Search results for "Activity coefficient"
showing 10 items of 60 documents
Calculation of proton activity in aqueous protolyte solutions
1980
Abstract A general and thermodynamically exact equation for the calculation of the proton (hydroxide ion) activity of aqueous solutions of monoprotic acidic (and basic) species is given. Under certain conditions, various approximate equations can be derived from the exact form; the applicability of these depends mainly on both the thermodynamic equilibrium constant, K p , of the protolytic reaction, and the stoichiometric concentration, C o , of the protolyte. Taking into account the mean ionic activity coefficients which are calculated by means of the Davies equation, diagrams are constructed exhibiting those combinations of K p and C o for which the respective approximations can be applie…
Macromolecules in ordered media III. A fluorescence study on the association of poly-2-vinylpyridine with a phospholipid bilayer
2007
Association of low molecular weight poly-2-vinylpyridine taken as a polycation model with unilamellar vesicles based on dimirystoylphosphatidic acid has been experimentally investigated by means of fluorescence energy transfer experiments. The conventional profiles for the binding isotherms were obtained, confirming strong deviations from the ideality of these complex fluid composites. Two approaches, named binding and partitioning equilibrium, respectively, were used to obtain the association constant, K A; the number of phospholipids that form a binding site, N; the partition coefficient, Λ; the activity coefficient, γ; and the effective charge, v. Analysis of these parameters as a functi…
Isobaric vapor-liquid equilibria for binary and ternary systems composed of water, 1-propanol, and 2-propanol at 100 kPa
1996
Isobaric vapor−liquid equilibria data were obtained for the 2-propanol + 1-propanol binary system and the water + 1-propanol + 2-propanol ternary system at 100 kPa. The data were found to be thermodynamically consistent according to the Van Ness−Byer−Gibbs method for the binary system and according to the McDermott−Ellis method for the ternary one. The binary system is well represented by assuming ideal behavior. The binary interaction parameters obtained from this and our previous work are used to predict the vapor−liquid equilibrium for the ternary system using the UNIQUAC, NRTL, and Wilson models. The ternary system is well predicted from binary data.
Vapor-liquid equilibria for the binary systems of methylcyclohexane with 1-propanol, 2-propanol, 1-butanol, and 2-butanol at 101.3 kPa
1997
Isobaric vapor−liquid equilibrium measurements at 101.3 kPa are reported for the binary systems methylcyclohexane + 1-propanol, + 2-propanol, + 1-butanol, and + 2-butanol. The systems show a strong positive deviation from ideality and present a minimum temperature azeotrope. The activity coefficients were found to be thermodynamically consistent by the methods of Van Ness−Byer−Gibbs and Wisniak. The date were correlated with five liquid-phase activity coefficient models (Margules, Van Laar, Wilson, NRTL, and UNIQUAC). According to the average deviations in temperature and in vapor composition the best model for the systems is NRTL.
Macromolecules in ordered media: 4. Poly(2-vinyl pyridine)-liposome association induced by electrostatic interactions
1997
Abstract We have investigated the interaction between vesicles based on dimyristoyl phosphatidic acid (DMPA) and a polymer, such as poly(2-vinyl pyridine) (P2VPy), on the basis of both partition and binding models. The resulting association curves are non monotonous being three regions clearly evidenced. The electrostatic and steric origin of the attractive or repulsive interactions are analyzed as a function of pH, ionic strength and temperature using the fluorescence spectroscopy technique. We emphasize the importance of differentiating the ideal definition of the binding constant from the theoretically evaluated including the activity coefficient, γ, to take into account shifts from the …
Thermodynamic studies of octyltrimethylammonium chloride in water
1992
Densities, heat capacities, enthalpies of dilution at 298 K and osmotic coefficients at 310 K of octyltrimethylammonium chloride were measured as functions of concentration. From the experimental data, the partial molar volumes, heat capacities, relative enthalpies, nonideal free energies and entropies at 298 K were derived as functions of concentration. A comparison between the above data and those of dodecyltrimethylammonium chloride reported in the literature shows that the increase of the alkyl chain length shifts the apparent molar volumevs. concentration curves towards greater values and the heat capacity, relative enthalpy and free energyvs. concentration curves towards smaller value…
Macromolecules in ordered media: 5. Poly(4-vinyl pyridine)—liposome association induced by electrostatic interactions
1997
Abstract The association of water-soluble vinyl polymers to dimyristoyl phosphatidic acid unilamellar vesicles as a function of pH, temperature and salt content using steady-state fluorescence and viscometry has been investigated. Poly(4-vinyl pyridine) fluorescence data were converted to association isotherms and discussed in terms of binding and partition models. The results of this report support previous suggestions: (1) in the case of polyions the inclusion of the activity coefficient in both models is essential; (2) the parameters calculated using the two different theoretical approaches can be directly compared by the relating equation proposed for us. Finally, the excellent agreemen…
Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of Diisopropyl Ether, 2-Propyl Alcohol, and n-Butyl Propionate at 101.3 kPa
2009
Consistent vapor−liquid equilibrium data at 101.3 kPa have been determined for the ternary system diisopropyl ether (1) + 2-propyl alcohol (2) + n-butyl propionate (3) and two constituent binary systems: diisopropyl ether (1) + n-butyl propionate (3) and 2-propyl alcohol (2) + n-butyl propionate (3). The diisopropyl ether (1) + n-butyl propionate (3) system does not present deviation from ideal behavior, and the 2-propyl alcohol (2) + n-butyl propionate (3) system shows light positive deviation from Raoult’s law. The activity coefficients of the solutions were correlated with their compositions by the Wilson, NRTL, and UNIQUAC models. Wisniak−Tamir equations were used to correlate the boili…
Thermodynamic properties of some N-alkyl-N-methylpiperidinium chlorides and N-alkylpiperidine hydrochlorides in water
1993
Densities and heat capacities at 25[degrees]C were measured for N-octyl-, N-decyl- and N-dodecyl-N-methylpiperidinium chlorides and for N-octyl- and N-dodecylpiperidine hydrochlorides in water as functions of concentration. Enthalpies of dilution at 25[degrees]C and osmotic coefficients at 37[degrees]C of the N-methyl-N-alkylpiperidinium chlorides were also measured as functions of concentration. The partial molar volumes, heat capacities, relative enthalpies, nonideal Gibbs energies and entropies at 25[degrees]C were derived as functions of the surfactant concentration. By increasing the alkyl chain length of the surfactant, both the apparent molar volume vs. concentration curves are shift…
Application of headspace analysis to the study of aroma compounds-lipids interactions
1998
Taking into account interactions between aroma compounds and food components is necessary to better manage the flavoring of food products. These interactions occur at a molecular level and reflect changes, at a macroscopic level, in thermodynamic equilibria, such as solubility or volatility. The rate of transfer of an aroma compound from the liquid to the vapor phase can be affected as well. The behavior of aroma compounds in water and lipid solutions was studied in two complementary ways, a thermodynamic and a kinetic approach (head-space analysis). The transfer rate of volatiles at the liquid-water interface does not only depend on the hydrophobicity of the aroma compounds. Vapor-liquid p…