Water in a hydrophobic environment and the effect of some organic substances on it

V. Turov, T. Krupska
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Abstract

The structure of water in the interparticle gaps of methyl silica was investigated using the method of low-temperature 1H NMR spectroscopy. It is shown that the main part of the interfacial water is in the form of large clusters, or nanodroplets, which freeze at a temperature of about 273 K. After freezing of this water, signals of strongly and weakly associated water are observed in the spectra, which melts at temperatures of 215–368 K. It is likely that the freezing of weakly associated of water occurs through the formation of clusters in which closely spaced water molecules interact not through hydrogen bonds, but through dipole-dipole interactions. In the presence of chloroform, the amount of weakly associated water increases several times. This is explained by the possibility of formation of chloroform hydrates, in which the mobility of water molecules is approximately the same as in strongly associated water clusters. If joint adsorption of chloroform and methane occurs on the hydrated surface of methyl silica, under the influence of CH4, weakly mobile weakly associated water is transformed into methane hydrates in quasi-liquid and solid states, while only mobile forms of hydrates are recorded in the spectra. DMSO reduces the possibility of formation of weakly associated water, but a certain amount of it is fixed even in the medium of liquid DMSO. At the same time, the freezing of water in systems containing DMSO occurs at much lower temperatures due to solvation of water and DMSO molecules. The difference in interphase energy in air and in organic media determines the solvation energy.
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疏水环境中的水以及一些有机物对其的影响
采用低温1H核磁共振波谱法研究了二氧化硅甲基颗粒间隙中水的结构。结果表明,界面水主要以大团簇或纳米液滴的形式存在,在273 K左右结冰。在这些水冻结后,在光谱中观察到强烈和弱相关水的信号,它们在215-368 K的温度下融化。弱缔合水的冻结很可能是通过形成团簇而发生的,在团簇中,紧密间隔的水分子不是通过氢键相互作用,而是通过偶极子-偶极子相互作用。在氯仿的存在下,弱缔合水的数量增加了几倍。这可以用氯仿水合物形成的可能性来解释,在氯仿水合物中,水分子的流动性与强相关的水团簇大致相同。如果氯仿和甲烷在甲基二氧化硅水合表面发生联合吸附,在CH4的作用下,弱流动弱缔合水转变为准液态和固态的甲烷水合物,而光谱中只记录到流动形态的水合物。DMSO降低了弱缔合水形成的可能性,但即使在液态DMSO介质中,也有一定量的弱缔合水是固定的。同时,在含有二甲基亚砜的系统中,由于水和二甲基亚砜分子的溶剂化作用,水的冻结发生在更低的温度下。空气和有机介质中相间能的差异决定了溶剂化能。
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