Water molecular state in 1-hexylpyridinium Hexafluorophosphate (cas 16919-18-9): Water mean cluster size as a function of water concentration

Add time:08/08/2019    Source:sciencedirect.com

The water sorption behavior of representative pyridinium-based ionic liquid (IL), 1-hexylpyridinium hexafluorophosphate ([C6Py][PF6]), was studied over the whole range of the water activity a using a continuous gravimetric method. The analysis of the water sorption isotherm using the combination of a two-mode sorption (i.e. Henry-clustering) allowed to better understand [C6Py][PF6]-water interactions. At low and intermediate activity (a ≤ 0.8), the water molecules revealed a very low affinity to [C6Py][PF6] and, consequently, the water uptake was rather low. On the contrary, at high water activity (a > 0.8), the water uptake increased exponentially and the water clustering easily occurred. The constant of the Henry-clustering equation as well as the water clustering mechanism in [C6Py][PF6] were discussed and compared to those of imidazolium-based ILs: 1-hexyl-3-methylimidazolium hexafluorophosphate [C6C1im][PF6] (water-immiscible IL) and 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1im][BF4] (water-miscible IL). It is shown that the sorption of water molecules by pyridinium-based ILs is controlled not only by the anion's nature, but also by the cation's nature. Moreover, the Zimm-Lundberg theory was used to determine the water mean cluster size (MCS) in [C6Py][PF6], [C6C1im][PF6] and [C4C1im][BF4]. The MCS results confirmed the strong capacity of water molecules to be aggregated in [C6Py][PF6]. In order to have a deeper insight into the water molecular state, infrared spectroscopy measurements were carried out as a function of the relative humidity value and the obtained results were correlated with the results of water sorption isotherms. It is found that at high water activity (a > 0.8), sorbed water molecules are strongly linked with ILs by hydrogen bonds and, therefore, are easily aggregated.

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