溶剂化的热力学集团展开理论

把二元溶液的过剩内能（excess energy）分成溶剂-溶剂、溶剂-溶质及溶质-溶质相互作用部分。利用集团展开方法给出了二元溶液在正则系综的配分函数的表达式,利用该表达式得到了溶质的偏摩尔内能(partial molar energy)和偏摩尔熵(partial molar entropy)的表达式。在无限稀溶液情形,过剩偏摩尔内能的溶剂-溶剂部分又称重组织内能（reorganization energy）,它反映了溶质存在时对其周围溶剂分子之间的相互作用能的影响。研究表明,在溶质的粒子数密度相对较大时,溶质分子之间的相互作用将影响过剩偏摩尔内能的溶剂-溶剂部分,对于稀溶液,过剩偏摩尔内能的溶剂-溶剂部分与溶质的摩尔分数成线性关系。对低密度二元溶液,溶质的过剩偏摩尔内能和过剩偏摩尔熵也与溶质的摩尔分数成线性关系。     

甲酰胺、乙酰胺、尿素在两种极性非水溶剂中的体积性质

以尿素、甲酰胺和乙酰胺为溶质,二甲基甲酰胺和二甲基亚砜为溶剂;或以二甲基甲酰胺、二甲基亚砜为溶质,以甲酰胺为溶剂,通过测定溶液在２９８．１５Ｋ下的密度数据,求得了溶质的表观摩尔体积以及与溶质－溶质相互作用相关的体积第二维里系数．利用定标粒子理论讨论了溶质分子的几何体积、溶质－溶剂相互作用对溶质偏摩尔体积的影响,结果表明,溶质的溶剂化与溶质－溶质相互作用的体积效应呈相反的变化趋势     

甲酰胺,乙酰胺,尿素在两种极性非水溶液中的体积性质

以尿素、甲酰胺和乙酰胺为溶质，二甲基甲酰胺和二甲基亚砜为溶剂；或以二甲基甲酰胺、二甲基亚砜为溶质，以甲酰胺为溶剂，通过测定溶液在２９８．１５Ｋ下的密度数据，求得了溶质的表观磨尔体积以及与溶质－溶质相互作用相关的体积第二维里系数。利用定标粒子理论讨论了溶质分子的几何体积、溶质－溶剂相互作用对溶质偏摩尔体积的影响，结果表明，熔质的溶剂化与溶质－溶质相互作用的体积效应呈相反的变化趋势。     

等价无穷小与合比定律在物理化学教学中的应用

利用等价无穷小的理论结合物理化学中环境熵变、理想稀溶液溶剂化学势和高聚物的相关概念分析了环境熵变、理想稀溶液溶剂化学势的计算公式和"黏度法测定高聚物相对分子质量"实验中的关键理论推导。利用合比定律与物理化学的杠杆规则、离子迁移数等知识点推导出杠杆定律和离子迁移数的相关公式。使抽象的、不易掌握的物理化学知识具体化,便于学生理解、掌握和运用。     

平衡法对理想稀溶液的讨论

利用平衡法讨论理想稀溶液,并通过亨利定律讨论获得溶剂分子与溶质分子之间作用力的基本方法和基本原理。     

肌醇在氯化钠水溶液中的稀释焓和焓对相互作用

应用微量热法测定了298.15K时肌醇在纯水和氯化钠水溶液中的稀释焓,根据McMillan-Mayer理论计算了肌醇在不同浓度的氯化钠溶液中的2到4阶焓相互作用系数.结果表明,肌醇在氯化钠溶液中的焓对相互作用系数h2均为负值,并且随着氯化钠浓度的增大,h2的值呈增大趋势.根据溶质-溶质相互作用和溶质-溶剂相互作用对焓对相互作用系数的变化趋势进行了解释.     

低密度溶液中溶剂的重组织性质

分析了溶液的微观结构,结果表明,单个溶质粒子影响其周围的溶剂的结构,溶质粒子间的相互作用也将影响溶剂的结构,溶质对溶剂结构的影响称作溶剂的重组织.提出了二阶重组织能及二阶重组织熵等概念,可以描述在两个溶质粒子发生碰撞时对其周围溶剂结构的影响.利用二元系的集团展开理论,给出了溶剂的一阶、二阶重组织能和重组织熵的表达式.统计热力学分析给出了溶剂-溶剂径向分布函数与溶质和溶剂化学势之间的关系,给出了无限稀溶液模型是否成立的宏观判据.提出的理论可用于低密度的二元溶液.     

丝氨酸在蔗糖水溶液中的稀释焓

利用LKB 2277生物活性检测仪分别测定了298.15 K时丝氨酸在不同组成的蔗糖水溶液中的稀释焓, 利用McMillan-Mayer理论,计算了丝氨酸在不同组成的蔗糖水溶液中的焓对相互作用系数,并与其在葡萄糖水溶液中的焓对相互作用系数h2进行了比较.结果表明,丝氨酸在蔗糖和葡萄糖水溶液中的焓对相互作用系数h2都是负值,并且随着糖浓度的增加,h2系数的绝对值逐渐减少.根据溶质-溶质相互作用和溶质-溶剂相互作用对结果进行了解释.     

水溶液中氯化铯与糖(D-葡萄糖、D-果糖和蔗糖)相互作用的热力学参数研究(298.15K)

用钾离子选择性电极为测量电极,氯离子选择性电极为参比电极,设计组成无液接电池,用于氯化铯-糖(葡萄糖、果糖及蔗糖)-水三元体系中组分之间弱相互作用的热力学性质研究.通过测量电池的电动势获得氯化铯在糖水溶液中的活度系数,根据Scatchard理论推测出糖在氯化铯水溶液中的活度系数.通过Mcmillan-Mayer理论将体系的过量热力学函数与溶液中溶质的相互作用参数相关联,获得氯化铯与糖在水溶液中相互作用的吉布斯自由能参数及盐效应常数.运用结构相互作用模型、糖的羟基水化效应及色散能理论,探讨体系中溶质-溶质、溶质-溶剂间的相互作用及糖的立体结构和金属离子体积对热力学参数的影响.     

葡萄糖与醇在甲酰胺溶液中的焓相互作用参数

利用量热法测定了298.15K时葡萄糖在一些醇(甲醇、乙醇、1-丙醇、1-丁醇)与甲酰胺的混合溶剂中的溶解热.采用McMilan-Mayer方法,将溶液热力学过量性质与溶液中粒子的相互作用参数相关联,求得了粒子间的焓对相互作用参数和三分子相互作用参数,并就溶质-溶质间的相互作用及溶剂的影响进行了讨论.     

The Law of Mixtures method for multivariate calibration

The Law of Mixtures (LM) method is a new so-called topological method for multivariate calibration. It is shown to be a very good method to predict the response for new objects that are inside the convex hull determined by the calibration data set. A method is also proposed for those that are outside the convex hull.     

Mathematical Aspects of the Periodic Law

We review different studies of the Periodic Law and the set of chemical elements from a mathematical point of view. This discussion covers the first attempts made in the 19th century up to the present day. Mathematics employed to study the periodic system includes number theory, information theory, order theory, set theory and topology. Each theory used shows that it is possible to provide the Periodic Law with a mathematical structure. We also show that it is possible to study the chemical elements taking advantage of their phenomenological properties, and that it is not always necessary to reduce the concept of chemical elements to the quantum atomic concept to be able to find interpretations for the Periodic Law. Finally, a connection is noted between the lengths of the periods of the Periodic Law and the philosophical Pythagorean doctrine.     

用不同方法收集端红玉兰(Magnolia Rufidula Law et Zhou)鲜花香气的研究

利用XAD-4树脂吸附、微波加热后XAD-4树脂吸附、减压水蒸汽蒸馏加尾气吸附．乙醚浸提等方法收集端红玉兰(Magnolia rufidula Law et zhou)鲜花香气，并用色-质联用法分析。乙醚浸提方法获得的香成分最丰富，与其它方法收集的香成分基本一致。微波加热法所需样品少，收集时间短，效果良好。     

海水中二甲基硫亨利常数的测定

 推导了多次相平衡顶空气相色谱法测定海水中二甲基硫 (DMS)亨利常数 (K)的理论关系式 ,根据两次或多次气、液相平衡的关系式 ,只测定DMS在气相中的浓度就可测定亨利常数。实测 2 2℃时DMS在胶州湾海水中的亨利常数是 0 0 89,相对标准偏差为 5 5 0 %。亨利常数的对数与环境水体中NaCl的质量分数 [w(NaCl) ]之间的关系为 :logK =0 0 688·w(NaCl) - 1 3 5 68,相关系数为 0 997。亨利常数的对数与环境水体的绝对温度 (T)的倒数之间的相关方程为 :logK =- 15 4 4 8/T + 4 2 112 ,相关系数为 0 996。     

Development and supply system of reference materials based on the Measurement Law in Japan

 Analytical instruments used for measurements of air and water pollution are calibrated by using reference materials such as standard gases and standard solutions. In Japan, since the middle of the 1970s, those reference materials which are traceable to the national standards maintained at national research institutes have been supplied to users by reference material producers. In order to establish the primary standards and to secure the traceability from the working standards to the national ones, various analytical methods such as coulometric, titrimetric and gravimetric analyses for purity determination and highly sensitive atomic spectrometry for trace analysis have been developed as the primary methods and reference methods. The Japanese Measurement Law, revised in 1992, has introduced a new traceability system in which a public organization, a "designated calibration body", can also prepare and maintain the national standards under the advice and instruction of national research institutes. The designated calibration body can provide calibration services to reference material producers (accredited calibration bodies) by using the national standards. The reference materials supplied in conformity with the traceability system include standard gases, pH standard solutions, metal standard solutions and non-metal ion standard solutions. Received: 4 October 1996 Accepted: 2 December 1996     

Entropy and the First Law of Thermodynamics

Plancks work on the Second Law of Thermodynamics in combination with a simple thermodynamic approach developed by Blinder show that the concept of entropy is introduced from the First and not the Second Law of Thermodynamics. In particular, it is proved that the First Law of Thermodynamics leads directly to the following statement: For every system of whatever complexity there exists an extensive function of state S defined from dS = q_rev/T, where q_rev is the infinitesimal quantity of heat exchanged reversibly between the system and the surroundings and T is the absolute temperature of the system. Thus, for reversible adiabatic processes we readily have from the First Law that dS = 0. Therefore, the Second Law should be properly reformulated, restricted to the inequality dS 0 for irreversible processes only.     

External validation of the biodegradability prediction model CATABOL using data sets of existing and new chemicals under the Japanese Chemical Substances Control Law

External validation of the biodegradability prediction model CATABOL was conducted using test data of 338 existing chemicals and 1123 new chemicals under the Japanese Chemical Substances Control Law. CATABOL predicts that 1089 chemicals will have a BOD?<?60% while 925 (85%) actually have an observed BOD<60%. The percentage of chemicals with an observed BOD value <60% tends to increase as the predicted BOD values decrease. In contrast, 340 chemicals were predicted to have a BOD?≥?60% and 234 (69%) actually had an observed BOD?≥?60%. The prediction of poor biodegradability was more accurate than the predictions of high biodegradability. The features of chemical structures affecting CATABOL predictability were also investigated.     

Analytical atomic spectrometry and imaging: Looking backward from 2020 to 1975

Some general aspects of the evolution of atomic spectrometry for chemical analysis over the period 1975 to now are described. Performance parameters such as detection limits and spatial analytical potential (lateral and depth resolution) are compared with the evolution of integrated circuit technology as described in Moore's Law. A few general trends of future development for the coming decade are postulated. Attention will be focused on analysis and imaging with beam techniques, especially secondary ion mass spectrometry and X-ray techniques on the basis of excitation with synchrotron radiation.