Colligative properties of various liquid blends vs. Temperature under confined space effects in pores of different adsorbents

V. Gun'ko, V. Turov
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Abstract

The temperature and interfacial behaviors of individual and mixed liquids are of importance from a practical point of view because changes in the phase state of compounds with decreasing temperature could lead to negative effects (e.g., frost damage of porous materials). However, the use of certain mixtures may prevent these negative effects due to the colligative properties of the solutions (cryscopic effects, CE) that lead to several effects including relative lowering of vapor pressure, boiling point elevation, and freezing point depression (FPD). Confined space effects (CSE) also leading to the freezing point depression can affect the colligative properties of liquid mixtures with respect to FPD. One could assume that for some systems with certain FPD due to CE for bulk solutions, there is no additivity (synergetic effect) of CSE and CE, but for others, the opposite results could be. To elucidate these interfacial phenomena, a set of liquid mixtures bound to different adsorbents could be studied using low-temperature NMR spectroscopy. The solutions included acids, bases, and salts as solutes, some liquids (e.g., dimethylsulfoxide, acetonitrile, n-decane) as co-sorbates and others (e.g., CDCl3, CCl4) as dispersion media. The adsorbents included various porous and highly disperse silicas, fumed alumina, carbons (activated carbons, graphene oxides), and porous polymers. So wide ranges of the systems studied could allow one a deeper insight into competitive or additive CSE and CE influencing the interfacial and temperature behaviors of bound liquids. The results of this analysis are of interest from both practical and theoretical points of view.
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在不同吸附剂孔隙的密闭空间效应下,各种液体混合物的胶粘性能与温度的关系
从实用角度来看,单独液体和混合液体的温度和界面行为非常重要,因为随着温度的降低,化合物相态的变化可能会导致负面影响(如多孔材料的冻害)。然而,使用某些混合物可以避免这些负面影响,这是因为溶液具有碰撞特性(晶体效应,CE),可产生多种效应,包括蒸汽压相对降低、沸点升高和冰点降低(FPD)。同样导致冰点降低的密闭空间效应(CSE)也会影响液体混合物在 FPD 方面的碰撞特性。我们可以假定,对于某些由于块状溶液的 CE 而具有一定 FPD 的体系,CSE 和 CE 不存在相加性(协同效应),但对于其他体系,结果可能恰恰相反。为了阐明这些界面现象,我们使用低温核磁共振光谱法研究了一组与不同吸附剂结合的液体混合物。溶液包括作为溶质的酸、碱和盐,一些液体(如二甲基亚砜、乙腈、正癸烷)作为助吸附剂,其他液体(如 CDCl3、CCl4)作为分散介质。吸附剂包括各种多孔和高分散硅、气相氧化铝、碳(活性碳、石墨烯氧化物)和多孔聚合物。所研究的系统范围如此之广,可以让我们更深入地了解竞争性或添加性 CSE 和 CE 对结合液体的界面和温度行为的影响。无论从实践角度还是理论角度来看,这一分析结果都具有重要意义。
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