Dielectric constant importance

Added to these interactions are the electrostatic forces related to the dielectric constants and which are important when it is necessary to separate ionic components. 

Luminescence has been used in conjunction with flow cells to detect electro-generated intennediates downstream of the electrode. The teclmique lends itself especially to the investigation of photoelectrochemical processes, since it can yield mfonnation about excited states of reactive species and their lifetimes. It has become an attractive detection method for various organic and inorganic compounds, and highly sensitive assays for several clinically important analytes such as oxalate, NADH, amino acids and various aliphatic and cyclic amines have been developed. It has also found use in microelectrode fundamental studies in low-dielectric-constant organic solvents. 

The dipole moments of the hydrogen halides decrease with increasing atomic number of the hydrogen, the largest difference occurring between HF and HCl, and association of molecules is not an important factor in the properties of FICl, HBr and HI. This change in dipole moment is reflected in the diminishing permittivity (dielectric constant) values from HF to HI. 

Solvents exert their influence on organic reactions through a complicated mixture of all possible types of noncovalent interactions. Chemists have tried to unravel this entanglement and, ideally, want to assess the relative importance of all interactions separately. In a typical approach, a property of a reaction (e.g. its rate or selectivity) is measured in a laige number of different solvents. All these solvents have unique characteristics, quantified by their physical properties (i.e. refractive index, dielectric constant) or empirical parameters (e.g. ET(30)-value, AN). Linear correlations between a reaction property and one or more of these solvent properties (Linear Free Energy Relationships - LFER) reveal which noncovalent interactions are of major importance. The major drawback of this approach lies in the fact that the solvent parameters are often not independent. Alternatively, theoretical models and computer simulations can provide valuable information. Both methods have been applied successfully in studies of the solvent effects on Diels-Alder reactions. 

Equations (10.17) and (10.18) show that both the relative dielectric constant and the refractive index of a substance are measurable properties of matter that quantify the interaction between matter and electric fields of whatever origin. The polarizability is the molecular parameter which is pertinent to this interaction. We shall see in the next section that a also plays an important role in the theory of light scattering. The following example illustrates the use of Eq. (10.17) to evaluate a and considers one aspect of the applicability of this quantity to light scattering. 

Electrical Properties. CeUular polymers have two important electrical appHcations (22). One takes advantage of the combination of inherent toughness and moisture resistance of polymers along with the decreased dielectric constant and dissipation factor of the foamed state to use ceUular polymers as electrical-wire insulation (97). The other combines the low dissipation factor and the rigidity of plastic foams in the constmction of radar domes. Polyurethane foams have been used as high voltage electrical insulation (213). 

Tables 1 and 2 Hst the important physical properties of formamide. Form amide is more highly hydrogen bonded than water at temperatures below 80°C but the degree of molecular association decreases rapidly with increa sing temperature. Because of its high dielectric constant, formamide is an excellent ionizing solvent for many inorganic salts and also for peptides, proteias (eg, keratin), polysaccharides (eg, cellulose [9004-34-6] starch [9005-25-8]) and resias.

In addition to the obvious effect of high dielectric constant glasses on the capacitance of the circuit elements iato which they enter, their dielectric strengths maybe more important. Siace the amount of energy a capacitor can store varies as the first power of the dielectric constant and the second power of the voltage, a glass with twice the dielectric strength is as effective as one with four times the dielectric constant. 

The most important electrical properties of insulation are dielectric strength, insulation resistance, dielectric constant, and power factor. Corona resistance, although not stricdy an electrical property, is usually considered also (10). 

Semiconductors (qv) are materials with resistivities between those of conductors and those of insulators (between 10 and 10 H-cm). The electrical properties of a semiconductor determine the hmctional performance of the device. Important electrical properties of semiconductors are resistivity and dielectric constant. The resistivity of a semiconductor can be varied by introducing small amounts of material impurities or dopants. Through proper material doping, electron movement can be precisely controlled, producing hmctions such as rectification, switching, detection, and modulation. 

The critical property for conformal coatings is resistance to chemicals, moisture, and abrasion. Other properties, such as the coefficient of thermal expansion, thermal conductivity, flexibiHty, and modulus of elasticity, are significant only in particular appHcations. The dielectric constant and loss tangent of the conformal coating are important for high speed appHcations. 

Polymers are used as inserts for pins and contacts. Important properties of the commonly used insert materials have been compiled (31). Polysulfones are high temperature thermoplastics that have high rigidity, low creep, excellent thermal stabiHty, flame resistance, low loss tangents, and low dielectric constants. The principal weakness of polysulfones is their low chemical resistance. 

Chemical and biological sensors (qv) are important appHcations of LB films. In field-effect devices, the tunneling current is a function of the dielectric constant of the organic film (85—90). For example, NO2, an electron acceptor, has been detected by a phthalocyanine (or a porphyrin) LB film. The mechanism of the reaction is a partial oxidation that introduces charge carriers into the film, thus changing its band gap and as a result, its dc-conductivity. Field-effect devices are very sensitive, but not selective. 

Alkaline-Earth Titanates. Some physical properties of representative alkaline-earth titanates ate Hsted in Table 15. The most important apphcations of these titanates are in the manufacture of electronic components (109). The most important member of the class is barium titanate, BaTi03, which owes its significance to its exceptionally high dielectric constant and its piezoelectric and ferroelectric properties. Further, because barium titanate easily forms solid solutions with strontium titanate, lead titanate, zirconium oxide, and tin oxide, the electrical properties can be modified within wide limits. Barium titanate may be made by, eg, cocalcination of barium carbonate and titanium dioxide at ca 1200°C. With the exception of Ba2Ti04, barium orthotitanate, titanates do not contain discrete TiO ions but ate mixed oxides. Ba2Ti04 has the P-K SO stmcture in which distorted tetrahedral TiO ions occur. 

The dielectric constant is a measure of the ease with which charged species in a material can be displaced to form dipoles. There are four primary mechanisms of polarization in glasses (13) electronic, atomic, orientational, and interfacial polarization. Electronic polarization arises from the displacement of electron clouds and is important at optical (ultraviolet) frequencies. At optical frequencies, the dielectric constant of a glass is related to the refractive index k =. Atomic polarization occurs at infrared frequencies and involves the displacement of positive and negative ions. 

As for the dielectric constant, when explicit solvent molecules are included in the calculations, a value of 1, as in vacuum, should be used because the solvent molecules themselves will perform the charge screening. The omission of explicit solvent molecules can be partially accounted for by the use of an / -dependent dielectric, where the dielectric constant increases as the distance between the atoms, increases (e.g., at a separation of 1 A the dielectric constant equals 1 at a 3 A separation the dielectric equals 3 and so on). Alternatives include sigmoidal dielectrics [80] however, their use has not been widespread. In any case, it is important that the dielectric constant used for a computation correspond to that for which the force field being used was designed use of alternative dielectric constants will lead to improper weighting of the different electrostatic interactions, which may lead to significant errors in the computations. 

Solvent effects on chemical equilibria and reactions have been an important issue in physical organic chemistry. Several empirical relationships have been proposed to characterize systematically the various types of properties in protic and aprotic solvents. One of the simplest models is the continuum reaction field characterized by the dielectric constant, e, of the solvent, which is still widely used. Taft and coworkers [30] presented more sophisticated solvent parameters that can take solute-solvent hydrogen bonding and polarity into account. Although this parameter has been successfully applied to rationalize experimentally observed solvent effects, it seems still far from satisfactory to interpret solvent effects on the basis of microscopic infomation of the solute-solvent interaction and solvation free energy. 

There is an important practical distinction between electronic and dipole polarisation whereas the former involves only movement of electrons the latter entails movement of part of or even the whole of the molecule. Molecular movements take a finite time and complete orientation as induced by an alternating current may or may not be possible depending on the frequency of the change of direction of the electric field. Thus at zero frequency the dielectric constant will be at a maximum and this will remain approximately constant until the dipole orientation time is of the same order as the reciprocal of the frequency. Dipole movement will now be limited and the dipole polarisation effect and the dielectric constant will be reduced. As the frequency further increases, the dipole polarisation effect will tend to zero and the dielectric constant will tend to be dependent only on the electronic polarisation Figure 6.3). Where there are two dipole species differing in ease of orientation there will be two points of inflection in the dielectric constant-frequency curve. 

Where plastics are to be used for electrical applications, then electrical properties as well as mechanical and other properties need to be considered. Whilst properties such as resistivity, power factor and dielectric constant are important, they may not be all-important. For example, although polyamides and many thermosetting plastics may show only moderate values for the above properties, they have frequently been used successfully in low-frequency applications. Perhaps more important for many purposes are the tracking and arcing resistance, which are frequently poor with aromatic polymers. 

Most organic reactions are done in solution, and it is therefore important to recognize some of the ways in which solvent can affect the course and rates of reactions. Some of the more common solvents can be roughly classified as in Table 4.10 on the basis of their structure and dielectric constant. There are important differences between protic solvents—solvents fliat contain relatively mobile protons such as those bonded to oxygen, nitrogen, or sulfur—and aprotic solvents, in which all hydrogens are bound to carbon. Similarly, polar solvents, those fliat have high dielectric constants, have effects on reaction rates that are different from those of nonpolar solvent media. 

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