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.     

Dielectric behaviour of propylene glycol-water mixtures studied by time domain reflectometry

Dielectric relaxation measurements on water mixtures of propylene glycol across the entire concentration range were carried out using time domain reflectometry at 25°C over the frequency range from 10 MHz to 4 GHz. For all the mixtures, only one dielectric loss peak was observed in this frequency range. The relaxation in these mixtures can be described by a single relaxation time using the Debye model. A plot of the calculated relaxation time of the mixtures gives a straight line against the mole fraction of water, X_w. It is reasoned that the diameter of the water cluster is nearly the same as the length of propylene glycol. Further, a plot of the dielectric relaxation strength δ? against X_w suggests that there is a changing pattern of dielectric behaviour from below X_w = 0.5 to higher values of X_w. The excess permittivity, the excess inverse relaxation time and the activation free energy have been determined, to confirm the formation of hydrogen bonded homogeneous and heterogeneous cooperative domains, the dynamics of solute-solvent interaction and the hindrance to molecular rotation in the hydrogen bonded glass forming propylene glycol-water system.     

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.     

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.     

The dielectric relaxation study of 2(2-alkoxyethoxy)ethanol-water mixtures using time domain reflectometry

Complex permittivity spectra of 2(2-alkoxyethoxy)ethanol-water mixtures for the entire concentration range and at 25 °C have been measured using time domain reflectometry technique up to 30 GHz. The relaxation processes have been obtained by fitting the complex permittivity spectra of the binary mixtures in 2-Debye equation. In glycol ether-water mixtures except for pure water and its rich region the double relaxation times, primary process (τ₁) and secondary process (τ₂) have been observed. The primary relaxation process (τ₁) may be due to cooperative relaxation of the H-bond network of mixture constituents and the secondary relaxation process (τ₂) may be due to its flexible parts attached to the carbon chain. The intra and intermolecular hydrogen bonding of 2(2-alkoxyethoxy)ethanol in pure form as well as in binary mixtures of water have been discussed using Kirkwood correlation factor, Excess dielectric properties and the Bruggeman factor.     

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.     

Influence of molecules with chloro group on the associative liquid methanol: A dielectric relaxation approach

The dielectric relaxation parameters, viz., static dielectric constant, ɛ, and relaxation times, τ, have been determined for chlorobenzene-methanol (CB-MET), 1,2 dichloro ethanemethanol (DE-MET) and dimethylene chloride-methanol (DC-MET) mixtures with thirteen different concentrations at three temperatures, viz., 15, 25 and 45°C. The experimental technique used for this work was the time domain reflectometry (TDR) in the frequency range of 10 MHz to 20 GHz using the Hewlett Packard HP 54750 sampling oscilloscope. The information regarding hydrogen bonding structural behavior in MET due to CB, DE and DC are obtained by using the theoretical models based on the excess properties. The data suggest that CB and DE are not influenced by hydrogen bonding in MET whereas DC is influenced by the hydrogen bonding mechanism in MET. It appears that the behavior of DC on MET is different from CB and DE in MET.     

Dielectric behaviour and hydrogen bond molecular interaction study of formamide-dipolar solvents binary mixtures

The dielectric constant of binary mixtures of formamide with some common dipolar aprotic and protic solvents has been investigated at sixteen molar concentrations over the entire mixing range at 30 °C. The solvents used for binary mixtures with formamide are water, dimethylsulphoxide, N,N-dimethylformamide, acetone, 1,4-dioxane, mono-, di- and trihydric alcohols, and homologous series of 2-alkoxyethanol, 2-(2-alkoxyethoxy)ethanol, and ethylene glycol oligomers. The concentration dependent plots of excess dielectric constant and Kirkwood correlation factor were used to explore the complexes formed between unlike molecules, the molar ratio of a stable adduct, dipolar ordering, hydrogen-bond molecular connectivities, and their strength in the binary mixtures. Results confirmed that the complexation strength of dipolar aprotic solvents with formamide strongly depends on the value of solvent dielectric constant. The dependence of the hydrogen-bond complexation on number of hydroxyl groups and molecular size of the homologous series of the solvents is recognized from the comparative excess dielectric constant values of the mixed solvents.     

Dielectric relaxation studies of aqueous sucrose in ethanol mixtures using time domain reflectometry

Time domain reflectometry method has been used in the frequency range of 10 MHz to 10 GHz to determine dielectric properties of aqueous sucrose in ethanol. The dielectric parameters, i.e., static dielectric constant and relaxation time were obtained from the complex permittivity spectra using the non-linear least squares fit method. The Luzar theory is applied to compute the cross-correlation terms for the mixtures. It adequately reproduces the experimental values of static dielectric constants. The Bruggeman model for the non-linear case has been fitted to the dielectric data for mixtures.     

Microwave dielectric absorption studies of hydrogen bonded polar binary mixtures of isobutanol with tertiary butyl amine

The dielectric behaviour of polar liquids like isobutanol, tertiary butyl amine and their equimolar binary mixture in nonpolar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218?GHz (J band), 9.880?GHz (X band), 16.331?GHz (P band) and 24.951?GHz (K band). Hamiltonian quantum mechanical calculations such as AM1, PM3 and MNDO optimized converged geometry operation is performed on isobutanol, tertiary butyl amine and their equimolar binary mixtures using Argus lab chemical modelling software, 2004. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method, and compared with the theoretical Hamiltonian quantum mechanical results. Conformational analysis of the formation of hydrogen bond between the isobutanol and tertiary butyl amine is supported by FT-IR and proton NMR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.     

Dielectric studies of alkyl acrylates with primary alcohols using time domain reflectometry

Binary polar–polar liquid mixtures of alkyl acrylates (methyl acrylate, ethyl acrylate and butyl acrylate) with primary alcohols (propan-1-ol, butan-1-ol and hexan-1-ol) were subjected to dielectric studies at 303?K for different concentrations using time domain reflectometry (TDR) over the frequency range from 10?MHz to 10?GHz. Static permittivity (ε₀) dielectric constant at high frequency (ε_∞) and relaxation time (τ) were found through dielectric measurements for different concentrations of each system. The Bruggeman dielectric factor, Kirkwood correlation factor and the excess inverse relaxation time were determined and discussed to yield information on the molecular interactions of the systems. Deviations from the linearity of various models suggest molecular association through hydrogen bonding between the ?OH group of alcohols and C=O group of esters. The results also show a dependence of dielectric parameters on the alkyl chain length of both the alcohols and esters.     

Triboelectric charging and dielectric properties of pharmaceutically relevant mixtures

Binary mixtures of pharmaceutically relevant powders were investigated using dielectric spectroscopy over a frequency range of 10⁻³ to 300 kHz. Two different binary mixtures were studied as a function of concentration; pseudoephedrine hydrochloride in dicalcium phosphate dihydrate and acetaminophen in microcrystalline cellulose, respectively. Dielectric properties obtained from measurements of these systems are reported and found to follow a trend similar to the observed triboelectric behavior after low-shear tumble blending. Powder samples for charge measurement were mixed using a stainless steel blender and dispensed directly into a Faraday pail. For the two binary mixtures studied, low-frequency conductivity calculated from the imaginary part of the complex permittivity (or loss factor) was observed to be sensitive to water content. Furthermore, the unanticipated trends previously reported in the measured specific charge after blending were observed to correspond with the surface charge density calculated from the capacitance of the composite material. The implications of moisture and the physical and chemical properties of these dielectric mixtures are also discussed with supporting results.     

Investigating low-frequency dielectric properties of a composite using the distribution of relaxation times technique

The distribution of relaxation times approach, a less frequently employed dielectric data analysis technique, is utilized to better understand the relaxation characteristics of composites consisting of metal-coated, hollow glass spheres dispersed in a paraffin wax matrix. The dielectric properties of the composite samples are measured by means of impedance spectroscopy in the frequency range 0.1?mHz to 10?MHz. The application of a mixture law is not appropriate for the analysis of the frequency-dependent properties of the considered system on this broad frequency range. However, utilization of the distribution of relaxation times procedure to study the dielectric behaviour shows clear trends in the mixtures’ relaxation spectra. Relaxation processes of the paraffin wax and those specific to the composites are found from the extracted distribution of relaxation times spectra. The influence of the filler concentration, q, on the dielectric properties is examined; a relaxation with a narrow distribution at intermediate frequencies becomes broad with the addition of the filler. This relaxation, in the form of the low-frequency-dispersions (also known as constant phase angle) phenomenon, dominates the dielectric properties of the composites with high bead concentration, q>0.15. The variation in dielectric properties of individual samples whose bead concentrations q are nominally the same is discussed in terms of possible microstructural variations.     

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.     

近红外光谱研究水与甲醇混合溶液的氢键作用

对于浓度为0～100wt％(浓度间隔为5wt％)的水-甲醇混合溶液的近红外光谱,通过分析OH组合谱带和倍频谱带随浓度的变化,探索了水-醇溶液中的氢键作用。由于OH谱带在近红外区域重叠比较严重,采用了不同的光谱分析方法——二阶导数、主成分分析和二维相关分析来提高光谱分辨率,进而达到从水-甲醇溶液的近红外光谱获取有用信息的目的。定性地阐述了水-醇混合溶液中的水和醇之间通过氢键的可能结合方式,为探索水-醇混合溶液中的氢键作用提供了一种新的可能性。     

Conformational and dielectric analysis of hydrogen bonded polar binary mixtures of propan-1-ol with propionaldehyde

The dielectric behaviour of polar liquids such as propan-1-ol, propionaldehyde and their equimolar binary mixture in non-polar solvent benzene is studied in the microwave frequency range using the cavity perturbation technique at 6.218 GHz (J band), 9.880 GHz (X band), 16.331 GHz (P band) and 24.951 GHz (K band). Ab initio geometry optimization is performed in the 6-31G (d) basis set using the Gaussian 94W program for both pure and binary systems of propan-1-ol and propionaldehyde. Dipole moments of the binary mixtures are calculated from the dielectric data using Higasi's method and compared with the ab initio results. Conformational analysis of the formation of hydrogen bond between the propan-1-ol and propionaldehyde is supported by the FT-IR spectra. The average relaxation times are calculated from their respective Cole–Cole plots.     

DC Breakdown of C3F8/Ar and C3F8/N2 Mixtures

Paschen curves are presented for C3F8/Ar and C3F8/N2 mixtures in the range of 500 torr · cm ? pds ? 1000 torr · cm. The dielectric strength and dynamic characteristics of these mixtures make them suitable candidates for diffuse discharge switches.     

Signature of a type-a glass transition and intrinsic confinement effects in a binary glass-forming system

We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, ^{2}H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.     

Ultrasonic and IR study of intermolecular association through hydrogen bonding in ternary liquid mixtures

Complex formation in ternary liquid mixtures of dimethylsulfoxide (DMSO) with phenol and o-cresol in carbontetrachloride has been studied by measuring ultrasonic velocity at 2 MHz, in the concentration range of 0.019-0.162 (in mole fraction of DMSO) at varying temperatures of 20, 30 and 40 degrees C. Using measured values of ultrasonic velocity, other parameters such as adiabatic compressibility, intermolecular free length, molar sound velocity, molar compressibility, specific acoustic impedance and molar volume have been evaluated. These parameters have been utilized to study the solute-solute interactions in these systems. The ultrasonic velocity shows a maxima and adiabatic compressibility a corresponding minima as a function of concentration for these mixtures. The results indicate the occurrence of complex formation between unlike molecules through intermolecular hydrogen bonding between oxygen atom of DMSO molecule and hydrogen atom of phenol and o-cresol molecules. The excess values of adiabatic compressibility and intermolecular free length have also been evaluated. The variation of both these parameters with concentration also indicates the possibility of the complex formation in these systems. Further, to investigate the presence of O-HO bond complexes and the strength of molecular association with concentrations, the infrared spectra of both the systems, DMSO-phenol and DMSO-o-cresol, have been recorded for various concentrations at room temperature (20 degrees C). The results obtained using infrared spectroscopy for both the systems also support the occurrence of complex formation through intermolecular hydrogen bonding in these ternary liquid mixtures.     

Dielectric permittivity studies of nematogenic compounds and their binary mixtures showing induced smectic Ad phase

The binary mixture of 4-n-pentyl phenyl 4-n′-hexyloxy benzoate (ME6O.5) and p-cyanophenyl trans-4-pentyl cyclohexane carboxylate (CPPCC) shows the presence of induced Smectic A_d phase. In the present work the phase diagram as well as static dielectric permittivity measurements of different mixtures throughout the composition range, are reported. The observed variation of dielectric anisotropy with molar concentration in the nematic and smectic phases is explained, assuming the formation of both homo- and hetero-dimers in the mixture.