The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M
2S subnets of M
2SO
x
(x = 3, 4) compounds (M = Na, K) when compared with the structures (room- and high-pressure phases) of their parent M
2S `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 M
2SO2 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 M
2S, M
2SO3 and M
2SO4 we have identified, and report, a series of unique linear relationships between the known Δf
H
o and Δf
G
o values of the alkali metal (M) sulfide (x = 0) and their oxyanion salts M
2SO
x
(x = 3 and 4), and the similarly between M
2S2 disulfide (x = 0) and disulfur oxyanion salts M
2S2O
x
(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 (Δf
H
o) for as yet unprepared compounds, M
2SO (x = 1) and M
2SO2 (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 Δf
S
o values, and then the Δf
G
o 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 ΔG
o 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.
Unique thermodynamic relationships for Δf
H
o and Δf
G
o for crystalline inorganic salts. I. Predicting the possible existence and synthesis of Na2SO2 and Na2SeO2