熔点和凝固点的准确测量

介绍了英国政府化学家研究所(IGC)和兵总第204所样品的熔点和凝固点的准确测量方法,熔点和凝固点的测量结果,并进行了讨论。     

双差示法测定溶液凝固点下降

提出一种测定溶液凝固点下降的新方法。将溶液和纯溶剂同时置于冷浴中，用半导体制冷块降温。用温度探头分别感应纯溶剂（Ｒ）、溶液（Ｓ）和冷浴（Ｗ）的温度：ＴＲ、ＴＳ和ＴＷ，并组成两个惠斯登电桥指示温差。当（ＴＲ－ＴＳ）－（ＴＳ－ＴＷ）出现最大值时，（ＴＲ－ＴＳ）为溶液凝固点下降值。本方法需要搅拌，降温速率以０８—３０Ｋ／ｍｉｎ为宜。测定了萘苯溶液的凝固点下降值，苯中萘浓度２０—７００ｍｍｏｌ／Ｌ时线性良好。     

关于凝固点降低的教材编写和教学建议

关于教材中凝固点降低的内容,存在两种具有分歧的表述方式,导致了师生在教学和学习过程中的困惑。本文通过图示的方式对凝固点定义的依据予以解析,提出了教材编写及教学中的一点建议。     

半导体凝固点测定仪的研制及其应用

为了配合物理化学实验“凝固点降级法测定萘的摩尔质量”,研制出半导体制冷凝固点测定仪,实现了凝固点测定和摩尔质量计算的自动化,解决了老式实验装置存在的问题。通过对环己烷凝固点和萘摩尔质量的测定,验证了该仪器的可靠性,同时还探讨了搅拌速率和冷阱的温度变化对凝固点测定值的影响。     

熔点8和凝固点的准确测量

介绍了英国政府化学研究所（ＬＧＣ）和兵总第２０４所样品的熔点和凝固点的准确测量方法，熔点和凝固点的测量结果，并进行了讨论。     

低温型高精度凝固点测量装置及其应用

介绍了低温型高精度凝固点测量装置的设计研制、系统组成、性能特征、测量原理及其应用实例,并对所测3种有机物测量的扩展不确定度进行了详细的分析,结果表明,本装置对有机物凝固点的测量具有较高的精度和准确度。     

凝固点降低法研究某些脂肪胺的自缔合作用

本工作利用计算机技术改进加热式凝固点测量装置的数据采集系统. 改进后装置的混合物凝固点测量再现性为±0.001 K; 溶剂偏摩尔过量自由能测量再现性为±0.1 J.mol~(-1). 用凝固点降低法测量正丙胺、异丙胺、正丁胺, 异丁胺、正戊胺、异戊胺、二乙胺、二异丙胺、三乙胺、三正丁胺分别与苯和对二甲苯构成二元混合物的溶剂活度系数. 并使用一个包含物理相互作用的三参数连续缔合模型拟合实验数据. 结果表明该模型能较好地刻画所研究的二元缔合混合物。     

凝固点降低法测定摩尔质量实验装置的改进

对凝固点降低法测定摩尔质量的实验装置进行了改进。改进后操作简单,所得结果准确。     

从熵的角度解读凝固点降低公式

利用△G=△H-T△S推导了稀溶液凝固点降低公式,根据形成溶液前后相变熵的改变,对公式的含义进行了解读,即凝固点的降低完全归结于溶解过程相比于熔化过程的熵变增加.并对公式的拓展应用进行了简要分析.     

基于凝固点下降的高纯有机物纯度定值技术研究进展

介绍凝固点测量方法的研究进展。阐述了凝固点下降技术用于高纯有机物纯度定值的基本原理和适用条件,详细介绍了静力学方法和动力学方法这两种凝固点的测量方法,并介绍了两种方法在纯度定值方面的应用情况,且对两种方法的特点进行了对比,展望了凝固点下降纯度定值技术的发展趋势。     

Calculations of Freezing Point Depression,Boiling Point Elevation,Vapor Pressure and Enthalpies of Vaporization of Electrolyte Solutions by a Modified Three-Characteristic Parameter Correlation Model

A method was proposed for calculating the thermodynamic properties, freezing point depression, boiling point elevation, vapor pressure and enthalpy of vaporization for single solute electrolyte solutions, including aqueous and nonaqueous solutions, based on a modified three-characteristic-parameter correlation model. When compared with the corresponding literature values, the calculated results show that this method gives a very good approximation, especially for 1-1 electrolytes. Although the method is not very suitable for some solutions with very high ionic strength, it is still a very useful technique when experimental data is scarce.     

强电解质稀溶液的依数性公式导出及实验验证

讨论了强电解质稀溶液的依数性,即凝固点降低、沸点升高和渗透压。以稀溶液的凝固点降低为例,利用Gibbs-Duhem公式,推导了强电解质稀溶液的凝固点降低公式,并利用Na Cl水溶液的凝固点降低实验验证了该公式的正确性。     

Freezing curve-based monitoring to quickly evaluate the viability of biological materials subject to freezing or thermal injury

This paper is aimed at investigating the roles of freezing dynamics of a liquid droplet to characterize the properties of the material. In particular, freezing curve-based monitoring was proposed to quickly evaluate the viability of biological materials subject to freezing, re-warming, or other kinds of injury, which is an extremely important issue in practices such as cryobiology, hyperthermia, or freshness evaluation of bio-samples. An integrated micro analysis device was fabricated which is simple in structure and cheap to make. Preliminary freezing results demonstrated that minor changes in a biological material due to freezing or warming injury might result in a significant deviation of its freezing curve from that of the intact biomaterials. Several potential thermal indexes to quantify the material features were pointed out. Further, experiments were performed on some freezing and thawing processes of small amount of water on a cooling surface to test the effects of droplet sizes, measurement sites, cooling strength, and cooling geometry, etc., on the freezing responses of a water droplet. Their implementation in developing a new micro analysis system were suggested. This freezing curve-based monitoring method may open a new strategy for the evaluation of biomaterials subject to destruction in diverse fields.     

Freezing Point of Mixtures of H2 16O with H2 17O and Those of Aqueous CD3CH2OH and CH3 13CH2OH Solutions

The freezing point of mixtures of H₂ ¹⁶O with H₂ ¹⁷O was measured as a function of the molal concentration. The freezing points rose linearly with increasing molal concentration above that of pure ordinary water, H₂ ¹⁶O, at 273.15 K. This confirms Kiyosawa's previous conclusion [K. Kiyosawa, J. Solution Chem. 20, 583 (1991).], drawn from findings on changes in the freezing point of mixtures of H₂ ¹⁶O with H₂ ¹⁸O or D₂ ¹⁶O that even a difference in the number of neutrons in the hydrogen or oxygen atoms of water molecules makes them behave as different entities with respect to the colligative properties of solutions. This has been confirmed to also occur in mixtures of H₂ ¹⁶O with H₂ ¹⁷O.     

Comment on “Freezing Point Mixtures of H216O with H217O and Those of Aqueous CD3CH2OH and CH313CH2OH Solutions”

In a recent article, Kiyosawa [J. Solution Chem. 33, 323 (2004)] reports that the freezing points of isotopic mixtures of ordinary water and ¹⁷O enriched water show an unexpectedly large linear dependence on the concentration of H₂¹⁷O. Surprisingly, the constant of proportionality to the H₂¹⁷O concentration is nearly five times larger than that of H₂¹⁸O found in earlier studies by Kiyosawa [J. Solution Chem. 20, 583 (1991)]. We show that the H₂¹⁷O result is not consistent with other data or models. For example, a recent determination of the triple point temperature dependence on isotopic composition in naturally and artificially depleted waters [White et al. in Temperature, Its Measurement and Control in Science and Industry, Vol. 7, D. C. Ripple, Ed., AIP CP 684, 221–226 (2003)] is consistent with the H₂¹⁸O and D₂O results from Kiyosawa (1991) [White and Tew in Report of the 22nd Meeting of the Consultative Committee for Thermometry, Document CCT/03-21, BIPM, Severes, France, 2003] but is inconsistent with the H₂¹⁷O results from Kiyosawa (2004). Additionally, the results from Kiyosawa (1991) are close to what would be found in ideal solutions for those isotopic forms, whereas the H₂¹⁷O proportionality from Kiyosawa (2004) is about 10 times larger than similarly predicted. One possible explanation is that the original ¹⁷O enriched water sample contained a small amount of D₂O, and the sample, if available, should be subject to isotopic analysis to help resolve these inconsistencies.     

Osmotic and Activity Coefficients of Copper(II) Chloride and Cadmium Chloride from Freezing Point Measurements

Osmotic coefficients and activity coefficients of copper(II) chloride and cadmium chloride in aqueous solutions were evaluated from freezing point depression in dilute solutions of concentration range below 0.1 molal. The association constants for the ion-pairs, CuCl⁺ and CdCl⁺ were calculated as 2.3±0.3 and 74±5, respectively.