Abstract

The Group I salts of 12-tungstophosphoric acid were studied in their limiting hydration state with use of both1H and 31P solid-state nuclear magnetic resonance (NMR). The bulk proton structures of the Li, Na, and Rb salts consist of both lone protons and water molecule protons. The K and Cs salts contain similar proton structures that reside in surface sites. Nonspinning 1H NMR results indicate that all protons in the limiting hydration state in each of the Group I salts are highly mobile at room temperature. 1H spin−lattice relaxation times obtained as a function of temperature indicate that the dominant mechanism responsible for proton relaxation in the Li, Na, and Rb salts is restricted rotation of water molecules while the K and Cs salts have proton spin−lattice relaxation that is dominated by translation of protons through surface sites of the material. Two stable Rb salt phases are crystallized when a stoichiometric amount of RbCl is added to aqueous 12-tungstophosphoric acid at room temperature.

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