萘二磺酸钠盐的等压渗透系数和活度系数

芳基磺酸及其盐是化学工业、染料、清洁剂和离子交换树脂等许多方面使用得非常广泛的化学材料之一。在有机化合物分子上引进磺酸基团可大大改善化合物在溶剂中的可溶性等性质.磺酸基在化学和物理现象上所引起的作用已有许多工作者进行过研究。文献[1.2.3]报导了一些苯磺酸及其盐水溶液渗透系数和活度系数的测量结果.为了比     

钨酸钠水溶液的活度系数和渗透系数

The activity coefficients and osmotic coefficients of Na_2WO_4 aqueous solution in the concentration range of 0.3--2.5 mol·kg~(-1) have been determined by the isopiestic method. The excess Gibbs free energies are evaluated with the correspording activity coefficientc and osmotic coefficients.     

含锂水盐体系热力学性质研究:LiCl-MgCl~2-H~O体系渗透系数和活度系数的等压测定

25℃下,用等压法测定了单盐水溶液(浓度范围分别为0.5-19.8mol.kg^-1,0.3-6.0mol.kg^-1)以及混合水溶液(离子强度范围为0.6-19.4mol.kg^-1)的水活度和渗透系数,同时测定了LiCl的溶解度.该体系的实验等水活度线符合本工作推导出的Zdanovskii规则扩展式,用Gibbs-Duhem方程和改进的Mckay-perring方法计算了单盐和混合盐水溶液的活度系数.由本实验获得的渗透系数拟合了Pitzer单盐和混合作用参数,检验了Pitzer方程对该体系渗透系数、活度系数和溶解度预测的适用性.用Pitzer方程取本工作得到的参数计算的溶解度与文献实验值基本一致.     

含锂水盐体系热力学性质研究:LiCl-MgCl~2-H~O体系渗透系数和活度系数的等压测定

25℃下,用等压法测定了单盐水溶液(浓度范围分别为0.5-19.8mol.kg^-1,0.3-6.0mol.kg^-1)以及混合水溶液(离子强度范围为0.6-19.4mol.kg^-1)的水活度和渗透系数,同时测定了LiCl的溶解度.该体系的实验等水活度线符合本工作推导出的Zdanovskii规则扩展式,用Gibbs-Duhem方程和改进的Mckay-perring方法计算了单盐和混合盐水溶液的活度系数.由本实验获得的渗透系数拟合了Pitzer单盐和混合作用参数,检验了Pitzer方程对该体系渗透系数、活度系数和溶解度预测的适用性.用Pitzer方程取本工作得到的参数计算的溶解度与文献实验值基本一致.     

等压法测定Li2SO4-MgSO4-H2O体系的渗透和活度系数

在25 ℃下, 离子强度范围分别为0.2—8.7、0.6—12.7和1.4—13.5 mol·kg~(-1)时, 测定了纯Li_2SO_4、MgSO_4及Li_2SO_4-MgSO_4混盐水溶液的渗透系数. 计算了Pitzer方程和Scatchard方程的离子作用参数. 用上述两种方程及由热力学关系式直接推导出的Mckay-Perring方程计算并比较了Li_2SO_4和MgSO_4在混合溶液中的平均活度系数, 三者在实验误差范围内一致. 利用获得的Pitzer参数计算该体系的溶解度与文献值基本一致.     

308.15K下NaCl-CaCl_2-H_2O体系热力学性质的等压研究

采用等压法研究了308.15K下NaCl-H2O、CaCl2-H2O和NaCl-CaCl2-H2O体系离子强度分别为0.5666～5.9265molkg-1、0.3943～5.5573molkg-1和0.6524～16.6631molkg-1的等压平衡浓度和水活度,计算了渗透系数及饱和蒸汽压,获得了该体系渗透系数和饱和蒸汽压随离子强度的变化规律.应用Pitzer离子相互作用模型,用实验数据用多元线性回归拟合了308.15K下该体系的NaCl和CaCl2的纯盐参数β(0)、β(1)、Cφ分别为0.3181、1.5346、-0.0014和0.07972、0.3067、0.00075,拟合标准偏差分别为0.00072、0.0049;混合离子作用参数θNa,Ca、ψNa,Ca,Cl分别为0.06821、-0.0076,拟合标准偏差为0.0063和0.0064.用Pitzer模型计算的渗透系数与实验结果吻合.本研究为含钠钙海卤水体系热力学模型建立提供了重要的热力学基础数据.     

含锂水盐体系热力学性质研究——LiCl-MgCl_2-H_2O体系渗透系数和活度系数的等压测定

25℃下,用等压法测定了单盐水溶液(浓度范围分别为0.5—19.8mol·kg~(-1),0.3—6.0mol·kg~(-1))以及混合水溶液(离子强度范围为0.6—19.4mol·kg~(-1))的水活度和渗透系数,同时测定了LiCl的溶解度.该体系的实验等水活度线符合本工作推导出的Zdanovskii规则扩展式.用(Gibbs-Duhem方程和改进的Mckay-Perring方法计算了单盐和混合盐水溶液的潘度系数.由本实验获得的渗透系数拟合了Pitzer单盐和混合作用参数,检验了Pitzer方程对该体系渗透系数、活度系数和溶解度预测的适用性,用Pitzer方程取本工作得到的参数计算的溶解度与文献实验值基本一致.     

钨酸钠水溶液的活度系数和渗透系数

在周期表第ⅥB族元素Cr、Mo、W六价含氧离子钠盐化合物中,钨酸盐及其在水溶液中的热力学性质是知道得最少的.钨酸钠在水溶液中的活度系数和渗透系数虽然有报道,但由于测量方法不同,给出的结果彼此相差较大.结合着无机盐水溶液热力学性质的研究,我们对钨酸钠在水溶液中的活度系数用等压法进行了测量,浓度范围从0.3到2.5mol·kg~(-1).     

5,10,15,20-四(对-磺酸苯基)卟啉四钠盐水溶液的稀释热和活度系数的研究

使用LKB 2107微热量计系统和等压法测量仪,分别测量了25℃时5,10,15,20-四(对-磺酸苯基)卟啉四钠盐水溶液的稀释热和活度系数,计算了相对偏摩焓。     

凝固点降低法研究卟啉苯磺酸锂盐的平均活度系数

凝固点降低法研究卟啉苯磺酸锂盐的平均活度系数徐瑛（武汉工业大学材料工程系４３００７０）吴鼎泉，屈松生（武汉大学化学系４３００７２）关键词凝固点降低法，５，１０，１５，２０─四（对─磺酸苯基）卟啉四锂盐，平均活度系数引言等蒸气压法和凝固点降低法均是测定...     

Isopiestic determination of osmotic and activity coefficients of aqueous solutions of aliphatic polyols at 298.15 K

The osmotic coefficients of 1,2-butanediol (12BD), 1,3-butanediol (13BD), 1,4-butanediol (14BD), 2,3-butanediol (23BD), 1,2,4-butanetriol (124BT) and 1,2,3,4-butanetetrol (1234BT) in water were measured by the isopiestic method at 298.15 K. Experimental osmotic coefficients were used to calculate water activity, solute activity coefficients and the pairwise Gibbs energy coefficients for solute–solute interactions.     

Thermodynamics of the Solubility of Water in 1-Hexanol, 1-Octanol, 1-Decanol, and Cyclohexanol

Summary. The solubility of water in 1-hexanol, 1-octanol, 1-decanol, and cyclohexanol was determined as a function of water activity by the isopiestic method at 298.2K. The solubility of water in the alcohol was expressed by a Setchenov type of equation and the correlation coefficients were related to the virial coefficients of the McMillan-Mayer theory of solution. From the solubility data both the activities and the osmotic coefficients of the alcohols were calculated. The Henrys law constants for the solubility of water in the alcohols are given. They depend linearly on the Gibbs energy of hydration. The excess Gibbs energy of mixing of water and alcohols is positive as a consequence of the strong intermolecular interactions of the two pure components of the mixture.     

用电势法测定混合电解质NaCl-Me4NCl-H2O体系在298．15K的活度系数

用电势法测定混合电解质ＮａＣｌ－Ｍｅ_４ＮＣｌ－Ｈ_２Ｏ体系在２９８．１５Ｋ的活度系数阎卫东,姚加,韩世钧,徐奕瑾（浙江大学化学系,杭州,３１００２７）关键词含季铵盐混合电解质,活度系数,渗透系数作为电解质溶液热力学研究工作［１］的继续,本文选择了含季...     

CaCl2在甘氨酸+水和丙氨酸+水混合溶剂中的活度系数

利用离子选择性电极(ISE)测定了298.15 K时CaCl2在甘氨酸+水和丙氨酸+水混合溶剂中的活度系数. CaCl2的质量摩尔浓度变化范围为0.01～0.20 mol/kg, 氨基酸的质量摩尔浓度变化范围为0.10～0.40 mol/kg. 用Debye-Hückel扩展方程和Pitzer方程进行理论计算得到的活度系数基本一致. 依据McMillan-Mayer理论, 计算了CaCl2从纯水到氨基酸水溶液的标准转移Gibbs自由能, 利用最小二乘法拟合求得了对相互作用参数(gEA)和盐效应常数(ks). 讨论了这两种氨基酸的加入对CaCl2的活度系数、热力学稳定性及盐效应常数的影响.     

Osmotic coefficient data and an excess Gibbs energy function for single-phase complex system of glucose + alcohol + water

Thermodynamics of single-phase complex systems of glucose + alcohol + water is significantly important in food and pharmaceutical industries. The water activity is a practical parameter in thermodynamic characterization in food and pharmaceutical and other biological industries, which its value has an important role in growing microorganisms and rate of reactions. In this work, the NRTL-NRF excess Gibbs function has extended for ternary system of water, different alcohols (as second molecular solvent) and a special molecular solute like a sugar. The extended NRTL-NRF model with three parameters was used for correlation of the osmotic coefficient of the aqueous systems of glucose and alcohol at different concentrations. The data of the osmotic coefficient of water for these systems are obtained by an isopiestic method. The adjustable parameters are calculated by optimization of the experimental data of the osmotic coefficient using the Nedler–Mead algorithm. It is shown that the results of the modified NRTL-NRF model demonstrate low deviation from the experimental data.     

NaOH-NaAl(OH)4-H2O溶液体系渗透系数的测定及离子作用模型

用等压法测定了在303.15 K时总碱质量摩尔浓度mNaOH(T)从0.61 mol/kg到5.72 mol/kg, 苛性比αK从1.98到7.04的NaOH-NaAl(OH)4-H2O溶液体系的等压平衡浓度和渗透系数, 并得到该溶液体系的水活度. 用Pitzer模型对实验结果进行了参数化研究, 拟合求得了离子相互作用参数. 用Pitzer模型计算的渗透系数值与实验结果一致. 用获得的参数计算了NaOH和NaAl(OH)4在NaOH-NaAl(OH)4-H2O溶液体系中的活度系数, 其值随总碱质量摩尔浓度的增加呈增加的趋势.     

298.15K下Li2B4O7-H2O体系水蒸汽分压及渗透系数的等压测定和离子相互作用模型

在已有研究含硼体系的文献中仅考虑了硼酸根B4O7^-2或B(OH)4^-和H3BO3的存在，而对Li2B4O7-H2O体系具有多种硼物种聚合平衡体系的热力学性质的研究尚未见报道．本文用等压法研究了Li2B4O7-H2O体系于298．15K下浓度由稀到过饱和溶液的平衡气相蒸汽压及渗透系数．考虑了水溶液中多种硼物种的存在，以Pitzer方程为基础，建立了可描述该含硼体系的离子相互作用模型。     

Phase Behavior of Aqueous Na–K–Mg–Ca–Cl–NO<Subscript>3</Subscript> Mixtures: Isopiestic Measurements and Thermodynamic Modeling

A comprehensive model has been established for calculating thermodynamic properties of multicomponent aqueous systems containing the Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻ and NO₃⁻ ions. The thermodynamic framework is based on a previously developed model for mixed-solvent electrolyte solutions. The framework has been designed to reproduce the properties of salt solutions at temperatures ranging from the freezing point to 300 °C and concentrations ranging from infinite dilution to the fused salt limit. The model has been parameterized using a combination of an extensive literature database and new isopiestic measurements for thirteen salt mixtures at 140 °C. The measurements have been performed using Oak Ridge National Laboratory’s (ORNL) previously designed gravimetric isopiestic apparatus, which can also detect solid phase precipitation. In addition to various Na–K–Mg–Ca–Cl–NO₃ systems, results are reported for LiCl solutions. Water activities are reported for mixtures with a fixed ratio of salts as a function of the total apparent salt mole fraction. The isopiestic measurements reported here simultaneously reflect two fundamental properties of the system, i.e., the activity of water as a function of solution concentration and the occurrence of solid–liquid transitions. The thermodynamic model accurately reproduces the new isopiestic data as well as literature data for binary, ternary and higher-order subsystems. Because of its high accuracy in calculating vapor–liquid and solid–liquid equilibria, the model is suitable for studying deliquescence behavior of multicomponent salt systems.     

等压法测定298.15K下LiCl-CaCl2-H2O体系的活度系数

电解质水溶液热力学性质的研究一直是一个很活跃的研究领域.对含锂水盐体系热力学性质的研究不仅对电解质水溶液理论,而且对盐湖锂资源的开放利用都有非常重要的意义.姚燕等对ＬｉＣｌＫＣｌＨ2Ｏ[1],ＬｉＣｌＭｇＣｌ2Ｈ2Ｏ[2],ＬｉＣｌＭｇＳＯ4Ｈ2Ｏ[3,4],ＬｉＣｌＬｉ2ＳＯ4Ｈ2Ｏ[5]体系多温下热力学性质进行了研究,应用Ｐｉｔｚｅｒ电解质水溶液理论模型进行处理,计算出ＬｉＣｌ在不同体系中,很大的浓度范围内的活度系数.但在盐湖卤水中,ＣａＣｌ2的存在很普遍.对ＬｉＣｌＣａＣｌ2混合物在水溶液中的热力学性质研究对理解ＬｉＣｌ在盐…