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High-temperature (867-1534 ºC) density measurements were performed in air on 10 liquids in the Na 2 O-Fe 2 O 3 -FeO-SiO 2  (NFS) system and 5 liquids in the K 2 O-Fe 2 O 3 -FeO-SiO 2  (KFS) system using Pt double-bob Archimedean method. Replicate measurements indicate an average reproducibility of 0.22%. Compositions (in mol%) range from 4 to 18 Fe 2 O 3 , 0 to 3 FeO, 18 to 39 Na 2 O, 25 to 37 K 2 O, and 43 to 67 SiO 2 . Errors in the gram formula weight are ~0.4%. The molar volumes were fitted to a linear compositional model, which gives a compositionally independent partial molar volume (±2σ) for the Fe 2 O 3  component (V̄ Fe₂O₃ ) of 41.52 ± 0.34 cm 3 /mol and zero thermal expansivity. The average residual to the fit is ±0.36% for our 57 measurements on 15 liquids at various temperatures. The value for V̄ Fe₂O₃  in silicate liquids when Fe 3+  is in fourfold vs. sixfold coordination is estimated to be ~45.5 ± 1 vs. ~34 ± 1 cm 3 /mol, respectively. Thus, the fitted value of 41.5 cm 3 /mol appears to reflect an average Fe 3+  coordination number between 4.5 and 5.0, which is consistent with recently published X-ray absorption fine structure (XAFS) spectroscopy and molecular dynamics (MD) simulations on Fe 3+ - bearing silicate glasses. In the literature,  V Fe 3+  is inferred to be present in trigonal bipyramidal sites, in contrast to the square pyramidal sites for  V Ti 4+ . The lack of a strong compositional or temperature dependence for V̄ Fe₂O₃  in these alkaline silicate liquids, in contrast to what is observed in the literature for V̄ TiO₂  in similar melts, may reflect the different geometries for  V Fe 3+  and  V Ti 4+ .

The partial molar volume of Fe 2 O 3 in alkali silicate melts: Evidence for an average Fe 3+ coordination number near five