AbstractInvestigations into the product recovery step of the extractive ethanol fermentation through partition experiments for ethanol‐water‐Adolr̀85 NF ternary systems were undertaken. Experimental liquid‐liquid equilibrium data for this ternary system were compared with numerical predictions based on the UNIFAC method. The influence of salts on distribution coefficients for ethanol extraction was also examined. An improvement in extraction characteristics was observed for ternary systems with salts. Flash vaporisation was used to subsequently examine the effect of liquid‐liquid ternary compositions on vapour‐liquid partitioning. The UNIFAC model was found to be very useful for semi‐quantitative analysis of such liquid extrac