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Ionic fluorination, with

Numerous ionic compounds with halogens are known but a noble gas configuration can also be achieved by the formation of a covalent bond, for example in halogen molecules, X2, and hydrogen halides, HX. When the fluorine atom acquires one additional electron the second quantum level is completed, and further gain of electrons is not energetically possible under normal circumstances, i.e... [Pg.312]

It must be noted that impurities in the ionic liquids can have a profound impact on the potential limits and the corresponding electrochemical window. During the synthesis of many of the non-haloaluminate ionic liquids, residual halide and water may remain in the final product [13]. Halide ions (Cl , Br , I ) are more easily oxidized than the fluorine-containing anions used in most non-haloaluminate ionic liquids. Consequently, the observed anodic potential limit can be appreciably reduced if significant concentrations of halide ions are present. Contamination of an ionic liquid with significant amounts of water can affect both the anodic and the cathodic potential limits, as water can be both reduced and oxidized in the potential limits of many ionic liquids. Recent work by Schroder et al. demonstrated considerable reduction in both the anodic and cathodic limits of several ionic liquids upon the addition of 3 % water (by weight) [14]. For example, the electrochemical window of dry [BMIM][BF4] was found to be 4.10 V, while that for the ionic liquid with 3 % water by weight was reduced to 1.95 V. In addition to its electrochemistry, water can react with the ionic liquid components (especially anions) to produce products... [Pg.104]

In 1996, Gratzel, Bonhote and coworkers published the synthesis and properties of ionic liquids with anions containing CF3- and other fluorinated alkyl groups [12]. These are usually highly hydrophobic melts with high stability (even under acidic conditions) against hydrolysis. [Pg.1390]

Under RP-Cis column separation conditions, no differentiation between conventional AE and fluorinated AE in retardation behaviour could be observed. The application of a perfluorinated RP-C8 column to a mixture of standards of non-ionic fluorinated surfactants and the extracts of wastewater sludges spiked with these compounds using realistic concentrations, however, resulted in good separation of AE and fluorinated AE (cf. mass traces and TIC in Fig. 2.9.46(a), (b) or (e) and Fig. 2.9.46(c), (d) or (e), respectively) or matrix and fluorinated AE surfactants (Fig. 2.9.46(f), (g) or (h), respectively) [52]. [Pg.308]

Partly fluorinated or perfluorinated sulfonic and carboxylic acids are compounds with excellent surface activity combined with an extreme stability against chemical or physico-chemical attacks as also described for non-ionic fluorine containing surfactant compounds. The anionic surfactants are shown with their structural formulae in Fig. 2.11.24(1)—(III). A selected ESI-FIA-MS(-) spectrum of a partly fluorinated surfactant (CF3-(CF2)4-(CH2)8-S03H, m/z 461) is presented in Fig. 2.11.25. The FIA spectrum also contains ions of the by-products CF3-(CF2)2-(CH2)8-S03H (m/z 361) and CF3-(CF2)3-(CH2)8-S03H (m/z 411). [Pg.363]

According to P. Pascal,0 fluorine is diamagnetic the specific magnetic susceptibility is —3447 X10 j and the atomic susceptibilitv calculated from the additive law of mixtures for organic compounds is —63X10-1. Ionic fluorine is univalent and negative. The decomposition voltage required to separate this element from its compounds is 1 75 volts.7 The ionic velocity (transport number) 8 of fluorine ions at 18° is 46 6, and 52-5 at 25° with a temp, coeff. of 0 0238. [Pg.10]

The Remaining Nonmetallic Elements.—The bonds formed by fluorine with all of the metals are essentially ionic in character, and those with the intermediate elements (II, B, P, etc.) have a little more than 50 percent ionic character. The C-—F, S—F, and I—F bonds are expected to have 44 percent ionic character. In CF4, SF0, IF, and IF7 the amounts of ionic character of the bonds are probably somewhat less than this value because of the transfer of positive charge to the central atom, which increases its x value and decreases the ionic character of the bonds. [Pg.102]

Interesting recently published examples include ionic liquids with fluorinated [30], functionalized [31] and chiral cations [32] and anions [33],... [Pg.108]

Hydrogen bond-A bond between a hydrogen nuclei and two other entities. One bond is a strong ionic bond (with the donor atom) while the second is a weak covalent bond (frequently shown by a dashed line) with a second structure. The only elements concerned in hydrogen bonding are nitrogen, oxygen, fluorine and sometimes chlorine. [Pg.10]

Hence the ionic liquids with the lowest viscosity tend to have highly fluorinated anions as these shield the charge density and result in low surface tensions. The cation also affects the viscosity of ionic liquids. For imidazolium cations, the viscosity initially decreases as the length of the R group increases, as the ion-ion interactions decrease and hence the surface tension decreases. However, as the alkyl group increases in size its mobility will decrease due to a lack of suitably sized voids for the cations to move into. This can be seen in the data presented by Tokuda ct al. who showed a minimum in viscosity for ethyl methyl imidazolium salts [129]. [Pg.41]

It is apparent from the above discussion that ionic mobility is controlled by the free volume of a liquid and the size of the ions. The size of the voids in the liquid and their effect on liquid density can be changed by decreasing the ion-ion interactions. This will manifest itself by a decrease in surface tension and, in general, the liquids with lower surface tensions are more fluid and have higher conductivities. This is the reason why ionic liquids with discrete, highly fluorinated anions such as PF6 and (F3CS02)2N have become popular. [Pg.42]

Another difference is that the 5/orbitals have a greater spatial extension relative to the Is and Ip orbitals than the 4/orbitals have relative to the 6s and 6p orbitals. The greater spatial extension of the 5/orbitals has been shown experimentally the esr spectrum of UF3 in a CaF2 lattice shows structure attributable to the interaction of fluorine nuclei with the electron spin of the U3+ ion. This implies a small overlap of 5/ orbitals with fluorine and constitutes an / covalent contribution to the ionic bonding. With the neodymium ion a similar effect is not observed. Because they occupy inner orbitals, the 4/ electrons in the lanthanides are not accessible for... [Pg.1130]

The number and position of substituents are important. One bulky group, e.g. naphthyl, or two substituents on a single olefinic carbon do not usually hinder polymerization. On the other hand, an ethylene derivative with a substituent on each of the two carbons does not undergo radical polymerization at conventional pressures and temperatures. Usually, however, it can be copolymerized with a suitable monomer or it can be polymerized by an ionic mechanism. With a larger number of substituents, the tendency to polymerization is further limited. The small fluorine atom represents an exception, as do the cases discussed in Sects. 1.3 and 5.2. [Pg.28]

The halogens, particularly fluorine, have very high electronegativity values (Table 19.6). They tend to form polar covalent bonds with other non-metals and ionic bonds with metals in their lower oxidation states. When a... [Pg.914]

Ignat ev N V, Welz-Biermann U, Kucheryna A, et al. New ionic liquids with tris(peifluoroalkyl)trifluorophosphate (FAP) anions. J. Fluorine Chem. 2005. 126, 1150-1159. [Pg.472]

Fluorine is the most electronegative of all the elements, so that the bonds it forms with most other elements have considerable ionic character. With the exception of the alkali halides most crystalline fluorides have structures different from those of the other halides of the same metal. A number of difluorides and dioxides have the same crystal structure, whereas the corresponding dichlorides, dibromides, and diiodides have in many cases structures similar to those of disulphides, diselenides, and ditellurides. The extreme electronegativity of fluorine enables it to form much stronger hydrogen bonds than any other element, resulting in the abnormal properties of HF as compared with the other acids HX, the much... [Pg.326]

Hydrophobicity or hydrophilicity is also an important property, which can be controlled by selecting an appropriate cation and anion combination. Longer alkyl chains on the cation have been found to result in increased hydrophobicity [80, 81]. Hydrophobicity also depends on the identity of the anion. For example, ionic liquids containing fluorinated anions such as tetrafluoroborate and hexafluorophosphate are considerably more hydrophobic than the halide salts of the same cation. Ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion [NTf2] are extremely hydro-phobic whereas their non-fluorinated analogues are sometimes completely miscible with water [82], The immiscibility of the ionic liquid with water or other solvents may be useful for phase separations, but it also has implications on the greenness of the ionic liquid in the event of accidental release into the environment [80],... [Pg.24]


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See also in sourсe #XX -- [ Pg.644 ]

See also in sourсe #XX -- [ Pg.327 ]




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Fluorination with

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