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.     

Densities,excess molar volumes,and partial molar volumes for binary mixtures of water with monoethanolamine,diethanolamine, and triethanolamine from 25 to 80°C

We have measured densities of binary mixtures of water with monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) over the full range of compositions and over the temperature range from 25 to 80°C. Results of these measurements have been used in calculating excess molar volumes and partial molar volumes. Knowledge of the volumetric properties of these mixtures is useful in connection with industrial treatment of acidic gases; derived excess molar volumes and partial molar volumes can be used as a basis for understanding some of the molecular interactions in water-organic mixtures.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

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.     

Experimental and predicted excess molar volumes of the ternary system.

Summary Experimental excess molar volumes for the ternary system x₁MTBE+x₂1-propanol+(1-x₁-x₂) heptane and the three involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The ternary mixture shows maximum values around the binary mixture MTBE+heptane and minimum values for the mixture MTBE+propanol. The ternary contribution to the excess molar volume is negative, with the exception of a range located around the rich compositions of 1-propanol. Several empirical equations predicting ternary mixture properties from experimental binary mixtures have been applied.     

Excess molar volume and isentropic compressibility of monoethanolamine in aqueous system at temperatures from 298.15 to 318.15 K

Densities and sound velocities for aqueous monoethanolamine (MEA) system are reported over the entire composition range at different temperatures (298.15, 303.15, 313.15 and 318.15 K). These experimental data have been further used in calculating the excess molar volume, partial molar volumes, isobaric thermal expansion coefficients and the deviation in isentropic compressibility. The excess molar volumes data were fitted to the Redlich–Kister polynomial equation to obtain their coefficients and standard deviations. The partial molar volume at infinite dilution of both water in MEA and MEA in water and have been determined using two different methods. Knowledge of the above properties of these mixtures is a basis for understanding some of the molecular interactions in these systems. From the analysis of the results, the type of interactions between the MEA and water is discussed in terms of the number and size of the alkyl groups attached to the nitrogen atom of MEA.     

Apparent molar volumes of aqueous sodium trifluoromethanesulfonate and trifluoromethanesulfonic acid from 283 K to 600 K and pressures up to 20 MPa

Relative densities of NaCF₃SO₃(aq) at molalities 0.073 ≤ m/(mol-kg^-1) ≤ 1.68 were measured with vibrating-tube densimeters from 283 K to 600 K and from 0.1 MPa to 20 MPa. Relative densities of HCF₃SO₃(aq) at molalities 0.12 < m/(mol-kg^-1) < 2.1 were determined at temperatures from 283 K to 328 K at 0.1 MPa. Apparent molar volumes calculated from the measured densities were represented by the Pitzer ion-interaction treatment. The temperature and pressure dependence of the standard partial molar volume and the second virial coefficients in the Pitzer equation were expressed by empirical expressions in which the compression coefficient of water and temperature were used as independent variables. The conventional standard partial molar volumes V‡(CF₃SO ₃ ^- , aq) fromT = 283 K to 573 K were calculated from the experimental values for V‡(NaCF₃SO₃, aq) and known values for V‡(Na⁺, aq). The values of V‡(CF₃SO_3/-, aq) at temperatures from 283 K to 328 K obtained from the values of V‡(NaCF₃SO₃, aq) and V‡(HCF₃SO₃, aq) agree to within 1.2 cm³-mol^-1.     

Partial molar volumes of monovalent ions in ethanolamine and water + ethanolamine mixtures at 25°C

Precise densities for sodium of chloride, bromide and iodide and potassium iodide in ethanolamine and water+ethanolamine mixtures (15, 30, 50, 60, 70, 80 and 90 mass% ethanolamine) up to a maximum salt molality of 0.15 mol-kg⁻¹ are reported from measurements at 25°C using a vibrating tube densimeter. The electrolyte apparent molar volumes were calculated and extrapolated to infinite dilution using the Masson equation to yield the limiting electrolyte partial molar volumes. The limiting ionic partial molar volumes V _ion ^o were estimated using Mukerjee's method. A correspondence principle proposed earlier for predicting ionic entropies could be used for the estimation of V _ion ^o for rubidium and cesium salts. The estimates of the contributions from geometric and the electrostrictive effects to V _ion ^o are also reported. The variations in these contributions with the change in solvent composition are discussed in terms of the changes in the solvent structure.     

Excess molar enthalpies of binary mixtures for (tributyl phosphate+methanol/ethanol) at 298.15 K

Excess molar enthalpies of binary mixtures for tributyl phosphate (TBP)+methanol/ethanol were measured with a TAM air Isothermal calorimeter at 298.15 K and ambient. The results for xTBP+(1–x)CH₃OH are negative in the whole range of composition, while the values for xTBP+(1–x)C₂H₅OH change from positive values at low x to small negative values at high x. The experimental results have been correlated with the Redlich–Kister polynomial. IR spectra of the mixtures were measured to investigate the effect of hydrogen bonding in the mixture.     

Excess molar volumes and molar refraction of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone+water water from 5 to 45°C

The excess molar volumes and molar refractionsR ₁₂ of 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU)+water have been determined over the entire mole fraction range at 10° intervals from 5 to 45°C and at atmosphere pressure. The excess volumes are all negative and they become more positive with increase of temperature. Limiting partial molar volumes for DMPU in water and water in DMPU are also reported.     

Excess and partial excess molar volumes of mixing of N,N-dibutyl-2-ethylhexamide with dodecanol

Excess and excess partial molar volumes of mixing of the system N,N-dibutyl-2-ethylhexylamide (DBEHA) + dodecanol (DDA) were determined at 25, 35, 45, 55 and 65°C. The excess molar volumes exhibit a maxima at each temperature at approximatelyx _DBEHA = 0.3 and a minima close tox _DBEHA = 0.9. The values of the excess volumes in general increase with the temperature. The partial excess molar volumes are calculated from the smoothed data and the results are discussed in the light of postulated amide-alcohol interactions.     

Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane

Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.     

Excess molar volumes and excess viscosities for then-hexane+dichloromethane+tetrahydrofuran ternary system at 25°C

Exces molar volumes, and excess viscosities of then-hexane+dichloromethane+tetrahydrofuran system have been determined at 25°C by measuring densities and viscosities. Different expressions exist in the literature to predict these excess properties from binary data. The empirical correlation of Cibulka is shown to be the best in this system.     

Experimental excess molar volumes of the ternary mixture and comparisonwith several empirical methods

Experimental excess molar volumes for the ternary system {x₁MTBE+x₂1-propanol+(1–x₁–x₂)nonane} and the three involved binary mixtures have been determined at 298.15 K and atmospheric pressure. Excess molar volumes were determined from the densities of the pure liquids and mixtures, using a DMA 4500 Anton Paar densimeter. The ternary mixture shows maximum values around the binary mixture MTBE+nonane and minimum values for the mixture MTBE+propanol. The ternary contribution to the excess molar volume is negative, with the exception of a range located around the rich compositions of 1-propanol. Several empirical equations predicting ternary mixture properties from experimental binary mixtures have been applied.     

Thermodynamics of aqueous mixtures of nonelectrolytes. IV. Excess volumes of water-acetonitrile mixtures from 15 to 35°C

Excess volumes of water-acetonitrile mixtures were obtained from measurements of density over the entire mole fraction range and at 5 degree intervals from 15 to 35°C. Partial molar excess volumes at the five temperatures, excess coefficients of thermal expansion at 25°C and partial molar excess expansibilities at 25°C were derived from the results. The values of the various volumetric properties are compared with data from the literature.Issued as NRCC No. 19500     

Molar excess heat capacities and volumes for mixtures of benzonitrile with cyclohexane between 10 and 45°C

The heat capacities and volumes for binary mixtures of benzonitrile with cyclohexane were determined at 10, 25, and 45°C. The dependence of the molar excess heat capacities on temperature and composition are interpreted in terms of the thermal relaxation of associated benzonitrile molecules into monomeric species.To whom correspondence should be addressed.     

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.     

Measurements and analysis of excess molar volumes for the ternary mixture MTBE + 1-pentanol + decane

Summary Densities at 298.15 K and atmospheric pressure have been measured, using a DMA 4500 Anton Paar densimeter, for the ternary mixture methyl tert-butyl ether (MTBE)+1-pentanol+decane and for the involved binary mixtures MTBE+1-pentanol and 1-pentanol+decane. The excess molar volumes for the binary mixture MTBE+decane was reported in an earlier work [1]. In addition, excess molar volumes were determined from the densities of the pure liquids and mixtures. Suitable fitting equations have been used in order to correlate adequately the excess molar volumes. The empirical expressions of Kohler [18], Jacob and Fitzner [19], Colinet [20], Knobeloch and Schwartz [21], Tsao and Smith [22], Toop [23], Scatchard et al. [24], Hillert [25], Mathieson and Thynne [26] were applied to estimate ternary properties from binary results.     

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.