Partial molar volumes at infinite dilution, 
$$\overline {V^0 } $$

 , in water at 25°C for organicelectrolytes and nonelectrolytes are described through a simple additivity schemebased on the intrinsic volume approach. The contributions to 
$$\overline {V^0 } $$

 of hydrocarbongroups were determined from the “experimental” CH2 increment assuming thatall hydrocarbon portions have the same packing efficiency in aqueous solution.Twenty-two charged and 51 uncharged groups, are assigned a 
$$\overline {V^0 } $$

 contribution and the partial molar volumes of nearly 400 monofunctional organic solutes arereproduced with a root mean square of deviation of 0.9 cm3-mol−1. The differentvolumetric behavior of linear, branched, and cyclic molecules is discussed. Acomparison is made of uncharged (hydrocarbon and polar) with charged groups,as well as of groups with small molecules and ions. A relative estimate is givenof the volume effects (cavity formation, hydrophobic hydration, solvent shrinkage,H bonding, and electrostriction) involved in the interaction of hydrophobic andhydrophilic groups with water. Deviations from additivity for mono- andpolyfunctional solutes, including polyelectrolytes, are analyzed in terms of (1) extensionof the hydration cosphere of different polar centers: (2) intramolecular interactionsand their dependence on nature, number, and mutual distance of interactinggroups. The van der Waals volume V
w is extensively used as molecular descriptor.Estimates of V
w for both charged and uncharged groups are presented.

Partial Molar Volumes of Ionic and Nonionic Organic Solutes in Water: A Simple Additivity Scheme Based on the Intrinsic Volume Approach

The use of supercritical fluids, and in particular supercritical carbon dioxide (SC-CO2), can be foreseen in a wide range of techniques and processes within pharmaceutical sciences. When dealing with both drugs and formulation adjuvants, the determination of the relevant solubilities in SC-CO2 represents a mandatory prerequisite, underlying the development of industrial scale operations. The aim of this work concerned the experimental determination of the solubility in SC-CO2 of vanillic acid and ketoprofen by means of an easy-to-use plant designed and assembled to operate in dynamic conditions. Its reliability was preliminarily checked by comparing solubility data obtained for salicylic acid and naphthalene with literature ones. Solubility measurements for ketoprofen and vanillic acid were carried out at 313 and 328 K in the 9−25 MPa pressure range. Crossover pressures of 16 MPa and 15 MPa were found for ketoprofen and vanillic acid, respectively. The solubility data were worked out according to a thermo...

Assessment of Solubility of Ketoprofen and Vanillic Acid in Supercritical CO2 under Dynamic Conditions

Experimental data on density and viscosity at 303.15 and 323.15 K are presented for the binary mixtures of sulfolane + benzene, toluene, ethylbenzene, p-xylene, o-xylene, and m-xylene. From these data, excess molar volumes and deviations in viscosity have been calculated. The computed quantities have been fitted to the Redlich−Kister equation to derive the coefficients and estimate the standard error values. The results are discussed in terms of the intermolecular interactions.

Excess Molar Volumes and Viscosities of Binary Mixtures of Sulfolane with Benzene, Toluene, Ethylbenzene, p-Xylene, o-Xylene, and m-Xylene at 303.15 and 323.15 K and Atmospheric Pressure

Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers

The solubilities of phenol and pyrocatechol (1,2-dihydroxybenzene) in supercritical carbon dioxide were measured over the temperature range from 333.15 K to 363.15 K and the pressure range from 100 bar to 350 bar. The data were obtained using a recirculating equilibrium apparatus, which was tested by measuring the solubility of naphthalene in supercritical carbon dioxide. The measured solubilities were correlated using a semiempirical model proposed by Bartle.

Solubilities of Phenol and Pyrocatechol in Supercritical Carbon Dioxide

Thermodynamic and physical properties of binary mixtures involving sulfolane. Excess volumes and dielectric constants of benzonitrile-sulfolane and acetonitrile-sulfolane systems

Thermodynamic properties of binary mixtures involving sulfolane. 1. Excess volumes on mixing sulfolane and propionitrile, butyronitrile, and valeronitrile

Cas des melanges mettant en jeu le sulfolanne et une substance polaire (DMSO, nitrobenzene, benzonitrile) ou non polaire (CCl 4 , dioxanne, benzene)

Liliana Jannelli

Papers

Thermodynamic and physical properties of binary mixtures involving sulfolane. Excess volumes and dielectric constants of benzonitrile-sulfolane and acetonitrile-sulfolane systems

Thermodynamic properties of binary mixtures involving sulfolane. 1. Excess volumes on mixing sulfolane and propionitrile, butyronitrile, and valeronitrile

Mixing enthalpies of six binary systems involving sulfolane over the entire composition range, at 303.16 K

Excess enthalpies of mixing sulfolane + acetonitrile, + propionitrile, + butyronitrile, + valeronitrile at 303.16 K

Partial molar volumes of C2-C5 normal and branched nitriles in sulfolane solutions at 30.degree.C