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
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

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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

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How is HF commonly sold ?

Package sizes
500 ml, 1000 ml
Analytical & research laboratories

Commonly used packages

2.5 l Gallons (3.8 l) 200 l drums 1,000 l totes

5l

Small scale industrial use

500 l IBCs

10,000 l ISO Containers

Concentrations
40 % HF 48-51 % HF
Subject to application and legislation

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Routes of entry
Critical contact areas
Skin
Most frequent

Areas

at risk

Respiratory tract

Eyes

Ingestion
Rare

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Types of exposure
Most HF exposures occur by
Liquid exposure (splash)
Dermal contact skin & eyes

HF gas blow-out

Gas exposure
Inhalation, 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.

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Prevention
BETRIEBSANWEISUNG
gem 20 GEFSTOFFV

Stand 04.08.99 Unterschrift

Best treatment for exposures is prevention

Administrative controls
Work instructions, SOPs

BTA - Nr 1000
07.01.2000

Geltungsbereich und Ttigkeiten Umgang mit Gefahrstoff in Produktion, Lager, Labor

GEFAHRSTOFFBEZEICHNUNG
Flusure (alle Konzentrationen)
Farblose, stechend riechende Flssigkeit wassermischbar Der HF-Gehalt im Dampf entspricht ca. dem in der Flssigkeit

GEFAHREN FR MENSCH UND UMWELT

T+
C

Sehr giftig

tzend

Sehr giftig beim Einatmen, Verschlucken und bei Berhrung mit der Haut! Verursacht schwerste Vertzungen (evtl. erst nach 1-2 Tagen erkennbar), d.h. zerstrt Gewebe der Atemwege, Augen, Haut und Verdauungswege. Beim Einatmen von greren Mengen von hoch-konzentrierter Flusure (u.U. tdliches) Lungendem mglich! Chronische Gesundheitsschden mglich! Wirkt stark korrodierend! Metall,Glas und silikathaltige Werkstoffe werden angegriffen! Schwach wassergefhrdender Stoff (Wassergefhrdungsklasse 1)!

SCHUTZMASSNAHMEN UND VERHALTENSREGELN

Jeden Kontakt sorgfltigst verhindern! Mglichst nur im geschlossenen System verarbeiten! System laufend auf Dichtigkeit kontrollieren! Auftretende Dmpfe und Nebel direkt an der Entstehungs- oder Austrittstelle absaugen! Einatmen von Dmpfen/Nebel , Berhrung mit Augen, Haut und Kleidung in jedem Fall verhindern! Vorbeugenden Hautschutz anwenden. Die persnliche Schutzausrstung hngt ab von der jeweiligen HFKonzentration und/oder Menge! Speziell bei offenem Umgang ist die QM-Arbeitsanweisung QMA-S-01 zum Tragen der persnlichen Schutzausrstung sorgfltigst einzuhalten!

Engineering controls
HF detectors, safety valves etc.

Personal protective equipment Training

VERHALTEN IM GEFAHRFALL

Notruf

290

Produkt ist nicht brennbar, im Brandfall Lschmanahmen auf Umgebung abstimmen! Brandbekmpfung nur mit umluftunabhngigem Atemschutz unter Vollschutz! Dmpfe und Nebel mit Wassersprhstrahl niederschlagen! Ausgelaufenes Produkt mit sehr viel Wasser verdnnen und in die Chemiegosse splen. Vorgesetzte informieren und bei Auslaufen von greren Mengen (>100 l) zustzlich ARA (Tel.391) benachrichtigen; Notfallplan beachten! Sureschutzanzug, Gummistiefel, HF-feste Handschuhe (geschlossen zum Schutzanzug!) und Atemschutzmaske mit B- oder ABEK-Filter tragen, der nach einmaligem Gebrauch zu entsorgen ist!

ERSTE HILFE
Hautkontakt

Notruf

444

: Mit viel Wasser absplen (Notdusche)! Verunreinigte Kleidung sofort ausziehen. Die vertzte Hautoberflche grndlich abwaschen und anschlieend sofort mit Calciumgluconatgel (befindet sich in den speziellen Erste-Hilfe-Ksten fr HF) wiederholt einreiben! Augenkontakt : Mindestens 10 Minuten unter flieendem Wasser oder mit Augenwaschflaschen bei gespreizten Lidern ausgiebig splen! Verschlucken : Kein Erbrechen vor Ort herbeifhren und nur bei Bewutsein wiederholt in kleinen Schlucken reichlich Wasser trinken lassen! Einatmen :Person an die frische Luft bringen, ruhen lassen, warm halten.

Immer sofort die Gesundheitsstation rufen; medizinisches Fachpersonal ist erforderlich; Hilfe anfordern (Vorgesetzte informieren)! SACHGERECHTE ENTSORGUNG
Ausgelaufenes Produkt mit sehr viel Wasser verdnnen und in die Chemiegosse splen! Ist dies nicht mglich, benetzte Flche mit ausreichend Bindemittel UNI-SAFE abstreuen und soweit mglich trocken aufnehmen! Reste in Kunststoff-(Polyethylen-)behltern sammeln, diese dicht verschlieen, beschriften und nach spezieller Anweisung der Betriebsleitung entsorgen!

General instruction for working with hazardous materials - HF

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HF is not like other acids

1. 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. Once absorbed it dissociates into [HFH]+ + F-. This penetration causes tissue necrosis.

How corrosive is HF? The initial extent of the burn depends on

Concentration Temperature Duration of contact Quantity exposed to
C

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HF reacts differently
Other than with HCl, 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- + Ca++ CaF2 2F- + Mg++ MgF2 Hypocalcemia and Hypomagnesemia can occur
Small HF burn on the back of a man's hand. It came from some grease which had absorbed a little HF. It was quickly treated by washing with water and applying calcium gluconate gel. The photo was taken after a couple of days.The burn healed up with no problems.

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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. After two hours the man was aware of the pain and went to medical treatment. The area was treated with towels soaked in iced benzalkonium chloride 0.13 % for 1 hour. The burn was OK the next day.

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HF is not like other acids

2. characteristic of HF as a hazardous material
Toxicity
Once absorbed HF forms toxic soluble salts. F- + Na+ NaF F- + K+ KF The soluble salts that form in the individual have cellular toxicity properties.

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+

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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.

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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

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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.

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Planning for emergency

SOP

Emergency Equipment

Remember:

Immediate action is essential

First aid box wall mounted close to critical areas.

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Planning for emergency

SOP
Personal Protective Equipment
Never work without it!

Remember:

The work instruction tells what to use

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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.

Dilute HF is indistinguishable from water

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Planning for emergency

SOP
Post the working area
Never work without it!

Remember:

Risk awareness is the first step

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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

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Planning for emergency

SOP
Closed systems Safe connections

Remember:

Minimize the risk of spills

Closed system filling unit with Fluoroware Quick Connect

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Planning for emergency

SOP
Closed systems Safe connections

Remember:

Minimize the risk of spills

Fluoroware Quick Connect - a safe and easy way to make close connections

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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

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Emergency happens - what now?

Think - Think - Think
Keep cool! Activate the buddy system
Help individual to eyewash /safety shower Flush the area with large amounts of water for 5 minutes. Have the victim remove all contaminated clothing while under the shower.

Primary Decontamination
Find eyewash / safety shower Remove all contaminated clothes, shoes, jewelry Remove goggles last
Face water and pull over head

Do not contaminate self

Maximum time is 5 minutes

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First aid
Safety shower & eyewash Emergency First Aid center

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First aid
Eyes
Use eye wash for 5 minutes Seek medical attention

Remember:

Any individual contaminated with HF must seek medical attention

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First aid
Skin exposure
Minor burns Major burns
more that 2 square inches = 3.5 x 3.5 cm or 4 cm

less that 2 square inches = 3.5 x 3.5 cm or 4 cm

Start self application of calcium gluconate gel

Note the time of initiation of the application
Marked area indicates the size of approx. 2 square inches or 12.5 cm.

Must seek medical attention

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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 % HF 48 hours later. The hand was treated with a 2.5 % calcium gluconate bath for 1 hour. The patient was sent home with a 2.5 % calcium gluconate gel for further self treatment.

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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.

Seek medical attention

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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, mouth, nose, anus, vagina Folds of neck, knees, groin Area below nails, hand, feet Areas covered with hair

Victims whose clothes or skin

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Remember

Hydrofluoric acid is most hazardous to work with but it is also the chemical basis of the modern world

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