Dielectric relaxation and hydrogen bond interaction study of diol-water mixtures

Complex dielectric permittivity measurements in the frequency range 10MHz-20GHz have been carried out in diol-water mixtures over the entire concentration range using a time domain reflectometry (TDR) method at 25°C. A hydrogen bonded theory is applied to compute the dielectric constant for the mixtures. It adequately reproduces the experimental values of static dielectric constants for the diol-water mixtures. The dielectric parameters confirm that the intermolecular homogeneous and heterogeneous hydrogen bonding vary significantly with the increase in concentration of the constituents of the diol-water mixtures.     

Dielectric relaxation study of pyridine-alcohol mixtures using time domain reflectometry

Time domain reflectometry is applied to dielectric relaxation measurements on pyridine-alcohol (methanol, ethanol, propan- 1-o1 and butan-1 -o1) mixtures over the entire concentration range and over the frequency range 10MHz-10GHz at 5, 15, 25 and 35°C. From the data, static permittivity and the dielectric relaxation time are extracted using a bilinear calibration method and a nonlinear least-squares fit method. These mixtures exhibit a principal dispersion of the Debye type at microwave frequencies. The Kirkwood correlation factor, which contains information regarding solute-solvent interaction and corresponding structural information, was obtained for these systems, and the excess inverse relaxation time and molar energy of activation for all these systems were determined. The values of the static permittivity, the relaxation time and the Kirkwood correlation factor decrease with increased pyridine concentration in alcohol. The static permittivity of the mixtures fits the modified Brugemann model well.     

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.     

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.     

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.     

Enhancement of electron density in the interaction of high-power electromagnetic waves with inhomogeneous magnetized plasma

Propagation characteristics of a high-power electromagnetic wave through an inhomogeneous magnetized plasma is investigated. Considering the momentum transfer equations for electrons and ions and taking into account the ponderomotive force, the distribution of electron density and dielectric permittivity are obtained. Using non-linear dielectric permittivity and Maxwell's equations in the absence of external current and charge densities, non-linear wave equations are achieved. The results indicate that the external static magnetic field can modify the profiles of both the electric and magnetic fields. It is also shown that the external static magnetic field enhances the amplitude of the electron density and the non-linear dielectric permittivity.     

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.     

Characterization of heterogeneous interaction in binary mixtures of ethylene glycol oligomer with water, ethyl alcohol and dioxane by dielectric analysis

The associating behaviour of the binary mixtures of ethylene glycol oligomer (EGO), i.e. ethylene glycol (EG), diethylene glycol (DEG) and poly(ethylene glycol)s (PEG200, PEG300, PEG400 and PEG600) with water (W), ethyl alcohol (EA) and 1,4-dioxane (DX) over the entire concentration range at 25 °C have been investigated through their accurately measured values of dielectric constant. The static dielectric constant ε_o, high frequency limiting dielectric constant ε_∞, dielectric relaxation strength Δε, excess dielectric parameters ε^E₀ and ε^E_∞, effective Kirkwood correlation factor g^eff and corrective correlation factor g_f of EGO–W, EGO–EA and EGO–DX mixtures were determined to obtain qualitative and quantitative information about the complex formation through H-bond in these systems. Most of the evaluated dielectric parameters of EG and DEG in different ‘cosolvents’ have different characteristics as compared to the PEG–cosolvent mixture. The observed linear and non-linear behaviour of Δε against EGO monomer unit mole fraction X confirms the variation in the homogeneous structures in their binary mixtures with concentration variation. Appearance of the maximum in ε^E₀ against X plots indicates that a complex stable adduct is formed in the EGO–W mixtures at stoichiometric ratio 1:1.7 for lower oligomers but this ratio seems to be 1.7:1 for higher EGO molecules, which confirms that the EGO size and chain flexibility affects the complex formation between EGO and W. In case of EG–EA mixture 1:1 stoichiometric ratio form stable adduct whereas for higher EGO–EA, it is 3:1, at EGO monomer unit level. The complex formation behaviour of DEG–EA has entirely different characteristics when compared to the other studied EGO–EA mixtures. Although, 1,4-dioxane has weak polar behaviour dielectric properties of EG–DX and DEG–DX confirm the formation of stable adducts at the stoichiometric ratio 2:1 of EGO monomer unit mole fraction to the DX. For the higher EGO–DX mixtures, stable adduct forms at the stoichiometric ratio 9:1. Except DEG–EA mixtures, the EGO–W and EGO–EA form the complex with reduction in the effective number of dipoles. In EG–DX mixtures, the heterogeneous species form with a large reduction in the effective number of dipoles, which changes as the effective number of dipoles increases with the increase in monomer repeat units of EGO. Further the net electronic polarization in these binary mixtures increases due to heterogeneous interaction over the entire mixing concentration range.     

Study of interaction through dielectrics: Behavior of − OH group molecules from 10 MHz to 20 GHz

The complex permittivity spectra for tert-butyl alcohol (TB) with 2-propanol (2P) were determined over the frequency range of 10 MHz to 20 GHz using the time domain reflectometry (TDR) in the temperature range 25 °C to 55 °C for 11 different concentrations of the system. The static dielectric constant (ε₀) and relaxation time (τ) have been determined these spectra using the Debye model. Excess properties and Kirkwood correlation factor of the mixtures have been determined. The excess permittivity is found to be positive in the tert-butyl alcohol rich region and negative in the 2-propanol rich region. However, the excess inverse relaxation time has different trend. The static dielectric constants for the mixtures have also been fitted with the modified Bruggeman model by assuming an additional parameter in the model. It appears that structure of the TB–2P dimer in the TB rich region favors parallel dipole orientation, whereas in the 2P rich region, it favors antiparallel orientation.     

Dielectric behaviour of aqueous CsCl solutions

Complex dielectric permittivity spectra, in the frequency range 10 MHz to 20 GHz are reported for aqueous cesium chloride (CsCl) solutions at 250C using time domain reflectometry technique. The static dielectric constant, relaxation time and conductivity have been determined using nonlinear least squares fit method. From the static dielectric constant, hydration numbers were determined by using measured solutions density at different concentrations.     

Excess properties of methanol-water binary system at various temperatures

Summary  In this study the viscosities of binary mixtures of methanol and water have been measured in the temperatures ranging from 15 to 45°C. The structural changes occurring as a consequence of molecular interactions in the solutions have been discussed in detail. Nevertheless, it would be of interest to see whether the information obtained from viscosity studies can be corroborated with that obtained from dielectric-constant data. With this aim, the present study on the dielectric behaviour of methanol-water binary solutions has been undertaken. The static dielectric constants, densities and refractive indices have been also measured on the methanol-water mixtures expressed by the mole fraction of methanol (0<x₂<1). Excess dielectric constants, excess volumes, excess viscosities and excess Gibbs energies of activation of the viscous flow and Kirkwood correlation factors have been evaluated using experimental results since these calculations may lead to conclusions concerning the deviation of the system from an ideal-mixture behaviour.     

Dielectric absorption in mixtures of anisole with some primary alcohols at microwave frequency

Dielectric properties of binary mixtures of anisole with methanol (MeOH), 1-propanol (1-PrOH), 1-butanol (1-BuOH) and 1-heptanol (1-HeOH) over an entire concentration range have been studied at a fixed temperature 40°C. The dielectric constant (ε′) and dielectric loss (ε″) of the binary mixtures of polar liquids have been determined at a microwave frequency of 9.1?GHz. The static dielectric permittivity (ε ₀) of the liquid samples was also determined using a precision LCR meter. Determined values of static dielectric permittivity (ε ₀) and dielectric permittivity (ε*) at 9.1?GHz frequency were used to evaluate relaxation time (τ) and high frequency limit dielectric permittivity (ε _∞). Dielectric parameters were interpreted in terms of molecular interaction between the anisole and alcohol molecules.     

Dielectric permittivity, density, viscosity and refractive index of binary mixtures of anisole with methanol and 1-propanol at different temperatures

Static dielectric permittivity, density, viscosity, and refractive index of anisole (AN), methanol (MeOH), 1-propanol (1-PrOH) and binary mixtures of AN with MeOH and 1-PrOH at nine different concentrations, were measured at 303, 313 and 323 K temperatures. Measured properties of pure AN, MeOH and 1-PrOH were compared with literature values and they were found in good agreement. The investigation of binary mixtures showed a systematic change in static dielectric permittivity, density and viscosity with change in concentration of anisole in the mixture. Measured properties of liquid samples were used to calculate Kirkwood correlation factor and excess parameters such as excess dielectric permittivity, excess molar volume and excess viscosity. Determined parameters have been interpreted in terms of molecular interaction among the molecular species of the binary mixtures.     

Temperature studies of dielectric permittivity and mass density pretransitional anomalies in binary mixtures

Results of temperature studies of dielectric permittivity and mass density in binary mixtures are presented. The anomaly of dielectric permittivity as a function of temperature in nitrobenzene-n-alkanes binary mixtures has been studied. Molar dielectric permittivity which takes into account the anomaly of dielectric permittivity and the mass density anomaly has been introduced.     

Static dielectric constant assessment from capacitance over a wide range of electrode separations

Static dielectric constant extraction from two-electrode capacitance measurement over a wide range of electrode separations and dielectric constants involves careful assessment of fringe fields. Finite-element method has been employed to compute capacitance and quantify fringe fields for parallel electrode capacitor of (finite thickness, radii r, electrode separation d), with a homogeneous dielectric medium extending up to the geometric limits of the electrodes. Two distinct regimes, in the fringe field contributions are seen. A procedure to extract the static dielectric constant has been proposed for the first regime and a validation has been provided for the same.     

Concentration and temperature dependent interaction studies using dielectric and thermodynamic methods on mixtures of anisole with o-toluidine and m-toluidine

Molecular interactions in mixtures of anisole with o-toluidine and anisole and m-toluidine have been studied at three different temperatures using the dielectric method with measurements of the static permittivity and permittivity at optical frequency. From the measured values, the Kirkwood correlation parameter, Bruggeman parameter, excess permittivity and thermodynamic excess free energy were computed for the mixtures. Positive and negative values of excess permittivity were obtained for both mixtures. The excess free energy for the anisole+o-toluidine mixture is positive at all three temperatures, whereas mixed values (positive and negative) are obtained for the anisole+m-toluidine mixture. Alignment of the dipoles in both mixtures was identified by Kirkwood factors. The investigation shows that the interaction between the components changes systematically with concentration and temperature and the change is minimum.     

Refractive indices of cadmium sulphide-telluride alloys

Cadmium sulphide-telluride alloys have been prepared in the form of this films, and their refractive indices have been measured using the interference fringes observed in the transmission spectrum.The composition dependence of the refractive index has been calculated using three previously published models, and it has been found that Brust's model of dielectric screening provides a useful method of calculating the dielectric constant in semiconductor alloys, provided that the non-linear composition dependences of the energy-gaps are taken into account.     

Correlation studies on dielectric and thermodynamic parameters in the binary mixtures of N-methyl aniline and alcohols

The dielectric and thermodynamic studies on polar binary mixtures of N- methyl aniline with alcohols — propan-1-ol and propan-2-ol have been carried out, at different temperatures and mole fractions. LF impedance analyzer, Microwave bench and Abbe’s refractometer are used respectively in radio, microwave (X-Band) and high frequency regions to determine the dielectric data. The experimental data is used to correlate the dielectric and thermodynamic parameters — static permittivity, high frequency permittivity, Kirkwood effective correlation factor, corrective Kirkwood correlation factor, excess permittivity, excess Helmholtz free energy, dipole moment, excessive dipole moment, relaxation time, excess inverse relaxation time and the excess thermodynamic parameters. These parameters are used to interpret the molecular interactions between the molecular species of the liquid mixtures.     

Non-linear refractive indices of CS2-CCI4 mixtures

We have determined the two independent fast non-linear refractive indices for liquid mixtures of CS₂ and CCI₄ to within 5% relatively and 8% absolutely over their range of more than a decade. These indices describe non-linear propagation of optical pulses of arbitrary polarisation, which are of a too short duration to be affected by electrostriction. We report measurements, having relative accuracy better than 1 %, of the static Kerr constants of these mixtures. We combine these results with recent data on Rayleigh wing depolarisation ratios for the same mixtures to deduce the desired non-linear indices with the aid of molecular theory. The non-linear refractive index for linearly polarised light is shown to be two-thirds (±5%) of the index difference measured by the Kerr effect, at least for molar concentrations of CS₂ greater than 10%. Our measured relative values of the mixture Kerr constants are predicted to within experimental error if one simply replaces the Lorentz local field factors in the classical theory by their 0.6 powers.     

Self-focusing of a laser beam in a strongly ionized plasma

In the presence of a strong Gaussian laser beam, the non-linearity in the dielectric constant of a strongly ionized plasma has been investigated. The non-linearity arises due to the heating and redistribution of the electrons; the loss of electron energy gained from the field has been assumed to be due to thermal conduction. This self-induced non-linearity causes a self-focusing and oscillatory waveguide propagation of the beam even when the non-linear dielectric constant does not fall in the saturating range. In a typical case of a 10¹⁰ W laser, the enhancement of axial intensity by a factor of 25 has been predicted in a length of 0.6 cm.Works supported by N.S.F. (USA).On leave from Malviya Regional Engeeniring College, Jaipur-4, India.