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Hydrofluoric acid

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CAS:7664-39-3
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CAS:7664-39-3
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  • Hydrofluoric acid
  • US $1.00 / kg
  • 2018-12-21
  • CAS:7664-39-3
  • Min. Order: 1kg
  • Purity: 95%-99%
  • Supply Ability: 100kg
Hydrofluoric acid Chemical Properties
Melting point -35°C
Boiling point 105°C
density 1.15 g/mL at 25 °C(lit.)
vapor density 1.27 (vs air)
vapor pressure 25 mm Hg ( 20 °C)
Fp 112°C
pka3.17(at 25℃)
form Liquid, Double Sub-Boiling Quartz Distillation
color max. 10
OdorAcrid, irritating odor
Water Solubility soluble
Sensitive Hygroscopic
Merck 14,4790
Stability:Stable. Hygroscopic. Incompatible with glass, alkali metals, light metals, alkaline earth metals
CAS DataBase Reference7664-39-3(CAS DataBase Reference)
NIST Chemistry ReferenceHydrogen fluoride(7664-39-3)
EPA Substance Registry SystemHydrofluoric acid(7664-39-3)
Safety Information
Hazard Codes T+,C,T,Xn
Risk Statements 26/27/28-35-36/37/38-20/21/22
Safety Statements 26-36/37/39-45-7/9-36/37-28-36
RIDADR UN 1790 8/PG 2
WGK Germany 2
RTECS MW7875000
Hazard Note Corrosive
TSCA Yes
HazardClass 8
PackingGroup II
Hazardous Substances Data7664-39-3(Hazardous Substances Data)
ToxicityLC50 (15 min.) in rats, guinea pigs: 2689, 4327 ppm (Rosenholtz)
MSDS Information
ProviderLanguage
Hydrofluoric acid English
SigmaAldrich English
ACROS English
ALFA English
Hydrofluoric acid Usage And Synthesis
Product descriptionHydrofluoric acid (HF) is an aqueous solution of hydrogen fluoride gas. At room temperature, it appears as colorless transparent to light yellow smoke liquid with pungent odor. It has a specific gravity of 0.98 which is slightly lighter than water. It has a boiling point of 19.4 °C, being highly volatile. It can release white smoke once placed in air. The aqueous solution containing less than 60% hydrogen fluoride appears as a colorless clear fuming liquid. Industrial products are usually aqueous solution containing 40 to 45% HF. It has pungent odor. It can react with sulfur trioxide or chlorosulfonic acid to generate fluoride sulfonic acid, and can react with halogenated aromatic hydrocarbons, alcohols, olefins, hydrocarbons to generate fluorine-containing organic compound. When being dissolved in water, it can produce highly corrosive acid, being medium-intensity acid. It is extremely smelly, being very toxic and is prone to cause ulceration when get touch with the skin with a severe extent being larger than any acids. If inhaled of its vapor, it can have fatal effects, thus strict attention should paid during usage.
1. Hydrofluoric acid can also react with general metals, metal oxides, and hydroxide, generating a variety of metal fluoride salts, but the effect is not as dramatic as hydrochloric acid. Gold, platinum, lead, paraffin and some plastics (polyethylene, etc.) does not react with it and thus being able to be used as containers.
2. Strong corrosiveness: it can erode glass and silicate to produce gaseous silicon tetrafluoride. The reaction is as follows: SiO2 + 4HF → H2O + SiF4 ↑, glass is a silicon compound so the hydrofluoric acid can’t be put into glass containers.
Hydrofluoric acid can form acid salt, hydrofluoric acid is a monobasic acid, but can produce a series of acid salts such as NaHF2, KHF2, NH4HF2, which are the other three kinds of halogen acid.
4. The weak acidity of hydrofluoric acid; because of the strong binding capability of hydrogen atom with fluorine atom, hydrofluoric acid can’t be completely dissociated in the water. In the hydrohalic acid, only hydrofluoric acid is weak acid (its ionization constant is 3.5 × 10 ^-4; its apparent ionization degree is about 10% at a concentration of 0.1mo1.L^-1, therefore, HF can reluctantly taken as a kind of strong acid. The ionization degree at high concentration is higher than that at low concentration. This property is different from other kinds of general weak electrolytes).
Chemical PropertiesIt appears as colorless fuming liquid. It is intensively exothermic when being dissolved in water and further become hydrofluoric acid.
Uses(1) Hydrofluoric acid is mainly used as the raw materials of fluorine compounds, also used in the manufacture of aluminum fluoride and cryolite. Moreover, it can be applied to semiconductor surface etching and used as alkylation catalyst.
In the electronics industry, it can be used as a strong acid corrosion agent, being able to be used in conjunction with nitric acid, acetic acid, ammonia and hydrogen peroxide.
(2) It can be used as analytical reagents, but also for the preparation of high purity fluoride.
(3) It is the indispensable fluoride source for fluorine salts, fluorine refrigerants, fluorine plastics, fluorine rubber and fluorine medicine and pesticides.
(4) It is the raw materials for the production of refrigerants, "Freon", fluorine-containing resins, organic fluoride and fluoride. In chemical production, it can be used as the catalysts of the organic synthesis such as alkylation, polymerization, condensation and isomerization. (5) It can also be used for corrosion of stratum upon the exploitation of certain deposits as well as the extraction of rare earth elements and radioactive elements. In the atomic energy industry and nuclear weapons production, it is the raw materials for the manufacture of uranium hexafluoride. It is also the raw materials for the production of rocket fuel and additives. Moreover, it can also be used for corrosion of glass and impregnation of wood.
(6) It is used for the manufacture of organic or inorganic fluoride, such as fluorocarbons, sodium fluoride, aluminum fluoride, uranium hexafluoride and cryolite. It can also be applied to stainless steel, non-ferrous metal pickling, glass instrumentation scale, glassware and the engraving and lettering of mirror as well as glassware polishing, frosted bulb and general bulb treatment, silicon-removing purification of metal graphite, desanding of the metal casting, the removal of the graphite ash and the manufacturing of semiconductor (germanium, silicon) manufacturing. It can also be used for dye synthesis and used as the catalyst for other organic synthesis. It can also used for electroplating, reagents, fermentation, ceramic processing and the manufacturing of fluorine-containing resin and flame retardant.
(7) It can be used for etching glass, pickling metal and production of inorganic fluoride products and chemical reagents.
(8) It can be applied to the atomic energy industry and the production of fluorine and fluoride. It can also used as catalyst, fluorinating agent for the manufacturing of organic or inorganic fluoride. Moreover, it can be applied to the pickling of stainless steel and non-ferrous metal, the scrub and pickling of glassware as well as the processing of frosted bulb.
Health HazardsHydrofluoric acid has irritating smell and acute toxicity, belonging to the medium strength & slightly weak acid. It is corrosive. It is commonly used in the manufacture of fluorocarbon, sodium fluoride, aluminum fluoride, uranium hexafluoride and cryolite and other organic or inorganic fluorine compounds. It can be applied to the pickling of stainless steel and non-ferrous metal. The semiconductor industry take it as a cleaning agent; glass etching industry as its etchant; the steel industry take it as a surface rust  removing agent; the petrochemical industry take it as a catalyst; the cleaning services take it as a dirt cleaning agent or as an external wall cleaning agent.
For professionals that are exposure to hydrofluoric acid in the daily work, improper use may cause non-negligible harm to the human body. Its exposure approaches include the skin and mucous membranes contact, respiratory inhalation and gastrointestinal uptake. Skin, if in contact with a over 50% concentrations of hydrofluoric acid, will immediately get painful feeling, whitening, swelling reaction. Blister can occur in 1 to 2 hours and the necrosis and ulceration can occur within 6 to 24 hours. People exposure to lower concentration (below 10%) will get pain and other symptoms in 6 hours or more. This may be overlooked by the parties, leading to extremely delayed treatment and finally permanent injury. Generally, the most common part of the injury is the finger.
In addition, if exposed from other approaches such as the respiratory tract and gastrointestinal tract, it will produce cough, burning and breathing difficulties and other symptoms, or causing abdominal pain, nausea, vomiting blood, intestinal perforation and other symptoms. The harm of hydrofluoric acid on the human body, in addition to acid corrosion damage, fluoride ions entering into the body may bind to calcium and magnesium ions, resulting in hypocalcemia, hypomagnesemia and hyperkalemia, further affecting the nervous and cardiovascular system.
Daily administration of hydrofluoric acid should avoid contact with the body, including skin, eyes and respiratory tract. In prevention of the contact with the skin, we should wear gloves of fluorinated polyethylene (PVDF) and natural rubber. Do not use cloth and cotton gloves and should do systemic protection in occasion easy to splash. We can wear the coverall protecting cloth and work boots of rubber material with the eye should wear goggles or full-face mask. If accidentally corroded by the hydrofluoric acid, immediately use large amount of water to rinse the affected area for at least 30 minutes until there is not any attached solid or liquid that can be observed in the body. Meanwhile, send the patients immediately to hospital for medical treatment as soon as possible. During the medical treatment, we should be brought the chemicals in contact to enable the timely and correct medical treatment by the medical staffs.
ToxicitySee also hydrofluoric acid.
Hydrofluoric acid is highly corrosive, being able to corrode glass and nail with its vapor being extremely poisonous. The maximum allowable concentration is 1 mg/m3 (LD501.276 × 10-3). Skin contact will cause swelling and burning sensation and the eyes will get blurred vision. After inhalation, people can get sore throat, cough and have difficulty in breathing. After entering into the digestive tract, people can get abdominal pain, diarrhea, and vomiting. For protection, people should pay attention to ventilation. The operator must wear protective equipment, preventing its contact with the skin. Upon inadvertently contacting the skin, immediately rinse with plenty of water; after rinse away the acid, you can generally use mercurochrome solution or gentian violet for coating the affected area. Upon serious case, the patients should be sent to hospital for treatment.
It has irritating and toxic effect with strong corrosive effect on the skin and eyes, being able to produce serious burns; burns do not immediately appear, and the treatment is relatively slow. Access to it must be conducted in a well-ventilated place or in a fume hood. The staff should wear fluoride resistant gloves of suitable size, boots and protective aprons and face shields. In case of contact or suspected contact with this product, rinse with plenty of water and seek for medical treatment immediately.
Production methodSulfuric acid method: mix the dried fluorite powder and sulfuric acid in the ratio of 1: (1.2~1.3), send into the rotary reaction furnace for reaction. The temperature of the furnace gas phase is controlled at 280 °C ± 10 °C. The post-reaction gas enters into the crude distillation tower for removal of most of the sulfuric acid, water and fluorite powder. The temperature of the tower kettle is controlled at 100 to 110 °C and the top temperature is 35 to 40 °C. The crude hydrogen fluoride gas is further condensed into a liquid state through a degassing tower with the temperature of the tower kettle being controlled at 20 to 23 °C and the top temperature of the tower being controlled at-8 °C ± 1 °C and then enters into the rectification tower for rectification with the temperature of the tower kettle being controlled at 30 to 40 °C and the temperature of the top of the column being controlled at 19.6 ° C ± 0.5 °C. The purified hydrogen fluoride is absorbed by water so the hydrofluoric acid product is obtained. The reaction formula is:
CaF2 + H2SO4 → 2HF + CaSO4
Sulfuric acid method: the hydrogen fluoride generated through sulfuric acid decomposition of fluorite is subject to the crude distillation, degassing and then be distilled to produce anhydrous hydrofluoric acid. And the reaction formula is:
CaF2 + H2SO4 → 2HF + CaSO4
Refining purification technology: the industrial grade hydrofluoric acid is purified by distillation with condensation to remove impurities, and filtered through a microporous membrane to remove dust particles, producing colorless and transparent electronic grade hydrofluoric acid.
DescriptionHydrofluoric acid is a solution of hydrogen fluoride in water. Hydrofluoric acid is highly corrosive inorganic acid. It is utilized widely in the manufacture of ceramics and graphite, in the electropolishing and pickling of metals, in the etching and frosting of glass, in the semiconductor industry as etchant and cleaning agent, in the chemical and oil-refining industries, and in cleaning solutions, laundry powder and pesticides. Hydrofluoric acid is also widely used in the preparation of many useful fluorine compounds, such as Teflon, Freon, fluorocarbons, and many medications such as fluoxetine (Prozac).
Chemical Propertiescolourless gas with a pungent odour
Physical propertiesColorless gas or liquid at ambient temperatures; fumes in air; highly irritating; gas density 0.878 g/L at 25°C; liquid density 1.002 g/mL at 0°C; boils at 19.85°C; freezes at –83.55°C; vapor pressure 360 torr at 0°C; critical temperature 187.85°C; critical pressure 63.95 atm; critical volume 69 cm3/mol; viscosity 0.256 centipoise at 0°C; surface tension 10.1x10–4 dyn/cm at 0°C; dielectric constant 83.6 at 0°C; highly soluble in water and alcohols; forms an azeotrope with water at a composition 38.2 HF: 61.8 H2O (weight percent); the azeotrope boils at 112.2°C; moderately soluble in benzene (2.55 g/100 g at 5°C). Hydrofluoric acid is a colorless, fuming liquid which is an aqueous solution of hydrogen fluoride; densities of 20%, 40% and 60% acid at 20°C are 1.070, 1.135, and 1.215 g/mL, respectively; a 70% solution boils at 66.4°C; the same solution freezes at –69°C to a solid phase that has a composition of HF•H2O; vapor pressure of 70% solution at 25°C 150 torr; partial pressures of HF over HF—H2O solutions at 20°C are 0.412, 12.4 and 115.3 torr, respectively, for 20, 50 and 70% HF solutions by weight; equivalent conductance of 0.01 M and 0.1 M solutions at 20°C, 93.5 and 37.7 mhos-cm2, respectively; a weak acid, pKa 3.20 at 25°C; a 0.1M aqueous solution ionized <10%
DefinitionChEBI: A diatomic molecule containing covalently bonded hydrogen and fluorine atoms.
UsesCleaning cast iron, copper, brass; removing efflorescence from brick and stone, or sand particles from metallic castings; working over too heavily weighted silks; frosting, etching glass and enamel; polishing crystal glass; decomposing cellulose; enameling and galvanizing iron; increasing porosity of ceramics. Its salts are used as insecticides and to arrest undesirable fermentation in brewing. Also used in analytical work to determine SiO2, etc.
ReactionsAlthough anhydrous hydrogen fluoride is a very strong acid, its aqueous solution, hydrofluoric acid, is weakly acidic, particularly when dilute. The Ka value of aqueous acid at 25°C is 6.46x10–4 mol/L. It is an excellent solvent for many inorganic fluorides, forming bifluoride anion:

HF + NaF → Na+ + HF2¯ At lower temperatures (below 200°C), HF forms molecular aggregates that are held by hydrogen bonding containing linear chains of –F—H—-F—H—- F—H—-. However, above this temperature the weak hydrogen bond breaks producing monomolecular HF. Thermal dissociation of HF into elements probably occurs only at very high temperatures. Forty to 50% HF probably dissociates around 4,000°C, indicating that it is one of the most stable diatomic molecules. The most important reactions of HF involve formation of inorganic fluoridesalts. HF gas or hydrofluoric acid reacts with oxides, hydroxides, carbonates, chlorides and other metal salts forming the corresponding fluorides. Some examples are:

Bi2O3 + 6HF → 2BiF3 + 3H2O

LiOH + HF → LiF + H2O

CaCO3 + 2HF → CaF2 +CO2 + H2O

FeCl3 + 3HF → FeF3 + 3HCl

CoCl2 + 2HF → CoF2 + 2HCl Reaction with potassium dichromate yields chromyl fluoride:

K2Cr2O7 + 6HF → 2CrO2F2 + 2KF + 3H2O When ammonia gas is bubbled through a 40% ice-cold solution of hydrofluoric acid, the product is ammonium fluoride:

NH3 + HF → NH4F The addition of equimolar amount of NaOH or Na2CO3 to 40% HF instantaneously precipitates NaF:

NaOH + HF → NaF + H2O Excess HF, however, yields sodium bifluoride, NaHF2:

NaOH + 2HF → NaHF2 + H2O Reaction with phosphorus trichloride yields phosphorus trifluoride; and with phosphoryl fluoride and sulfur trioxide, the product is phosphorus pentafluoride:

PCl3 + 3HF → PF3 + HCl

POF3 + 2HF + SO3 → PF5 + H2SO4

Air & Water ReactionsFumes in air. Fumes are highly irritating, corrosive, and poisonous. Generates much heat on dissolution [Merck, 11th ed., 1989]. Heat can cause spattering, fuming, etc.
Reactivity ProfileHydrofluoric acid attacks glass and any other silica containing material. May react with common metals (iron, steel) to generate flammable hydrogen gas if diluted below 65% with water. Reacts exothermically with chemical bases (examples: amines, amides, inorganic hydroxides). Can initiate polymerization in certain alkenes. Reacts with cyanide salts and compounds to release gaseous hydrogen cyanide. May generate flammable and/or toxic gases with dithiocarbamates, isocyanates, mercaptans, nitrides, nitriles, sulfides. Additional gas-generating reactions may occur with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (SO2), and carbonates. Can catalyze (increase the rate of) chemical reactions. Reacts explosively with cyanogen fluoride, methanesulfonic acid or glycerol mixed with nitric acid. Reacts violently with arsenic trioxide, phosphorus pentachloride, acetic anhydride, alkali metals, ammonium hydroxide, chlorosulfonic acid, ethylenediamine, fluorine, potassium permanganate, oleum, propylene oxide, vinyl acetate, mercury(II) oxide. Emits highly corrosive fumes of hydrogen fluoride gas when heated [Sax, 9th ed., 1996, p. 1839]. Contact with many silicon compounds and metal silicides causes violent evolution of gaseous silicon tetrafluoride [Mellor, 1956, Vol. 2, suppl. 1, p. 121].
HazardToxic by ingestion and inhalation, highly corrosive to skin and mucous membranes.
Health HazardAnhydrous hydrogen fluoride and hydrofluoric acid are extremely corrosive to all tissues of the body. Skin contact results in painful deep-seated burns that are slow to heal. Burns from dilute (<50%) HF solutions do not usually become apparent until several hours after exposure; more concentrated solutions and anhydrous HF cause immediate painful burns and tissue destruction. HF burns pose unique dangers distinct from other acids such as HCl and H2SO4: undissociated HF readily penetrates the skin, damaging underlying tissue; fluoride ion can then cause destruction of soft tissues and decalcification of the bones. Hydrofluoric acid and HF vapor can cause severe burns to the eyes, which may lead to permanent damage and blindness. At 10 to 15 ppm, HF vapor is irritating to the eyes, skin, and respiratory tract. Exposure to higher concentrations can result in serious damage to the lungs, and fatal pulmonary edema may develop after a delay of several hours. Brief exposure (5 min) to 50 to 250 ppm may be fatal to humans. Ingestion of HF can produce severe injury to the mouth, throat, and gastrointestinal tract and may be fatal. HF has not been reported to be a human carcinogen. No acceptable animal test reports are available to define the developmental or reproductive toxicity of this substance
Health HazardIngestion of an estimated 1.5 grams produced sudden death without gross pathological damage. Repeated ingestion of small amounts resulted in moderately advanced hardening of the bones. Contact of skin with anhydrous liquid produces severe burns. Inhalation of anhydrous hydrogen fluoride or hydrogen fluoride mist or vapors can cause severe respiratory tract irritation that may be fatal.
Fire HazardWhen heated, Hydrofluoric acid emits highly corrosive fumes of fluorides. Its corrosive action on metals can result in formation of hydrogen in containers and piping to create fire hazard. Toxic and irritating vapors are generated when heated. Will attack glass, concrete, and certain metals, especially those containing silica, such as cast iron. Will attack natural rubber, leather, and many organic materials. May generate flammable hydrogen gas in contact with some metals.
Fire HazardHydrogen fluoride is not a combustible substance
storageAll work with HF should be conducted in a fume hood to prevent exposure by inhalation, and splash goggles and neoprene gloves should be worn at all times to prevent eye and skin contact. Containers of HF should be stored in secondary containers made of polyethylene in areas separate from incompatible materials. Work with anhydrous HF should be undertaken using special equipment and only by well-trained personnel familiar with first aid procedures.
Purification MethodsIt can be purified by trap-to-trap distillation, followed by drying over CoF2 at room temperature and further distillation. Alternatively, it can be absorbed on NaF to form NaHF2 which is then heated under vacuum at 150o to remove volatile impurities. The HF is regenerated by heating at 300o and is stored with CoF3 in a nickel vessel, being distilled as required. (Water content should be ca 0.01%.) To avoid contact with base metal, use can be made of nickel, polychlorotrifluoroethylene and gold-lined fittings [Hyman et al. J Am Chem Soc 79 3668 1957]. An aqueous solution is hydrofluoric acid (see above). It is HIGHLY TOXIC and attacks glass.
IncompatibilitiesHF reacts with glass, ceramics, and some metals. Reactions with metals may generate potentially explosive hydrogen gas.
Flammability and ExplosibilityHydrogen fluoride is not a combustible substance
Waste DisposalExcess hydrogen fluoride and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines. For more information on disposal procedures, see Chapter 7 of this volume.
References[1] David J. Monk, and David S. Soane, A review of the chemical reaction mechanism and kinetics for hydrofluoric acid etching of silicon dioxide for surface micromachining applications, Thin Solid Films, 1993, vol. 232, 1-12
[2] P. Sanz-Gallen, S. Nogue, P. Munne and A. Faraldo, Hybocalcaemia and hypomagnesaemia due to hydrofluoric acid, Occup Med (Lond), 2001, vol. 51, 294-295
Hydrofluoric acid Preparation Products And Raw materials
Raw materialsSulfuric acid -->SULFURIC ACID-->Calcium chloride-->Calcium chloride hexahydrate-->Calcium fluoride-->Microvoid filter film-->HYDROGEN FLUORIDE GAS
Preparation ProductsZinc tetrafluoroborate-->ZINC TETRAFLUOROBORATE HYDRATE-->3-TRIFLUOROMETHYL BENZOTRICHLORIDE-->1,1,1-Trichlorotrifluoroethane-->Potassium fluoroaluminate-->1-CHLORO-3-FLUOROISOPROPANOL-->9-fluoro-11beta,21-dihydroxypregna-1,4,16-triene-3,20-dione 21-acetate -->emulsifier acid-->5-(trifluoromethyl)thiazol-2-amine-->Boron trifluoride acetonitrile complex-->TANTALUM(V) OXIDE-->Potassium heptadecafluoro-1-octanesulfonate-->2,4-Dichlorobenzotrifluoride-->9-Fluoro-11,16,17,21-tetrahydroxypregna-1,4-diene-3,20-dione 21-acetate-->2-Chloro-6-fluorotoluene-->Sevoflurane-->CHLOROTRIFLUOROMETHANE-->6alpha,9-difluoro-11beta,17,21-trihydroxypregna-1,4-diene-3,20-dione 17,21-di(acetate) -->6,9-Difluoropregn-4-ene-11,17,21-triol-3,20-dione17,21-diacetate-->1,3-Bis(trifluoromethyl)-benzene-->Sodium trifluoromethanesulfonate-->Lithium hexafluorophosphate-->Ethyl 2-methylbutyrate-->9-Fluoropregna-1,4-diene-11,17,21-triol-3,20-dione17,21-diacetate-->Potassium hexafluoraluminate-->Copper(II) borofluoride -->Barium fluoride-->Strontium fluoride-->Doxycycline-->Dichloromonofluoromethane-->Titanium tetrafluoride-->Magnesium fluoride-->1,1,1,2,3,3,3-Heptafluoropropane-->Lithium fluoride-->Neodymium trifluoride-->YTTRIUM FLUORIDE-->1-Chloro-1,1-difluoroethane-->Chromium(III) fluoride tetrahydrate-->CHROMIUM(III) FLUORIDE-->LANTHANUM FLUORIDE
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