Excess molar volumes of (ethyl formate or ethyl acetate + an isomer of hexanol) at 298.15 K

Excess molar volumes V_m^E were determined over the entire composition range at 298.15 K for ethyl formate or ethyl acetate + hexan-1-ol, +2-methylpentan-1-ol, +3-methylpentan-2-ol, +2-methylpentan-3-ol, +3-methylpentan-3-ol, +2-methylpentan-2-ol, +4-methyl-pentan-2-ol, and +hexan-2-ol. Excess volumes were determined from density measurements made with a vibrating-tube densimeter. The V_m^E values were all positive, decreasing with the n value of the ester: C_n?1H_2n?1CO₂C₂H₅.     

Excess enthalpies of 2-propanol + cyclohexane and 2-propanol + benzene + cyclohexane at 298.15 K

With an isothermal dilution calorimeter excess enthalpies have been determined at 298.15 K for 2-propanol + cyclohexane and 2-propanol + benzene + cyclohexane mixtures. The results are fitted with an associated-solution model. Predicted excess enthalpies for the ternary mixture agree well with the experimental results.     

Liquid-liquid equilibria of (cyclohexane + acetonitrile + methylcyclohexane + toluene) and of {(acetonitrile + methylcyclohexane) + benzene or + toluene or + cyclohexane or + chlorobenzene} at 298.15 K

Tie-line results at 298.15 K and atmospheric pressure are reported for (cyclohexane + acetonitrile + methylcyclohexane + toluene) and for {(acetonitrile + methylcyclohexane) + benzene or + toluene or + cyclohexane or + chlorobenzene). The extended UNIQUAC and UNIQUAC equations are used to correlate binary vapour-liquid equilibria and mutual solubilities for 10 mixtures constituting the ternary mixtures and to predict the ternary and quaternary liquid-liquid equilibria by use of only binary parameters.     

Excess volumes,enthalpies, and Gibbs free energies for mixtures of benzene + p-xylene

Excess thermodynamic properties of benzene + p-xylene have been obtained at 288.15, 298.15, and 313.15 K. V^E was obtained with a Sodev vibrating-tube densimeter, H^E with a Picker flow microcalorimeter, and G^E was calculated from solid + liquid phase equilibria measurements. Measurements were also made of the heat capacity of liquid p-xylene as a function of temperature using the heat-capacity unit of the Picker flow microcalorimeter.     

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.     

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 enthalpies and complex formation of acetonitrile with acetone,chloroform, and benzene

Excess enthalpies of binary systems of acetonitrile—acetone, chloroform—acetone and chloroform—benzene, and ternary systems of acetonitrile—chloroform—acetone and acetonitrile—chloroform—benzene are reported at 25°C. The results are analyzed with thermodynamic association theory for complex ternary liquid mixtures. The theory involves two types of self-association of acetonitrile, formation and binary complexes for component pairs of a ternary system, and a nonspecific interaction term expressed by the NRTL equation between various chemical species.     

Excess enthalpies of some aromatic aldehydes in n-hexane, n-heptane and benzene

Calorimetric measurements of molar excess enthalpies, H^E, at 298.15 K, of mixtures containing aromatic aldehydes of general formula C₆H₅(CH₂)_mCHO (with m = 0, 1 and 2) + n-hexane, n-heptane or benzene are reported, together with the values of H^E at equimolar composition compared with the corresponding values of H^E for the aromatic ketones in the same solvents. The experimental results clearly indicate that the intermolecular interactions between the carbonyl groups (CHO) are influenced by the intramolecular interactions between the carbonyl and phenyl groups, particularly for the mixtures containing benzaldehyde.     

Heat capacities and volumes of interaction between mixtures of alcohols in water at 298.15 K

The heat capacities and densities of mixtures of aqueous solutions of normal alcohols (methanol to n-butanol) and t-butanol were measured at 298.15 K at low molalities. The results were used to calculate the thermodynamic pair and triplet interaction parameters between solutes for heat capacities and volumes. The pair parameters are approximately a linear function of the total number of carbon atoms of the two solutes. The enthalpic pair and triplet interaction parameters for (ROH + H₂O) are also reported. The temperature dependence of the pair parameters for Gibbs free energies, enthalpies, entropies, heat capacities, and volumes are discussed in terms of structural changes in the aqueous solutions.     

Excess heat capacities of binary mixtures of carbon tetrachloride with n-alkanes at 298.15 K

A Picker flow microcalorimeter was used to determine molar excess heat capacities C_P^E at 298.15 K for mixtures of carbon tetrachloride + n-heptane, n-nonane, and n-decane. The excess heat capacities are negative in all cases. The absolute value |C_P^E| increases with increasing chain length of the alkane. A formal interchange parameter, c_P12, is calculated and its dependence on n-alkane chain length is discussed briefly in terms of molecular orientations.     

Vapor—liquid equilibria for the ternary Ethanol—2-butanone—benzene system at 298.15 K

Vapor—liquid equilibrium data for the ternary ethanol—2-butanone—benzene system and its constituent binary systems at 298.15 K are presented. The results are correlated with the Wilson, original and modified UNIQUAC equations and the UNIFAC group contribution method.     

The apparent molar heat capacities and volumes of aqueous NaCl from 0.01 to 3 mol kg−1 in the temperature range 274.65 to 318.15 K

The heat capacities per unit volume of aqueous solutions of NaCl were measured with a flow microcalorimeter. The molality and temperature range covered were 0.01 to 3 mol kg^?1 and 274.65 to 318.15 K. The derived apparent molar heat capacities C₂, φ, when extrapolated to infinite dilution, give standard partial molar heat capacities C₂^o which are in excellent agreement with those of Criss and Cobble. The excess apparent molar heat capacities (C₂, φ - C₂^o) can be used to predict the temperature dependence of (H₂, φ - H₂^o), the excess apparent molar enthalpy. The calculated values of ΔH₂, φ agree within experimental uncertainty with the integral enthalpies of dilution of Ensor and Anderson and of Messikomer and Wood up to 323.15 K. Above this temperature significant differences are observed. The densities of the solutions were also remeasured in the same range of temperature and molality with a flow densimeter, and the derived apparent molar volumes agree with the literature values.     

The thermodynamic properties of acetals+heptane mixtures at 298.15 K

Excess enthalpies and excess volumes were determined at 298.15 K for: dimethoxymethane+heptane, diethoxymethane+heptane, 1,1-dimethoxyethane+heptane, 1,1-diethoxyethane+heptane, 2,2-dimethoxypropane+heptane and 1,1-diethoxypropane+heptane.     

Excess enthalpies of (methyl propanoate or methyl pentanoate + 1-alkanol) at 298.15 K

The excess molar enthalpies H_m^E of methyl propanoate or methyl pentanoate + 1-butanol, + 1-hexanol, + 1-octanol, and + 1-decanol have been determined experimentally at 298.15 K using a Calvet microcalorimeter. For all these mixtures H_m^E > 0; the values increase with the chain length of the alkanol but decrease as the ester chain lengthens.     

Electrochemical bromination of benzene,toluene and xylene in acetonitrile

A method for the preparation of bromo derivative compounds of aromatics is proposed and the electrodic process involved in the bromination on the third wave of the system Br^?/aromatic substrate in acetonitrile is discussed.