Isothermal vapor–liquid equilibria and excess molar volumes for 2-methyl pyrazine (2MP) containing binary mixtures

2-Methyl pyrazine (2MP) has led to significant interest for its industrial and pharmaceutical uses. The new vapor–liquid equilibria (VLE) at 353.15 K and excess molar volumes (V^E) at 298.15 K over the whole mole fraction range for seven binaries (water, n-hexane, cyclohexane, n-heptane, methylcyclopentane (MCP), methylcyclohexane (MCH) and ethyl acetate (EA) with 2MP) have been measured. VLE were measured by using headspace gas chromatography and V^E were determined using precision density meter. The water+2MP system has only the minimum boiling azeotrope. The experimental VLE and V^E data were well correlated in terms of common g^E models and Redlich–Kister equation, respectively.     

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.     

Estimating the excess molar volume using the new generation geometric model

In the present article, the general geometrical model is extended to estimate the excess molar volume in multicomponent systems. The model can overcome the inherent defects of the asymmetrical and symmetrical models, and more reasonable in the theoretical consideration and more reliable in the practical application. The integration process is avoided by applying the general relations between the “similarity coefficient” and the parameters of the binary R-K type polynomial, which greatly simplifys the calculation. The successful applications of the general geometrical model to four ternary systems show that it is possible to calculate the molar volume with this method.     

Determination of the excess molar and partial molar volumes of the constituents in the binary mixtures with tri-ethylamine

The excess molar volume and excess partial molar volumes of binary mixtures of tri-ethylamine with toluene (Tn), ethylbenzene (Ebz) and n-propylbenzene (n-PBz) have been calculated using the MS-Excel method. The excess molar volumes have been found to be negative throughout the entire range of composition. The temperature effects are found to be insignificant, so the mixtures may be termed regular mixtures of Hildebrand.     

Vapor-liquid equilibrium predictions of refrigerant mixtures from a cubic equation of state with a G-EoS mixing rule

A modified excess Gibbs energy model which is based on the local composition concept and assigns a single energy parameter per pair of components, is incorporated into the G^E—EoS thermodynamic formalism for vapor-liquid equilibrium (VLE) calculations of simple and complex refrigerant mixtures. One temperature set of data close to 273 K is used to obtain the model's parameters, which are used to extrapolate the VLE at other temperatures and pressures. A one-parameter form of the model based on the Wong-Sandler mixing rule is presented for several simple systems. The physical significance of the model's energy parameter is connected to the preference of the mixture for like to unlike interactions. The model is applied for VLE predictions of the ternary system R14-R23-R13, and the results are compared to calculations using the 3PWS model [H. Orbey. S.I. Sandler, Ind. Eng. Chem. Res. 34 (1995) 2520–2525] and the van der Waals mixing rule. Modelling of a few complex systems with only three data points given at each temperature is shown with a two parameter version of our model on the basis of the Huron-Vidal mixing rule.     

Prediction of excess molar volumes of binary mixtures of organic compounds from refractive indices

The excess molar volumes of 51 binary mixtures containing diverse groups of organic compounds: alcohols (methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol, and heptan-1-ol), (cyclo-) alkanes (hexane, heptane, octane, nonane, decane, undecane, dodecane, and cyclohexane), esters (diethyl carbonate and ethyl chloroacetate), aromatics (o-xylene, m-xylene, p-xylene, and ethylbenzene), ketones (acetone), and ethers (anisole), were predicted from the refractive index data, using three types of equations coupled with several different mixing rules for refractive index calculations: the Lorentz-Lorenz, Dale-Gladstone, Eykman, Arago-Biot, Newton, and the Oster. These systems were chosen since they belong to different classes of organic species forming molecular interactions and intermolecular forces during mixing resulting in positive or negative, smaller or larger deviations from ideal behaviour. The obtained results were analysed in terms of the applied equation and mixing rule, the nature of compounds of the mixtures and the influence of alkyl chain length of the alkane or alcohol molecule. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Excess molar volume along with viscosity,refractive index and relative permittivity for binary mixtures of exo-tetrahydrodicyclopentadiene with four octane isomers

The fundamental physical properties including density, viscosity, refractive index and relative permittivity, have been measured for binary mixtures of exo-tetrahydrodicyclopentadiene (JP-10) with four octane isomers (n-octane, 3-methylheptane, 2,4-dimethylhexane and 2,2,4-trimethylpentane) over the whole composition range at temperatures T = (293.15 to 313.15) K and pressure p = 0.1 MPa. The values of excess molar volume $\left(V_{\text{m}}^{\text{E}}\right)$, viscosity deviation (Δη), refractive index deviation (Δn_D) and relative permittivity deviation (Δε_r) are then calculated. All of the values of $V_{\text{m}}^{\text{E}}$ and Δη are observed to be negative, while those of Δn_D and Δε_r are close to zero. The effects of temperature and composition on the variation of $V_{\text{m}}^{\text{E}}$ values are discussed. The negative values of $V_{\text{m}}^{\text{E}}$ and Δη are conductive to high-density and low-resistance of fuels, which is favorable for the design and preparation of advanced hydrocarbon fuels.     

Excess molar volumes of binary mixtures of 4-methyl-2-pentanone and some hydrocarbons

Summary Excess molar volumes (V ^E) for binary mixtures of 4-methyl-2-pentanone and some hydrocarbons (cyclohexane, benzene, toluene, andp-xylene) over the whole mole fraction range are determined by density measurement at 293.15 K. The variation of theV ^E values with the composition for all binary systems is symmetrical except for benezene where the dependence is sigmoid. TheV ^E values are positive for the binary mixture of the ketone with cyclohexane. For the other hydrocarbons, theV ^E values are progressively negative over the entire mole fraction range except the system containing benzene, where a few values at higher mole fractions of benzene are positive. The results are discussed in terms of molecular interactions steric effects.

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Molare Zusatzvolumina von binären Mischungen von 4-Methyl-2-pentanon und einigen Kohlenwasserstoffen

Zusammenfassung Molare Zusatzvolumina (V ^E) von binären Mischungen von 4-Methyl-2-pentanon und einigen Kohlenwasserstoffen (Cyclohexan, Benzol, Toluol undp-Xylol) wurden bei 293.15 K durch Dichtemessungen über den gesamten Molenbruchbereich bestimmt. Mit Ausnahme der binären Mischung mit Benzol (sigmoide Kurvenform) ist die Änderung vonV ^E in Abhängigkeit von der Zusammensetzung der Mischungen symmetrisch. Für das System Keton/Cyclohexan sind dieV ^E-Werte stark positiv, während sie für die anderen Gemische negativ sind. Eine Ausnahme bildet wieder das System mit Benzol als Kohlenwasserstoff, wo einige Werte bei höheren Molenbrüchen von Benzol positiv sind. Die Ergebnisse werden im Zusammenhang mit intermolekularen Wechselwirkungen und dem Einfluß sterischer Faktoren diskutiert.

     

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.     

Excess molar enthalpies of binary mixtures containing ethylene glycols or poly(ethylene glycols) + ethyl alcohol at 308.15 K and atmospheric pressure

Excess molar enthalpies, , of binary mixtures containing ethylene glycols and poly(glycols) + ethyl alcohol were measured by a flow microcalorimeter at 308.15 K and at atmospheric pressure over the whole composition range. Binary mixtures contain ethyl alcohol + ethylene glycol, + di(ethylene glycol), + tri(ethylene glycol), + tetra(ethylene glycol), + poly(ethylene glycol)-200, + poly(ethylene glycol)-300, + poly(ethylene glycol)-400, + poly(ethylene glycol)-600. Effects of the molecular weight distribution (MWD), of the polymer were investigated too, by preparing three additional samples of poly(ethylene glycol) with the same number average molecular weight (M_n ≈ 300), but different MWD. For all mixtures, results were fitted to the Redlich–Kister polynomial. curves are asymmetrical, showing positive values which vary from 280 J mol⁻¹ (diethylene glycol + ethyl alcohol) to 1034 J mol⁻¹ (mixture containing PEGs (200 + 400) + ethyl alcohol). Effects of changes in the glycols chain length and in MWD on the molecular interactions among the mixture components are discussed.     

Variation of excess volumes with temperature for binary mixtures ofp-xylene withn-hexane andn-hexadecane

The variation of the molar volume with temperature from 25 to 50 °C of binary mixtures of p-xylene + n-hexane and p-xylene + n-hexadecane has been measured by a dilatometric method over the complete mole fraction range. From the experimental results we have calculated v^E/T)_p. Literature values of v^E at 25°C together with the integration of v^E/T)_p yield v^E as a function of temperature. The excess volumes of p-xylene + n-hexane at 40 °C and p-xylene + n-hexadecane at 40 and 45 °C have also been measured by a dilatometric method, and the results were compared to those obtained from the integration of . The results from both methods are in excellent agreement within experimental error.The experimental values of are negative for the system p-xylene + n-hexane and positive for p-xylene + n-hexadecane. We have interpreted our experimental results in terms of the order present in p-xylene and n-alkanes.     

High-pressure densities and derived volumetric properties (excess, apparent, and partial molar volumes) of binary mixtures of {methanol (1) + [BMIM][BF4] (2)}

The density of seven {(0.0087, 0.0433, 0.1302, 0.2626, 0.4988, 0.7501, and 0.9102) mole fraction of [BMIM][BF₄]} binary {methanol (1) + [BMIM][BF₄] (2)} (1-butyl-3-methylimidazolium tetrafluoroborate) mixtures has been measured with a vibrating-tube densimeter. Measurements were performed at temperatures from (298 to 398) K and at pressures up to 40 MPa. The total uncertainties of density, temperature, pressure, and concentration measurements was estimated to be less than 0.15 kg · m⁻³, 15 mK, 5 kPa, and 10⁻⁴, respectively. The uncertainties reported in this paper are expanded uncertainties at the 95% confidence level with a coverage factor of k = 2. The effect of temperature, pressure, and concentration on the density and derived volumetric properties such as excess, apparent, and partial molar volumes was studied. The measured densities were used to develop a Tait-type equation of state for the mixture. The structural properties such as direct and total correlation function integrals and cluster size were calculated using the Krichevskii function concept and the equation of state for the mixture at infinite dilution.     

Partial molar enthalpy properties and correlation of excess molar enthalpy data of acetonitrile + diethylamine or S-butylamine mixtures at various temperatures and atmospheric pressure

Experimental data of excess molar enthalpy of binary mixtures of acetonitrile + diethylamine or S-butylamine mixtures as a function of composition at 288.15, 293.15, 298.15 and 303.15 K at atmospheric pressure have been used to calculate excess partial molar enthalpy and partial molar enthalpy of each component as a function of composition as well as partial molar enthalpy properties at infinite dilution. The Flory and Prigogine–Flory–Patterson (PFP) theories were applied to correlate the data. The results of the calculations as well as the influence of temperature and isomers chain on the partial molar enthalpy properties are discussed.     

Density and surface tension of binary mixtures of 1-ethyl-3-methylimdazolium nitrate with alcohols

New experimental data of densities and surface tensions are presented for the binary mixtures of the ionic liquid 1-ethyl-3- methyl imidazolium nitrate（[EMIM]NO₃） with methanol and ethanol.Measurements were performed at 298.15 K and atmospheric pressure,covering the whole composition range.Excess molar volumes V^E and the surface tension deviations Sy have been determined.For the excess molar volumes of binary mixture,there is a region of negative V^E at low IL mole fraction,passing through a minimum and then V^E increases and becomes positive,showing maximum at higher IL mole fraction.It is shown that the surface tension deviations Sy of[EMIM]NO₃ + methanol system are positive but those of[EMIM]NO₃ + ethanol system are negative over the entire mole fraction range.     

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.     

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.