Thermodynamic properties for binary liquid mixtures of 1-chlorobutane+n-alkanes

Isothermal compressibilities K and isobaric thermal expansion coefficients _p have been measured at 25 and 45°C for pure components and the following binary mixtures: 1-chlorobutane+normal alkanes (n-C_n) where n=6, 8, 10, 12, 14 and 16. With these results and other thermodynamic data from literature the next mixing quantities have also been reported: (V ^E/T)_P, – (V)^E/P)_T, K _S ^v , H ^E/P)_T, (_pVT and C_v. The obtained results have been compared at 25°C with the calculated values by using the Prigogine-Flory-Patterson theory of liquid mixtures. The theory predicts the excess volume V^E and V ^E/P)_T values rather well, the C _P ^E quite poorly, while for V ^E/T)_P and V ^E/P)_T it is only predicted the trend with the chain length of the n-alkane. The last two quantities show deviations between theoretical and experimental, slightly higher in systems with longer n-alkanes than for shorter ones. Our conclusion is that a nonrigid linear molecule, like 1-chlorobutane, has a low ability as a breaker of the pure n-C_n orientation correlations, in between that which we found for toluene and p-xylene and much smaller than for cyclohexane or benzene.     

Excess volumes and isentropic compressibilities of binary mixtures of di- n -butylamine with iso-alkanols at 303.15 K

Volumes of mixing and deviations in isentropic compressibility for binary mixtures of di-n-butylamine with iso-propanol, iso-butanol and iso-pentanol were measured at 303.15 K. The excess volumes and deviations in isentropic compressibility are negative over the entire range of mole fractions in all the systems. The results point out that there is a strong H-bond interaction between unlike molecules     

Excess molar volumes and deviation in viscosities of binary liquid mixtures of acrylic esters with hexane-1-ol at 303.15 and 313.15 K

Densities and viscosities for the four binary liquid mixtures of methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate with hexane-1-ol at temperatures 303.15 and 313.15 K and at atmospheric pressure were measured over the entire composition range. These values were used to calculate excess molar volumes and deviation in viscosities which were fitted to Redlich–Kister polynomial equation. Recently proposed Jouyban Acree model was also used to correlate the experimental values of density and viscosity. The mixture viscosities were correlated by several semi-empirical approaches like Hind, Choudhary–Katti, Grunberg–Nissan, Tamura and Kurata, McAllister three and four body model equations. A graphical representation of excess molar volumes and deviation in isentropic compressibility shows positive nature whereas deviation in viscosity shows negative nature at both temperatures for all four binary liquid mixtures. Positive values of excess molar volumes show that volume expansion is taking place causing rupture of H-bonds in self associated alcohols. The results were discussed in terms of molecular interactions prevailing in the mixtures.     

Thermodynamic properties of binary mixtures containing alkanenitriles. II. Excess volumes of alkanenitriles + 1-chloroalkanes

Excess molar volumes of twelve binary alkanenitrile + 1-chloroalkane mixtures (ethanenitrile, propanenitrile or butanenitrile + 1-chlorobutane, + 1-chloropentane, + 1-chlorohexane or + 1-chlorooctane) have been measured using a vibrating-tube densimeter. Excess volumes for these mixtures are positive except for butanenitrile + 1-chlorobutane.     

Excess molar volumes of binary mixtures of γ-butyrolactone and a glycol at 303.15 K

Excess molar volumes at 303.15 K for the binary mixture of ethylene glycol+, diethylene glycol+, triethylene glycol+ and tetraethylene glycol+ γ-butyrolactone were determined from precise density measurements over the whole mole fraction range. The excess molar volumes are positive over the whole mole fraction range for ethylene glycol and diethylene glycol systems. For triethylene glycol and tetraethylene glycol systems, V^E curves are sigmoid with a positive lobe at low mole fraction of glycol and a negative lobe at high mole fraction. The excess molar volumes V^E, results are interpreted qualitatively in terms of several opposing effects.     

Excess volumes of ternary mixtures of N,N-dimethylformamide-diethyl ketone-1-alkanols at 303.15K

Volume changes on mixing of ternary liquid mixtures of N,N-dimethylformamide and diethyl ketone with 1-alkanols have been measured as a function of composition at 303.15 K. The alkanols include 1-propanol, 1-butanol, 1-pentanol and 1-hexanol. The measured V^E values are negative in the mixtures of N,N-dimethylformamide, diethyl ketone and 1-propanol, or 1-butanol. The V^E data exhibits an inversion in sign in the mixture containing 1-pentanol and positive excess volumes are observed in the mixture containing 1-hexanol. The measured data are compared with predicted values based upon empirical relations. The excess volume for the binary mixture of N,N-dimethylformamide with diethyl ketone has been measured over the entire range of composition at 303.15 K. The V^E values are negative for the binary mixture.     

Thermodynamic and transport properties of binary liquid acid—base mixtures. Part 1

Densities and viscosities were determined at five different temperatures for the systems quinoline (Q) with: phenol (P); ortho-chlorophenol (CP); and meta-cresol (MC). From the experimental results the excess volumes, excess viscosities, partial molar excess volumes and the partial molar volumes were calculated. From the dependency of viscosity on temperature, the thermodynamic parameters of activation of flow were also calculated and these results were discussed in terms of the type of interaction between the two components in solution.     

Excess heat capacities and excess volumes of binary liquid mixtures of chloroform with cyclic ethers at 298.15 K

Molar excess heat capacities at constant pressure, C^E_p, of binary liquid mixtures chloroform + oxolane, chloroform + 1,3-dioxolane, chloroform + oxane, and chloroform + 1,4-dioxane have been determined at 298.15 K from measurements of volumetric heat capacities in a Picker flow microcalorimeter. A precision of ±0.04 J K^?1 mole^? was achieved by using the stepwise procedure. Experimental molar excess heat capacities are compared with values derived from H^E results at different temperatures. Excess molar volumes, V^E, for the same systems at 298.15 K have been determined by measuring the density of the pure liquids and solutions with a high-precision digital flow densimeter.     

Excess heat capacities and excess volumes of binary liquid mixtures of 1,1,1,-trichloroethane with cyclic ethers at 298.15 K

Measurements of volumetric heat capacities at constant pressure, C_p/V (V being the molar volume), at 298.15 K, of the binary liquid mixtures 1,1,1-trichloroethane + oxolane, +1,3-dioxolane, +oxane, +1,3-dioxane, and +1,4-dioxane were carried out in a Picker-type flow microcalorimeter. Molar heat capacities at constant pressure. C_p, and molar excess heat capacities, C^E_p, were calculated from these results as a function of the mole fraction. C^E_p values for these systems are positive and the magnitude depends on the size of the cycle and on the relative position of the oxygen atoms in the cyclic diethers. The precision and accuracy for C^E_p are estimated as better than 2%. Molar excess volumes, V^E, for the same systems, at 298.15 K, have been determined from density measurements with a high-precision digital flow densimeter. The experimental results of V^E and C^E_p, are interpreted in terms of molecular interactions.     

Excess molar volumes and viscosities of binary mixtures of 1,2-diethoxyethane with chloroalkanes at 298.15 K

Excess molar volumes (V _m ^E ) and viscosities (η) of the binary mixtures of 1,2-diethoxyethane with di-, tri- and tetrachloromethane have been measured at 298-15 K and atmospheric pressure over the entire mole fraction range. The deviations in viscosities (δlnη) and excess energies of activation (δG*^E) for viscous flow have been calculated from the experimental data. The Prigogine-Flory-Patterson (PFP) model has been used to calculateV _m ^E , and the results have been compared with experimental data. The Bloomfield and Dewan model has been used to calculate viscosity coefficients and these have also been compared with experimental data for the three mixtures. The results have been discussed in terms of dipole-dipole interactions between 1,2-diethoxyethane and chloroalkanes and their magnitudes decreasing with the dipole character of the molecules. A short comparative study with results for mixtures with polyethers and chloroalkanes is also described.     

Excess volumes of chlorobenzene and bromobenzene with some chloroethanes at 303.15 and 313.15 K

Volume changes on mixing for the binary systems formed by chlorobenzene with 1,2-dichloroethane, 1,1,1-trichloroethane and 1,1,2,2-tetrachloroethane, and by bromobenzene with 1,2-dichloroethane, 1,1,1-trichloroethane and 1,1,2,2-tetrachloroethane, have been measured as functions of composition at 303.15 and 313.15 K. The measured excess volumes are positive over the entire range of composition for the binary systems chlorobenzene + 1,2-dichloroethane and bromobenzene + 1,2-dichloroethane at 303.15 K, and for chlorobenzene + 1,1,2,2-tetrachloroethane at 313.15 K. The measured volumes V^E are negative over the entire composition range for the remaining systems, except for the system chlorobenzene + 1,1,2,2-tetrachloroethane at 303.15 K, where an inversion of the sign of V^E is observed over part of the concentration range.     

Excess volumes for binary liquid mixtures of trichloroethylene with anisole,pyridine, quinoline and cyclohexane at 298.15 and 308.15 K

Dilatometric measurements of excess volumes V^E have been made for binary liquid mixtures of trichloroethylene (CHClCCl₂) with anisole, pyridine, quinoline and cyclohexane at 298.15 and 308.15 K. At both temperatures, and values of V^E have been found to be slightly negative for CHClCCl₂ + anisole, CHClCCl₂ + pyridine, highly negative for CHClCCl₂ + quinoline, and highly positive for CHClCCl₂ + cyclohexane. The negative values of V^E for the systems CHClCCl₂ + anisole, CHClCCl₂ + pyridine, and CHClCCl₂ + quinoline, have been explained as due to the existence of specific interaction of CHClCCl₂ with anisole, pyridine and quinoline in the liquid state.     

Excess molar volumes and viscosities of binary mixtures of cyclohexane and n-alkane at 298.15 K

Awwad, A.M. and Salman, M.A., 1986. Excess molar volumes and viscosities of binary mixtures of cyclohexane and n-alkane at 298.15 K. Fluid Phase Equilibria, 25: 195-208.Excess molar volumes, viscosities, excess molar viscosities, and excess molar activation energies of viscous flow were determined for binary mixtures of cyclohexane + n-pentane, + n-hexane, + n-heptane, + n-octane, + n-nonane, + n-decane, + n-dodecane, + n-tetradecane and + n-hexadecane at 298.15 K. The effect of orientational order of n-alkane on solution molar volumes and viscosities is investigated as well as the adequacy of the Flory theory and free volume theories used to predict solution molar volumes and viscosities. For longer n-alkanes V^E, η^E and ΔG*^E are positive and associated with the orientational order.     

Thermodynamic properties of binary mixtures combining two pyridinium-based ionic liquids and two alkanols

Densities and speeds of sound have been determined for the binary mixtures containing an ionic liquid (1-butyl-3-methylpyridinium tetrafluoroborate or 1-butyl-4-methylpyridinium tetrafluoroborate) and an alkanol (methanol or ethanol) over the temperature range (293.15 to 323.15) K. Excess volumes and excess isentropic compressibilities have been calculated from density and speed of sound data and correlated. All the mixtures show negative values for these excess properties. Furthermore, the isothermal (vapour + liquid) equilibrium has been measured at T = (303.15 and 323.15) K, and the corresponding activity coefficients and excess Gibbs functions have been obtained. In this case, positive excess Gibbs functions have been found. We have carried out an exhaustive interpretation of the experimental results in terms of structural and energetic effects taking also into account the thermodynamic information of pure compounds. Finally, in order to study the influence of both, the presence and the position of methyl group in the cation, we have compared the results of these systems with those obtained for the mixtures formed by 1-butylpyridinium tetrafluoroborate and methanol or ethanol.     

Thermodynamics of weak interactions: Excess enthalpies of some binary bromoform mixtures

Excess enthalpies of bromoform + toluene, +o-xylene +m-xylene and +p-xylene have been determined at 308.15 K. These compounds have been examined for Barker's theory in order to understand the magnitude and nature of various interactions between the components of these mixtures. It has been concluded that the H-atom and one bromine atom of bromoform interact with the π cloud of the aromatic ring. These conclusions have been supplemented by n.m.r. studies. An approximate distance of the bromoform proton from the plane of the aromatic ring has also been calculated and examined in the light of the proposed geometry of the molecular complexes. Equilibrium constants for the complexations reaction have also been determined.     

Excess functions of binary liquid mixtures at varying pressures

The present investigation comprises of theoretical evaluation of the thermodynamic excess functions, viz. excess energy and excess entropy for five binary liquid mixtures at varying pressures. A statistical mechanical theory, along with the Schaaff’s equation for sound velocity was used in order to calculate the above-mentioned excess properties directly through the use of the experimental data of ultrasonic velocity and density only.     

Thermodynamic studies of some binary mixtures containing a self-associated component. II. Excess volumes of some mixtures of tetrahydrofuran with alcohols

Excess volumes of mixing, V^E, for binary mixtures of tetrahydrofuran (THF) with methanol, ethanol, n-butanol, tert-butanol, 2-bromoethanol and ethylene glycol have been determined from the experimental density measurements at 298.15 K over the entire composition range. The V^E data follow the order: ethylene glycol < 2-bromoethanol < methanol < ethanol < n-butanol < tert-butanol. The results have been explained in terms of self-association and the hydrogen bond-donating abilities of alcohols.     

Excess thermodynamic properties of binary liquid mixtures containing cyclohexylamine at 30°C

The excess volumes of mixing of cyclohexylamine with n-hexane, n-heptene, n-octane, n-nonane, benzene, toluene, nitrobenzene, chlorobenzene and bromobenzene have been measured at 30°C. For all systems except for n-hexane, V ^E is positive over the entire mole fraction range. For the n-hexane mixtures, a sigmoid curve is obtained with negative V ^E at high mole fraction of amine.