Excess molar enthalpies for binary liquid mixtures of furfural with some aromatic hydrocarbons

The excess molar enthalpies H _m ^E for the binary mixtures of furfural with the aromatic hydrocarbons namely benzene, toluene, ethylbenzene and o-, m-, and p-xylenes were determined at 35°C. The values for all the mixtures studied are positive over the entire range of composition and follow the order: o-xylene>m-xylene>ethylbenzene>p-xylene>benzene>toluene. The results are discussed in terms of the unlike specific interactions present in the binary mixtures.     

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.     

正烷醇/异丙醇二元体系过量焓的测定

用LKB 2277 Bioactivity Monitor测定了一些正烷醇(甲醇到正己醇)与异丙醇二元体系在298.15K的常压过量焓H^E的数据, 对丙醇/异丙醇, 正丁醇/异丙醇和正戊醇/异丙醇还测定了308.15K和313.15K的常压过量焓数据。同时给出了关联实验结果的多项式方程的各参数。     

Vapour–liquid equilibria, azeotropic data, excess enthalpies, activity coefficients at infinite dilution and solid–liquid equilibria for binary alcohol–ketone systems

Isothermal vapour–liquid equilibria (VLE), solid–liquid equilibria and excess enthalpies have been measured for the systems cyclohexanone + cyclohexanol and 2-octanone + 1-hexanol. Additionally in this paper binary azeotropic data at different pressures for 1-pentanol + 2-heptanone and 1-hexanol + 2-octanone have been determined with the help of a wire band column. Furthermore activity coefficients at infinite dilution for methanol, ethanol, 1-butanol and 1-propanol in 2-octanone at different temperatures have been measured with the help of the dilutor technique. These data together with literature data for alcohol–ketone systems were used to fit temperature-dependent group interaction parameters for the group contribution method modified UNIFAC (Dortmund) and the group contribution equation of state VTPR.     

Experimental and theoretical study of excess molar volumes and enthalpies for the ternary mixture butyl butyrate + 1-octanol + decane at 308.15 K

This paper reports measurements on excess thermodynamic properties for the ternary system: butyl butyrate+1-octanol+decane at the temperature 308.15 K and atmospheric pressure.The binary and ternary experimental data were correlated using the Redlich-Kister and Cibulka equation, respectively. Experimental values were compared with the predictions obtained by several contribution models and several empirical equations.     

Activity coefficient at infinite dilution, azeotropic data, excess enthalpies and solid–liquid-equilibria for binary systems of alkanes and aromatics with esters

Binary azeotropic data have been measured at different pressures for ethyl acetate + heptane, methyl acetate + heptane, isopropyl acetate + hexane and isopropyl acetate + heptane by means of a wire band column. Additionally activity coefficients at infinite dilution have been determined for ethyl acetate and isopropyl acetate in decane and dodecane in the temperature range between 303.15 and 333.15 K with the help of the dilutor technique. Furthermore excess enthalpies for the binary systems methyl acetate + hexane, methyl acetate + decane, ethyl acetate + hexane and ethyl acetate + decane at 363.15 and 413.15 K have been studied with the help of isothermal flow calorimetry. Finally solid–liquid equilibria for the systems ethyl myristate + benzene and ethyl myristate + p-xylene have been investigated by a visual technique. All these data have been used for the revision and extension of the group interaction parameters of the group contribution method modified UNIFAC (Dortmund) and the group contribution equation of state VTPR. The experimental data was compared with the results predicted using the group contribution method modified UNIFAC (Dortmund) and the group contribution equation of state VTPR.     

Experimental and predicted excess molar enthalpies of some working pairs for absorption cycles

In this work, the measured excess molar enthalpies of absorption heat pump working pairs (refrigerant + absorbent), viz. water + mono-, di- and tri-ethylene glycol, water + glycerol, and ethanol + di- and tri-ethylene glycol mixtures are presented at 298.15 K and ambient pressure using a Setaram Calvet C80 calorimeter. The experimental results are represented and correlated by a Redlich–Kister type equation. Modeling of the excess enthalpies has been performed using the UNIFAC molecular group-contribution method, and UNIQUAC Gibbs energy model. In addition, the data and results are used to predict the Gibbs energy of all binary systems. This allows a preliminary evaluation of the suitability of the binary systems as heat pump working pairs.     

Excess molar volumes and excess molar enthalpies of binary mixtures for 1,2-dichloropropane + 2-alkoxyethanol acetates at 298.15 K

The excess molar volumes and excess molar enthalpies over the whole range of composition have been measured for the binary mixtures formed by 1,2-dichloropropane (1,2-DCP) with three 2-alkoxyethanol acetates at 298.15 K and atmospheric pressure using a digital vibrating-tube densimeter and an isothermal calorimeter with flow-mixing cell, respectively. The 2-alkoxyethanol acetates are ethylene glycol monomethyl ether acetate (EGMEA), ethylene glycol monoethyl ether acetate (EGEEA), and ethylene glycol monobutyl ether acetate (EGBEA). The of the mixture has been shown positive for EGMEA, ‘S-shaped’ for EGEEA, being negative at low and positive at high mole fraction of 1,2-DCP, and negative for EGBEA. All the values for the above mixtures showed an exothermic effect (negative values) which increase with increase in carbon number of the 2-alkoxyethanol acetates, showing minimum values varying from −374 J mol⁻¹ (EGMEA) to −428 J mol⁻¹ (EGBEA) around 0.54–0.56 mol fraction of 1,2-DCP. The experimental results of and were fitted to Redlich–Kister equation to correlate the composition dependence of both excess properties. In this work, the experimental excess enthalpy data have been also correlated using thermodynamic models (Wilson, NRTL, and UNIQUAC) and have been qualitatively discussed.     

Measurement of vapor–liquid equilibria (VLE) and excess enthalpies (H) of binary systems with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and prediction of these properties and γ using modified UNIFAC (Dortmund)

Vapor–liquid equilibria (VLE) and excess enthalpies (H^E) were measured for a variety of alkanes, alkenes, aromatics, alcohols, ketones and water in several ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM]⁺[BTI]⁻, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [BMIM]⁺[BTI]⁻, 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [HMIM]⁺[BTI]⁻ and 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [OMIM]⁺[BTI]⁻, covering the temperature range from 323.15 to 413.15 K. The new data were used together with the already available experimental data for imidazolium compounds to fit the required group interaction parameters for modified UNIFAC (Dortmund). The results show that in the future modified UNIFAC (Dortmund) can be applied successfully also for systems with ionic liquids.     

Excess enthalpies of some 2-alkanone + 1-chloroalkane binary mixtures at 25 and 35°C

Excess molar enthalpies h^E at 25 and 35° C and atmospheric pressure, are reported for the binary mixtures formed by a 2-butanone and 2-pentanone with 1-chlorobutane, 1-chloropentane, 1-chlorohexane, or 1-chlorooctane. The h^E values for all the mixtures are positive, increasing as the 1-chloroalkane length increases and as the ketone length decreases. Excess molar enthalpies depend slightly on the temperature. The experimental values together with those from the literature were used to calculate the interaction parameters for the Dang-Tassios version of the UNIFAC model.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Excess enthalpies and excess heat capacities of the binary mixtures of acetonitrile,dimethylformamide, and benzene at 298.15 K

Excess enthalpies and excess isobaric heat capacities of binary mixtures consisting of acetonitrile, dimethylformamide and benzene were measured at 298.15 K. Excess enthalpy of acetonitrile + benzene is positive and that of acetonitrile + dimethylformamide is negative. That of dimethylformamide + benzene is positive and nearly equals to zero as shown in the previous report [1]. Excess heat capacities of acetonitrile + benzene and benzene + dimethylformamide change sign from negative to positive with increase of benzene. That of acetonitrile + dimethylformamide is not simple. It is slightly positive near both ends of mole fraction and not so large negative in the middle of mole fraction. The curve tends to flatten in that region.

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Zusammenfassung An binären Gemischen aus Acetonitril, Dimethylformamid und Benzol wurden bei 298.15 K die Überschußenthalpien und die isobaren Überschußwärmekapazitäten gemessen. Die Überschußenthalpie von Acetonitril + Benzol ist positiv, die von Acetonitril + Dimethylformamid ist negativ. Die Überschußenthalpie ist bei Dimethylformamid positiv und wie bereits berichtet [1] annähernd Null. Die Überschußwärmekapazität von Acetonitril + Benzol und Benzol + Dimethylformamid wechselt bei Zunahme von Benzol das Vorzeichen von negativ zu positiv. Die von Acetonitril + Dimethylformamid ist nicht einfach. An beiden Enden der Molenbruchskaie ist sie leicht positiv und nicht allzu negativ in der Mitte der Molenbruchskale. Die Kurve flacht in dieser Region ab.

     

Excess enthalpies and (vapour + liquid) equilibrium data for the binary mixtures of dimethylsulphoxide with ketones

Excess enthalpies (H^E), at ambient pressure and T = 298.15 K, have been measured by using a solution calorimeter for the binary liquid mixtures of dimethyl sulphoxide (DMSO) with ketones, as a function of composition. The ketones chosen in the present investigation were methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The H^E values are positive over the entire composition range for the three binary mixtures. Furthermore, the (vapour + liquid) equilibrium (VLE) was measured at 715 Torr for these mixtures, of different compositions, with the help of Swietoslawski-ebulliometer. The experimental temperature-mole fraction (t-x) data were used to compute Wilson parameters and then used to calculate the equilibrium vapour-phase compositions as well as the theoretical points for these binary mixtures. These Wilson parameters are used to calculate activity coefficients (γ) and these in turn to calculate excess Gibbs free energy (G^E). The intermolecular interactions and structural effects were analyzed on the basis of the measured and derived properties.     

Excess molar enthalpies at 298.15 k of the binary mixtures

We have determined the excess molar enthalpies H _m ^E at 298.15 K and normal atmospheric pressure for the binary mixtures containing tert-butyl methyl ether (MTBE)+(methanol, ethanol, 1-propanol, 1-pentanol) using a Calvet microcalorimeter. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study on the effect of increasing the chain length of the alkanol in excess molar enthalpies of mixtures containing 2-methoxy-2-methylpropane, 1-alkanol,decane

Excess molar enthalpies for the ternary system {x₁ 2-methoxy-2-methylpropane + x₂ ethanol + (1 − x₁ − x₂) decane} and the involved binary mixture {x ethanol + (1 − x) decane} have been measured at the temperature of 298.15 K and atmospheric pressure, over the whole composition range. No experimental excess enthalpy values were found in the currently available literature for the ternary mixture under study. The results were fitted by means of different variable-degree polynomials. Smooth representations of the results are presented and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. The excess molar enthalpies for the binary and ternary system are positive over the whole range of composition. The binary mixture {x ethanol + (1 − x) decane} is asymmetric, with its maximum displace toward a high mole fraction of decane. The ternary contribution is also positive, and the representation is asymmetric.     

Excess molar enthalpies of binary mixtures of 1-hexene with some cyclic and aromatic hydrocarbons at 298.15 K

Microcalorimetric measurements of excess molar enthalpies, at 298.15 K, are reported for the four binary systems formed by mixing 1-hexene with the cycloalkanes: cyclohexane and methylcyclohexane, and with the aromatic hydrocarcons: benzene and toluene. Smooth Redlich-Kister representations of the results are presented. It was found that the Liebermann-Fried model also provided good representations of the results.     

ERAS modeling of the excess molar enthalpies of binary liquid mixtures of 1-pentanol and 1-hexanol with acetonitrile at atmospheric pressure and 288, 298, 313 and 323 K

This work reports experimental data on the excess molar enthalpy as a function of composition of acetonitrile + 1-pentanol and acetonitrile + 1-hexanol mixtures at 288.15, 298.15, 313.15 and 323.15 K under atmospheric pressure. The data show positive values over the whole composition range for both systems and for all temperatures studied, they also increase with temperature and with alkanol chain length. The experimental curves have a parabolic shape with maximum point around 0.5 mole fraction. The extended real associated solution (ERAS) model was applied to correlate the experimental data. The ERAS model adequately described the main features of the behavior of the mixtures.     

Measurement and correlation of excess molar enthalpies for the partially miscible systems 2-butanone+water and methanol+hexane

The excess molar enthalpies of the systems 2-butanone+water and methanol+hexane which show limited miscibility were measured at 283.15–298.15 K using a flow microcalorimeter. The experimental data were correlated using three local-composition (LC) models (NRTL, modified Wilson and modified EBLCM). These models were also used to predict the liquid–liquid equilibria for both systems with the parameters obtained from the excess enthalpy data.