Sharif Digital Repository

Interfacial tension of both 36 binary and 6 ternary liquid-liquid systems at 298 K, has been predicted through a reliable thermodynamic model. To properly predict interfacial tension, it is necessary to calculate interfacial area of each constituent of the mixtures. For such estimation, two empirical correlations have been proposed for binary mixtures whose one component is water and experimental data have been used to calculate interfacial area of ternary mixtures. The UNIQUAUC Excess Gibbs Free energy model and its parameters have been used to calculate the concentration and activity coefficients in the bulk and interface phases. The overall average deviation of the predicted binary... 

The solubility of carbon dioxide in a series of 1-(2-hydroxyethyl)-3-methylimidazolium ([hemim]+) based ionic liquids (ILs) with different anions, viz. hexafluorophosphate ([PF6]-), trifluoromethanesulfonate ([OTf]-), and bis-(trifluoromethyl)sulfonylimide ([Tf2N]-) at temperatures ranging from 303.15 K to 353.15 K and pressures up to 1.3 MPa were determined. The solubility data were correlated using the Krichevsky-Kasarnovsky equation and Henry's law constants were obtained at different temperatures. Using the solubility data, the partial molar thermodynamic functions of solution such as Gibbs free energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of CO2... 

In two-phase system, curvature of interface leads to increase of solute concentration in matrix. This effect plays a significant role in solidification, precipitation, nucleation and growth and coarsening. There are number of models and formulas for Gibbs-Thomson effect in binary alloys. In this paper with the help of CALPHAD calculations, new approach for describing this effect in binary and multicomponent systems is proposed. In this generalized method no traditional simplifying assumption are considered and this yield to more accurate result for Gibbs-Thomson phenomenon. This model is compared with previous formulas in some case alloying systems. © 2006 Elsevier B.V. All rights reserved  

Rhenium distribution between Tri-n-butyl phosphate (TBP) dissolved in kerosene and sulfuric aqueous media is investigated under different temperatures, acidities, and TBP concentrations. Results show an exothermic extraction reaction with a distribution factor that decreases with the increase of the temperature and increases with the increase of the acidity and the TBP concentration. The stoichiometry of the reaction indicates neutralization of 1 mole of H+ with 1 mole of ReO4- and solvating of a neutral molecule with four molecules of TBP. The structure of the complexes formed is, therefore, 4TBP · HReO4. The apparent Gibbs free energy of the formation of 4TBP · HReO4 from TBP, ReO4-, and... 

The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF6]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF4]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf2N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky-Kasarnovsky equation and Henry's constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained... 

This paper presents a new segment-based thermodynamic model containing the combinatorial and energetic contributions to the excess Gibbs energy for correlating/predicting of the vapor-liquid equilibrium (VLE) of polymer solutions. The model is derived from the UNIQUAC-NRF model, recently proposed by Haghtalab and Asadollahi, following the idea to associate the nonideality of polymer-solvent mixture with polymer segment-solvent interaction parameters, Segment activity coefficients are calculated by means of the UNIQUAC-NRF model. At the present state of development, 16 binary segmental interaction parameters have been estimated, The capability of the model is demonstrated with successful... 

Gasification of biomass in supercritical water is a successful technology for hydrogen production especially by using wet biomass. The whole process, from feeding to purification of hydrogen, consists of a lot of equipment, such as pumps, heat exchangers, heaters, reactors, etc. Because the main reactions take place in the gasification reactor, the gasifier is the most important equipment of the process. In this article, a thermodynamic model, including chemical equilibrium in the reactor that is based on Gibbs free energy minimization, is developed to estimate equilibrium composition for gasification of biomass in supercritical water for hydrogen production. For this analysis, we use three... 

In this research, copper matrix composites reinforced with different amounts of titanium carbide particles were produced by mechanical milling and in-situ formation of reinforcements. Morphology and size of milled powders were inspected by scanning electron microscopy (SEM) several times during milling process. Changes in lattice parameter, crystallite size, lattice strain, dislocation density and Gibbs free energy changes (due to increasing in dislocation densities and grain boundaries) in different samples (with different TiC particles contents) were studied by X-Ray Diffraction technique with Cu-kα radiation and using Nelson-Riley method and Williamson-Hall equation. Microstructure of... 

In this work, the selectivity coefficients of ionic liquids in liquid-liquid systems were correlated and predicted by the NRTL, UNIQUAC, and Wilson-NRF Gibbs free energy models and also by an artificial neural network system. The three thermodynamic models need six binary interaction parameters between solvent(1)-solvent(2), solvent(1)-ionic liquid, and solvent(2)-ionic liquid pairs in obtaining the selectivity of ionic liquid in liquid-liquid systems. Also, the selectivity coefficients of ionic liquids were modeled using an artificial neural network system. In the proposed neural network system, temperature, molecular weight of ionic liquid, molecular weight of solvents, and mole fractions... 

In this paper, the polymer chain of rotator (PCOR) equation of state (EOS) was used together with an EOS/GE mixing rule (MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers. The results of the proposed method compared with two equation of state (van der Waals and GC-Flory) and three activity coefficient models (UNIFAC, UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results. The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data... 

The solubility of hydrogen sulfide gas in ionic liquids (ILs) 1-ethyl-3-methylimidazolium hexafluorophosphate ([emim][PF6]) at temperatures from (333.15 to 363.15) K and 1-ethyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide ([emim][Tf2N]) at temperatures ranging from (303.15 to 353.15) K and pressures up to about 2.0 MPa was measured using a volumetric based static apparatus. The solubility data were correlated using two models: the Krichevsky - Kasarnovsky (KK) equation, and the extended Henry's law combined with the Pitzer's virial expansion for the excess Gibbs energy. Henry's law constants (at zero pressure) were obtained at different temperatures from the obtained experimental... 

The solubility of hydrogen sulfide in a series of 1-(2-hydroxyethyl)-3-methylimidazolium ([HOemim]+)-based ionic liquids (ILs) containing different anions, viz. hexafluorophosphate ([PF6]-), trifluoromethanesulfonate ([OTf]-), and bis-(trifluoromethyl)sulfonylimide ([Tf2N]-) at temperatures ranging from 303.15 to 353.15K and pressures of up to about 1.8MPa was measured by a volumetric based static apparatus. The solubility data were correlated using two models: (1) the Krichevsky-Kasarnovsky equation and (2) the extended Henry's law combined with the Pitzer's virial expansion for the excess Gibbs energy. Henry's law constants (at zero pressure) in mole-fraction and molality scales were... 

Adsorption and dissociation of NO on RhxCu4-x(x = 0–4) nano clusters were investigated using density functional theory. Adsorption energy, total charge on NO, NO bond length, and NO vibrational frequency for various modes of NO adsorption were analyzed. Adsorption from the nitrogen end of NO on the Rh atom(s) of the clusters are more favored and adsorption energies are in the −1.02 eV to −2.59 eV range. NO binds stronger to Rh-Cu mixed clusters compared to pure Cu4 cluster, so N[sbnd]O bond is significantly weakened upon adsorption on the former. NO binding to more atoms of the clusters results in a corresponding decrease of the N[sbnd]O vibrational frequency. Dissociation of NO was also... 

In this work, an expression for the free volume Gibbs energy model based on the local composition concept (LCC) has been proposed in correlating the solubility, the partitioning and the surface tension of β-lactam, tetracycline, fluoroquinolone and chloramphenicol antibiotic groups in water, alcohol, ketone, trihalomethane, ether and ester solvent groups. Similar to the LCC models the proposed model has two combinatorial and residual terms. The extended Guggenheim model is used as combinatorial term and a new local composition-based model, which is the extended local area fraction NRTL-NRF model, is proposed for the residual term. The results obtained from the proposed model have been... 

In this work, the partition coefficients of Cephalexin in aqueous two-phase systems containing PEG [poly(ethylene glycol)] 4000, 10000 and K 2HPO4, Na3Citrate (C6H 5Na3O7 5, 5H2O) have been measured. The experimental data were obtained in a wide range of temperatures, (28.2 to 37.2) °C. The effects of temperature, pH, polymer concentration, polymer molecular weight, and salt concentration on the partitioning of Cephalexin were also studied. The results showed that salt concentration has a large effect on the partition coefficient, and temperature has an almost negligible effect. The Chen-NRTL Gibbs energy model was used to correlate the experimental results. © 2009 American Chemical Society  

The wetting property of spherical particles in a hexagonal close-packed (HCP) ordering from extended Gibbs free energy (GFE) and Laplace pressure view points is studied. A formalism is proposed to predict the contact angle (θ) of a droplet on the HCP films and penetration angle (α) of the liquid on the spherical particles. Then, the extended Laplace pressure for the layered HCP ordering is calculated and a correlation between the wetting angle, sign of pressure, and pressure gradient is achieved. Our results show that the sign and the slope of pressure are important criteria for determining the wettability state and it is found that the contact angle is independent of the particle radius, as... 

In this article, we report the computational examination of the impact of hydrogen bonding (HB) on the stereoselectivity of a series of Diels-Alder (DA) reactions. Four different types of diene/dienophile couples were studied including (a) cyclopenta-2,4-dien-1-ol and heteroatom-substituted cyclopentenes, (b) substituted cyclopentadienes andN-protonated 2,5-dihydro-1H-pyrrole, (c) furan andN-protonated 5-azabicyclo[2.1.1]hex-2-ene, and (d)N-protonated cyclopenta-2,4-dien-1-amine and α,β-unsaturated carbonyl compounds. These systems were designed such that the HB can only exist in theexoreaction pathway. The optimized structures of the transition states (TSs) and products, along with the... 

Ionic liquids, which are designable and nonvolatile, have become a hot topic in the field of CO2 separation from industrial gases. In order to utilize the nonvolatile and low heat capacity of ionic liquids, it is necessary to solve the problem of high viscosity of pure ionic liquids. In the present study, ether functionalized pyridinium ion [E1Py]+ with good biodegradability and low viscosity was selected as cation. Ions containing cyano groups were used as anions, such as thiocyanate ion [SCN]-, dicyanamide ion [N(CN)2]-, tricyanomethanide ion [C(CN)3]-. Three ionic liquids with low viscosity were synthesized and characterized by 1HNMR, 13CNMR and FTIR. The physiochemical properties of... 

Metallic nanoparticles are interesting because of their use in catalysis and sensors. The surface energy of the FCC platinum nanoparticles are investigated via molecular dynamics simulation using Quantum Sutton-Chen (QSC) potential. We have calculated the Gibbs free energy for the FCC platinum bulk and also for its nanoparticle. All calculations have been carried out at zero pressure. We have used the thermodynamic integration method to obtain the Gibbs free energy. The total Gibbs free energy is taken as the sum of its central bulk and its surface free energy. We have calculated the free energy of a platinum nanoparticle as a function of temperature