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Mesoscale solubilization and critical phenomena in binary and quasi binary solutions of hydrotropes

机译:中尺度溶解和二元和准的临界现象   水溶助长剂的二元溶液

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摘要

Hydrotropes are substances consisting of amphiphilic molecules that are toosmall to self assemble in equilibrium structures in aqueous solutions, but canform dynamic molecular clusters H bonded with water molecules. Somehydrotropes, such as low molecular weight alcohols and amines, can solubilizehydrophobic compounds in aqueous solutions at a mesoscopic scale, around 100nm, with formation of long lived mesoscale droplets. In this work, we report onthe studies of near critical and phase behavior of binary, 2,6-lutidine - H2O,and quasibinary, 2,6-lutidine - H2O - D2O, and tert-butanol - 2-butanol - H2Osolutions in the presence of a solubilized hydrophobic impurity, cyclohexane.In additional to visual observation of fluid phase equilibria, two experimentaltechniques were used - light scattering and small - angle neutron scattering.It was found that the increase of the tert-butanol to 2-butanol ratio affectsthe liquid - liquid equilibria in the quasi-binary system at ambient pressurein the same way as the increase of pressure modifies the phase behavior ofbinary 2-butanol - H2O solutions. The correlation length of criticalfluctuations near the liquid-liquid separation and the size of mesoscaledroplets of solubilized cyclohexane were obtained by dynamic light scatteringand by small - angle neutron scattering. It is shown that the effect of thepresence of small amounts of cyclohexane on the near - critical phase behavioris twofold - the transition temperature changes towards increasing thetwo-phase domain, and long-lived mesoscopic inhomogeneities emerge in themacroscopically homogeneous domain. These homogeneities remain unchanged uponapproach to the critical point of macroscopic phase separation and do not alterthe universal nature of criticality. However, a larger amount of cyclohexanegenerates additional liquid-liquid phase separation at lower temperatures.
机译:水溶助长剂是由两亲分子组成的物质,该两亲分子太小而无法在水溶液中的平衡结构中自组装,但可以形成与水分子结合的动态分子簇H。一些水溶助长剂,例如低分子量的醇和胺,可以在100nm左右的介观尺度上溶解水溶液中的疏水化合物,并形成长寿命的介观液滴。在这项工作中,我们报告了关于二元,2,6-二甲基吡啶-H2​​O和准二元,2,6-二甲基吡啶-H2​​O-D2O和叔丁醇-2-丁醇-H2O溶液的近临界和相行为的研究。除了目视观察液相平衡外,还使用了两种实验技术-光散射和小角度中子散射。发现叔丁醇与2-丁醇的比率增加会影响准二元体系在环境压力下的液-液平衡与增加压力的方式相同,从而改变了2-丁醇-H2O二元溶液的相态。通过动态光散射和小角度中子散射获得了液-液分离附近临界涨落的相关长度和可溶环己烷的中尺度液滴的大小。结果表明,少量环己烷的存在对近临界相行为的影响是双重的,转变温度随着向两相域的增加而变化,并且在宏观均匀的域中出现了长寿命的介观不均匀性。在接近宏观相分离的临界点时,这些均匀性保持不变,并且不会改变临界的普遍性质。但是,大量的环己烷会在较低温度下产生额外的液相分离。

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