Volumetric and Ultrasonic Behaviour of 1-Heptanol with Some Chloroethanes and Chloroethenes at 303.15 K

Abstract

Excess volumes (V^E ) and deviations in isentropic compressibilities (K_s ) were reported over the entire mole fraction range for mixtures of 1-heptanol with 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethene and tetrachloroethene, at 303.15 K. The values of V^E and K_s are positive for the systems, 1-heptanol + 1,2-dichloroethane, +1,1,1-trichloroethane, + trichloroethene and + tetrachloroethene. Inversion in sign of V^E and K_s from positive to negative is observed in mixtures of 1-heptanol with 1,1,2,2-tetrachloroethane. The experimental data were used to explain the effect of successive chlorination and unsaturation of ethane molecule on V^E and K_s .     

Densities and Viscosities of Binary Mixtures of <Emphasis Type="Italic">m</Emphasis>-Cresol with Some Chlorohydrocarbons

Densities and viscosities of the binary mixtures of m-cresol with 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane and tetrachloroethylene were measured at 303.15, 313.15 and 323.15 K. The measured results are used to compute the excess volumes (V^E), deviations in viscosity (Δη) and excess Gibbs energy for activation of flow (ΔG^E). The excess volumes, deviations in viscosity, and Gibbs energies for activation of flow are fitted to a polynomial-type equation suggested by Scharlin et al. [J. Chem. Thermodyn. 34, 927 (2002)] and are discussed in general terms.     

Bubble points of the binary mixtures formed by ethylbenzene with some chloroaliphatics and substituted benzenes at p = 94.7 kPa

Bubble points at a pressure of 94.7 kPa, over the entire composition range are measured for the binary mixtures formed by ethylbenzene with: 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and nitrobenzene making use of a Swietoslawski type ebulliometer. The liquid phase composition versus temperature measurements are found to be well represented by the Wilson model.     

Refractive Indices Measurement and Correlation for Selected Binary Systems of Various Polarities at 25 °C

New refractive indices at 25 °C were measured and are reported here for 19 binary mixtures of pentan-3-one+1,2-dichloroethane, +1,3-dichloropropane, +1,4-dichlorobutane, +trichloromethane, +1,1,1-trichloroethane, +1,1,2,2-tetrachloroethane; cyclopentanone+1-chlorobutane, +1,1,2,2-tetrachloroethane; cyclohexanone+1,1,2,2-tetrachloroethane; 5-chloro-2-pentanone+n-hexane, +toluene, +ethylbenzene; nitromethane+trichloromethane; and nitromethane or nitroethane, +1,2-dichloroethane, +1,3-dichloropropane, +1,4-dichlorobutane. The experimental refractive index deviations from linear mixing behavior have been evaluated and correlated consistently with the 3-parameter Redlich–Kister equation with good results. The molar refraction was also examined for the systems including pentan-3-one, cyclopentanone, cyclohexanone and 5-chloro-2-pentanone for which densities and excess molar volumes are available from previous works. Different theoretical (n, ρ) mixing rules were tested for these systems. The excess Gibbs energy G ^E and excess enthalpy H ^E values were considered together with the excess molar volumes V ^E, excess refractive indexes $ n_{\text{D}}^{\text{E}} $ , molar refraction R and excess molar refractions R ^E on mixing in the discussion of the influence of the alkyl chain length or of the nature of the second component in the mixture in terms of molecular interactions.     

Physico-chemical properties of binary mixtures of 1-butanol with chloroethanes or chloroethenes at 298.15 K

The densities ρ, speeds of sound u, and viscosities η, of pure 1-butanol, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, and tetrachloroethylene and those of their binary mixtures have been measured at 298.15 K and atmospheric pressure over the entire range of compositions. Excess molar volumes V ^E, viscosity deviations Δη, deviation in compressibilities Δκ_s and excess Gibbs energy of activation G*^E, were obtained from the experimental results and those were fitted to Redlich–Kister's type function in terms of mole fractions. Viscosities, speeds of sound and isentropic compressibilities of the binary mixtures have been correlated by means of several empirical and semi-empirical equations. The experimental data are analysed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Boiling temperature measurements on the binary mixtures formed by acetonitrile with some chloroethanes and chloroethylenes at 94.6 kPa

Boiling temperatures at 94.6 kPa, over the entire composition range are measured for the binary mixtures, formed by acetonitrile with 1,2,-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene and tetrachloroethylene, making use of a Swietoslawski type ebulliometer. The liquid phase composition versus temperature measurements are found to be well represented by the Wilson model.     

Boiling temperature measurements on the binary mixtures formed by dimethyl carbonate with some chloroethanes and chloroethylenes at 95.8 kPa

Boiling temperatures at 95.8 kPa, over the entire composition range are measured for the binary mixtures formed by dimethyl carbonate with 1,2,-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene and tetrachloroethylene—making use of a Swietoslawski-type ebulliometer. The liquid phase composition versus temperature measurements are found to be well represented by the Wilson model.     

Enthalpies molaires de melange a T=303,15 K des systemes binaires liquides de cyclohexanone avec chloroethanes

Experimental heats of mixing Δ_mix H at 303.15 K and normal atmospheric pressure were obtained for the binary mixtures cyclohexanone+(1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane,1,1,2,2-tetrachloroethane or pentachloroethane), using a Calvet microcalorimeter. The Δ_mix H values for all the mixtures were negative, indicated that important interaction occur between the ketoxy group and chloroalcane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Volumetric behaviour of binary liquid mixtures of dimethylsulphoxide with substituted benzenes at 303.15 k

Excess molar volumes (V ^E ) for binary mixtures of dimethyl sulphoxide (DMSO) with substituted benzenes have been measured at 303.15?K. The substituted benzenes include toluene, ethylbenzene, chlorobenzene, bromobenzene and nitrobenzene. The measured V ^E data is positive for the mixtures of DMSO with nitrobenzene and is completely negative over the entire composition range in the mixtures of toluene, ethylbenzene and chlorobenzene and an inversion in sign is observed in the bromobenzene system. The experimental results are analysed in terms of intermolecular interactions and effect of substitutents on benzene ring between unlike molecules.     

Vapor–liquid equilibria of selected binary mixtures formed by 2-methylpyrazine at 94.7 kPa

Vapor–liquid equilibria at 94.7?kPa, over the entire composition range are obtained for the binary mixtures formed by 2-methylpyrazine with 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene, tetrachloroethylene, N,N-dimethylformamide and N,N-dimethylacetamide. A Swietoslawski type ebulliometer is used to measure the bubble point temperatures necessary to determine the vapor–liquid equilibria. The Wilson equation is used to represent measured liquid phase composition versus temperature data.     

Excess enthalpies of di-n-butyl ether and methyl-tert-butyl ether with chloroalkanes at 26.9°C

Excess enthalpies of di-n-butyl ether and methyl-tert-butyl ether with trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane have been determined at 26.9°C. Excess enthalpies H _m ^E for all (except di-n-butyl ether + dichloroethane and + trichloroethane) of the binary mixtures are found to be negative. Enthalpies are generally more negative for mixtures containing methyl-tert-buthyl ether. The results have been compared with our earlier data on tetrahydrofuran and tetrahydropyran with chloroalkanes.     

Excess Molar Volumes and Partial Molar Volumes of Binary Mixtures Containing Diethylcarbonate with Benzene and Substituted Benzenes at 293.15 K

Densities of the binary mixtures of diethylcarbonate with benzene and substituted benzenes, namely toluene, bromobenzene, chlorobenzene and nitrobenzene have been measured as a function of the composition, at 293.15 K and atmospheric pressure using a bicapillary pycnometer with an accuracy of 4 parts in 10⁴.The calculated excess molar volumes, V ^E were correlated with Redlich-Kister equation. The excess molar volumes are negative over the entire range of composition for the systems diethylcarbonate with benzene, toluene, bromobenzene and nitrobenzene. An inversion of the sign of V ^E is observed over some concentration for mixtures of diethylcarbonate with chlorobenzene. Partial molar volumes, V_i are also evaluated and their values have been extrapolated to zero concentration to obtain the limiting value at infinite dilution, V^o _i . The numerical values of the excess molar volumes for binary mixtures decrease in the order: chlorobenzene > benzene > bromobenzene ≈ toluene > nitrobenzene. The results are explained in terms of dissociation of the self-associated solute molecules and the formation of aggregates between unlike molecules.     

Influence of chain length and degree of branching of alcohol + chlorobenzene mixtures on determination and modelling of V by CEOS and CEOS/G mixing rules

The densities of binary mixtures of (1-propanol, or 1-butanol, or 2-butanol, or 1-pentanol + chlorobenzene) have been measured at temperatures 288.15, 293.15, 298.15, 303.15, 308.15 and 313.15 K and atmospheric pressure while for the system (2-methyl-2-propanol + chlorobenzene) measurements were performed at the same pressure and temperatures 303.15, 308.15, 313.15, 318.15 and 323.15 K. All measurements were performed by means of an Anton Paar DMA 5000 digital vibrating-tube densimeter. Excess molar volumes V^E were determined and fitted by the Redlich–Kister equation. It was observed that in all cases, V^E increase with rising of temperature. The values of limiting excess partial molar volumes have been calculated, as well. The obtained results have been analysed in terms of specific molecular interactions present in these mixtures taking into consideration effect of the chain length of alcohols, degree of branching in the chain, relative position of the alkyl and OH group in an alcohol and the effect of temperature on them. In addition, the correlation of V^E binary data was performed with the Peng–Robinson–Stryjek–Vera cubic equation of state (PRSV CEOS) coupled with the van der Waals (vdW1) and CEOS/G^E mixing rule introduced by Twu, Coon, Bluck and Tilton (TCBT). Also, the possibility of cross prediction between V^E and VLE by means of the NRTL parameters of G^E model available in literature and those incorporated in the TCBT model was tested.     

Excess molar volumes of methyl tert-butyl ether with chloroalkanes at 30°C

Excess molar volumes are reported for binary mixtures of methyl tert-butyl ether with trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, or 1,1,1,2,2-pentachloroethane at 30°C over the entire composition range of the mixtures. Excess volumes for all the mixtures are found to be negative. A qualitative interpretation of the results in terms of O–H–C and Cl–O interactions is presented. The Prigogine-Flory-Patterson theory has been used to analyze the results.     

Excess molar volume and viscosity deviation for binary mixtures of polyethylene glycol dimethyl ether 250 with 1,2-alkanediols (C3–C6) at T = (293.15 to 323.15) K

In this work, density and viscosity have been determined for (polyethylene glycol dimethyl ether 250 + 1,2-propanediol, or 1,2-butanediol, or 1,2-pentanediol, or 1,2-hexanediol) binary systems over the whole concentration range at temperatures of (293.15, 303.15, 313.15, 323.15) K and atmospheric pressure. Experimental data of mixtures were used to calculate the excess molar volumes V^E, and viscosity deviations Δη. These results were fitted by the Redlich–Kister polynomial relation to obtain the coefficients and standard deviations.     

Volumetric properties of binary mixtures of alcoxyethanols with tert-butyl ethyl ether at various temperatures

Densities at 293.15, 298.15, 303.15, 308.15 and 313.15 K of the binary liquid mixtures made of tert-butyl ethyl ether with either 2-ethoxyethanol, or 2-(2-ethoxy)ethoxyethanol, or 2-[2-(2-ethoxy)ethoxy]ethoxyethanol have been measured over the whole mixture compositions. These data have been used to compute the excess molar volumes (V^E). The excess molar volumes always are negative over the entire range of composition for all the binary mixtures investigated. The changes of V^E with variations of the composition and the chain-length of the alkyl groups in the alkoxyethanol molecules are discussed in terms of possible intermolecular interactions.     

Densities, Viscosities, Speeds of Sound, FT-IR and 1H-NMR Studies of Binary Mixtures of n-Butyl Acetate with Ethanol, Propan-1-ol, Butan-1-ol and Pentan-1-ol at?298.15, 303.15, 308.15 and 313.15?K

Densities, viscosities and speeds of sound of binary mixtures of ethanol, propan-1-ol, butan-1-ol and pentane-1-ol with n-butyl acetate have been measured over the entire range of composition at temperatures of 298.15, 303.15, 308.15 and 313.15 K and atmospheric pressure. From the experimental densities, viscosities and speeds of sound, the excess molar volumes V ^E, deviations in viscosity ????, and deviations in isentropic compressibility ???? _S have been calculated. The excess molar volumes and deviations in isentropic compressibility are positive for all the binary systems studied over the whole composition, while deviations in viscosities are negative for all of the binary mixtures. The excess molar volumes, deviations in viscosity, and deviations in isentropic compressibility have been fitted to a Redlich?CKister type polynomial equation. FTIR and ¹H-NMR studies of these mixtures are also reported.     

Thermodynamic properties of binary mixtures containing 1-alkanols

Densities (ρ) of pure liquids and their mixtures have been measured at 303.15 and 313.15 K and atmospheric pressure over the entire composition range for the binary mixtures of benzylalcohol with 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol by using Rudolph Research Analytical digital densitometer (DDM-2911 model). Further, the ultrasonic sound velocities for the above said mixtures were also measured at 303.15 and 313.15 K. The measured density data were used to compute excess molar volumes (V ^E) and these were compared with the values obtained by Hwang equation. Isentropic compressibility (κ _S) and excess isentropic compressibilities (κ _S ^E ) were evaluated from experimental sound velocity and density data. Moreover, the experimental sound velocities were analyzed in terms of theoretic models namely, collision factor theory and free length theory. The experimental results were discussed in terms of intermolecular interactions between component molecules.     

Excess Volumes of 1,1,1-Trichloroethane with Normal Alkanols at 303.15 K

Abstract

New experimental data for excess volume of five binary mixtures are reported at 303.15 K. The mixtures contain 1,1,1-trichloroethane as common component and 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol as noncommon components. V^E exhibits inversion in sign in all mixtures except that containing 1-pentanol. In this mixture V^E is positive over the whole range of composition. The results have been interpreted in terms of the relative strength of structure breaking and structure making effects.     

Excess enthalpies of mixing tetrahydrofuran and tetrahydropyran with some chloroalkanes at 26.9°C

Excess enthalpies of mixing H _m ^E of tetrahydrofuran and tetrahydropyran with trichloromethane, tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane have been determined at 26.9°C and are found to be negative over the entire composition range for both sets of the ether mixtures. H _m ^E decreases in the sequence; dichloroethane > tetrachloromethane > trichloroethane > trichloromethane > tetrachloroethane. The results are explained on the basis of strong O...H-C and weak Cl...O specific interactions. Flory's theory has been used to correlate the experimental data with good agreement found between the theoretical and experimental values of H _m ^E .