Study of molecular interactions in binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol at varying temperatures

The thermophysical properties of binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol have been investigated in this article. Densities, refractive index, ultrasonic velocity and viscosity for the two binary mixtures viz. formamide with 2-methoxyethanol and 2-ethoxyethanol have been measured over the entire composition range at 293, 303 and 313 K and at atmospheric pressure. The excess molar volume, the molar refraction deviation, excess Gibb's free energy of activation for viscous flow, excess isentropic compressibility, deviation in viscosity, excess free volume and excess molar enthalpy have been computed using experimental data. These excess parameters have been correlated with Redlich–Kister polynomial equation. The results have been interpreted on the basis of strength of intermolecular interaction occurring in these mixtures. Densities, refractive index and ultrasonic velocity were correlated with second-order polynomial equation. The molar volume and excess partial molar volume at infinite dilution have also been calculated for both the mixtures.     

Preparation of Gold Nanoparticles Using 2-Ethoxyethanol, 2-Methoxyethanol and 1,3-Butyleneglycol Supported in Chitosan

The aim of this work was to prepare and characterize several properties of Au nanoparticles colloids prepared by the “chemical liquid deposition” method, which involves the co-deposition of metallic Au with organic vapors (2-ethoxyethanol, 2-methoxyethanol and 1,3-butylenglycol at 77 K). AuNPs supported on chitosan were performed by solvated metal atom dispersed method. Then, colloids were characterized by transmission electron microscopy (TEM), electron diffraction (ED), UV–Vis spectroscopy, electrophoretic mobility, physical stability, medium–far infrared spectroscopy and thermogravimetric analysis. These studies had demonstrate that Au nanoparticles solvated with 1,3-butylenglycol and 2-ethoxyethanol, shows higher stability, due to their high dielectric constant and a better NPs solvation. TEM analysis showed a size distribution between 4.61 and 48.8 nm. From ED, a face-centered cubic structure was found. UV–Vis analysis showed lower stability of nanoparticles solvated with 2-methoxyethanol. FTIR spectra showed that the solvent was incorporated and surround the Au NPs. The thermograms shows that thermal decomposition of AuNPs–chitosan decreases with the metal presence. Bioassays of acute toxicity on fishes with AuNPs–chitosan with 1,3-butylenglycol were carried out due to the lower toxicity. The bioassay showed that 0.94 mL/L produce mortality of 50 % (LD 50) of fishes exposed 96 h calculated with a confidence interval of 0.810–1.148 mL/L.     

Ionization constants for water and for very weak organic acids in aqueous organic mixtures

A potentiometric method using a glass electrode has been applied to the determination of apparent ionization constants for water in binary mixtures of water with 11 organic solvents at 25°C. Further calculations with these apparent ionization constants permit evaluation of the acid ionization constant for some of the organic solvents as solutes in purely aqueous solvent by two different methods. Resulting values of pK _a derived from this work are: 1,2-propanediol (14.8 and 14.8), 2,3-butanediol (15.0 and 14.7), 1,3-butanediol (15.5 and 14.8), 1,4-butanediol (14.5 and 14.4), 2-butene-1,4-diol (14.0 and 13.9), 2-butyne-1,4-diol (12.1 and 12.4), 2-methoxyethanol (15.2 and 14.8), 2-ethoxyethanol (15.0 and 14.5), and triethylene glycol (14.6 and 14.3). None of the 11 solvents shows appreciable basicity.     

Totally inclusive cubic equation of state with five parameters for pure fluids

A totally inclusive cubic equation of state (cubic EOS) is proposed. Although, its form is fairly simple as compared with the present cubic equations, it can include all of them as special cases. The EOS has five parameters. By fitting the experimental critical isothermal for six typical substances combining the critical conditions, the generalized expressions for the five parameters at critical temperature are established. The temperature coefficients of the five parameters for 43 substances are determined by fitting the experimental data of vapor pressure and saturated liquid density. These coefficients are correlated with the critical compressibility factor and acentric factor to obtain the generalized expressions. The predicted saturated vapor pressure, saturated liquid density, critical isothermal and coexistence curve near the critical point show that the equation gives the best results when compared with the Redlich–Kwong–Soave (RKS) and Peng–Robinson (PR) EOS.     

Vapor-liquid equilibria simulation and an equation of state contribution for dipole-quadrupole interactions

A systematic investigation on vapor-liquid equilibria (VLEs) of dipolar and quadrupolar fluids is carried out by molecular simulation to develop a new Helmholtz energy contribution for equations of state (EOSs). Twelve two-center Lennard-Jones plus point dipole and point quadrupole model fluids (2CLJDQ) are studied for different reduced dipolar moments micro*2=6 or 12, reduced quadrupolar moments Q*2=2 or 4 and reduced elongations L*=0, 0.505, or 1. Temperatures cover a wide range from about 55% to 95% of the critical temperature of each fluid. The NpT+test particle method is used for the calculation of vapor pressure, saturated densities, and saturated enthalpies. Critical data and the acentric factor are obtained from fits to the simulation data. On the basis of this data, an EOS contribution for the dipole-quadrupole cross-interactions of nonspherical molecules is developed. The expression is based on a third-order perturbation theory, and the model constants are adjusted to the present 2CLJDQ simulation results. When applied to mixtures, the model is found to be in excellent agreement with results from simulation and experiment. The new EOS contribution is also compatible with segment-based EOS, such as the various forms of the statistical associating fluid theory EOS.     

Effect of cosolvent hydrophobicity on the aquation of cis- and trans-chloro(nitro)bis(ethylenediamine)cobalt(III) ions

The kinetics of aquation of cis- and trans-[Co(en)2NO2Cl]+ have been investigated in aqueous mixtures of 2-methoxyethanol, 2-ethoxyethanol, isopropoxyethanol, 2-butoxyethanol, 1,2-dimethoxyethane, ethylene glycol and n-propanol over a range of temperatures. The results are discussed in terms of the hydrophobic effect in these systems.     

Density and relative permittivity of (pyridine + 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol,and 2-butoxyethanol) binary mixtures at 298.15 K

The densities and relative permittivities of binary mixtures of pyridine 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) and the deviation in the relative permittivity (Δε) from a mole fraction average have been calculated. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Thermodynamic properties of n-alkoxyethanols+organic solvent mixtures: XVIII. Excess volumes at 298.15 K for 2-(2-alkoxyethoxy)ethanol+n-polyether

Excess molar volumes, V^E at 298.15 K and atmospheric pressure for 2-(2-methoxyethoxy)ethanol or 2-(2-butoxyethoxy)ethanol+2,5-dioxahexane, +2,5,8-trioxanonane, +3,6,9-trioxaundecane, +5,8,11-trioxapentadecane, and +2,5,8,11,14-pentaoxapentadecane, or for 2-(2-ethoxyethoxy)ethanol+2,5,8-trioxanonane, +3,6,9-trioxaundecane, and +5,8,11-pentaoxapentadecane have been obtained from densities measured with and Anton-Paar DMA 602 vibrating-tube densimeter.The V^E values are usually negative indicating that interactions between unlike molecules are predominant over other effects. The investigated mixtures behave similar to those with 2-methoxyethanol, 2-ethoxyethanol or 2-butoxyethanol and the same oxaalkanes.     

Viscosities of ternary mixtures 2-alkoxyethanol + sulfolane + ethylene glycols at T = 303.15 K

Viscosities of the ternary mixtures containing 2-methoxyethanol (ME) or 2-ethoxyethanol (EE), sulfolane (SULF) and ethylene glycols [ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) and tetraethylene glycol (TETRAEG)] have been measured, at T?=?303.15?K and atmospheric pressure, over the whole composition range. From these experimental data, the deviations in viscosities (Δη ₁₂₃) were calculated. These quantities were fitted to the Cibulka polynomial equation to derive the ternary adjustable parameters and standard errors. The results are discussed on the basis of intermolecular interactions between the components of the analysed mixtures.     

Novel corresponding-states principle approach for the equation of state of isotopologues: H2(18)O as an example

The corresponding-states principle (CSP) has been considered for the development of the equations of state (EOS) of minor isotopologues that are usually unknown. We demonstrate that, for isotopologues of a given molecular fluid, a general extended multi-parameter corresponding-states EOS can be reduced to the three-parameter EOS, utilizing the critical parameters (temperature and density) and Pitzer's acentric factor as correlation parameters. Appropriate general CSP mathematical formalism and equations for constructing the EOS of minor isotopologues are described in detail. The formalism and equations were applied to isotopologues of water and demonstrated that the isotopic effect on the critical parameters and the acentric factor of H(2)(18)O can be successfully calculated from the EOS of H2O and experimental data on the isotope effects (liquid-vapor isotope fractionation factor and molar volume isotope effect). We have also shown that the experimental data on the vapor pressure isotope effect (VPIE) for 18O-substituted water are inconsistent within the framework of thermodynamics with the liquid-vapor oxygen isotope fractionation factor. The novel approach of CSP to isotopologues developed in this study creates a new opportunity for constructing the EOS of minor isotopologues for many other molecular fluids.     

A new three-parameter cubic equation of state for calculation physical properties and vapor–liquid equilibria

A new three-parameter cubic equation of state is presented by combination of a modified attractive term and van der Waals repulsive expression. Also a new alpha function for the attractive parameter of the new EOS is proposed. The new coefficients of alpha function and the other parameters of the attractive term are adjusted using the data of the saturated vapor pressure and liquid density of almost 60 pure compounds including heavy hydrocarbons. The new EOS is adopted for prediction of the various thermophysical properties of pure compounds such as saturated and supercritical volume, enthalpy of vaporization, compressibility factor, heat capacity and sound velocity. Following successful application of the new EOS for the pure components, using vdW one-fluid mixing rules, the new EOSs are applied to prediction of the bubble pressure and vapor mole fraction of the several binary and ternary mixtures. The accuracy of the new EOS for phase equilibrium calculation is demonstrated by comparison of the results of the present EOSs with the PT, PR, GPR and SRK cubic EOSs.     

An effective modification of the Benedict–Webb–Rubin equation of state

A modification of the BWR equation of state is proposed, which is a simplified form of a previously proposed one. It applies to systems formed by hydrocarbons and related compounds, with particular attention to the critical conditions. The range of treatable compounds was extended to a value 0.9 of the acentric factor, corresponding to C₂₀ hydrocarbons. The critical compressibility factor Z_c was made independent of the acentric factor, for a more accurate prediction of pure-component properties (the previous equation did not give the same improvement). Mixing rules require one binary interaction constant for each component pair. Zero binary constants can be used for methane–alkane and alkane–alkane pairs. Examples of applications to pure hydrocarbons and their mixtures are given.     

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.     

A new cubic equation of state for simple fluids: pure and mixture

A two-parameter cubic equation of state is developed. Both parameters are taken temperature dependent. Methods are also suggested to calculate the attraction parameter and the co-volume parameter of this new equation of state. For calculating the thermodynamic properties of a pure compound, this equation of state requires the critical temperature, the critical pressure and the Pitzer’s acentric factor of the component. Using this equation of state, the vapor pressure of pure compounds, especially near the critical point, and the bubble point pressure of binary mixtures are calculated accurately. The saturated liquid density of pure compounds and binary mixtures are also calculated quite accurately. The average of absolute deviations of the predicted vapor pressure, vapor volume and saturated liquid density of pure compounds are 1.18, 1.77 and 2.42%, respectively. Comparisons with other cubic equations of state for predicting some thermodynamic properties including second virial coefficients and thermal properties are given. Moreover, the capability of this equation of state for predicting the molar heat capacity of gases at constant pressure and the sound velocity in gases are also illustrated.     

Isobaric (vapor + liquid) equilibria for the binary systems (1-methoxy-2-propanol + 2-methoxyethanol), (2-butanone + 2-methoxyethanol) and (water + 2-methoxyethanol) at pressures of (74.5, 101.3, and 134.0) kPa

Isobaric (vapor + liquid) equilibria of three binary systems (1-methoxy-2-propanol + 2-methoxyethanol), (2-butanone + 2-methoxyethanol) and (water + 2-methoxyethanol), was measured using an apparatus with dynamic recirculation and gas chromatography analysis for both phases. The measurements were carried out at pressures of (74.5, 101.3, and 134.0) kPa and temperature ranged from (343 to 407) K. No partial liquid miscibility was observed for any of the systems studied. Azeotropic behavior was verified for the system (water + 2-methoxyethanol) at the water-rich region. Thermodynamic modeling of the data measured was successfully accomplished for (2-butanone + 2-methoxyethanol) and (water + 2-methoxyethanol). In order to represent the no-ideality of the liquid phase, three alternatives for the activity coefficient model were used, Non Random Two Liquid, van Laar and Wilson. Results showed that the relative root mean square deviations from the experimental molar fractions were, <12% for the vapor phase, and <1% for the liquid phase.     

Thermochemical investigations of hydrogen-bonded solutions. Part 11. Expressions for predicting anthracene solubilities in alcohol+alkoxyalcohol mixtures based on mobile order theory

Experimental solubilities are reported for anthracene dissolved in eight binary mixtures containing 2-ethoxyethanol with 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 3-methyl-1-butanol and 1-octanol, and also in binary 1-pentanol+2-methoxyethanol and 2-methyl-1-propanol+2-propoxyethanol solvent systems at 25°C. Results of these measurements, combined with previously reported anthracene solubility data in 22 different alcohol +2-alkoxyethanol (2-methoxyethanol, 2-propoxyethanol and 2-butoxyethanol) solvent mixtures, are used to test the limitations and applications of expressions derived from Mobile Order theory. The first predictive expression assumes only formation of homogeneous self-associated hydrogen-bonded species, whereas the second equation includes additional terms to account for heterogeneous complex formation between the dissolved alcohol and 2-alkoxyethanol solvent molecules. Both equations predict the observed anthracene solubilities to within an average absolute deviation of about 3%.     

A new cubic equation of state for reservoir fluids

A new three-parameter cubic equation of state is developed with special attention to the application for reservoir fluids. One parameter is taken temperature dependent and others are held constant. The EOS parameters were evaluated by minimizing saturated liquid density deviation from experimental values and satisfying the equilibrium condition of equality of fugacities simultaneously. Then, these parameters were fitted against reduced temperature and Pitzer acentric factor. For calculating the thermodynamic properties of a pure component, this equation of state requires the critical temperature, the critical pressure, the acentric factor and the experimental critical compressibility of the substance. Using this equation of state, saturated liquid density, saturated vapor density and vapor pressure of pure components, especially near the critical point, are calculated accurately. The average absolute deviations of the predicted saturated liquid density, saturated vapor density and vapor pressure of pure components are 1.4%, 1.19% and 2.11%, respectively. Some thermodynamic properties of substances have also been predicted in this work.     

Ion Association and Solvation Behavior of Some 1-1 Electrolytes in 2-Ethoxyethanol Probed by a Conductometric Study

Precise measurements of the electrical conductances of solutions of potassium thiocyanate (KCNS), ammonium thiocyanate (NH₄CNS), sodium nitrate (NaNO₃) and ammonium nitrate (NH₄NO₃) in 2-ethoxyethanol (EE) at temperatures 35, 40, 45 and 50,^∘C are reported. The conductance data have been analyzed by the 1978 Fuoss conductance equation. A thermodynamic analysis of the ionic association processes has also been made and the Coulombic forces are found to play a major role in the association processes. The ionic contributions to the limiting equivalent conductances have been determined using the reference electrolyte method. Strong association was found for all these electrolytes in this solvent medium. The cations are found to be substantially solvated in 2-ethoxyethanol, whereas the anions appear to have only weak interaction with the solvent molecules.     

Theoretical study of anharmonic force field and spectroscopic constants for 1-chlorophosphaethene,CH2PCl and CD2PCl

The anharmonic force field and spectroscopy constants for CH₂PCl are determined using CCSD(T), VPT2, and density functional theory employing cc-pVQZ basis sets. The molecule structure, rotational spectroscopic constants, and vibrational wave numbers are compared with the available experimental data. Anharmonicity constants, vibration-rotation interaction constants and cubic force constants are predicted. Vibrational wave numbers and rotational constants for CD₂PCl are also determined using the same levels. The isotopic shifts of vibrational wave numbers are remarkable by D atom substitution for 1-chlorophosphaethene.     

Thermodynamic properties of n-alkoxyethanols + organic solvent mixtures: XVI. Excess molar volumes at 298.15 K for 2-alkoxyethanol + n-polyether systems

Excess molar volumes (V_m^E) at 298.15 K and atmospheric pressure for 2-methoxyethanol or 2-butoxyethanol + 2,5-dioxahexane, +2,5,8-trioxanonane, +3,6,9-trioxaundecane, +5,8,11-trioxapentadecane, or +2,5,8,11,14-pentaoxapentadecane, or for 2-ethoxyethanol + 2,5,8-trioxanonane, +3,6,9-trioxaundecane, or +5,8,11-pentaoxapentadecane have been obtained from densities measured with and Anton-Paar DMA 602 vibrating-tube densimeter.They are usually small in absolute value. It is due to a compensation between positive and negative contributions to the excess molar volume. For example, free volume effects present in solutions with the pentaether are compensated by the positive contribution to V_m^E from the rupture of dipole-dipole interactions between ether molecules.