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  • 1
    ISSN: 1572-8927
    Keywords: Activities ; relative enthalpies ; volumes ; heat capacities ; expansibilities ; phase diagrams ; 2,6-dimethylpyridine-water mixtures ; 2-isobutoxyethanol-water mixtures ; critical demixing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques.
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  • 2
    ISSN: 1572-8927
    Keywords: Volumes ; apparent molal ; heat capacities ; apparent molal ; ultrasonic vibration potential ; acetonitrile ; electrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ultrasonic vibration potentials and apparent molal volumes for many inorganic and organic electrolytes were measured in acetonitrile at 25°C and combined to obtain ionic contributions to the standard partial molal volumes V°(ion). Monatomic cations and anions of the same size essentially have the same V°(ion). Their size dependence can be interpreted through Hepler's equation. The apparent molal heat capacities were also measured in acetonitrile and used to derive standard values. Various methods of estimating C p 0 (ion) were investigated and an ionic scale is proposed. It is concluded that C p 0 (ion) of large organic ions are very close to the intrinsic heat capacities of the ions, and the solvation contribution to monatomic ions is positive for both cations and anions.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 21 (1992), S. 433-443 
    ISSN: 1572-8927
    Keywords: Volumes ; phase diagrams ; heat capacities ; liquid mixtures ; non-ideality
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Liquid systems which have strong non-idealities, as seen from their thermodynamic properties, often show evidence of these interactions in the solid-liquid phase diagrams. This suggests that some of the structures present in the solid state can persist in the solution state, on a time average, up to temperatures much higher than the melting point. Volumes and heat capacities of typical systems were either taken from the literature or measured to illustrate this correlation with the phase diagrams. With mixtures of aprotic solvents which show nearly-ideal simple eutectic phase diagrams, the properties of the solutions are also nearly ideal. Examples of systems investigated which show strong non-idealities are ionic surfactant solutions, alcohol-water mixtures, chloroform-triethylamine mixtures and lithium salts in aprotic solvents.
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  • 4
    ISSN: 1572-8927
    Keywords: Association constant ; Bjerrum model ; electrolyte ; conductivity ; water ; acetonitrile ; propylene carbonate ; γ-butyrolactone ; propanol ; butanone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Bjerrum association model, developed in 1926, is now incorporated in many conductance theories of electrolyte systems to extract Λ0 and K A from experimental data. The Bjerrum concept is simply a convenient way of taking into account short-range electrostatic interactions between ions. The equations of the Bjerrum model can be applied to the prediction of the temperature and pressure dependencies of K A from the value of K A at a reference T and P and from the dielectric properties of the solvent. This feature will be essential when the relaxation effect is taken into account when applying the model to heat capacities and compressibilities. These equations were tested against literature K A values (obtained from treatment of conductance data by equations that incorporate the Bjerrum concept) in aqueous electrolyte solutions at high temperatures and pressures and in some electrolyte systems in acetonitrile, 2-butanone, propylene carbonate, γ-butyrolactone, and propanol. In the absence of specific interactions in solution, the agreement between experimental and predicted K A are generally quite good. Notable exceptions are acids and bases in water, lithium perchlorate in most solvents, and the majority of electrolytes in propylene carbonate, suggesting that specific interactions in these systems may cause the model to fail.
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  • 5
    ISSN: 1572-8927
    Keywords: Association constant ; Bjerrum model ; electrolyte ; heat capacity ; compressibility ; volume ; standard partial molar quantities ; water ; acetonitrile ; propylene carbonate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Bjerrum association model, which has already been applied successfully to volumes and enthalpies of dilution of electrolyte solutions, has now been extended to apparent molar heat capacities and compressibilities of these systems. The proposed method of calculation, which takes into account the relaxation effect observed in second derivatives of the excess Gibbs free energy, can be used to extrapolate to infinite dilution the experimental data for systems showing a wide range of association constants in acetonitrile, propylene carbonate, and water. The concentration dependence of the thermodynamic properties can be reproduced quantitatively by the addition of one or two virial coefficients. Literature data for C P,2,ψ and K S,2,ψ of electrolytes in aprotic solvents were refitted with this equation. For dissociated or slightly associated systems (K A 〈 10), the standarY 2 o d infinite dilution quantities () are in excellent agreement with literature values. For systems with high K A, Y 2 o obtained by the model are systematically lower than those reported in the literature. This is not surprising, since the traditional method of extrapolation using the Debye–Hückel limiting law or the Pitzer equation does not take association into account. A computer software that performs the calculations for the application of the Bjerrum model to thermodynamic properties has been designed and is presented in the appendix.
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  • 6
    ISSN: 1572-8927
    Keywords: Ethylammonium nitrate ; acetonitrile ; water ; solid-liquid phase diagram ; volume ; heat capacity ; expansibility ; conductivity ; viscosity ; ion association
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethylammonium nitrate (ETAN), a low melting fused salt which is completely miscile in water and in many non-aqueous solvents, was used as a model system for the study of concentrated non-aqueous electrolyte solutions. Acetonitrile (AN) was chosen as a representative aprotic solvent. Some data were also obtained for water as solvent. The properties investigated over the whole mole fraction range, many as a function of temperature, were solid-liquid phase diagram, volume, heat capacity, conductivity and viscosity. Most properties in both solvents vary in a regular fashion over the whole mole fraction range and the properties at high concentration rapidly tend to those of the molten salt. The apparent volumes and heat capacities vary linearly with lnX2 over a large mole fraction range. There is evidence of significant association in AN (K A =1094 l-mol−) but not in water. The low concentration thermodynamic data were fitted with an association model using the above K A to obtain the partial molar quantities of ETAN at infinite dilution and in the associated state. These latter values are of the same magnitude as the molar quantities of the molten electrolyte.
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