scholarly journals On the direct determination of the electrostatic moments of molecules

According to Faraday's ideas, the specific inductive capacity of a substance is due to the polarisation of the molecules as wholes. This is the basis of the old Clausius-Mosotti theory of dielectrics, on which it is shown first that the polarisation P is proportional to the polarising field, i. e. , P = k E, k being the dielectric constant, and second that δ being the density of the dielectric, k - 2/ k + 2 ·1/δ = constant. Now it is known that some substances have large negative temperature coefficients for their dielectric constants which cannot thus be accounted for. To provide for this Debye proposed the theory that the molecules were permanently polarised and that they were systematically orientated in the field. This leads to the equation k - 2/ k + 2 = a T -1 + b T -2 , to represent the change of specific inductive capacity with temperature. This theory has been developed by Gans and others, and a number of measurements have been made by Smyth and others, who have found the molecular moments of many substances by measuring the dielectric constants at different temperatures.

The theories of Debye, Onsager, and Falkenhagen, stressing the connexion between the dielectric constant and the other properties of solutions of electrolytes, have focussed a considerable amount of attention on the problem of the accurate determination of the dielectric properties of conducting solutions. The results, however, of work published by various investigators during the past few years show wide discrepancies and, in fact, it can hardly be said that even the sign of the effect of electrolytes upon the dielectric constant of water has yet been established with any degree of certainty. That the results have been so unsatisfactory is not altogether surprising in view of the inherent difficulties of the problem; the system itself is a complicated one, consisting of simple water dipoles, the polymers dihydrol and trihydrol, and the solute molecules or ions dispersed throughout the liquid; furthermore, the experimental technique is frequently complicated by the requirement that the dielectric constants shall be determined at frequencies low enough to permit of computation of the maximum possible polarization of the system, including the rotational polarization of all polar molecules which may be present. Methods involving the direct determination of the capacity of a condenser containing the liquid, whether by capacity-bridge or by resonance, are rendered difficult or inaccurate through the poor capacity sensitivity of such systems in presence of an appreciable ohmic conductivity between the condenser plates. This difficulty is minimized by the use of very high frequencies, and a considerable amount of work has been carried out under these conditions by Wien, Röver, Falkenhagen, and others in connexion with the theory of strong electrolytes. The need has arisen, however, for the values of the dielectric constants of solutions of large polar molecules such as long-chained amino acids, polypeptides, and soluble proteins. Such substances have considerably enhanced periods of relaxation, and proportionately low frequencies of alternating current must be employed to avoid loss of the orientation polarization of the system. In the case of pure egg-albumin solution, dispersion of hertzian waves occurs at all frequencies above about 10 5 sec. -1 . In view of this difficulty it seemed desirable that a thorough investigation should be made into the question as to whether precision results might be obtained from some general method which uses comparatively low frequencies of alternating current. The “force” method theoretically developed by Fürth, in 1924, seemed the most promising. Various modifications of this method have been used by many workers, unfortunately, however, with by no means concordant results, so far as conducting solutions are concerned. It consists broadly in the determination of the force exerted upon an ellipsoid, mounted to rotate about one of its minor axes, in a liquid dielectric across which an alternating field is applied in a direction at right angles to the axis of rotation of the ellipsoid. For such a system Fürth has shown that the torque on the ellipsoid may be expressed by εE 2 sin2θA, where ε represents the dielectric constant of the liquid, E the potential gradient, θ the angle between the major axis of the ellipsoid and the direction of the field, and A a constant involving the dimensions of the ellipsoid. This form of Fürth’s equation applies only so long as the resistance of the liquid dielectric is high relative to that of the ellipsoid itself.


It has long been recognised that the dielectric constant of a substance gives an important indication of its constitution, and the classical papers of Nernst and Drude giving methods for the determination of dielectric constants, have been followed by a long series of papers giving the dielectric constants of several hundreds of pure liquids and solutions. Since the publication of Debye’s dipole theory in 1912, the literature of the subject has become even more voluminous than before. In surveying the mass of data one is struck by the very large discrepancies which exist in the values obtained by different observers for any one substance, and it is very difficult to decide whether they are due to the difficulty of pre­paring and purifying the substance, differences in experimental conditions such as frequency of the applied E. M. F., or errors in the methods of measure­ment. In order to make it possible to compare the results of different observers, and to provide a fundamental basis for new measurements, it is important that the value of at least one standard liquid should be known with unquestion­able accuracy. The object of the present investigation was to provide such a value. Benzene was chosen as the standard liquid since it has been very widely used in the past, and it is used as a standard in the measurement of other physical properties.


1947 ◽  
Vol 25b (6) ◽  
pp. 566-574 ◽  
Author(s):  
R. McIntosh ◽  
L. McLeod ◽  
H. S. Johnson ◽  
N. Hollies

A measure of the dielectric constants of several substances adsorbed on silica gel has been obtained by measuring the change in the capacity of an electrical condenser when measured amounts of the substances were adsorbed on silica gel situated between the plates of the condenser. The substances examined were ethyl chloride, n-butane, and ethylene oxide. The plot of capacity change vs. amount adsorbed was found, in all cases, to consist of two or more quite distinct sections, each approximating to linearity. The temperature coefficients of dielectric constant were evaluated. The dielectric constant calculated for adsorbed n-butane was close to that calculated for the bulk liquid, whereas the value calculated for adsorbed ethyl chloride was significantly lower than the value calculated for the liquid.


RSC Advances ◽  
2016 ◽  
Vol 6 (73) ◽  
pp. 69381-69386 ◽  
Author(s):  
S. J. Park ◽  
S. A. N. Yoon ◽  
Y. H. Ahn

In this paper, we demonstrate that terahertz (THz) metamaterials are powerful tools for determination of dielectric constants of polymer films and polar liquids.


Sensors ◽  
2018 ◽  
Vol 18 (11) ◽  
pp. 3727 ◽  
Author(s):  
Giovanna Capparelli ◽  
Gennaro Spolverino ◽  
Roberto Greco

Time domain reflectometry (TDR) is one of the most widely used techniques for indirect determination of soil volumetric water content (θ). TDR measures the relative dielectric constant (εr) which, in a three-phase system like the soil, depends on water, air, and solid matrix dielectric constants. Since dielectric constant of water is much larger than the other two, εr of bulk soil mainly depends on water content. In many cases, the application of TDR requires a specific calibration of the relationship θ(εr) to get quantitatively accurate estimates of soil water content. In fact, the relationship θ(εr) is influenced by various soil properties, such as clay content, organic matter content, bulk density, and aggregation. Numerous studies have shown that pyroclastic soils often exhibit a peculiar dielectric behavior. In Campania (Southern Italy) wide mountainous areas are covered by layered pyroclastic deposits of ashes (loamy sands) and pumices (sandy gravels), often involved in the triggering of landslides induced by rainwater infiltration. Reliable field measurements of water content of such soils are therefore important for the assessment of landslide risk. Hence, in this paper, the θ(εr) relationship has been experimentally determined on samples of typical pyroclastic soil of Campania, collected around Sarno, reconstituted with different porosities. The aim of the study is to identify specific calibration relationships for such soils based not only on empirical approaches. In this respect, a three-phase dielectric mixing model with a variable exponent is introduced, and the variable value of the exponent is related to the different dielectric properties of bond and free water within the soil pores.


Author(s):  
Boen Houng ◽  
Wei-Chueh Chien ◽  
Chen-Kai Sun

Zinc Oxide (ZnO) mixed with various amount of glasses were sintered at different temperatures. The densification behavior of zinc oxide with glass addition and its microstructure and dielectric constant sintered from 900° to 1200°C have been investigated. A unique glass composition contained GeO2, MoO3, and V2O5 (GMV) was designed to act as the sintering aid to enhance the densification and to adjust the dielectric constant of ZnO. The effect of sintering temperature on the densification behavior and dielectrics properties of ZnO was investigated by dilatometer, x-ray diffractometer, scanning electron microscopy and LCR meter.  The glass additive formed a thin continuous liquid phase and rearranged ZnO particles into a dense microstructure at relatively low temperature. The dielectric constants of glass added ZnO ceramics were found to vary with the glass concentration and sintering temperature.


The determination of the dielectric constant of one constituent of a mixture, when the dielectric constants of the other component and the mixture itself are known, has been a problem which has been given much attention for many years. The familiar Clausius-Mossotti relationship for the dielectric constant of any substance is: ε-1/(ε + 2) d = A, where ε is the dielectric constant of the substance, d the density, and A a constant depending upon the polarizability of the molecule. This relation was developed independently by Clausius, Mossotti, Lorenz, Lorentz, Rayleigh, and Debye; but even in the case of pure liquids deviations well outside the experimental error have been found.


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