strongly increases in the vicinity of a phase transition, but varies smoothly in the temperature ranges excluding these transformations. C _p data were fitted by an equation, which provided a satisfactory representation up to the temperatures of C _p discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the liquid phase, which had been previously measured. The results obtained agreed satisfactorily with these experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

烟酸铬(Ⅲ)的配位结构与生物活性关系

合成了2种新型吡啶-3-羧酸(烟酸)铬(Ⅲ)螯合物,通过元素分析、热分析、红外光谱和电子光谱证明烟酸作为双齿配位体,形成具有3个六员环的螯合物Cr(Nic)3和具有2个六员环与2个H2O单体的混型配合物[Cr(Nic)2(H2O)2]Cl。通过使用效能等试验表明,在猪饲料中添加不同配位结构的烟酸铬均有明显提高饲料利用率、促进生长和显著提高机体对葡萄糖的清除率等作用。试验还表明,双齿配位的烟酸铬具有较高的生物活性、无毒、饲用后在肌体内无残留,作为饲料添加剂具有广阔的应用前景。     

Arsenidostannate mit Arsen-analogen [SnAs]-Schichten: Darstellung und Struktur von Na[Sn2As2], Na0,3Ca0,7[Sn2As2], Na0,6Sr0,6[Sn2As2], Na0,6Ba0,4[Sn2As2] und K0,3Sr0,7[Sn2As2]

Arsenidostannates with [SnAs] Nets Isostructural to Grey Arsenic: Synthesis and Crystal Structure of Na[Sn₂As₂], Na_0.3Ca_0.7[Sn₂As₂], Na_0.4Sr_0.6[Sn₂As₂], Na_0.6Ba_0.4[Sn₂As₂], and K_0.3Sr_0.7[Sn₂As₂] The metallic lustrous compounds Na[Sn₂As₂], Na_0.3Ca_0.7[Sn₂As₂], Na_0.4Sr_0.6[Sn₂As₂], Na_0.6Ba_0.4[Sn₂As₂] and K_0.3Sr_0.7[Sn₂As₂] were prepared from melts of mixtures of the elements. The compounds crystallize in the trigonal system (space group R3 m, No. 166, Z = 3) with lattice constants see in “Inhaltsübersicht”. The structures are isotypic to Sr[Sn₂As₂] containing puckered [SnAs] nets which are stacked with a sequence of six layers. The E(I)/E(II) atoms are located between each second [SnAs] layer in trigonal antiprismatic interstices formed by As atoms. In the resulting [Sn₂As₂] double layers the _∞²[SnAs] nets are stacked in such a way that additional Sn—Sn contacts arise.     

Effects of different alkali metal ions on the cationization of poly(ethylene glycol)s in matrix-assisted laser desorption/ionization mass spectrometry: a new selectivity parameter

The cationization of poly(ethylene glycol)s, PEG 4000 and PEG 6000, under matrix-assisted laser desorption/ionization conditions was studied by using different concentration ratios of the sodium ion, as the reference ion, and another alkali metal ion (Li(+), K(+), Rb(+), Cs(+)). A linear correlation was found between the intensity ratio of the sodiated PEGs and PEGs cationized with alkali metal ions versus the initial concentration ratio of sodium and alkali metal ions. The slopes of these straight lines are proposed as a novel selectivity ratio for the ionization process. The intensity distribution of the cationized PEGs was also investigated. It was found that the cationized oligomers follow Poisson statistics. The M(n) and M(w) values were also evaluated. An explanation for the observed effects is given.     

Proton-ionizable crown compounds. 12. Proton-Coupled selective membrane transport of Li+ using a proton-ionizable pyridono macrocycle

The macrocycle-mediated fluxes of several alkali metal cations have been determined in a H₂O-CH₂Cl₂-H₂O liquid membrane system. Water-insoluble proton-ionizable macrocycles of the pyridono type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H⁺ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. The desired separation of a particular metal ion involves its selective complexation with the macrocycle, subsequent extraction from the aqueous phase to the organic phase, and exchange for H⁺ at the organic phase-receiving phase interface. Factors affecting transport which were studied include ring size, source phase pH, and receiving phase pH. Lithium was transported at a rate higher than that of the other alkali metals in both single and competitive systems using a 15-crown-5 pyridono carrier.     

Enthalpies of Dilution of Aqueous Solutions of NaOH, KOH, and CsOH at 300, 325, and 350°C

Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of KOH and CsOH at 300°C and 11.0 MPa, 325°C and 14.8 MPa, and for aqueous solutions of NaOH, KOH, and CsOH at 350°C and 17.6 MPa. Previously collected dilution enthalpies for aqueous solutions of NaOH at 300°C and 9.3 MPa and at 325°C and 12.4 MPa were included when fitting the Pitzer parameters. The concentration range of the hydroxide solutions was 0.5–0.02 molal. Parameters for the Pitzer excess Gibbs ion-interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat capacity changes for alkali metal ion association with hydroxide ion were estimated from the heat data. For all systems, the enthalpy changes and entropy changes were positive and had accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.     

Proton-ionizable crown compounds. 17. Transport studies of alkali metal ions in a H2O-CH2Cl2-H2O liquid membrane system by macrocycles containing two sulfonamide groups derived fromo- andm-phenylene diamine

The transport of alkali metal cations by several macrocycles possessing two sulfonamide groups as a part of an 18-, 20-, or 21-membered macroring has been studied. Some of these compounds were found to be more effective transport agents than the proton-ionizable pyridone- and triazole-containing crown ethers reported previously. The factors affecting transport, such as ring size, source and receiving phase pH, and the nature of the groups attached to the sulfonamide nitrogen atoms were examined. Also, extraction experiments by some of the ligands were performed. The behavior of sulfonamide type crowns in single and competitive transport of the alkali metal cations is explained. The mechanism of transport appears to be complex. Transport of one or two cations per molecule of the disulfonamide carriers occurs. Complexation of these cations appears to occur both within and outside the macrocycle cavity. Our results also suggest that kinetic factors may play a significant role in transport rates and selectivities.Deceased: September 5, 1987.