Using a series of time- and temperature-resolved synchrotron diffraction experiments, the relationship between multiple polymorphs of ZnCl and its respective hydrates is established. The δ-phase is found to be the pure anhydrous phase, while the α, β, and γ phases result from partial hydration. Diffraction, gravimetric, and calorimetric measurements across the entire ZnCl· HO, 0 > > ∞ composition range using ultrapure, doubly sublimed ZnCl establish the ZnCl : HO phase diagram.
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