Studies on the Physical Properties of Alkanes Using Edge-adjacency Information Topological Index

Edge-adjacency index and information topological index for 82 molecules of alkanes nave been constructed and calculated. The topological indices were used to correlate with seven physical properties of the alkanes. Some empirical equations were obtained through regression. The regression and calculation results show a good agreement of the topological indices and the properties.     

疏水性咪唑类混合离子液体的物理化学性质

本文选取疏水性和疏水性离子液体混合物作为研究对象, 将疏水性离子液体1-甲基-3-n-丁基咪唑三氟甲基磺酰胺盐[BMImN(CF3SO2)2]与BMImPF6以不同的比例进行混合, 对混合离子液体及其相应单组分离子液体进行了相关物理化学性质的测试和对比, 讨论由于混合导致的物理化学效应.     

新型苯并噻唑类离子液体的合成及其理化性质研究

以苯并噻唑为原料,采用"一锅"法合成了一系列新型的苯并噻唑类离子液体,其结构经1H NMR和MS表征。系统考察了其密度、溶解性、电导率、吸水性等理化性质,发现了其结构对理化性质有不同程度的影响。     

用原子特性自相关拓扑指数预测链烷烃的热力学性质

原子特征值 ( Si)被定义为 :Si=ni- 1ki mi( ∑Eij+ hi Ei)。由 Si建构原子特征自相关拓扑指数 ( F )及原子特征连接性指数 ( Y)的公式为 :F =∑( Si· Sj) 0 .5、Y=∑ ( Si·Sj) - 0 .5。它们与 85种链烷烃热力学性质 ( P)的二元线性回归方程为 :P =a + b F +c Y(或 P3) 。 P为标准生成焓、标准熵、标准生成自由能的二元相关指数依次为 0 .9953、0 .9992、0 .9941 ,优于文献方法     

吗啉离子液晶的合成和介晶行为

一系列吗啉离子液晶被合成,包括N-烷基-N-甲基吗啉类盐(Mor1, nX, n = 10, 12, 14, 16, X = BF4-) 和酸性N-十六烷基吗啉类盐(Mor16X, X = BF4-, CH3SO3- and p-CH3C6H4SO3-) 。它们的介晶性质通过差示扫描量热仪,偏光显微镜表征。N-十六烷基-N-甲基吗啉氟硼酸离子液晶的分子结构通过单晶衍射和变温小角X射线衍射进行研究。结果表明,氟硼酸阴离子利于介晶化合物的形成和稳定,且它与吗啉阳离子形成的氢键导致了介晶相变过程中的构造变化。     

一个新的量子拓扑指数及其对镧系元素理化性质的预测

在基态原子价壳层电子隐核图的基础上，基于拓扑化学原理以及原子价壳层电子量子结构特征，构建了原子价壳层电子量子拓扑指数QTI，它对基态原子实现唯一性表征，具有优良的结构选择性。用QTI指数与镧系元素的16种物理化学性质按数学模型P=aQTI+b进行关联。结果表明，QTI不仅与镧系元素的16种理化性质具有良好的相关性，而且较其他文献所报道的研究工作物理意义更明确，方法更简单。     

The Physical Properties of Aqueous Solutions of the Ionic Liquid [BMIM][BF4]

We report here the systematic study of the effect of concentration on the physical properties of aqueous solutions of the room-temperature ionic liquid [BMIM][BF₄]. The measurements of density, ρ, refractive index △n, viscosity η, specific conductivity κ and surface tension, γ, were made over the whole concentration range. The equivalent conductance Λ _m was calculated. The observed linear variations of density and refractive index with the molar concentration are established as those of an ideal solution. The surface tension varied most rapidly in the dilute region whereas the viscosity changed much more rapidly in the concentrated region. Two regions with different composition dependences were found after the analyses of the relationship between the conductivity and the concentration of [BMIM][BF₄]. A proposed model for a structural change in the mixtures was described. The physical origin of the observed concentration dependence of these properties is discussed. The physical properties of the solutions vary with changes of association between anions and cations and the interaction between [BMIM][BF₄] and water.     

离子液体BMIBF4性质的研究

用最大气泡法和韦氏天平法,在278．15～343．15K范围内测定了离子液体BMIBF4的表面张力和密度;讨论了这个离子液体的体积性质和表面性质;根据离子个头大又极不对称的特点,提出了离子液体的空隙模型．根据空隙模型计算的离子液体恒压热膨胀系数与实验值相比,偏差在10％左右。     

功能化离子液体中Ag纳米微粒的制备及摩擦学性能研究

合成了1-甲基-3-羟乙基咪唑四氟硼酸盐离子液体([C₂OHmim]BF₄)，用红外光谱表征了其结构。以所合成的离子液体作为还原剂、稳定剂与反应介质制备了Ag纳米微粒，用XRD和TEM对微粒的结构和形貌进行了表征。在四球摩擦磨损实验机上研究了[C₂OHmim]BF₄离子液体及掺入Ag纳米微粒后的离子液体的摩擦学性能。掺入银纳米微粒后，离子液体在高载荷下的润滑性有了大幅的改善。用SEM和XPS分别对磨痕表面的形貌和元素组成、化学状态进行了分析，结果表明：在低、高载荷分别起润滑作用的是有机膜和金属-有机复合膜。     

咪唑基离子液体固定分离CO2的研究进展

以咪唑基离子液体为代表,综述了近期普通咪唑基离子液体、功能咪唑基离子液体、支撑咪唑基离子液体和聚合咪唑基离子液体在分离固定CO2方面的研究进展,说明了各类咪唑基离子液体分离固定CO2的可行性及优缺点,并总结了离子液体固定CO2的影响因素和分离机制.     

稀散金属铟的离子液体EMIInCl4的热化学性质研究

在充满干燥氩气的手套箱中用直接混合等物质的量的EMIC(氯化1-甲基-3-乙基咪唑)和高纯无水InCl₃的方法, 制备了含稀散金属铟的离子液体EMIInCl₄. 在298.15 K下, 利用自行组装的具有恒温环境的溶解反应热量计, 测定了离子液体EMIInCl₄和EMIC在水中的反应溶解热, 并将这些实验数据按Pitzer方程作拟合, 分别得到了EMIInCl₄和EMIC的无限稀释摩尔溶解热Δ_sH_m⁰和Pitzer溶解焓参数. 根据溶解热和水化热数据, 估算了InCl₄^－(g)解离成In^3＋(g)和4Cl^－(g)的解离热, 还估算了反应: EMIC＋InCl₃→EMIInCl₄的摩尔反应热Δ_rH_m＝(－60.37±1.8) kJ•mol^－1. 在合成离子液体EMIInCl ₄中也观察到了放热现象, 这表明在合成过程中生成了InCl₄^－.     

Review on Comparative Study of Solid Polymer Electrolyte Polyethylene Oxide (PEO) Doped with Ionic Liquid

Future demands for energy shortages have prompted a lot of effort to be put into finding alternatives. The use of renewable energies as a revolutionary energy source has gained acceptance. Due to their high flexibility and the interaction between the electrode and the electrolyte, solid polymer electrolytes are employed as a favorable electrolyte for application of electrochemical devices to storage renewable energy. As these are easy in synthesis, have much lower mass density, shows high mechanical stability, also have low binding energy with salts, and high mobility of charge carriers, polyethylene Oxide (PEO) based electrolyte has attracted a lot of interest. Configuration rectification combining PEO with ionic liquids has been introduced to enhance the low ionic conductivity and poor thermodynamic stability of the PEO materials in high-voltage devices at ambient temperature. This configuration modification can successfully validate the applications of PEO polymer electrolyte with large electro-stable voltage ranges. Solution casting method has been used for the synthesis of polymer electrolyte. The essential physical characteristics of PEO in polymer matrices work as a polymer host in SPEs has been described in this review paper, along with several modifications to overcome these limitations. It has been seen that the addition of ionic liquid increases the all over conductivity of the solid polymer electrolyte in most cases also improves the electrical stability of the electrolyte.     

取代脂环烃物理化学性质的拓扑化学研究

为了探讨有机化合物的分子结构与理化性质的关系,作者在以前的工作基础上,基于一阶分子连通性拓扑指数构建了一个信息拓扑指数.将拓扑指数与取代脂环烃系列分子的气态标准生成热、气态标准熵、气态标准生成自由能、沸点、临界温度、临界压力、临界体积、汽化热、密度、热容及表面张力等十一种热力学性质及物理化学性质相关联,用一个通用公式对各类性质进行概括,然后用已有的实验数据与拓扑指数进行回归分析,得到一系列计算各性质的经验公式.回归结果发现,分子的理化性质与拓扑指数有较好的相关性,有5类性质的复相关系数大于0.99.用经验公式对各类性质进行重新计算,其结果与实验值比较符合,用实验值对计算值作图,发现各数据点紧靠对角线,说明误差较小.残差分布呈正态分布.     

The Effect of Fluorinated Solvents on the Physicochemical Properties,Ionic Association,and Free Volume of a Prototypical Solvate Ionic Liquid

Solvate ionic liquid (SIL) synthesis and properties depend on a delicate balancing of cation-solvent and cation-anion interactions to produce materials containing only cation-solvent complexes and solvent-separated anions. Most SILs meeting these characteristics fall within the paradigm of oligomeric ethylene oxides (e.g. glymes and glycols) and lithium salts. Targeted functionalization of solvent molecules to achieve desired properties is a relatively unexplored avenue of research. Fluorinated solvents have significantly different electric charge distributions compared to their nonfluorinated analogs. We test the impact of solvent fluorination for a SIL created from equimolar mixtures of lithium bis(trifluoromethylsulfonyl)imide (LiNTf₂) and triethylene glycol (TEG), hereafter [(TEG)₁Li]NTf₂. In the first experiment, TEG is partially substituted with 2,2,4,4,5,5,7,7-octafluoro-3,6-dioxaoctane-1,8-diol (FTEG). This leads to a precipitous decrease in ionic conductivity and larger quantities of ionically-associated Li(NTf₂)₂⁻ species, as detected with vibrational spectroscopy. These observations suggest FTEG does not readily coordinate Li⁺ ions in a manner analogous to TEG. Computational studies reinforce this conclusion. Relative complex cation stabilities are ranked as [(FTEG)₁Li]⁺>[(TEG)₁Li]⁺. A second experiment adds FTEG as a diluent to [(TEG)₁Li]NTf₂. This places FTEG and TEG in competition to coordinate a limited number of Li⁺ ions. The resulting mixtures exhibit conductivity enhancement over the parent SIL and minimal changes in ion speciation due to the poor Li⁺ binding by FTEG compared to TEG. Positron annihilation lifetime spectroscopic studies point to increased amounts of free volume upon dilution of FTEG. This likely explains the origin of the conductivity and viscosity enhancements.     

Ionic Liquid Crystalline Calixarene with Photo-Switchable Proton Conduction

We have developed a new strategy for the preparation of a light-responsive ionic liquid crystal (LC) that shows photo-switchable proton conduction. The ionic LC consists of a bowl-shaped calix[4]arene core ionically functionalized with azobenzene moieties. The non-covalent architectures were obtained by the formation of ionic salts between the carboxylic acid group of an azo-derivative and the terminal amine groups of a calixarene core. The presence of ionic salts results in a hierarchical self-assembly process that extends to the formation of a nanostructured lamellar LC arrangement (smectic A phase). In this LC phase, the ionic LC calixarene is able to display proton conductive properties, since the ionic nanosegregated areas (formed by the ionic pairs) generate the continuous channels that favor proton transport. The optical and photo-responsive properties were studied by UV-Vis spectroscopy, demonstrating that the azobenzene moieties of the ionic LC undergo reversible (E)-to-(Z) isomerization by irradiation with UV light. Interestingly, this (E)-to-(Z) photoisomerization results in a decrease of the proton conductivity values since the bent-shaped (Z)-isomer disrupts the lamellar LC phase. This isomerization process is totally reversible and leads to an ionic LC material with unique photo-switchable proton conductive properties.     

室温离子液体BMIGaCl4热力学性质研究

An ionic liquid （IL） BMIGaCh was prepared by directly mixing GaCl3 and 1-methyl-3-butylimidazolium chloride with molar ratio of 1/1 under argon atmosphere. The densities and surface tensions of this pure ionic liquid were determined in the temperature range of 268.15 to （338.15±0.1） K. A new theoretical model of ionic liquids, an interstice model, was applied to calculate the thermal expansion coefficient of IL BMIGaCh, a, and the magnitude order of its value calculated by the theory was the same as experimental one. Both Raman scattering and ab initio calculations indicate that GaCl4^- is the only species containing Ga in the ionic liquid BMIGaCl4.     

Enhancing the Thermal Stability of Ionogels: Synthesis and Properties of Triple Ionic Liquid/Halloysite/MCC Ionogels

In this study, an ionic liquid (IL), 1-butyl-3-methylimidazolium acetate, was used to prepare ionogels with microcrystalline cellulose (MCC) and halloysite (Hal). SEM, XRD, TG, DSC, FTIR spectroscopy, conductometry and mechanical tests were used to study the morphology, structure, thermal behaviour and electrophysical and mechanical characteristics of synthesised ionogels. XRD analysis showed a slight decrease in the interlayer space of halloysite in ionogels containing MCC, which may have been associated with the removal of residual water molecules resulting from hydrophilic IL anions and polymer macromolecules. A change in conductivity and glass-transition temperature of the ionic liquid was revealed due to intercalation into halloysite (a confinement effect) and modification with cellulose. For triple IL/Hal/MCC ionogels, the characteristic thermal degradation temperatures were higher than the corresponding values for IL/Hal composites. This indicates that the synthesised IL/Hal/MCC ionogels are characterised by a greater thermal stability than those of IL/Hal systems.     

离子液体二维结构制备及其特性研究进展

由于阴阳离子间特殊的静电、氢键作用,具有二维结构的离子液体呈现出独特的结构特征及热力学、动力学特性,在化学化工和材料领域都有着巨大的应用前景,已成为离子液体领域重要的研究方向之一.本综述重点介绍了离子液体二维结构常用的制备方法,包括自组装法、Langmuir-Blodgett法以及物理气相沉积法,并总结了这些制备方法相应的优缺点.随后归纳了离子液体二维结构的相变特征及在力学和电学方面的特性,并综述了其在摩擦润滑领域的应用.最后展望了离子液体二维结构的发展方向及应用前景.     

Measurement and Correlation of the Ionic Conductivity of Ionic Liauid-Molecular Solvent Solutions

The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate （[Bmim][BF4]） or 1-n-butyl-3-methylimidazolium hexafluorophosphate （[Bmim][PF6]） and different molecular solvents （MSs） were measured at 298.15 K. The molar conductivity of the ionic liquids （ILs） increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.     

烧绿石型复合氧化物结构及离子导电性

本文结合这两年来作者的研究工作,综述了烧绿石型复合氧化物的结构及离子导电性研究进展.系统介绍了烧绿石型复合氧化物的结构特点,分析了其传导机理、离子传导特性及国内外研究现状、应用前景和发展趋势.