Dielectric relaxation in aqueous solutions and suspensions

A method is proposed for measuring the relaxational dielectric losses of liquids at radio frequencies on a background of large conductivity losses. The absorption of the electromagnetic field energy is explained by structural relaxation, i.e., by the processes of formation and destruction of clusters.Translated from Isvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 81–85, February, 1975.     

Dielectric relaxation studies of alkanols solubilized by sodium dodecyl sulphate aqueous solutions

Considerable attention has been paid in recent years to the influence of alcohols on ionic micellar structures, alcohol co-surfactants most commonly employed in the preparation of microemulsions. Dielectric relaxation spectroscopy (DRS) is a versatile tool to monitor the dynamic process of such micellar systems. We report here the changes in the dielectric constant of the medium and the relaxation time of micellar solutions of sodium dodecyl sulphate (SDS) in water in the presence and absence of alkanols—hexan-1-ol, octan-l-ol, decan-l-ol and 1,2-ethanediol. The time domain dielectric data were obtained in the reflection mode in the frequency range of 10 MHz to 20 GHz using a HP54750A sampling oscilloscope and HP 54754A TDR plug-in-module. The sample is held at 303 K in a SMA cell with an effective pin length of 1.35 mm. We have determined the relaxation time (τ) using the Cole–Cole method. The relative viscosity ηr on the micellar solutions were also determined. The result shows that the dielectric constant increases linearly with SDS concentration in pure aqueous solutions up to 400 mM and decreases thereafter. The relaxation times are of the order of 15 ps to 25 ps and are far greater than that of Debye rotational relaxation of the monomer species. It is assigned to the dispersion step to water molecules surrounding to hydrophobic particles or the “bound water”. The addition of alcohols results in a linear increase in relaxation time in all the systems. As the concentration of SDS increases τ/ηr attains a near constant value showing that solubilization becomes more difficult at these concentrations. Our results show that the alcohol molecules are solubilized at the surface of the SDS micelle (i.e.) the micelle–water interface.     

Dielectric relaxation in YTTRIA-doped Ceria solid solutions

The nature of the defects present in Y₂O₃-doped CeO₂ is explored by means of dielectric relaxation, employing primarily the thermally-stimulated depolarization current (TSDC) technique. For Y₂O₃ concentrations ? 1 mole %, two relaxation peaks are observed. The lower-temperature peak shows a dielectric relaxation rate, τ^?1 which is $\text{1}\text{2}$ the relaxation rate of the corresponding anelastic relaxation. This proves that the peak is due to nn, 〈111〉 oriented, (YV_O) pairs, where V_O represents the oxygen vacancy. These pairs are positively charged defects which are compensated by an equal number of isolated Ý. The upper peak is a broad peak whose position varies with Y₂O₃ concentration in the same manner as the activation enthalpy for the ionic conductivity. The peak is not due to simple dipoles, but to relaxation of the array of alternately charged (YV_O) and Ý defects by the redistribution of oxygen-ion vacancies. A simple model, in which these defects form a superlattice containing wrong pairs, explains the essential features of the upper peak.     

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.     

Proton spin-lattice relaxation in aqueous ionic solutions

The proton spin-lattice relaxation time, T ₁, has been measured for aqueous solutions of sodium, potassium, rubidium and magnesium chlorides up to a concentration of about 4N at 25°c. The sodium and the magnesium chloride solutions were also measured at 60°c and 100°c. The variation of 1/T ₁ is not linear with concentration, at least above about ¼N, in contrast with previous reports [1, 2]. The behaviour depends markedly on the nature of the salt and on the temperature. It is shown that almost the whole of the variation of T ₁ as compared with that of water can be directly and simply related to the corresponding changes in the shear viscosity of the solutions. It is noted that the viscosity correction is better the higher the temperature of the solution.     

Chemical relaxation spectrometry in aqueous surfactant solutions

Chemical Relaxation Spectrometry is the term coined by Eigen to describe the range of experimental techniques which enable the study of the kinetics of fast reactions in solution in the time range 1–10⁻¹⁰s. This paper reviews the progress in the application of some of these techniques as well as the interpretation of the data in various surfactant solutions since the pioneering work in the early 1970's.     

Dielectric relaxation time and dipole moment of isometric butanols in benzene solutions.

Measurements of static permittivity at 100 KHz, refractive index (for Sodium D line) and complex permittivity at 7.73 GHz have been made for Butane 1-01, Iso-butyl alcohol, Sec. butyl alcohol and Tert. butyl alcohol at 35°C. in dilute solutions of benzene. Dielectric relaxation time (τ) have been determined following the three methods, viz., method of Higasi et al, Gopal Krishna's method and Higasi's method. The value of τ and the distribution parameter (α) show evidence for existence of morethan one relaxation mechanism. This has been interpreted in terms of intramolecular orientation of O-H. group occuring simultaneously with the end over end molecular orientation. The > values for all these compounds have been found much larger than the corresponding compounds of similar structure. This behaviour has been explained as due to the formation of dimers by association and solute solvent interaction. This is also confirmed from the tan δ concentration curves. The values of the dipole moments determined from the Higasi's method, Gopal Krishna's method and Guggenheim's method are found to be in good agreement.     

Dielectric relaxation of 1-propanol/water solutions

Time domain measurements of solutions at seven compositions and 25°C have been Fourier transformed to obtain complex permittivities in the range 50 MHz to 8 GHz. These can be represented by a sum of two Debye relaxation functions. The principal, slower, one has a relaxation time changing smoothly from 320 ps for 1-propanol to 8 ps for water (by extrapolation from 0.75 mole fraction of water). The second is quite small for 1-propanol, but increases with added water, and remarkably has a relaxation time of ca. 20 ps which is independent of concentration to within the accuracy of the data and fitting. The significance of the behavior is discussed in terms of diffusion like models for molecular reorientations and local conformational changes in hydrogen bonding, with the conclusion that the latter provides a more likely explanation, particularly of the faster relaxation.     

35Cl N.M.R. relaxation in aqueous sodium perchlorate solutions

The relaxation time, T _1ρ, for ³⁵Cl in perchlorate ion in aqueous solutions is found to be 0·25 s. T _1ρ is insensitive to the presence of most first row transition metals; however, a weak complex with manganous ion is demonstrated, and the perchlorate ion-manganous exchange rate is shown to be between 3 × 10⁴ s^-1 and 3·6 × 10⁷ s^-1. In the absence of manganous ion, the relaxation is dominated by the nuclear electric quadrupole interaction; however, a dipolar contribution is observed with manganous ion present.     

Dielectric relaxation studies of some aliphatic alcohols and their mixtures in benzene solutions

Dielectric absorption of four aliphatic alcohols, viz., methyl alcohol, ethyl alcohol, n-propyl alcohol, tert-butyl alcohol and their binary mixtures, mixtures of these alcohols with dimethyl formamide and 2-fluoroaniline has been studied in the 3 cm microwave region at a temperature of 30°C in benzene. In alcohols and their mixtures the tan σ - concentration curve shows a marked increase in the concentration range 0.02 – 0.05 weight fraction. This behaviour has been explained as due to the formation of complex via self and hetero-association. The alcohols + DMF systems show complex formation at a very low concentration range. The study of systems alcohols + 2 - fluoroaniline indicate that the 2-fluoroaniline produces dissociating effects in these alcohols.     

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.     

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.     

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.     

Electron paramagnetic relaxation in aqueous solutions of manganese (II) ions

The processes of the electron paramagnetic relaxation, molecular motions and structural changes in aqueous solutions of manganese nitrate have been investigated by direct measurement of spin-lattice (T ₁) and spin-spin (T ₂) relaxation times for a wide range of concentrations, temperatures and viscosities. T ₁ and T ₂ were measured by a non-resonance absorption method.

It was discovered that some structural regions exist at the different concentrations of Mn(II) ions in solution. So, the structure of highly concentrated solutions may be considered as one of the corresponding crystallohydrate. The structural microinhomogeneities were observed also in the intermediate concentration range at definite temperatures. It is shown that the relaxation mechanism proposed by Bloembergen and Morgan is not effective in the concentration range studied by us.

The analysis of relaxation times and E.P.R. spectra has shown the formation of ‘liquid microphases’ at the freezing point of the solution. Such microphases can exist at temperatures a few tenths of a degree below the solvent freezing point, and its composition considerably differs from the initial solution.

The correlation times for intramolecular and intermolecular electron relaxation mechanisms are evaluated and their nature is discussed.     

Dielectric relaxation in Ih ice

Relaxation processes in Ih ice are studied in the temperature interval 77–27G°K and frequency band 5 Hz–500 kHz. A new maximum in thermally stimulated currents was found at 97°K, clarifying the nature of the relaxing defects. The parameters of the peaks of the thermally stimulated currents at 97, 127, 139, and 158°K are determined, and the concentrations of L defects and oriented H₂O dipoles are evaluated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 72–76, October, 1986.     

Consequences of (129)Xe-(1)H cross relaxation in aqueous solutions.

We have investigated the transfer of polarization from (129)Xe to solute protons in aqueous solutions to determine the feasibility of using hyperpolarized xenon to enhance (1)H sensitivity in aqueous systems at or near room temperatures. Several solutes, each of different molecular weight, were dissolved in deuterium oxide and although large xenon polarizations were created, no significant proton signal enhancement was detected in l-tyrosine, alpha-cyclodextrin, beta-cyclodextrin, apomyoglobin, or myoglobin. Solute-induced enhancement of the (129)Xe spin-lattice relaxation rate was observed and depended on the size and structure of the solute molecule. The significant increase of the apparent spin-lattice relaxation rate of the solution phase (129)Xe by alpha-cyclodextrin and apomyoglobin indicates efficient cross relaxation. The slow relaxation of xenon in beta-cyclodextrin and l-tyrosine indicates weak coupling and inefficient cross relaxation. Despite the apparent cross-relaxation effects, all attempts to detect the proton enhancement directly were unsuccessful. Spin-lattice relaxation rates were also measured for Boltzmann (129)Xe in myoglobin. The cross-relaxation rates were determined from changes in (129)Xe relaxation rates in the alpha-cyclodextrin and myoglobin solutions. These cross-relaxation rates were then used to model (1)H signal gains for a range of (129)Xe to (1)H spin population ratios. These models suggest that in spite of very large (129)Xe polarizations, the (1)H gains will be less than 10% and often substantially smaller. In particular, dramatic (1)H signal enhancements in lung tissue signals are unlikely.     

The influence of macromolecular polymerization of spin-lattice relaxation of aqueous solutions

The docking or polymerization of globular proteins is demonstrated to cause changes in proton NMR spin-lattice (T1) relaxation times. Studies on solutions of lysozyme, bovine serum albumin, actin, and tubulin are used to demonstrate that two mechanisms account for the observed changes in T1. Polymerization displaces the hydration water sheath surrounding globular proteins in solution that causes an increase in T1. Polymerization also slows the average tumbling rate of the proteins, which typically causes a contrary decrease in T1. The crystallization reaction of lysozyme in sodium chloride solution further demonstrates that the "effective" molecular weight can either decrease or increase T1 depending on how much the protein is slowed. The displacement of hydration water increases T1 because it speeds up the mean motional state of water in the solution. Macromolecular docking typically decreases T1 because it slows the mean motional state of the solute molecules. Cross-relaxation between the proteins and bound water provides the mechanism that allows macromolecular motion to influence the relaxation rate of the solvent. Fast chemical exchange between bound, structured, and bulk water accounts for monoexponential spin-lattice relaxation. Thus the spin-lattice relaxation rate of water in protein solutions is a complex reflection of the motional properties of all the molecules present containing proton magnetic dipoles. It is expected, as a result, that the characteristic relaxation times of tissues will reflect the influence of polymerization changes related to cellular activities.     

Dielectric relaxation in amorphous polyepichlorhydrin and polyepibromhydrin

The variation of the dielectric permittivity and loss factor with frequency and temperature has been measured for two polyethers with polar side groups, polyepichlorhydrin and polyepibromhydrin. Both polymers showed two distinct relaxation processes. The high-temperature relaxations correlate with the glass-to-rubber transition temperatures in accord with the WLF equation. For the low-temperature relaxations, attributed to rotational motion of the side groups, the activation energy for the bulkier—CH₂Br case is smaller than—CH₂Cl. This effect and the extreme broadness of these relaxations are explained by considering dipole-dipole interactions. Calculations for selected model conformations show that intramolecular dipole-dipole interactions are weak, but that inter-molecular dipole-dipole interactions can account for the observed order of activation energies.     

Hydrogen bond network relaxation in aqueous polyelectrolyte solutions: the effect of temperature

Dielectric spectroscopy data over the range 100 MHz–40 GHz allow for a reliable analysis of two of the major relaxation phenomena for polyelectrolytes (PE) in water. Within this range, the dielectric relaxation of pure water is dominated by a near-Debye process at ν = 18.5 GHz corresponding to a relaxation time of τ = 8.4 ps at 25?°C. This mode is commonly attributed to the cooperative relaxation specific to liquids forming a hydrogen bond network (HBN) and arising from long range H-bond-mediated dipole–dipole interactions. The presence of charged polymers in water partially modifies the dielectric characteristics of the orientational water molecule relaxation due to a change of the dielectric constant of water surrounding the charges on the polyion chain. We report experimental results on the effect of the presence of a standard flexible polyelectrolyte (sodium polyacrylate) on the HBN relaxation in water for different temperatures, showing that the HBN relaxation time does not change by increasing the polyelectrolyte density in water, even if relatively high concentrations are reached (0.02 monomol l(?1) ≤ C ≤ 0.4 monomol l(?1)). We also find that the effect of PE addition on the HBN relaxation is not even a broadening of its distribution, rather a decrease of the spectral weight that goes beyond the pure volume fraction effect. This extra decrease is larger at low T and less evident at high T, supporting the idea that the correlation length of the water is less affected by the presence of charged flexible chains at high temperatures.     

Dielectric permittivity of aqueous solutions of electrolytes probed by THz time-domain and FTIR spectroscopy

We have measured the dielectric permittivity of pure water and aqueous chlorides solutions in the range 0.2-1.5 THz. We considered the relaxation spectral function as the weighted sum of two independent single-parameter Debye functions. Such an approach allowed to drastically reduce the number of the parameters used in the fit which we set only by physical considerations. The resulting functions allow to fit the experimental data for pure water and solutions of LiCl, KCl, NaCl, and CsCl and to predict the excess response on the high frequency side of the relaxation without “ad hoc” corrective terms.