Metallurgical and Materials Transactions B

, Volume 49, Issue 5, pp 2332–2342 | Cite as

Three-Dimensional Predominance Volume Diagrams: The Ni-As-S-O System

  • Stanley M. HowardEmail author


The 3D predominance volume diagram (PVD) for the Ni-As-S-O system at 700 K (427 °C) was constructed using independent gases O2, SO2, and As4O6. The system has 15 four-condensed-phase invariant points. Invariant points, fixed by any combination of boundaries and condensed phases totaling four, were determined by a Gibb’s minimization routine that searched from a corner of the PVD along each undetermined line emanating from this and subsequently-identified invariants. The search direction was determined from the cross product of the two independent planes’ normal direction vectors. The 0.25 atm and 1.00 atm isobaric surfaces intersect the Ni3As2O8, NiO, NiSO4, Ni1−xS, NiS2, and Ni11As8 phases. The 1.00 atm surface also intersects the NiAs phase. The PVD results agree with published ternary and quaternary phase diagram Alkemade lines. If the roasting of gersdorffite (NiAsS) parallels the roasting of enargite (Cu3AsS4), gersdorffite is expected to initially react irreversibly with O2 in the roasting gas to form NiS and NiSO4 topochemical layers with arsenic being expelled as As4O6 gas and perhaps As4 gas once a diffusion-controlled topochemical reaction sequence is established. Thermochemical calculations showed that the formation of NiO from NiSO4 and Ni3As2O8, if present, becomes more favorable as the temperature is increased with complete conversion to NiO above 1086 K and 1160 K (813 °C and 887 °C), respectively, at 1.00 atm.


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© The Minerals, Metals & Materials Society and ASM International 2018

Authors and Affiliations

  1. 1.Department of Materials and Metallurgical EngineeringSouth Dakota School of Mines and TechnologyRapid CityUSA

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