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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 .     

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.     

Isobaric vapour–liquid equilibria for mixtures containing halogenated hydrocarbons at atmospheric pressure: I. Binary mixtures of trichloromethane+1,2-dichloroethane, 1,2-dichloroethane+1,1,2,2-tetrachloroethane,trichloromethane+1,1,2,2-tetrachloroethane and n-heptane+1,1,2,2-tetrachloroethane

Vapour–liquid equilibria at atmospheric pressure for mixtures of trichloromethane+1,2-dichloroethane, 1,2-dichloroethane+1,1,2,2-tetrachloroethane, trichloromethane+1,1,2,2-tetrachloroethane and n-heptane+1,1,2,2-tetrachloroethane have been determined. These have been shown to be thermodynamically consistent.     

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.     

Total vapour pressure and excess Gibbs energy for binary mixtures of 1,1,2,2-tetrachlorethane or tetrachloroethene with cyclohexane at nine temperatures

Vapour pressures of (cyclohexane + 1,1,2,2-tetrachloroethane (TCANE)) or (cyclohexane + tetrachloroethene (TCENE)) mixtures at nine temperatures between 283.15 and 323.15 K were measured by a static method. The reduction of the vapour pressures to obtain activity coefficients and excess molar Gibbs energies was carried out by fitting the vapour-pressure data to the Redlich–Kister polynomial according to Barker’s method. A comparative analysis about the thermodynamic behaviour of both systems is performed, taking into account the resonance effect in tetrachloroethene. For 1,1,2,2-tetrachloroethane + cyclohexane mixtures, we have tested the DISQUAC model observing that reproduces satisfactorily the G^E experimental values at all temperatures.     

Molar heat capacity of binary liquid mixtures: 1,2-dichloroethane + cyclohexane and 1,2-dichloroethane + methylcyclohexane

The molar heat capacity at constant pressure, C_P, of the two binary liquid mixtures 1,2-dichloroethane + cyclohexane and 1,2-dichloroethane + methylcyclohexane were determined at 298.15 K from measurements of the volumetric heat capacity, C_P/V, in a Picker flow microcalorimeter (V is the molar volume). For the molar excess heat capacity, C_P^E, the imprecision of the adopted stepwise procedure is characterized by a standard deviation of about ± 0.05 J K^?1 mole^?1, which amounts to ca. 3% of C_P^E. Literature data on ultrasonic velocities, on molar volumes, and on coefficients of thermal expansion were used to calculate the molar heat capacity at constant volume, C_v, and the isothermal compressibility, β_T, of the pure substances, as well as the corresponding excess quantities C_V^E and (Vβ_T)^E of the binary mixture 1,2-dichloroethane + cyclohexane. A preliminary discussion of our results in terms of external and internal rotational behavior (trans-gauche equilibrium of 1,2-dichloroethane) is presented.     

Response surface optimisation applied to a headspace-solid phase microextraction-gas chromatography-mass spectrometry method for the analysis of volatile organic compounds in water matrices

A new method for the simultaneous determination of 12 volatile organic compounds (trans-1,2-dichloroethene, 1,1,1-trichloroethane, benzene, 1,2-dichloroethane, trichloroethene, toluene, 1,1,2-trichloroethane, tetrachloroethene, ethylbenzene, m-, p-, o-xylene) in water samples by headspace solid phase microextraction (HS–SPME)–gas chromatography mass spectrometry (GC–MS) was described, using a 100?µm PDMS (polydimethylsiloxane) coated fibre. The response surface methodology was used to optimise the effect of the extraction time and temperature, as well as the influence of the salt addition in the extraction process. Optimal conditions were extraction time and temperature of 30?min and ?20°C, respectively, and NaCl concentration of 4?mol?L^?1. The detection limits were in the range of 1.1?×?10^?3–2.3?µg?L^?1 for the 12 volatile organic compounds (VOCs). Global uncertainties were in the range of 4–68%, when concentrations decrease from 250?µg?L^?1 down to the limits of quantification. The method proved adequate to detect VOCs in six river samples.     

Isobaric vapour–liquid equilibria for binary mixtures of 1,2-dibromoethane with 1,2-dichloroethane,trichloromethane, and 1,1,2,2-tetrachloroethane at atmospheric pressure

Vapour–liquid equilibria at atmospheric pressure have been determined for binary mixtures of 1,2-dibromoethane + 1,2-dichloroethane, +trichloromethane, and +1,1,2,2-tetrachloroethane. These have been shown to be thermodynamically consistent.     

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 Volumes of Binary Mixtures of Benzene + 1-Alkanols at 303.15 K

Abstract

Excess molar volumes V^E of binary mixtures of benzene + 1-propanol, + 1-butanol, + 1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-nonanol and 1-decanol were measured at 303.15 K. The V^E values are positive over the entire range of composition for these mixtures. The results are discussed in terms of intermolecular interactions.     

Preferential Solvation in Mixed Solvents

The Kirkwood–Buff integrals and the volume-corrected preferential solvation parameters for the first solvation shell of binary mixtures of tetrahydrofuran with many organic solvents, calculated from reported thermodynamic data at the temperatures for which these data were available, are reported. The co-solvents include c-hexane, methyl-c-hexane, n-heptane, i-octane, benzene, toluene, ethylbenzene, 1-chlorobutane, dichloromethane, 1,2-dichloroethane, chloroform, 1,1,1-trichloroethane, tetrachlorom-ethane, tetrachloroethene, hexafluoro benzene, ethanol, 1-propanol, 2-propanol, dibutyl ether, acetic acid, acetone, dimethyl sulfoxide, tetramethylene sulfone (sulfolane), acetonitrile, pyrrolidine, and triethylamine. The preferential solvation parameters of these mixtures are discussed in terms of the interactions that occur.