Equilibres liquide-vapeur isothermes de melanges binaires de la piperidine et de la N-methyl piperidine avec certains ethers

The authors have measured the vapour pressure of the four binary systems, piperidine +tert-butyl methyl ether, piperidine +1,4 dioxane, piperidine + tetrahydropyrane and N-methyl piperidine +tert-butyl methyl ether. The measurements were carried out using an isoteniscope built by J. Jose [1], The vapour pressure, excess Gibbs free energies at 298.15, 303.15, 313.15, 323.15, 333.15 and 343.15 K, are reported for these mixtures. The excess Gibbs free energies have been fitted to the Redlich-Kister equation.

     

Equilibres liquide-vapeur isothermes de melanges binaires de la piperidine et de la N-methyl piperidine avec certains ethers

The authors have measured the vapour pressure of the binary four systems, piperidin +1,4-dioxan, piperidin+tetrahydropyran, piperidin+tert-butyl methyl ether and N-methyl piperidin+tert-butyl methyl ether. The measurements were carried out using an isoteniscope built by J. Jose [1]. The vapour pressure, excess Gibbs free energies at 298.15 K, 303.15 K, 313.15 K, 323.15 K, 333.15 K and 343.15 K, are reported for these mixtures. The excess Gibbs free energies have been fitted to the Redlich-Kister equation.     

Equilibres Liquide-vapeur Isothermes De Melanges Binaires, Amine+amine

The authors have measured the vapour pressure of the binary systems, piperidine+n -butylamine, piperidine+dipropylamine, piperidine+N-methyl piperidine, piperidine+N,N-dimethyl amino butane and N-methyl piperidine+n -butylamine. The measurements were carried out using an isoteniscope built by Jose [1]. The vapour pressure, excess Gibbs free energies at 298,15, 303,15, 313,15, 323,15, 333,15, and 325,15 K, are reported for these mixtures. The excess Gibbs free energies have been fitted to Redlich-Kister equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Isobaric vapour–liquid phase diagram and excess properties for the binary system 1,4-dioxane + water at 298.15 K, 318.15 K and 338.15 K

Isobaric vapour–liquid equilibrium (VLE) data have been measured for the binary system (1,4-dioxane + water) at atmospheric pressure. The compositions of the two phases in equilibrium were taken from the refractive indices curve of the system. The equilibrium data show a positive deviation from ideality and reveal an azeotrope. VLE data have been used to calculate the activity coefficients of the two components at 298.15 K, 318.15 K and 338.15 K. The excess properties have been deduced at these temperatures. Molar Gibbs free energy at liquid state was expressed as a function of composition and temperature. At the liquid state, excess entropies of the present system are negative over the entire composition range. Molecular-scale segregation in this system was proved.     

Molar excess volumes of 1,4-dioxane+ acetonitrile,n-butylamine+acetonitrile andn-butylamine+1,4-dioxane at different temperatures

Molar excess volumes and partial molar volumes are reported for binary mixtures of 1,4-dioxane + acetonitrile, n-butylamine + acetonitrile and n-butylamine + 1,4-dioxane at five different temperatures and over the complete concentration range. The Prigogine-Flory-Patterson model of solution thermodynamics has been used to predict the excess molar volumes. This work shows the importance of the three contributions: interactional, internal pressure and free volume, to the excess volume.     

Freezing points and enthalpies of dilute aqueous solutions of tetrahydropyran, 1,3-dioxane, 1,4-dioxane,and 1,3,5-trioxane. Free energies and enthalpies of solute-solute interactions

The enthalpies of dilute aqueous solutions of tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,2,5-trioxane, and an equimolal mixture of tetrahydropyran and 1,3,5-trioxane were measured at 25°C and at molalities from about 0.1 to 1.0 mol kg¹. The freezing points of the same aqueous solutions (except for 1,3-dioxane) were measured over a similar molality range. The results were used to calculate the enthalpies and Gibbs free energies of the pair-wise interactions of the above solutes in dilute aqueous solutions at 25°C. From these results, the additivity principle proposed by Savage and Wood was used to get the Gibbs free energy and enthalpies of interaction for the ether-ether and ether-methylene groups. Because of the limited number of measurements, the interaction parameters were not determined with great precision. Nevertheless, the standard errors for the predicted enthalpies and Gibbs free energies are quite reasonable. The signs and magnitudes are similiar to those determined for other polar groups.     

Thermodynamics of binary mixtures: excess gibbs free energies of 1,2-Dibromoethane mixtures with benzene,cyclohexane, carbon tetrachloride and dioxane at 20°C

The excess Gibbs free energies of 1,2-dibromoethane mixtures with benzene, cyclohexane, carbon tetrachloride and dioxane have been determined by a static vapour pressure method at 20°C. The results have been analysed in the light of the current theories of solutions due to Prigogine and Flory. Both the theories fail to fit the results with useful accuracy.     

Excess Gibbs free energies at several temperatures and excess enthalpies and volumes at 298.15 K of butanenitrile with 2-methyl-1-propanol or 2-methyl-2-propanol

Vapour pressures of butanenitrile +2-methyl-1-propanol or +2-methyl-2-propanol at several temperatures between 278.15 and 323.15 K were measured by a static method. Excess molar enthalpies and volumes were also measured at T = 298.15 K. Reduction of the vapour pressures to obtain activity coefficients and excess molar Gibbs free energies was carried out by fitting the vapour pressure data to the Redlich-Kister correlation according to Barker's method. Azeotropic mixtures with a minimum boiling temperature were observed over the whole temperature range, except for 2-methyl-2-propanol at T = 323.15 K.     

Molar excess free energy of mixing of 1-propanol or 2-propanol with cyclohexane at 298.15 and 308.15 K in terms of association model with a Flory contribution term

Excess molar Gibbs free energies of mixing for 1-propanol or 2-propanol + cyclohexane over the whole composition range at 298.15 and 308.15 K have been calculated from vapour pressure data measured by static method. The data have been analysed in terms of a Mecke-Kempter association model with a Flory contribution term.     

Freezing temperatures of aqueous solutions of hexamethylenetetramine with polyols,amides, and ethers

Freezing temperatures of dilute aqueous solutions of hexamethylenetetramine and mixtures of hexamethylenetetramine with myo-inositol, d-mannitol, cyclohexanol, formamide, acetamide, 1,4-dioxane, and 1,3,5-trioxane have been measured. These data yield pairwise molecular Gibbs energies of interaction between the molecules in an aqueous solution. Using the additivity principle, the results also yield the pairwise functional group Gibbs energies of interaction in an aqueous solution for the amine nitrogen with itself and with the hydroxyl, amide, ether, and methylene groups.     

Isothermal vapour–liquid equilibrium for cyclic ethers with 1-chloropentane

Isothermal vapour–liquid equilibrium measurements for mixtures containing cyclic ethers: tetrahydrofuran, tetrahydropyran, 1,3-dioxolane or 1,4-dioxane and 1-chloropentane at the temperatures of 298.15, 313.15 and 328.15 K are reported. The thermodynamic consistency of the VLE measurements was satisfactorily checked with the van Ness method. Activity coefficients were correlated with Wilson, NRTL, and UNIQUAC equations. The calculated excess Gibbs functions for tetrahydrofuran and tetrahydropyran are negative over the whole composition range while for 1,3-dioxolane and 1,4-dioxane the excess Gibbs functions are positive.     

Isothermal (vapour + liquid) equilibria and excess Gibbs free energies in some binary (cyclopentanone + chloroalkane) mixtures at temperatures from 298.15 K to 318.15 K

The vapour pressures of binary (cyclopentanone + 1-chlorobutane, +1,3-dichloropropane, and +1,4-dichlorobutane) mixtures, were measured at the temperatures of (298.15, 308.15, and 318.15) K. The vapour pressures vs. liquid phase composition data have been used to calculate the excess molar Gibbs free energies G^E of the investigated systems, using Barker’s method. Redlich–Kister, Wilson and NRTL equations, taking into account the vapor phase imperfection in terms of the second virial coefficient, have represented the G^E values. No significant difference between G^E values obtained with these equations has been observed.     

Thermodynamic functions for the systems 1-butanol, 2-butanol,andt-butanol + cyclohexane

The following properties of mixtures of the butanols with cyclohexane were measured over the whole range of composition: 1-butanol+cyclohexane and 2-butanol+cyclohexane; excess enthalpies at 15, 25, 35 and 45°C, excess volumes at 25 and 45°C, activity coefficients and excess Gibbs free energies at 45°C. 2-Methylpropan-2-ol (tertiary butanol)+cyclohexane; excess enthalpies at 26, 35, and 45°C, excess volumes at 26 and 45°C, activity coefficients and excess Gibbs free energies at 45°C. From these data, activity coefficients at the temperatures of the excess enthalpy measurements below 45°C have been computed, as a source of test data for models of alcohol association through hydrogen bonding.     

Vapour—liquid equilibrium in binary systems formed by acetonitrile, 2-butanone and 1,2-dichloroethane

Isothermal vapour—liquid equilibria have been determined for 2-butanone + acetonitrile at 333.67 K, and for 2-butanone + 1,2-dichloroethane and acetonitrile + 1,2-dichloroethane at 333.15 K using a dynamic method. The apparatus used in these studies for the precise measurement of complete vapour—liquid equilibrium data is described and the reliability and accuracy of the measured data are considered in terms of the activity coefficients and of the dependences of the molar excess Gibbs energies on composition. Experimental inaccuracies are estimated for statistical treatment of the data both in terms of correlations and in consistency tests.     

Excess Gibbs free energies and excess enthalpies for triethylamine + n-hexane,triethylamine + n-octane,and tributylamine + n-hexane at 298.15 K

Total vapour pressures have been measured by the isoteniscope method for triethylamine + n-hexane, triethylamine + n-octane, and tributylamine + n-hexane at 298.15 K. The excess Gibbs free energies G^E for the liquid phase have been calculated from the measurements; G^E is positive for the triethylamine systems and negative for the tributylamine system. The excess enthalpies H^E for these three mixtures and for tributylamine + n-octane have been measured at the same temperature. Except for tributylamine + n-hexane, all these H^E's are positive.     

Freezing temperatures of aqueous solutions of methyl formate and ethyl acetate with a variety of nonelectrolytes. Gibbs energy of interaction of the ester group with other functional groups

Freezing temperatures of dilute aqueous solutions of ethyl acetate and mixtures with myo-inositol, D-mannitol, formamide, 1,3,5-trioxane, 1,4-dioxane, acetamide, hexamethylenetetramine, and methyl formate have been measured. In addition, freezing temperatures of dilute aqueous solutions of methyl formate and mixtures with the above solutes have been measured. From these data, the pairwise molecular Gibbs energies of interaction between the molecules were calculated. Using the additivity principle, the pairwise functional group Gibbs energies of interaction were calculated for ester group interactions with a variety of other functional groups.     

Density and Speed of Sound for Binary Mixtures of a Cyclic Ether with a Butanol Isomer

Densities and speeds of sound of the binary mixtures 1,3-dioxolane + 1-butanol, 1,3-dioxolane + 2-butanol, 1,4-dioxane + 1-butanol, and 1,4-dioxane + 2-butanol have been measured at 25 and 40°C. The excess molar volumes and excess isentropic compressibility coefficients were calculated from experimental data and fitted to a Redlich–Kister polynomial function. Results were analyzed in terms of molecular interactions and compared with literature data.     

Ternary excess molar enthalpies for the mixtures of methanol and ethanol with tetrahydropyran or 1,4-dioxane at 298.15 K

Ternary excess molar enthalpies, H_m^E, at 298.15 K and atmospheric pressure measured by using a flow microcalorimeter are reported for the (methanol+ethanol+tetrahydropyran) and (methanol+ethanol+1,4-dioxane) mixtures. The pseudobinary excess molar enthalpies for all the systems are found to be positive over the entire range of compositions. The experimental results are correlated with a polynomial equation to estimate the coefficients and standard errors. The results have been compared with those calculated from a UNIQUAC associated solution model in terms of the self-association of alcohols as well as solvation between unlike alcohols and alcohols with tetrahydropyran or 1,4-dioxane. The association constants, solvation constants and optimally fitted binary parameters obtained solely from the pertinent binary correlation predict the ternary excess molar enthalpies with an excellent accuracy.     

Interactions in aqueous nonelectrolyte systems. Gibbs energy of interaction of the ether group with the hydroxyl group and the amide group

Freezing temperatures of dilute aqueous solutions of equimolar mixtures of 1,3,5-trioxane with myo-inositol, d-mannitol, cyclohexanol, formamide, and acetamide, and 1,4-dioxane with myo-inositol, d-mannitol, formamide, and acetamide have been measured. These data yield pairwise Gibbs energies of interactions between the molecules in an aqueous solution. Using the group additivity principle, the results also yield the pairwise functional group Gibbs energies of interaction for the ether group with the hydroxyl and amide group. These results have been combined with all available data from the literature to yield the Gibbs energy and enthalpy of interaction of amides, ethers, alcohols, and saccharides in aqueous solution.To whom correspondence should be addressed.