Apparent Molal Volumes and Heat Capacities of Urea and Methyl-Substituted Ureas in H2O and D2O at 25 °C

Abstract
The apparent molal volumes and heat capacities of urea, 1,1- and 1,3-dimethylurea, and tetramethylurea were measured in H2O and D2O at 25 °C. From these data, urea–water interactions seem to cause an overall structure-breaking effect and the substituted ureas, an overall structure-making effect. The effect of the hydrogen-bonding interactions to the volume and heat capacity seems to be small compared with the intrinsic and hydrophobic contributions of a methylene group, as reflected by the isotope effect. Furthermore, transfer values seem to show a significant specificity to the degree and position of methyl substitution.