“Compounds of fluorine”的意思、由来-开放百科全书

For many elements (but not all) the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others (elements in certain groups) the highest oxidation states of oxides and fluorides are always equal.^[4]

Difluorine

While an individual fluorine atom has one unpaired electron, molecular fluorine (F₂) has all the electrons paired. This makes it diamagnetic (slightly repelled by magnets) with the magnetic susceptibility of −1.2×10⁻⁴ (SI), which is close to theoretical predictions.^[5] In contrast, the diatomic molecules of the neighboring element oxygen, with two unpaired electrons per molecule, are paramagnetic (attracted to magnets).{{sfn|Mackay|Mackay|Henderson|2002|p=72}}

The fluorine–fluorine bond of the difluorine molecule is relatively weak when compared to the bonds of heavier dihalogen molecules. The bond energy is significantly weaker than those of Cl₂ or Br₂ molecules and similar to the easily cleaved oxygen–oxygen bonds of peroxides or nitrogen–nitrogen bonds of hydrazines.^[6] The covalent radius of fluorine of about 71 picometers found in F₂ molecules is significantly larger than that in other compounds because of this weak bonding between the two fluorine atoms.^[7] This is a result of the relatively large electron and internuclear repulsions, combined with a relatively small overlap of bonding orbitals arising due to the small size of the atoms.{{sfn|Greenwood|Earnshaw|1998|p=801}}

The F₂ molecule is commonly described as having exactly one bond (in other words, a bond order of 1) provided by one p electron per atom, as are other halogen X₂ molecules. However, the heavier halogens' p electron orbitals partly mix with those of d orbitals, which results in an increased effective bond order; for example, chlorine has a bond order of 1.12.^[8] Fluorine's electrons cannot exhibit this d character since there are no such d orbitals close in energy to fluorine's valence orbitals.^[8] This also helps explain why bonding in F₂ is weaker than in Cl₂.{{sfn|Greenwood|Earnshaw|1998|p=801}}

Reactivity

Reactions with elemental fluorine are often sudden or explosive. Many substances that are generally regarded as unreactive, such as powdered steel, glass fragments, and asbestos fibers, are readily consumed by cold fluorine gas. Wood and even water burn with flames when subjected to a jet of fluorine, without the need for a spark.{{sfn|Jaccaud et al.|2005|p=2}}^[10]

[https://www.youtube.com/watch?v=TLOFaWdPxB0 Fluorine reacting with caesium], video by the Royal Institution.

Reactions of elemental fluorine with metals require different conditions that depend on the metal. Often, the metal (such as aluminium, iron, or copper) must be powdered because many metals passivate by forming protective layers of the metal fluoride that resist further fluoridation.{{sfn|Greenwood|Earnshaw|1998|p=804}} The alkali metals react with fluorine with a bang (small explosion), while the alkaline earth metals react not quite as aggressively. The noble metals ruthenium, rhodium, palladium, platinum, and gold react least readily, requiring pure fluorine gas at 300–450 °C (575–850 °F).{{sfn|Lidin|Molochko|Andreeva|2000|pp=442–455}}

Fluorine reacts explosively with hydrogen in a manner similar to that of alkali metals.{{sfn|Greenwood|Earnshaw|1998|p=844}} The halogens react readily with fluorine gas{{sfn|Jaccaud et al.|2005|p=3}} as does the heavy noble gas radon.^[11] The lighter noble gases xenon and krypton can be made to react with fluorine under special conditions, while argon will undergo chemical transformations only with hydrogen fluoride.^[12] Nitrogen, with its very stable triple bonds, requires electric discharge and high temperatures to combine with fluorine directly.{{sfn|Lidin|Molochko|Andreeva|2000|p=252}}

Chemical characteristics, effects of presence in a molecule

Fluorine's chemistry is dominated by its strong tendency to gain an electron. It is the most electronegative element and elemental fluorine is a strong oxidant. The removal of an electron from a fluorine atom requires so much energy that no known reagents are known to oxidize fluorine to any positive oxidation state.^[13]

Therefore, fluorine's only common oxidation state is −1. It differs from this value in elemental fluorine, where the atoms are bonded to each other and thus at oxidation state 0, and a few polyatomic ions: the very unstable anions {{chem|F|2|-}} and {{chem|F|3|-}} with intermediate oxidation states exist at very low temperatures, decomposing at around 40 K.{{sfn|Wiberg|Wiberg|Holleman|2001|p=422}} Also, the {{chem|F|4|+}} cation and a few related species have been predicted to be stable.^[14]

Fluorine forms compounds with all elements except neon and helium. In particular, it forms binary compounds, named fluorides, with all said elements except argon. All of the elements up to einsteinium, element 99, have been checked except for astatine and francium,^[15] and fluorine is also known to form compounds with mendelevium, element 101,^[16] rutherfordium, element 104,^[17] and seaborgium, element 106.^[18]

As a result of its small size and high negative charge density, the fluoride anion is the "hardest" base (i.e., of low polarizability). Because of this, fluorides in real salt crystals often have higher effective charges than oxides of the same metal, even though oxygen's formal charge is twice as great as fluorine's.{{citation needed|date=June 2013}}

As a part of a molecule, it is a part with great inductive effect. In the latter case, it significantly increases the acidity of a molecule: the anion formed after giving the proton off becomes stable as a result. Consider acetic acid and its mono-, di-, and trifluoroacetic derivatives and their pK_a values (4.74, 2.66, 1.24, and 0.23{{#tag:ref|Lower numbers mean greater acidity; note the scale is logarithmical.||group="note"}});{{sfn|Siegemund et al.|2005|p=29}} in other words, the trifluoro derative is 33,800 times stronger an acid than acetic.^[19] Fluorine is a principal component of the strongest known charge-neutral acid, {{Chem|H|2|FSbF|6}}.^[22] There is evidence for an even stronger acid, {{Chem|H|2|FAuF|6}}, but it has not proved isolable.^[20]

In a molecule that is composed of a central atoms and fluorines attached to it, the intermolecular bonding is not very strong. Moreover, the dense negative balls that fluorines are repel each other. Therefore, the intermolecular bonding strength falls further down, a result of which is the low melting point of high fluorides.{{citation needed|date=June 2013}}

Hydrogen fluoride

Fluorine combines with hydrogen to make a compound (HF) called hydrogen fluoride or, especially in the context of water solutions, hydrofluoric acid. The H-F bond type is one of the few capable of hydrogen bonding (creating extra clustering associations with similar molecules). This influences various peculiar aspects of hydrogen fluoride's properties. In some ways the substance behaves more like water, also very prone to hydrogen bonding, than one of the other hydrogen halides, such as HCl.^[21]^[22]^[23]

Hydrogen bonding amongst HF molecules gives rise to high viscosity in the liquid phase and lower than expected pressure in the gas phase. Hydrogen fluoride does not boil until 20 °C in contrast to the heavier hydrogen halides which boil between −85 °C and −35 °C (−120 °F and –30 °F). HF is fully miscible with water (will dissolve in any proportion), while the other hydrogen halides have large solubility gaps with water. Hydrogen fluoride and water also form several compounds in the solid state, most notably a 1:1 compound that does not melt until −40 °C (−40 °F), which is 44 degrees Celsius (79 degrees Fahrenheit) above the melting point of pure HF.{{sfn|Greenwood|Earnshaw|1998|pp=812–816}}

Unlike other hydrohalic acids, such as hydrochloric acid, hydrogen fluoride is only a weak acid in water solution, with acid dissociation constant (pK_a) equal to 3.19.{{sfn|Wiberg|Wiberg|Holleman|2001|p=425}} HF's weakness as an aqueous acid is paradoxical considering how polar the HF bond is, much more so than the bond in HCl, HBr, or HI. The explanation for the behavior is complicated, having to do with various cluster-forming tendencies of HF, water, and fluoride ion, as well as thermodynamic issues.{{#tag:ref|See citation for more detailed explanation.^[24]|group="note"}} At great concentrations, a property called homoconjugation is revealed. HF begins to accept fluoride ions, forming the polyatomic ions (such as bifluoride, {{chem|HF|2|-}}) and protons, thus greatly increasing the acidity of the compound.^[25] Hydrofluoric acid is also the strongest of the hydrohalic acids in acetic acid and similar solvents.^[26] Its hidden acidity potential is also revealed by the fact it protonates acids like hydrochloric, sulfuric, or nitric.^[27] Despite its weakness, hydrofluoric acid is very corrosive, even attacking glass (hydrated only).^[25]

Dry hydrogen fluoride dissolves low-valent metal fluorides readily. Several molecular fluorides also dissolve in HF. Many proteins and carbohydrates can be dissolved in dry HF and can be recovered from it. Most non-fluoride inorganic chemicals react with HF rather than dissolving.{{sfn|Greenwood|Earnshaw|1998|pp=816–819}}

Metal fluorides

Metal fluorides have similarities with other metal halides but are more ionic. In many respects, metal fluorides differ from other metal halides (chlorides, bromides, iodides), very similar to each other. Instead, fluorides are more similar to oxides, often having similar bonding and crystal structures.{{sfn|Greenwood|Earnshaw|1998|p=819}}

The metal fluorides show broad trends based on the charge of the metal. Metals in an oxidation state of +3 or lower tend to form ionic, refractory, fluorides. Metals charged +5 or higher tend to form covalently bonded fluorides, polymers or discrete molecules, and are more volatile. (The tetrafluorides are a transition zone.) The bonding variations mean that metal fluorides can be solids,{{sfn|Lide|2004|p=4-76}} liquids,{{sfn|Lide|2004|p=4-71}} or gases{{sfn|Lide|2004|p=4-92}} at room temperature.

The solubility of fluorides varies greatly but tends to decrease as the charge on the metal ion increases. Dissolved fluorides produce basic solutions. (F⁻ is a weak base because HF is a strong acid.)^[28]

Low oxidation state metal fluorides

The alkali metals form monofluorides. All are soluble and have the sodium chloride (rock salt) structure,{{sfn|Aigueperse et al.|2005|loc="Fluorine Compounds, Inorganic," pp. 25–27}} which is also adopted by some alkaline earth oxides such as CaO.^[29] Because the fluoride anion is weakly basic, many alkali metal fluorides form bifluorides with the formula MHF₂. Among other monofluorides, only silver(I)^[34] and thallium(I)^[30] fluorides are well-characterized. Both are very soluble, unlike the other halides of those metals.

Unlike the monofluorides, the difluorides may be either soluble or insoluble. Several transition metal difluorides, such as those of copper(II) and nickel(II), are soluble.^[34] The alkaline earth metals form difluorides that are insoluble.^[34] In contrast, the alkaline earth chlorides are readily soluble.^[34]

Many of the difluorides adopt the fluorite structure, named after calcium fluoride (and also adopted by several metal dioxides such as CeO₂, UO₂, ThO₂, etc.), which surrounds each metal cation with 8 fluorides. Some difluorides adopt the rutile structure, named after a form of titanium dioxide and adopted by several other metal dioxides also. The structure is tetragonal and puts metal atoms in octahedral coordination.

Beryllium difluoride is different from the other difluorides. In general, beryllium has a tendency to bond covalently, much more so than the other alkaline earths and its fluoride is partially covalent (although still more ionic than its other halides). BeF₂ has many similarities to SiO₂ (quartz) a mostly covalently bonded network solid. BeF₂ has tetrahedrally coordinated metal and forms glasses (is difficult to crystallize). When crystalline, beryllium fluoride has the same room temperature crystal structure as quartz and shares many higher temperatures structures also.

Beryllium difluoride is very soluble in water,^[31] unlike the other alkaline earths. (Although they are strongly ionic, they do not dissolve because of the especially strong lattice energy of the fluorite structure.) However, BeF₂ has much lower electrical conductivity when in solution or when molten than would be expected if it were fully ionic.{{sfn|Emeléus|Sharpe|1983|pp=256–277}}^[32]{{sfn|Mackay|Mackay|Henderson|2002|p=243–244}}^[33]

Many metals form trifluorides, such as iron, bismuth, the rare-earth elements, and the metals in the aluminium and scandium columns of the periodic table. The trifluorides of many rare earths, as well as bismuth, have the YF₃ structure. Trifluorides of plutonium, samarium (at high temperature), and lanthanum adopt the LaF₃ structure. Iron and gallium trifluorides have the FeF₃ structure, which is similar to rhenium trioxide. Only ScF₃ is cubic (ReO₃) at ambient temperature; this material also has the unusual property of negative thermal expansion, meaning it shrinks on heating, over a quite broad temperature range.

Gold trifluoride adopts a structure of linked –AuF₄– squares that align in a helix (spiral chain).^[34] In contrast to gold's distinctly ionic trifluoride, its trichloride and tribromide are volatile dimeric molecules.{{sfn|Wiberg|Wiberg|Holleman|2001|p=1286}} Aluminium trifluoride is a high melting point solid which is a monomer in the gas phase, while its other trihalides are low-melting, volatile molecules or linear polymeric chains that form dimers as gases phase.{{sfn|Wiberg|Wiberg|Holleman|2001|p=1047}} No trifluoride is soluble in water, but several are soluble in other solvents.^[35]

The tetrafluorides show a mixture of ionic and covalent bonding. Zirconium, hafnium, plus many of the actinides form tetrafluorides with an ionic structure that puts the metal cation in an 8-coordinate square antiprism.^[36]^[37] Melting points are around 1000 °C.{{sfn|Lide|2004|pp=4-60, -76, -92, -96}}

Titanium and tin tetrafluorides are polymeric, with melting points below 400 °C. (In contrast, their tetrachlorides are molecular and liquids at room temperature.) Vanadium tetrafluoride has a similar structure to tin's^[38] and disproportionates at 100–120 °C to the trifluoride and the pentafluoride.

The tetrafluorides of iridium, platinum, palladium, and rhodium all share the same structure which was not known until 1975. They have octahedrally coordinated metal atoms with four of the fluorines shared and two unshared. The melting points, where known, are below 300 °C.

Manganese tetrafluoride is an unstable solid that decomposes even at room temperature.^[39] Only one of the two allotropes, α-MnF₄, is understood. In this compound, manganese forms –MnF₆– octahedra which share bridging fluorines to make –Mn₄F₂₀– rings which are then further connected three dimensionally.^[40]

High oxidation state metal fluorides

Metal penta- and higher fluorides are all covalently bonded and volatile. This behavior contrasts with the corresponding oxides. Oxygen is a weaker oxidant and inherently more likely to form covalent bonds, but it only forms molecules with six metals (manganese heptoxide, technetium heptoxide, ruthenium tetroxide, osmium tetroxide, plutonium tetroxide,^[41] and iridium tetroxide^[50]). Fluorine forms molecules with fourteen metals because its small size and single charge as an ion allows surrounding metal atoms with more fluorines than oxygen.

Vanadium, niobium, and tantalum lie in a periodic table column that typically reaches +5 as the highest oxidation state. They form pentafluorides as their highest fluoride. Vanadium pentafluoride is the only non-volatile high-charged metal fluoride, with vanadium being centers of –VF₆– octahedrons. The niobium and tantalum pentafluorides, have the same tetrahedra in their structures, with the difference being the formation of the tetra- (rather than poly-) meric molecules.{{sfn|Emeléus|Sharpe|1983|p=105}}

Bismuth's highest fluoride is a volatile penta species that is a powerful fluorinating agent. In the solid state, it is polymeric, consisting of linear chains of octahedra, sharing axial fluorides. In combination with alkali metals, pentavalent bismuth can form hexafluorobismuthate, [BiF₆]⁻, upon reaction with a fluoride donor, either strong (such as NaF^[42]{{sfn|Wiberg|Wiberg|Holleman|2001|p=770}}) or not (such as XeF₄^[43]).

Many metals that form hexafluorides also can form pentafluorides. For instance, uranium, which has a well-known hexafluoride, also forms two different pentafluoride structures. The room-temperature (alpha) form has the same linear chain structure as bismuth pentafluoride. As a molecular (gas) species, UF₅ has a square pyramidal structure.

The metals that make well-characterized hexafluorides include nine metals in the center of the periodic table (molybdenum, technetium, ruthenium, rhodium, tungsten, rhenium, osmium, iridium, and platinum) along with elements 92–94: uranium, neptunium, and plutonium. At room temperature, tungsten hexafluoride is a gas. Molybdenum hexafluoride and rhenium hexafluoride are liquids. The rest are volatile solids.

Metal hexafluorides are oxidants because of their tendency to release fluorines: for example, platinum hexafluoride was the first compound to oxidize molecular oxygen^[44] and xenon.^[45] Polonium also forms a hexafluoride, but it is understudied.{{sfn|Wiberg|Wiberg|Holleman|2001|p=594}}

Rhenium is the only metal known to bond with seven fluorides, which is the record for number of charged ligands for a charge-neutral metal compound.^[46]Rhenium heptafluoride adopts a pentagonal bipyramid molecular geometry. Calculations shows that the currently unknown but perhaps possible iridium heptafluoride{{sfn|Bayerische Julius-Maximilians-Universität Würzburg|2006|p=93}} (report of synthesis is being prepared^[47]), technetium heptafluoride,^[48] and osmium heptafluoride{{sfn|Bayerische Julius-Maximilians-Universität Würzburg|2006|p=102}} will also have this structure).

Osmium octafluoride was first reported in 1913, but in 1958 that compound was shown to be actually osmium hexafluoride.^[49] A 1993 theoretical study predicted very weak bonds in osmium octafluoride and said that it would be difficult to ever detect experimentally. The study predicted that, if made, OsF₈ would have Os–F bonds of two different lengths.^[59]

Nonmetal fluorides

The nonmetal binary fluorides are volatile compounds. They show a great difference between period 2 and other fluorides. For instance, period 2 elements elements fluorides never exceed the octet in their atoms. (Boron is an exception due to its specific position in the periodic table.) Lower-period elements, however, may form hypervalent molecules, such as phosphorus pentafluoride or sulfur hexafluoride.^[50] The reactivity of such species varies greatly—sulfur hexafluoride is inert, while chlorine trifluoride is extremely reactive—but there are some trends based on periodic table locations.

Silicon tetrafluoride, similar to carbon tetrafluoride and germanium tetrafluoride, adopts a molecular tetrahedral structure.^[52] SiF₄ is stable against heating or electric spark, but reacts with water (even moist air), metals, and alkalies, thus demonstrating weak acidic character.{{sfn|Aigueperse et al.|2005|p=28}} Reactions with organomagnesium compounds, alcohols, amines, and ammonia yield adduction compounds.{{sfn|Aigueperse et al.|2005|p=28}} Fluorosilicic acid, a derivative of SiF₄, is a strong acid in aqueous solution (the anhydrous form does not exist).{{sfn|Aigueperse et al.|2005|p=30}}

The chalcogens (oxygen's periodic table column) are somewhat similar: The tetrafluorides are thermally unstable and hydrolyze, and are also ready to use their lone pair to form adducts to other (acidic) fluorides. Sulfur and selenium tetrafluorides are molecular while TeF₄ is a polymer.^[58] The hexafluorides are the result of direct fluorination of the elements (compare: other hexahalides of these elements do not even exist). They increase in reactivity with atomic number: SF₆ is extremely inert, SeF₆ is less noble (for example, reacts with ammonia at 200 °C (400 °F)), and TeF₆ easily hydrolyzes to give an oxoacid.^[58] Oxygen's highest fluoride is oxygen difluoride,^[58] but fluorine can theoretically (as of 2012) oxidize it to a uniquely high oxidation state of +4 in the fluorocation: {{chem|OF|3|+}}.^[59] In addition, several chalcogen fluorides occur which have more than one chalcogen (O₂F₂,{{sfn|Greenwood|Earnshaw|1998|p=639}} S₂F₁₀,{{sfn|Greenwood|Earnshaw|1998|p=686}} etc.).

The well-characterized heavier halogens (chlorine, bromine, and iodine) all form mono-, tri-, and pentafluorides: XF, XF₃, and XF₅. Of the neutral +7 species, only iodine heptafluoride is known.{{sfn|Wiberg|Wiberg|Holleman|2001|p=435}} While chlorine and bromine heptafluorides are not known, the corresponding cations {{chem|ClF|6|+}} and {{chem|BrF|6|+}}, extremely strong oxidizers, are.{{sfn|Wiberg|Wiberg|Holleman|2001|p=436}} Astatine is not well-studied, and although there is a report of a non-volatile astatine monofluoride,^[60] its existence is debated.^[61] Many of the halogen fluorides are powerful fluorinators. Chlorine trifluoride is particularly noteworthy—readily fluorinating asbestos and refractory oxides—and may be even more reactive than chlorine pentafluoride. Used industrially, ClF₃ requires special precautions similar to those for fluorine gas because of its corrosiveness and hazards to humans.{{sfn|Greenwood|Earnshaw|1998|pp=828–830}}^[62]

Superacids

Several important inorganic acids contain fluorine. They are generally very strong because of the high electronegativity of fluorine. One such acid, fluoroantimonic acid (HSbF₆), is the strongest charge-neutral acid known.^[22] The dispersion of the charge on the anion affects the acidity of the solvated proton (in form of {{chem|H|2|F|+}}): The compound has an extremely low pK_a of −28 and is 10 quadrillion (10¹⁶) times stronger than pure sulfuric acid.^[63] Fluoroantimonic acid is so strong that it protonates otherwise inert compounds like hydrocarbons. Hungarian-American chemist George Olah received the 1994 Nobel Prize in chemistry for investigating such reactions.^[64]

Noble gas compounds

The noble gases are generally non-reactive because they have fully filled electronic shells, which are extremely stable. Until the 1960s, no chemical bond with a noble gas was known. In 1962, Neil Bartlett used fluorine-containing platinum hexafluoride to react with xenon. He called the compound he prepared xenon hexafluoroplatinate, but since then the product has been revealed to be mixture of different chemicals. Bartlett probably synthesized a mixture of monofluoroxenyl(II) pentafluoroplatinate, [XeF]⁺[PtF₅]⁻, monofluoroxenyl(II) undecafluorodiplatinate, [XeF]⁺[Pt₂F₁₁]⁻, and trifluorodixenyl(II) hexafluoroplatinate, [Xe₂F₃]⁺[PtF₆]⁻.{{sfn|Wiberg|Wiberg|Holleman|2001|pp=392–393}} Bartlett's fluorination of xenon has been called one of the ten most beautiful experiments in the history of chemistry.^[65] Later in 1962, xenon was reported to react directly with fluorine to form the di- and tetrafluorides. Since then, chemists have made extensive efforts to form other noble gas fluorides.

Having started the noble gases–fluorine compounds class, xenon is also the noble gas to have the most well-known such compounds. Its binary compounds include xenon difluoride, xenon tetrafluoride, and xenon hexafluoride, as well as their derivatives.{{sfn|Wiberg|Wiberg|Holleman|2001|p=438}} Xenon forms several oxyfluorides, such as xenon oxydifluoride, XeOF₂, by reaction of xenon tetrafluoride with water.{{sfn|Wiberg|Wiberg|Holleman|2001|p=400}} Its upper neighbor, krypton, is the only other one to form a well-established compound: krypton difluoride. Krypton tetrafluoride was reported in 1963,^[66] but was subsequently shown to be a mistaken identification; the compound seems to be very hard to synthesize now (although even the hexafluoride may exist).^[67]

In strong accordance with the periodic trends, radon is notably more reactive to oxidizers, including fluorine. It has been shown to readily react with fluorine to form a solid compound, which is generally thought to be radon difluoride. The exact composition is uncertain as the compound is prone to decomposition. Calculations indicate that radon difluoride may be ionic, unlike all other binary noble gas fluorides.^[60]

The lighter noble gases (helium through argon) do not form stable binary fluorides. Argon forms no binary fluoride, but reacts in extreme conditions with hydrogen fluoride to form argon fluorohydride; it is the only "stable"{{#tag:ref|In the context of the noble gas compounds, "stable" means not decaying chemically over time under certain (any count) conditions; other ("meta-stable") compounds are not treated in this overview article.|group="note"}} argon compound. Helium and neon do not form any stable chemical compounds at all. Helium forms helium fluorohydride; it has been shown to be unstable in gas phase, but there are specific conditions for which it may be stable.^[69] Neon, the least reactive element,{{#tag:ref|Even though helium and neon have no known stable compounds, calculations show that helium may be called slightly less unreactive than neon (it may, unlike neon, form some neutral-charged compounds that will not decay over time in specific conditions, and a stable cation of helium (HeH⁺), the strongest acid of all species,^[70] yet existent) has been known since 1925, while no neon cations are. Additionally, clathrates are known for every noble gas but neon.{{sfn|Lewars|2008|pp=70–78}}|group="note"}} is not now expected to form a stable compound capable of synthesis.

Oganesson, the last currently known group 18 element, is predicted to form oganesson difluoride, {{chem|Og||F|2}}, and oganesson tetrafluoride, {{chem|OgF|4}}, which is likely to have the tetrahedral molecular geometry.^[71] However, only a few atoms of oganesson have been synthesized,^[72] and its chemical properties have not been examined.

Highest oxidation states: fluorine versus oxygen

Elements frequently have their highest oxidation state in the form of a binary fluoride. Several elements show their highest oxidation state only in a few compounds, one of which is the fluoride; and some elements' highest known oxidation state is seen exclusively in a fluoride.

For groups 1–5, 10, 13–16, the highest oxidation states of oxides and fluorides are always equal. Differences are only seen in chromium, groups 7–9, copper, mercury, and the noble gases. Fluorination allows some elements to achieve relatively low^[73] highest oxidation states that are otherwise hard to achieve. For example, no binary oxide is known for krypton, but krypton difluoride is well-studied.{{sfn|Wiberg|Wiberg|Holleman|2001|p=398}} At the same time, for some other elements, certain very high oxidation states are known only for the oxygen-based species, not the fluorine-based ones. For the previously mentioned volatile oxides, there are no corresponding hepta- or octafluorides. (For example, ruthenium octafluoride is unlikely to be ever synthesized,^[91] while ruthenium tetroxide has even found an industrial use.^[74]) The main problem that prevents fluorine from forming the highest states in covalent hepta- and octafluorides is that it is hard to attach such a large number of ligands around a single atom; the number of ligands is halved in analogous oxides.{{sfn|Bayerische Julius-Maximilians-Universität Würzburg|2006|p=34}}{{#tag:ref|Note that aside from the molecular one, other forms of the highest fluorides are not considered to be possible. Such compounds are extremely unlikely to be completely ionic because of large sixth, seventh, and eighth oxidation energies of all elements, which make the reactions that may produce such compounds highly unfavorable (even though the possible osmium octafluoride may be mostly ionic^[75]).|group="note"}} However, octafluoride anions, such as the octafluoroiodate ({{chem|IF|8|-}}), octafluorozirconate ({{chem|ZrF|8|4-}}), and octafluoroxenate ({{chem|XeF|8|2-}}) anions are well-known.

The highest oxidation states may be uncommon to everyday life, or even industrial usage. For example, the synthesis of mercury tetrafluoride, the first compound to achieve an oxidation state above +2 for a group 12 element, breaking the filled 5d-shell, again showing the significance of the relativistic effects on the heavy elements, and fueling the debate over whether mercury, cadmium, and zinc are transition metals,^[76] occurred at cryogenic temperatures and the compound decomposes at the temperatures of solid nitrogen.^[77] More unstable still, the only cobalt(V) species, the {{chem|CoF|4|+}} cation, has only been observed in gas phase (with no interactions with other atoms, thus no shown stability in any chemical environment).^[78] The reason why such unstable species exist is complicated, yet can be summarized as follows on the example of the hypothesized {{chem|NF|5}} molecule: According to the modern calculations, five fluorine atoms and one nitrogen atoms can theoretically arrange themselves in different ways, such as {{chem|NF|3}} and {{chem|F|2}}, {{chem|NF|4|•}} and {{chem|F|•}}, {{chem|NF|5}}, etc. The {{chem|NF|3}}+{{chem|F|2}} system is of the smallest energy (most stable). However, if a {{chem|NF|5}} molecule was synthesized, it would have to go through a high-energy transitional state, from which it could decay into two molecules. But since the transitional state is higher in energy than the hexatomic molecule, the energy difference would need to be added to reach the transitional state and thus allow the decay. This energy is called reaction activation barrier. (The second decay mode has an analogical position.) Thus if little energy was added (low temperatures), then the compound could exist; however, the synthesis is a serious problem (not yet solved).{{sfn|Lewars|2008|pp=60–61}}

Organofluorine compounds

The carbon–fluorine chemical bond of the organofluorine compounds is the strongest bond in organic chemistry.^[79] Along with the low polarizability of the molecules, these are the most important factors contributing to the great stability of the organofluorines.{{sfn|Siegemund et al.|2005|p=2}}

The carbon–fluorine bond of the smaller molecules is formed in three principal ways: Fluorine replaces a halogen or hydrogen, or adds across a multiple bond. The direct reaction of hydrocarbons with fluorine gas can be dangerously reactive, so the temperature may need to be lowered even to −150 °C (−240 °F).{{sfn|Siegemund et al.|2005|p=4}} "Solid fluorine carriers", compounds that can release fluorine upon heating, notably cobalt trifluoride,{{sfn|Jaccaud et al.|2005|p=13}} may be used instead, or hydrogen fluoride. After the reaction, the molecular size is not changed significantly, as the elements have very similar van der Waals radii.{{sfn|Siegemund et al.|2005|p=2}} Direct fluorination becomes even less important when it comes to organohalogens or unsaturated compounds reactions, or when a prefluorocarbon is desired (then HF-based electrolysis is typically used).{{sfn|Siegemund et al.|2005|pp=3–5}} In contrast, the fluoropolymers are formed by polymerizing free radicals; other techniques used for hydrocarbon polymers do not work in that way with fluorine.{{sfn|Carlson|Scmiegel|2005|p=3}}

The range of organofluorine compounds is diverse, reflecting the inherent complexity of organic chemistry. A vast number of small molecules exist with varying amounts of fluorine substitution, as well as many polymers—research into particular areas is driven by the commercial value of applications.^[80]

Small molecules

Monofluoroalkanes (alkanes with one hydrogen replaced with fluorine) may be chemically and thermally unstable, yet are soluble in many solvents; but as more fluorines are in instead of hydrogens, the stability increases, while melting and boiling points, and solubility decrease. While the densities and viscosities are increased, the dielectric constants, surface tensions, and refractive indices fall.{{sfn|Siegemund et al.|2005|pp=7–8}}

Partially fluorinated alkanes are the hydrofluorocarbons (HFCs). Substituting other halogens in combination with fluorine gives rise to chlorofluorocarbons (CFCs) or bromofluorocarbons (BFCs) and the like (if some hydrogen is retained, HCFCs and the like). Properties depend on the number and identity of the halogen atoms. In general, the boiling points are even more elevated by combination of halogen atoms because the varying size and charge of different halogens allows more intermolecular attractions.^[99] As with fluorocarbons, chlorofluorocarbons and bromofluorocarbons are not flammable: they do not have carbon–hydrogen bonds to react and released halides quench flames.^[81]

When all hydrogens are replaced with fluorine to achieve perfluoroalkanes, a great difference is revealed. Such compounds are extremely stable, and only sodium in liquid ammonia attacks them at standard conditions. They are also very insoluble, with few organic solvents capable of dissolving them.{{sfn|Siegemund et al.|2005|pp=7–8}}

However, if a perfluorocarbon contains double or triple bonds (perfluoroalkenes or -alkynes), a very reactive towards ligand accepting result, even less stable than corresponding hydrocarbons.{{sfn|Siegemund et al.|2005|p=18}} Difluoroacetylene, which decomposes even under liquid nitrogen temperatures,^[82] is a notable example. If such a molecule is asymmetric, then the more fluorinated carbon is attacked, as it holds positive charge caused by the C–F bonds and is shielded weakly{{sfn|Siegemund et al.|2005|p=18}} (similarly to that how unsaturated hydrocarbons attacked by HF add hydrogen to the more hydrogen-rich atom per Markovnikov's rule{{sfn|Siegemund et al.|2005|p=5}}).

The perfluoroalkanesulfonic acids are also very notable for their acidity. The sulfonic acid derivative, trifluoromethanesulfonic acid, is comparable in strength to perchloric acid.{{sfn|Siegemund et al.|2005|p=32}} These compounds lower surface energy; for this reason, they, especially perfluorooctanesulfonic acid (PFOS, formerly the active component in brand "Scotchgard") have found industrial use as surfactants (see above).{{sfn|Siegemund et al.|2005|p=32}}

If a perfluorinated compound has a fluorinated tail, but also a few non-fluorinated carbons (typically two) near the functional group, it is called a fluorotelomer (such molecules are commercially treated as perfluorinated), but such molecules are more of industrial value than chemical. The chain end may similarly be attached to different functiuonal groups (via the hydrogenized terminal carbon), such as hydroxyl resulting in fluorotelomer alcohols, sulfonate resulting in fluorotelomer sulfonates, etc.^[84]

Polymers

Fluoropolymers are similar in many regards with smaller molecules; adding fluorine to a polymer affects the properties in the same manner as in small molecules (increasing chemical stability, melting point, reducing flammability, solubility, etc.). Each fluoropolymer has own characteristic properties, though.{{sfn|Carlson|Scmiegel|2005|p=3}}

The simplest fluoroplastic is polytetrafluoroethylene (PTFE, DuPont brand Teflon), which is a simple linear chain polymer with the repeating structural unit:–CF₂–. PTFE has a backbone of carbons single bonded in a long chain, with all side bonds to fluorines. It contains no hydrogens and can be thought of as the perfluoro analog of polyethylene (structural unit: –CH₂–). PTFE has high chemical and thermal stability, as expected for a perfluorocarbon, much stronger than polyethylene. Its resistance to van der Waals forces makes PTFE the only known surface to which a gecko cannot stick.^[85] The compound, however, lacks an ability to transform upon melting, which is not a problem for various PTFE deratives, namely FEP (fluorinated ethylene propylene, with some fluorines replaced with the–CF₃ group) or PFA (perfluoroalkoxy, some fluorines replaced with –OCF₃). They share most properties with PTFE, but there are still differences, namely maximum usage temperature (highest for the non-flexible PTFE).{{sfn|Carlson|Scmiegel|2005|pp=3–4}}

There are other fluoroplastics other than perfluorinated. Polyvinylidene fluoride (PVDF, structural unit: –CF₂CH₂–), is an analog of PTFE with half the fluorines. PVF (polyvinyl fluoride, structural unit: –CH₂CHF–) contains one one-fourth the fluorines of PTFE. Despite this, it still has many properties of more fluorinated compounds.{{sfn|Carlson|Scmiegel|2005|p=4}} PCTFE (polychlorotrifluoroethylene, structural unit: –CF₂CFCl–) is another important compound. It differs from PTFE by having a quarter of fluorine replaced with chlorines, yet this difference brings even greater hardness, creep resistance, and moisture persistence.{{sfn|Carlson|Scmiegel|2005|p=4}}

Mild fluorination of polyethylene gives does not make all of the plastic lose its hydrogens for fluorine; only a thin layer (0.01 mm at maximum) is then affected. This is somewhat similar to metal passivation: the bulk properties are not affected, but the surface properties are, most notably, a greater vapor barrier. Therefore, they are a cheaper alternative to the perfluoro plastics if only surface is important.^[86]

Fluoroelastomers, like other elastomers (artificial rubbers), consist of disordered polymer chains connected in three dimensions. The main challenges in making fluorelastomers are cross-linking (reacting the unreactive polymers), as well as removing the HF formed during curing. There are three main families of fluoroelasters. VDF/HFP is a copolymer system of vinylidene fluoride and (at least 20%) hexafluoropropylene. TFE/propylene is another copylymer system with better chemical resistance to some solvents. TFE/PMVE (perfluoromethylvinyl ether) is a copolymer system which creates a perfluorinated fluoroelastomer.^[88]

Notes

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3. ^In this article, metalloids are not treated separately from metals and nonmetals, but among elements they are closer to. For example, germanium is treated as a metal, and silicon as a nonmetal. Antimony is included for comparison among nonmetals, even though it is closer to metals chemically than to nonmetals. The noble gases are treated separately from nonmetals; hydrogen is discussed in the Hydrogen fluoride section and carbon in the Organic compounds section. P-block period 7 elements have not been studied and thus are not included. This is illustrated by the adjacent image: the dark gray elements are metals, the green ones are nonmetals, the light blue ones are the noble gases, the purple one is hydrogen, the yellow one is carbon, and the light gray elements have unknown properties.
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