Transport properties and electroanalytical response characteristics of drotaverine ion-selective sensors

The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10^–6 to 5×10^–2 mol L^–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10^–6 mol L^–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography.     

光度分析中协同系数补偿方法的研究──三次标准加入法同时测定钼、钨和钛

本文在两次标准加入法[1]的基础上，提出了三组份同时测定的三次标准加入法，并应用于钼、钨和钛的流动注射同时测定。测定条件：［水杨基荧光酮（SAF）］＝1．25　×10-4mol／L，［溴化＋六烷基三甲基铵（CTMAB）」＝2．5×10－3mol／L，pH1．35，25℃，采样、进样时间分别为10s和18s，进样频率128次／h。为消除组份间协同作用引起的吸光度加合性的偏离，定义了三组份协同系数。将其引入三组份同时测定方法，补偿了吸光度对线性的偏离。补偿后钼、钨和钛的测定范围分别为0．05～0．35，0．25～1．00，0．025～0．30mg／L。测定了钢样及模拟样品中钼、钨和钛含量，结果较好。     

Pitzer model parameters for sparingly soluble salts from solubility measurements. The systems TlCl+SrCl2+H2O and TlCl+BaCl2+H2O at 25°C

The solubility of thallium(I) chloride has been determined in aqueous solutions of strontium chloride and barium chloride at concentrations up to 1.5 mol kg^–1. The data were analyzed using Pitzer's equations without making explicit assumption of association to ion pairs by assuming =3 instead of =2, with the ⁽¹⁾ term for TlCl being equivalent to the ⁽²⁾ term for 2-2 electrolytes. Best values of ⁽⁰⁾ and ⁽¹⁾ for TlCl are recommended together with K _s , the activity solubility product. These were used to fit the present solubility data and derive the Pitzer model mixture parameters relevant to the systems, _fTIN and _fTINCl (N=Sr, Ba). Mixture parameters for TlCl+MCl+H₂O systems are also derived to complete the parameter base. The fit of the experimental data was found to be worse when higher-order terms for asymmetrical mixing were included in the analysis. Activity coefficients for thallium(I) chloride in the mixtures are derived.     

Experimental study of the concentration dependence of the soret coefficient by thermal field-flow fractionation: the case of polystyrene in decalin

Summary Thermal field-flow fractionation separates polymers with high selectivity according to their Soret coefficient,S _τ, hence, according to their molar mass, and therefore consitutes an efficeint physicochemical tool for the determination of the Soret coefficient of a given polymer in the carrier liquid from its retention time. However, the polymer concentration in the sample influences the retention time and, hence, the value ofS _τ derived from it. An experimental study of the influence of sample concentration on retention,S _τ, and peak shape was performed for the polystyrene-decalin system over a relatively large temperature domain and for various molar masses. It is found that the retention time and the value ofS _τ increase with increasing sample concentration, the more so as the cold wall temperature is lower. This appears to be in contradiction with the general non-equilibrium thermodynamic expression derived for polymer-solvent systems with positive second virial coefficients, such as the present system over the temperature range investigated. There seems to be a temperature for which the dependence ofS _τ on sample concentration vanishes. This temperature is about 375 K for the polystyrene-decalin system. As the sample concentration increases, the peak barycentre and the standard deviation increases. As the peaks are fronting, the skewness is negative and becomes more negative as the sample concentration increases. The peak skewness appears to be a good indicator of the onset of sample concentration effects. The threshold concentration, for which these effects begin to become significant, decreases with increasing molar mass.     

Role of Ion exchange in permeation processes

The single ion transport of transition metal ions like Cu²⁺, Co²⁺, Ni²⁺ and Zn²⁺ were carried out through the H⁺ and alkali metal ion forms of Nafion membrane. These studies showed that the ion exchange selectivity coefficient of the permeating ion had an effect on its transport process. It was found that the diffusion coefficient values (D) were directly proportional to the selectivity coefficient (K). This shows that the initial stage of permeation is governed by ion exchange process (effect of K on D).     

Dielectric properties of beryllia ceramics in the near-millimeter wavelength range

We report the refractive indices and absorption coefficients for four beryllia (BeO) ceramic samples. These dielectric properties have been measured over the range from 4 to 18 cm^–1 by use of a Michelson interferometer. The index n, follows the linear relationship n=0.6517 cm³/g×+0.7130 with density, , over the range 2.8<<3.0 g/cm³.     

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) x (x=2.5–5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La_0.67Mg_0.33 (Ni_0.8Co_0.1Mn_0.1) _x (x=2.5–5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5–3.5 is LaMg₂Ni₉ phase with a PuNi₃-type rhombohedral structure, but the main phase of the alloys with x=4.0–5.0 is LaNi₅phase with a CaCu₅-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg₂Ni₉phase and the LaNi₅ phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I ₀) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.     

用水合五氧化二锑分离放射性母子体的研究─—一个新的~(201)Pb—~(201)T1发生器的制备

本文研究了无机离子交换剂—水合五氧化二锑（Sb2O5·nH2O）的制备，并用它分离了放射性母子体，制备了一个新的201Pb—201Tl放射性发生器。结果表明，末发生器具有高效、快速、简便的特点，此外还讨论了离子交换反应的机理。     

超临界CO2中甲醇和乙醇无限稀释扩散系数的分子动力学模拟与实验测定

采用分子动力学模拟(MD)方法对甲醇和乙醇在超临界二氧化碳中的无限稀释扩散系数进行了模拟计算, 并应用泰勒分散理论, 采用超临界色谱仪对模拟结果进行了实验验证. 模拟计算值与实验值较吻合, 且变化规律基本一致, 表明采用这种新方法可以准确有效地预测超临界体系的扩散性质, 能够方便地应用于工程设计.     

Predictive models to describe VLE in ternary mixtures water + ethanol + congener for wine distillation

The modeling of liquid–vapor equilibrium in ternary mixtures that include substances found in alcoholic distillation processes of wine and musts is analyzed. In particular, vapor–liquid equilibrium in ternary mixtures containing water + ethanol + cogener has been modeled using parameters obtained from binary mixture data only. The congeners are substances that although present in very low concentrations, of the order of part per million, 10⁻⁶ to 10⁻⁴ mg/L, are important enological parameters [1] and [2]. In this work two predictive models, the PSRK equation of state and the UNIFAC liquid phase model and two semipredictive activity coefficient models: NRTL and UNIQUAC have been used. The results given by these different models have been compared with literature data and conclusions about the accuracy of the models studied are drawn, recommending the best models for correlating and predicting the phase equilibrium in this type of mixtures.