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Metal ions in aqueous solution


A metal ion in aqueous solution (aqua ion) is a cation, dissolved in water, of chemical formula [M(H2O)n]z+. The solvation number, n, determined by a variety of experimental methods is 4 for Li+ and Be2+ and 6 for elements in periods 3 and 4 of the periodic table. Lanthanide and actinide aqua ions have solvation number of 8 and 9. The strength of the bonds between the metal ion and water molecules in the primary solvation shell increases with the electrical charge, z, on the metal ion and decreases as its radius, r, increases. Aqua ions are subject to hydrolysis. The logarithm of the first hydrolysis constant is proportional to z2/r for most aqua ions. The aqua ion is associated, through hydrogen bonding with other water molecules in a secondary solvation shell. Water molecules in the first hydration shell exchange with molecules in the second solvation shell and molecules in the bulk liquid. The residence time of a molecule in the first shell varies among the chemical elements from about 100 picoseconds to more than 200 years. Aqua ions are prominent in electrochemistry.

Most chemical elements are metallic and form simple aqua ions with the formula [M(H2O)n]z+ when the oxidation state is 1, 2 or 3. With the higher oxidation states the simple aqua ions dissociate losing hydrogen ions to yield complexes that contain both water molecules and hydroxide or oxide ions, such as the vanadium(IV) species [VO(H2O)5]2+. In the highest oxidation state only oxyanions, such as the permanganate(VII) ion, MnO
4
are known.


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