Molecular relaxation behaviour of mixtures of some polar non-associative liquids

Molecular relaxation studies have been made on rigid polar solutes dibenzofuran and s-trioxane and their mixtures with benzophenone, ortho- and meta-dichlorobenzenes in the microwave region over a range of temperatures in dilute benzene solutions. The relaxation times and the thermodynamic parameters for the activated state have been determined using the measured dielectric data. The results obtained have been discussed in terms of the molecular motion of the system and are consistent with those of other rigid molecules studied previously. The results are also compared with the computed values obtained by employing a relation proposed by us earlier.     

Dielectric relaxation of mixtures of non-rigid polar molecules in benzene

The dielectric absorption of three compositions of Isobutyl-methacrylate and Allyl-methacrylate, both consisting of non-rigid molecules, has been studied at 9.92 GHz over a range of temperatures in the dilute solutions of benzene. The various relaxation times τ_o, τ(1) and τ(2), the distribution parameter, α and the thermodynamic parameters for the activated states, both for relaxation and the viscous flow processes have been determined using the measured dielectric data. The results indicate that the properties of the single component systems, such as existence of intramolecular and overall rotations, and absence of solid rotator phase, are retained in the two component system. The values of molar entropy of activation for the relaxation process indicate that the cooperative orientation of the molecules in the single component system changes into non-cooperative orientation in the binary system. A comparison of the experimental values of the most probable relaxation time τ₀ with those calculated on the basis of simple and reciprocal mixing rules and also by a procedure suggested by M.P. Madan [5] reveals that none of these procedures can successfully predict the experimental data.     

Dielectric studies in dilute solutions

Dielectric studies in dilute solutions of cyclohexane and benzene have been carried out in the temperature range 294–318°K. The observed data have been utilized to evaluate the relaxation times and thermodynamic parameters of these molecules. The high values ofα for 2-acetyl pyridine indicate the occurrence of more than one relaxation time. In the remaining systems, the observed lowα values indicate their rigid behaviour. The variation in the dielectric relaxation time is mostly correlated with the change in the heterocyclic configuration of the system.     

Dielectric relaxation study of aqueous 2-ethoxyethanol using time domain reflectometry technique

The complex permittivity spectra of 2-ethoxyethanol in water solutions have been studied at different concentrations and temperatures using a picosecond time domain reflectometry technique. The complex dielectric permittivity spectrum of 2-ethoxyethanol shows Cole-Davidson type behavior. Increase in dielectric relaxation time may be due to increase in hetero molecular interaction strength. Minimum in Excess dielectric constant values provides the information about stable complex adduct. The Kirkwood correlation factor, thermodynamic properties and Bruggeman factor have also been determined and the results are interpreted in terms of hydrogen bonding and interactions among the solute — solvent molecules.     

A comparative study of non-polar solvents effect on dielectric relaxation and dipole moment of binary mixtures of mono alkyl ethers of ethylene glycol and of diethylene glycol with ethyl alcohol

Dielectric relaxation and dipole moment of binary mixtures of homologous series of mono alkyl ethers of ethylene glycol and of diethylene glycol, i.e., mono methyl, mono ethyl and mono butyl ethers of ethylene glycol (ROCH₂CH₂OH) and mono methyl, mono ethyl and mono butyl ethers of diethylene glycol (ROCH₂CH₂OCH₂CH₂OH) with ethyl alcohol (C₂H₅OH) of different concentrations were studied in dilute solutions of benzene, dioxane and carbon tetrachloride at 35 °C. Permittivity (ε′) and loss (ε″) at 10.1 GHz, static dielectric constant ε_o at 1 MHz and high frequency limiting dielectric constant ε_∞ = n_D² at optical frequency of these molecules and their binary mixtures at different concentration were measured in dilute solutions of non-polar solvents. The average relaxation time τ_o, relaxation times corresponding to overall molecular reorientation τ₁ and group rotations τ₂ were determined using Higasi's single frequency measurement equations for dilute solutions. The evaluated values of relaxation times and free energy of activation ΔF were used to explore the solvent effect on molecular dynamics of these polar binary systems in non-polar solvents. The excess inverse relaxation time and excess free energy of activation were determined to confirm the existence of hydrogen-bonded heterogeneous cooperative domains of the ethers and alcohol molecules at different concentration their binary mixtures in non-polar solvents. The dipole moment of the binary mixtures was evaluated using Higasi's and Guggenheim's equation for dilute solutions. The evaluated values of dipole moments and computed dipole moment values using a simple mixing equation of the polar molecules binary mixture were used to explore the effect of non-polar solvent environment on heterogeneous molecular interactions between ethers and alcohol molecules. The effect of number of carbon atoms in the molecular structure of these homologous series molecules was also considered for the interpretation of various evaluated dielectric parameters.     

Conformation transitions of blood proteins under influence of physical factors on microwave dielectric method

In this article, the influence of γ-irradiation and temperature on albumin and fibrinogen conformation and dielectric properties of protein solutions have been studied by the microwave dielectric method. Both the values of the real part ε′ (dielectric permittivity) and the imaginary part ε″ (dielectric losses) of the complex dielectric permittivity of the aqueous solution of bovine serum albumin and human fibrinogen as functions of temperature and γ-irradiation dose have been obtained. The time of dielectric relaxation of water molecules in the protein solutions was calculated. The hydration of the albumin and fibrinogen molecules was determined. The temperature dependencies of hydration are non-monotonous and have a number of characteristic features at the temperatures 30-34 and 44-47 °C for serum albumin, and 24 and 32 °C for fibrinogen.     

Chain length effect on dynamical structure of poly (vinyl pyrrolidone)-polar solvent mixtures in dilute solution of dioxane studied by microwave dielectric relaxation measurement

Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol⁻¹) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol⁻¹) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.     

On a hydration model utilized in the discussion of dielectric spectra of aqueous solutions

A solution model is discussed which allows the microwave part of the permittivity spectrum of aqueous solutions to be related to characteristics of the hydration water. The parameters, which can be derived from measured dielectric spectra thereby are the hydration water relaxation time, the number of hydration water molecules per molecule of solute, the static orientational polarizability of the hydration water, and a quantity, which refers to the distribution of hydration water relaxation times. The (continuum) model, appropriate for solutions of (nearly) spherically shaped solute particles, has regard to internal electric fields resulting from polarization charges at interfaces. Possible errors in the parameter values are indicated, which may arise if the internal fields are only incompletely taken into account. Previously measured spectra for a series of aqueous solutions of 1,4-diazabicyclo[2,2,2]octane have been evaluated on the basis of the present model. The results for these (favourable) solutions are presented to show, that the found dependence of the parameter values on solute concentration is consistent with the idea of the proposed hydration model.     

Dielectric relaxation study of dipropylsulfoxide/water mixtures

The complex dielectric spectra of dipropylsulfoxide (DPSO)/water mixtures in the whole concentration range have been measured as a function of frequency between 100 MHz and 20 GHz at four temperatures between 298.15 K and 328.15 K. The dielectric parameters, static dielectric constant (ε_s), relaxation time (τ) and relaxation strength (Δε) have been obtained by the least squares fit method. The relaxation in these mixtures can be described by two Debye functions, whereas for pure DPSO Cole-Davidson type is valid. The relaxation times of the mixtures show a maximum at about x(DPSO) ≈ 0.3. In the concentration range where a maximum appears, the interaction of DPSO with water is presumably the result of hydrogen bonding between water and the sulfonyl group of the sulfoxide molecule. The concentration and temperature dependent excess dielectric constant and effective Kirkwood correlation factor of the binary mixtures have been determined. The excess permittivity is found to be negative for all concentrations.     

Bound water: Evidence from and implications for the dielectric properties of aqueous solutions

Broadband dielectric spectra of a variety of aqueous solutions are evaluated as to indications of water that may be considered bound. Static permittivity decrements due to depolarizing internal electric fields, from kinetic depolarization, as well as from dielectric saturation are discussed. The latter effect reflects the preferential orientation of water permanent dipole orientations within strong Coulombic field of small ions, especially multivalent cations. Such water may be considered bound even though rapid rotations around the orientation of the electric dipole moment are definitely possible and also a fast exchange of water molecules between the hydration region and the bulk may take place. Water exhibiting large dielectric relaxation times, as typical for regions with large local concentration of foreign matter, may also be named bound. However, no clear evidence for interaction energies exceeding the hydrogen bond energy of pure water has been found. Rather enhanced relaxation times at low water content reflect the small concentration of hydrogen bonding sites and thus low probability density for the formation of a new hydrogen bond. Potential interferences of the water relaxation with relaxations from other molecules or from ionic structures are mentioned briefly.     

Dielectric relaxation of polar molecules in mixtures of non-polar solvents.

The relaxation times of some rigid polar molecules are studied in very diluted mixtures of heptane-carbontetrachloride and heptanedecaline, Exponential relation between relaxation time and a characteristic length of the polar solute (r_eff) is found. The structure factor of the mixture which contains the contributions of both solvents cannot be composed by adding the features of each component only. Furthermore, the measured collision times seem not to follow a simple sum rule.     

Dielectric relaxation and hydrogen bonding studies of 1,3-propanediol–dioxane mixtures using time domain reflectometry technique

The complex permittivity, static dielectric constant and relaxation time for 1,3-propanediol, 1,4-dioxane and their mixtures have been studied using time domain reflectometry (TDR). The excess permittivity, excess inverse relaxation time and Kirkwood correlation factor have also been determined at various concentrations of dioxane. Hydrogen bonded theory was applied to compute the correlation terms for the mixtures. The Bruggeman model for the nonlinear case has been fitted to the dielectric data for mixtures.     

Rotational Diffusion of Coumarins in Aqueous DMSO

The rotational dynamics of four structurally similar polar molecules viz., coumarin 440, coumarin 450, coumarin 466 and coumarin 151 has been studied in binary mixtures comprising of dimethyl sulphoxide and water at room temperature using the steady state fluorescence depolarization method and time correlated single photon counting technique. The binary mixtures are characterized by the fact that at a particular composition the viscosity (η) of the solution reaches a maximum value that is higher than the viscosities of either of the two co-solvents. The dielectric properties of the solution change across the composition range and the qualitative features of the solvent relaxation dynamics in complex systems are known to differ from those in simple solutions. A hook type profile of rotational reorientation time (τ _r ) vs viscosity (η) is obtained for all the solutes in dipolar aprotic mixture of dimethyl sulphoxide-water, with the rotational reorientation times being longer in organic solvent-rich zone, compared to the corresponding isoviscous point in water-rich zone due to strong hydrogen bonding. Fluorescence lifetimes as well as rotational reorientation times are sensitive to the composition of the binary solvent system under study than to the viscosity suggesting the importance of local structure. The results are discussed in the light of hydrodynamic and dielectric friction models. Dedicated to Professor M.I. Savadatti on his 77^th Birthday.     

Determination of the Maier-Saupe strength parameter from dielectric relaxation experiments: a molecular dynamics simulation study

Molecular dynamics simulations have been performed to investigate the rotational motion in the nematic and isotropic phases of a model mesogenic system in which the interactions between the molecules are represented by the Gay-Berne potential. First-rank end-over-end rotational relaxation times, analogous to those measured using dielectric relaxation spectroscopy for real mesogens with a longitudinal electric dipole, have been determined as a function of temperature and density. The relaxation times at temperatures throughout the nematic region are found to be larger than the values extrapolated from the isotropic phase to the same temperature. The simulation results are compared with the extended Debye theory for dielectric relaxation in the nematic phase. This relates the reduction in the relaxation rate to the retardation factor which depends on the Maier-Saupe strength parameter, and in turn is defined uniquely by the second-rank orientational order parameter. The simulations indicate that the retardation factor at constant strength parameter is density dependent, a feature neglected in the relaxation theory. We compare the simulation results where possible with experiment.     

Study of heterogeneous interaction in binary mixtures of 2-methoxyethanol-water using dielectric relaxation spectroscopy

The dielectric relaxation measurements on binary mixtures of 2-methoxyethanol with water have been carried out over entire concentrations and at temperature range of 0 °C to 25 °C using a picosecond time domain reflectometry technique. The complex dielectric permittivity spectra of 2-methoxyethanol/water mixtures were fitted using Havriliak-Negami equation. The static dielectric constant and relaxation time for all concentrations were obtained using least square fit method. The principal relaxation time is small if compared to that of corresponding alcohol/water mixtures this may be due to the hydrogen bonding ether oxygen in the 2-ME-water system. Excess dielectric properties, Kirkwood correlation factor, thermodynamic properties and Bruggeman factor are also determined and the results are interpreted in terms of heterogeneous interactions among the unlike molecules due to hydrogen bonding.     

Structural study of aqueous solutions of tetrahydrofuran and acetone mixtures using dielectric relaxation technique

The complex permittivity, static dielectric constant and relaxation time for tetrahydrofuran-water and acetone-water mixtures have been determined at 0°, 10°, 25° and 35°C using time domain reflectometry technique (TDR). The behaviour of relaxation time of the mixture shows a maxima for the mixture with 30% of water by volume. This suggests that the tendency to form cluster between water and solute molecule is maximum for this mixture. The excess permittivity for both tetrahydrofuran-water mixture and acetone-water mixtures, are found to be negative. The Kirkwood correlation factor has been determined at various concentrations of water. Static dielectric constant for the mixtures have been fitted well with the modified Bruggeman model. The values of the Bruggeman parametera for tetrahydrofuran is found to be more than the corresponding value for acetone.     

Dielectric spectroscopy on aqueous solutions of some zwitterionic amino acids

The complex (electric) permittivity of aqueous solutions of dipolar solutes has been measured as a function of frequency between 1 MHz and 40 GHz. Solutes are the isomers DL-2-aminobutyric acid, DL-3-aminobutyric acid, and 4-aminobutyric acid, and also 6-aminohexanoic acid. The measured dielectric spectra show two dispersion/dielectric loss regions, one due to the orientational diffusion of the solute molecules the other one due to the dielectric relaxation of the solvent water. A relaxation spectral function based on a model of the solutions has been fitted to the measured frequency dependence of the complex permittivity. The values for the electric dipole moment and reorientation time of the zwitterionic part of the solute particles derived by this analysis from the measurements fairly agree with theoretical predictions. Quite remarkably, the dipole moment in solution of 4-aminobutyric acid and 6-aminohexanoic acid up to remarkably high solute concentrations is nearly constant. A noteworthy result for the hydration water of the amino acids is, that its relaxation time is almost independent of the solute dipole moment.     

Phase diagrams and dielectric studies of binary mixtures exhibiting intermediate nematic and induced smectic phases

Investigations on the phase diagrams of two bi-component mixtures of liquid crystals are presented. Whereas in one of the bi-component systems, smectic A (SmA) phase is seen to be induced, in the other case the so-called nematic “island” has been observed. The dielectric properties of magnetically oriented sample forming nematic phase and induced smectic phase in one of the mixtures, and a nematic “island” and SmA phase in the other mixture, were measured in the frequency range from 1?Hz to 10?MHz at different temperatures. The transition temperatures obtained from the polarizing microscope and differential scanning calorimeter measurements agree well with the dielectric relaxation data.     

Dielectric dispersion studies of aromatic ketones in non-polar solvents

Measurements of dielectric constant (ε′) and loss (ε″) have been made at five different microwave frequencies from 1000 MHz to 67.7 GHz for acetophenone, benzophenone and propiophenone in four different non-polar solvents namely benzene, cyclohexane, 1-4-dioxane and n-heptane. Results are reported at five different temperatures from 25°C to 60°C. The dielectric data of these ketones in different solvents are analysed in terms of the Cole-Cole arc plots and superposition of two Debye-type absorptions. Values of mean relaxation times (τ_o), dipolement (μ), overall relaxation time (τ₁) and group relaxation time (τ₂) have been obtained and presented here. The values of relaxation time and dipolemoment are in reasonable good agreement, at the temperatures, at which there are available known data.     

Thermally stimulated currents in poly(vinyl chloride): Tacticity and molecular weight influence

Thermally stimulated currents (TSC) have been measured in several samples of poly(vinyl chloride) differing in tacticity and molecular weight as a result of polymerizing them at different temperatures. This has allowed us to characterize the relaxation behavior of PVC. No dielectric relaxation can be observed by this experimental technique at temperatures between liquid helium and liquid nitrogen. The β relaxation is observed around 173°K, with similar parameters in all samples studied. Around the glass transition the relaxation times isolated in the α peak follow a compensation law. Molecular weight and tacticity have a strong influence on the temperature of the maximum and the intensity of this relaxation, respectively.