乙醇-环己烷体系中NaI活度系数的测定与计算

由于非水溶剂的应用日趋广泛,促使物理化学工作者对于溶剂和溶液性质进行研究,同时开展了有关物理化学数据的测定和积累工作,以利于指导实践[1]。目前文献报道含水混合溶剂中的电解质活度系数较多,但非水混合溶剂中电解质活度系数报道较少。电解质浓溶液活度系数的计算方法目前应用较广的是Pitzer半经验算法[2]。Pitzer的算法中具体物系的β(0)、β(1)等系数需从实测活度系数数据拟合求得。孙仁义等通过测定汽液平衡盐效应的方法研究了盐在混合溶剂中的活度系数[3-4]。最近孙仁义等[5]提出了双液比固定条件下含盐体系汽液平衡数据热力学一…     

三元无限稀释活度系数的实验测定

三元无限稀释活度系数的实验测定鲍坚斌，周秋红，李昂，韩世钧（浙江大学化学系，杭州，３１００２７）关键词三元无限稀释活度系数，气提法，汽液平衡，液液平衡传统的无限稀释活度系数一般是指二元无限稀释活度系数，即（ｉ为无限稀释单组分溶质，ｊ为单组分溶剂），它...     

甲醇-苯混合溶剂中NaI活度系数的测定与计算

测定了甲醇-苯-NaI体系在恒压条件下的汽液平衡数据,采用双标准检验法对数据进行检验,检验结果全部合格.应用P itzer强电解质在水溶液中的活度系数模型,采用全部合格的汽液平衡数据拟合出方程中的维利系数,从而获得在双液比固定条件下盐在甲醇-苯混合溶剂中的活度系数.计算结果表明,正常泡点温度下在具有固定双液比的甲醇-苯混合溶剂中,NaI的平均活度系数随盐浓度的增加先减小,经过一个极小值后又增加.     

C_8芳烃异构体+异丙醇或叔丁醇体系的恒压汽液平衡

这是为了较好地解决高效分离混合二甲苯所进行的一项基础性研究。准确测定了 0 .0 999MPa压力下邻、间、对二甲苯或乙苯 +异丙醇或叔丁醇八个体系的恒压汽液平衡数据 ,计算了该压力下八个体系中二组分的活度系数 ,作出了各体系的汽液平衡曲线及活度系数曲线 ,并讨论所呈现的规律。     

丙酮—环烷烃体系的无限稀释活度系数的气提法测定研究

如果溶剂是高挥发性物质,当用气提法测定无限稀释活度系数时需要加预饱和釜以消除气提时因溶剂量损失过大而带来的问题.本文就丙酮-甲基环戊烷、丙酮-环己烧和丙酮-甲基环己烷3个体系在298.2～318.2K温度范围内的γ~∞作了测定,用所得数据作全浓度范围的汽液平衡推算,与文献中实验值对比,发现Wilson方程结果最佳.     

二元系挥发组分活度系数的测定

活度系数和活度是物理化学教学中要求掌握的基本概念,溶液活度系数的测定是物理化学实验的基本内容之一,但在一般实验指导书中仅介绍气液色谱法测无限稀活度系数.而用静态平衡釜测定二元系恒温下的总压～液相组成(P～X)数据的实验,在基础物理化学实验室中是没有条件进行     

新型斜式沸点仪及无限稀释活度系数的测定

本文设计制作了两种新型斜式(搅拌式和非搅拌式)沸点仪,采用非分析的方法测定了丙酮-甲醇等14组二元体系的无限稀释活度系数,并用以进行了全浓度范围汽液平衡数据的推算,获得了满意的结果。     

大值无限稀释活度系数的测定

测定无限稀释活度系数γ~∞的气提法自1977年由Leroi 等提出至今已有十余年的历史,其发展十分迅速.应用该方法可测定常规的如醇烃、烃烃、酮烃等体系的γ~∞,还用来测定高粘度体系、含食品或油类体系的γ~∞,显示出这种方法具有适应面广的特点.本工作将进一步尝试拓宽其测定范围—提出连续采样技术实现大值无限稀释活度系数(γ~∞>10~2)的测定.     

分析化学教材中关于离子活度系数计算公式的讨论

在处理电解质溶液的化学平衡理论中,有关离子的活度和活度系数的计算或估算都有比较严谨的理论公式或经验公式,而国内分析化学教材中关于经验公式的表述略显随意。以0.050 mol·L^-1AlCl₃水溶液中Cl^-和Al³⁺的活度计算为例,结合国内外分析化学教材中关于活度系数计算的经验公式进行讨论。由计算结果可知,关于活度系数计算的经验公式需给出明确的使用条件。     

电解质活度系数测定装置的改进

电动势测定的应用之一——电解质离子的平均活度系数测定,是物理化学课程的基本内容。如能在基础物理化学实验中开设此实验,将有助于学生对该法的深刻理解。文献中所介绍的装置多数是带有双液封的H-型电池结构或更为复杂的电池结构.这类电池结构不仅仪器加工困难,而且由于电池结构复杂,造成体系中溶解氧不易赶出的“死角”(如连接两电极管的“桥”中的溶液),致使电池电动势难以达到平衡值。又因要采用两条通氢管路,使操作复杂     

关于测定二元系中挥发组分活度系数的GLPC方法的研究

GLPC法测定二元系中挥发组分有限浓度时的活度系数曾为Chueh和Ziegler、Conder和Purnell、Chch和Parcher等所探讨,但因后续工作太少,迄今未能成熟,将这一方法得到肯定,对于研究二元溶液的热力学是有意义的,经过反复比较,我们决定对Chueh和Ziegler的方法作进一步探讨。     

一些苯磺酸钠盐的等压渗透系数和活度系数

用等压法测量了苯亚磺酸钠、苯磺酸钠、对羟基苯磺酸钠、间硝基苯磺酸钠和对氨基苯磺酸钠水溶液在298.15K时的渗透系数和活度系数。由此计算了它们的超额吉布斯自由能。对活度系数随浓度的变化规律进行了讨论     

等压法测定298.15K下LiCl-CaCl2-H2O体系的活度系数

The isopiestic method was used to determinate isopiestic molality and osmotic coefficients in single-salt solutions of LiCl-H2O(molality range from 0.5 to 9.0 mol· kg-1),CaCl2-H2O(molality range from 0.35 to 5.2 mol· kg-1) and multisalt solution LiCl-CaCl2-H2O(ionic strength range from 0.5 to 15.7 mol· kg-1) at 298.15K,from which Pitzer's interaction parameters of single salt ,mixed salts of the systems were obtained.The mean ionic activity coefficients of LiCl、 CaCl2 in pure and mixed solutions were reported.     

热解吸调制,顶空—毛细管气相色谱法测定二元液系的活度系数

本文采用热解吸调制器作毛细管气相色谱直接顶空进样测定二元液体混合物苯－甲苯和丙酮－氯仿的活度系数。热解吸调制器是在毛细管柱前端的一段短的加热段。调制器段外部镀以一薄层导电膜。所体样品连续不断地流经调制器和毛细管柱。     

Activity Coefficients of Potassium Chloride and Sodium Chloride in the Quaternary System KCl-NaCl-Water-Ethanol

Activity coefficients of KCl and NaCl were determined in the quaternary system KCl-NaCl-water-ethanol, for 10 and 20% (w/w) ethanol in the solvent, from experimental electromotive force data. The molalities varied from 0.1 mol kg^–1 to near saturation and measurements were taken in the temperature range 20 to 50°C. The Pitzer-Simonson equations were used to describe the nonideal behavior of both electrolytes and the corresponding activity coefficients were determined for each solvent and temperature.     

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.     

Determination of Hydrogen Single Ion Activity Coefficients in Aqueous HCl Solutions at 25°C

The single ion activity coefficients of hydrogen and chloride ions in aqueous HCl solutions have been estimated at 25°C at concentrations up to 1 mol-kg^–1, using potentiometric measurements with ion-selective electrodes and appropriate calibration procedures. Two methods are described for an internal calibration of the electrodes in the extended Debye–Hückel concentration range. The results are compared to the conventional pH calibration with external buffer solutions. Since the latter calibration method does not account for the liquid junction potential E _J which arises at the reference electrode, the resulting activity coefficients are quite different in HCl solutions of higher concentration. These differences between internal and external calibration decrease significantly, when a correction for E _J is introduced into the conventional pH calibration. Hence, in solutions of higher ionic strength the accuracy of the conventional pH electrode calibration using buffer solutions is very limited, when exact H⁺ activities are required. The consistency of the results indicates that the liquid junction potentials in the examined systems calculated by the Henderson/Bates approximation are of reasonable precision.     

Limiting Activity Coefficients of Phenol in Hydrocarbons

The activity coefficients of phenol in a number of hydrocarbons were determined from experimental data on phenol distribution between aqueous and hydrocarbon liquid phases, using data on the limiting activity coefficients of phenol in water. Ten systems containing saturated and aromatic hydrocarbons were examined in the temperature range 283–328 K.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 214–218.Original Russian Text Copyright © 2005 by I. Dobryakova, Yu. Dobryakov.