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The Aqueous Chemistry of Oxides$
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Bruce C. Bunker and William H. Casey

Print publication date: 2016

Print ISBN-13: 9780199384259

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780199384259.001.0001

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (oxford.universitypressscholarship.com). (c) Copyright Oxford University Press, 2021. All Rights Reserved. An individual user may print out a PDF of a single chapter of a monograph in OSO for personal use. date: 17 June 2021

Solvated Ions in Water

Solvated Ions in Water

4 Solvated Ions in Water
The Aqueous Chemistry of Oxides

Bruce C. Bunker

William H. Casey

Oxford University Press

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−.

Keywords:   Pauling’s First Rule, absolute reaction-rate theory, effective charge, formal charges, hydrolysis products, ionic radius, ligand, outer-sphere complex, solvation shells, waters of hydration

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