Prediction and verification of heat capacities for pure ionic liquids

The heat capacity of ionic liquids is an important physical property,and experimental measuring is usually used as a common method to obtain them.Owing to the huge number of ionic liquids that can be potentially synthesized,it is desirable to acquire theoretical predictions.In this work,the Conductor-like Screening Model for Real Solvents(COSMO-RS) was used to predict the heat capacity of pure ionic liquids,and an intensive literature survey was conducted for providing a database to verify the prediction of COSMO-RS.The survey shows that the heat capacity is available for 117 ionic liquids at temperatures ranging 77.66-520 K since 2004,and the 4025 data points in total with the values from 76.37 to 1484 J·mol~(-1)·K~(-1) have been reported.The prediction of heat capacity with COSMO-RS can only be conducted at two temperatures(298 and 323 K).The comparison with the experimental data proves the prediction reliability of COSMO-RS,and the average relative deviation(ARD) is 8.54%.Based on the predictions at two temperatures,a linear equation was obtained for each ionic liquid,and the heat capacities at other temperatures were then estimated via interpolation and extrapolation.The acquired heat capacities at other temperatures were then compared with the experimental data,and the ARD is only 9.50%.This evidences that the heat capacity of a pure ionic liquid follows a linear equation within the temperature range of study,and COSMO-RS can be used to predict the heat capacity of ionic liquids reliably.     

Determination and Correlation of Solubilities of Four Novel Benzothiazolium Ionic Liquids with PF6^- in Six Alcohols

Four novel benzothiazolium ionic liquids with 6PF- （[C1Bth][PF6], [C4Bth][PF6], [C5Bth][PF6] and [C6Bth][PF6]） were synthesized, and the rang of their melting points were determined between 358.35 K-424.05 K. The relationship of their melting points and the length of the straight alkyl chain on cation reflected‘S’ type ten-dency. Then, the solubilities of the four ionic liquids in six lower alcohols （methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-1-propanol） were measured in the temperature rang of 253.15-383.15 K at at-mospheric pressure with static analytical method, respectively. It was found that [C6Bth][PF6] in all investigated ionic liquids had the largest solubility in six alcohols and the solubility of [C4Bth][PF6] in methanol was very sensi-tive for temperature in 313.15-333.15 K, which was so-called “temperature-sensitivity”. This feature is of great significance to their application of catalyzing reaction or extraction process, and makes the recovery and reuse of ionic liquids （ILs） become easier. Moreover, the experimental solubility data were correlated with the modified Apelblat equation andλh equation, respectively. It was found that the result of correlation using two divided tem-perature ranges was better than that of using the whole temperature range.     

离子液体捕集二氧化碳的研究进展(英文)

Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.     

氯化胆碱·xZnCl_2离子液体在生物柴油制备中的应用(英文)

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.     

酮麝香、二甲苯麝香和1,3-二甲基-2,4-二硝基-5-叔丁基苯固-液相平衡研究

The solid-liquid equilibria of musk ketone musk xylene, musk xylene 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are measured by differential scanning calorimeter (DSC), these systems are proved to be simple eutectics. Moreover the melting points and the fusion enthalpies of musk ketone, musk xylene and 1,3-dimethyl-2,4-dinitro-5-tert-butyl benzene are also measured by the DSC. These solid-liquid equilibrium data and the heats of fusion are reported for the first time. Then UNIFAC model is used to correlate the solid-liquid equilibrium data.It is shown that the solid-liquid equilibria of musk systems can be predicted bv the UNIFAC model.     

离子液介质中生物催化与生物转化的研究进展

Ionic liquids have negligibly low vapor pressure, high stability and polarity. They are regarded as green solvents. Enzymes, especially lipases, as well as whole-cell of microbe, are catalytically active in ionic liquids or aqueous-ionic liquid biphasic systems. Up to date, there have been many reports on enzyme-exhibited features and enzyme-mediated reactions in ionic liquids. In many cases, remarkable results with respect to yield, catalytic activity, stability and (enantio-, regio-) selectivity were obtained in ionic liquids in comparison with those observed in conventional media. Accordingly, ionic liquids provide new possibilities for the application of new type of solvent in biocatalytic reactions.     

离子液介质中生物催化与生物转化的研究进展

Ionic liquids have negligibly low vapor pressure, high stability and polarity. They are regarded as green solvents. Enzymes, especially lipases, as well as whole-cell of microbe, are catalytically active in ionic liquids or aqueous-ionic liquid biphasic systems. Up to date, there have been many reports on enzyme-exhibited features and enzyme-mediated reactions in ionic liquids. In many cases, remarkable results with respect to yield, catalytic activity, stability and (enantio-, regio-) selectivity were obtained in ionic liquids in comparison with those observed in conventional media. Accordingly, ionic liquids provide new possibilities for the application of new type of solvent in biocatalytic reactions.     

Statistical mechanics and artificial intelligence to model the thermodynamic properties of pure and mixture of ionic liquids

In this paper, the volumetric properties of pure and mixture of ionic liquids are predicted using the developed statistical mechanical equation of state in different temperatures, pressures and mole fractions. The temperature dependent parameters of the equation of state have been calculated using corresponding state correlation based on only the density at 298.15 K as scaling constants. The obtained mean of deviations of modified equation of state for density of al pure ionic liquids for 1662 data points was 0.25%. In addition, the performance of the arti-ficial neural network (ANN) with principle component analysis (PCA) based on back propagation training with 28 neurons in hidden layer for predicting of behavior of binary mixtures of ionic liquids was investigated. The AADs of a col ection of 568 data points for al binary systems using the EOS and the ANN at various temperatures and mole fractions are 1.03%and 0.68%, respectively. Moreover, the excess molar volume of all binary mixtures is predicted using obtained densities of EOS and ANN, and the results show that these properties have good agree-ment with literature.     

Removal of mercaptans from light oils using ionic liquid–NaOH aqueous solution as extractants

The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added into the Na OH(aq) to remove the mercaptans. The influences of anion species and cation alkyl chain length of the imidazolium-based ionic liquids on the performance of mercaptan removal from light oils have been discussed.The efficiency of extraction for mercaptans exhibited the order of [Ac]~-N [OH]~-≈ [Br]~-N [BF4]~-. The longer alkyl chain imidazolium-based ionic liquids contributed to enhance desulfurization rate of 1-butyl mercaptan.100% desulfurization rate of 1-butyl mercaptan was achieved by the anion of Ac-ionic liquids and Na OH(aq)at a volume ratio of 40:1(V(oil):V(ionic liquid)) and a short equilibrium time within 10 min.     

Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry. In this study, a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied. Among these ionic liquids, 1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl₄]) with the highest selectivity was used as the ext...     

Thermodynamic Properties of Caprolactam Ionic Liquids

A series of caprolactam ionic liquids (ILs) containing incorporated halide anions were synthesized. Their physical properties, such as melting points, heats of fusion and heat capacities, were measured by differential scanning calorimeter (DSC). The results indicate that these ionic liquids exhibit proper melting points, high value of heats of fusion, and satisfying heat capacities which are suitable for thermal energy storage applications.     

离子液体物理化学性质数据库及QSPR分析

收集了1984~2004年文献中报道的有关离子液体物理性质的数据,建立了离子液体物理性质数据库. 数据库共包含600多种离子液体,约3500条数据. 基于这些数据,进行了离子液体定量结构-性质相关性(QSPR)的研究,对两种常见体系(双取代咪唑四氟硼酸盐和双取代咪唑六氟磷酸盐)的熔点进行了关联和预测. 研究结果对离子液体的设计与应用具有指导意义.     

Thermodynamic studies of solid polyethers: 5. Crystalline-amorphous interfacial thermal properties

The influence of the crystalline-amorphous interface on the bulk melting phenomena of poly(ethylene oxide) and poly(octamethylene oxide) was studied. For this purpose, heats of solution of various kinds of specimens prepared by precise heat treatment were measured at various temperatures with an isoperibol calorimeter. The crystallinity and the lamellar thickness were determined by dilatometric and small-angle X-ray scattering methods, respectively. Melting points of each sample were determined using a differential scanning calorimeter. The thermodynamic quantities obtained were correlated by theoretical consideration, so that the effects of crystalline-amorphous interfacial thermal properties on bulk quantities such as heat of fusion were derived.     

DSC法测定醋酸-水溶液的比热

利用差示扫描热量计(DSC)测定了醋酸水溶液在温度范围为293.15~359.15K和整个组成范围下的比热,并把比热的测量值与文献值进行了比较, 实验的测量误差小于±2%, 测得的醋酸-水的比热数据完全能满足工程设计的需要。同时把醋酸-水的比热与组成与温度进行了关联,并利用最小二乘法回归出所提方程中的参数,最后导出了一个计算Cp的多项式方程,此方程中既包含温度又包含组成,因此利用此方程可以计算醋酸-水体系在测定温度和组成下的Cp。把用该方程的计算值与实验值进行了比较,117个数据点的总绝对平均相对误差为0.54%。所提方程可应用于对苯二甲酸生产中换热器的设计及相关体系热量平衡的计算,具有实用意义。     

离子液体在传热及相变储热中的应用研究进展

离子液体具有与传统的传热、储热材料相当,甚至更加优越的性质,如蒸气压低,储热密度高,物理和化学稳定性好,热传导性好,熔点低和可设计性等。因此,离子液体在太阳能集热、建筑节能、电力谷峰调控、低品位余热存储、吸附式热泵等领域具有良好的应用潜力。综述了离子液体在传热和储热中的应用研究进展,包括作为热传导液用于太阳能集热,作为吸附介质应用于制冷(制热),以及作为相变储热材料等。最后,指出离子液体的一些性质,如腐蚀性、毒性和长期稳定性等,也是离子液体在储热和传热应用中需要考察的问题。     

Physical and electrochemical properties of 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium iodide,and 1-butyl-3-methylimidazolium tetrafluoroborate

The density, viscosity, refractive index, heat capacity, heat of dilution, ionic conductivity, and electrochemical stability of 1-butyl-3-methylimidazolium bromide ([bmim][Br]), 1-butyl-3-methylimidazolium iodide ([bmim][I]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) were measured at room temperature or over a temperature range of 293.2 to 323.2 K. The density and refractive index values of [bmim][I] appeared to be the highest among three ionic liquids (ILs). However, the experimental viscosity values of [bmim][Br] were higher than those of [bmim][BF₄], while the heat capacities and heats of dilution of [bmim][BF₄] were higher than those of [bmim][Br]. The cyclic voltammogram of [bmim][br] and [bmim][BF₄] indicated electrochemical windows in the stability range from 2.7 V of [bmim][[Br] to 4.7 V of [bmim][BF₄].     

NaCl对urea-ZnCl_2离子液体性能的影响

研究了NaCl添加剂对urea-ZnCl2低共熔离子液体熔点、电导率的影响规律。结果表明:NaCl加入不能改变离子液体熔点随组分氯化锌摩尔分数[x(ZnCl2)]的变化规律,但可以降低离子液体的熔点。在x(ZnCl2)≤25%的范围内,离子液体的熔点随着NaCl加入量的增加而降低;但在x(ZnCl2)25%的范围内,随着NaCl浓度的进一步增加,体系的熔点逐渐升高。此外,NaCl对离子液体的电导率影响也与x(ZnCl2)密切相关。当x(ZnCl2)22%时,NaCl的加入可以改善离子液体电导率,且随NaCl浓度的增加而稍稍提高;但x(ZnCl2)超过22%,NaCl的加入反而降低离子液体的电导率。     

离子液体萃取金属离子的研究进展

室温离子液体具有低蒸汽压、低熔点、宽电化学窗口、良好离子导电性、导热性及高热稳定性等特点,故近年来在各种金属离子液／液萃取领域的应用日益受到关注。本文系统的评述了离子液体萃取金属离子特点,并展望了该分离方法在环境分析化学领域的应用前景。     

Physical and electrochemical properties of lithium-doped 1-butyl-3-methylimidazolium salts

Two well known room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]) and 1-butyl-3-methylimidazolium iodide ([BMIm][I]), were synthesized. Their physical properties such as reflective indices, densities, viscosities, heat capacities, and heats of dilution were measured. The overall properties of [BMIm][BF₄] obtained after two-step reactions were superior to those of the IL with a halide anion. The incorporation of lithium ions using lithium tetrafluoroborate (LiBF₄) in each IL was carried out and ionic conductivities as a function of temperature and Li ion concentration were investigated. The isothermal conductivity graph showed a parabolic curve shape suggesting that the maximum values exist at a specific concentration condition while they continuously increased as the temperature increased. The conductivities reached as high as 10⁻³ S·cm⁻¹.