Dielectric liquids irradiated

Casanovas, J., Grob, R., Blanc, D., Brunet, G., and Mathieu, J, Dependence of free ion yield on electrical field strength in a dielectric liquid irradiated by Co-y-rays, J. Chem. Phys., 63, 3673,1975. 

Kinetics of Electron-Ion Recombination in Irradiated Dielectric Liquids... 

Infelta PP, de Haas MP, Warman JM. (1977) The study of the transient conductivity of pulse irradiated dielectric liquids on a nanosecond timescale using microwaves. RadiatPhys Chem 10 353-365. 

A chemical destruction method that has been used for the treatment of PCBs in contaminated dielectric liquids or soil is based on the reaction of a polyethylene glycol/potassium hydroxide mixture with PCBs (De Filippis et al. 1997). This method can be used successfully for the destruction of higher chlorinated PCBs with an efficiency of >99%, but was found to be unsuitable for the treatment of di- and trichlorobiphenyls due to low destruction efficiencies (Sabata et al. 1993). Irradiation of PCBs in isooctane and transformer oil by y-radiation resulted in degradation of PCBs to less chlorinated PCBs and PCB-solvent adducts (Arbon et al. 1996). Supercritical fluid technology has shown promise as a method for extraction of PCBs from soils, coupled with supercritical water oxidation of the extracted PCBs (Tavlarides 1993,1998a). Hofelt and Shea (1997) demonstrated the use of semipermeable membrane devices to accumulate PCBs from New Bedford Harbor, Massachusetts water. Another method showing... 

Chemical reagents are primarily dielectric liquids or solids. Magnetic losses are, however, observed for microwave-irradiated metal oxides, for example ferrites. As for dielectrics, a complex magnetic permeability is defined as given by Eq. (40) ... 

In this section we shall discuss the increase in conductivity produced when a nonpolar liquid is subjected to a constant intensity of low LET radiation. This condition implies that the distribution of ionizing events throughout the measurement volume is homogeneous. Irradiation of a nonpolar dielectric liquid leads to an increase of the electrical conductivity due to the generation of free charge carrier pairs. For the following considerations, it is assumed that the intrinsic conductivity is much smaller than the conductivity produced by radiation. In the steady state with no electric field applied, the rate of generation is equal to the rate of recombination, i.e.. 

This definition of electrochemistry disregards systems in which nonequilibrium charged species are produced by external action in insulators for example, by electric discharge in the gas phase (electrochemistry of gases) or upon irradiation of liquid and sohd dielectrics (radiation chemistry). At the same time, electrochemistry deals with certain problems often associated with other fields of science, such as the structure and properties of sohd electrolytes and the kinetics of ioific reactions in solutions. 

A selective heating in liquid/liquid systems was exploited by Strauss and coworkers in a Hofmann elimination reaction using a two-phase water/chloroform system (Fig. 2.10) [32]. The temperatures of the aqueous and organic phases under micro-wave irradiation were 110 and 55 °C, respectively, due to the different dielectric properties of the solvents (Table 2.3). This temperature differential prevented decomposition of the final product. Comparable conditions would be difficult to obtain using traditional heating methods. A similar effect has been observed by Hallberg and coworkers in the preparation of /3,/3-diarylated aldehydes by hydrolysis of enol ethers in a two-phase toluene/aqueous hydrochloric acid system [33],... 

For liquid products (solvents), only polar molecules selectively absorb microwaves, because nonpolar molecules are inert to microwave dielectric loss. In this context of efficient microwave absorption it has also been shown that boiling points can be higher when solvents are subjected to microwave irradiation rather than conventional heating. This effect, called the superheating effect [13, 14] has been attributed to retardation of nucleation during microwave heating (Tab. 3.1). 

In microwave-assisted synthesis, a homogeneous mixture is preferred to obtain a uniform heating pattern. For this reason, silica gel is used for solvent-free (open-vessel) reactions or, in sealed containers, dipolar solvents of the DMSO type. Welton (1999), in a review, recommends ionic liquids as novel alternatives to the dipolar solvents. Ionic liquids are environmentally friendly and recyclable. They have excellent dielectric properties and absorb microwave irradiation in a very effective manner. They exhibit a very low vapor pressure that is not seriously enhanced during microwave heating. This makes the process not so dangerous as compared to conventional dipolar solvents. The polar participants of organic ion-radical reactions are perfectly soluble in polar ionic liquids. 

Figure 14 (a) Time-dependent behavior of cation radicals in liquid -dodecane monitored at 790 nm. The dotted and the solid lines represent the experimental curve and the simulation curve, respectively. The parameters of the electron dilfusion coefficient (De) = 6.4 x 10 " cm /sec, the cation radical diffusion coefficient (D + ) = 6.0 x 10 cm /sec, the relative dielectric constant e = 2.01, the reaction radius R = 0.5 nm, and the exponential function as shown in Eq. (19) with ro = 6.6 nm were used, (b) Time-dependent distribution function obtained from fitting curve of (a), r indicates the distance between the cation radical and the electron. The solid line, dashed line, and dots represent the distribution of cation radical-electron distance at 0, 30, and 100 psec after irradiation, respectively. 

Irradiated liquids do possess electrical conductivity, clearly indicating the existence of ionic species as in gaseous systems. Some results for cyclohexane23 are shown in Fig. 2. Dielectric breakdown of the liquid occurs, however, before a saturation value of the current is reached. 

As with all solvent alternatives discussed in this book, palladium catalysed C-C bond-forming reactions in RTILs have been studied at length. Because of the low volatility of ionic liquids and their rapid dielectric heating upon microwave irradiation, reaction times for Heck couplings have been significantly reduced by combining the two technologies. ... 

Although it is essentially a conductivity technique, the experimental setup is very similar to that used for optical absorption measurements. In simple terms, the attenuation of the amplitude of the microwave resulting from its passage through the irradiated system is measured. Actually, the microwaves are reflected back through the medium by a metal plate at the back of the cell, but because micro-waves undergo reflection at any dielectric discontinuity, such as the gas-liquid interface at the front of the cell, interference effects arise due to the coherent nature of the microwave radiation. 

---