Rare fluorides

Fourth, differently, and with diminishing ease, alkyl iodides (R-I), bromides (R-Br), chlorides (R-Cl), and (rarely) fluorides (R-F), also react with a variety of metals (M).The conditions of the reaction can be adjusted either to isolate only the reduced haloalkane or to produce some organometallic intermediary species (frequently written as R-M-X) species. In the organometallic compounds, electron transfer from the metal has generally been accomplished so that hydrolysis produces the corresponding hydrocarbon. 

One hypothesis says that fluorine can be substituted for hydrogen wherever it occurs in organic compounds, which could lead to an astronomical number of new fluorine compounds. Compounds of fluorine with rare gases have now been confirmed in fluorides of xenon, radon, and krypton. 

Naturally occurring krypton contains six stable isotopes. Seventeen other unstable isotopes are now recognized. The spectral lines of krypton are easily produced and some are very sharp. While krypton is generally thought of as a rare gas that normally does not combine with other elements to form compounds, it now appears that the existence of some krypton compounds is established. Krypton difluoride has been prepared in gram quantities and can be made by several methods. A higher fluoride of krypton and a salt of an oxyacid of krypton also have been... 

The availability of lanthanum and other rare earths has improved greatly in recent years. The metal can be produced by reducing the anhydrous fluoride with calcium. 

Gr. aktis, aktinos, beam or ray). Discovered by Andre Debierne in 1899 and independently by F. Giesel in 1902. Occurs naturally in association with uranium minerals. Actinium-227, a decay product of uranium-235, is a beta emitter with a 21.6-year half-life. Its principal decay products are thorium-227 (18.5-day half-life), radium-223 (11.4-day half-life), and a number of short-lived products including radon, bismuth, polonium, and lead isotopes. In equilibrium with its decay products, it is a powerful source of alpha rays. Actinium metal has been prepared by the reduction of actinium fluoride with lithium vapor at about 1100 to 1300-degrees G. The chemical behavior of actinium is similar to that of the rare earths, particularly lanthanum. Purified actinium comes into equilibrium with its decay products at the end of 185 days, and then decays according to its 21.6-year half-life. It is about 150 times as active as radium, making it of value in the production of neutrons. 

Ion-exchange and solvent extraction techniques have led to much easier isolation of the rare earths and the cost has dropped greatly in the past few years. Praseodymium can be prepared by several methods, such as by calcium reduction of the anhydrous chloride of fluoride. 

Gadolinium is found in several other minerals, including monazite and bastnasite, both of which are commercially important. With the development of ion-exchange and solvent extraction techniques, the availability and prices of gadolinium and the other rare-earth metals have greatly improved. The metal can be prepared by the reduction of the anhydrous fluoride with metallic calcium. 

Terbium has been isolated only in recent years with the development of ion-exchange techniques for separating the rare-earth elements. As with other rare earths, it can be produced by reducing the anhydrous chloride or fluoride with calcium metal in a tantalum crucible. Calcium and tantalum impurities can be removed by vacuum remelting. Other methods of isolation are possible. 

L. Holmia, for Stockholm). The special absorption bands of holmium were noticed in 1878 by the Swiss chemists Delafontaine and Soret, who announced the existence of an "Element X." Cleve, of Sweden, later independently discovered the element while working on erbia earth. The element is named after cleve s native city. Holmia, the yellow oxide, was prepared by Homberg in 1911. Holmium occurs in gadolinite, monazite, and in other rare-earth minerals. It is commercially obtained from monazite, occurring in that mineral to the extent of about 0.05%. It has been isolated by the reduction of its anhydrous chloride or fluoride with calcium metal. 

The order of alkyl halide reactivity in nucleophilic substitutions is the same as their order m eliminations Iodine has the weakest bond to carbon and iodide is the best leaving group Alkyl iodides are several times more reactive than alkyl bromides and from 50 to 100 times more reactive than alkyl chlorides Fluorine has the strongest bond to car bon and fluonde is the poorest leaving group Alkyl fluorides are rarely used as sub states m nucleophilic substitution because they are several thousand times less reactive than alkyl chlorides... 

Chlorination is carried out m a manner similar to brommation and provides a ready route to chlorobenzene and related aryl chlorides Fluormation and lodmation of benzene and other arenes are rarely performed Fluorine is so reactive that its reaction with ben zene is difficult to control lodmation is very slow and has an unfavorable equilibrium constant Syntheses of aryl fluorides and aryl iodides are normally carried out by way of functional group transformations of arylammes these reactions will be described m Chapter 22... 

Eluorspar assay may be completed by fluoride determination alone, because the mineralogical grouping rarely iacludes fluorine minerals other than fluorite. Calcium can be determined as oxalate or by ion-selective electrodes (67). SiUca can be determined ia the residue from solution ia perchloric acid—boric acid mixture by measuriag the loss ia weight on Aiming off with hydrofluoric acid. Another method for determining siUca ia fluorspar is the ASTM Standard Test Method E463-72. 

CoF is used for the replacement of hydrogen with fluorine in halocarbons (5) for fluorination of xylylalkanes, used in vapor-phase soldering fluxes (6) formation of dibutyl decalins (7) fluorination of alkynes (8) synthesis of unsaturated or partially fluorinated compounds (9—11) and conversion of aromatic compounds to perfluorocycHc compounds (see Fluorine compounds, organic). CoF rarely causes polymerization of hydrocarbons. CoF is also used for the conversion of metal oxides to higher valency metal fluorides, eg, in the assay of uranium ore (12). It is also used in the manufacture of nitrogen fluoride, NF, from ammonia (13). 

Re OPe . The final step in the chemical processing of rare earths depends on the intended use of the product. Rare-earth chlorides, usually electrolytically reduced to the metallic form for use in metallurgy, are obtained by crystallisation of aqueous chloride solutions. Rare-earth fluorides, used for electrolytic or metaHothermic reduction, are obtained by precipitation with hydrofluoric acid. Rare-earth oxides are obtained by firing hydroxides, carbonates or oxalates, first precipitated from the aqueous solution, at 900°C. 

Fused Salt Electrolysis. Only light RE metals (La to Nd) can be produced by molten salt electrolysis because these have a relatively low melting point compared to those of medium and heavy RE metals. Deposition of an alloy with another metal, Zn for example, is an alternative. The feed is a mixture of anhydrous RE chlorides and fluorides. The materials from which the electrolysis cell is constmcted are of great importance because of the high reactivity of the rare-earth metals. Molybdenum, tungsten, tantalum, or alternatively iron with ceramic or graphite linings are used as cmcible materials. Carbon is frequently used as an anode material. 

SoHd lubricants ate added to help control high friction characteristics in high speed or heavy-duty appHcations where high temperatures are generated. Molybdenum disulfide [1317-33-5] M0S2, may be used alone or in a complex compound formed by grinding with fine natural graphite, and zinc sulfide [1314-98-3] ZnS. Other compounds include calcium fluoride, cryoHte [15096-52-3] Na AlF, rare-earth oxides, and metal sulfides, eg, iron, antimony, or zinc (see LUBRICATION AND LUBRICANTS). 

Calcium metal is an excellent reducing agent for production of the less common metals because of the large free energy of formation of its oxides and hahdes. The following metals have been prepared by the reduction of their oxides or fluorides with calcium hafnium (22), plutonium (23), scandium (24), thorium (25), tungsten (26), uranium (27,28), vanadium (29), yttrium (30), zirconium (22,31), and most of the rare-earth metals (32). 

The compositions of the conversion baths are proprietary and vary greatly. They may contain either hexavalent or trivalent chromium (179,180), but baths containing both Cr(III) and Cr(VI) are rare. The mechanism of film formation for hexavalent baths has been studied (181,182), and it appears that the strength of the acid and its identity, as well as time and temperature, influences the film s thickness and its final properties, eg, color. The newly prepared film is a very soft, easily damaged gel, but when allowed to age, the film slowly hardens, assumes a hydrophobic character and becomes resistant to abrasion. The film s stmcture can be described as a cross-linked Cr(III) polymer, that uses anion species to link chromium centers. These anions may be hydroxide, chromate, fluoride, and/or others, depending on the composition of the bath (183). 

The last example represents a fairly rare elimination of hydrogen fluoride in preference to hydrogen chloride, a reaction that deserves a more detailed discussion A comparison of bond dissociation energies of carbon-halogen bonds shows that the carbon-fluorine bond is much stronger than the carbon-chlorine, carbon-bromine, and carbon-iodme bonds 108-116, 83 5, 70, and 56 kcal/mol, respec-... 

Cyclohexyl bromide, for exfflnple, is converted to cyclohexene by sodium ethoxide in ethanol over 60 times faster than cyclohexyl chloride. Iodide is the best leaving group in a dehydrohalogenation reaction, fluoride the poorest. Fluoride is such a poor leaving group that alkyl fluorides are rarely used as starting materials in the preparation of alkenes. 

Compounds of the same stoichiometry type usually have the same type crystal structure within the row of alkali metals K - Rb - Cs rarely the same type structure with sodium-containing analogues and never ciystallize similarly with lithium-containing compounds. The crystal structure analysis of different fluoride and oxyfluoride compounds clearly indicates that the steric similarity between all cations and tantalum or niobium must be taken into account when calculating the X Me ratio. 

A residual phase, usually consisting of insoluble fluorides and oxyfluorides of alkali earth and rare earth metals, is separated from the solution by filtration. The mechanism of the chemical decomposition of raw materials of the tantalum- and niobium-containing oxide type seems to be complicated, and unfortunately, the process has yet to be adequately investigated. 

The first experiments on the plasma chemical decomposition of fluoride solutions containing tantalum or niobium to obtain tantalum and niobium oxides were reported about fifteen years ago [524]. Subsequent publications were devoted to further development and expansion of the method for other refractory rare metals such as titanium and zirconium [525 - 532]. 

We solved the first problem by bombarding large amounts of uranyl nitrate with neutrons at the cyclotrons at the University of California and Washington University plutonium concentrates were derived from these sources through the efforts of teams of chemists who used ether extractions to separate the bulk of the uranium and an oxidation-reduction cycle with rare earth fluoride carrier to concentrate the product. I managed to convince chemists trained in the techniques of ultramicrochemistry to join us to solve the second problem—Burris B. Cunningham and Louis B. Werner of the University of California and Michael Cefola from New York University. 

This precipitate of 94, which was viewed under the microscope and which was also visible to the naked eye, did not differ visibly from the rare-earth fluorides. 

---