Application of the PFV EoS correlation to excess molar volumes of (1-ethyl-3-methylimidazolium ethylsulfate + alkanols) at different temperatures

The experimental densities for the binary systems of an ionic liquid and an alkanol {1-ethyl-3-methylimidazolium ethylsulfate [EMIM]⁺ [EtSO₄]^? + methanol or 1-propanol or 2-propanol} were determined at T = (298.15, 303.15, and 313.15) K. The excess molar volumes for the above systems were then calculated from the experimental density values for each temperature. The Redlich–Kister smoothing polynomial was used to fit the experimental results and the partial molar volumes were determined from the Redlich–Kister coefficients. For all the systems studied, the excess molar volume results were negative over the entire composition range for all the temperatures. The excess molar volumes were correlated with the pentic four parameter virial (PFV) equation of state (EoS) model.     

Excess molar volumes and isentropic compressibility of binary systems {trioctylmethylammonium bis(trifluoromethysulfonyl)imide + methanol or ethanol or 1-propanol} at different temperatures

This paper reports measurements of densities for the binary systems of an ionic liquid and an alkanol at T = (298.15, 303.15, and 313.15) K. The IL is trioctylmethylammonium bis(trifluoromethylsulfonyl)imide [OMA]⁺[Tf₂N]^? and the alkanols are methanol, or ethanol, or 1-propanol. The speed of sound at T = 298.15 K for the same binary systems was also measured. The excess molar volumes and the isentropic compressibilities for the above systems were then calculated from the experimental densities and the speed of sound, respectively. Redlich–Kister smoothing polynomial equation was used to fit the excess molar volume and the deviation in isentropic compressibility data. The partial molar volumes were determined from the Redlich–Kister coefficients. For all the systems studied, the excess molar volumes have both negative and positive values, while the deviations in isentropic compressibility are negative over the entire composition range.     

Excess molar enthalpies and excess molar volumes of (an alkanol + a nitrile compound) atT = 298.15 K andp = 0.1 MPa

Excess molar enthalpies and excess molar volumes at T =  298.15 K andp =  0.1 MPa are reported for (methanol, or ethanol, or 1-propanol  +  1,4-dicyanobutane, or butanenitrile, or benzonitrile). For all the mixtures investigated in this work the excess molar enthalpy is large and positive. The excess molar enthalpy decreases as the carbon chain number of the alkanol species increases from methanol to propanol. The excess molar volumes are both positive and negative. The Extended Real Associated Solution and the Flory–Benson–Treszczanowicz models were used to represent the data. Both these models describe better the excess molar enthalpy than the excess molar volumes of (an alkanol  +  a nitrile compound).     

Excess molar volume of (linalool + an alkanol) atT = 303.15 K

In this paper, densities of (linalool  +  methanol, or ethanol, or n -propanol, or n -butanol) are determined at T =  303.15 K using a vibrating-tube densimeter. The excess molar volumes V_m^Evalues are negative in all the systems over the entire composition range and correlated by the Redlich–Kister equation. The effects of chain length of alkanols onV_m^E have been discussed.     

Thermodynamic excess properties for binary mixtures of (butanenitrile + a carboxylic acid) atT = 298.15 K

Excess molar enthalpies and excess molar volumes for (butanenitrile  +  acetic acid, or propanoic acid, or butanoic acid, or 2-methylpropanoic acid, or pentanoic acid, or 3-me thylbutanoic acid) atT =  298.15 K are presented. The excess molar enthalpy values are found to be positive for all six systems, whereas the excess molar volumes are found to be negative. The excess molar enthalpy values are correlated by the UNIQUAC and NRTL models and also by the Redlich–Kister polynomial.     

Excess molar enthalpies of {diethyl oxalate + (methanol, + ethanol, + 1-propanol,and + 2-propanol)} at T = (288.2, 298.2, 313.2, and 328.2) K and p = 101.3 kPa

A flow-mixing isothermal microcalorimeter was used to measure excess molar enthalpies for four binary systems of {diethyl oxalate + (methanol, + ethanol, + 1-propanol, and + 2-propanol)} at T = (288.2, 298.2, 313.2, and 328.2) K and p = 101.3 kPa. The densities of the diethyl oxalate at different temperature were measured by using a vibrating-tube densimeter. All systems exhibit endothermic behaviour over the whole composition range, which means that the rupture of interactions is energetically the main effect. The excess molar enthalpies increase with temperature and the molecular size of the alcohols. The experimental results were correlated by using the Redlich–Kister equation and two local-composition models (NRTL and UNIQUAC).     

Excess molar volumes and viscosities of (1,1,2,2-tetrabromoethane + 1-alkanols) at T = (293.15 and 303.15) K

Density and viscosity measurements for binary mixtures of (1,1,2,2-tetrabromoethane + 1-pentanol, or + 1-hexanol, or + 1-heptanol, or + 1-octanol, or + 1-decanol) at T = (293.15 and 303.15) K, have been conducted at atmospheric pressure. The excess molar volumes V^E, have been calculated from the experimental measurements, and the results were fitted to Redlich–Kister equation. The viscosity data were correlated with the model of Grunberg and Nissan, and McAllister four-body model. The excess molar volumes of (1,1,2,2-tetrabromoethane + 1-pentanol, or + 1-haxanol, or + 1-heptanol, or + 1-octanol) had a sigmoidal shape and the values varied from negative to positive with the increase in the molar fraction of 1,1,2,2-tetrabromoethane. The remaining binary mixture of (1,1,2,2-tetrabromoethane + 1-decanol) was positive over the entire composition range. The effects of the 1-alkanol chain length as well as the temperature on the excess molar volume have been studied. The results have been qualitatively used to explain the molecular interaction between the components of these mixtures.     

Densities and volumetric properties of (N-(2-hydroxyethyl)morpholine + ethanol, + 1-propanol, + 2-propanol, + 1-butanol,and + 2-butanol) at (293.15, 298.15, 303.15, 313.15, and 323.15) K

Densities of binary mixtures of N-(2-hydroxyethyl)morpholine with ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol were measured over the entire composition range at temperatures from (293.15 to 323.15) K and atmospheric pressure using a vibrating-tube densimeter. The excess molar volumes, V^E were calculated from density data and fitted to the Redlich–Kister polynomial equation. Apparent molar volumes, partial molar volume at infinite dilution and the thermal expansion coefficient of the mixtures were also calculated. The V^E values were found to be negative over the entire composition range and at all temperatures studied and become less negative with increasing carbon chain length of the alkanols.     

Volumetric properties of ternary (IL + 2-propanol or 1-butanol or 2-butanol + ethyl acetate) systems and binary (IL + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate) systems

The experimental densities for the binary or ternary systems were determined at T = (298.15, 303.15, and 313.15) K. The ionic liquid methyl trioctylammonium bis(trifluoromethylsulfonyl)imide ([MOA]⁺[Tf₂N]⁻) was used for three of the five binary systems studied. The binary systems were ([MOA]⁺[Tf₂N]⁻ + 2-propanol or 1-butanol or 2-butanol) and (1-butanol or 2-butanol + ethyl acetate). The ternary systems were {methyl trioctylammonium bis(trifluoromethylsulfonyl)imide + 2-propanol or 1-butanol or 2-butanol + ethyl acetate}. The binary and ternary excess molar volumes for the above systems were calculated from the experimental density values for each temperature. The Redlich–Kister smoothing polynomial was fitted to the binary excess molar volume data. Virial-Based Mixing Rules were used to correlate the binary excess molar volume data. The binary excess molar volume results showed both negative and positive values over the entire composition range for all the temperatures.The ternary excess molar volume data were successfully correlated with the Cibulka equation using the Redlich–Kister binary parameters.     

Volumetric properties of (piperidine + water) binary system: Measurements and modeling

Densities of pure piperidine (CAS No.: 110-89-4) and of its mixtures with water have been measured over the whole range of compositions at temperatures from 283.15 K to 347.15 K using Anton Paar? digital vibrating tube densimeter. The density of this system has been found increasing with mass fraction of water. Excess molar volumes have been calculated using the measured experimental densities and correlated using the Redlich–Kister equation. Redlich–Kister equation parameters have been adjusted on experimental data. In addition, partial molar volumes and partial excess molar volumes at infinite dilution have been calculated for each component.     

Ultrasound speeds and molar isentropic compressions of (3-ethoxypropane-1-amine + water) mixtures from T = (283.15 to 303.15) K

Alkoxyamines containing two hydrophilic groups with great affinity to water are multipurpose compounds with important applications, either on theoretical or practical grounds. The thermodynamic characterization of aqueous mixtures of these compounds is scant. Ultrasound speed measurements have been made in 53 mixtures of the aqueous ethoxypropane-1-amine binary system, across the entire composition range and temperatures between T = (283.15 and 303.15) K, at atmospheric pressure. By combining ultrasound speed and density data, values of the isentropic compressibility were derived. Excess molar isentropic compressions were estimated and analytically fitted to Redlich–Kister polynomial equations. Excess partial molar quantities were then calculated including their limiting values, which were obtained from the Redlich–Kister fitting coefficients. The temperature dependences of limiting partial molar isentropic compressions and isobaric expansions were also scrutinized. Compressibility changes associated with different patterns of aggregation and hydration over the whole composition range are identified.     

Densities,excess molar volumes,and refractive indices of 1,1,2,2-tetrabromoethane and 1-alkanols binary mixtures

Densities, excess molar volumes, refractive indices, and changes in refractive index on mixing for (1,1,2,2-tetrabromoethane + 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-decanol) have been determined at T = 293.15 K and at T = 303.15 K. The excess molar volumes and changes in refractive index have been fitted to Redlich–Kister polynomials. The effect of the chain length of the 1-alkanol on the excess molar volume and the change in the refractive index of its mixtures with 1,1,2,2-tetrabromoethane are discussed. In addition, the refractive indices are compared with calculated values using mixing rules proposed by several authors, and a good agreement is obtained.     

Densities,excess molar volumes,and refractive indices of 1,1,2,2-tetrachloroethane and 1-alkanols binary mixtures

Densities, excess molar volumes, refractive indices, and changes in refractive index on mixing for 1,1,2,2-tetrachloroethane + 1-pentanol, or 1-hexanol, or 1-heptanol, or 1-octanol, or 1-decanol have been determined at T = (293.15 and 303.15) K. The excess molar volumes and changes in refractive index have been fitted to Redlich–Kister polynomials. The effect of the chain length of the 1-alkanol on the excess molar volume and the change in the refractive index of its mixtures with 1,1,2,2-tetrachloroethane was discussed. In addition, the refractive indices were compared with calculated values using mixing rules proposed by several authors, and a very good agreement was obtained.     

Excess molar enthalpies and excess molar volumes of (1,3-dimethyl-2-imidazolidinone + an aromatic hydrocarbon) atT = 298.15 K

Excess molar enthalpies H_m^Eand excess molar volumesV_m^E of (1,3-dimethyl-2-imidazolidinone  +  benzene, or methylbenzene, or 1,2-dimethylbenzene, or 1,3-dimethylbenzene, or 1,4-dimethylbenzene, or 1,3,5-trimethylbenzene, or ethylbenzene) over the whole range of compositions have been measured at T =  298.15 K. The excess molar enthalpy values were positive for five of the seven systems studied and the excess molar volume values were negative for six of the seven systems studied. The excess enthalpy ranged from a maximum of 435 J · mol ^− 1for (1,3-dimethyl-2-imidazoline  +  1,3,5-trimethylbenzene) to a minimum of  − 308 J · mol ^− 1for (1,3-dimethyl-2-imidazoline  +  benzene). The excess molar volume values ranged from a maximum of 0.95cm³mol ^− 1 for (1,3-dimethyl-2-imidazoline  +  ethylbenzene) and a minimum of  − 1.41 cm³mol ^− 1for (1,3-dimethyl-2-imidazoline  +  methylbenzene). The Redlich–Kister polynomial was used to correlate both the excess molar enthalpy and the excess molar volume data and the NRTL and UNIQUAC models were used to correlate the enthalpy of mixing data. The NRTL equation was found to be more suitable than the UNIQUAC equation for these systems. The results are discussed in terms of the polarizability of the aromatic compound and the effect of methyl substituents on the benzene ring.     

Excess molar enthalpies for (benzonitrile + an aromatic hydrocarbon) atT = 298.15 K

The excess molar enthalpies of (benzonitrile  +  benzene, or methylbenzene, or 1,2-dimethylbenzene, or 1,3-dimethylbenzene, or 1,4-dimethylbenzene, or 1,3,5-trimethylbenzene, or ethylbenzene) have been determined at T =  298.15 K. The excess molar enthalpies range from  − 10 J · mol ^− 1for methylbenzene to 130 J · mol ^− 1for 1,3,5-trimethylbenzene. The Redlich–Kister equation, the NRTL, and UNIQUAC models were used to correlate the data. The results indicate a relatively strong association between benzonitrile and each of the aromatic compounds, decreasing with increasing methyl substitution on the benzene moiety.     

Experimental densities,refractive indices,and speeds of sound of 12 binary mixtures containing alkanes and aromatic compounds at T = 313.15 K

Densities, speeds of sound, and refractive indices of 12 binary systems of alkanes (hexane, heptane, octane, and nonane) with aromatics (benzene, or toluene, or ethylbenzene) at T = 313.15 K and at atmospheric pressure were determined over the whole composition range, and are presented in this paper. From the experimental results, the derived and excess properties (isentropic compressibility, excess molar volumes, and excess molar isentropic compressibility) at T = 313.15 K were calculated and satisfactorily fitted to the Redlich–Kister equation.     

Experimental and predicted excess molar enthalpies for 1,4-dioxane + octane + cyclohexane at 303.15 K

Excess molar enthalpies for the ternary system 1,4-dioxane (1) + n-octane (2) + cyclohexane (3) and for the three constituent binary systems have been measured by a Calvet microcalorimeter at 303.15 K and ambient pressure. The experimental binary results were fitted by the Redlich–Kister equation. The excess molar enthalpies of the ternary system were correlated using the Cibulka equation. The DISQUAC group contribution model was applied to predict the excess molar enthalpy for this mixture.     

Thermophysical properties of the binary mixtures (1,8-cineole + 1-alkanol) at T = (298.15 and 313.15) K and at atmospheric pressure

This work presents the measurements of the density, speed of sound, refractive index and enthalpy of binary mixtures containing {1,8-cineole + 1-alkanol (ethanol, 1-propanol, 1-butanol, and 1-pentanol)} at two temperatures (298.15 and 313.15) K and atmospheric pressure. The determination of excess molar volume, speed of sound deviation, refractive index deviation, molar refraction, molar refraction deviation, excess isentropic compressibility, and excess molar enthalpy are also given. Redlich–Kister equation was used to fit these derivate properties. The experimental data of the constituent binaries were analysed to discuss the nature and strengths of intermolecular interactions. Eventually some models, SAFT and PC-SAFT for density, Free Length and Collision Factor for speed of sound, Gladstone-Dale Arago-Biot for refractive index, and UNIFAC for excess molar enthalpy, among others, were successfully applied.     

Excess molar enthalpies of binary systems containing 2-octanone,hexanoic acid,or octanoic acid at T = 298.15 K

An isothermal titration calorimeter was used to measure the excess molar enthalpies (H^E) of six binary systems at T = 298.15 K under atmospheric pressure. The systems investigated include (1-hexanol + 2-octanone), (1-octanol + 2-octanone), (1-hexanol + octanoic acid), (1-hexanol + hexanoic acid), {N,N-dimethylformamide (DMF) + hexanoic acid}, and {dimethyl sulfoxide (DMSO) + hexanoic acid}. The values of excess molar enthalpies are all positive except for the DMSO- and the DMF-containing systems. In the 1-hexanol with hexanoic acid or octanoic acid systems, the maximum values of H^E are located around the mole fraction of 0.4 of 1-hexanol, but the H^E vary nearly symmetrically with composition for other four systems. In addition to the modified Redlich–Kister and the NRTL models, the Peng–Robinson (PR) and the Patel–Teja (PT) equations of state were used to correlate the excess molar enthalpy data. The modified Redlich–Kister equation correlates the H^E data to within about experimental uncertainty. The calculated results from the PR and the PT are comparable. It is indicated that the overall average absolute relative deviations (AARD) of the excess enthalpy calculations are reduced from 18.8% and 18.8% to 6.6% and 7.0%, respectively, as the second adjustable binary interaction parameter, k_bij, is added in the PR and the PT equations. Also, the NRTL model correlates the H^E data to an overall AARD of 10.8% by using two adjustable model parameters.     

Densities,excess molar volumes,and refractive indices of ethyl acetate and aromatic hydrocarbon binary mixtures

Densities, excess molar volumes, refractive indices, and changes in refractive index on mixing for (ethyl acetate  +  benzene, or methylbenzene, or ethylbenzene, or 1-4-dimethylbenzene, or 1-methylethylbenzene, or 1-3-5-trimethylbenzene, or 1-1-dimethylethylbenzene) have been determined atT =  298.15 K. The excess molar volumes and changes in refractive index have been fitted to Redlich–Kister polynomials. The π -electrons interactions of the benzene ring and the peculiar plate shape of the aromatic molecules are noticeably modified by the presence of the ethyl acetate molecules of a different nature. The intermolecular interactions are strongly modified and result in positive excess volumes except for toluene or p -xylene whose values are close to zero. The refractive indices were compared with calculated values using mixing rules proposed by several authors.