Environment Fluorine

The popularity of aerosols has been declining. A widely used group of propellants, the fluorinated hydrocarbons, have been restricted in use since it was found that they can harm the environment by reducing the o2one layer of the upper atmosphere (see AiRPOLLUTlON ATMOSPHERIC MODELING Ozone). 

Oxygen is by far the most abundant element in cmstal rocks, composing 46.6% of the Hthosphere (4). In rock mineral stmctures, the predominant anion is, and water (H2O) itself is almost 90% oxygen by weight. The nonmetaUic elements fluorine, sulfur, carbon, nitrogen, chlorine, and phosphoms are present in lesser amounts in the Hthosphere. These elements aU play essential roles in life processes of plants and animals, and except for phosphoms and fluorine, they commonly occur in earth surface environments in gaseous form or as dissolved anions. 

Lead will resist chlorine up to about 100°C , is used for dry bromine at lower temperatures and is fairly resistant to fluorine . Hydrofluoric acid does not passivate lead, so lead should not be used in this environment. Lead is very resistant to sulphur dioxide and fairly resistant to sulphur trioxide, wet or dry, over a wide temperature range . ... 

Tantalum is severely attacked at ambient temperatures and up to about 100°C in aqueous atmospheric environments in the presence of fluorine and hydrofluoric acids. Flourine, hydrofluoric acid and fluoride salt solutions represent typical aggressive environments in which tantalum corrodes at ambient temperatures. Under exposure to these environments the protective TajOj oxide film is attacked and the metal is transformed from a passive to an active state. The corrosion mechanism of tantalum in these environments is mainly based on dissolution reactions to give fluoro complexes. The composition depends markedly on the conditions. The existence of oxidizing agents such as sulphur trioxide or peroxides in aqueous fluoride environments enhance the corrosion rate of tantalum owing to rapid formation of oxofluoro complexes. 

Thermogravimetric data indicate that the structure of a polymer affects stability in a neutral environment (HI). A polymer such as Teflon, with carbon-carbon bonds which are (by comparison) easily broken, and with strong carbon-fluorine bonds, is quite stable thermally. However, polyethylene, also with carbon-carbon bonds but containing carbon-hydrogen bonds which are broken relatively easily in comparison with the carbon-fluorine bond, is less stable than Teflon. In turn, polyethylene is more stable than polypropylene. This difference in stability is probably caused by tertiary carbon-hydrogen bonds in polypropylene. Polypropylene is more stable than polyisobutylene or polystyrene, which decompose principally by unzipping mechanism. 

Borides are relatively inert, especially to non-oxidizing reagents. They react violently with fluorine, often with incandescence. Reaction with other halogens is not as violent and may require some heat. Resistance to oxidation, acids, and alkalis is summarized in Table 17.5. In oxidation conditions, a layer of boric oxide is formed on the surface which passivates it to some degree. Boric oxide melts at 450°C and vaporizes at 1860°C. It offers good protection up to 1500°C in a static environments but it has low viscosity at these temperatures and tends to flow under stress and the protection it offers is limited.f k l... 

Harnisch J (1999) Reactive Fluorine Compounds. Handbook Environ Chem 4E 81-111. 

Harper DB, D O Hagan, CD Murphy (2003) Fluorinated natural products occurrence and biosynthesis. Handbook Environ Chem 3P 141-169. 

Key BD, RD Howell, CS Criddle (1997) Fluorinated organics in the biosphere. Environ Sci Technol 31 2445-2454. 

Londry KL, PM Fedorak (1993) Use of fluorinated compounds to detect aromatic metabolites from m-cresol in a methanogenic consortium evidence for a demethylation reaction. Appl Environ Microbiol 59 2229-2238. 

Neilson AH, A-S Allard (2002) Degradation and transformation of organic fluorine compounds. Hand Environ Chem 3N 137-202. 

Jaffe R, RA Hites (1985) Identification of new, fluorinated biphenyls in the Niagara River Lake Ontario area. Environ Sci Technol 19 736-740. 

Reid KA, JTG Hamilton, RD Bowden, D O Hagan, L Dasaradhi, MR Amin, DB Harper (1995) Biosynthesis of fluorinated secondary metabolites by Streptomyces cattleya. Microbiology (UK) 141 1385-1393. Sembries S, RL Crawford (1997) Production of Clostridium bifermentans spores as inoculum for bioremediation of nitroaromatic contaminants. Appl Environ Microbiol 63 2100-2104. 

Because fluorine is relatively sensitive to its environment and has such a large range of chemical shifts, considerable changes in chemical shift can be observed when a nearby atom is replaced by an isotope. For example, replacement of 12C by 13C for the atom to which the fluorine is attached, gives rise to a quite measurable shift, usually to lower frequency. A consequence of this isotope effect is the observation that the 13C satellites in a fluorine spectrum are not symmetrical about the 12C—F resonance. 

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