Group contribution method for standard molar volumes of aqueous aliphatic alcohols, ethers and ketones over extended ranges of temperature and pressure

CHAPTER 8. Partial Molar Volumes of Non-Ionic Solutes at Infinite Dilution

“…[88][89][90][91] Extensive experimental data available for the V 0 m,2 (T,p) surfaces in the range from (298 K to 573 K) and up to 30 MPa were utilised for the evaluation of the 1 st order group contributions in aqueous cyclic ethers, 19 cyclic ketones, 81 and open-chain aliphatic mono-and bifunctional alcohols, ethers, and ketones. 82 Structural corrections were introduced for bifunctional solutes having functional groups in close vicinity (-C(OH)-C(OH)-, -O-C-O-, -CO-C-CO-). Tests of predictive abilities even showed an agreement in predictions of sign inversions of (@V 0 m,2 /@T) p and (@V 0 m,2 /@p) T observed experimentally at high temperatures for highly hydrophilic polyhydric alcohols (propane-1,2,3-triol, pentane-1,2,3,4,5-pentaol, 2,2-bis(hydroxymethyl)propane-1,3-diol).…”

“…Any reasonably selected value of the co-volume can be introduced for open-chain solutes but the selection significantly affects the values of group contributions. 63,82 It has been shown that none or small (theoretical) co-volume leads to rather peculiar values of group contributions and their variations with temperature and pressure. 82 Instead of introducing an a priori fixed co-volume, an additional constraint deduced at the molecular level 82 can also be imposed to determine the co-volume term.…”

“…63,82 It has been shown that none or small (theoretical) co-volume leads to rather peculiar values of group contributions and their variations with temperature and pressure. 82 Instead of introducing an a priori fixed co-volume, an additional constraint deduced at the molecular level 82 can also be imposed to determine the co-volume term. On the other hand, the dependency of the co-volume on the properties of the solvent, consistent with the SPT theory, has been proven.…”

“…n ¼ 1, 2,2-dimethylpropane-1-ol; n ¼ 2, 2,2-dimethylpropane-1,3-diol; n ¼ 3, 2,2-bis(hydroxymethyl)propane-1-ol; n ¼ 4, 2,2-bis(hydroxymethyl)propane-1,3-diol. before thermally decomposing the solutes) in 5 K wide steps; for saturated pressure of water; and for p ¼ 30 MPa from smoothing polynomials evaluated for various classes of aqueous solutes that included aliphatic alcohols, ketones, ethers, 77,78,82,83 cyclic ketones, 81 cyclic ethers, 19 cycloalkanols, 18 phenylalkanols, 84 as well as benzene and toluene 6 (a total of 53 solutes). The extremities of the plot correspond to the high-temperature range; the most hydrophobic solutes (benzene, toluene, monohydric alcohols, monoethers, monoketones) are on the right-hand side with both a 0 p,2 and k 0 T,2 positive, while strongly hydrophilic solutes (pentane-1,2,3,4,5-pentaol, 2,2-bis(hydroxymethyl)propane-1,3-diol, propane-1,2,3-triol) are located at the left-hand side with both a 0 p,2 and k 0 T,2 negative.…”

Partial molar volumes of organic solutes in water. XXIV. Selected alkane-α,ω-diols at temperatures T= 298 K to 573 K and pressures up to 30 MPa

“…Horizontal dotted lines represent the values of the contribution reported in ref. [23] for respective temperatures starting from 298.15 K (the lowest line).…”