溶液的热压力系数及内压

在作者的前一篇论文中,已由修正的Van der Waals模型建立了一个液体热压力系数与密度的关系式并据此得到了一个计算液体内压的公式 2)式中pm是液体摩尔体积V_m的倒数,称为摩尔密度,T是热力学温度,R是通用气体常数,A     

液体的热压力系数及内压

本文从排斥体积要随密度改变的概念出发,修正了原始的Van der Waals理论,并建立了一个计算液体热压力系数的公式 (P/I)_v=R_(ρm)/(1-A_(ρm) B_(ρ~2m))式中ρm=1/V_m是液体的摩尔密度,A和B都是与分子大小有关的两个特性常数。因此,利用Lennard-Jones位能函数中的参数σ_(LJ)便能预测液体在不同温度下的热压力系数及内压值。     

醇类的缔合作用与热压力系数

测定了甲醇、正丙醇、正丁醇和正癸醇在25-85℃温度范围的热压力系数, 并为正构醇液体建立了一个热压力系数与密度间的通式。这个通式可用来预测正构醇在各种温度下的内压值。用同形物近似法, 本文还获得了正构醇缔合作用的若干重要信息和估计其缔合度的近似方法。     

聚合物内压测定及对应状态模型

实验测定了PEG(M~n=200),PEG(M~n=300),PEG(M~n=400),PDMS(M~w=15000)和PDMS(M~w=20000)在20-90℃温度范围的热压力系数和密度,它们的热压力系数和内压几乎与分子量无关。据此还建立了一个聚合物内压的对应状态模型,它只含一个可调参数,能满意地适用于各种聚合物。     

乙醇和环己烷液体混合物的内压

测定了25-65℃温度范围内乙醇和环己烷液体混合物的热压力系数, 它们都很好地遵守我们先前提出的修正van der Waals模型。从模型参数B/A^2, 可以得到乙醇自缔合的破坏与浓度间的定量关系。混合物的内压不仅取决于两个组分的内压, 而且还与相互作用参数A12有关。     

乙醇在正己烷中的解缔与超额焓

测定了不同温度和浓度下乙醇与正己烷液体混合物的热压力系数及内压,并用修正的van der Waals模型关联了这些实验数据,从模型参数B/A2得到了一个乙醇自缔合随组成而遭破坏程度的公式.根据这个公式设想了一个醇与烃的混合模型,建立了混合物的超额焓方程,它能够满意地描述上述混合物的超额焓随组成的变化规律,并显示物理和化学作用对HE的贡献     

醇类液体的热压力系数及内压

本文测定25-85℃温度范围内正戊醇.正已醇.正庚醇和正辛醇的热压力系数,发现这些醇类液体的内压几乎不随温度而变,本文还将修正的vander waals 模型推广到了醇类液体,与非缔合液体一样,它们的排斥体积亦与密度呈线性关系.但是,模型参数之比B/A^2不再是个常数,而是随醇分子中碳原子数的增多而快速地减小, 这个比值可作为合能力的一种量度.     

液体的内压和内能的统计热力学理论

利用分布函数理论导出了液体的内能和内压公式.液体的内压和过剩内能可以表示成体积的幂级数形式,其中的系数可以用多体相互作用势和多体径向分布函数表出,它们仅仅与温度有关.讨论了液体仅存在第n次多体相互作用势情形的内压和过剩内能的表达式,结果与Egelstaff的微扰理论结果具有相同的形式,不仅给出了相应参数的表达式而且适用于多体相互作用较强的情形.定义了物性参数α(T)和m,得到的液体过剩内能和内压的表达式与Frank实验结果具有相同的形式,其结果不仅给出了参数α(T)和m的表达式,而且指出了Frank的过剩内能和内压公式只适用于参数α(T)和m与体积无关的液体.     

理想稀溶液的分子模型与Henry系数

提出了一个理想稀溶液的分子模型,并利用Boltzmann分布定律和Laplace方程导出一个简单的Henry系数表示式,它与溶质分子周围溶剂的内压力或溶剂压密切相关。利用Hildebrand内压力方程,并以纯溶剂的摩尔体积代人,关联了11种气体在正十六烷中的Henry系数随温度变化的实验数据。     

离子液体的QSPR/QSAR研究

离子液体以其独特的性质广受关注,人们对其潜在的应用价值做了大量的研究,但对离子液体特性和结构与性质/活性相关的研究却很少。本文综述了离子液体定量结构-性质/活性相关(QSPR/QSAR)研究的最新进展,重点介绍了QSPR/QSAR的基本原理和离子液体的熔点、有机化合物在离子液体中的无限稀释活度系数、离子液体的界面张力、有机物在离子液体中的溶解系数和分配系数、离子液体的电导率和黏度以及离子液体的毒性等性质与分子结构的定量关系,并对离子液体分子结构与性质/活性的定量相关研究的发展趋势进行了展望。     

Fabrication of heterogeneous binary arrays of nanoparticles via colloidal lithography

Heterogeneous binary arrays of metallic nanoparticles have been constructed by consecutively depositing gold and silver into monolayers of hexagonally close-packed latex spheres at the incidence angles of 15 and -15 degrees, followed by removal of the colloidal masks. The present approach is independent of the chemical nature of both colloidal masks and deposition materials. The pattern feature of the resulting binary nanoparticle arrays is dependent on the colloidal mask registry.     

正丁醇、乙酸乙酯、正己烷的二元及三元体系的超额焓测量和关联

用等温稀释量热计测定了正己烷+正丁醇、正己烷+乙酸乙酯二元体系在303.15K、308.15K及正丁醇+乙酸乙酯+正己烷三元体系在303.15K的超额焓,用Kretschrner-Wiebe理论组合UNIQUAC方程所得数学模型对二元体系在303.15K的超颠焓进行了关联,并预测了所测三元体系在303.15K的超额焓,预测结果与实验值比较,平均偏差为6％。     

Physical procedures for the analysis of mixtures of polychloroethanes

A mixture of seven polychloroethanes has been analysed by fractionation into binary mixtures using a combination of continuous fractionation and the technique of total reflux with intermittent take-off. The binary mixtures were analysed by refractive index measurements. The relationship between binary mixture refractive index and component mass fraction was found to be linear. The temperature dependence of the refractive indices of the polychloroethanes over the range, 15–35°, was also determined.     

Phase Behaviour of Poly(styrene-co-methacrylic acid)/ Poly(styrene-co-N,N-dimethylacrylamide)/Poly(styrene-co-4-vinylpyridine) Ternary Blends by DSC and FTIR

Summary: we have investigated by DSC and FTIR the miscibility and phase behaviour of binary and ternary blends of different ratios of poly(styrene-co-methacrylic acid) containing 15 mol% of methacrylic acid (SMA15) with poly(styrene-co-N,N-dimethylacrylamide) containing 17 mol% of N,N,-dimethylacrylamide (SAD-17) and poly(styrene- co-4-vinylpyridine) containing 15 mol% of 4-vinylpyridine. SMA15 is miscible with both SAD17 and S4VP15 and interacts more strongly with S4VP15 than with SAD17 as evidenced by the positive deviations from linear average line observed with these blends and the appearance of new bands in the 1800–1550 cm⁻¹ region. This behaviour is known as ΔK effect. The FTIR study confirms that though the specific intermolecular interactions that occurred with each pair of the SMA15/S4VP15 and SMA15/SAD17 binary components are of different strength, they still exist in the ternary blend. Even though the three binary polymer pairs are individually miscible, the ternary system of SMA15/S4VP15/SAD17 exhibits only partial miscibility with small loop of immiscibility due to a significant ΔK effect. These results obtained by DSC and FTIR are in a fair agreement with theoretical prediction applying the Painter-Coleman association model.     

A complexation study of 15-crown-5 with Co2+ cation in some pure and mixed organic solvents

The stability constant (log K _f) and the thermodynamic parameters (free energies, enthalpies, and entropies) of the complexation of Co²⁺ cation with 15-crown-5 (15C5) in acetonitrile-methanol (AN/MeOH), acetonitrile-nitrobenzene (AN/NB), acetonitrile-dichloromethane (AN/DCM) and acetonitrile-1,2-dichloroethane (AN/DCE) binary solvent solutions were calculated from the experimental conductance data at different temperatures. The complexation behavior of the crown ether used in these media was discussed in view of the estimated parameters. In all solvent systems, 15-crown-5 formed a 1: 1 complex with Co²⁺ cation. The stability order of (Co-15C5)²⁺ complex in the binary mixed solvents at 25°C was found to be: AN/NB > AN/DCM ≈ AN/DCE > AN/MeOH. In most cases, a non-linear relationship was observed for changes of log K _f of (Co-15C5)²⁺ complex versus the composition of the binary mixed solvent systems. The experimental results show that the standard thermodynamic parameters of the complexation process change with the nature and composition of the binary solvent solutions.     

Binary Assembly of Au Nanoparticles with Controllable Two‐dimensional Architecture Directed by Phosphate Backbone Modified Oligonucleotide

A three complementary strand oligonucleotide system was employed to assemble two different‐sized, 15 and 25 nm, Au nanoparticles into binary two‐dimensional (2D) structures. First, two non‐complementary strands of phosphate backbone modified oligonucleotides (PM oligo‐DNA) were loaded on the surface of the 15 and 25 nm Au nanoparticles, respectively. Upon the addition of the third linker DNA, which was half complementary to each of the modified DNA, the Au nanoparticles would be assembled to binary 2D aggregates. The number of the 15 nm Au nanoparticles around a 25 nm Au naoparticle can be readily controlled by the length of the DNA helix used.     

金-硫团簇负离子组成特征的探讨

报导了金/硫靶在静态二次离子质谱实验条件下形成的组成通式为Au1－15S0－5的团簇负离子.其中,Aun组成系列具有典型的奇数优势,属于金的一元团簇负离子.其余组成系列（Au1－15S1－5）则属于金 硫二元团簇负离子.研究发现,金 硫团簇负离子具有以下与组成密切相关的特征: （1）它们继承了金一元团簇负离子的奇数优势;（2）它们中硫原子数仅限于5,而金原子数则在较大范围变化;（3）它们完全没有多数其它金属与非金属（包括硫）二元团簇正/负离子共有的MenNn型组成优势;（4）它们以上组成特征及其它细节恰似碳 磷这样的典型非金属二元团簇正/负离子.基于这样的组成特征可提出,金 硫团簇负离子在构成上包含着相对完整的金一元团簇组件,在形成机制上源于金一元团簇与硫一元团簇（或称为:限于五原子的多硫单元）之间的再团簇化.关于再团簇化机制中的相互作用问题,即两类团簇间是依靠末端原子交叉成键还是依赖两类团簇中异种原子之间静电诱导力等“非共价键”作用的问题,则有待于今后研究证实.     

Prediction of Ternary Liquid Adsorption on Solids from Binary Data

The adsorption behavior of the ternary n-hexane/n-octane/n-tetradecane mixture and the binary n-hexane/n-octane, n-octane/n-tetradecane, n-hexane/n-tetradecane mixtures on the well-characterized TA 95 activated carbon has been studied. Measured binary data at 25 degrees C are used to predict the ternary data which are compared with measured ones. With the measured binary data at 15 degrees C, a prediction of ternary data is proposed without ternary experimental support. To predict ternary data from the binary ones, a thermodynamical model combining the methods of Myers and Price and Danner is used. Copyright 2000 Academic Press.     

四氢呋喃开环聚合的研究——Ⅳ.发烟硫酸-高氯酸引发四氢呋喃及环氧丙烷的共聚合

用21％或28％发烟硫酸-高氯酸引发四氢呋喃及环氧丙烷(THF:PO=100:5-15(克))进行共聚合反应,收率为50—60％,四氢呋喃的损耗不超过10—15％,产物分子量在1000—2000之间可调。与通常用三氟化硼或五氯化磷及二元醇制备的四氢呋喃-环氧丙烷共聚醚不同;当环氧丙烷用量低时,收率并不降低;产物的端羟基官能度为2;以伯醇端基为主(约65—70％)。     

STUDIES ON THE RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN Ⅳ. COPOLYMERIZATION OF TETRAHYDROFURAN AND PROPYLENE OXIDE INITIATED BY FUMING SULFURIC ACID AND PERCHLORIC ACID CATALYST SYSTEM

The yield of copolymerization of tetrahydrofuran and propylene oxide (THF:PO=100:5—15, by wt.) using a binary catalyst of fuming sulfuric acid (21% or 28%) and perchloric acid is around 50—60%, and the loss of THF in the reaction is below 10—15%. The average molecular weight of the product can be controlled in the range of 1000—2000 by varying the binary catalyst system. The present method, which is different from the usual copolymerization initiated by BF_3-diol or SbCl_5-diol system, shows the pecularities i.e. the yield of copolymerization with the low PO feed is not decreased, the hydroxyl functionality is equal to 2, and the end-groups are predominantly primary hydroxyls (around 65—70%).