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

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.

1968 ◽  
Vol 46 (6) ◽  
pp. 841-845 ◽  
Author(s):  
J. Crossley ◽  
S. Walker

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.


1971 ◽  
Vol 49 (7) ◽  
pp. 1106-1114 ◽  
Author(s):  
M. D. Magee ◽  
S. Walker

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.


1969 ◽  
Vol 47 (4) ◽  
pp. 681-686 ◽  
Author(s):  
S. W. Tucker ◽  
S. Walker

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.


1968 ◽  
Vol 46 (14) ◽  
pp. 2369-2372 ◽  
Author(s):  
J. Crossley ◽  
S. Walker

Dielectric constant and loss data have been obtained at microwave frequencies for acridine, 4-methyl-pyridine, phthalazine, quinoline, and isoquinoline in both cyclohexane and p-xylene solution. The data have been used to calculate relaxation times and apparent dipole moments. For phthalazine, quinoline, and isoquinoline in cyclohexane at 50 °C the distribution coefficient is zero and their relaxation times are very similar. Although the axes about which these three molecules may relax lead to different volumes being swept out, no variation in relaxation behavior has been detected, and each system can be characterized by one relaxation time. The relaxation times for all the heterocyclic molecules except quinoline and acridine in p-xylene are appreciably longer than in cyclohexane. Relaxation time values appear a sensitive means of detecting the weak molecular interaction between the amine and the p-xylene. The difference in behavior between the quinoline and acridine as opposed to isoquinoline could be attributed to a more appreciable steric effect in the former two, hindering the approach of the π-electrons of the p-xylene molecules to the hybridized lone pair on the nitrogen atom. No interaction is, in fact, detectable in the case of quinoline and acridine. The importance of allowing for weak intermolecular forces, even in dilute solution, when relaxation values are being anticipated, is emphasized.


1969 ◽  
Vol 47 (24) ◽  
pp. 4645-4650 ◽  
Author(s):  
D. B. Farmer ◽  
S. Walker

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.


1970 ◽  
Vol 25 (11) ◽  
pp. 1685-1687
Author(s):  
F. F. Hanna ◽  
K. N. Abd-El-Nour

Abstract The dielectric constant (ε′) and dielectric loss (ε′′) of 3,5 dimethyl 3-hexanol in heptane have been measured for dilute and concentrated solutions at five wavelengths between 25 cm and 2 mm and at 20°, 40° and 60 °C. The data have been analysed and two relaxation times are obtained. The long relaxation time is attributed to the rotation of the whole molecule and the short relaxation time to the relaxation of the OH-group. For the range of concentrations used, the results show that associates are hardly detectable.


1986 ◽  
Vol 64 (11) ◽  
pp. 1534-1536 ◽  
Author(s):  
F. F. Hanna ◽  
K. N. Abdel-Nour ◽  
A. M. Ghoneim

The dielectric absorption of dilute solutions of nitrobenzene, chlorobenzene, and their mixtures in cyclohexane and Decalin® have been measured in the microwave region at three temperatures between 20 and 40 °C. The relaxation times and thermodynamic parameters are determined. A single relaxation time is found for the mixtures, and the results are discussed.


1975 ◽  
Vol 53 (1) ◽  
pp. 23-28 ◽  
Author(s):  
M. P. Madan

The dielectric absorption of solutions of 2-hexanone, 4- and 5-nonanone, and 2-decanone has been examined in the microwave region over a range of temperatures in n-heptane, cyclohexane, and benzene. The relaxation times and the thermodynamic parameters for the activated states have been determined using the measured dielectric data. The values of relaxation time are in reasonable agreement at the temperature at which there are available known data. Both the relaxation behavior and the thermodynamic processes are discussed and, where possible, compared with corresponding results of the other workers.


1982 ◽  
Vol 60 (2) ◽  
pp. 257-260 ◽  
Author(s):  
P. B. K. Sarma ◽  
P. V. G. K. Murthy ◽  
C. R. K. Murty

Dipole moments (μ) and relaxation times (τ) of seven azo central group liquid crystal compounds have been determined using the dilute solution method at radio and microwave frequencies. The results agree fairly well with the estimated values of the dipole moments. The angle, β, between the direction of the dipole moment and the long axis of the molecule, is determined for each molecule from structural considerations. The predicted sign of the dielectric anisotropy (Δε) from the estimated value of p is confirmed experimentally.


2018 ◽  
Vol 9 ◽  
pp. 233-241 ◽  
Author(s):  
Emil Petrescu ◽  
Cristina Cirtoaje

The dynamic behavior of a nematic liquid crystal with added carbon nanotubes (CNTs) in an electric field was analyzed. A theoretical model based on elastic continuum theory was developed and the relaxation times of nematic liquid crystals with CNTs were evaluated. Experiments made with single-walled carbon nanotubes dispersed in nematic 4-cyano-4’-pentylbiphenyl (5CB) indicated a significant difference of the relaxation time when compared to pure liquid crystal. We also noticed that the relaxation time when the field is switched off depends on how long the field was applied. It is shorter when the field is switched off immediately after application and longer when the field was applied for at least one hour.


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