Static solvent permittivity Debye model

Solvent permittivity — is an index of the ability of a solvent to attenuate the transmission of an electrostatic force. This quantity is also called the -> dielectric constant. -> permittivity decreases with field frequency. Static (related to infinite frequency) and optical op (related to optical frequencies) permittivities are used in numerous models evaluating the solvation of ions in polar solvents under both static and dynamic conditions. Usually the refractive index n is used instead of op (n2 = eop), as these quantities are available for the majority of solvents. The theory of permittivity was first proposed by Debye [i]. Systematic description of further development can be found in the monograph of Frohlich [ii]. Various aspects of application to reactions in polar media and solution properties, as well as tabulated values can be found in Fawcetts textbook [iii]. 

According to the Debye model there are three parameters associated with dielectric relaxation in a simple solvent, namely, the static permittivity s, the Debye relaxation time td, and the high-frequency permittivity Eoq. The static permittivity has already been discussed in detail in sections 4.3 and 4.4. In this section attention is especially focused on the Debye relaxation time td and the related quantity, the longitudinal relaxation time Tl. The significance of these parameters for solvents with multiple relaxation processes is considered. The high-frequency permittivity and its relationship to the optical permittivity Eop is also discussed. 

Dielectric properties describe the polarization, P, of a material as its response to an applied electric field E (bold symbols indicate vectors) [1—3], In the field of solution chemistry, the discussion of dielectric behavior is often reduced to the equilibrium polarization, Pq = So(s — V) Eq (eq is the electric field constant), of the isotropic and nonconducting solvent in a static field, Eq. Characteristic quantity here is the static relative permittivity (colloquially dielectric constant ), , which is a measure for the efficiency of the solvent to screen Coulomb interactions between charges (i.e., ions) embedded in the medium. As such, enters into classical electrolyte theories, like Debye-Hiickel theory or the Bom model for solvation free energy [4, 5] and is used... 

Calculation of the dielectric permittivity of an isotropic polar material involves the problem of the permanent dipole contribution to polarizability and the problem of calculation of the local field acting at the molecular level in terms of the macroscopic field applied. Debye s model for static permittivity considers the local field equal to the external field. This assumption is valid only for gases at low density or dilute solutions of polar molecules in nonpolar solvents. Several workers... 

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