Studies on the internal structure of the binary mixtures of N,N-dimethylacetamide with 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol by means of measuring their densities and relative permittivities at 298.15 K

ABSTRACT

The densities and relative permittivities of binary mixtures of N,N-dimethylacetamide with 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol have been measured as a function of composition, at T = 298.15 K. From the experimental data the excess molar volume (V^E) from a mole fraction and the excess relative permittivity (ε^E) from a volume fraction average have been calculated. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Refractive properties of binary mixtures containing 2-methoxyethanol and diethylamine,triethylamine, and propylamine

Refractive indexes (n _D ) of numerous binary mixtures of 2-methoxyethanol + diethylamine, 2-methoxyethanol + triethylamine, and 2-methoxyethanol + propylamine, between 288.15 and 308.15?K, are reported. Furthermore, the excess molar refraction (R ^E ) and deviation from ideality refractive index (Δn _D ) have been examined, in order to identify the presence of intermolecular complexes in these binary liquid mixtures.     

Refractive Properties of Binary Mixtures Containing 2-Methoxyethanol and n-Butylamine,Isobutylamine, sec-Butylamine and tert-Butylamine

Refractive index (n) and related properties such as molar refraction (R) have been investigated for 2-methoxyethanol (ME) + n-butylamine (n-BA) and 2-methoxyethanol (ME) + isobutylamine (iso-BA), 2-methoxyethanol (ME) + sec-butylamine (sec-BA) and 2-methoxyethanol (ME) + tert-butylamine (tert-BA) binary mixtures over the entire composition range, at different temperatures in the range 291.15 ≤? T/K ≤? 313.15. Furthermore, the excess molar refraction (R^E ) and deviation from ideality refractive index (Δn) have been examined, in order to identify the presence of intermolecular complexes in these binary liquid mixtures. The results obtained have been interpreted on the basis of specific intermolecular interactions between species.     

Density, Refractive Index, and Related Properties for 2-Butanone + n-Hexane Binary Mixtures at Various Temperatures

Density refractive index n and the related properties molar volume V and molar refraction R have been investigated for 2-butanone + n-hexane liquid binary mixtures over the entire composition range and a wide range of temperatures. Some well-known relationships have been applied to study the temperature and composition dependence of the measured and derived quantities. Furthermore, the deviations of the respective excess properties V ^E, n ^E, and R ^E have been examined, with the aim of identifying particular intermolecular interaction patterns responsible for the macroscopic behavior of these binary mixtures. The results have been interpreted on the basis of structural and geometric effects between the components.     

Viscosimetric and ultrasonic studies of intermolecular interactions of 2-methoxyethanol with diethylene glycol,triethylene glycol and tetraethylene glycol binary mixtures

The viscosities at T = (293.15, 298.15 and 303.15) K and ultrasonic speeds at T = 298.15 K in the binary liquid mixtures of 2-methoxyethanol with diethylene glycol, triethylene glycol and tetraethylene glycol have been measured over the entire mixture compositions. From the experimental data, deviations in the viscosity (Δη), ultrasonic speed (Δu), and excess energies of activation for viscous flow (ΔG* ^E ) have been calculated. The viscosity data were correlated with equations of Hind et al., Grunberg and Nissan, Frenkel, and McAllister. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Topological investigations of the molecular species and molecular interactions that characterize pyrrolidin-2-one + lower alkanol mixtures

Molar excess volumes, V^E, molar excess enthalpies, H^E, and speeds of sound data, u, of pyrrolidin-2-one (i) + ethanol or propan-1-ol or propan-2-ol or butan-1-ol (j) binary mixtures have been determined over entire composition range at 308.15 K. The observed speeds of sound data have been utilized to predict excess isentropic compressibilities, of the investigated binary mixtures. The observed excess thermodynamic properties V^E, H^E and have been analyzed in terms of Graph theory. The analysis of V^E data by the Graph theory suggests that pyrrolidin-2-one exists mainly as a mixture of cyclic and open dimer; ethanol as a mixture of dimer and trimer; butan-1-ol and propan-2-ol as mixture of monomer and dimer and propan-1-ol as a dimer in the pure state, and their mixtures contain 1:1 molecular complex. The IR studies lend additional credence to the nature and extent of interactions for the proposed molecular entities in the mixtures. Also, it has been observed that V^E, H^E and values predicted by the Graph theory compare well to with their corresponding experimental values.     

Excess Molar Volumes,Viscosity Deviations and Isentropic Compressibility of Binary Mixtures Containing 1,3-Dioxolane and Monoalcohols at 303.15 K

The excess molar volume (V ^E), viscosity deviations (Δη) and Gibbs excess energy of activation for viscous flow (G^∗E) have been investigated from density (ρ) and viscosity (η) measurements of eight binary mixtures of 1,3-dioxolane with methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, and i-amyl alcohol over the entire range of mole fractions at 303.15 K. The viscosity data have been correlated with the Grunberg and Nissan equation. Furthermore, excess isentropic compressibilities (K_S^E) have been calculated from ultrasonic speed measurements of these binary mixtures at 303.15 K. The deviations have been fitted by a Redlich–Kister equation and the results are discussed in terms of molecular interactions and structural effects. The excess properties are found to be either negative or positive depending on the molecular interactions and the nature of the liquid mixtures. The systems studied exhibit very strong cross association through hydrogen bonding.     

2-Metoxyethanol-Acetonitrile Binary Mixtures and Their Physicochemical Properties

Abstract

Densities (d ₁₂) and relative permittivities (\Varepsilon₁₂) have been measured for 2-metoxyethanol (ME) and acetonitrile (ACN) binary liquid mixtures over their whole compositions ranges at various temperatures ranging from 288.15K to 308.15K. The experimental data were used to test some empirical equations of the type: y ₁₂=y ₁₂(t) and y ₁₂=y ₁₂(X ₁) (where: y ₁₂-d ₁₂ or \Varepsilon₁₂). From all these data, the excess molar volumes (V ^E _m), temperature coefficients of relative permittivities (α₁₂) and the excess extrathernmodynamic parameters \Varepsilon^E were calculated. The ¹H-NMR spectra of liquid binary mixtures of ME and ACN, were recorded at 298 K over almost the whole range of the mixed solvent compositions. From these data the values of the values of the spectral structural parameters were found, Δδ(ME-ACN). The values of these structural parameters are discussed in terms of interactions of 2-metoxyethanol with acetonitrile.     

Density,relative permittivity,viscosity and speed of sound for 2-methoxyethanol + isobutylamine mixtures

Densities (ρ), relative permittivities (ε), viscosities (η), and speeds of sound (u) at 298.15?K of binary mixtures of 2-methoxyethanol (1)?+?isobutylamine (2), are reported. From all those data, the excess molar volumes, and deviations from mole fraction additivity of the relative permittivity (Δε), viscosity (Δη), speed of sound (Δu), and isentropic compressibility (Δκ) have been calculated. The results for V ^E, Δε, Δln?η, Δu, and Δκ are discussed on the basis of intermolecular interactions between the components of the analysed mixtures.     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

H-NMR Spectral and Dielectric Behaviours of the 2-Metoxyethanol-Tetrahydrofuran Solvent System

Abstract

Relative permittivities (E ₁₂) have been measured for 2-metoxyethanol (ME)-tetrahydrofuran (THF) binary liquid mixtures over the whole compositions range at various temperatures ranging from 291.15 K to 308.15 K. The experimental data were used to test some empirical equations of the type: y ₁₂ = y ₁₂(t) and y ₁₂ = y ₁₂ (X ₁) [where: y ₁₂-E ₁₂]. From all these data, the temperature coefficients of relative permittivities (α₁₂) and the excess extrathermodynamic parameters ε^E were calculated. The ¹H-NMR spectra of liquid binary mixtures of ME and THF, were recorded at 298 K over almost the whole range of the mixed solvent compositions. From these data the values of the values of the spectral structural parameters were found, δδ(ME-THF). These structural parameters as a function concentration suggest the formation of stable 3ME.THF types intermolecular complexes.     

Thermodynamic and transport properties of binary liquid mixtures of cyclohexanol with isomeric chlorotoluenes

Densities (ρ) at different temperatures from 303.15 to 318.15 K, speeds of sound (u) and viscosities (η) at 303.15 K were measured for the binary mixtures of cyclohexanol with 2-chlorotoluene, 3-chlorotoluene and 4-chlorotoluene over the entire range of composition. The excess volumes (V^E) for the mixtures have been computed from the experimental density data. Further, the deviation in isentropic compressibilities (Δκ_s) and deviation in viscosities (Δη) for the binary mixtures have been calculated from the speed of sound and viscosity data, respectively. The V^E values and Δκ_s values were positive and Δη data were negative for all the mixtures over the whole range of composition at the measured temperatures. The calculated excess functions V^E, Δκ_s and Δη were fitted to Redlich–Kister equation. The excess functions have been discussed in terms of molecular interactions between component molecules of the binary mixtures.     

Densities,Viscosities and Speeds of Sound of Binary Mixtures of Ethyl Benzoate + Hydrocarbons at (303.15, 308.15 and 313.15) K

Densities, viscosities and speeds of sound of binary mixtures of ethyl benzoate with cyclohexane, n-hexane, heptane and octane have been measured over the entire range of composition at (303.15, 308.15 and 313.15) K and at atmospheric pressure. From these experimental values, excess molar volume (V ^E), deviation in viscosity (Δη) and deviation in isentropic compressibility (ΔK _s) have been calculated. The viscosities of binary mixtures were calculated theoretically from the pure component data by using various empirical and semi-empirical relations and the results compared with the experimental findings.     

Solvatochromic Probes Absorbance Behavior in Mixtures of 2-Hydroxy Ethylammonium Formate with Methanol,Ethylene Glycol and Glycerol

Solute-solvent and solvent-solvent interactions were investigated for binary mixtures of an ionic liquid (IL) 2-hydroxy ethylammonium formate as with methanol, ethylene glycol and glycerol. The physicochemical properties of the solvent mixtures at 25 °C, over the whole range of mole fractions, were determined using solvatochromic probes. High normal polarity (E_T^NE_{T}^{N}) in the alcohol-rich region confirms solute-solvent interactions in this medium. Dipolarity/polarizability (π ^∗) show a different trend to E_T^NE_{T}^{N} with a positive deviation from ideal behavior in IL-glycerol mixtures. However, these deviations for other solvent mixtures are insignificant. Contrary to what is observed for E_T^NE_{T}^{N} and π ^∗, hydrogen-bond donor (HBD) acidity and hydrogen-bond acceptor (HBA) basicity demonstrate similar trends. The applicability of the combined nearly-ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation for the correlation of various parameters provides a simple computational model to correlate and/or predict various solvatochromic parameters for many binary solvent systems.     

Viscosity of binary mixtures of 2-ethoxyethanol with ethylene glycol,diethylene glycol,triethylene glycol and tetraethylene glycol systems at T = (293.15, 298.15 and 303.15) K

Viscosities, at T = 293.15, 298.15 and 303.15 K, in the binary mixtures of 2-ethoxyethanol with ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol have been measured as a function of composition. From the experimental data the deviations in the viscosity have been calculated. The viscosity data, at T = 298.15 K, were correlated with equations of Hind et al., Grunberg and Nissan, and Frenkel. The results are discussed in terms of intermolecular interactions and structural properties of studied binary mixtures.     

Surface tension and density of binary mixtures of monoalcohols,water and acetonitrile: equation of correlation of the surface tension

Measurements of the surface tension (σ) and density (ρ) of binary mixtures of monoalcohols, water and acetonitrile at 298.15 K and at atmospheric pressure, as a function of mole fraction (x) have been made. The experimental values of the deviation of surface tension and the excess of molar volume (Δσ, V ^E) have been correlated by the Redlich–Kister equation. An empirical correlation equation is presented for the study of the surface tension of these mixtures, and comparisons are made of the experimental values of surface tension versus those obtained with the correlation equation and with other models of correlation. Finally, with the purpose of corroborating the validity of the correlation equation, the latter is applied to other reference binary mixtures.     

Volumetric properties of binary mixtures of alcoxyethanols with tert-butyl ethyl ether at various temperatures

Densities at 293.15, 298.15, 303.15, 308.15 and 313.15 K of the binary liquid mixtures made of tert-butyl ethyl ether with either 2-ethoxyethanol, or 2-(2-ethoxy)ethoxyethanol, or 2-[2-(2-ethoxy)ethoxy]ethoxyethanol have been measured over the whole mixture compositions. These data have been used to compute the excess molar volumes (V^E). The excess molar volumes always are negative over the entire range of composition for all the binary mixtures investigated. The changes of V^E with variations of the composition and the chain-length of the alkyl groups in the alkoxyethanol molecules are discussed in terms of possible intermolecular interactions.     

Studies on Acoustic Behavior, Viscosity, and Density of Some Commercial Extractants and Their Molecular Interaction with Diluent, Modifier, and Extractant

Acoustical and viscosity measurements have been made for binary liquid mixtures of commercially available solvent extractants, LIX reagents such as LIX 622 and LIX 860 in benzene, amyl alcohol, and tri-n-butyl phosphate (TBP) at 303.15 K. The measured values of ultrasonic velocity, density, and viscosity have been utilized to compute some acoustic as well as thermodynamic parameters such as intermolecular free length, L _f, isentropic compressibility, _s, molar volume, V, and Gibb's excess free energies of activation of viscous flow, G*^E. These parameters along with the derived values of isentropic compressibility, _s ^E, intermolecular free length, L _f ^E, and molar volume, V ^E, have been utilized for a comparative study of molecular interactions between the components present in different liquid systems. The experimental ultrasonic velocities for aforementioned mixtures have been compared with theoretically estimated velocities using different empirical relations, and the relative merits of these theories and relations have been discussed in terms of percentage variation.     

Thermodynamic and transport properties of binary mixtures of dimethyl sulfoxide with t-butyl alcohol,butyl acetate, 2-butanone and butyl amine at different temperatures

Densities and viscosities of binary mixtures of dimethyl sulfoxide (DMSO) with tert-butyl alcohol, butyl acetate, butanone, and butyl amine were determined over the entire range of mole fractions at temperatures of 298.15, 308.15, and 318.15 K. At each temperature, the excess molar volume (V ^E), viscosity deviations (Δη), and Gibbs excess free energy of activation for viscous flow (ΔG ^*E) have been investigated from these measured density (ρ) and viscosity (η) values. The experimental viscosity data were correlated by means of the equations of Grunberg-Nissan, Tamura and Kurata, and Hind et al. The deviations have been fitted to a Redlich-Kister equation, and the results are discussed in terms of molecular interactions and structural effects.

     

Ionic strength effects in binary aqueous mixtures: Study of the reaction between Co(en)2(2-pzCO2)2+ and Fe(CN)5H2O3−

The reaction between Co(en)₂(2?pzCO₂)²⁺ (bis-ethylenediamine (2-pyrazinecarboxylato)cobalt(III)) and Fe(CN)₅H₂O^3? (aquopentacyanoferrate(II)) to form the binuclear complex [(en)₂Co( μ-pzCO₂)Fe(CN)₅]^? has been studied in several isodielectric binary mixtures at 298.2 K (cosolvents: methanol, ethanol, tertbutyl alcohol, ethyleneglycol, and glycerol). Results were rationalized by using a free energy relationship. The importance of correcting the rate constants obtained in the different mixtures from the ionic strength influence has been shown. © 1995 John Wiley & Sons, Inc.