Abstract

• Enthalpies of solution of bicaret (tetraethylglycoluril) in H 2 O and D 2 O were measured. • D 2 O–H 2 O enthalpy-isotopic effect is negative and decreasing with temperature. • Enthalpic coefficients h 22 for pairwise solute–solute interactions were derived. • Quantity of h 22 is negative and becoming the more negative in heavy water. • Prevailingly hydrophobic hydration of bicaret is weakened with rising temperature. The molar enthalpies of solution of bicaret or 2,4,6,8-tetraethyl-2,4,6,8-tatraazabicyclo[3.3.0]octane-3,7-dione in ordinary (H 2 O) and heavy (D 2 O) water at (278.15, 288.15, 298.15, 308.15, and 318.15) K as well as the enthalpies for dilution of its H/D isotopically distinguishable aqueous solutions at 298.15 K were measured calorimetrically. The standard (at infinite dilution) molar enthalpies and heat capacities of solution, and the enthalpic coefficients for pair ( h 22 ) and triplet ( h 222 ) interactions between hydrated solute molecules, along with D 2 O–H 2 O solvent isotope effects (IEs) on the studied quantities were computed. The enthalpic effects of bicaret dissolution and corresponding IEs were found to be negative and decreasing in magnitude with increasing temperature. On the contrary, the h 22 and h 222 values as well as IEs on them were found to be positive. These facts indicate that the bicaret hydration being predominantly hydrophobic is enhanced in the D 2 O medium. The hydration behavior of the solute considered was discussed in comparison with that for mebicar or 2,4,6,8-tetramethyl-2,4,6,8-tatraazabicyclo[3.3.0]octane-3,7-dione using the previously obtained data.

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