Densities of urea (U) and tetramethylurea (TMU) solutions
in formamide
(FA) and water with a solute molality of up to ∼2 mol kg–1 were measured at T = 288.15, 298.15,
308.15, 318.15, and 328.15 K and p = 99.6 kPa. All
experiments were performed using a precision vibrating U-tube densimeter
at measuring uncertainty not exceeding 0.03 kg m–3. Standard partial and excess molar volumes as well as volume-related
parameters of solute–solute interactions for U and TMU in both
solvents under comparison were computed. The derived results were
discussed on the assumption that FA, like water or ethylene glycol
(EG), is a solvent having a capability to form the spatial hydrogen-bonding
network, inducing effects of solvophobic solvation. It was found that
a structure-compression effect during the solvation of TMU in FA becomes
somewhat enhanced with increasing temperature. In turn, the process
of forming the “solvation complex” of U in FA is accompanied
already by structure loosening at temperatures higher than T = 288 K. The same goes for both (EG + TMU) and (EG + U)
systems, too, but the “loosening effect” in the last
case appeared at T > 308 K only. Similarly to
aqueous
solutions, the temperature has a differentiating effect on trends
of changing in both the standard partial molar expansibility of U
and TMU and volume coefficients of the U–U and TMU–TMU
pair interactions in FA as well as EG. The data obtained here confirm
the fact that the solvophobity of TMU in water is markedly stronger
pronounced than it occurs in FA and EG media. Herewith, the previous
conclusion that, in a thermochemical sense, the solvation behavior
of compared ureas in FA is more “waterlike” than in
liquid EG is overall true for the solute TMU only.