• Journal of the Korean Applied Science and Technology
• /
• v.17 no.2
• /
• pp.132-138
• /
• 2000

Excess enthalpies ($H^{E}$) were measured by isothermal flow calorimetry for the nonionic amphiphile 2-butoxyethanol/water mixtures at 10 different temperatures (48.5 to $70^{\circ}C$) around and above the lower consolute solution temperature, $T_{lc}$. $H^{E}$ exhibits U-shape for the binary mixtures, and is large and negative which reflects substantial interaction between two chemical species. When the commonly used, semi-empirical Redlich-Kister (RK) polynomials were fitted to the measured $H^{E}$, plots of $H^{E}$ vs. weight fraction provided more accurate fitting with fewer parameters than conventionally drawn $H^{E}$ vs. mole fraction plots. This was due to the enhanced symmetry of $H^{E}$ vs. weight fraction plots. Using the fitted Redlich-Kister polynomials and the Gibbs-Helmholtz relation, temperature dependence of the activity coefficients were found and compared to the values determined from vapor-liquid equilibria. The activity coefficients were in the range of one to three, indicating that the binary system deviates from ideality but not substantially. They slightly depended on temperature and the temperature effect was equivalent to 10 % change in the activity coefficients.

• Korean Chemical Engineering Research
• /
• v.47 no.6
• /
• pp.755-761
• /
• 2009

To a first approximation, phase behavior of a system becomes increasingly skew in proportion to the boiling point difference of system-forming constituents. Therefore, phase behavior data of a system of a large boiling point difference are to be experimentally measured for thorough understanding of the thermodynamic characteristics of such system. In this work, isobaric vapor-liquid equilibrium of a mixture consisting of toluene and cresol, which shows a large boiling point difference of nearly $100^{\circ}C$ and is consequently expected to be considerably nonideal, was measured by using a recirculating equilibrium cell at various subatmospheric pressures ranging from 10 kPa to 60 kPa. The measured VLE data were correlated with NRTL and UNIQUAC models in a satisfactory manner and the accompanying thermodynamic consistency test represented soundness of the measurements. In addition, the excess molar volume of the mixture was also measured with a vibrating densitometer and correlated with a Redlich-Kister polynomial. A negative excess volume prevailed over the whole concentration range, which indicates a favorable attraction between toluene and cresol isomers and results in an extensive miscibility.

• Applied Chemistry for Engineering
• /
• v.21 no.3
• /
• pp.295-300
• /
• 2010

A binary system of 1-propanol and bromochloromethane which exhibits an azeotropic point and a considerable nonideal phase behavior probably due to the large boiling point difference is not amenable in the actual chemical processes such as the distillation tower and absorber. Therefore, experimental data of phase behavior data of this mixture are indispensable in understanding the inherent thermodynamic characteristics for an efficient application of the system in the industrial processes. In this work, the isobaric vapor-liquid equilibrium of a binary mixture consisting of 1-propanol and bromochloromethane was measured by using a recirculating equilibrium cell at various pressures ranging from 30 to 70 kPa. The measured VLE data were correlated in a satisfactory manner by using the UNIQUAC and NRTL models along with the thermodynamic consistency test based on Gibbs/Duhem equation. In addition, the excess molar volume of the mixture was also measured by using a vibrating densitometer and correlated with a Redlich-Kister polynomial.

• Journal of the Korean Chemical Society
• /
• v.54 no.1
• /
• pp.71-76
• /
• 2010

The densities and viscosities of 2-bromopropane-methanol binary mixtures had been determined using an digital vibrating U-tube densimeter and Ubbelohde capillary viscometer respectively from (298.15 to 318.15) K. The dependence of densities and viscosities on temperature and concentration had been correlated. The excess molar volume and the excess viscosity of the binary system were calculated from the experimental density and viscosity data. The excess molar volumes were related to compositions by polynomial regression and regression parameters and total RMSD deviations were obtained; the excess viscosities was related to compositions by Redlich-Kister equation and regression coefficients and total RMSD deviation of the excess viscosity for 2-bromopropane and methanol binary system were obtained. The results showed that the model agreed very well with the experimental data.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.1686-1692
• /
• 2012

Densities (${\rho}$), Viscosities (${\eta}$) and ultrasonic speeds (u) of pure acetophenone (AP), propiophenone (PP), $p$-methyl acetophenone ($p$-MeAP), $p$-chloroacetophenone ($p$-ClAP) and those of their binary mixtures with $N$-ethyl aniline ($N$-EA) as a common component, were measured at 303.15 K over the entire composition range. These experimental data were used to calculate the excess volume $V^E$, deviation in ultrasonic speeds ${\Delta}u$, isentropic compressibility $K_s$, intermolecular free length $L_f$, acoustic impedance Z, deviations in isentropic compressibility ${\Delta}K_s$, deviation in viscosity ${\Delta}{\eta}$ and excess Gibbs free energy of activation of viscous flow ($G^{*E}$) at all mole fractions of $N$-ethyl aniline. These parameters, especially excess functions, are found to be quite sensitive towards the intermolecular interactions between component molecules. Theoretical values of viscosity of the binary mixtures were calculated using different empirical relations and theories. The relative merits of these relations and theories were discussed. The experimental results were correlated by using the polynomial proposed by Redlich-Kister equation.

• Korean Chemical Engineering Research
• /
• v.56 no.4
• /
• pp.536-541
• /
• 2018

Excess molar volumes ($V_m^E$) of binary mixtures of 1-propanol or 2-propanol (1) + cyclohexane or n-hexane (2) were measured with V-shaped dilatometer at 303.15 K. The $V_m^E$ data for these mixtures varied as: 2-propanol > 1-propanol and were higher for cyclohexane than n-hexane for both propanol systems. The experimental data were correlated with Redlich-Kister polynomial. The $V_m^E$ data were interpreted qualitatively as well as quantitatively in terms of Flory-Treszczanowicz-Benson model and Prigogine-Flory-Patterson theory. Both models correctly described the sign and shape of $V_m^E$ vs $x_1$ curves. The values calculated by both the models agree well with the experimental data.

• Journal of the Korean Chemical Society
• /
• v.56 no.4
• /
• pp.424-430
• /
• 2012

Densities, viscosities, refractive indices and speed of sounds of the binary mixtures of Acetophenone with Ethylchloroacetate were measured over the entire mole fractions at (303.15, 313.15 and 323.15) K. From these experimental results, excess molar volume $V^E$, viscosity deviation ${\Delta}{\eta}$, refractive index deviation ${\Delta}n_D$, deviations in speed of sound ${\Delta}u$, deviations in isentropic compressibility ${\Delta}k_s$ and excess intermolecular free length ${\Delta}L_f$ were calculated. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind et al., Tamura and Kurata, Katti and Chaudri, Sedgwick, Krishnan-Laddha and McAllister. The thermo physical properties under study were fit to the Jouyban-Acree model. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. It was found that in all cases, the data obtained fitted with the values correlated by the corresponding models very well. The results are interpreted in terms of molecular interactions occurring in the solution.

• Korean Chemical Engineering Research
• /
• v.57 no.1
• /
• pp.78-84
• /
• 2019

Recently, bio-butanol is being promoted as environmentally friendly sustainable energy. However, some problems are still obstacle for commercialization of bio-butanol: the development of cheap biomass and enhancement of fermentation ratio and preparation of economical separation process for fermented products. In the conventional ABE biobutanol fermentation process, organic acids with acetone, butanol, and ethanol are produced. Therefore, it is necessary to study phase equilibrium data and mixture properties for the design and operation of separation process. However, there is lack of design data for organic acids except acetic acid contained system. In this study, therefore, binary solid-liquid equilibria (SLE) and mixture properties: the excess molar volumes ($V^E$), molar refraction deviation (${\Delta}R$) and deviation of viscosity (${\Delta}v$) at 298.15 for $C_3-C_6$ organic acid were reported. The experimental SLE data were correlated with the NRTL and UNIQUAC activity coefficient model with less than 0.5 K of root mean square deviation (RMSD). In addition, $V^E$, ${\Delta}R$ and ${\Delta}v$ for the same binary systems were satisfactorily fitted using the Redlich-Kister polynomial with less than ca. 0.004 standard deviation.

• Korean Chemical Engineering Research
• /
• v.55 no.4
• /
• pp.520-529
• /
• 2017

Viscosity data were measured at 298.15 K and 308.15 K for formamide + 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol or 2-methyl-2-propanol mixtures. For an equimolar mixture, deviation in viscosity follows the sequence: 2-methyl-2-propanol >2-methyl-1-propanol>1-butanol>2-propanol>1-propanol. The viscosity data were further analyzed in terms of graph theory. Free energy of activation was also calculated from experimental viscosity data along with previously reported excess volume data. The deviation in viscosity and free energy of activation were fitted to Redlich-Kister polynomial equation. The viscosity data were also correlated by correlations like Grunberg-Nissan, Tamura-Kurata, HindMcLaughlin-Ubbelohde, and Katti-Chaudhari relation. Various adjustable parameters, $G_{12}$, $T_{12}$, $H_{12}$, and $W_{vis}/RT$, of various correlations were used to predict viscosity deviation of binary mixtures. Positive value of $G_{12}$ indicates strong interaction in the studied systems. Grunberg-Nissan relation has lowest deviation among the four correlations for formamide + 1-propanol or 2-propanol mixtures; and for mixtures of formamide with 1-butanol or 2-methyl-1-propanol, TamuraKurata has lowest deviation. Grunberg-Nissan gives lowest deviation for formamide + 2-methyl-2-propanol mixtures.

• Korean Chemical Engineering Research
• /
• v.58 no.2
• /
• pp.257-265
• /
• 2020

Densities (ρ) for binary mixtures of ethanol (1) + diisopropyl ether (DIPE) or cyclohexane or alkane (C₆-C₉) (2) were measured at 298.15 K, 308.15 K and 318.15 K. The excess molar volume (V^E_m) of binary mixtures was calculated using ρ data and correlated with Redlich-Kister polynomial equation. The V^E_m values for binary mixtures of ethanol (1) + cyclohexane or n-alkane (C₆-C₉) (2) were positive, whereas for ethanol (1) + DIPE (2) these were negative. The magnitude of V^E_m values follows the order: cyclohexane > n-nonane > n-octane > n-heptane > n-hexane > DIPE. The V^E_m values have been interpreted qualitatively and also quantitatively in terms of Flory-Treszczanowicz-Benson (FTB) model and Prigogine-Flory-Patterson (PFP) theory. The values V^E_m predicted using FTB model agree well with experimental V^E_m values at all mole fractions. But the PFP theory describes well V^E_m data in ethanol-rich region (x₁ > 0.5) for all binary mixtures and is able to predict the sign of V^E_m vs x₁ curve for ethanol-lean region (x₁ < 0.5) except for ethanol (1) + nonane (2) mixtures.