Mobile phase dielectric constant

At very high frequencies, the displacement of individual defects between direction changes of the field is small hence, there is no or little interaction between them, and the displacement is in phase with the applied field. The total conductivity is simply the sum of the contributions from each type of defect, the defect with the largest contribution (the majority defect) determining the over-all conductivity. (The majority or minority character of a given type of defect is determined by the product of concentration times mobility.) The dielectric constant is low. 

At lower frequencies, orientational polarization may occur if the glass contains permanent ionic or molecular dipoles, such as H2O or an Si—OH group, that can rotate or oscillate in the presence of an appHed electric field. Another source of orientational polarization at even lower frequencies is the oscillatory movement of mobile ions such as Na". The higher the amount of alkaH oxide in the glass, the higher the dielectric constant. When the movement of mobile charge carriers is obstmcted by a barrier, the accumulation of carriers at the interface leads to interfacial polarization. Interfacial polarization can occur in phase-separated glasses if the phases have different dielectric constants. 

The variations of dielectric constant and of the tangent of the dielectric-loss angle with time provide information on the mobility and concentration of charge carriers, the dissociation of defect clusters, the occurrence of phase transitions and the formation of solid solutions. Techniques and the interpretation of results for sodium azide are described by Ellis and Hall [372]. 

It is important to know the influence of the physicochemical parameters of the mobile phase (dipole moment, dielectric constant, and refractive index) on solvent strength and selectivity. The main interactions in planar chromatography between the molecules of the mobile phases and those of solutes are caused by dispersion forces related to the refractive index, dipole-dipole forces related to the dipole moment, induction forces related to a permanent dipole and an induced one, hydrogen bonding, and dielectric interactions related to the dielectric constant. Solvent strength depends mainly on the dipole moment of the mobile phase, whereas the solvent selectivity depends on the dielectric constant of the mobile phase. 

The dielectric constant of the mobile phase influences the pK value of the dissociable substructure of the analyte, it decreases with decreasing dielectric constant. This relationship can be approximately described by... 

The most commonly used LC/MS interfaces in pharmaceutical analysis are ESI and APCI. An ESI interface on the majority of commercial mass spectrometers utilizes both heat and nebulization to achieve conditions in favor of solvent evaporation over analyte decomposition. While ionization in APCI occurs in the gas phase, ionization using ESI occurs in solution. Attributes of a mobile phase such as surface tension, conductivity, viscosity, dielectric constant, flow rate and pFi, all determine the ionization efficiency. They therefore need to be taken into consideration and controlled. 

Eluents used in reversed-phase chromatography with bonded nonpolar stationary phases are genei ly polar solvents or mixtures) of polar solvents, such as acetonitrile, with water. The properties of numerous neat solvents of interest, their sources, and their virtues in teversed-phase chromatography have been reviewed (128). Properties of pure solvents which may be of value as eluents are summiuized in Table. VII. The most significant properties are surface tension, dielectric constant, viscosity, and eluotropic value. Horvath e/ al. 107) adapted a theory of solvent effects to consider the role of the mobile phase in determinmg the absolute retention and the selectivity found in reversed-phase chromatography. 

In mobile equilibria, the increase in the dielectric constant of the solution should enhance the population of the conformer with higher polarity (SOM 18), as is also proved by theoretical calculations. The solvation energy may lead to inversion in isomer stability on going from the vapor phase to a solution of a certain polarity, as occurs for furan-2-carboxaldehyde (72T3015). Inversion in conformer stability may also occur on going from the vapor to the liquid or solid state. 

The applicability of electrochemical detection in LC is frequently limited by the fact that die mobile phase must always be electrically conductive. In many cases, it is feasible to add a salt such as a buffer at suitable concentration in the mobile phase without affecting the separation. As an alternative, this problem can be circumvented by postcolumn addition of a suitable high-dielectric-constant solvent plus supporting electrolyte. An additional limitation that stems out from the electroactivity or not of the analyte can be overcome by pre- or postcolumn derivatization. 

The impedance for the study of materials and electrochemical processes is of major importance. In principle, each property or external parameter that has an influence on the electrical conductivity of an electrochemical system can be studied by measurement of the impedance. The measured data can provide information for a pure phase, such as electrical conductivity, dielectrical constant or mobility of equilibrium concentration of charge carriers. In addition, parameters related to properties of the interface of a system can be studied in this way heterogeneous electron-transfer constants between ion and electron conductors, or capacity of the electrical double layer. In particular, measurement of the impedance is useful in those systems that cannot be studied with DC methods, e.g. because of the presence of a poor conductive surface coating. 

Although the ionic strength of the eluant may remain the same throughout the run, the background conductivity can decrease due to the changing dielectric constant. These baseline changes can be compensated either by chemical means or by computer baseline subtraction. Often, mobile phase ion chromatography is used to elute ions which are very... 

The majority of CEC separations reported to date have been performed in the reversed-phase mode. Under these conditions, the hydrophobicity of the stationary phase determines the selectivity of the separation, and retention can easily be controlled by adjusting either the composition of the mobile phase or the hydrophobicity of the surface, with the first option being easier to implement. However, in contrast to the rich variety of solvents available for use in HPLC, acetonitrile-based solvent systems are employed in most CEC applications due to their high dielectric constant and low viscosity [30,35,51,64,70],... 

The compatibility of electrochemical detection with the various modes of liquid chromatography is limited. For all practical purposes, electrochemical detection is not suitable for use with normal phase adsorption or partition chromatography due to the solvents of low dielectric constant used as the mobile phase. On the other hand, reverse-phase adsorption and partition (including ion-exchange or ion-pairing systems) are highly com-... 

Thomlinson [78] was the first chromatographer to point out that the classical electrostatic ion-pair concept did not hold for IPRs that were usually bulky hydrophobic ions he also emphasized that in the interfacial region between the mobile and the stationary phases, the dielectric constant of the medium is far lower than that of the aqueous phase. Chaotropes that break the water structure around them and lipophilic ions that produce cages around their alkyl chains, thereby disturbing the ordinary water structnre, are both amenable to hydrophobic ion-pairing since they are both scarcely hydrated. The practical proof of such ion-pairing mode can be found in References 80 and 81 many examples of such pairing modes are reported in the literature [79-86],... 

The nature of the analyte interactions with liophilic ions could be electrostatic attraction, ion association, or dispersive-type interactions. Most probably all mentioned types are present. Ion association is essentially the same as an ion-pairing used in a general form of time-dependent interionic formation with the average lifetime on the level of 10 sec in water-organic solution with dielectric constant between 30 and 40. With increase of the water content in the mobile phase, the dielectric constant increases and approaches 80 (water) this decrease the lifetime of ion-associated complexes to approximately 10 sec, which is still about four orders of magnitude longer than average molecular vibration time. 

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