Characterization of Heterogeneous Interaction Behavior in Ternary Mixtures by a Dielectric Analysis: Equi-Molar H–bonded Binary Polar Mixtures in Aqueous Solutions

The heterogeneous associating behavior of the aqueous binary mixtures of ethyl alcohol, ethylene glycol, glycerol and mono alkyl ethers of ethylene glycol, and aqueous ternary mixtures of equi-molar binary systems (i.e., mono alkyl ethers of ethylene glycol with ethyl alcohol, ethylene glycol and glycerol) have been investigated over the entire concentration range using accurately measured dielectric constants at 25 ^∘C. The concentration dependent values of the excess dielectric parameter ε^E and effective Kirkwood correlation factor g ^eff were determined using the measured values of the static dielectric constant, ε_o, at 1 MHz and the high frequency limiting dielectric constant ε_∞ = n _D ². The observed ε^E values in aqueous binary and ternary mixtures are negative over the entire concentration range, which implies the formation of heterogeneous complexes between these molecules that reduces the effective number of dipoles. The stoichiometric ratio corresponding to the maximum interaction in alcohol + water mixtures increases with an increase in the number of hydroxyl groups of the alcohol molecules, but for mono alkyl ethers of ethylene glycol + water mixtures it decreases with the increase in the molecular size of the mono alkyl ethers. In aqueous ternary mixtures the stoichiometric ratio for the maximum extent of heterogeneous interaction is governed by the molecular size of the mono alkyl ethers. It was also found that the strength of the heterogeneous H–bond connectivities in the water + alcohol systems decrease with an increase in the number of hydroxyl groups of the alcohol molecules. However in the case of water + mono alkyl ether binary mixtures and in ternary mixtures, the strength of H–bond connectivities increases with the increase in the molecular size of the mono alkyl ether. An analysis of the g ^eff values confirms that the heterogeneous interaction involves the orientation of molecular dipoles in the studied systems.     

Microwave dielectric spectra and molecular relaxation in formamide-N,N-dimethylformamide binary mixtures

The dielectric dispersion and absorption spectra of formamide (FA), N,N-dimethylformamide (DMF) and their binary mixtures are investigated in the frequency range of 500 MHz to 20 GHz at 30 °C in view of the organic synthesis by microwaves heating using amides solvents. The concentration dependent values of molecular reorientation relaxation times lower than that of the ideal mixing behaviour have been attributed to the cooperative dynamics of H-bonded FA–DMF structures. The molar ratio of stable adduct is 2:1 of FA to the DMF, which is determined from the concentration dependent excess static dielectric constant and the relaxation time plots of these binary mixtures. Electrode polarization effect and ionic conduction in FA and DMF were investigated from their dielectric dispersion spectra in the low frequency region of 20 Hz to 1 MHz.     

Preferential Solvation and Solvatochromic Parameters in Mixtures of Poly(ethylene glycol)-400 with Some Molecular Organic Solvents

Polyethylene glycols have become more popular alternate reaction media due to interesting properties like non-toxicity, bio-degradability, and full miscibility with water and organic solvents. Binary mixtures of polyethylene glycols with common solvents can be useful to tune their physical and chemical properties and to facilitate chemical and physical processes. In this study, solvatochromic parameters were spectrophotometrically determined for binary solvent mixtures of poly(ethylene glycol)-400 (PEG-400) with methanol, 2-propanol, 1-butanol, dimethyl sulfoxide, N,N-Dimethylformamide, and dichloromethane under ambient conditions, over the whole range of mole fractions. The solvatochromic parameters showed different trends in protic and aprotic solvents mixed with PEG-400. Methanol/PEG-400 mixtures showed special properties in polarity and polarizability so that the mixtures are more dipolar/polarizable than their pure components. Positive or negative deviations from ideal behavior confirmed that the indicators were involved in a preferential solvation process in the solvent mixtures. These deviations from ideality can be attributed to strong solvent–solvent interactions in the binary mixtures.     

Surface thermodynamics of binary mixtures of ethylene glycol + cyclohexanol or cyclopentanol

Surface tension data of binary mixtures of ethylene glycol + cyclohexanol and ethylene glycol + cyclopentanol was measured over the entire concentration range at various temperatures. The experimental values were correlated with temperature and with mole fraction. The values of the surface entropy, surface enthalpy and excess surface tension for these mixtures were also calculated.     

Hydrogen network fluctuations of associating liquids: dielectric relaxation of ethylene glycol oligomers and their mixtures with water

Complex dielectric spectra of ethylene glycol and of various derivatives as well as of mixtures of water with an ethylene glycol oligomer and with a poly(ethylene glycol) dimethyl ether oligomer have been measured. The spectra can be well represented by a Cole-Cole [Cole and Cole, J. Chem. Phys. 9, 341 (1941)] spectral function. The extrapolated low frequency (static) permittivity of this function has been evaluated to yield the effective dipole orientation correlation factor of the liquids. The relaxation time of the ethylene glycols displays a characteristic dependence upon the ratio of concentrations of hydrogen bond donating and accepting groups, indicating two opposing effects. With increasing availability of hydrogen bonding sites effects of association and also of dynamical destabilization increase. Both effects exist also in the mixture of water with the oligomers. They are discussed in terms of a wait-and-switch model of dipole reorientation in associating liquids. Another feature in the dependence of the dielectric relaxation time of poly(ethylene glycol)/water mixtures upon mixture composition has been tentatively assigned to precritical demixing behavior of the binary liquids in some temperature range.     

Simultaneous determination of glycols based on fluorescence anisotropy

Simultaneous determination of non-fluorescent glycols in mixtures without separation or chemical transformation steps is described. Two methods based in the measure of fluorescence anisotropy of a probe such as fluorescein dissolved in the analyte or analyte mixtures are described. In the first method, the anisotropy spectra of pure and mixtures of analytes are used to quantitative determination (if the fluorophor concentration is in a range where fluorescence intensity is proportional to concentration). In the second method, a calibration curve anisotropy-concentration based on the application of the Perrin equation is established. The methods presented here are capable of directly resolving binary mixtures of non-fluorescent glycols on the basis of differences on the fluorescence anisotropy of a fluorescence tracer. Best analytical performances were obtained by application of the method based on Perrin equation. This method is simple, rapid and allows the determination of mixtures of glycols with reasonable accuracy and precision. Detection limits are limited by the quantum yield and anisotropy values of the tracer in the solvents. Recovery values are related to the differences in anisotropy values of the tracer in the pure solvents. Mixtures of glycerine/ethylene glycol (GL/EG), ethylene glycol/1,2-propane diol (EG/1,2-PPD) and polyethylene glycol 400/1,2-propane diol (PEG 400/1,2-PPD) were analysed and recovery values are within 95-120% in the Perrin method. Relative standard deviation are in the range 1.3-2.9% and detection limits in the range 3.9-8.9%.     

Dielectric Parameters and Hydrogen Bond Interaction Study of Binary Alcohol Mixtures

The formation of hydrogen bonds between different types of molecules in binary alcohol mixtures (methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol and glycerol) have been investigated (each system at 21 mixture concentrations) by an analysis of their dielectric parameters. The static dielectric constant ε _o, limiting high-frequency dielectric constant ε _∞, excess dielectric parameters ε _o^E and ε _∞^E, effective Kirkwood correlation factor g ^eff, and corrective Kirkwood correlation factor g _f of the binary alcohol mixtures were determined at 25 °C in order to explore hydrogen-bond interactions and the strength of molecular connectivities between unlike alcohol molecules and their dipole alignment. These results confirm that the different alcohol mixtures form hydrogen-bonded structures, which are strongly influenced by the numbers of hydroxyl groups and carbon atoms of the alcohol molecules and vary with the concentrations of the mixtures.     

Static Dielectric Constants and Kirkwood Correlation Factor of the Binary Mixtures of N-Methylformamide with Formamide,N,N-Dimethylformamide and N,N-Dimethylacetamide

Static dielectric constant values of the binary mixtures of N-methylformamide with formamide, N,N-dimethylformamide and N,N-dimethylacetamide have been measured in the whole composition range at 303 K. The Kirkwood correlation factor values of the amide–amide mixtures were determined from the measured values of the static dielectric constant and high-frequency limit dielectric constant. The evaluated values of the excess dielectric constant and deviation in the Kirkwood correlation factor infer that deviations of their mixture values occur from the mole-fraction mixture law. Results confirm that there are strong hydrogen-bond interactions between unlike molecules of amide–amide mixtures and that 1:1 complexes are formed.     

Solvent extraction of europium from aqueous-organic solutions by solvating extractants

The partition of Eu(III) between benzene containing solvating extractants (TBP, TOPO, dioctylsulfoxide) and aqueous nitrate, perchlorate and thiocyanate solutions containing various organic solvents miscible with water (alcohols, acetone, acetonitrile, ethylene glycol, dimethyl sulfoxide and dimethylformamide) was investigated. Depending on the specific extraction system, the presence of organic solvents in the mixed phase showed various effects on the distribution ratio of Eu(III). These were discussed in terms of solute-solvent interactions. The results in the systems containing dimethylformamide and dimethyl sulfoxide indicated complexation of Eu(III) with these solvents in the polar phase.     

Dielectric properties of oligomers. VII. Low-molecular-weight propylene glycols

The dielectric properties of low-molecular-weight propylene glycols HO? [CH(CH₃)CH₂O]_n? H (n = 3, 4, 5) were investigated to clarify the effect of chain length on the dielectric properties. The measurement of dielectric constant and dielectric loss was carried out over the frequency range 30 Hz to 30 MHz at temperatures of ?20 to ?65°C. The static dielectric constants of these glycols are between 10 and 30, slightly smaller than values for the corresponding ethylene glycols of the same degree of polymerization. All of the Cole–Cole arcs, even that for pentapropylene glycol, can be represented by the empirical Davidson–Cole equation. The dielectric properties of homologous propylene glycols are compared with those for the ethylene glycols and are discussed in terms of the effects of chain length and intermolecular hydrogen bonds.     

Conductance of potassium lodide in mixed solvents

The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants K_A are in the range 0.3–2.0; no correlation between K_A and solvent properties could be established. For lower dielectric constants, K_A increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases K_A regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product A_o is also decreased by the addition of proton acceptors.     

Effect of microheterogeneity on bulk and surface properties of binary mixtures of polyoxyethene glycol monobutyl ethers with water

Solution properties of aqueous mixtures of the homologous series of polyoxyethene glycol mono-n-butyl ethers C₄H₉O(CH₂CH₂O) _m H (where m=1 to 3) have been investigated using surface tension, density, viscosity and¹³C NMR techniques. From the experimental data, excess volume and deviation of viscosity and free energy of activation of flow were evaluated and discussed in terms of the molecular interactions between the components. Surface activity of polyoxyethene glycol mono ethers in aqueous dilute solutions was evident from surface tension measurements. Thermodynamic properties of adsorption and apparent micellization or critical aggregation concentration (CAC) in these systems were evaluated and discussed. The CAC values and the aggregation numbers obtained from¹³C NMR chemical shift data indicate an increase in hydrophobicity with an increase in the value of m, in the polyoxyethene glycol mono-n-butyl ethers, and also agrees with the results obtained from surface tension measurements.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Gas Chromatographic Analysis in the Synthesis of Poly (Ethylene Oxide) Dimethyl Ethers

ABSTRACT

Gas chromatography (GC) was used in the analysis of the synthesized oligomeric mixtures, involving poly(ethylene glycol)s, poly(ethylene oxide) monomethyl ethers, poly(ethylene oxide) dimethyl ethers and crown ethers. It was demonstrated that the samples could be successfully analyzed on the wide bore capillary column with cross-linked polar stationary phase (FFAP) without derivatization. An on-column injection technique is used to avoid possible sample distortion. Identification and quantitative analysis were achieved taking advantage of the GC homologues retention rule and the FID effective carbon number response rule, thus the limitations of some standard availability and purity problems were avoided. Much useful information such as average molecular weight, polydisperse distribution and so on were obtained by the established method, which is very important in the process monitoring and product quality control.     

Effect of solvent polarity on the self-assembly and dielectric dynamics of non-aqueous lyotropic liquid crystalline phases

Binary mixtures comprising cetylpyridinium chloride and non-aqueous solvents of varying polarity [ethylene glycol (ε ~ 37.2) and formamide (ε ~ 109)] were studied via X-ray diffraction, polarisation optical microscopy, differential scanning calorimetry and dielectric spectroscopy. Layered lamellar mesophase was observed in both mixtures. Formamide-based mesophase was found more ordered and stable up to higher temperature (140°C). Ordering and stability of the mesophase was explained considering the higher polarity and dipolar–dipolar interactions of formamide. Dielectric spectroscopy demonstrates the large magnitudes of capacitance and permittivity (Cp ≈ 9 µF and ε ≈ 2428) for mesophase derived from formamide. Dynamical relaxation parameters of both mixtures were discussed and correlated with their structural aspects.     

Effects of organic solvent addition on the aggregation and micellar growth of cationic dimeric surfactant 12-3-12,2Br-

The micellization and micellar growth of cationic dimeric surfactant propanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide, 12-3-12,2Br-, have been studied in several water-organic solvent mixtures. The organic solvents were ethylene glycol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, acetonitrile, dioxane, formamide, and N,N-dimethylformamide. Results showed that the aggregation process was less favored in the binary mixtures than in pure water, which was explained by considering the influence of the solvophobic effect on micellization. The addition of organic solvents was accompanied by a diminution in the average aggregation number, Nagg, of the dimeric micelles. This diminution was due to the decrease in the interfacial Gibbs energy contribution, Delta G0interfacial, to the Gibbs energy of micellization caused by the decrease in the hydrocarbon/bulk-phase interfacial tension. As a result of the micelle size diminution, the concentration at which the sphere-to-rod transition occurred, C*, was higher in the mixtures than in pure water. Micelle size reduction is accompanied by a decrease in the ionic interactions and in the extra packing contribution to the deformation of the surfactants tails, making the formation of cylindrical micelles less favorable.     

Excess molar enthalpies of binary mixtures containing ethylene glycols or poly(ethylene glycols) + ethyl alcohol at 308.15 K and atmospheric pressure

Excess molar enthalpies, , of binary mixtures containing ethylene glycols and poly(glycols) + ethyl alcohol were measured by a flow microcalorimeter at 308.15 K and at atmospheric pressure over the whole composition range. Binary mixtures contain ethyl alcohol + ethylene glycol, + di(ethylene glycol), + tri(ethylene glycol), + tetra(ethylene glycol), + poly(ethylene glycol)-200, + poly(ethylene glycol)-300, + poly(ethylene glycol)-400, + poly(ethylene glycol)-600. Effects of the molecular weight distribution (MWD), of the polymer were investigated too, by preparing three additional samples of poly(ethylene glycol) with the same number average molecular weight (M_n ≈ 300), but different MWD. For all mixtures, results were fitted to the Redlich–Kister polynomial. curves are asymmetrical, showing positive values which vary from 280 J mol⁻¹ (diethylene glycol + ethyl alcohol) to 1034 J mol⁻¹ (mixture containing PEGs (200 + 400) + ethyl alcohol). Effects of changes in the glycols chain length and in MWD on the molecular interactions among the mixture components are discussed.     

Solute-solvent and solvent-solvent interactions in the preferential solvation of 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide in 24 binary solvent mixtures

The molar transition energy (E(T)) polarity values for the dye 4-[4-(dimethylamino)styryl]-1-methylpyridinium iodide were collected in binary mixtures comprising a hydrogen-bond accepting (HBA) solvent (acetone, acetonitrile, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF)) and a hydrogen-bond donating (HBD) solvent (water, methanol, ethanol, propan-2-ol, and butan-1-ol). Data referring to mixtures of water with alcohols were also analyzed. These data were used in the study of the preferential solvation of the probe, in terms of both solute-solvent and solvent-solvent interactions. These latter interactions are of importance in explaining the synergistic behavior observed for many mixed solvent systems. All data were successfully fitted to a model based on solvent-exchange equilibria. The E(T) values of the dye dissolved in the solvents show that the position of the solvatochromic absorption band of the dye is dependent on the medium polarity. The solvation of the dye in HBA solvents occurs with a very important contribution from ion-dipole interactions. In HBD solvents, the hydrogen bonding between the dimethylamino group in the dye and the OH group in the solvent plays an important role in the solvation of the dye. The interaction of the hydroxylic solvent with the other component in the mixture can lead to the formation of hydrogen-bonded complexes, which solvate the dye using a lower polar moiety, i.e. alkyl groups in the solvents. The dye has a hydrophobic nature and a dimethylamino group with a minor capability for hydrogen bonding with the medium in comparison with the phenolate group present in Reichardt's pyridiniophenolate. Thus, the probe is able to detect solvent-solvent interactions, which are implicit to the observed synergistic behavior.     

Effects of head group size on the reaction methyl 4‐nitrobenzenesulfonate + Br− in water‐ethylene glycol cetyltrialkylammonium bromide micellar solutions

The reaction methyl 4‐nitrobenzenesulfonate + Br^? has been studied in water‐ethylene glycol cetyltrialkylammonium bromide (alkyl = methyl, ethyl, propyl, and butyl) micellar solutions by changing surfactant concentration as well as the weight percentage of ethylene glycol present in the bulk phase. The pseudophase model was adequate to rationalize quantitatively the micellar kinetic effects. Information about the influence of the head group size on the second‐order rate constant of the process and on the binding equilibrium constant of the organic substrate to the cationic micelles in water–ethylene glycol mixtures was obtained. Kinetic data taken from the literature were compared to those obtained in this work in order to examine the different effects produced by an alcohol that is localized in the bulk phase, such as ethylene glycol, with those caused by an alcohol that distributes between the bulk and micellar pseudophases, such as 1‐butanol. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 346–352, 2007     

Solvation of amides of carboxylic acids in aqueous solutions of ethylene glycol

Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg^–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.     

Mixed micelle behavior of poly(ethylene glycol) alkyl ethers with series of monomeric cationic, phosphonium cationic, and zwitterionic surfactant

The steady state fluorescence measurements have been carried out for the binary mixtures of poly(ethylene glycol) alkyl ethers (C _i E _j ) with series of monomeric cationic (MC), zwitterionic (ZI), and phosphonium cationic (PC) surfactants over the whole mole fraction range by using pyrene as fluorescence probe. The cmc values for all the binary mixtures, thus, determined have been further evaluated by using the regular solution theory. The various micellar parameters such as regular solution interaction parameter (β), micropolarity (I ₁/I ₃), and mean micelle aggregation number (N _agg) have been determined. A strong influence of hydrophobicity of both nonionic as well as cosurfactant (CS) components has been observed on the nature of mixed micelles. The presence of bulky head groups of PC surfactants significantly contributes towards the unfavorable mixing.