Surface excess isotherms of organic solvent mixtures in a system made of liquid carbon dioxide and a silicagel surface

• Surface excess isotherms of organic solvents were measured in pure CO2, on a silica column.
• These solvents include methanol, ethanol, isopropyl-alcohol and acetonitrile.
• The minor disturbance or system peak method was used.
• The results show an enrichment of the organic modifier at the adsorbent surface.
• The interactions of alcohols with silica are much stronger than those of acetonitrile.

The surface excess isotherms of methanol, ethanol, 2-propanol and acetonitrile from liquid carbon dioxide on a silica adsorbent were measured, using the minor disturbance method. The minor disturbance peaks – or system peaks – of each organic modifier were recorded using UV-detection in the whole composition range of the organic/liquid carbon dioxide mixtures, the whole composition range was completed by injecting the modifiers into pure liquid carbon dioxide as well. The excess isotherms were calculated based on the retention of the organic solvent signals. Our results show an enrichment of the organic modifier at the adsorbent surface. The alcohols show multilayer adsorption with an extremely high retention on the silica surface while acetonitrile shows weaker interactions and only a slight trend toward the formation of a multilayer above the surface.