Molar volume calculated at various pressures and the Pippard relations close to the melting point in benzene

The molar volume of solid and liquid benzene was calculated at various pressures (at constant temperatures), and the Pippard relations were examined close to the melting point in this organic molecule.

The molar volume calculated is in good agreement with the observed data, which decreases as the pressure increases up to about 150 MPa. The Pippard relations are also valid within this pressure range at constant temperatures studied here for the solid and liquid phases of benzene.     

基于团簇结构模型的Na2O-Al2O3-SiO2三元体系熔体吉布斯混合摩尔自由能计算

以三元硅酸盐熔体团簇结构模型为基础,选取了Na₂O-Al₂O₃-SiO₂体系不同成分的团簇结构,采用半经验量子化学方法MNDO/d分别计算该三元体系熔体中不同结构的团簇基元在1473、1873、2000 K温度下的熵、焓、热容和自由能等热力学数据,计算得出不同团簇结构基元的混合自由能,并根据统计热力学波尔兹曼分布定律,推导计算得出Na₂O-Al₂O₃-SiO₂三元体系各成分下的混合摩尔自由能。三元硅酸盐熔体的热力学性质与该熔体的微观结构密切相关。     

醋酸离子液体[C2mim][OAc]水溶液的摩尔表面Gibbs自由能

在288.15-318.15 K温度范围内测定了不同浓度离子液体1-乙基-3-甲基咪唑醋酸盐([C₂mim][OAc])水溶液的表面张力和密度;在改进李以圭等人的溶液表面张力模型基础上,提出摩尔表面Gibbs自由能新概念,建立了摩尔表面Gibbs自由能随溶液浓度变化的线性经验方程,利用这个经验方程估算了[C₂mim][OAc]水溶液的摩尔表面Gibbs自由能,并进一步预测了该溶液的表面张力,其预测值与相应的表面张力实验值高度相关并非常相似。由此可见,摩尔表面Gibbs自由能与等张比容极其类似,可能成为预测离子液体及其溶液性质的一种新的半经验方法。在指定溶液浓度下,根据溶液的摩尔表面Gibbs自由能随温度呈线性变化的规律,得到了新的Eötvös方程,与传统的Eötvös方程相比,新Eötvös方程的每一个参数都有明确的物理意义:斜率的负值是摩尔表面熵,截距是摩尔表面焓,在指定浓度的溶液中摩尔表面焓几乎不随温度变化。     

吡啶基离子液体[C_6py][DCA]热力学性质及利用新E?tv?s方程预测其表面张力

制备了吡啶类离子液体N-己基吡啶二氰胺盐[C_6py][DCA],并用核磁共振氢谱(~1H NMR)、核磁共振碳谱(~(13)C NMR)、差热扫描量热(DSC)、傅里叶变换红外(FT-IR)光谱对其进行表征。在288.15–338.15 K温度范围内,采用标准加入法,测定其密度(ρ)、表面张力(γ)和折光率(n_D)。在测得的实验数据的基础上,得到了离子液体[C_6py][DCA]的分子体积(V_m)、表面能(E_a)、摩尔极化度(R_m)和极化率(α_p)。结果显示E_a、R_m和α_p几乎不随温度的变化而发生改变。本文还提出了摩尔表面Gibbs自由能(g_s)的概念,并改进了E?tv?s方程。同时还计算了gs、临界温度(T_c)和E?tv?s方程经验参数(kE),并预测了离子液体[C_6py][DCA]的表面张力,预测值与实验值具有较好的一致性。     

3, 4-二乙氧基苯甲酸与2, 2'-联吡啶三元稀土配合物的合成、晶体结构及热化学性质

本文合成了两种三元稀土配合物[Ln（3, 4-DEOBA）₃DIPY]₂DIPY（Ln=Er（1）,Gd（2）;3, 4-DEOBA：3, 4-二乙氧基苯甲酸根;DIPY：2, 2'-联吡啶）,通过元素分析,红外光谱和单晶X-射线衍射对配合物进行表征和分析。实验表明两种配合物是同种晶型的双核分子,相邻结构单元通过π-π作用形成一维链状和二维层状的超分子结构。同时还利用同步热分析与傅里叶变换红外联用（TG-FTIR）技术对配合物的热分解机理进行分析。通过差示扫描量热（DSC）技术,测得两种配合物的摩尔热容,将所得配合物的摩尔热容与折合温度进行多项式拟合,并根据热力学方程,计算得到了两种配合物的舒平摩尔热容和热力学函数值。     

Determination of molar ratio of primary secondary and tertiary amines in polymers by applying derivatization and NMR spectroscopy

A trifluoroacetic acid derivatization combined with ¹H NMR spectroscopy method for determining the molar ratio of primary, secondary, and tertiary amines in small molecules and polymers was discussed. Amines reacted with trifluoroacetic acid to form their salts RNH₃⁺, R₂NH₂⁺, and R₃NH⁺. The ¹H NMR signals of these protonated amines (NH₃⁺, NH₂⁺, and NH⁺) were separated well in the spectra. Based on the integration of these protonated amine signals, the molar ratio of primary, secondary, and tertiary amines can be calculated.     

三维氢键网络配位化合物[Ni(C5H4NCOO)2·(H2O)4]的合成、晶体结构及光学性能研究

通过水热法合成了[N i(C5H4NCOO)2.(H2O)4]晶体。对其进行了元素分析、红外光谱以及热重分析,并通过单晶X-射线衍射确定了其晶体结构。该晶体属于三斜晶系,空间群为P1,晶胞参数为a=0.62878(7)nm,b=0.69008(8)nm,c=0.92440(10)nm,α=96.500(10),°β=105.130(10)°,γ=113.320(10)°。通过UV-VIS-NIR反射光谱研究了其光学性质,表明其在近红外区有强吸收,而在可见区域基本为透明,对太阳辐射的吸光系数(ε)为0.014μm-1。     

Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

Effect of replacing calcium oxide with calcium halide on crystallization and some physical properties of calcium vanadium phosphate glass ceramics

The effect of halide ions on density, electrical, magnetic and crystallization kinetics for (20X-50P₂O₅-30V₂O₅) mole% has been investigated, where X=CaO, CaF₂, CaCl₂ and CaBr₂. Halide ions reduce the glass transition temperature, crystallization temperature and activation energy of crystallization. Density, electrical conductivity and magnetic susceptibility increase while molar volume, glass thermal stability and interatomic distance between transition metal ions decrease as the halide ions replace the oxygen ions in these glasses.     

Molar concentration-depth profiles at the solution surface of a cationic surfactant reconstructed with angle resolved X-ray photoelectron spectroscopy

In the current work, we first reconstructed the molar fraction-depth profiles of cation and anion near the surface of tetrabutylammonium iodide dissolved in formamide by a refined calculation procedure, based on angle resolved X-ray photoelectron spectroscopy experiments. In this calculation procedure, both the transmission functions of the core levels and the inelastic mean free paths of the photoelectrons have been taken into account. We have evaluated the partial molar volumes of surfactant and solvent by the densities of such solutions with different bulk concentrations. With those partial molar volumes, the molar concentration-depth profiles of tetrabutylammonium ion and iodide ion were determined. The surface excesses of both surfactant ions were then achieved directly by integrating these depth profiles. The anionic molar concentration-depth profiles and surface excesses have been compared with their counterparts determined by neutral impact ion scattering spectroscopy. The comparisons exhibit good agreements. Being capable of determining molar concentration-depth profiles of surfactant ions by core levels with different kinetic energies may extend the applicable range of ARXPS in investigating solution surfaces.