Amorphous/Crystalline (A/C) Thermodynamic “Rules of Thumb”: Estimating Standard Thermodynamic Data for Amorphous Materials Using Standard Data for Their Crystalline Counterparts

Abstract

Standard thermochemical data (in the form of Δ(f)H° and Δ(f)G°) are available for crystalline (c) materials but rarely for their corresponding amorphous (a) counterparts. This paper establishes correlations between the sets of data for the two material forms (where known), which can then be used as a guideline for estimation of missing data. Accordingly, Δ(f)H°(a)/kJ mol(-1) ≈ 0.993Δ(f)H°(c)/kJ mol(-1) + 12.52 (R(2) = 0.9999; n = 50) and Δ(f)G°/kJ mol(-1) ≈ 0.988Δ(f)H°(c)/kJ mol(-1) + 0.70 (R(2) = 0.9999; n = 10). Much more tentatively, we propose that S°(298)(c)/J K(-1) mol(-1) ≈ 1.084S°(298)(c)/J K(-1) mol(-1) + 6.54 (R(2) = 0.9873; n = 11). An amorphous hydrate enthalpic version of the Difference Rule is also proposed (and tested) in the form [Δ(f)H°(M(p)X(q)·nH(2)O,a) - Δ(f)H°(M(p)X(q),a)]/kJ mol(-1) ≈ Θ(Hf)n ≈ -302.0n, where M(p)X(q)·nH(2)O represents an amorphous hydrate and M(p)X(q) the corresponding amorphous anhydrous parent salt.