Effect of mono-, di- and tri-ethanolammonium tetrafluoroborate protonic ionic liquids on the volatility of water, ethanol, and methanol

Vapor pressure data were measured for nine binary systems containing water, ethanol, or methanol with one of three protonic ionic liquids (PILs), viz. mono-, di- and tri-ethanolammonium tetrafluoroborate ([HMEA][BF₄], [HDEA][BF₄], and [HTEA][BF₄]), at varying temperatures and PIL-contents using a quasi-static ebulliometer. The vapor pressure data were correlated by NRTL model with an overall average absolute relative deviation (AARD) of 0.0175. It is showed that the effect of PILs on the vapor pressure lowering of solvents follows the order of [HMEA][BF₄] > [HDEA][BF₄] > [HTEA][BF₄], and the vapor pressure lowering degree follows the order of water > methanol > ethanol. Besides, the activity coefficients of solvent for binary system {solvent + PIL} at fixed PIL mole fraction of 0.10 were calculated using the regressed NRTL parameters. The results indicate that three PILs can give rise to a negative deviation from the Raoult's law for water and methanol and a positive deviation for ethanol to a varying degree, leading to the variation of relative volatility of a solvent.     

An evaluation of thermodynamic models for the prediction of drug and drug-like molecule solubility in organic solvents

Prediction of solubility of active pharmaceutical ingredients (API) in different solvents is one of the main issue for crystallization process design. Experimental determination is not always possible because of the small amount of product available in the early stages of a drug development. Thus, one interesting perspective is the use of thermodynamic models, which are usually employed for predicting the activity coefficients in case of Vapour-Liquid equilibria or Liquid-Liquid equilibria (VLE or LLE). The choice of the best thermodynamic model for Solid-Liquid equilibria (SLE) is not an easy task as most of them are not meant particularly for this. In this paper, several models are tested for the solubility prediction of five drugs or drug-like molecules: Ibuprofen, Acetaminophen, Benzoic acid, Salicylic acid and 4-aminobenzoic acid, and another molecule, anthracene, a rather simple molecule. The performance of predictive (UNIFAC, UNIFAC mod., COSMO-SAC) and semi-predictive (NRTL-SAC) models are compared and discussed according to the functional groups of the molecules and the selected solvents. Moreover, the model errors caused by solid state property uncertainties are taken into account. These errors are indeed not negligible when accurate quantitative predictions want to be performed. It was found that UNIFAC models give the best results and could be an useful method for rapid solubility estimations of an API in various solvents. This model achieves the order of magnitude of the experimental solubility and can predict in which solvents the drug will be very soluble, soluble or not soluble. In addition, predictions obtained with NRTL-SAC model are also in good agreement with the experiments, but in that case the relevance of the results is strongly dependent on the model parameters regressed from solubility data in single and mixed solvents. However, this is a very interesting model for quick estimations like UNIFAC models. Finally, COSMO-SAC needs more developments to increase its accuracy especially when hydrogen bonding is involved. In that case, the predicted solubility is always overestimated from two to three orders of magnitude. Considering the use of the most accurate equilibrium equation involving the ΔC_p term, no benefits were found for drug predictions as the models are still too inaccurate. However, in function of the molecules and their solid thermodynamic properties, the ΔC_p term can be neglected and will not have a great impact on the results.     

Activity coefficients of electrolytes from the E.M.F. of liquid membrane cells. II - multicharged electrolyte solutions

The activity coefficients of Co(en)₃Cl₃ and K₂SO₄ were measured by means of a cell with ion-exchange liquid membranes following the method described in paper I. The results prove that this method is even more valuable with multicharged salts than with 1-1 electrolytes. The values obtained are precise and reliable down to dilution limits never before accessible, e.g., 4×10^–5 mol-kg^–1 in Co(en)₃Cl₃. High dilution levels are of particular importance when dealing with highly charged electrolytes since the trend at higher concentrations often leads to errors both in extrapolation to infinite dilution and in the absolute activity coefficients. As an application, the activity coefficients of [Co(en)₃]₂(SO₄)₃-suspected to be wrongly evaluated in past literature-were measured, and their values at low concentrations were actually lower than those quoted before.     

柠檬酸对Ru/AC氨合成催化剂结构和活性的影响

使用柠檬酸(CA)修饰石墨化活性炭(AC)和钌以改善Ru/AC催化剂中钌粒子的尺寸分布和催化剂的活性, 并通过透射电镜(TEM)、热重分析(TGA)、CO化学吸附和N2物理吸附等方法研究了柠檬酸对AC和Ru/AC催化剂织构、钌的分散度和催化剂的活性等性质的影响. 结果表明, 负载的柠檬酸优先吸附于活性炭微孔, 少量柠檬酸即可大幅度降低活性炭的比表面积, 增加活性炭表面含氧官能团的数量, 改善了钌粒子分布. 最佳负载顺序是柠檬酸和氯化钌依次负载. 在活性炭中添加适量的柠檬酸对催化剂的低温活性有显著影响. 柠檬酸处理后的Ru/AC催化剂活性最大提高幅度为21.4%.     

Pt/Cu双金属纳米颗粒的制备及其催化制氢活性

采用化学共还原法合成了聚乙烯吡咯烷酮保护的Pt/Cu双金属纳米颗粒(BNPs),并采用紫外可见吸收光谱、透射电子显微镜、高分辨透射电子显微镜等对所合成的Pt/Cu BNPs进行了表征。研究了化学组成对Pt/Cu BNPs催化Na BH4水解制氢性能的影响。结果表明,所制备的Pt/Cu BNPs平均粒径为1.8~2.3nm,其催化活性远高于单金属Pt和Cu NPs的活性,其中Pt90Cu10BNP的催化活性最高,其在30℃的条件下,催化Na BH4制氢的活性可达6570mol-H2·mol-cat-1·h-1,约为相同粒径的Pt单金属NP的1.6倍。密度泛函理论的计算结果表明,Pt/Cu BNPs优异的催化性能可归因于电荷转移效应,Pt原子与Cu原子之间发生的电子转移使得Pt原子带负电而Cu原子带正电,荷电的Pt和Cu原子成为催化反应的活性中心。     

黄豆铁蛋白提取新方法及其与豌豆铁蛋白活性比较

铁蛋白是广泛存在于动物、微生物及植物体中的一种铁贮藏蛋白, 具有去除二价铁的毒性以及调节机体细胞铁代谢平衡的作用. 本文以黄豆种子为原料, 开发出黄豆铁蛋白提取新方法, 即将黄豆粗提液在55 ℃下加热15 min, 再将冷却后的上清液分别用500 mmol/L MgCl2和700 mmol/L柠檬酸三钠进行盐析. 离心得到的铁蛋白粗提液经透析后, 用DEAE-cellulose弱阴离子交换层析和Sephacryl S-300凝胶过滤层析进一步分离, 得到电泳纯的铁蛋白. Native-PAGE电泳测得分子量约为560000, SDS-PAGE电泳结果表明, 黄豆铁蛋白含有两种亚基, 分子量分别为28000和26500. 活性研究显示, 黄豆铁蛋白与豌豆铁蛋白铁氧化沉淀和还原释放反应的活性明显不同.     

Activity coefficients of NaCl in the NaCl + NaBF4 + H2O ternary system at 298.15 K

The activity coefficients of sodium chloride in the NaCl + NaBF₄ + H₂O ternary system were experimentally determined at 298.15 K, at ionic strengths of 0.3. 0.5, 1, 2 and 3 mol kg⁻¹ from emf from the bi-ISE cell without liquid junction:

ISE-Na|NaCl(m_A), NaBF₄(m_B)|ISE-Cl

Measurement and prediction of activity coefficients at infinite dilution (γ), vapor–liquid equilibria (VLE) and excess enthalpies (H) of binary systems with 1,1-dialkyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide using mod. UNIFAC (Dortmund)

Activity coefficients at infinite dilution (γ^∞), vapor–liquid equilibria (VLE) and excess enthalpies (H^E) were measured for alkanes and alkenes in the ionic liquids 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [BMPYR]⁺[BTI]⁻, 1-hexyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [HMPYR]⁺[BTI]⁻ and 1-octyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [OMPYR]⁺[BTI]⁻.     

Evaluation of dissociation constants of ammonium ion in aqueous lithium perchlorate and lithium chloride-sodium chloride mixed solutions

The Pitzer approach has been applied to the evaluation of dissociation constants of ammonium ion in lithium perchlorate and lithium chloride-sodium chloride mixed solutions at 25°C. The calculated values showed good agreement with the observed values, provided all the higher-order interaction terms ('s and 's) concerned were introduced. The unknown (NH₄LiClO₄) value was determined from the isopiestic measurements of NH₄ClO₄–LiClO₄ mixed solutions. Parameters in the Pitzer formalism for ammonia-ion interactions involved in LiCl and NaCl media were determined by use of the activity coefficients of ammonia measured in LiCl–NaCl mixed solutions by a transpiration method.     

Thermodynamic properties of electrolyte solutions: An EMF study of the activity coefficients of KCl in the system KCl−KNO3−H2O at 25, 35 and 45°C

Electromotive force measurements were carried out on the system KCl–KNO₃–H₂O at constant total ionic strengths of 0.5, 1.0, 2.0 and 3.0 mol-kg^–1 and at 25, 35 and 45°C using a cell consisting of a potassium ionselective electrode and a Ag/AgCl electrode. The Harned coefficients and the Pitzer binary and ternary interaction parameters for the system have been evaluated at each temperature. The osmotic coefficients, excess free energies of mixing and heats of mixing of the system have been predicted at each of the experimental temperatures and ionic strengths. The solubility data at 25°C are also interpreted.