Unique thermodynamic relationships for ΔfHo and ΔfGo for crystalline inorganic salts. I. Predicting the possible existence and synthesis of Na2SO2 and Na2SeO2

• Published in: Acta crystallographica. Section B, Structural science Structural science, 2012-10, Vol.68 (5), p.511-527
• Main Authors: Vegas, Ángel, Liebman, Joel F., Jenkins, H. Donald Brooke
• Format: Article
• Language: English
• Subjects: condensed phases; oxidation-pressure concept; structural science; volume-based thermodynamics (VBT)
• ISSN: 0108-7681; 1600-5740
• DOI: 10.1107/S0108768112030686

The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M2S subnets of M2SOx (x = 3, 4) compounds (M = Na, K) when compared with the structures (room‐ and high‐pressure phases) of their parent M2S `alloy' [Martínez‐Cruz et al. (1994), J. Solid State Chem.110, 397–398; Vegas (2000), Crystallogr. Rev.7, 189–286; Vegas et al. (2002), Solid State Sci.4, 1077–1081]. These structural changes suggest that if M2SO2 would exist, its cation array might well have an anti‐CaF2 structure. On the other hand, in an analysis of the existing thermodynamic data for M2S, M2SO3 and M2SO4 we have identified, and report, a series of unique linear relationships between the known ΔfHo and ΔfGo values of the alkali metal (M) sulfide (x = 0) and their oxyanion salts M2SOx (x = 3 and 4), and the similarly between M2S2 disulfide (x = 0) and disulfur oxyanion salts M2S2Ox (x = 3, 4, 5, 6 and 7) and the number of O atoms in their anions x. These linear relationships appear to be unique to sulfur compounds and their inherent simplicity permits us to interpolate thermochemical data (ΔfHo) for as yet unprepared compounds, M2SO (x = 1) and M2SO2 (x = 2). The excellent linearity indicates the reliability of the interpolated data. Making use of the volume‐based thermodynamics, VBT [Jenkins et al. (1999), Inorg. Chem.38, 3609–3620], the values of the absolute entropies were estimated and from them, the standard ΔfSo values, and then the ΔfGo values of the salts. A tentative proposal is made for the synthesis of Na2SO2 which involves bubbling SO2 through a solution of sodium in liquid ammonia. For this attractive thermodynamic route, we estimate ΔGo to be approximately −500 kJ mol−1. However, examination of the stability of Na2SO2 raises doubts and Na2SeO2 emerges as a more attractive target material. Its synthesis is likely to be easier and it is stable to disproportionation into Na2S and Na2SeO4. Like Na2SO2, this compound is predicted to have an anti‐CaF2 Na2Se subnet.