Azeotropy of alcohol–water mixtures from the viewpoint of cluster-level structures

Abstract We showed that there is a close relation between evaporation properties and cluster-level structures in alcohol–water binary mixtures, on the basis of the mass spectrometric analyses of clusters generated through fragmentation of liquid droplets. The azeotropy for alcohol (ethanol, 1-propanol or 1-butanol)–water mixtures is caused by the change of the evaporation properties attributed to the cluster-level structures in the mixtures. When the hydrogen-bonding network of water molecules is stable at the cluster level in the water-rich mixtures, the alcohol molecules included in the water-rich clusters are evaporated primarily. On the other hand, when the alcohol self-association clusters are formed with an increase of the alcohol concentration in the mixtures, evaporation of the water existing around the alcohol self-association clusters is increased.