Dielectric relaxation studies of 1-hexanol and 1,2-hexanediol in heptane

Solutions of 1-hexanol and 1,2-hexanediol in heptane have been investigated tigated by means of dielectric time domain spectroscopy (TDS). The permittivity spectrum of 1-hexanol in heptane is characterized by a model function containing a sum of three elementary Debye dispersions, while 1,2-hexanediol in heptane is best described by a Cole-Davidson model function. It is shown that dilute solutions of 1-hexanol in heptane have a completely different behavior to that of 1,2-hexanediol. For the diol, the relaxation time levels off at a high value indicating an existence of higher hydrogen bonded complexes. It is possible to quantify the relative amount of monomeric 1-alcohol molecules from the dielectric spectrum. The monomerization rate for 1-hexanol upon dilution with heptane is initially low, but increases rapidly for mole fractions of heptane exceeding 0.4.     

Dielectric properties of alcohol electrolyte solutions

Dielectric properties of ethanol and 1-hexanol solutions containing LiCl, CaCl₂·2H₂O and Ca(NO₃)₂·4H₂O, respectively, have been determined. It is found that LiCl reduces the static permittivity in ethanol, but CaCl₂·2H₂O and Ca(NO₃)₂·4H₂O both give an initial increase in _s. All the electrolytes studied increase the mean relaxation time of the ethanol solutions. In 1-hexanol the static permittivity is rather invariant for all studied electrolytes at low concentrations, while the same lengthening of the mean relaxation time is observed. When water is added in addition to the hydration water of the electrotyte, the static permittivity in hexanol is almost unaltered while the relaxation time is drastically shortened. The experimental result is discussed in terms of a formation of ion pairs, solvation sheaths, and kinetic depolarization, a partial release of hydration water and a structuring influence on the alcohol structure by the hydrated cation.     

Dielectric relaxation of electrolyte solutions in acetonitrile

Complex permittivity spectra in the frequency range 0.95v (GHz)89 for acetonitrile and its solutions of LiBr, NaI, NaClO₄, and Bu₄NBr at 25°C show one Debye equation for the neat solvent whereas the superposition of a Debye process for the solute and a Cole-Cole distribution for the solvent is necessary to account for the dielectric relaxation behavior of the solutions. The reorientation of bulk acetonitrile is diffusive and only weakly coupled to viscosity. The number of solvent molecules irrotationally bound to the electrolyte is in good agreement with conventional solvation numbers for all electrolytes, when kinetic depolarization is assumed to be negligible. The solute relaxation process is dominated by the formation kinetics and reorientation of contact ion pairs. There is evidence for solvent-shared ion pairs in dilute NaClO₄ solutions.     

Dielectric properties of solutions of tetra-iso-pentylammonium nitrate in dioxane-water mixtures

Dielectric properties of solutions of tetra-iso-pentylammonium nitrate, i-Pen ₄ NNO ₃ . in various dioxane-water mixtures have been studied using dielectric time domain spectroscopy (TDS). The static permittivity of the solutions _s increases for low concentrations of solute but levels off to asymptotic values at higher concentrations. The limiting sloped_s dc, and the asymptotic value depend on the static permittivity of the solvent mixture. The relaxation time due to the solute varies with solute concentration and depends on the solvent mixture. In the solvent mixtures of lowest permittivity the plots of relaxation time vs. concentration go through a maximum, while in the mixtures of highest permittivity the relaxation time initially decreases and then levels off to an asymptotic value. The concentration dependence of the dielectric parameters is discussed in relation to ion association.     

L-丝氨酸在丙二醇-水和丁二醇-水混合溶剂中的体积性质

利用精密数字密度计测定了L-丝氨酸分别在不同组成的1,2-丙二醇-水和1,2-丁二醇-水混合溶剂中的密度, 计算了丝氨酸的表观摩尔体积、极限偏摩尔体积、迁移偏摩尔体积和理论水化数. 根据结构水合作用模型讨论了迁移偏摩尔体积和理论水化数的变化规律. 结果表明, 丝氨酸两性离子头基和亲水侧链与醇分子中—OH基团间的相互作用占主导地位, 导致丝氨酸在醇-水混合溶剂中的迁移偏摩尔体积为正值; 此外, 这种亲水相互作用削弱了丝氨酸带电中心对周围水分子的电致收缩效应, 造成了水化数的减小.     

Dielectric relaxation in carbosilane dendrimers with cyanobiphenyl end groups

Carbosilane dendrimers of generation 1 and 2 are functionalized with mesogenic end groups (cyanobiphenyl) via spacers of 5 and 11 carbons. The dielectric relaxation is measured over broad frequency (1 Hz–1 GHz) and temperature (170–470 K) ranges. Two relaxation regimes are observed and characterized as δ and β relaxation. The δ relaxation is nearly a single Debye process and varies strongly with temperature. The S_E to S_A transition observed for the dendrimers with long spacers causes a jump in the relaxation rate of the δ process. The β process displays an Arrhenius-type temperature dependence with an activation energy of 35 kJ/mol. The relaxation time depends on spacer length. The dielectric relaxation reflects the mutual distortion of the dendrimer scaffold and the smectic layers. Received: 9 June 1999 Accepted in revised form: 21 July 1999     

Dielectric relaxation studies of binary mixtures of N-methylacetamide and N-methylformamide in benzene solutions using microwave absorption data

Using standard microwave X-band technique and by following Gopala Krishna's single frequency (9.90?GHz) concentration variational method, the dielectric relaxation times (τ) and the dipole moments (μ) of dilute solution of N-methylacetamide (NMA), N-methylformamide (NMF) and NMA?+?NMF binary mixtures in benzene solutions have been calculated at different temperatures. The energy parameters for the dielectric relaxation process for NMA?+?NMF binary mixture containing 30?mol% NMF have been calculated at 25, 30, 35 and 40°C and compared with the corresponding viscosity parameters. A good agreement between the free energy of activation from these two sets of values shows that the dielectric relaxation process like the viscous flow process can be treated as the rate process. From relaxation time behavior of NMA and NMF binary mixture in benzene solution, solute–solute types of the molecular association has been proposed.     

Dielectric Spectroscopy Study on Vesicles of CTAB/SDBS System

IntroductionWhen the cationic and anionic surfactants in which the total carbon number is equal to or greater than 20 are mixed, then the vesicles can form spontaneously due to the strong interactions or by sonication1. Vesicle is of bilayer structure containing a closed aqueous room, resembling the structure of a real cell. So it seems to be imperative to study the membrane mimicry system like vesicle in order to understand the structure and functions of real cells further. In addition, it ca…     

Dielectric relaxation spectroscopy of aqueous micellar electrolyte solutions: A novel application to infer Dukhin number and zeta potential of a micelle

The complex permittivities of aqueous SDS solutions, with and without the addition of sodium chloride (NaCl), are measured in the frequency range from 200 MHz to 14 GHz. The SDS concentrations are chosen such that the SDS molecules aggregate to micelles. In this frequency range, the measured spectra allow for the identification of two different relaxation processes. That is, the relaxation of the water molecules at frequencies above 1 GHz and the micellar relaxation at frequencies lower than 1 GHz. It is found that the addition of NaCl to the system mostly affects the micellar relaxation process. In detail, the time constant as well as the amplitude of the relaxation decrease by adding NaCl. These effects are attributed to the change in the solution conductivity that changes the properties of the micelle's electrical double layer. We also extract the Dukhin number of the micelles as a function of surfactant and electrolyte content from the measurements. The Dukhin number is a dimensionless group that describes the influence of the surface conductivity on a phenomena. A regression between Dukhin numbers and free sodium ions is found so that all data collapses on a single curve independent of the surfactant concentration. The surface conductivity is a manifestation of the electrical double layer and we use the Bikerman equation to infer the zeta potential of the micelles. Comparison to literature data shows very good agreement and proves that dielectric relaxation spectroscopy can be engaged to infer the zeta potential of micelles. Abbreviations: CMC critical micelle concentration, DRS dielectric relaxation spectroscopy, EDL electrical double layer     

Dielectric properties of ion-exchange beads of sulfonic acid type dispersed in aqueous solutions — effect of fixed charge density

Ion-exchange beads with different densities of fixed charges were prepared by sulfoethylation of dextran gel beads. The relative permittivities and the electrical conductivities of the ion-exchange beads in a sodium form were evaluated by a dielectric technique consisting of the following two procedures proposed in a previous study (2): (a) Dielectric measurements for densely packed sediments of the ion-exchange beads; (b) Analysis of the observed dielectric relaxations by means of a theoretical equation of interfacial polarization for suspensions of spherical particles. The deduced permittivities of the ionexchange beads in equilibrium with water were about 60, which is lower than those of outer aqueous phases. The deduced conductirities were of the order of 1 to 10 mS cm^–1 and were increased reasonably with the fixed charge density. Closer consideration on these deduced values indicates that no specific interaction exists between the counter ions and the fixed charges irrespective of changes in fixed charge density and temperature.     

Temperature dependent dielectric relaxation study of ethylene glycol-water mixtures

Using the picosecond time domain reflectometry method, dielectric relaxation measurements for 13 ethylene glycol (EG)-water mixtures have been studied from 0 to 40°C. The dielectric relaxations in the mixtures show a Debye-type behavior, whereas the relaxation in pure EG can be described by the Cole-Cole model. The static dielectric constant ₀, the relaxation time and the dielectric constant at high frequency have also been determined at various temperatures. The dielectric relaxation data suggests that there is no tendency to form hydrogen bonds with the addition of water to EG unlike other alcoholic systems but this tendency becomes increasingly important with decreasing temperature. The activation energy decreases with increased water content in the mixture as expected.     

Dielectric relaxation in a new double perovskite oxide Ho2MgZrO6

A new double perovskite oxide holmium magnesium zirconate Ho₂MgZrO₆ (HMZ) was prepared by solid state reaction technique. The crystal structure has been determined by powder X-ray diffraction which shows monoclinic phase at room temperature with cell parameters a = 9.3028 ± 0.0030 Å, b = 5.2293 ± 0.0008 Å, c = 4.4009 ± 0.0009 Å, β = 103.3746 ± 0.0166°. An analysis of complex permittivity with frequency was carried out assuming a distribution of relaxation times. The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. At the high temperature range, conductivity data satisfy the variable range hopping (VRH) model. In this regime, the conductivity of sample obeys Mott’s T^1/4 law, characteristic of VRH. High temperature data indicates the formation of thermally activated small polarons. The scaling behaviour of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures.     

Dielectric Spectroscopy of Cesium Fluoride in Methanol

Dielectric relaxation spectra have been measured at frequencies up to 20 GHz for CsF solutions in methanol (MeOH) at concentrations up to about 1 mol-L at 25°C. Spectra were also obtained for a few concentrations of the much less soluble KF. The data show that CsF forms a solvent shared ion pair (SSIP) in MeOH solutions. Detailed consideration of the possible geometries and comparison with earlier conductometric data suggest that the ion pair involves an oriented solvent molecule located at a vertex of one of the coordination sites of the cesium, rather than a conventional SSIP. Solvation numbers of the ions, estimated via the modified Cavell equation, are unrealistically large. This suggests, consistent with the large dielectric decrement and the conductivity data, that the ions significantly break down the chain structure of MeOH.     

Dielectric relaxation of poly(ester-ether-carbonate) multiblock terpolymers

The dielectric properties of a series of poly(ester-ether-carbonate) multiblock terpolymers have been investigated as a function of ether and carbonate composition in the frequency range of 10³–10⁶ Hz. The degree of polymerization of the samples was determined by viscosimetry measurements. The weight fraction, degree of crystallinity, and melting temperatures were characterized by means of x-ray diffraction and DSC methods. Dielectric behavior has been discussed in terms of Havriliak-Negami formulation. The variation of the dielectric properties with temperature has been associated with two relaxation processes: a) the -relaxation process observed at low temperature, which is associated to local motion of polar groups attached to both the soft and the hard segments, and b) the process assigned to long-range molecular motions above the glass transition temperature.     

Dielectric relaxation and hydrogen bonding studies of chlorobutane-dioxane mixtures using a time domain technique

Complex permittivity spectra have been computed for the binary mixtures of Chlorobutane (CLB) with 1, 4-Dioxane (DX) using Time Domain Reflectometry (TDR) for different concentrations and temperatures in the frequency range from 10 MHz to 30 GHz. The static dielectric permittivity and relaxation time have been obtained by fitting complex permittivity spectra to the Debye relaxation using least squares fit method. The Kirkwood correlation factor have been determined at various concentrations of 1, 4-dioxane. The Bruggeman model for the non-linear case has been fitted to the dielectric data for the mixtures.     

Dielectric Relaxation Study of Chloro Group with Associative Liquids. II. 1,2-Dichloroethane with Methanol, Ethanol, and 1-Propanol

Frequency spectra of the complex permittivity for 1,2-dichloroethane–alcohol binary mixtures have been determined over the frequency range 10 MHz to 20 GHz at 15, 25, 35, and 45°C, using the time-domain reflectometry (TDR) technique, for 11 compositions of each 1,2 dichloroethane–alcohol system. The alcohols used in the study were methanol, ethanol, and 1-propanol. The relaxation in these systems can be described by a single relaxation time using the Debye model. The static dielectric constant, relaxation time, the corresponding excess dielectric properties, Kirkwood correlation factor, and Bruggeman factor of the mixtures have been determined. The static dielectric constants for the mixtures have been fitted with the modified Bruggeman model.     

Dielectric properties of thermally degraded chloroprene rubber

We performed dielectric measurements on thermally aged carbon-black-filled chloroprene rubber (CR). Primary and secondary processes were observed in unaged and thermally aged CR. The primary process is due to the cooperative motion of chloroprene chains in CR, and the secondary process is due to the local motion of chloroprene chains. For the primary process, the relaxation time slightly increases and symmetric shape parameter of the loss spectrum decreases with increasing aging time. For the secondary process, the relaxation strength decreases with increasing aging time, and reaches zero after 50 h. These changes in the dielectric relaxation parameters are due to the progress of the dehydrochlorination reaction at the chloroprene chains.     

Dielectric relaxation studies of aromatic polyamides

Dielectric relaxation spectroscopy (DRS) is presented for a family of four aromatic polyamides trying to relate the structure of the lateral groups to the molecular mobility. A prominent sub-T_g absorption is always seen followed in some cases by remanent dielectric activity at room temperature and a subsequent increase of the loss permittivity. The low temperature relaxation is analyzed in terms of a Fuoss–Kirkwood equation to obtain the broadness and the strength of these relaxations as well as the activation energy (ranging from 10 to 11 Kcal/mol). The low frequency conductive peak shows in each case a half-width higher (1.30) than those corresponding to a single relaxation time peak (1.144). These values of the half-width are an indication of the complex character of these phenomena. A final discussion of the rotational barriers of the lateral chains rules out that such motions are the only molecular origin for the gamma relaxation. Instead, some kind of motion involving the main chain and where the interchain interactions play a significant role should be considered as responsible for that relaxation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 919–927, 1997     

时域反射谱法研究烷基丙烯酸酯与酚复合的介电弛豫

The dielectric relaxation measurements on binary mixtures of esters (methyl acrylate, ethyl acrylate, and butyl acrylate) with phenol derivatives (p-cresol, p-chlorophenol, and 2,4-dichlorophenol) were carried out at different concentrations at 303 K using the time domain reflectometry (TDR) over the frequency range from 10 MHz to 20 GHz. The Kirkwood correlation factor and excess inverse relaxation time were determined and discussed to yield information on the molecular interactions of the systems. The relaxation time increased with increasing concentration of phenols and increasing chain length of esters. The excess inverse relaxation time values were negative for all the systems, which indicated the solute-solvent interaction existing between esters and phenols producing a field in such a way that the effective dipole rotation was hindered.