Solvated Ions in Water

In most undergraduate chemistry classes, students are taught to consider reactions in which cations and anions dissolved in water are depicted as isolated ions. For example, the magnesium ion is depicted as Mg2+, or at best Mg2+(aq). For anions, these descriptions may be adequate (if not accurate). However, for cations, these abbreviations almost always fail to describe the critical chemical attributes of the dissolved species. A much more meaningful description of Mg2+ dissolved in water is [Mg(H2O)6]2+, because Mg2+ in water does not behave like a bare Mg2+ ion, nor do the waters coordinated to the Mg2+ behave anything like water molecules in the bulk fluid. In many respects, the [Mg(H2O)6]2+ ion acts like a dissolved molecular species. In this chapter, we discuss the simple solvation of anions and cations as a prelude to exploring more complex reactions of soluble oxide precursors called hydrolysis products. The two key classes of water–oxide reactions introduced here are acid–base and ligand exchange. First, consider how simple anions modify the structure and properties of water. As discussed in Chapter 3, water is a dynamic and highly fluxional “oxide” containing transient rings and clusters based on tetrahedral oxygen anions held together by linear hydrogen bonds. Simple halide ions can insert into this structure by occupying sites that would normally be occupied by other water molecules because they have radii (ranging from 0.13 to 0.22 nm in the series from F− to I−) that are comparable to that of the O2− ion (0.14 nm). Such substitution is clearly seen in the structures of ionic clathrate hydrates, where the anion can replace one and sometimes even two water molecules. Larger anions can also replace water molecules within clathrate hydrate cages. For example, carboxylate hydrate structures incorporate the carboxylate group within the water framework whereas the hydrophobic hydrocarbon “tails” occupy a cavity within the water framework, as in methane hydrate (see Chapter 3). Water molecules form hydrogen bonds to dissolved halide ions just as they can to other water molecules, as designated by OH−Y−.

Crystal engineering and characterization of a structure-H ionic clathrate hydrate

Ionic hydrates are known to form numerous clathrate structures in which either the cations or anions sit in cages and the counterions are incorporated into the water framework. Due to the inclusion of the ionic species, such ionic clathrate hydrates not only show many peculiar features such as metal ion encagement and superoxide ion generation, but also exhibit notable physicochemical properties such as outstanding ionic conductivity and thermal stability. Thus, the ionic clathrate hydrates are considered for their potential applicability in various fields, including those that involve solid electrolytes, gas sensors, and energy storage. In this study, we report the design, synthesis, and characterization of the first ionic clathrate hydrate of the hexagonal structure-H (Str.H) crystal type. Diethyl-dimethyl-ammonium hydroxide hydrate was synthesized with CH4 and Xe as help gases, and the crystal structure was identified by powder X-ray diffraction analysis. Further confirmation of the formation of Str.H was obtained from Raman spectroscopy and 13C, 129Xe, and 2H solid-state NMR spectroscopy. From 13C NMR and ab initio calculations, it was shown that the quaternary ion occupies the large cage of Str.H with a conformation different from that in solution, due to constraints imposed by the dimensions of the cage. The H deficiency introduced by substitution of OH– for a water molecule appears, from 129Xe NMR, to be disordered over the framework, and, from 2H NMR, to substantially increase the rate of reorientational mobility of the D atoms in the framework, over that observed for a Str.I hydrate and for ice. The Str.H hydrates are commonly more stable than other structures, thus the present findings on the ionic Str.H clathrate hydrate may offer a new approach for improving the stability of ionic clathrate hydrates for their practical application.