含盐二元素的等压气液平衡研究

本文用改进的Rose分别测定了在750mmHg压力下的丙酮-甲醇-NaI体系和700mmHg压力下的异丙醇-水-LiCl, CaCl2, NH4Cl, (CH3)4NCl体系的气液平衡数据。当双液系组成固定时, 盐的浓度与沸点之间存在线性关系, 与热力学导出的线性关系基本相符。     

含盐二元系的等压气液平衡研究

本文用改进的Rose釜分别测定了在750mmHg压力下的丙酮－甲醇－NaI体系和700mmHg压力下的异丙醇－水－LiCl、CaCl2、NH4Cl、(CH3)4NCl体系的气液平衡数据，当双液系组成固定时，盐的浓度与沸点之间存在线性关系,与热力学导出的线性关系基本相符。     

加碱萃取精馏制取无水乙醇

乙醇-水体系存在共沸点，难以通过普通精馏方法制取高纯度乙醇，萃取精馏是分离共沸体系的有效途径。目前常用的萃取溶剂是乙二醇。在分离乙醇-水体系的过程中，将适当的盐类(醋酸钾)溶于乙二醇形成溶盐萃取剂，会有效提高溶剂的选择性。本文用萃取精馏方法并加入乙二醇分离效果更明显。     

非水混合溶剂体系的盐效应

采用改进的Rose釜测定了在101.33kPa下, 甲醇-二氧六环-NaSCN, 甲醇-二氧六环-NaI和甲醇-四氢呋喃-LiCl, 甲醇-四氢呋喃-CuCl2体系的汽液平衡数据。实验结果和热力学基本原理确证了体系的沸点与加入盐浓度间的线性关系, 计算了各双液组成下体系的盐效应常数, 分析了实验中产生"异常"现象的原因, 探讨了溶液内部粒子相互作用的规律, 通过用相律、盐效应理论、静电理论、溶剂化理论的解释, 得到了一些具有理论价值的结论。     

拟静态沸点计法测定非水电解质溶液的渗透系数

本文将非分析循环沸点计［1，2］和拟静态方法[3]应用于非水电解质溶液体系的渗透系数的测定，建立了一套拟静态沸点计法测定非水电解质溶液渗透系数的实验装置．经NaCl、NaBr两个甲醇盐溶液体系的检验，相对标准误差小于1％，与传统的苦态法和等压法比较，拟静态沸点计法是一种快速、准确、方便的方法．用该装置分别测定了29巳15K时，＊d、Me。＊Q和BU4＊Br甲酸盐溶液渗透系数，实验值用Pitier方程关联，用关联得到的Pitier相互作用参数计算了盐的活度系数．1实验部分1．1实验原理在等温的条件下，电解质溶液处于汽液平衡时，如果测出…     

稀土硝酸盐冠醚配合物Y(NO_3)_3·3H_2O—B15C5—CH_3CN三元体系18℃时溶解度的研究

提出了一种适用于金属盐-冠醚-有机溶剂三元体系溶解度测定的半微量相平衡研究方法.用该法研究了Y(NO_3)_3·3H_2O-B15C5-CH_3CN三元体系在18℃时的溶解度.实验证明该体系中生成的配合物只有一种组成,而且该配合物存在的相区相当大,排除了其它组成的配合物存在的可能性,为在乙腈中合成该配合物合理选择盐、醚比提供了依据.考查了由水合钇盐引入体系的水的去向.制得了固态配合物Y(NO_3)_3·B15C5·3H_2O,研究了它的某些性质和热分解过程.还考查了该配合物的水合度与它所处条件的关系.     

双液系气液平衡相图实验的研究

二组分完全互溶的双液系的气液平衡相图实验是物理化学实验的基本内容之一,通常是用沸点仪在常压条件下测定双液系在不同组成时的沸点和气、液两相呈平衡时的组成,从而作出沸点-组成相图。外界压力不同时,同一双液系的相图也不尽相同,所以恒沸点和恒沸混合物组成与外压有关。因此,通常情况下,用标准数据去衡量学生实验所得的恒沸点和恒沸混合物的数据就不够精确。本文是用自制的简易恒压沸点仪,在不同的压力下,对丙酮-氯仿和异丙醇-环己烷体系的恒沸点,恒沸混合物组成进行了研     

含盐乙腈水溶液的T-P-X关系

本文采用CPⅡ型沸点仪测定了富水端乙腈-水-(KCl,CaCl_2,KI)体系在26.66～93.33 kPa压力下及盐质量摩尔浓度从0.1～0.7 mol·kg~(-1)范围内的T-P-X关系.由热力学基本原理导出含盐二元系Clausius-Clapeyron方程类型的具体形式.该方程在特定条件下可退化为各种类型的现有方程,实验结果验证了理论推导的正确性.     

铜(Ⅱ)-1,10-二氮菲-铬天青S和十二烷基硫酸钠四元体系的分光光度研究及铬天青S纯度的测定

本文研究了在柠檬酸盐存在下,铜(Ⅱ)-1,10-二氮菲-铬天青S和十二烷基硫酸钠四元体系的分光光度性质。在pH6.5—10.0,该体系形成蓝色的四元配合物,其最大吸收波长在596nm处,摩尔吸光系数为1.08×10~5,0.00—10.0微克/毫升CAS具有良好的线性关系。本法用于测定市售CAS的纯度,方法灵敏可靠。     

桑色素—Triton X—100—β—环糊精荧光光度法测定痕量锡

本文用荧光光度法研究了桑色素-Triton X-100-β-环糊精-锡(Ⅳ)体系的测定方法及条件,在0.1mol/L HC1介质中,检测限为1.7ng/ml,锡的含量在10～130ng/ml范围内呈线性关系,本法灵敏度高,选择性好,可不经有机溶剂萃取,在水相中直接进行测定地质和合金样品中微量锡,结果满意。     

Studies of Molecular Interactions in Adsorption Liquid Chromatography with Binary Mobile Phases

Abstract

For all examined chromatographic systems with binary mobile phases the linear relationship taking into account the specific molecular interactions was stated. This relationship correlates all equilibrium constants (association and adsorption) characterizing LSC process. In the case of strong polar component of the mobile phase the association and solvation equilibrium constants can be evaluated separately.     

Problems related to the optimum separation conditions in liquid adsorption chromatography

Summary Relationships derived from the thermodynamic formulation of TLC with a binary mobile phase are discussed. The adsorption equilibrium constant is determined from the linear form of a basic equation considering the adsorption process. This linear relationship is examined with help of TLC data obtained by using six different chromatographic systems. The adsorption equilibrium constant obtained from the TLC data is compared to the equilibrium constant determined from adsorption measurements. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

线性参数logI对反相液相色谱中的非极性小分子溶质体系的表征

从理论上阐明了计量置换平衡常数的对数ｌｏｇＫａ对液相色谱中计量置换保留模型的线性参数ｌｏｇＩ起着主导作用。ｌｏｇＩ表示溶质对固定相的亲合势，且具有热力学平衡常数的性质。     

Compensation Theory of Adsorption: Correlation and Prediction of Henry Constants for Linear Paraffins on Zeolite Adsorbents

Experimental Henry's Law equilibrium data for linear paraffins show a well defined linear variation of adsorption energy with carbon number and a linear relationship between the entropy and energy of adsorption (compensation effect). Such correlations, are presented for sorption of linear paraffins on NaX, NaY, USY, silicalite and silica gel as well as for two commercial (faujasite based) catalysts and provide a concise way to predict the adsorptive behavior of the higher paraffins.     

Moment analysis of retention equilibrium, mass transfer kinetics, and thermodynamic properties in reversed-phase liquid chromatography using phenyl bonded silica gel

Information about retention equilibrium, mass transfer kinetics, and related thermodynamic properties of chromatography using phenyldimethylsilyl (Ph)-silica gel was derived by moment analysis of pulse response peak profiles. The results for the Ph-silica gel were compared with those for octadecyldimethylsilyl (C18)-silica gel. Some parameters characterizing the chromatographic behavior of the two stationary phases were correlated with the hydrophobic surface area of sample molecules. Surface diffusion had a predominant role for intraparticle diffusion. An enthalpy-entropy compensation was established for both the retention equilibrium and surface diffusion. A linear correlation was observed between the logarithm of surface diffusion coefficient (Ds) and that of retention equilibrium constant (Ka), suggesting the establishment of a linear free energy relationship. The ratio of Ds to molecular diffusivity (Dm) decreased with increasing Ka and was correlated by a single curved line. The value of Ds was of the same order of magnitude with Dm when Ka became negligible. These results suggest the presence of a sort of correlation between surface diffusion and molecular diffusion and the restriction of the molecular mobility by surface diffusion due to the retention strength.     

氨基酸在甲醇—水混合溶剂中的气液平衡

采用改进的Ｒｏｓｅ釜测定了在３３３Ｋ和３３８Ｋ下，氨基乙酸、ＤＬ－氨基丙酸及Ｌ－氨基异戊酸在甲醇－水混合溶剂中的气液平衡数据。实验结果表明，当甲醇－水混合溶剂的相对组成固定时，体系的平衡压力与加入的氨基酸的浓度间存在线性关系，使已建立的含盐混合溶剂的“广义线性定理”进一步扩展到含有非挥发性物质的混合溶剂中。用热力学原理导出了线性方程的数学解析式；讨论了引入氨基酸对混合溶剂结构及性质的影响规律。     

单硫醚气相色谱保留指数拓扑化学研究

在分子拓扑化学理论的基础上,根据分子中原子的特性,用分子中原子的平衡电负性对分子图进行着色,在距离矩阵的基础上结合分子中各原子的支化度构建一组新的拓扑指数NPm(m=1,2,3),利用多元线性回归技术将单硫醚在4种极性固定相的气相色谱保留指数与NPm(m=1,2,3)建立相应的定量结构-保留相关关系模型(QSRR),并用这种模型对单硫醚的气相色谱保留指数进行预测,结果表明,预测结果和实验值吻合较好。     

Linear calibration graph applicable to the indirect determination of sulphate

Equations based on the equilibrium relationship between a sulphate-containing solution and solid lead sulphate were derived and applied to calibration graphs for the determination of sulphate. The special character of the linear graphs extends not only the applicability of linear calibration and standard addition procedures to the indirect determination of sulphate, but also the reliability of the analytical results. Experiments with the flow-injection technique confirmed the applicability of the proposed linear graphs.     

固相微萃取技术在估算多环芳烃的辛醇-水分配系数中的应用

 采用固相微萃取 气相色谱／质谱联用技术分析了水中１１种多环芳烃,并获得其平衡时的分配系数。当固相微萃取纤维上涂渍的固定液被视为一种有机溶剂时,根据萃取系统间线性的自由能关系,建立了聚二甲基硅氧烷 水分配系数（Ｋｓｗ）与正辛醇 水分配系数（Ｋｏｗ）间的关系式,并将其应用于估算其它多环芳烃的未知的醇 水分配系数。所建立的方法简单、快速,与Ｌｅｏ碎片法相比,可以更精确地估算取代基位置不同的同分异构体的Ｋｏｗ。