Changes in partial molar volume and isentropic partial molar compressibility of self-association of purine and caffeine in aqueous solution at 1–1600 bar

Ultrasound measurements of purine and caffeine in aqueous solution as function of pressure are reported at 25°C and used to calculate the changes in their partial molar volumes and partial molar compressibilities due to self-association. The effect of pressure is to increase the association. The volume changes are negative for the self-association process, becoming less negative with increasing pressure. This is caused by the monomer in the associated state. The partial molar volume of the monomer in the associated state increases with pressure, contrary to what is expected for nonelectrolytes in water. Hydration of the associated monomer must be a key to this increase. The result suggest that dipole-induced dipole interactions is a possible mechanism for the association process and not hydrophobic interactions. The change in the partial molar compressibility of the association is positive, decreasing with increasing pressure.