Phenomenon of "negative partial molar expansibility" of water in tetrahydrofuran: How plausible is it? Discussion on the paper "Volumetric properties on the (tetrahydrofuran + water) and (tetra-n-butylammonium bromide + water) systems: Experimental measurements and correlations" by Veronica Belandria, Ammir H. Mohammadi and Dominique Richon [J. Chem. Thermodyn. 41 (2009) 1382 1386]
In order to answer the question: is a solute water "negatively expansible" in tetrahydrofuran or not (?), a comparative analysis of own and literature data on the temperature-dependent partial volumes at the infinite dilution of water isotopologues in tetrahydrofuran have been carried out. Used for computing the limiting partial (apparent) volumes of water isotopologues, densities of H2O and D2O solutions in the solvent studied, with the solute mole fractions ranging up to about 0.043, were measured with an error of 1.5 x 10-5 cm3 mol-1 at (278.15, 288.15, 298.15, 308.15, and 318.15) K and atmospheric pressure using a vibrating tube densimeter. It has been shown that the partial molar volume of H2O or D2O at infinite dilution increases with rising temperature; that is, the isotopically distinguishable solutions of water in tetrahydrofuran do not have the unusual structure-packing behavior being characteristic of the water-containing system with the so-called phenomenon of "negative partial molar expansibility".
Compounds
#
Formula
Name
1
C4H8O
tetrahydrofuran
2
H2O
water
3
D2O
water-d2
Datasets
The table above is generated from the ThermoML associated json file (link above).
POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied;
the numbers refer to the table of compounds on the left.