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.     

Conductometric and fluorometric studies of sodium dodecyl sulphate in aqueous solution and in the presence of amino acids

The critical micelle concentration (CMC) of sodium dodecyl sulphate (SDS) in pure water and in the presence of amino acids (0.01, 0.02 and 0.03 mol kg^?1), L-valine (Val) and L-leucine (Leu) was determined from conductometric and fluorometric methods using pyrene as luminescence probe. Depression in the CMC at low concentration of amino acids is attributed to the increased hydrophobic–hydrophobic interaction between the non-polar groups of the surfactant, while, at high concentration, amino acids bind strongly with the anion, DS^?, head groups of SDS, thereby, delaying the micelle formation, resulting in increased CMC. A pronounced decrease in the CMC, while a marked increase in λ⁰₊, with decrease in the solvated radius (rather than crystal radius) of the counterions is observed. Negative values of ΔG⁰_m and ΔH⁰_m indicate that micellisation of SDS in the presence of amino acids is thermodynamically spontaneous and exothermic. Highest negative value of ΔH⁰_m in 0.01 m Val, with lowest CMC value, shows that 0.01 m aqueous Val is the most suitable medium favouring the micellisation of SDS. Decrease in I₁/I₃ from Val to Leu confirms the relative hydrophobicity of two amino acids. The observed values of the packing parameter, P, of SDS in water and in aqueous amino acids suggest that micelles formed are spherical in nature.     

Dielectric relaxation in aqueous solutions and suspensions I. Solutions and suspensions

The dielectric constants and dielectric loss factors of aqueous solutions and suspensions are measured as a function of the specific electrical conductivity, temperature, and electric field frequency. The dispersion of the dielectric constant and the dielectric loss factor in solutions is explained by the formation of a electric double layer at the electrodes and the redistribution of the electric field between the region adjoining the electrodes and the remaining volume of the measuring cell. An equivalent-circuit calculations for suspensions displays acceptable agreement with experiment.     

Synergetic effect of ultrasound and sodium dodecyl sulphate in the formation of CdS nanostructures in aqueous solution

High aspect ratio (>1000) CdS nanostructures were prepared via ultrasound treatment of parent nanowires (NWs) dispersed in sodium dodecyl sulfate (SDS) aqueous solution. The CdS parent NWs were prepared using ordered mesoporous silica, SBA-15, as a template. The elongated nanostructures (ENS), namely, NWs, nanoribbons and nanotubes, form stable dispersions in aqueous solutions. Electron microscopy and X-ray diffraction techniques were used to characterize both the parent NWs and the ENS. While the structure of the parent NWs is crystalline cubic, the ENS are amorphous. We show that the amorphous ENS bud from the parent bundled NWs. Ultrasound power and duration, presence of commensurate surfactant and calcination temperature of the templating SBA-15 are critical parameters in the formation of ENS in aqueous solution.     

Regularities of triplet-triplet annihilation of aromatic hydrocarbons in aqueous micellar solutions of sodium dodecyl sulfate

Investigation of deactivation processes in triplet states of a series of aromatic hydrocarbon molecules (antracene, 1,2-benzantracene, and 3,4-benzpyrene) made it possible to reveal the presence of triplet-triplet annihilation of the molecules in aqueous micellar solutions of sodium dodecyl sulfate. It is shown that the effect of microheterogeneous solutions on the process of triplet-triplet annihilation manifests itself in an increase in the probability of excimerization upon dissociation of triplet pairs of 1,2-benzantracene and 3,4-benpyrene molecules compared to one-component solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 626–628, September–October, 1997.     

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 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.     

Small angle neutron scattering studies of mixed micelles of sodium cumene sulphonate with cetyl trimethylammonium bromide and sodium dodecyl sulphate

The aqueous solutions of sodium cumene sulphonate (NaCS) and its mixtures with each of cetyl trimethylammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) are characterized by small angle neutron scattering (SANS). NaCS when added to CTAB solution leads to the formation of long rod-shaped micelles with a dramatic increase in the CTAB aggregation number. Its addition to SDS on the other hand results in the formation of smaller mixed micelles where part of SDS molecules in the micelle is replaced by NaCS molecules.      

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 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.     

A thermodynamic and photophysical study of the effects of thiourea on the micellar properties of aqueous sodium dodecyl sulphate solution

The micellar properties of sodium dodecyl sulphate (SDS) in aqueous thiourea solutions were investigated with the aim of studying the effect of thiourea on these properties. The critical micelle concentrations (cmc) and the degree of dissociation of the micelle were determined by the conductometric method over the temperature range 298–323 K for different concentrations of thiourea. The cmc values of the surfactant in the presence of thiourea were obtained by following the change in the relative intensities of vibrational fine structure of the pyrene fluorescence spectra. The aggregation numbers were determined by employing the static quenching fluorescence method. The cmc values in the presence of varying electrolyte concentrations (NaCl) were obtained with 8-anilinonaphthalene 1-sulphonate (ANS) as a fluorescence probe, and from these values the degree of dissociation was calculated. The mass action model was applied in the present study to obtain various thermodynamic parameters of micellization. All these properties were compared with the micellar properties of an aqueous urea/SDS system, and it was found that thiourea is a better demicellization agent.     

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 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.     

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.     

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.     

Dielectric relaxation and ac conductivity of sodium tungsten phosphate glasses

Studies of dielectric relaxation and ac conductivity have been made on three samples of sodium tungsten phosphate glasses over a temperature range of 77–420 K. Complex relative permitivity data have been analyzed using dielectric modulus approach. Conductivity relaxation frequency increases with the increase of temperature. Activation energy for conductivity relaxation has also been evaluated. Measured ac conductivity (σ_m(ω)) has been found to be higher than σ_dc at low temperatures whereas at high temperature σ_m(ω) becomes equal to σ_dc at all frequencies. The ac conductivity obeys the relation σ_ac(ω)=Aω ^S over a considerable range of low temperatures. Values of exponent S are nearly equal to unity at about 78 K and the values decrease non-linearly with the increase of temperature. Values of the number density of states at Fermi level (N(E _F)) have been evaluated at 80 K assuming values of electron wave function decay constant α to be 0.5 (Å)^?1. Values of N(E _F) have the order 10²⁰ which are well within the range suggested for localized states. Present values of N(E _F) are smaller than those for tungsten phosphate glasses.     

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 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.     

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.