Hydrofluoric acid
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Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling point near room temperature. It is used to make most organofluorine compounds; examples include the commonly used pharmaceutical antidepressant medication fluoxetine (Prozac) and the material PTFE (Teflon). Elemental fluorine is produced from it. It is commonly used to etch glass and silicon wafers.
Uses
Production of organofluorine compounds
The principal use of hydrofluoric acid is in organofluorine chemistry. Many organofluorine compounds are prepared using HF as the fluorine source, including Teflon, fluoropolymers, fluorocarbons, and refrigerants such as freon. Many pharmaceuticals contain fluorine.<ref name=Ullmann/>
Production of inorganic fluorides
Most high-volume inorganic fluoride compounds are prepared from hydrofluoric acid. Foremost are Na3AlF6, cryolite, and AlF3, aluminium trifluoride. A molten mixture of these solids serves as a high-temperature solvent for the production of metallic aluminium. Other inorganic fluorides prepared from hydrofluoric acid include sodium fluoride and uranium hexafluoride.<ref name=Ullmann/>
Etchant, cleaner
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It is used in the semiconductor industry as a major component of Wright etch and buffered oxide etch, which are used to clean silicon wafers. In a similar manner it is also used to etch glass by treatment with silicon dioxide to form gaseous or water-soluble silicon fluorides. It can also be used to polish and frost glass.<ref name=":0" />
A 5% to 9% hydrofluoric acid gel is also commonly used to etch all ceramic dental restorations to improve bonding.<ref>Template:Cite book</ref> For similar reasons, dilute hydrofluoric acid is a component of household rust stain remover, in car washes in "wheel cleaner" compounds, in ceramic and fabric rust inhibitors, and in water spot removers.<ref name=":0" /><ref>Template:Cite journal</ref> Because of its ability to dissolve iron oxides as well as silica-based contaminants, hydrofluoric acid is used in pre-commissioning boilers that produce high-pressure steam. Hydrofluoric acid is also useful for dissolving rock samples (usually powdered) prior to analysis. In similar manner, this acid is used in acid macerations to extract organic fossils from silicate rocks. Fossiliferous rock may be immersed directly into the acid, or a cellulose nitrate film may be applied (dissolved in amyl acetate), which adheres to the organic component and allows the rock to be dissolved around it.<ref name=Edwards1982>Template:Cite journal</ref>
Oil refining
In a standard oil refinery process known as alkylation, isobutane is alkylated with low-molecular-weight alkenes (primarily a mixture of propylene and butylene) in the presence of an acid catalyst derived from hydrofluoric acid. The catalyst protonates the alkenes (propylene, butylene) to produce reactive carbocations, which alkylate isobutane. The reaction is carried out at mild temperatures (0 and 30 °C) in a two-phase reaction.
Production
Hydrofluoric acid was first prepared in 1771, by Carl Wilhelm Scheele.<ref>Template:Greenwood&Earnshaw1st</ref> It is now mainly produced by treatment of the mineral fluorite, CaF2, with concentrated sulfuric acid at approximately 265 °C.
- CaF2 + H2SO4 → 2 HF + CaSO4
The acid is also a by-product of the production of phosphoric acid from apatite and fluoroapatite. Digestion of the mineral with sulfuric acid at elevated temperatures releases a mixture of gases, including hydrogen fluoride, which may be recovered.<ref name=Ullmann>Template:Ullmann</ref>
Because of its high reactivity toward glass, hydrofluoric acid is stored in fluorinated plastic (often PTFE) containers.<ref name=Ullmann/><ref name=":0">Template:Cite web</ref>
Properties
In dilute aqueous solution, hydrogen fluoride behaves as a weak acid.<ref name="Pearson/Prentice Hall">Template:Cite book</ref> Infrared spectroscopy has been used to show that, in solution, dissociation is accompanied by formation of the ion pair Template:H3O+·F−.<ref name="Giguère"/> <ref name="Spectral Signatures and Molecular O">Template:Cite journal</ref>
- Template:H2O + HF Template:Eqm Template:H3O+⋅F−Template:PadpKa = 3.17
This ion pair has been characterized in the crystalline state at very low temperature.<ref name=mootz> Template:Cite journal</ref> Further association has been characterized both in solution and in the solid state.Template:Citation needed
- HF + F− Template:Eqm Template:ChemTemplate:Padlog K = 0.6
It is assumed that polymerization occurs as the concentration increases. This assumption is supported by the isolation of a salt of a tetrameric anion Template:Chem<ref>Template:Cite journal</ref> and by low-temperature X-ray crystallography.<ref name=mootz/> The species that are present in concentrated aqueous solutions of hydrogen fluoride have not all been characterized; in addition to Template:Chem which is known<ref name="Giguère"/> the formation of other polymeric species, Template:Chem, is highly likely.
The Hammett acidity function, H0, for 100% HF was first reported as −10.2,<ref name="HymanKilpatrick1957">Template:Cite journal</ref> while later compilations show −11, comparable to values near −12 for pure sulfuric acid.<ref name="Jolly">Template:Cite book</ref><ref name="Cotton 109">Template:Cite book</ref>
Acidity
Unlike other hydrohalic acids, such as hydrochloric acid, hydrogen fluoride is only a weak acid in dilute aqueous solution.<ref>Template:Cite book</ref> This is in part a result of the strength of the hydrogen–fluorine bond, but also of other factors such as the tendency of HF, Template:Chem, and Template:Chem anions to form clusters.<ref>Template:Cite web</ref> At high concentrations, HF molecules undergo homoassociation to form polyatomic ions (such as bifluoride, Template:Chem) and protons, thus greatly increasing the acidity.<ref name="H+">Template:Cite book</ref> This leads to protonation of very strong acids like hydrochloric, sulfuric, or nitric acids when using concentrated hydrofluoric acid solutions.<ref>Template:Cite book</ref> Although hydrofluoric acid is regarded as a weak acid, it is very corrosive, even attacking glass when hydrated.<ref name="H+"/>
Dilute solutions are weakly acidic with an acid ionization constant Template:Math (or Template:Math),<ref name="Pearson/Prentice Hall"/> in contrast to corresponding solutions of the other hydrogen halides, which are strong acids (Template:Math). However concentrated solutions of hydrogen fluoride are much more strongly acidic than implied by this value, as shown by measurements of the Hammett acidity function H0(or "effective pH"). During self ionization of 100% liquid HF the H0 was first measured as −10.2<ref name="HymanKilpatrick1957" /> and later compiled as −11, comparable to values near −12 for sulfuric acid.<ref name="Jolly" /><ref name="Cotton 109"/>
In thermodynamic terms, HF solutions are highly non-ideal, with the activity of HF increasing much more rapidly than its concentration. The weak acidity in dilute solution is sometimes attributed to the high H—F bond strength, which combines with the high dissolution enthalpy of HF to outweigh the more negative enthalpy of hydration of the fluoride ion.<ref>C. E. Housecroft and A. G. Sharpe "Inorganic Chemistry" (Pearson Prentice Hall, 2nd ed. 2005), p. 170.</ref> Paul Giguère and Sylvia Turrell<ref name="Giguère">Template:Cite journal</ref><ref name="Spectral Signatures and Molecular O"/> have shown by infrared spectroscopy that the predominant solute species in dilute solution is the hydrogen-bonded ion pair Template:H3O+·F−.<ref name="Cotton 104">Template:Harvp</ref>
- Template:H2O + HF Template:Eqm Template:H3O+⋅F−
With increasing concentration of HF the concentration of the hydrogen difluoride ion also increases.<ref name="Giguère"/> The reaction
- 3 HF Template:Eqm Template:Chem + H2F+
is an example of homoconjugation.
Health and safety
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In addition to being a highly corrosive liquid, hydrofluoric acid is also a powerful contact poison. Since it can penetrate tissue, poisoning can occur readily through exposure of skin or eyes, inhalation, or ingestion. Symptoms of exposure to hydrofluoric acid may not be immediately evident, and this can provide false reassurance to victims, causing them to delay medical treatment.<ref name="pmid11505130">Template:Cite journal</ref> Despite its irritating vapor, HF may reach dangerous levels without an obvious odor.<ref name=":0" /> It interferes with nerve function, meaning that burns may not initially be painful. Accidental exposures can go unnoticed, delaying treatment and increasing the extent and seriousness of the injury.<ref name="pmid11505130" /> Symptoms of HF exposure include irritation of the eyes, skin, nose, and throat, eye and skin burns, rhinitis, bronchitis, pulmonary edema (fluid buildup in the lungs), and bone damage<ref>Template:Cite web</ref> due to HF strongly interacting with calcium in bones.<ref>Template:Cite web</ref> In a concentrated form, HF can cause severe tissue destruction through lesions and mucous membrane damage, but dilute HF is still dangerous because of its high lipid affinity, leading to cellular death of nerves, blood vessels, tendons, bones, and other tissues.<ref>Template:Cite journal</ref> Cases of intestinal damage from contact with hydrofluoric acid requiring surgical intervention are rare but known in medical literature.<ref>Template:Cite journal</ref>
Hydrofluoric acid burns should be rapidly treated with calcium gluconate gel.Template:Fact
In popular culture
- In the episodes "Cat's in the Bag..." and "Box Cutter" of the crime drama television series Breaking Bad, Walter White and Jesse Pinkman use hydrofluoric acid to chemically degrade the corpses of gangsters.<ref>Template:Cite web</ref><ref>Template:Cite web</ref>
- In "Of Past Regret and Future Fear", a Season 4 episode of the television medical drama ER, a patient is brought in with severe chemical burns from hydrofluoric acid that prove to be fatal.
- Hydrofluoric acid is mentioned in the novel Virtual Destruction by Kevin J. Anderson and Doug Beason. A character named Jose Aragon comes in contact with the acid on his hand, prompting him to seek treatment at a medical center.