And fluorination

The lubricant properties of alkanethiols and fluorinated alkanes have been studied extensively by scanning probe techniques [163]. In agreement with experiments on LB monolayers it was found that the fluorocarbon monolayers show considerably higher friction than the corresponding hydrocarbon monolayers [164, 165 and 166] even though the fluorocarbons are known to have the lowest surface free energy of all organic materials. 

The element before carbon in Period 2, boron, has one electron less than carbon, and forms many covalent compounds of type BX3 where X is a monovalent atom or group. In these, the boron uses three sp hybrid orbitals to form three trigonal planar bonds, like carbon in ethene, but the unhybridised 2p orbital is vacant, i.e. it contains no electrons. In the nitrogen atom (one more electron than carbon) one orbital must contain two electrons—the lone pair hence sp hybridisation will give four tetrahedral orbitals, one containing this lone pair. Oxygen similarly hybridised will have two orbitals occupied by lone pairs, and fluorine, three. Hence the hydrides of the elements from carbon to fluorine have the structures... 

This ability to bring out high oxidation states is exhibited also by fluorine it is to be attributed to the high electronegativities of oxygen and fluorine.)... 

The enthalpies for the reactions of chlorine and fluorine are shown graphically in Figure 11.2 as the relevant parts of a Born-Haber cycle. Also included on the graph are the hydration energies of the two halogen ions and hence the enthalpy changes involved in the reactions... 

The large value for fluorine, and the marked decrease from fluorine to iodine, are points to be noted. The high value for fluorine means that the bond between an element M and fluorine is likely to be more ionic (more polar) than a bond formed by M with any other elements. The low value for iodine indicates the possibility that iodine may be electropositive in some of its compounds. 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Following Bartlett s discovery of xenon hexafluoroplatinate(VI), xenon and fluorine were found to combine to give several volatile, essentially covalent fluorides, and at least one fluoride of krypton has been obtained. From the xenon fluorides, compounds containing xenon-oxygen bonds have been made much of the known chemistry of xenon is set out in Figure 12.1. 

The H—F bond is polarized so that hydrogen is par tially positive (blue) and fluorine partially negative... 

Key properties are its flexibility, translucency, and resistance to all known chemicals except molten alkali metals, elemental fluorine and fluorine precursors at elevated temperatures, and concentrated perchloric acid. It withstands temperatures from —270° to 250°C and may be sterilized repeatedly by all known chemical and thermal methods. 

R. J. Ring and D. Royston, d Repiew of Fluorine Cells and Fluorine Production Facilities, Austrahan Atomic Energy Commission, AAEC/E 281 /, Sept. 1973. 

The balance of hydrogen fluoride is used ia appHcations such as stainless steel pickling inorganic fluoride production, alkylation (qv), uranium enrichment, and fluorine production. Hydrogen fluoride is used to convert uranium oxide to UF which then reacts with elemental fluorine to produce volatile UF. ... 

Hydrogen fluoride or compounds that can produce it and fluorine-containing oxidizers should be handled with adequate safety equipment and extreme care by weU-trained personnel. Often the effect of skin exposure is not immediately evident, especially when dilute solutions are handled. Pain may develop several hours later. 

Na AlFg, 5—7% AIF., 5—7% CaF2, 2—6% AI2O2, and 0—7% LiF with an operating temperature of 950°C. Ideally fluorine is not consumed in the process, but substantial quantities of fluorine are absorbed by the cell lining and fluorine is lost to the atmosphere. Modem aluminum industry plants efficiently recycle the fluorine values. 

Significant amounts of cryoHte are also recovered from waste material ia the manufacture of aluminum. The carbon lining of the electrolysis ceUs, which may contain 10—30% by weight of cryoHte, is extracted with sodium hydroxide or sodium carbonate solution and the cryoHte precipitated with carbon dioxide (28). Gases from operating ceUs containing HF, CO2, and fluorine-containing dusts may be used for the carbonation (29). 

Table 5. Boron Trifluoride Adducts with Compounds Containing Chlorine and Fluorine...

An equiHbrium exists between chlorine trifluoride, chlorine monofluoride, and fluorine gas (38). The equiHbrium constant may be expressed as... 

Chlorine Trifluoride. Chlorine trifluoride is produced commercially by the continuous gas-phase reaction of fluorine and chlorine ia a nickel reactor at ca 290°C. The ratio of fluorine to chlorine is maintained slightly in excess of 3 1 to promote conversion of the chlorine monofluoride to chlorine trifluoride. Sufficient time ia the reactor must be provided to maintain high conversions to chlorine trifluoride. Temperature control is also critical because the equiHbrium shift of chlorine trifluoride to chlorine monofluoride and fluorine is significant at elevated temperatures. 

Iodine Pentafluoride. Iodine pentafluoride is produced by the reaction of iodine and fluorine. Because iodine has a high melting poiat, the reaction is either performed ia a solvent or the reaction is maintained at a temperature where the iodine is Hquid. In a continuous process usiug a solvent (104), ca 1% I2 is dissolved iu IF and passed to a reactor where it is contacted with F2 gas. The IF is continuously discharged from the reactor where a small portion is taken off as product and the larger portion of the stream is recycled. 

Iodine pentafluoride is an easily storable Hquid source of fluorine having Httie of the hazards associated with other fluorine sources. It is used as a selective fluorinating agent for organic compounds. For example, it adds iodine and fluorine to tetrafluoroethylene in a commercial process to produce a usefiil telomer (124). 

Chemicals. Both organic and inorganic fluorine-containing compounds, most of which have highly speciali2ed and valuable properties, are produced from HF. Typically these fluorinated chemicals are relatively complex, sometimes difficult to manufacture, and of high value. These materials include products used as fabric and fiber treatments, herbicide and pharmaceutical intermediates, fluoroelastomers, and fluorinated inert Hquids. Other products include BF, SF, and fluoborates. 

Three other binary compounds of molybdenum and fluorine are known to exist molybdenum trifluoride [20193-58-2] MoF, molybdenum tetrafluoride [23412-45-5] MoF, and molybdenum pentafluoride [13819-84-6] MoF. Also known are the two oxyfluorides, molybdenum dioxydifluoride [13824-57-2] M0O2F2, and molybdenum oxytetrafluoride [14459-59-7] MoOF. The use of these other compounds is limited to research appHcations. 

In aqueous solution, OF2 oxidizes HCl, HBr, and HI (and thek salts), Hberating the free halogens. Oxygen difluoride reacts slowly with water and a dilute aqueous base to form oxygen and fluorine. The rate of this hydrolysis reaction has been determined (23). 

The two stable salts of potassium and fluorine of commercial significance are the normal fluoride [7789-23-3] KF, and potassium bifluoride [7789-29-9] KHF2. 

The known binary compounds of sulfur and fluorine range in character from ephemeral to rock-like and provide excellent examples of the influence of electronic and stmctural factors on chemical reactivity. These marked differences are also reflected in the diversified technological utiUty. 

Disulfur decafluoride does not react rapidly with water, mercury, copper, or platinum at ambient temperatures. There is evidence that it slowly decomposes on various surfaces in the presence of water when stored in the vapor state (118). It is decomposed by molten KOH to give a mixture of potassium compounds of sulfur and fluorine. The gas reacts vigorously with many other metals and siUca at red heat (114). At ca 156°C it combines with CI2 or Br2 to form SF Cl or SF Br (119,120). At ca 200°C, S2F2Q is almost completely thermally decomposed into the hexa- and tetrafluoride (121). 

The main binary tin fluorides are stannous fluoride and stannic fluoride. Because the stannous ion,, is readily oxidized to the stannic ion,, most reported tin and fluorine complexes are of tin(IV) and fluorostannates. Stannous fluoroborates have also been reported. 

To achieve the very low initial fluorine concentration in the LaMar fluorination process initially a helium or nitrogen atmosphere is used in the reactor and fluorine is bled slowly into the system. If pure fluorine is used as the incoming gas, a concentration of fluorine may be approached asymptotically over any time period (Fig. 3). It is possible to approach asymptotically any fluorine partial pressure in this manner. The very low initial concentrations of fluorine in the system greatiy decreases the probabiUty of simultaneous fluorine coUisions on the same molecules or on adjacent reaction sites. 

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