A Cu-rich complex sulpfide concentrate (containing Sb as sulphosalts and gudmundite, and As as arsenopyrite) is roasted in Nitrogen atmosphere carrying traces of oxygen ($${\text{p}}^{{\text{O}}_{2}} \approx {10}^{-5.3}\text{ bar)}$$
p
O
2
≈
10
-
5.3
bar)
. In situ measurements through QMS indicated that the volatilized species are mainly elemental sulfur, S2(g), and gaseous sulfur oxides. Sb- and As-bearing volatilized species could not be detected, owing to their low concentrations in the gas phase. Characterization studies through XRD and SEM-EDS confirmed that the condensates collected at room temperature during the roasting experiments comprised of (1) cyclo-octa sulfur, S8(s) and polysulfur oxides, Sn−xOx(s); (2) amorphous trisulfides of Sb and As; (3) and cubic crystalline trioxides of Sb and As. The solid phases in the condensate were found to be fine-sized (sub-micronic) and widely intermixed. Consequently, quantification of the solid phases in the condensates through direct measurement techniques like QEMSCAN was not possible. A novel approach of partial quantification of solid phases in the condensate through a stochastic model-based calculation approach is also presented. The model results suggested the occurrence of vapor-phase complexation of sulfides of Sb and As in the gas phase. Additional attributes of the volatilized species could be determined through a thermodynamic equilibrium calculation showing that the formation of the complex oxides, As4−nSbnO6(g), would be negligible compared to that of the complex sulfides, As4−nSbnS6(g).