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Comprehensive information on hydrofluoric acid (HF), including its chemical properties, exposure limits, health hazards, and handling procedures. It covers the effects of HF on various routes of exposure, such as dermal, inhalation, and oral, and discusses the potential for systemic toxicity and fatalities. The document also emphasizes the importance of proper protective equipment and spill response measures.
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Hydrofluoric acid (HF) differs from other acids because the fluoride ion readily penetrates the skin, causing destruction of deep tissue layers, including bone. Pain associated with exposure to solutions of HF (1-50%) may be delayed for 1-24 hours. If HF is not rapidly neutralized and the fluoride ion bound, tissue destruction may continue for days and result in limb loss or death. HF is similar to other acids in that the initial extent of a burn depends on the concentration, the temperature, and the duration of contact with the acid.
Chemical Name : Hydrofluoric Acid Chemical Family : Inorganic Acid Chemical Formula : HF Molecular Weight : 20. CAS Number : 7664-39-
Description : Colorless gas or fuming liquid (below 153°F) with a strong, irritating odor. Boiling Point : 153° F (67° C) Specific Gravity : 1.2 (H 2 O = 1) Ionization Potential : 15.98 eV
Synonyms : HF, Hydrofluoride, Fluoric Acid
Solubility in Water : Miscible Vapor Density : 2.21 (Air = 1) Odor Threshold : 0.5 – 3 ppm (caution: reported range is very broad)
ACGIH Threshold Limit Value (TLV) : Listed as Hydrogen fluoride, as F: (ACGIH, 2000)
OSHA Permissible Exposure Limit (PEL) : Listed as Hydrogen fluoride (as F) (OSHA, 1996a)
NIOSH Recommended Exposure Limit (REL) : (NIOSH, 1996)
NOTE: A TWA concentration is for an 8-hour workday (ACGIH-TLV, OSHA-PEL) and up to a 10-hour workday (NIOSH-REL) during a 40-hour workweek. A STEL value is a 15-minute TWA exposure that should not be exceeded at any time during a workday. A Ceiling value should never be exceeded for even an “instantaneous” exposure period.
DERMAL EXPOSURE - HF is an inorganic acid that is highly corrosive and readily penetrates the skin, causing deep tissue layer destruction. Severity and rapidity of onset of signs and symptoms depends on the concentration, duration of exposure, and penetrability of the exposed tissue. Pain may be delayed.
DECONTAMINATION – Remove all exposed clothing taking necessary precautions to prevent self- exposure. Immediately wash all exposed areas with copious amounts of water.
CALCIUM GLUCONATE OR CARBONATE GEL – Application of 2.5 to 33% calcium gluconate or carbonate gel or slurry, either placed into a surgical glove into which the affected extremity is then placed, or rubbed into the burn, is recommended. This therapy is more easily administered and less painful than infiltration. Use calcium gluconate for dermal treatment only.
CALCIUM GLUCONATE INFILTRATION – (Medical Assistance) – Continued tissue destruction and pain may be minimized by subcutaneous administration of calcium gluconate. Consider infiltration with CALCIUM GLUCONATE if (1) exposure results in immediate tissue damage or (2) erythema and pain persist following adequate irrigation. Infiltrate each square centimeter of affected dermis and subcutaneous tissue with about 0.5 mL of 10% CALCIUM GLUCONATE using a 30 gauge needle. Repeat as needed to control pain. Split or remove nails to treat nail bed burns. The earlier this is administered, the more rapidly symptoms resolve. CAUTION: Avoid administering large volumes of subcutaneous calcium gluconate as this will result in decreased tissue perfusion and potential necrosis.
DO NOT USE CALCIUM CHLORIDE – Calcium chloride is irritating to the tissues and may cause injury.
SYSTEMIC TOXICITY – Systemic fluoride toxicity may result from ingestion, inhalation, or extensive dermal burns. Hypocalcemia, hypomagnesemia, hyperkalemia (potassium), pulmonary edema, metabolic acidosis, ventricular arrhythmias, and death are possible.
EYE EXPOSURE – May result in severe ocular damage with concentrations greater than 0.5%. Fume exposure commonly causes eye irritation and can also cause ocular injury. Signs and symptoms may be delayed.
ORAL EXPOSURE – Ingestion may result in vomiting and abdominal pain; painful necrotic lesions, hemorrhagic gastritis, and pancreatitis have been reported after significant exposure. Rectal administration has caused acute colitis with perforation.
INHALATION EXPOSURE – Inhalation of hydrofluoric acid vapors may cause severe throat irritation, cough, dyspnea, cyanosis, lung injury and pulmonary edema resulting in death.
Store in a cool, dry place away from incompatible materials. HF reacts with many materials therefore avoid contact with glass, concrete, metals, water, other acids, oxidizers, reducers, alkalis, combustibles, organics and ceramics. Store in containers made of polyethylene or fluorocarbon plastic, lead, or platinum. Place storage bottles in polyethylene secondary containment trays.
Never store HF in glass containers.
Ensure all areas where HF is used are equipped with proper spill response equipment. Small spills can be neutralized by covering with magnesium sulfate (dry) and absorbed with spill control pads or other absorbent materials. Add sodium bicarbonate or magnesium oxide to any absorbent and place in a plastic container for disposal. Wash the spill site with a sodium bicarbonate solution.
3M's Universal Sorbent is recommended, as it does not react with HF. If the spill is large, in a confined space, or in an area where there is not adequate ventilation, evacuate the room and immediately report the spill to 911.
Hydrogen fluoride is non-combustible, but may create irritating and corrosive fumes of fluorides when heated or in combination with steam or water. Since hydrogen fluoride does not burn, use an extinguishing agent suitable for surrounding fire. Use water to absorb fumes and keep containers cool. Heat released when water or steam combines with hydrogen fluoride or hydrofluoric acid could be hazardous. For fires involving hydrofluoric acid, apply water in flooding quantities. Hydrofluoric acid and various metals may form hydrogen (extremely flammable gas) creating a fire hazard.
Flammability Class: Nonflammable Gas Flash Point: NA Lower Explosion Limit: NA Upper Explosion Limit: NA
Extract from Australian Institute of Occupational Hygienists Newsletter, December 1994:
An accident in Perth highlighted just how hazardous this acid can be and it is worth recounting for the benefit of any lab working or hygienists whose work may involve advising others who use this substance.
On November 12, a 37 year old man died in the Intensive Care Unit of Fremantle Hospital after he accidentally splashed about 100 ml of a 70% solution on his right leg on October 28. It was estimated that the extent of the spill covered about 10% of his total body area. The individual was working as a technician in a small paleontology laboratory, which was attached to a private residence. HF is used in the industry to digest silicates in ore samples. The victim immediately attempted to remove the spill from his clothing hosing himself down with a hose attached to a sink in the laboratory. He then ran from the laboratory to the swimming pool in the garden, and he remained in the pool until the ambulance arrived within the hour. At the time he appeared confused, possibly as a result of shock.
The following week his right leg was amputated, however despite this, the individual eventually succumbed to the toxic effects of the hydrofluoric acid 2 weeks after the initial spill. There are a number of points that need to be emphasized as a result of this, which are relevant to all users of HF:
Posted By: William M. Rich, MD Faculty, University Med. Center
Hydrogen fluoride is a gas which when in solution with water forms hydrofluoric acid, HF. Although a weak acid, i.e., it is not strongly disassociated, is used to etch glass. Like it's sister, HCl acid, it reacts with water with the release of heat and can cause burns on the skin. Hydrofluoric acid has an even more detrimental effect that can affect many internal structures. Fatalities have been reported from a skin exposure to as little as 2.5% of body surface area. The weak disassociation allows it to be absorbed through the skin as the intact molecule.
Once it penetrates the skin it slowly disassociates into the hydrogen ion and fluoride ion. The fluoride ion affects tissue integrity and metabolism by liquefaction necrosis, decalcification and destruction of bone, and production of insoluble salts. Loss of calcium, (hypocalcemia), results from precipitation of calcium form the blood as CaF2. This will eventually result in loss of calcium from the bones to try to equilibrate the decreased serum calcium. This may be a delayed fatal event. The rapid development of hypocalcemia can be rapidly fatal because calcium is important for muscles, including cardiac muscle, to function properly. Without calcium, many metabolic pathways breakdown.
Fluoride from any source has the same toxicity. A mass poisoning occurred at a state hospital many years ago when a bug poison containing NaF was mistaken for powdered milk and added to scrambled eggs. There were reported to be 47 deaths. In some regions of the country the levels of fluoride in the water are too high and this causes mottling of the teeth and loss of calcium from the bones.
Inhalation of HF produces an immediate injury to the lining of the lungs with hemorrhage pulmonary edema and death. It may take only about 5 minutes of exposure to inhaled HF to produce death in a couple of hours.
All in all, fluoride from whatever source can be very dangerous.