0000000000170835
AUTHOR
Alessandro D'aprano
showing 21 related works from this author
Conductance in isodielectric mixtures. III.i-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dichlorobenzene, 1,2-dichloroethane, andn-pentanol
1975
The conductance of tetrabutylammonium tetraphenylboride, picrate, perchlorate, and nitrate has been measured at 25°C in mixtures ofi-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dicholorobenzene, 1,2-dichloroethane, andn-pentanol covering the range of dielectric constants 10≤D≤20. In these mixtures of polar solvents, both association constants and ionic mobilities depend on ion-solvent interaction energies and on free volume in a manner that is specific for each system. This failure of the primitive model (rigid charged spheres in a continuum) is shown to be the consequence of short-range spatial and energetic interactions between ions and adjacent solvent molecules.
Influence of solvent structure on ion pair association: The conductance of potassium perchlorate in ethylene carbonate-acetonitrile mixtures at 25�C
1974
The conductance of potassium perchlorate in mixtures of ethylene carbonate and acetonitrile covering the range 82.6 ≥ D ≥ 36.0 in dielectric constant has been measured. The Walden products in these aprotic solvents are approximately one-half as large as the products for the same salt in isodielectric mixtures of water and tetramethylene sulfone. This alters the distribution between electrostatic and hydrodynamic terms in the theoretical conductance function in such a way that the calculated association constants for potassium perchlorate are much smaller in the aprotic mixtures.
Precipitation of slightly soluble silver salts in reversed AOT micelles: Calorimetric investigation
1991
The enthalpies of precipitation, of AgCl, Agl, Ag2S and silver tetraphenylborate (AgTPB) in water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio R (R=[water]/[AOT]) at various concentrations of AOT and reagent salts, were measured by a calorimetric technique. The molar enthalpies of precipitation are independent of the surfactant concentration but are dependent on the concentration of the reagent salts and the R value. The molar enthalpies for the same processes in bulk water are not approached even at the highest R value. Effects due to the smallness of the microcrystals and to the interactions between ions and mice…
Molecular association in water-isomeric pentanol mixtures at 25�C
1982
The results of static dielectric constant and viscosity measurements on solutions of water (concentration range 0 to 0.3 mole fraction) in 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol together with previous results for solutions of water in n-pentanol are discussed in terms of the information that they provide on the nature and the extent of molecular association in these solutions. We conclude that in most systems this association leads to the formation of tetrahedral complexes such as H2O(ROH)4. Evidences of the correlation of water-alcohol interactions with molecular parameters (position of OH group, steric hindrance of alkyl chain) of alcohols a…
Dielectric polarization and polarizability of 1-pentanol+n-octane mixtures from static dielectric constant and refractive index data at 0,25 and 45�C
1990
Static dielectric constants and refractive indices of 1-pentanol+n-octane mixtures were measured in the temperature range between 0 and 45°C. Data discussed in terms of Kirkwood correlation factor and Lorentz-Lorenz molar refractivity give information on the short range intermolecular interactions between the components. The role played by the nonpolar n-octane in the destruction of 1-pentanol oligomers is also pointed out.
Conductance in isodielectric mixtures. I.n-butyronitrile with dioxane, benzene, and carbon tetrachloride
1974
The conductance of tetrabutylammonium tetraphenylboride, picrate, nitrate, and bromide has been measured at 25°C inn-butyronitrile and in mixtures of this solvent with dioxane, benzene, and carbon tetrachloride covering the range of dielectric constants from 10–24.26. For the picrate, nitrate, and bromide, the association constants at a given dielectric constant are independent of the chemical composition of the solvent. The changes of Walden products with solvent composition, however, are different, depending on which other solvent is mixed with the butyronitrile.
Hydrogen bond studies on n-pentanol and 2-methyl-2-butanol by Raman spectroscopy
1986
Polarized Raman spectra of n-pentanol and its isomer 2-methyl-2-butanol are obtained in the liquid phase near the melting points and at superheated temperatures. The measurements are performed in the intramolecular O-H stretching region. Our analysis of the Raman data provides an interpretation of the spectral features in terms of symmetric O-H bands, originated by various degrees of intermolecular coupling, for which mechanism is different for the two isomers. Temperature dependence of the spectra is also discussed in terms of available structural and dynamical models for these H-bonded liquids.
Calorimetric study on the solubilization of some primary alcohols by reversed AOT micelles
1989
A calorimetric method to evaluate, at the same time, the distribution constant and the standard enthalpy of transfer of a solute partitioned between organic phase and reversed micelles is proposed. The method was applied to the partition of methanol, 1-propanol and 1-pentanol between n-heptane and AOT reversed micelles containing water at 25°C. The results show that the distribution constant decreases as the alcohol alkyl chain length increases and that the solubilization site can change as the water content of reversed AOT micelles increases. In particular, at sufficiently high water content, methanol seems to be preferably solubilized in the aqueous pseudophase whereas 1-pentanol prefers …
The transport of ions across monoolein bilayers mediated by synthetic macrocyclic carriers
1989
The efficiency as carriers for the alkali and the alkaline earth ions across monoolein bilayers of three macrocyclic compounds has been investigated by conductometric measurements. The results show that although the three compounds have the optimum cavity size for fitting potassium and barium cations, their efficiency in ionic transport is quite different. These discrepancies are rationalized on the basis of the overlap of the water-diazacrown and cation-ligand interactions on the carrier mechanism.
Viscosity studies of solutions of water inn-aliphatic alcohols at various temperatures
1979
Viscosity measurements have been made at 25°C on solutions of water inn-propanol, and at 15, 25, 35, and 45°C on solutions of water inn-butanol,n-pentanol, andn-hexanol over the respective solubility ranges. For most of the systems, water decreases the viscosity of the dry alcohols, while for the lower members of the series literature data report an increase in viscosity on addition of water. These results are rationalized in terms of two kinds of interaction between water molecules and alcohols: participation of water molecules in chain formation for the lower alcohols and formation of water-centered complexes for butanol and higher alcohols.
The static dielectric constant of solutions of water inn-alcohols at 15, 25, 35, and 45°C
1979
Dielectric constants (measured at 1 MHz) are reported for solutions of water (concentration range 0 to 0.2 mole fraction) in 1-propanol at 25°C, and in 1-butanol, 1-pentanol, and 1-hexanol at 15, 25, 35, and 45°C. These results, together with literature values for solutions of water in methanol, ethanol, 1-heptanol, and 1-octanol, show that water interacts with alcohols in at least two ways: (1) it can participate in the formation of dynamic hydrogen-bonded chains, thereby raising the polarizability; (2) it can form relatively stable structures such as H2O(ROH)4 which have zero net dipole moment and consequently diminish volume polarizability. For C n H 2n+1 OH alcohols,n≥4, most of the ini…
Complexation of the potassium ion by diaza crown compounds in aqueous solutions
1988
The conductance behavior of potassium nitrate in water with and without 1,7,10,16-tetraoxa-4,13-diazacyclooctandecane[2.2] and 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-8.8.8-exacosane[2.2.2] macrocyclic ligands have been studied in order to analyze the complexation behavior of potassium cations in water. The absence of the complexation found in the [2.2] system is discussed in terms of the ligand structural features (presence of hydrogen bond donor and acceptor sites). The ion pair association constant of potassium cryptate as obtained from conductance measurements is also reported and discussed.
Conductance of potassium lodide in mixed solvents
1976
The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants KA are in the range 0.3–2.0; no correlation between KA and solvent properties could be established. For lower dielectric constants, KA increases exponentially with decreasing dielectric constant. Addition of a pro…
Interactions in water-alcohol mixtures: Conductance of lithium picrate in solutions of water and isomeric pentanols at 25�C
1982
Conductance measurements of lithium picrate in solutions of water in n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol have been carried out at 25°C. Ionic association and conductance were found to change with water content and with the molecular structure of the alcohols (i.e. position of the OH group and degree of branching of the alkyl chain). These results indicate that both conductance and ion pair formation are not the consequence of the simple motion of ions in the electrical field as required by the continuum model. A more realistic approach, involving the internal structure of the solvent mixtures, has been considered.
Ion pair association in isodielectric mixtures at 25�C
1974
Conductance measurements of potassium perchlorate and iodide have been carried out on the following mixtures: methanol-ethylene carbonate, acetone-ethylene carbonate, acetonitrile-ethylene carbonate, sulfolane-ethylene carbonate, isodielectric with water; and in benzene-sulfolane, benzene-acetonitrile, ethanol-sulfolane, isodielectric with methanol. The extent of ionic association at a given concentration in two solvents of the same dielectric constant is greater in the aprotic solvent.
Thermodynamics of binary mixtures: Volumes, heat capacities, and dilution enthalpies for then-pentanol+2-methyl-2-butanol system
1983
The densities, heat capacities, and dilution enthalpies ofn-pentanol+2-methyl-2-butanol mixtures have been measured, in many cases as a function of temperature, over the complete mole fraction range. Excesses thermodynamic properties, apparent and partial molar heat capacities, volumes and expansibilities were derived. The concentration and temperature dependences of these functions are discussed in terms of the variations of the structure of the system caused by the participation of the two alcohol molecules (with quite different steric hindrance of the alkyl chain around the-OH group) in the dynamic intermolecular association process through hydrogen bonding.
Static dielectric constant, viscosity, and structure of pure isomeric pentanols
1981
Static dielectric constants, viscosities, densitites and refractive indices of 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol and 2-methyl-2-butanol were measured at 15, 25, 35 and 45°C. These results together with the previous data on n-pentanol have been analyzed in terms of the Kirkwood correlation factor g k and of the energy of activiation for viscous flow. With the exception of 2-methyl-2-butanol, g k was found to be greater than unity. These results show that the monomeric units of isomeric pentanols interact by means of hydrogen bonding to form dynamic structures essentially of two types: linear chains where co-association raises the total polarizability and cyclic d…
Molecular interactions in 1-pentanol +2-methyl-2-butanol mixtures: Static dielectric constant, viscosity and refractive index investigations at 5, 25…
1989
Static dielectric constants, refractive indices and viscosities of 1-pentanol +2-methyl-2-butanol mixtures were measured at 5, 25 and 45°C. The results show that the mixing of the two isomers modifies the polarizability and the resistence of viscous flow of the system depending on the composition and temperature. Short range intermolecular interactions producing hetero-alcohol open dimers are considered.
Molecular association and dynamics in n-pentanol and 2-methyl-2-butanol
1985
Static dielectric constant, viscosity, density, ultrasonic and dielectric relaxation measurements are reported for two pentanol isomers (n-pentanol and 2-methyl-2-butanol) in a wide range of temperatures. The results show a different extent of H-bonds self-association in relation to the molecular geometry of the alcohol. The activation energies obtained from dielectric and ultrasonic studies are compared with those obtained from viscous flow. Such a comparison, together with the analysis of all the dielectric and ultrasonic relaxation data, show that in n-pentanol a correlation between viscosity and ultrasonic relaxation exists, while dielectric relaxation is not correlated with the other t…
The conductance of lithium-7 fluoride in dioxane-water mixtures at 25�C
1990
Conductance data for lithium-7 fluoride in dioxane-water mixtures covering the range 78.35>D>36 in dielectric constant are presented. These data and other previous data on lithium-7 chloride and lithium-7 iodide were analyzed by the Fuoss 1980 conductance equation in order to find the limiting conductance Δo, the pairing distance R and the conductometric association constant Kλ. Setting Ka=Kλ/VM (where VM is the molar volume of the solvent), the thermodynamic pairing constant and the corresponding change of the free energy Δg were calculated. Correlation among the values found for R and Δg=Δh−TΔs and the properties characteristic of the ions and solvents are discussed.
Volumetric and transport properties of aerosol-OT reversed micelles containing light and heavy water
1992
Densities and viscosities of sodium bis(2-ethylhexyl) sulfosuccinate (AOT in-heptane system containing light and heavy water, as a function of the molar ratio R (R=[H2O or D2O]/[AOT]) were measured at 0, 5, 25 and 40°C. At low R values, the apparent molar volume of deuterium oxide is smaller than that of light water. The difference is related to the strength of the hydrogen bonding H2O and D2O. The viscosities of both H2O-AOT-n-heptane and D2O-AOT-n-heptane systems were explained in terms of intermicellar interactions mainly governed by hydration of the head groups of AOT.