Using Hydrofluoric Acid Safely

A presentation by Wolfgang J Sievert, Ph.D. Honeywell Specialty Chemicals Seelze GmbH Dept. Electronic Chemicals - TSD D-30918 Seelze - Germany wolfgang.sievert@honeywell.com

What is Hydrofluoric acid ?

Colorless liquid with strong irritating odor Weak mineral acid
But: attacks glass!

Properties of HF
Pungent odor already at low concentrations
Ö Decent warning property

Extremely corrosive acid Nonflammable Very soluble in water

Irritation to nose and throat at 3 ppm OSHA PEL = 3 ppm (8 hr shift) OSHA STEL = 6 ppm (15 min) IDLH = 30 ppm

OSHA PEL STEL IDLH

Occupational Safety and Health Administration Permissible Exposure Limit Short Term Exposure Limit Immediately Dangerous to Life and Health

HON-HF-Safety.PPT BSEC-TSD WJS

Common uses of HF
Industrial use of fluoropolymers
× Plastics production
Fluoropolymers

× Production & purification of radioactive materials
Uranium hexafluoride

× Microchip fabrication
Silicon etching

× Printed circuit board cleaning
Fluorinated solvents

×Glass etching

Frosted lamps, bottles

Source: elf Atochem

HON-HF-Safety.PPT BSEC-TSD WJS

000 l totes 5l Small scale industrial use 500 l IBCs × 10.How is HF commonly sold ? Package sizes × 500 ml. 1000 ml Analytical & research laboratories Commonly used packages × 2.8 l) × 200 l drums × 1.PPT BSEC-TSD WJS .000 l ISO Containers Concentrations × 40 % HF 48-51 % HF Subject to application and legislation HON-HF-Safety.5 l Gallons (3.

PPT BSEC-TSD WJS .Routes of entry Critical contact areas × Skin Most frequent Areas at risk × Respiratory tract × Eyes × Ingestion Rare HON-HF-Safety.

skin & eyes Secondary contamination × Victims exposed to HF via inhalation do not pose substantial risks of secondary contamination × Victims whose clothes or skin are contaminated present a risk of secondary contamination Man wearing fully encapsulated suit with breathing air supply working to stop a bad leak of HF in a refinery. HON-HF-Safety.PPT BSEC-TSD WJS .Types of exposure Most HF exposures occur by × Liquid exposure (splash) Dermal contact skin & eyes HF gas blow-out × Gas exposure Inhalation.

stechend riechende Flüssigkeit wassermischbar Der HF-Gehalt im Dampf entspricht ca.Prevention BETRIEBSANWEISUNG gemäß §20 GEFSTOFFV Stand 04. Notfallplan beachten! Säureschutzanzug. erst nach 1-2 Tagen erkennbar).PPT BSEC-TSD WJS . Gummistiefel. Beim Einatmen von größeren Mengen von hoch-konzentrierter Flußsäure (u.08. × Personal protective equipment × Training VERHALTEN IM GEFAHRFALL Notruf 290 Produkt ist nicht brennbar. zerstört Gewebe der Atemwege. dem in der Flüssigkeit GEFAHREN FÜR MENSCH UND UMWELT T+ C Sehr giftig Ätzend Sehr giftig beim Einatmen. Immer sofort die Gesundheitsstation rufen. Hilfe anfordern (Vorgesetzte informieren)! SACHGERECHTE ENTSORGUNG Ausgelaufenes Produkt mit sehr viel Wasser verdünnen und in die Chemiegosse spülen! Ist dies nicht möglich. safety valves etc.U. Labor GEFAHRSTOFFBEZEICHNUNG Flußsäure (alle Konzentrationen) Farblose.391) benachrichtigen. beschriften und nach spezieller Anweisung der Betriebsleitung entsorgen! General instruction for working with hazardous materials . Lager. medizinisches Fachpersonal ist erforderlich. Die verätzte Hautoberfläche gründlich abwaschen und anschließend sofort mit Calciumgluconatgel (befindet sich in den speziellen Erste-Hilfe-Kästen für HF) wiederholt einreiben! Augenkontakt : Mindestens 10 Minuten unter fließendem Wasser oder mit Augenwaschflaschen bei gespreizten Lidern ausgiebig spülen! Verschlucken : Kein Erbrechen vor Ort herbeiführen und nur bei Bewußtsein wiederholt in kleinen Schlucken reichlich Wasser trinken lassen! Einatmen :Person an die frische Luft bringen.Nr 1000 07.oder ABEK-Filter tragen. Haut und Kleidung in jedem Fall verhindern! Vorbeugenden Hautschutz anwenden. warm halten.Glas und silikathaltige Werkstoffe werden angegriffen! Schwach wassergefährdender Stoff (Wassergefährdungsklasse 1)! SCHUTZMASSNAHMEN UND VERHALTENSREGELN Jeden Kontakt sorgfältigst verhindern! Möglichst nur im geschlossenen System verarbeiten! System laufend auf Dichtigkeit kontrollieren! Auftretende Dämpfe und Nebel direkt an der Entstehungs.01.oder Austrittstelle absaugen! Einatmen von Dämpfen/Nebel . im Brandfall Löschmaßnahmen auf Umgebung abstimmen! Brandbekämpfung nur mit umluftunabhängigem Atemschutz unter Vollschutz! Dämpfe und Nebel mit Wassersprühstrahl niederschlagen! Ausgelaufenes Produkt mit sehr viel Wasser verdünnen und in die Chemiegosse spülen. benetzte Fläche mit ausreichend Bindemittel UNI-SAFE abstreuen und soweit möglich trocken aufnehmen! Reste in Kunststoff-(Polyethylen-)behältern sammeln. d. diese dicht verschließen. Verschlucken und bei Berührung mit der Haut! Verursacht schwerste Verätzungen (evtl.2000 Geltungsbereich und Tätigkeiten Umgang mit Gefahrstoff in Produktion.h. der nach einmaligem Gebrauch zu entsorgen ist! ERSTE HILFE Hautkontakt Notruf 444 : Mit viel Wasser abspülen (Notdusche)! Verunreinigte Kleidung sofort ausziehen. Die persönliche Schutzausrüstung hängt ab von der jeweiligen HFKonzentration und/oder Menge! Speziell bei offenem Umgang ist die QM-Arbeitsanweisung QMA-S-01 zum Tragen der persönlichen Schutzausrüstung sorgfältigst einzuhalten! × Engineering controls HF detectors. HF-feste Handschuhe (geschlossen zum Schutzanzug!) und Atemschutzmaske mit B. Vorgesetzte informieren und bei Auslaufen von größeren Mengen (>100 l) zusätzlich ARA (Tel.99 Unterschrift Best treatment for exposures is prevention × Administrative controls Work instructions. Berührung mit Augen. SOPs BTA . tödliches) Lungenödem möglich! Chronische Gesundheitsschäden möglich! Wirkt stark korrodierend! Metall. ruhen lassen. Haut und Verdauungswege. Augen.HF HON-HF-Safety.

This penetration causes tissue necrosis. characteristic of HF as a hazardous material × Corrosivity Weak mineral acid that on contact with live tissue produces immediate necrosis and pain at high concentrations but delayed in showing up at low concentrations At the air-tissue interface HF penetrates the cells as HF. How corrosive is HF? The initial extent of the burn depends on × Concentration × Temperature × Duration of contact × Quantity exposed to C HON-HF-Safety.HF is not like other acids 1.PPT BSEC-TSD WJS . Once absorbed it dissociates into [HFH]+ + F-.

HNO3 etc. × HF first aid treatment is not limited to washing off the skin × HF is readily absorbed into the skin × HF binds the Calcium and Magnesium in the body to form insoluble salts 2F. The photo was taken after a couple of days.PPT BSEC-TSD WJS . HON-HF-Safety.HF reacts differently Other than with HCl.+ Mg++ ð MgF2 Hypocalcemia and Hypomagnesemia can occur Small HF burn on the back of a man's hand. It was quickly treated by washing with water and applying calcium gluconate gel.The burn healed up with no problems.+ Ca++ ð CaF2 2F. It came from some grease which had absorbed a little HF.

PPT BSEC-TSD WJS .Delayed reaction The onset of pain depends on the concentration Concentration × <1-20 % HF × 20-50 % HF × 50-70 % HF × > 70 % HF Reaction up to 24 hours 1-8 hours less than 1 hour immediate Minor HF burn caused by splashing of diluted HF on a man's leg. The area was treated with towels soaked in iced benzalkonium chloride 0. After two hours the man was aware of the pain and went to medical treatment.13 % for 1 hour. HON-HF-Safety. The burn was OK the next day.

characteristic of HF as a hazardous material × Toxicity Once absorbed HF forms toxic soluble salts.+ K+ ð KF The soluble salts that form in the individual have cellular toxicity properties. F.PPT BSEC-TSD WJS . How toxic is HF? × Interferes with calcium and magnesium metabolism by forming insoluble salts × Direct cellular poisoning effects through the formation of soluble salts T+ HON-HF-Safety.HF is not like other acids 2.+ Na+ ð NaF F.

HON-HF-Safety.HF is not like other acids Fatal Statistics × As little as 7 ml of anhydrous HF in contact with the skin untreated can bind all the free calcium in a normal size adult male × With burns involving greater than 25 square inches (161 cm2) significant and sometimes fatal hypocalcemia can occur × That is equivalent to exposure of 1 % of BSA to HF 50 % or greater × Or exposure of 5 % of BSA to any HF solution 1 % BSA (Body Surface Area) = Palm of hand.PPT BSEC-TSD WJS .

Planning for emergency Training × Every individual working with HF must be trained and authorized × Every individual working with HF must be familiar with the work place related SOP (Standard Operation Procedure) Using HF Safely T+ Remember: The best treatment is prevention HON-HF-Safety.PPT BSEC-TSD WJS .

PPT BSEC-TSD WJS .Planning for emergency Standard Operation Procedure SOP × Buddy System Never work alone! × Engineering Controls Early warning system Men wearing fully encapsulated suit with breathing air supply working on a part removed from an HF application. HON-HF-Safety.

PPT BSEC-TSD WJS .Planning for emergency SOP × Emergency Equipment Remember: Immediate action is essential First aid box wall mounted close to critical areas. HON-HF-Safety.

PPT BSEC-TSD WJS .Planning for emergency SOP × Personal Protective Equipment Never work without it! Remember: The work instruction tells what to use HON-HF-Safety.

Dilute HF is indistinguishable from water HON-HF-Safety.Planning for emergency SOP × Label all containers Never work without it! × Label all reactors and pipes × Label all residues and wastes Remember: HF warning labels on UHP HF manufacturing unit.PPT BSEC-TSD WJS .

Planning for emergency SOP × Post the working area Never work without it! Remember: Risk awareness is the first step HON-HF-Safety.PPT BSEC-TSD WJS .

PPT BSEC-TSD WJS .Planning for emergency SOP × Splash protection × Closed systems Remember: Proper design reduces the risks and helps to control the hazards Filling area with transparent splash protection and clean room environment HON-HF-Safety.

Planning for emergency SOP × Closed systems × Safe connections Remember: Minimize the risk of spills Closed system filling unit with Fluoroware Quick Connect HON-HF-Safety.PPT BSEC-TSD WJS .

a safe and easy way to make close connections HON-HF-Safety.Planning for emergency SOP × Closed systems × Safe connections Remember: Minimize the risk of spills Fluoroware Quick Connect .PPT BSEC-TSD WJS .

PPT BSEC-TSD WJS .Planning for emergency SOP × Closed systems × Safe connections × Full personal protection Remember: Always follow the SOP instructions Person filling a drum within the clean room area using Fluoroware Quick Connect HON-HF-Safety.

Think .PPT BSEC-TSD WJS . Have the victim remove all contaminated clothing while under the shower.Emergency happens .Think × Keep cool! × Activate the buddy system Help individual to eyewash /safety shower Flush the area with large amounts of water for 5 minutes.what now? Think . jewelry × Remove goggles last Face water and pull over head × Do not contaminate self × Maximum time is 5 minutes HON-HF-Safety. shoes. Primary Decontamination × Find eyewash / safety shower × Remove all contaminated clothes.

PPT BSEC-TSD WJS .First aid Safety shower & eyewash Emergency First Aid center HON-HF-Safety.

PPT BSEC-TSD WJS .First aid Eyes × Use eye wash for 5 minutes × Seek medical attention Remember: Any individual contaminated with HF must seek medical attention HON-HF-Safety.

5 cm or 4 cm Ø × Start self application of calcium gluconate gel Note the time of initiation of the application Marked area indicates the size of approx.First aid Skin exposure × Minor burns × Major burns more that 2 square inches = 3.5 x 3. × Must seek medical attention HON-HF-Safety.5 cm². 2 square inches or 12.5 x 3.PPT BSEC-TSD WJS .5 cm or 4 cm Ø less that 2 square inches = 3.

5 % calcium gluconate gel for further self treatment. 5 % HF 48 hours later. The patient was sent home with a 2.Treatment of choice Calcium gluconate gel × Neutralizes the HF Binds the fluoride ion to prevent deep tissue distruction and systemic absorption × Easy to use × Treatment can be started immediately × Treatment fast and effective Victim reported the exposure to approx.5 % calcium gluconate bath for 1 hour. The hand was treated with a 2. HON-HF-Safety.PPT BSEC-TSD WJS .

× Seek medical attention HON-HF-Safety.PPT BSEC-TSD WJS .First aid Inhalation × Inhalation hazards result from exposure to gas as well as fumes from contaminated items Decontaminate everything contaminated and move to fresh air Ingestion × A conscious patient may be given high amounts of calcium or magnesium based antacid or only water × Do not induce vomiting × Seek medical attention × Emergency personnel should begin oxygen Application only by authorized personnel.

PPT BSEC-TSD WJS . nose. knees. anus. hand. groin × Area below nails.Secondary decontamination Secondary contamination Remember: × Victims exposed to HF vapors via inhalation do not pose significant risk of secondary contamination are contaminated with HF liquid or solution present a risk of secondary contamination by direct contact or through offgassing vapors Secondary decontamination May include examining and decontaminating the following × Ear canal. vagina × Folds of neck. feet × Areas covered with hair × Victims whose clothes or skin HON-HF-Safety. mouth.

PPT BSEC-TSD WJS .Remember Hydrofluoric acid is most hazardous to work with but it is also the chemical basis of the modern world HON-HF-Safety.