连、偏、均三甲苯在水-叔丁醇混合溶剂中的溶解度和疏水作用

在283.15, 288.15, 293.15, 298.15 K温度下,测定了连、偏、均三甲苯在水-叔丁醇混合溶剂中的溶解度,其中混合溶剂中叔丁醇的摩尔分数分别为0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080,0.100.　以此为基础,对甲烷与苯四聚过程的疏水相互作用Gibbs自由能进行了研究,并从微观上讨论了溶剂结构和溶质聚集状态对疏水作用的影响.     

苯、甲苯、联苯在水-叔丁醇混合溶剂中的溶解度和疏水作用

在283.15,288.15,293.15,298.15 K温度下,测定了苯、甲苯、联苯在水-叔丁醇混合溶剂中的溶解度,其中混合溶剂中叔丁醇的物质的量分数分别为0.000,0.010,0.020,0.030,0.040,0.045,0.050,0.060,0.080,0.100. 以此为基础计算了苯、甲苯、联苯在不同温度和溶剂组成条件下的标准溶解Gibbs自由能和相关过程的疏水相互作用Gibbs自由能,并从微观上讨论了溶剂结构对溶解度和疏水作用的影响.     

萘由水到水-叔丁醇混合溶剂的迁移热力学函数

通过溶解度法研究了萘从水到水-叔丁醇(TBA)混合溶剂中的标准迁移热力学性质.结果表明, 标准迁移自由能随叔丁醇摩尔分数x(TBA)的增加表现出复杂的下降趋势.标准迁移熵和标准迁移焓呈现双峰变化.迁移熵和迁移焓的双峰变化, 表明系列H2O-TBA混合溶剂的微观结构经历了从相对的有序到无序到再有序、再无序、再有序的变化过程；H2O-TBA混合溶剂中除了在富水区存在着笼合物特殊结构外, 在x(TBA) 约为0.08处还存在着一相对有序的结构.     

反气相色谱技术与汉森溶解参数法测定咪唑基醋酸盐类离子液体的溶解度参数

采用反气相色谱技术在353.15~393.15 K温度范围内测定了4种咪唑基醋酸盐离子液体的溶解度参数.结果表明,在实验温度范围内,反气相色谱技术测定的离子液体的溶解度参数值随温度的升高而线性减小.通过外推法得到333.15 K时4种离子液体的溶解度参数分别为26.14,24.38,23.60和23.04 MPa~(1/2).采用Hansen溶解度参数软件在333.15 K时对4种离子液体的溶解度参数进行模拟计算,结果分别为26.52,23.99,23.45和22.00 MPa~(1/2).2种方法测定结果在±1.05 MPa~(1/2)的误差范围内一致,说明2种方法均适用于咪唑基醋酸盐溶解度参数的测定.     

应用离子选择性电极进行溶液热力学研究——Ⅴ.KCl在283.15K～318.15K间七个温度下由H_2O至DMF-H_2O混合溶剂的标准转移Gibbs自由能和转移熵的测定

本文应用Corning一价阳离子选择电极与氯离子选择电极组成无液接可逆电池,测定电池在283.15K～318.15K间七个温度下的标准电动势及其温度系数,计算KCl从纯水到相应的DMF-H_2O混合溶剂的标准转移Gibbs自由能ΔG_t~0和标准转移熵ΔS_t~0,得出ΔG_t~0和ΔS_t~0随混合溶剂中DMF的摩尔分数x_(DMF)及温度T的变化规律.发现KCl的ΔS_t~0随x_(DMF)变化的趋势和NaCl的相反.从离子溶剂化作用及其对溶剂结构的影响作了讨论.     

反气相色谱法测定有机溶剂型木质素的溶解度参数

采用反气相色谱法(IGC),于333.15～373.15 K温度范围内测定了有机溶剂型木质素的溶解度参数(δ2)及相关指标。以正辛烷(n-C8)、正癸烷(n-C10)、正十二烷(n-C12)和正十四烷(n-C14)为探针溶剂,计算了探针溶剂的特性保留体积(V0g)、摩尔吸收焓(ΔHs1)、无限稀释摩尔混合焓(ΔH∞1)、摩尔蒸发焓(ΔHv)、无限稀释活度系数(Ω∞1)以及探针溶剂与有机溶剂型木质素的Flory-Huggins相互作用参数(χ∞12)。结果表明,上述4种探针溶剂在测定的温度范围内均为有机溶剂型木质素的不良溶液;在同一温度下,参数χ∞12随着探针溶剂碳数的增加而降低。测得的有机溶剂型木质素的δ2为19.03 (J\5cm-3)1/2。     

反相气相色谱法测定高密度聚乙烯溶解度参数

采用反相气相色谱(IGC)技术测定了高密度聚乙烯(HDPE)在303.15～343.15 K温度范围内的溶解度参数(δ2)及相关指标。以正己烷(n-C6)、正庚烷(n-C7)、正辛烷(n-C8)、正壬烷(n-C9)、三氯甲烷(CHCl3)及乙酸乙酯(EtAc)作为探针分子溶剂,经计算获得了探针溶剂的比保留体积(V0g)、摩尔吸收焓(ΔHS1)、无限稀释摩尔混合焓(ΔH∞l)、摩尔蒸发焓(ΔHv)、无限稀释活度系数(Ω∞1)以及探针溶剂与HDPE的Flory-Huggins相互作用参数(χ∞1,2)等指标。结果表明,上述6种探针溶剂在测定温度范围内均为HDPE的不良溶剂。此外,还推导出了HDPE在室温(298.15 K)下的溶解度参数δ2为19.00 (J/cm3)0.5。     

不同有机溶剂中C~6~0溶解度与温度的关系

本文测定了温度280K以上C~6~0在一些有机溶剂中的溶解度与温度的依赖关系,发出280K以上C~6~0在正己烷、甲苯、二甲苯中溶解度随温度上升而减小, 表现出放热的溶解过程。与此相反, 在环己烷中C~6~0的溶解度却有所不同, 随着温度的升高而增大, 表现出吸热的溶解过程。     

电势法测定KI在CH_3OH-H_2O混合溶剂中的活度系数

用无液接电势电池测定了303.15 K时,KI在甲醇-水混合溶剂中的电动势,用扩展的Debye-Hückel方程及Pitzer方程关联不同溶剂组成下电动势的实验值,得到电池的标准电动势E°和KI在混合溶剂中的活度系数.结果表明,在一定的溶剂比例下,随KI浓度的增大,其平均活度系数先随它的浓度增加而下降,经过一个最低点后又上升;或者随浓度增加而单调递减.当KI浓度固定时,它的平均活度系数随溶剂中甲醇的含量增加而下降.表明KI在甲醇中有微弱的缔合.     

四苯硼铵从H2O到H2O-TBA的ΔG()t和介质效应

电解质在水和含水混合溶剂间的迁移热力学性质,对于研究解析电解质与溶剂间的相互作用及其变化规律有着重要的作用.因此,长期以来一直受到人们的重视.碱金属及类碱金属四苯硼盐(MBPh4)是典型的大阴离子强电解质,由于其阴离子(BPh－4)具有较强的疏水作用,因此在水与有机混合溶剂中表现出与纯无机盐明显不同的热力学行为.水与叔丁醇(TBA)是一种特殊的混合溶剂,其性质已有很多报导[1－3].许多作者指出,在富水区存在着H2O与TBA分子形成的笼合物,这使该混合溶剂在富水区表现出许多反常特性,如蒸汽压、偏摩尔体积、密度等都出现了极大或极…     

Solubilities of 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene in t-butyl alcohol+water mixtures and hydrophobic interaction

The solubilities of 1,2,3- trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fractions of TBA [x(TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0. 1000. The Gibbs energies of hydrophobie interaction (HI) for the aggregating process of three methane molecules with one benene molecule in the mixed solvent are studied, and the effect of solvent structure and solute aggregating state on the strength of HI is discussed.     

四苯硼铵从H2O到H2O-TBA的ΔGΘt和介质效应

Solubilities of ammonium tetraphenylborate (NH4BPh4) in water-t-butyl alcohol (TBA) mixed solvents at 283.15,293.15,298.15,303.15 and 308.15K have been determined by spectrophotometry.The standard Gibbs energy of transfer (ΔGΘt) of NH4BPh4 from water to H2)-TBA mixtures and the primary medium effect of NH4BPh4 from 283.15 to 308.15K were studied.The results show that-ΔGΘt exhibits a complicated variation pattern with the increase in the mole fraction of TBA [x(TBA)] at the same temperature.When x(TBA)<0.06,-ΔGΘt increases very slowly with x(TBA),the-ΔGΘt increases rapidly with x(TBA) when x(TBA) from 0.06 to 0.2.For x(TBA)>0.2,the -ΔGΘtdecreases with increasing x(TBA).The largest value of -ΔGΘt occurs at x(TBA)=0.2.The main reason for this variation was analyzed and discussen.     

Solubilities of benzene, toluene and diphenyl in the t-butyl alcohol+water mixtures and hydrophobic interaction

The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100, respectively. The standard Gibbs energies of solution of benzene, toluene and diphenyl in the mixed solvent have also been calculated based on the solubility data. The hydrophobic interactions (HI) for the pairs of benzene-benzene, methane-benzene and methane-methane in the mixed solvent were calculated and discussed.     

Hydrophobic interaction of the aggregation of methane and benzene in (water + TBA)

The solubilities of o-xylene, m-xylene, and p-xylene in mixed solvents of t-butyl alcohol (TBA) and water at T=(283.15, 288.15, 293.15, and 298.15) K have been determined by spectrophotometry. The mole fractions of TBA in the mixed solvents are x=(0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100), respectively. The Gibbs energies of hydrophobic interaction (HI) for the aggregating process of two methane molecules with one benzene molecule in the mixed solvents have been studied, and the effects of solvent structure and solutes gathering state on the strength of HI have also been discussed.     

Effect of Different Salts on the Solubilities of Benzene and Diphenyl in t—Butyl Alcohol—Water Mixture and Hydrophobic Interaction

The solubilities of benzene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water with different salts have been determined at T=298.15,303.15,308.15 and 313.15K.The molar fraction of TBA [x(TBA)] in mixed solvent is 0.045,and the molality of the salts (ms) in mixed solvents are 0.000,0.250,0.500,0.750 and 1.000mol/kg ,respectively.The standard Gibbs energies of solution of benzene and diphenyl in the mixed solvents have also been calculated based on the solubility data.The effects of different salts on the hydrophobic interaction (HI) for benzene-benzene pair in the systems were discussed.     

RbCl由H2O至混合溶剂(H2O-DMF)标准迁移熵的测定

电解质迁移热力学性质的测定,对于离子溶剂化的研究具有重要意义.迁移自由能主要反映离子与溶剂分子间的相互作用,迁移熵则主要反映不同溶剂分子间的相互作用,迁移熵随温度及溶剂组成的改变可为溶剂的原有结构推测及溶液秩序改变提供信息.我们曾运用离子选择性电极测定了部分碱金属卤化物在水及含水混合溶剂中的热力学性质[1-3].本文用离子选择性电极方法,通过测定不同温度下电池的标准电动势,根据溶液热力学原理,求得ＲｂＣｌ由Ｈ2Ｏ至混合溶剂(Ｈ2ＯＤＭＦ)的标准迁移自由能ΔＧｔ及其温度系数,计算ＲｂＣｌ的标准迁移熵ΔＳｔ.结果尚未见…     

Concentration fluctuations and collective properties in mixed liquid systems: Rayleigh-Brillouin spectra of tert-butyl alcohol/2,2'-dimethylbutane liquid mixture

Rayleigh-Brillouin spectra have been measured in a range of temperatures and compositions of t-butyl alcohol/2,2(')-dimethylbutane liquid mixture. The mixture mole fraction has been varied from pure alkane (x(TBA)=0) to pure alcohol (x(TBA)=1) at temperatures between 283 and 323 K. In the same composition and temperature ranges the authors also executed measurements of mass density, shear viscosity, and refractive index. From light scattering spectra the authors have extracted the hypersound velocities and adiabatic compressibilities and evaluated their excess values. Moreover, the authors attempted to evaluate the isothermal (40 degrees C) Landau-Placzek ratios at various mole fractions, but these values proved to be subject to significant errors due to great uncertainty in the central component intensity measurements. Thus, in discussing the results, this latter quantity was considered only from a qualitative point of view. These results highlight a nonideal behavior of the studied liquid mixture with a probable azeotropic composition around x(TBA)=0.7 due to formation of small clusters of hydrogen-bonded alcohol tetramers that are completely surrounded by solvent molecules and analogous or smaller clusters. These clusters, shaped as inverse micelles, offer their hydrophobic moiety towards the molecules that constitute the solvation shell, resulting in a low polarity solution structure that minimizes the solute-solvent interactions. Differences in thermal and compositional behavior of excess molar volumes and adiabatic compressibilities have been interpreted by attributing different weights to the solute-solvent interaction forces and to the hydrogen bond connectivity effects.     

Heterogeneity in binary mixtures of (water + tertiary butanol): temperature dependence across mixture composition

The temperature dependence of solution heterogeneity in binary mixtures of water and tertiary butanol (TBA) and its effects on a chemical reaction have been investigated by using steady-state and time-resolved spectroscopic experiments within the temperature range of 278 ≤ T/K ≤ 373. Eleven different mole fractions of TBA, covering extremely low TBA mole fractions to pure TBA, have been considered. An organic chromophore that undergoes a photoexcited intramolecular charge-transfer reaction is employed to reveal the signature of the solution heterogeneity. Upon increasing the solution temperature, the absorption spectrum of the dissolved chromophore exhibits a red shift at very low TBA concentrations but shifts toward higher energy (blue shift) at higher alcohol concentrations. This is a reflection of temperature-assisted aggregation of TBA molecules in very dilute aqueous solutions. The magnitude of the temperature-induced red shift is the largest at around 0.04 mol fraction of TBA, and a larger variation of the spectral line width across the temperature suggests enhanced solution heterogeneity. Reaction time constants measured at various mixture compositions are found to follow an Arrhenius-type temperature dependence. The average activation energy, when plotted as a function of mixture composition, steeply rises with TBA concentration in the limit of the very low TBA mole fraction and then suddenly levels off to a plateau upon further addition of TBA. The alcohol concentration-dependent activation energy abruptly changes its slope at a TBA mole fraction ～0.1, at which a transition from the three-dimensional water-type network to the zigzag alcohol chain structure is known to occur. The plateau value of the activation energy is ～6k(B)T and agrees well with the earlier estimate for the same chromophore from the pure solvent data at room temperature. The observed increase in the spectral red shift with temperature at low TBA mole fractions is in general agreement with the existing experimental results which support the view that temperature assists the aggregation of TBA molecules in dilute aqueous solutions of TBA. However, unlike in the small-angle neutron scattering study [ Bowron, D. T.; Finney, J. L. J. Phys. Chem. B 2007, 111, 9838], which finds clustering of TBA molecules reaching a maximum at ～353 K, the present data do not indicate any such temperature maximum within the temperature range of 278 ≤ T/K ≤ 373.