Effect of methylimidazolium-based ionic liquids on vapor–liquid equilibrium behavior of tert-butyl alcohol + water azeotropic mixture at 101.3 kPa

Three ionic liquids(ILs),1-ethyl-3-methylimidazolium bromine([EMIM]Br),1-butyl-3-methylimidazolium bromine([BMIM]Br),and 1-hexyl-3-methylimidazolium bromine([HMIM]Br),were used as the solvent for separation of {tert-butyl alcohol(TBA)+ water} azeotrope.Vapor–liquid equilibrium(VLE)data for {TBA + water + IL}ternary systems were measured at 101.3 k Pa.The results indicate that all the three ILs produce an obvious effect on the VLE behavior of {TBA + water} system and eliminate the azeotropy in the whole concentration range.[EMIM]Br is the best solvent for the separation of {TBA + water} system by extractive distillation among the three ILs.The experimental VLE data for the ternary systems are correlated with the NRTL model equation with good correlations.Explanations are given with activity coefficients of water and TBA,and the experimental VLE-temperature data for {TBA or water + IL} binary systems.

Modeling p VT Properties and Vapor-Liquid Equilibrium of Ionic Liquids Using Cubic-plus-association Equation of State

与一个协会模型一起的状态(曙光女神) 的联合 Peng-Robinson (PR ) 方程由刘等源于盾粘的方法(SSM ) ，一个新 cubic-plus-association (CPA ) 曙光女神被建议描述纯离子的液体(IL ) 和他们的混合物的热力学的性质。为 25 IL 的新分子的参数被在宽温度和压力范围上适合试验性的密度数据获得，并且全面平均偏差是 0.22% 。为相应 IL 的模型参数 b 与他们的分子的团显示出一种好线性关系，因此模型参数的数字有效地被减少。用一温度无关的二进制可调节的参数 kij，为 IL + 的二进制混合物的蒸汽液体 equilibria (VLE ) 的令人满意的关联联系溶剂的非联系的溶剂和 + 与全面一般水准被获得蒸汽压力 2.91% 和 7.01% 的偏差分别地。另外， VLE 为 IL + 结果从 CPA，格子液体(LF ) 和有可变范围(SWCF-VR ) 的方形井的链液体曙光女神的非联系的混合物被比较。

Equilibrium between titanium ions and high-purity titanium electrorefining in a NaCl-KCl melt

TiClx （x=2.17） was prepared by using titanium sponge to reduce the concentration of TiCl4 in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiClx melt was employed as the electrolyte, and two parallel crude titanium plates and one high-purity titanium plate were used as the anode and cathode, respectively. A series of electrochemical tests were performed to investigate the influence of electrolytic parameters on the current efficiency and quality of cathodic products. The results indicated that the quality of cathodic products was related to the current efficiency, which is significantly dependent on the current density and the initial concentration of titanium ions. The significance of this study is the attainment of high-purity titanium with a low oxygen content of 30× 10^-6.

双阳离子液体分离甲苯-正庚烷共沸体系——综合实验的设计与探索

构建了一种全新的专业设计型实验体系:双阳离子液体的制备及萃取分离甲苯-正庚烷共沸体系。合成并表征新型“绿色溶剂”双阳离子液体;以双阳离子液体作为萃取剂,测定其对甲苯-正庚烷共沸体系的分离能力并进行相图绘制。通过该综合实验教学,既促进学生对多学科基础知识的掌握,又能激发学生科研探索兴趣,培养其绿色化学意识与理念。

锂离子电池绿色回收在物理化学教学中的应用

随着锂离子电池的日益普及,废旧锂离子电池的数量越来越多;锂离子电池绿色回收对固体废物治理和资源的可持续利用具有重要意义。物理化学是化学、化工相关专业的一门重要基础课程。物理化学中的热力学第一定律、热力学第二定律、多组分热力学、相平衡、化学平衡、电解质溶液、可逆电池的电动势、电解池与极化、动力学、胶体界面等章节融入锂离子电池绿色回收对物理化学课程的建设、环境治理和绿色高质量发展提供科学依据和理论指导。

环己烷-乙醇-离子液体液液相平衡数据测定及关联

环己烷-乙醇是化工生产中常见的共沸体系,溶剂萃取是分离环己烷-乙醇的重要途径。在常压,303.15 K实验条件下,以[EMIM][OTF](1-乙基-3-甲基咪唑三氟甲烷磺酸盐)、[EMIM][SCN](1-乙基-3-甲基咪唑硫氰酸盐)、[EMIM][DCA](1-乙基-3-甲基咪唑双氰胺盐)3种离子液体为萃取剂,测定环己烷-乙醇的液液相平衡数据。利用分配系数和选择性评价不同离子液体的萃取性能。此外,根据Othmer-Tobias和Hand方程对相平衡实验数据进行一致性和可靠性校验。最后,采用Aspen Plus软件选择NRTL模型对相平衡数据进行关联,获得二元交互作用参数,并将其用于计算相应的相平衡组成。通过研究发现,计算值和实验值的均方根偏差小于0.02,表明NRTL模型能够准确描述三元相平衡过程。

离子液体+正己烷+异丙醇液液相平衡数据的测定及关联

通过COSMO-RS模型筛选出1-乙基-3-甲基咪唑三氟乙酸盐([EMIM][TFA])、1-乙基-3-甲基咪唑二氰胺盐([EMIM][DCA])、1-乙基-3-甲基咪唑磷酸二乙酯([EMIM][DEP])三种离子液体作为萃取剂分离正己烷-异丙醇体系。在303.15 K、101.3 kPa下,测定正己烷+异丙醇+[EMIM][DCA]/[EMIM][TFA]/[EMIM][DEP]的三元液液相平衡实验数据,通过计算得出选择性与分配系数,分析离子液体各自的分离性能。通过Othmer-Tobias,Bachman,Hand方程对实验数据进行一致性检验。采用Aspen Plus v11流程模拟软件中NRTL模型进行数据关联拟合,获得均方根偏差(RMSD)和二元交互作用参数。模拟结果表明,选择性与分配系数均大于1,说明三种离子液体均可作为萃取剂;方程的回归系数均大于0.95,说明实验数据可靠;得到RMSD均小于3%,说明模拟计算数据能较好地关联实验数据。

乙醇-碳酸甲乙酯-离子液体体系液液相平衡数据的测定及关联

在常压、303.15 K条件下,以离子液体(IL)1-乙基-3-甲基咪唑磷酸二氢盐([EMIM][DHP])、1-丙基-3-甲基咪唑磷酸二氢盐([PMIM][DHP])、1-丁基-3-甲基咪唑磷酸二氢盐([BMIM][DHP])为萃取剂,测定了乙醇-碳酸甲乙酯(EMC)-IL体系的液液相平衡(LLE)数据,分别计算了不同IL对乙醇-EMC体系的分配系数和选择性系数,并研究了IL对乙醇-EMC共沸体系相平衡行为的影响。采用Aspen Plus软件中的NRTL模型对乙醇-EMC-IL体系的LLE数据进行模型关联,得到相应的非随机参数和二元相互作用参数,为IL萃取分离乙醇-EMC的工艺设计奠定基础。实验结果表明,以[EMIM][DHP],[PMIM][DHP],[BMIM][DHP]为萃取剂分离乙醇-EMC共沸体系的选择性系数均大于1,3种ILs都具有良好的分离效果,其中,[EMIM][DHP]的选择性系数最高;采用NRTL模型关联得到的计算值与实验值的均方根偏差小于5%,表明NRTL模型关联乙醇-EMC-ILs三元体系的LLE数据准确性较好。

Equilibrium on the Hydrolysis of Boron Trifluoride in Large Amount of Water

In order to clarify the equilibrium components in the hydrolysis solution of boron trifluoride(BF_3-H_2O),the BF_3-H_2O was prepared by mixing BF_3-CH_3OH with large amount of water,in which the stoichiometric concentration of BF_3 is less than 0.1 mol/L.Two ionic equilibrium models were proposed to simulate the hydrolysis equilibrium of BF_3 and tested by special acid-base titration technique.The most accurate ion equilibrium constants were determined.The model,which was assumed to have no HF,was proved to be more representative for the real system and used to simulate the hydrolysis equilibrium of BF_3.The simulation suggested that H^+,BF_4^-,BF_3OH^- and H_3BO_3 were the main species in the dilute hydrolysis solution,while BF_2(OH)_2^- and F^- were insignificant species whose concentrations were both in the order of 10^(-4) mol/L magnitude,and BF(OH)_3^- could be omitted because its concentration almost equaled zero.Meanwhile,the equilibrium constant of the overall ionic reaction at 25℃ was obtained as 161.6.

Vapor-Liquid Equilibrium Measurements and Modeling for Ternary System Water ＋ Ethanol ＋ 1-Butyl-3-methylimidazolium Acetate

Vapor-liquid equilibrium(VLE) data were measured for ternary system water + ethanol + 1-butyl-3methylimidazolium acetate([bmim][OAc]),in a relatively wide range of ionic liquid(IL) mass fractions up to 0.8.Six sets of complete T-x-y data were obtained,in which the mole fraction of ethanol on IL-free basis was fixed separately at 0.1,0.2,0.4,0.6,0.8,and approximate 0.98.The non-random-two-liquid(NRTL) and electrolyte non-random-two-liquid(eNRTL) equations were used for correlation,showing similar deviations.The ternary VLE was also modeled with the correlation from two data sets,with the mole fractions of ethanol on IL-free basis being 0.1 and approximate 0.98.The VLE data were also reproduced satisfactorily.With the eNRTL model,the root-mean-square deviation for temperature is 0.79 K and that for vapor-phase mole fraction is 0.0094.The calculations are in good agreement with experimental data.The effect of the IL on the VLE behavior of the volatile components is also illustrated.

Determination of Vapor Pressures for Binary and Ternary Mixtures Containing Ionic Liquid 1-propyl-3-methylimidazolium Bromide

二元体系的蒸汽压价值浇+乙醇，水+ionic liquidl-propyl-3-methylimidazolium 溴化物([ PMIM ][浓缩])，乙醇+[ PMIM ][浓缩]并且三元体系水 +ethanol +[ PMIM ][浓缩]被在各种各样的集中使用修改沸点法在不同温度测量(16.66%,33.7%)，，并且((17.4%,33.9%)，并且(16.5%,32%)离子的液体的集体百分比， respectively.The 溶剂的试验性的蒸汽压被theAntoine类型很好相关方程，并且绝对偏差( AAD )被发现是0.39% .Theexperimental 的全面一般水准为包含离子的液体的混合物结果显示溶剂的蒸汽压能由于离子的液体和溶剂之间的亲密关系差别显著地被减少到不同程度，它类似于普通的无机的盐的盐效应。作为结果，离子的液体可以与一个低分离系数或甚至为 azeotropic 为系统在萃取蒸馏发现工业应用。

Modified DIX model for ion-exchange equilibrium of L-phenylalanine on a strong cation-exchange resin

L-phenylalanine,one of the nine essential amino acids for the human body,is extensively used as an ingredient in food,pharmaceutical and nutrition industries.A suitable equilibrium model is required for purification of L-phenylalanine based on ion-exchange chromatography.In this work,the equilibrium uptake of L-phenylalanine on a strong acid-cation exchanger SH11 was investigated experimentally and theoretically.A modified Donnan ion-exchange(DIX) model,which takes the activity into account,was established to predict the uptake of L-phenylalanine at various solution pH values.The model parameters including selectivity and mean activity coefficient in the resin phase are presented.The modified DIX model is in good agreement with the experimental data.The optimum operating pH value of 2.0,with the highest L-phenylalanine uptake on the resin,is predicted by the model.This basic information combined with the general mass transfer model will lay the foundation for the prediction of dynamic behavior of fixed bed separation process.

Fractional variant of Stokes–Einstein relation in aqueous ionic solutions under external static electric fields

Both ionic solutions under an external applied static electric field E and glassy-forming liquids under undercooled state are in non-equilibrium state.In this work,molecular dynamics(MD)simulations with three aqueous alkali ion chloride(NaCl,KCl,and RbCl)ionic solutions are performed to exploit whether the glass-forming liquid analogous fractional variant of the Stokes–Einstein relation also exists in ionic solutions under E.Our results indicate that the diffusion constant decouples from the structural relaxation time under E,and a fractional variant of the Stokes–Einstein relation is observed as well as a crossover analogous to the glass-forming liquids under cooling.The fractional variant of the Stokes–Einstein relation is attributed to the E introduced deviations from Gaussian and the nonlinear effect.

燕麦K^(+),Na^(+)积累与AsSOS1基因表达对盐胁迫的响应

为了解盐胁迫对燕麦(Avena sativa L.)K^(+),Na^(+)积累和质膜Na^(+)/H+逆向转运蛋白基因(AsSOS1)表达的影响,本研究以耐盐的‘青永久195’和敏盐的‘709’为材料,分别用0,30,60,90,120,150 mmol·L^(-1)NaCl和0,0.5,1,2,4,8 mmol·L^(-1)KCl处理24 h,并用30,150 mmol·L^(-1)NaCl和0.5,8 mmol·L^(-1)KCl互作处理0,12,36,72 h,分析燕麦根和叶中K^(+),Na^(+)积累、离子平衡及AsSOS1基因的表达情况。结果表明:K^(+)含量和K^(+)/Na^(+)随盐浓度的增加和处理时间的延长有所下降,‘青永久195’的K^(+)含量和K^(+)/Na^(+)高于‘709’;叶片中的K^(+)含量和K^(+)/Na^(+)高于根系,Na^(+)含量变化与之相反,且‘709’中的Na^(+)含量高于‘青永久195’,根系中的Na^(+)含量高于叶片。AsSOS1基因在燕麦根、叶中均有表达,盐胁迫会显著提高其表达水平(P<0.05),多数处理下根系中的表达量高于叶片,‘青永久195’中的表达量高于‘709’。AsSOS1通过限制Na^(+)向地上部运输、维持较高的K^(+)/Na^(+)来减缓高盐胁迫造成的伤害。

含硫酸氢盐离子液体的水+乙酸体系汽液平衡数据测定

为探究离子液体(ILs)作为催化剂对酯化反应精馏体系汽液平衡产生的影响,采用Dvorak-Boublik平衡釜测定了5种压力下水(1)+乙酸(2)二元体系的汽液平衡数据,并测定了不同压力和不同离子液体摩尔分数下的水(1)+乙酸(2)+1-磺酸丁基-2-甲基吡啶硫酸氢盐([HSO_(3)-BMPy][HSO_(4)])(3)三元体系的汽液平衡数据。通过COSMOlogic软件对[HSO_(3)-BMPy][HSO_(4)]几何结构进行优化,模拟获取屏蔽电荷密度图(σ-Profile)。结果表明,加入[HSO_(3)-BMPy][HSO_(4)]提高了二元体系的平衡温度,且对水的影响更大,减压使其平衡温度降低。[HSO_(3)-BMPy][HSO_(4)]易与水结合,使水与乙酸更难分离。测得的汽液平衡数据可为含[HSO_(3)-BMPy][HSO_(4)]体系的酯化反应精馏模拟计算提供热力学基础数据。

以三丁基甲基醋酸铵为萃取剂萃取精馏分离乙酸乙酯-乙醇共沸物

以三丁基甲基醋酸铵([N_(4,4,4,1)][AC])为萃取剂,分离乙酸乙酯和乙醇的共沸体系。在101.3 kPa下测定了二元共沸体系(乙酸乙酯+乙醇)和三元体系(乙酸乙酯+乙醇+[N_(4,4,4,1)][AC])的气液相平衡数据。通过Aspen Plus软件中NRTL模型关联这些数据,发现当[N_(4,4,4,1)][AC]摩尔分数达到0.022时,系统不再共沸;以年化成本最小为要求对操作参数进行流程模拟优化,得到萃取精馏过程的最佳操作条件。

离子液体-乙醇-庚烷液液相平衡数据的测定关联

文中采用平衡釜法测定在常压下温度为303.15 K时{[BMIM][TFA](一丁基三甲基咪唑三氟乙酸盐)、[BMIM][DCA](一丁基三甲基咪唑双氰胺盐)和[BMIM][SCN](一丁基三甲基咪唑硫氰酸盐)}+乙醇+庚烷三元体系的液液相平衡数据,使用Bachman方程和Othmer-Tobias方程对实验数据的热力学一致性进行检验,其线性相关系数均大于0.99。通过实验数据计算的分配系数和选择性比较了3种离子液体的分离性能,利用Aspen Plus v11模拟软件对实验数据回归得到二元相互作用参数,对比实验值得到的E_(RMSD)均小于4%。综上所述,使用离子液体萃取分离乙醇-庚烷体系是可行的,其中双氰胺根离子液体具有更好的探究价值。

离子液体二元体系等压汽液相平衡的综合实验设计

为了让学生更好地理解非理想体系汽液相平衡的特点,基于学科前沿和研究基础,设计了乙醇-离子液体等压汽液相平衡测定的综合创新实验。该实验主要包括等压汽液相平衡的实验操作、非理想物系相平衡数据分析、阿贝折光仪分析样品含量、模型关联以及分子水平机理分析等,是一个涵盖了化工热力学、物理化学、物理光学、数值分析和量子化学等学科的综合实验。与传统二元体系汽液相平衡实验相比,该实验更具有探索性和创新性,操作简便省时,重复性高,提高了学生创新思维能力和科学研究意识,训练了学生发现问题和分析解决问题的综合能力。

引进红树拉关木和两种乡土红树离子平衡及光合作用的比较研究

为了比较引进红树与乡土红树的耐盐性差异,该研究以引进红树植物拉关木(Laguncularia racemosa)和乡土红树植物木榄(Bruguiera gymnorrhiza)与秋茄(Kandelia obovata)幼苗作为实验材料,分析其在不同Na Cl浓度(100、200、300、400 mmol·L^(-1))处理下各器官离子浓度(Na^+、Cl~–、K^+、Ca^(2+)和Mg^(2+))和叶光合作用的变化。结果表明:(1)高盐胁迫(400 mmol·L^(-1)Na Cl,28 d)处理下,拉关木根系Na^+增幅较小,秋茄根、叶Cl~–含量增幅均高于木榄和拉关木,说明拉关木在较高的盐浓度时能限制根系对Na^+、Cl~–的吸收,减少向地上部分运输。(2)高盐胁迫均增加3种红树根、叶的K^+浓度(木榄叶K^+略有降低,差异不显著),表明3种红树均可吸收K^+,来限制Na^+对植物的伤害;同时,降低3种红树根Ca^(2+)浓度,但拉关木根Ca^(2+)下降幅度小于秋茄和木榄,说明拉关木具有更强的防止Ca^(2+)流失的能力。(3)拉关木根维持Na^+/K^+、Na^+/Ca^(2+)平衡的能力强于秋茄和木榄。(4)高盐胁迫引起秋茄与木榄光合速率均降低,而拉关木光合速率却增加了54.1%。综上所述,拉关木能限制根系对Na Cl的吸收,有效维持Na^+/K^+、Na^+/Ca^(2+)的平衡,并保持较高的光合速率,这表明拉关木与木榄和秋茄相比具有更高的耐盐性。

盐碱混合胁迫对小麦幼苗阳离子吸收和分配的影响

为探讨盐碱胁迫下小麦阳离子吸收和分配特点,采用两种中性盐(NaCl和Na2SO4)和两种碱性盐(NaHCO3和Na2CO3)混合模拟不同浓度盐碱胁迫条件,对龙麦26和克旱16两种不同基因型春小麦幼苗进行14 d胁迫处理,测定和分析了叶片和根系中Na+、K+、Ca2+、Mg2+含量的变化。结果表明,盐碱混合胁迫增加了小麦幼苗Na+含量,且随着盐浓度的增加和碱性盐比例的提高,Na+含量逐渐增加;龙麦26幼苗K+的吸收规律与Na+相同,而克旱16幼苗K+含量变化与之相反;盐碱混合胁迫通过降低植株的K/Na限制了Ca2+、Mg2+的吸收量,且阻碍了Ca2+、Mg2+由根向地上部的运转,致使叶片中Ca2+、Mg2+含量降低。盐碱混合胁迫下,小麦对Na+、K+等一价阳离子与Ca2+、Mg2+等二价阳离子的吸收上表现为拮抗作用。