A relationship has been observed between increasing ethanol content in gasoline and increased particulate matter (PM) emissions from direct injection spark ignition (DISI) vehicles. The fundamental cause of this observation is not well understood. One potential explanation is that increased evaporative cooling as a result of ethanol's high HOV may slow evaporation and prevent sufficient reactant mixing resulting in the combustion of localized fuel rich regions within the cylinder. In addition, it is well known that ethanol when blended in gasoline forms positive azeotropes which can alter the liquid/vapor composition during the vaporization process. In fact, it was shown recently through a numerical study that these interactions can retain the aromatic species within the liquid phase impeding the in-cylinder mixing of these compounds, which would accentuate PM formation upon combustion. To better understand the role of the azeotrope interactions on the vapor/liquid composition evolution of the fuel, distillations were performed using the Advanced Distillation Curve apparatus on carefully selected samples consisting of gasoline blended with ethanol and heavy aromatic and oxygenated compounds with varying vapor pressures, including cumene, p-cymene, 4-tertbutyl toluene, anisole, and 4-methyl anisole. Samples collected during the distillation indicate an enrichment of the heavy aromatic or oxygenated additive with an increase in initial ethanol concentration from E0 to E30. A recently developed distillation and droplet evaporation model is used to explore the influence of dilution effects versus azeotrope interactions on the aromatic species enrichment. The results suggest that HOV-cooling effects as well as aromatic species enrichment behaviors should be considered in future development of predictive indices to forecast the PM potential of fuels containing oxygenated compounds with comparatively high HOV.