Molecular Interactions in 1-Ethyl-3-Methylimidazolim Tetrafluoroborate + Amide Mixtures: Excess Molar Volumes, Excess Isentropic Compressibilities and Excess Molar Enthalpies

The densities, ρ ₁₂, and speeds of sound, u ₁₂, of 1-ethyl-3-methylimidazolium tetrafluoroborate (1) + N-methylformamide or N,N-dimethylformamide (2) binary mixtures at (293.15. 298.15. 303.15, 308.15 K), and excess molar enthalpies, $ H_{12}^{\text{E}} $ H 12 E , of the same mixtures at 298.15 K have been measured over the entire mole fraction range using a density and sound analyzer (Anton Paar DSA-5000) and a 2-drop microcalorimeter, respectively. Excess molar volume, $ V_{12}^{\text{E}} $ V 12 E , and excess isentropic compressibility, $ \left( {\kappa_{S}^{\text{E}} } \right)_{12} $ ( κ S E ) 12 , values have been calculated by utilizing the measured density and speed of sound data. The observed data have been analyzed in terms of: (i) Graph theory and (ii) the Prigogine–Flory–Patterson theory. Analysis of the $ V_{12}^{\text{E}} $ V 12 E data in terms of Graph theory suggest that: (i) in pure 1-ethyl-3-methylimidazolium tetrafluoroborate, the tetrafluoroborate anion is positioned over the imidazoliun ring and there are interactions between the hydrogen atom of (C–H{edge}) and proton of the –CH₃ group (imidazolium ring) with fluorine atoms of tetrafluoroborate anion, and (ii) (1 + 2) mixtures are characterized by ion–dipole interactions to form a 1:1 molecular complex. Further, the $ V_{12}^{\text{E}} $ V 12 E , $ H_{12}^{\text{E}} $ H 12 E and $ \left( {\kappa_{S}^{\text{E}} } \right)_{12} $ ( κ S E ) 12 values determined from Graph theory compare well with their measured experimental data.     

Excess Molar Volumes and Excess Partial Molar Volumes of Triethylene Glycol Monoethyl Ether–n-Alcohol Mixtures at 25°C

We have measured excess molar volumes V^E _m of binary mixtures of triethylene glycol monoethyl ether with methanol, ethanol, 1-propanol, 1-pentanol, and 1-hexanol over the full range of compositions at 25°C. The measurements were carried out with a continuous-dilution dilatometer. The excess molar volumes V^E _m are negative over the entire range of composition for the systems triethylene glycol monoethyl ether + methanol, + ethanol, and + 1-propanol and positive for the remaining systems, triethylene glycol monoethyl ether + 1-pentanol, and + 1-hexanol. The excess V^E _m increases in the positive direction with increasing chain length of the n-alcohol. The measured excess volumes have been compared to our previous published data with an effort to assess the effects of replacing methyl by ethyl groups and of inserting oxyethylene groups. The results have been used to estimate the excess partial molar volumes V^E _m,i of the components. The behavior of V^E _m and V^E _m,i with composition and the number of carbon atoms in the alcohol molecule is discussed.     

Excess Molar Volumes and Excess Partial Molar Volumes of Triethylene Glycol Monomethyl Ether–n-Alcohol Mixtures at 25°C

The excess molar volumes V ^E have been measured for binary mixtures of triethylene glycol monomethyl ether with methanol, ethanol, 1-propanol, 1-pentanol, and 1-hexanol as a function of composition using a continuous–dilution dilatometer at 25°C at atmosphere pressure. V ^E are negative over the entire range of composition for the systems triethylene glycol monomethyl ether + methanol, + ethanol, and + 1-propanol, and positive for the remaining systems, containing 1-pentanol and + 1-hexanol. V ^E increases in a positive direction with increasing carbon chain length of the n-alcohol. The excess partial molar volumes V _i ^E of the components were evaluated from the V ^E results. The behavior of V ^E and V _i ^E with composition and the number of carbon atoms in the alcohol molecule is discussed.     

Excess Chemical Potentials, Excess Partial Molar Enthalpies, Entropies, Volumes, and Isobaric Thermal Expansivities of Aqueous Glycerol at 25°C

The vapor pressures p the excess partial molar enthalpies of glycerol H _Gly ^E the densities d and the thermal expansivities _p of aqueous glycerol were measured at 25°C. From the vapor pressure data, the excess chemical potential of H₂O µ _W ^E was calculated, assuming that the partial pressure of glycerol p _Gly is negligibly small. The excess chemical potential of glycerol µ _Gly ^E was estimated by applying the Gibbs–Duhem relation and these data were used to calculate the excess partial molar entropies S _Gly ^E . From the density data, the excess partial molar volumes of glycerol V _Gly ^E and from the thermal expansivity data, the normalized cross fluctuations ^SV, introduced by us earlier, were evaluated. While the detailed manner in which glycerol modifies the molecular arrangement of H₂O in its immediate vicinity is yet to be elucidated, the hydrogen bond probability in the bulk H₂O away from solute molecules is reduced gradually as the glycerol composition increases to the point where putative presence of icelike patches is no longer possible. Thereupon, a qualitatively different mixing scheme seems to set in.     

Studies on Lattice Parameter,Molar Volume and Excess Molar Volume of Pb-based a-phase Solid Solution in Pb-Sn-Cd Ternary System

The lattice parameters a and the molar volumes Km of Pb-based a-phase solid solutions in the Pb-Sn-Cd ternary system were determined by means of X-ray diffraction. The lattice parameters a vary linearly with the molar fractions, the molar volumes show a positive deviation from the ideal solution behaviour, and the contribution of the solute Cd to the excess molar volumes V is much larger than that of the solute Sn. According to Vegard' s law orsub-regular solution model, the relationship between the experimental data of a or Vm andthe compositions of alloy is obtained by the mathematic regressive method, the prediction precisions of the both formulae are within the limits of experiment error.     

Excess Molar Volume,Viscosity, and Molar Refraction Deviations,and Liquid–Vapor Equilibrium at 303.15 K for Chloroform + Acetonitrile Binary Mixture. An Infrared Study

Excess molar volume, viscosity deviation, and molar refraction deviation for the chloroform #x002B; acetonitrile system at 303.15 K were calculated from binary experimental results of density, viscosity, and refractive index over the whole mole fraction range, respectively. Isothermal vapor–liquid equilibrium data at the same temperature were also obtained and the excess molar Gibbs energy was calculated from these data. Each one of the properties was fitted to a Redlich–Kister type equation using least squares in order to obtain their dependencies on concentration. The presence of intermolecular association complexes was inferred from the viscosity deviations, leading to a 1:1 stoichiometric relationship. The recorded FTIR spectra confirm the existence of this type of hydrogen-bonded complex, making it possible, furthermore, to calculate the heteroassociation constant and enthalpy of formation of the hydrogen bond.     

Excess Molar Volumes and Partial Molar Volumes of Dipropylene Glycol Monomethyl Ether + n-Alkanol Mixtures at 25°C

The excess molar volumes V^E for binary liquid mixtures containing dipropylene glycol monomethyl ether and methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol have been measured using a continuous dilution dilatometer over the whole mole fraction range at 25°C at atmospheric pressure. V^E are negative over the whole composition range except for the systems containing 1-pentanol, 1-hexanol, or 1-heptanol which are positve at every composition. V^E increases in a positive direction with increase in chain length of the n-alcohol. The results have been used to estimate the excess partial molar volumes V_i^E of the components. The change of V^E and V_i^E with composition and the number of carbon atoms in the alcohol molecule are discussed as a basis to understand some of the molecular interactions present in the mixtures:     

Excess Molar Volumes and Excess Isentropic Compressibilities of o-Toluidine + Tetrahydropyran with Pyridine or Benzene or Toluene Ternary Mixtures at 298.15, 303.15 and 308.15 K

The densities, ρ ₁₂₃, and speeds of sound, u ₁₂₃, of ternary o-toluidine (OT, 1) + tetrahydropyran (THP, 2) + pyridine (Py) or benzene or toluene (3) mixtures have been measured as a function of composition at 298.15, 303.15 and 308.15 K. Values of the excess molar volumes, $ V_{123}^{\text{E}} , $ and excess isentropic compressibilities, $ (\kappa_{\text{S}}^{\text{E}} )_{123} , $ of the studied mixtures have been determined by employing the measured experimental data. The observed thermodynamic properties were fitted with the Redlich–Kister equation to determine adjustable ternary parameters and standard deviations. The $ V_{123}^{\text{E}} $ and $ (\kappa_{\text{S}}^{\text{E}} )_{123} $ values were also analyzed in terms of Graph theory. It was observed that Graph theory correctly predicts the sign as well as magnitude of $ V_{123}^{\text{E}} $ and $ (\kappa_{\text{S}}^{\text{E}} )_{123} $ values of the investigated mixtures. Analysis of the data suggests strong interactions and a more close packed arrangement in OT (1) + THP (2) + Py (3) mixtures as compared to those of the OT (1) + THP (2) + benzene (3) or toluene (3) mixtures. This may be due to the presence of a nitrogen atom in Py which results in stronger interactions for the OT:THP molecular entity as compared to those with benzene or toluene.     

Excess Molar Volumes of Binary Mixtures of Hexanol and Polyethers at 25°C

Excess molar volumes V_m^E at 25°C and atmospheric pressure over the entire composition range for binary mixtures of 1-hexanol with n-polyethers: 2,5-dioxahexane, 3,6-dioxaoctane, 2,5,8-trioxanonane, 3,6,9-trioxaundecane, 5,8,11-trioxapentadecane, 2,5,8,11-tetraoxadodecane, and 2,5,8,11,14-pentaoxapentadecane are reported from densities measured with a vibrating-tube densimeter. Systems containing 2,5-dioxahexane, 2,5,8-trioxanonane, 2,5,8,11-tetraoxadodecane or 2,5,8,11,14-pentaoxapentadecane are characterized by V_m^E > 0, probably due to predominant positive contributions to V_m^E from the disruption of H bonds of 1-hexanol and to physical interactions. In contrast, mixtures with 3,6-dioxaoctane, 3,6,9-trioxaundecane, and 5,8,11-trioxapentadecane are characterized by V_m^E < 0, indicating that the negative contribution to V_m^E from interstitial accommodation is more important.     

Excess Molar Volumes and Viscosities of Binary Mixtures of Methanol and the Ionic Liquid 4-Methyl-N-butylpyridinium Tetrafluoroborate at 25, 40, and 50°C

Experimental data of densities and viscosities are presented for the system 4-methyl-N-butylpyridinium tetrafluoroborate + methanol at 25, 40, and 50, 323.15 K and ambient pressure using a vibratage-tube densimeter and an Ubbelohde viscometer. Excess molar volumes V ^E and excess logarithm viscosities (ln )^E have been determined. V ^E is negative and (ln )^E positive over the entire mixture composition.     

Theoretical Description of Excess Molar Functions in the Case of Very Small Excess Values. Investigation of Excess Molar Volumes of Propan-2-ol + Alkanol Mixtures

The densities of propan-2-ol + pentan-1-ol, + hexan-1-ol, + heptan-1-ol, + octan-1-ol + nonan-1-ol and speeds of sound in propan-2-ol + pentan-1-ol, + heptan-1-ol, + nonan-1-ol have been measured over the whole composition range at 298.15 K. Excess molar functions determined from the experimental data have been plotted as functions of composition. The excess molar volumes have been interpreted on the basis of the Symmetrical Extended Real Associated Solution Model (S-ERAS).     

Excess Molar Volumes and Excess Viscosities of the Propan-2-ol + Tetrahydrofuran + 1-Chlorobutane Ternary System at 25°C

Excess molar volumes and excess viscosities of the propan-2-ol + tetrahydrofuran+ 1-chlorobutane system have been determined at 25°C from measurements ofdensities and viscosities. Various expressions are proposed in the literature tocalculate these excess properties from binary data. The empirical correlation ofCibulka is shown to be the best in this system for excess volume, viscosity, andenergy of activation for viscous flow. An application to excess molar volumeshas been made by using Flory's theory. For viscosities, we applied the equations ofGrunberg and Nissan, Katti and Chaudhri, Bloomfield and Dewan, and Wu—andfinally the GC-UNIMOD model.     

Excess Chemical Potentials and Partial Molar Enthalpies in Aqueous 1,2- and 1,3-Propanediols at 25°C

Excess chemical potentials and excess partial molar enthalpies of 1,2- and 1,3-propanediols (abbreviated as 12P and 13P), ^E _i, and H ^E _i (i = 12P or 13P) were determined in the respective binary aqueous solutions at 25^°C. For both systems, the values of ^E _i are almost zero, within ±0.4 kJ-mol^–1. However, the excess partial molar enthalpies, H ^E _i show a sharp mole fraction dependence in the water-rich region. Thus, the systems are highly nonideal, in spite of almost zero ^E _i. Namely, the enthalpy-entropy compensation is almost complete. From the slopes of the H ^E _i against the respective mole fraction x _i we obtain the enthalpic interaction functions between solutes, H _i–i ^E, (i = 12P or 13P). Using these quantities and comparing them with the equivalent quantities for binary aqueous solutions of 1-propanol (1P), 2-propanol (2P), glycerol (Gly), and dimethyl sulfoxide (DMSO), we conclude that there are three composition regions in each of which mixing schemes are qualitatively different. Mixing Schemes II and III, operative in the intermediate and the solute-rich regions, seem similar in all the binary aqueous solutions mentioned above. Mixing Scheme I in the water-rich region is different from solute to solute. 12P shows a behavior similar to that of DMSO, which is somewhat different from typical hydrophobic solute, 1P or 2P. 13P, on the other hand, is less hydrophobic than 12P, and shows a behavior closer to glycerol, which shows hydrophilic behavior.     

Densities,Excess Molar Volumes,and Thermal Expansion Coefficients of Aqueous Aminoethylethanolamine Solutions at Temperatures from 283.15 to 343.15 K

The densities of aqueous mixtures of aminoethylethanolamine (CAS #000111-41-1) were measured over the entire compositional range at temperatures of 283.15–343.15 K. The results of these measurements were used to calculate excess molar volumes and isobaric thermal expansion coefficients, and partial molar and apparent molar volumes and excess isobaric thermal expansion coefficients were subsequently derived. The excess molar volumes were correlated as a function of the mole fraction using the Redlich–Kister equation. Temperature dependences of the Redlich–Kister coefficients are also presented. The partial molar volumes at infinite dilution of AEEA in water were determined using two different methods. In addition, the solution density was correlated using a Joubian–Acree model. Aqueous solutions of AEEA exhibit similar properties to the aqueous solutions of other alkanolamines (like monoethanolamine) used in acid gas sweetening.     

A Study of Excess Molar Enthalpies and Excess Molar Volumes of Binary Mixtures of 1-Chloropentane + 1-Alkanol (from 1-Butanol to 1-Octanol) at 25°C.

Excess molar enthalpies H ^E _mand excess molar volumes V ^E _m at 25°Cand normal atmospheric pressure for the binary mixtures 1-chloropentane + 1-alkanol(from 1-butanol to 1-octanol) have been determined using a Calvet microcalorimeterand from density measurements using a vibrating tube densimeter. The H ^E _m valuesfor all the mixtures are positive and V ^E _m values are positive or negative dependingon the mole fraction of the chloroalkane. Experimental H ^E _m results are comparedwith the predictions of UNIFAC group-contribution models proposed by Dang andTassios and by Larsen et al., and are discussed in terms of molecular interactions.     

Excess Molar Volumes and Viscosities for Binary Mixtures of 1-Alkoxypropan-2-ols with 1-Butanol, and 2-Butanol at 298.15 K and Atmospheric Pressure

Excess molar volumes Vm^E and kinematic viscosities v have been measured as a function of composition for binary mixtures of propylene glycol monomethyl ether （1-methoxy-2-propanol）, MeOCH2CH（OH）Me, propylene glycol monoethyl ether （1-ethoxy-2-propanol）, EtOCH2CH（OH）Me, propylene glycol monopropyl ether （1-propoxy-2-propanol）, PrOCH2CH（OH）Me, propylene glycol monobutyl ether （1-butoxy-2-propanol）, BuOCH2CH（OH）Me, and propylene glycol tert-butyl ether （1-tert-butoxy-2-propanol）, t-BuOCH2CH（OH）Me with 1-butanol, and 2-butanol, at 298.15 K and atmospheric pressure. The excess molar volumes are negative across the entire range of composition for all the systems with 1-butanol, and positive for the systems 2-butanol＋ 1-methoxy-2-propanol, and ＋1-propoxy-2-propanol, negative for the systems 2-butanol＋1-butoxy-2-propanol, and change sign for the systems 2-butanol＋ 1-ethoxy-2-propanol, and ＋ 1-tert-butoxy-2-propanol. From the experimental data, the deviation in dynamic viscosity η from ∑χiηi has been calculated. Both excess molar volumes and viscosity deviations have been correlated using a Redlich-Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard errors.     

Measurements of the Molar Heat Capacities and Excess Molar Heat Capacities for Water + Organic Solvents Mixtures at 288.15 K to 303.15 K and Atmospheric Pressure

Experimental molar heat capacity data (Cp _m) and excess molar heat capacity data (Cp^E_m\mathit{Cp}^{\mathrm{E}}_{\mathrm{m}}) of binary mixtures containing water + (formamide or N,N-dimethylformamide or dimethylsulfoxide or N,N-dimethylacetamide or 1,4-dioxane) at several compositions, in the temperature range 288.15 K to 303.15 K and atmospheric pressure, have been determined using a modified 1455 PAAR solution calorimeter. The excess heat capacities are positive for aqueous solutions containing 1,4-dioxane, N,N-dimethylformamide or dimethylsulfoxide, negative for solutions containing water + formamide and show a sigmoid behavior for mixtures containing water + N,N-dimethylacetamide, over the whole composition range. The experimental excess molar heat capacities are discussed in terms of the influence of temperature and of the organic solvent type present in the binary aqueous mixtures, as well as in terms of the existing molecular interactions and the organic solvent’s molecular size and structure.     

Limiting Partial Molar Excess Heat Capacities and Volumes of Selected Organic Compounds in Water at 25°C

Well-known Picker flow microcalorimeters for the differential measurements of volumetric heat capacities have been employed in conjunction with vibrating tube densimeters to determine the molar heat capacity, volume, and the apparent properties in dilute aqueous solutions for 17 organic solutes of moderate hydrophobicity. The dependence on concentration of the apparent properties allowed the limiting partial molar quantities at infinite dilution to be extrapolated and the limiting partial molar excess quantities to be evaluated. Comparison with available literature data shows good agreement. The application of group contribution rules to the limiting partial properties has been tested using the original method and parameters proposed by Cabani et al. The predicted values of the partial molar volumes are in fair agreement with the present data except for some less common solutes. With partial molar heat capacities, the agreement is less satisfactory. To improve the performance of the method, missing parameters for some types of monofunctional and bifunctional molecules have been evaluated.     

Apparent Molar Volume and Apparent Molar Refraction of Mono-, Di-, Tri-, and Tetra(oxyethylene) Glycol in Aqueous, 1,4-Dioxane,and Benzene Solutions at 298.15 K

Summary. The density and refractive index of aqueous, 1,4-dioxane, and benzene solutions of poly (oxyethylene) glycols of the type HO–(CH₂CH₂O) _n –H (n varying from 1 to 4) were measured at 298.15K. From these experimental data the apparent molar volume and the apparent molar refraction at infinite dilution were calculated. The limiting apparent molar volume of the investigated compounds in a definite solvent depends linearly on the number of oxyethylene groups. From these data, the volume of the monomeric unit was evaluated and found to be greater in non-aqueous solvents than in water. The limiting apparent molar refraction of the solute for the investigated systems, within the experimental uncertainties, is equal to the molar refraction of the pure solute. The electronic polarizability of the solute molecule depends linearly on the number of monomeric units and the ratio of the electronic polarizability to the molecular van der Waals volume is constant and independent of the number of oxyethylene groups.Received February 24, 2003; accepted (revised) April 10, 2003 Published online August 18, 2003     

Apparent Molar Volume and Apparent Molar Refraction of Mono-, Di-, Tri-, and Tetra(oxyethylene) Glycol in Aqueous, 1,4-Dioxane, and Benzene Solutions at 298.15?K

The density and refractive index of aqueous, 1,4-dioxane, and benzene solutions of poly (oxyethylene) glycols of the type HO–(CH₂CH₂O) _n –H (n varying from 1 to 4) were measured at 298.15K. From these experimental data the apparent molar volume and the apparent molar refraction at infinite dilution were calculated. The limiting apparent molar volume of the investigated compounds in a definite solvent depends linearly on the number of oxyethylene groups. From these data, the volume of the monomeric unit was evaluated and found to be greater in non-aqueous solvents than in water. The limiting apparent molar refraction of the solute for the investigated systems, within the experimental uncertainties, is equal to the molar refraction of the pure solute. The electronic polarizability of the solute molecule depends linearly on the number of monomeric units and the ratio of the electronic polarizability to the molecular van der Waals volume is constant and independent of the number of oxyethylene groups.