Metal fluoride

AX NaCl Alkali fluorides and alkaline-earth oxides 

10 ohm cm at 370 K with an activation energy of 0.14 eV appears to be the best known fluoride-ion conductor. 

When MFg octahedra are shared, magnetic interaction between localized spins on 

KCuFj is a ID antiferromagnet (A type) with the spins lying in the ab plane. The magnetic behaviour is again a consequence of antiferrodistortive ordering of distorted octahedra. Interaction between two half-filled orbitals occurs along the c axis 

Ionic fluorides with large optical gaps exhibit high transparency to electromagnetic radiation. MgF2, for instance, is transparent from 10 cm (corresponding to the energy threshold for the electronic transition from the valence band to the conduction band) to 10 cm (maximum frequency of lattice vibrations). The transparency of metal fluorides has led to their use as windows and prisms in optical instruments (see 

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Perchloric acid (HCIO4 Ho —13.0), fluorosulfuric acid (HSO3F Ho — 15.1), and trifluoromethanesulfonic acid (CF3SO3H Ho —14.1) are considered to be superacids, as is truly anhydrous hydrogen fluoride. Complexing with Lewis acidic metal fluorides of higher valence, such as antimony, tantalum, or niobium pentafluoride, greatly enhances the acidity of all these acids. 

The reactivity of fluorine compounds varies from extremely stable, eg, compounds such as sulfur hexafluoride [2551-62 ] nitrogen trifluoride [7783-54-2] and the perfluorocarbons (see Fluorine compounds, organic) to extremely reactive, eg, the halogen fluorides. Another unique property of nonionic metal fluorides is great volatiUty. Volatile compounds such as tungsten hexafluoride [7783-82-6] molybdenum hexafluoride [7783-77-9] ... 

Fluorination of tungsten and rhenium produces tungsten hexafluoride, WF, and rhenium hexafluoride [10049-17-9J, ReF, respectively. These volatile metal fluorides are used in the chemical vapor deposition industry to produce metal coatings and intricately shaped components (see Thin films,... 

In aqueous solutions Sbp3 reacts with many metal fluorides to form compounds such as MSbF where M = Li [72121 -39-2] Na [34109-83-6] K [15273-81-1], Cs [36195-09-0], [54189-44-5], andM2Sbp3 where M = K [20645-41-4], Cs [40902-54-3], 2md5 5lJ32516-50-0]. In addition,... 

Arsenic pentafluoride can be prepared by reaction of fluorine and arsenic trifluoride or arsenic from the reaction of NF O and As (16) from the reaction of Ca(FS02)2 and H AsO (17) or by reaction of alkaH metal or alkaline-earth metal fluorides or fluorosulfonates with H AsO or H2ASO2F (18). 

Hexafluoroarsenic acid [17068-85-8] can be prepared by the reaction of arsenic acid with hydrofluoric acid or calcium fluorosulfate (29) and with alkaH or alkaline-earth metal fluorides or fluorosulfonates (18). The hexafluoroarsenates can be prepared directly from arsenates and hydrofluoric acid, or by neutrali2ation of HAsF. The reaction of 48% HF with potassium dihydrogen arsenate(V), KH2ASO4, gives potassium hydroxypentafluoroarsenate(V)... 

Metal halides react with BF (33) when heated to form BX and the metal fluoride. For example,... 

The physical and chemical properties are less well known for transition metals than for the alkaU metal fluoroborates (Table 4). Most transition-metal fluoroborates are strongly hydrated coordination compounds and are difficult to dry without decomposition. Decomposition frequently occurs during the concentration of solutions for crysta11i2ation. The stabiUty of the metal fluorides accentuates this problem. Loss of HF because of hydrolysis makes the reaction proceed even more rapidly. Even with low temperature vacuum drying to partially solve the decomposition, the dry salt readily absorbs water. The crystalline soflds are generally soluble in water, alcohols, and ketones but only poorly soluble in hydrocarbons and halocarbons. 

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). 

Table 3. Solubility of Metal Fluorides in Anhydrous Hydrogen Flnoride ...

Sulfuric acid loss is approximately 1.84% H2SO4 for each percentage of R2O2. Oleum consumption is increased to consume the water that is formed. The metal sulfates are more stable than metal fluorides under furnace conditions and are discharged from the process with the residue. 

Molybdenum hexafluoride is used in the manufacture of thin films (qv) for large-scale integrated circuits (qv) commonly known as LSIC systems (3,4), in the manufacture of metallised ceramics (see MetaL-MATRIX COMPOSITES) (5), and chemical vapor deposition of molybdenum and molybdenum—tungsten alloys (see Molybdenumand molybdenum alloys) (6,7). The latter process involves the reduction of gaseous metal fluorides by hydrogen at elevated temperatures to produce metals or their alloys such as molybdenum—tungsten, molybdenum—tungsten—rhenium, or molybdenum—rhenium alloys. 

K [14881-07-3], Rb [72151 -96-3], and Cs [72138-72-8]), are prepared by reaction of elemental fluorine, chlorine trifluoride, or xenon difluoride and a mixture of nickel fluoride and alkaH metal fluorides or other metal haHdes (16,17). If the fluorination is carried out using mixed fluorides, a lower temperature can be used, yields are quantitative, and the final products are of high purity. Bis(tetrafluoroammonium) hexafluoronickelate [6310540-8], (NE 2N iF6> prepared from Cs2NiF3 and NE SbE by a metathesis in anhydrous HE, is also known (18). 

As a result of the development of electronic applications for NF, higher purities of NF have been required, and considerable work has been done to improve the existing manufacturing and purification processes (29). N2F2 is removed by pyrolysis over heated metal (30) or metal fluoride (31). This purification step is carried out at temperatures between 200—300°C which is below the temperature at which NF is converted to N2F4. Moisture, N2O, and CO2 are removed by adsorption on 2eohtes (29,32). The removal of CF from NF, a particularly difficult separation owing to the similar physical and chemical properties of these two compounds, has been described (33,34). 

Reactions with Metals. Many common metals react with OF2, but the reaction stops after a passive metal fluoride coating is formed (3,4). 

The main products of SF arc decomposition in the presence of air are SOF2, SF, and SOF plus metal fluorides and sulfides (28). 

Thiothionyl Fluoride and Difluorodisulfane. Thiothionyl fluoride [1686-09-9] S=SF2, and difluorodisulfane [13709-35-8] FSSF, are isomeric compounds which may be prepared as a mixture by the action of various metal fluorides on sulfur vapor or S2CI2 vapor. Chemically, the two isomers are very similar and extremely reactive. However, in the absence of catalytic agents and other reactive species, FSSF is stable for days at ordinary temperatures and S=SF2 may be heated to 250°C without significant decomposition (127). Physical properties of the two isomers are given in Table 6. The microwave spectmm of S=SF2 has been reported (130). 

Potassium fluoride [7789-23-3], KF, is the most frequently used of the alkaU metal fluorides, although reactivity of the alkaU fluorides is in the order CsF > RbF > KF > NaF > LiF (6). The preference for KF is based on cost and availabiUty traded off against relative reactivity. In its anhydrous form it can be used to convert alkyl haUdes and sulfonyl haUdes to the fluorides. The versatility makes it suitable for halogen exchange in various functional organic compounds like alcohols, acids and esters (7). For example, 2,2-difluoroethanol [359-13-7] can be made as shown in equation 9 and methyl difluoroacetate [433-53 ] as in equation 10. 

Replacement of Hydrogen. Three methods of substitution of a hydrogen atom by fluorine are (/) reaction of a G—H bond with elemental fluorine (direct fluorination, (2) reaction of a G—H bond with a high valence state metal fluoride like Agp2 or GoF, and (J) electrochemical fluorination in which the reaction occurs at the anode of a cell containing a source of fluoride, usually HF. 

Reaction with a Metal Fluoride. A second technique for hydrogen substitution is the reaction of a higher valence metal fluoride with a hydrocarbon to form a fluorocarbon ... 

The principal advantage to this method is that the heat evolved for each carbon—fluorine bond formed, 192.5 kj/mol (46 kcal/mol), is much less than that obtained in direct fluorination, 435.3 kJ/mol (104 kcal/mol). The reaction yields are therefore much higher and less carbon—carbon bond scisson occurs. Only two metal fluorides are of practical use, Agp2 and GoF. ... 

The reactivity of the metal fluoride appears to be associated with the oxidation potential of the metal. For example, AgF replaces halogen in organic compounds, whereas Agp2 replaces hydrogen. 

Fluorination of organic compounds using high valency metallic fluorides (14) may be represented as follows ... 

Fiber-reactive dyes containing the fluorotriaziayl group are based on the condensation of chromophores containing amino groups with 6 - sub s titute d- 2,4- diflu o r o triaziae s. The latter can be prepared from cyanuric fluoride or from the reaction of alkah metal fluorides with... 

Several alkali metal fluoride complexes withXeOF are known, such as 3KF XeOF [12186-19-5], 3RbF -2K.eO [12186-23-1], CsF XeOF ... 

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