Dielectric studies. Part XVII. Relaxation processes and corresponding enthalpies of activation of some mono-substituted benzenes

1968 ◽  
Vol 46 (6) ◽  
pp. 841-845 ◽  
Author(s):  
J. Crossley ◽  
S. Walker
Keyword(s):  
Relaxation Times ◽  
Molecular Size ◽  
Relaxation Processes ◽  
Dielectric Studies ◽  
Molecular Reorientation ◽  
Substituted Benzenes ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Expected Increase ◽  
Xylene Solution

The dielectric absorption at several microwave frequencies of liquid ethylbenzene, isopropylbenzene, and phenyltrimethylsilane at 15, 37.5, and 50 °C and cyclohexane solutions of t-butylbenzene and benzotrichloride at 15, 37.5, 45, and 50 °C has been examined. Benzotrichloride has also been studied in cyclohexane and p-xylene solution at 25 °C. Only molecular reorientation can be detected for benzotrichloride, whereas the remainder are all characterized by an absorption that may be analyzed into two relaxation times, one associated with molecular reorientation (τ1) and a shorter relaxation time (τ2) which appears to be attributable to an intermolecular process. The enthalpies of activation of the τ1 process show the expected increase with increasing molecular size, while no temperature dependence is detectable for the shorter relaxation process.

Dielectric studies. Part XVIII. Dipole moments and relaxation times of some symmetrically substituted alkylbenzenes

1968 ◽  
Vol 46 (6) ◽  
pp. 847-851 ◽  
Author(s):  
J. Crossley ◽  
S. Walker
Keyword(s):  
Relaxation Time ◽  
Dipole Moments ◽  
Relaxation Times ◽  
Pure Liquid ◽  
Dielectric Studies ◽  
Molecular Reorientation ◽  
Microwave Frequencies ◽  
Short Relaxation Time ◽  
Dielectric Absorption ◽  
Liquid Benzene

The dielectric absorption at four microwave frequencies of pure liquid benzene and p-cymene at 25 °C, p-xylene and mesitylene at 25, 40, 50, and 60 °C, and solutions of durene and hexamethylbenzene in mesitylene at 60 °C has been examined. All show measurable loss factors and apparent dipole moments of about 0.1 to 0.2 D. These moments are less in magnitude than those associated with the short relaxation time (τ2) process for the polar monoalkylbenzenes. o-xylene and m-xylene. Their relaxation times are too short for molecular reorientation and there is a rough correlation between the number of collisions/molecule s and the reciprocal relaxation time.

Dielectric studies. Part XXV. Methoxy group rotation in anisole and three para-substituted anisoles

1969 ◽  
Vol 47 (24) ◽  
pp. 4645-4650 ◽  
Author(s):  
D. B. Farmer ◽  
S. Walker
Keyword(s):  
Relaxation Process ◽  
Methoxy Group ◽  
Relaxation Times ◽  
Pure Liquid ◽  
Relaxation Processes ◽  
Molecular Relaxation ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Weight Factors ◽  
Group Rotation

The dielectric absorption at several microwave frequencies of anisole, p-methylanisole, and p-bromoanisole in the solvent p-xylene, and p-dimethoxybenzene in the solvent cyclohexane has been investigated at 4 to 6 temperatures. Anisole, p-methylanisole, and p-dimethoxybenzene were all found to relax mainly by methoxy group rotation, whereas the relaxation process in p-bromoanisole was very largely molecular relaxation. In the literature, considerable divergence exists for the analyses of the dielectric data of anisole and substituted anisoles into contributions from two relaxation times and the magnitude of the weight factors governing each relaxation process. Such divergencies have been explored and justifiable analyses established for these systems where the weight factors governing the relaxation processes are shown to be roughly of the same order as those estimated from group moment data. The weight factor for molecular relaxation in the pure liquid appears considerably greater than that for a dilute solution of it in a non-polar solvent.

Dielectric Studies of a Substance with Negative Dielectric Anisotropy

1998 ◽  
Vol 53 (3-4) ◽  
pp. 134-140 ◽  
Author(s):  
S. Urban ◽  
B. Gestblom ◽  
R. Dąbrowski ◽  
H. Kresse
Keyword(s):  
Relaxation Times ◽  
Mean Field ◽  
Dielectric Anisotropy ◽  
Relaxation Processes ◽  
Network Analyzer ◽  
Dielectric Studies ◽  
Molecular Reorientation ◽  
Transverse Relaxation ◽  
Activation Barriers ◽  
The Mean

Abstract The results of dielectric studies of 6BAP(F) (1-[4-(hexylbicyclo[2,2,2]octyl]-2-(3-fluoro-4-methoxy-phenyl)ethane) in the nematic and isotropic phases are presented. The substance has a negative dielectric anisotropy. By applying two experimental techniques, using a network analyzer and time domain spectrometer (TDS), the two main relaxation processes, connected with the molecular reorientation around the short and long axes, respectively, were resolved in the phases studied. The activation barriers hindering the motions were obtained. By extrapolation of the longitudinal and transverse relaxation times from the isotropic to the nematic phase the retardation factors, g∥ and g⊥, and the nematic potential versus temperature could be calculated. These are discussed together with the order parameter S obtained from the refractive index, and are compared with the predictions of the mean-field theories.

Relaxation processes of quinoline, isoquinoline, and their mixtures

1980 ◽  
Vol 58 (1) ◽  
pp. 20-24 ◽  
Author(s):  
M. P. Madan
Keyword(s):  
Thermodynamic Parameters ◽  
Molecular Motion ◽  
Polar Solvent ◽  
Relaxation Times ◽  
Relaxation Processes ◽  
Polar Components ◽  
Dielectric Absorption ◽  
System A ◽  
Dielectric Data ◽  
Activated State

The dielectric absorption of quinoline, isoquinoline, and their binary mixtures has been studied in the microwave region over a range of temperatures in dilute benzene and n-heptane solutions. The relaxation times and the thermodynamic parameters for the activated state have been determined using the measured dielectric data. The results obtained have been discussed in terms of the molecular motion of the system. A relation has been proposed to represent the relaxation behavior of a system of two Debye-type polar components in a non-polar solvent. The relation has been tested by comparing the calculated values with those determined experimentally for a few systems consisting of similar, simple rigid polar molecules.

Dielectric Studies. Part XXXI. Analysis of the Dielectric Data of Phenol and its Polymerized Forms

1971 ◽  
Vol 49 (7) ◽  
pp. 1106-1114 ◽  
Author(s):  
M. D. Magee ◽  
S. Walker
Keyword(s):  
Dipole Moment ◽  
Relaxation Time ◽  
Mole Fraction ◽  
The State ◽  
Distribution Parameter ◽  
Dielectric Studies ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Dielectric Data ◽  
Intramolecular Process

The dielectric absorption and dispersions of several solutions of phenol in p-xylene have been measured at four microwave frequencies and at 2 MHz at a temperature of 25 °C. The data have been analyzed in terms of a mean relaxation time, a distribution parameter, and an apparent dipole moment which are useful empirical parameters for assessing the state of aggregation of the phenol molecules. The relaxation time at the lowest practicable concentration (0.02 mole fraction) is long for a molecule expected to relax predominantly by an intramolecular process. This and the behavior of the relaxation time and apparent dipole moment with increasing concentration are considered in terms of a model based on progressive association into an extended series of multimers, the trimer having a zero (or low) dipole moment and higher multimers becoming increasingly flexible.

Dielectric studies. Part XXIII. Relaxation data and apparent dipole moments of aniline and some disubstituted aromatic amines

1969 ◽  
Vol 47 (4) ◽  
pp. 681-686 ◽  
Author(s):  
S. W. Tucker ◽  
S. Walker
Keyword(s):  
Aromatic Amines ◽  
Dipole Moments ◽  
Frequency Dispersion ◽  
Dielectric Studies ◽  
Relaxation Data ◽  
Time Model ◽  
Electric Dipole Moments ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Dielectric Results

Dielectric studies have been carried out at microwave frequencies on dilute solutions of aniline, p-chloro-, p-bromo-, and m-chloro-anilines, and o-, m-, and p-toluidines at 25 °C in cyclohexane and p-xylene. The static dielectric constant has also been measured at 2 MHz. In addition o- and m-toluidines have been measured at 50 °C and p-toluidine at 15, 35, and 50 °C.The dielectric results, particularly those at 70.01 GHz, establish that there is more than one relaxation process present and the data have been analyzed on a two relaxation time model, the longer of which τ1, is identified as molecular relaxation. The cause of the lower electric dipole moments found from this method as opposed to the non-dielectric absorption methods is discussed. It follows that there is either an additional higher frequency dispersion or (and) a high atomic polarization for aniline and o-, m-, and p-toluidines. Work at still higher frequencies is required to study this further and to establish more precise values of τ2.

Dielectric Studies. Part XXXV. Relaxation Studies of Benzaldehyde and Fourpara-Substituted Aideliydes

1974 ◽  
Vol 52 (18) ◽  
pp. 3229-3234 ◽  
Author(s):  
P. F. Mountain ◽  
S. Walker
Keyword(s):  
Hydrogen Bonding ◽  
Relaxation Time ◽  
Intermolecular Hydrogen Bonding ◽  
Dielectric Studies ◽  
Molecular Relaxation ◽  
Relaxation Data ◽  
Dielectric Absorption ◽  
The Mean ◽  
Relaxation Studies ◽  
Xylene Solution

The dielectric absorption has been determined for benzaldehyde, p-fluoro-, p-chloro-, p-bromo-, and p-nitro-benzaldehyde in p-xylene solution at mainly five or six frequencies in the 6.70 to 70.1 GHz region. For all three p-halo-substituents the mean relaxation time values indicate that some mechanism faster than molecular relaxation occurs whereas none was apparent in benzaldehyde itself. A detailed study has been made of p-chlorobenzaldehyde in p-xylene solution at five temperatures, and the data have been analyzed into contributions from a molecular relaxation process and a shorter relaxation time τ2. In the p-xylene solutions of benzaldehyde the relaxation data indicate weak intermolecular hydrogen bonding between the solute and the solvent which is probably of the type [Formula: see text]

The dielectric relaxation of some diols in p-dioxane solution

1978 ◽  
Vol 56 (3) ◽  
pp. 352-354 ◽  
Author(s):  
J. Crossley
Keyword(s):  
Dielectric Constant ◽  
Dielectric Relaxation ◽  
Relaxation Process ◽  
Alkyl Group ◽  
Relaxation Times ◽  
Dielectric Dispersion ◽  
Dioxane Solution ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Dielectric Constant And Loss

Dielectric constant and loss data at up to nine microwave frequencies have been obtained for 1-butanol, 1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-do-decanediol at 25 °C, and for 1,6-hexanediol at 15, 25, 40, and 55 °C, in p-dioxane. In each case the dielectric dispersion is adequately described by a Cole-Cole distribution. The relaxation times for the diols are almost independent of the length of the alkyl group. An intramolecular relaxation process appears to be primarily responsible for the dielectric absorption.

Macroscopic viscosity and the dielectric relaxation of some substituted benzenes

1976 ◽  
Vol 54 (9) ◽  
pp. 1418-1424 ◽  
Author(s):  
S. C. Srivastava ◽  
J. Crossley
Keyword(s):  
Relaxation Times ◽  
Dielectric Constants ◽  
The Other ◽  
Relaxation Processes ◽  
Substituted Benzenes ◽  
Microwave Dielectric ◽  
Paraffin Oil ◽  
Oil Mixtures ◽  
Insight Into ◽  
Dielectric Results

Microwave dielectric constants and losses, and viscosities (η) have been obtained for acetophenone, anisole, bromobenzene, and p-dimethoxybenzene in n-heptane, n-hexadecane, paraffin oil, and three n-heptane + paraffin oil mixtures between 15 and 60 °C. The dielectric results have been analyzed for mean relaxation times (τ0). Plots of ln τ0T against ln η for bromobenzene are compared with those for the other solutes in an attempt to determine the effect of contributions from intramolecular relaxation processes. The results suggest that measurements employing several solvents at one temperature provide a better insight into mechanisms of dipole reorientation than those with one solvent at several temperatures.

Dielectric relaxation of acetyl- and benzoyl-acetones

1989 ◽  
Vol 67 (5) ◽  
pp. 804-808 ◽  
Author(s):  
R. K. Khanna ◽  
Abha Bhatnagar
Keyword(s):  
Dielectric Relaxation ◽  
Dipole Moments ◽  
Relaxation Times ◽  
Weight Fraction ◽  
Relaxation Mechanism ◽  
Relaxation Processes ◽  
Dielectric Absorption ◽  
Molar Polarization ◽  
Distribution Parameters ◽  
Few Data

Dielectric absorption measurements are reported at radio and microwave frequencies (at six different wavelengths) for acetylacetone and benzoylacetone solutions in benzene, in a temperature range 25–60 °C. Analysis of dielectric data in terms of Cole–Cole arc plots and multiple relaxation processes reveals that, at higher temperatures, overall molecular relaxation is the dominant relaxation mechanism in these β-diketones. The observed relaxation times, distribution parameters, and dipole moments are in reasonable agreement with the few data reported for some temperatures, in the literature. The activation energy parameters are also evaluated assuming dielectric relaxation to be a rate process. Molar polarization vs. weight fraction (concentration) plots show anomalous behaviour for acetylacetone. Keywords: dielectric properties, dielectric losses, relaxation times, dipole moment, dielectric absorption and dispersion, microwave measurements.

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