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Safetygram 39 - ClF3

Safetygram 39 - ClF3

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Published by Nathaniel Wise
This chemical. This chemical sounds AWESOME, and I really want some. "The ClF3 dissolved the 30 cm (12 inch) thick concrete floor and another 90 cm (36 inches) of gravel underneath the spill. The fumes that were generated (chlorine trifluoride, hydrogen fluoride, chlorine, hydrogen chloride, etc.) severely corroded everything that was exposed.3 One eyewitness described the incident by stating, 'The concrete was on fire!'"
This chemical. This chemical sounds AWESOME, and I really want some. "The ClF3 dissolved the 30 cm (12 inch) thick concrete floor and another 90 cm (36 inches) of gravel underneath the spill. The fumes that were generated (chlorine trifluoride, hydrogen fluoride, chlorine, hydrogen chloride, etc.) severely corroded everything that was exposed.3 One eyewitness described the incident by stating, 'The concrete was on fire!'"

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Published by: Nathaniel Wise on Oct 28, 2011
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Safetygram #39 
Chlorine Trifluoride 
Introduction 
Chlorine trifluoride (ClF
3
) is a toxic, corrosive, veryreactive liquefied compressed gas packaged incylinders as a liquid under its own vapor pressureof 1.55 kg/cm
2
at 21°C (22 psia at 70°F). ClF
3
isa very useful chemical in operations requiring ahigh-energy fluorinating agent or incendiary mate-rial, especially since it can be handled at roomtemperatures. However, those same factors thatmake it quite useful also contribute to several highhazard potentials for the product. Air Products has been the primary manufacturerand distributor of ClF
3
in North America for the past35 years, and the compound represents one of thehighest-reactivity products that Air Products cur-rently manufactures or handles worldwide.
Lessons from History 
Fluorine (F
2
) has been recognized as the mostpowerful oxidizing agent of all known elements.Due to difficulties handling F
2
in its most reactivestate (liquid), substitutes were evaluated in thelate 1920s to find similarly reactive compoundswith easier handling. Ruff and Krug successfullyisolated ClF
3
in 1930 after experimental tests withchlorine monofluoride suggested the presence of ahigher fluoride species.
1
Liquid ClF
3
is consideredmore reactive than vapor-phase F
2
reactions sincemore moles of fluorinating agent are present perunit area of reactant surfaces. Also, liquid ClF
3
 may demonstrate even higher reactivity in certaincircumstances than liquid F
2
because the F
2
liquidtemperature is cryogenic, thus reducing its activitypotential.German interest in ClF
3
during World War IIprompted the first industrial bulk productioncapability for the material. The Germans producedClF
3
in tonnage quantities for military use inflamethrowers due the liquid’s extreme hypergolicnature with fuels (self-igniting) and as a generalincendiary material. Following the war, inter-est in the use of ClF
3
for organic synthesis work increased although the material was eventuallyconsidered to be too reactive for practical useand mostly abandoned for these applications.
2
 Synthesis reactions proved difficult to control andusually led to a wide variety of reaction by-products that were hazardous.Many fluorinating compounds were evaluated aspotent oxidizers for liquid-fueled rockets in the late1940s through the early 1950s to overcome thestorage and handling disadvantages of liquid F
2
.ClF
3
was first tested in the U.S. in 1948 on a liquidpropellant rocket motor using hydrazine as thefuel. Additional testing yielded favorable results.However, all rocket materials of construction(including metals and seals) that could contact ClF
3
 had to be scrupulously selected, cleaned, and pas-sivated to prevent the components from burningduring reaction.
3
ClF
3
was also recognized as anextremely hazardous propellant due to its re-activity, toxicity, and toxic by-products offluorination.During the liquid rocket propellant era, a majorincident involving ClF
3
occurred the first time aone-ton steel container was loaded with liquid ClF
3
 for bulk shipment. The container had been cooledwith dry ice to perform the liquid transfer and helpmake the product safer to handle, since the ClF
3
 vapor pressure would only be about 0.007 kg/cm
2
 (0.1 psia) in the subcooled state. However, the dryice bath embrittled the steel container wall, whichsplit while it was being maneuvered onto a dolly,instantaneously releasing 907 kg (2,000 lb) of coldClF
3
liquid onto the building floor. The ClF
3
dis-solved the 30 cm (12 inch) thick concrete floor andanother 90 cm (36 inches) of gravel underneaththe spill. The fumes that were generated (chlorinetrifluoride, hydrogen fluoride, chlorine, hydrogenchloride, etc.) severely corroded everything thatwas exposed.
3
One eyewitness described the inci-dent by stating, “The concrete was on fire!”
Warning:
Improper storage, handling or use of chlorine trifluoride can result in serious injury and/or prop-erty damage. Use this product in accordance with the Air Products Material Safety Data Sheet (MSDS).
 
In the 1990s the semiconductor industry beganusing ClF
3
in the cleaning process for certainchemical vapor deposition (CVD) tool chambers.In situ cleaning of the tool was desirable becausethe solid residues on the chamber interior wereremoved from the walls without dismantling thetool or risking personnel exposure to the hazardousresidues or cleaning agents. It also yielded quickerturnaround time for the tool to resume waferprocessing. The high reactivity of ClF
3
allowed theoperation to be accomplished at relatively lowtemperatures, without requiring plasma or hightemperature heating to dissociate it for use duringthe cleaning process. The use of vapor-phase ClF
3
 for CVD chamber cleaning has demonstrated theability to prolong chamber component life throughthe lack of high temperature, plasma use, and tooldismantling requirements.Because the use of ClF
3
in semiconductor appli-cations had increased due to its excellent per-formance in tool chamber cleaning, Air Productsdecided to empirically test the reactivity of ClF
3
 with materials of construction, personal protec-tive equipment, contaminants commonly foundin systems and equipment, and other materialsthat may come into contact with the product. ThisSafetygram discusses the results of these testsand provides current recommendations to thosewho are manufacturing, handling, and performingemergency response with chlorine trifluoride.
Safety Considerations 
Health 
Chlorine trifluoride is toxic by itself and also reactswith moisture to form a variety of other toxic andcorrosive materials, including hydrofluoric acid.When the product escapes into the environment,it hydrolyzes with the moisture in the air or, inthe case of human contact, with the moisture inthe human body. Direct contact with ClF
3
vaporor liquid can result in a thermal burn in additionto the chemical burns produced by the hydrolysisproducts. See Figure 1 to see the result of directproduct contact with a piece of raw chicken beingused to simulate flesh.Since hydrogen fluoride is the major product ofhydrolysis, the health hazards associated withhydrofluoric acid (HF) can be considered as pri-mary health hazards for ClF
3
. Medical treatmentfor hydrofluoric acid exposures is very specialized. Air Products’ Safetygram-29, “Treatment Protocolfor Hydrofluoric Acid Burns,” provides detailedinformation on the health effects and treatmentfor HF. All users of ClF
3
should use copies of thisSafetygram to educate their employees, emer-gency people and local medical providers so theymay know in advance what is required to addressthese exposures in the way of supplies and treat-ment. It should be noted that hydrofluoric acidexposure requires immediate specific and special-ized medical treatment. Not only can this strongacid cause burns, but also the fluoride ion can bequickly absorbed through the skin, attack under-lying tissues, and be absorbed into the blood-stream. If inhaled in high concentrations, HF cancause obstruction of the airway and acute pulmo-nary edema.Table 2 gives the exposure levels for chlorine tri-fluoride and hydrogen fluoride.
Reactivity 
Chlorine trifluoride is hypergolic (will initiate thecombustion of many materials without an ignitionsource) with many materials. It is extremely re-active with most inorganic and organic materials.These reactions can be very violent or in somecases explosive. Therefore, all materials that comeinto contact with chlorine trifluoride must beevaluated.
Hydrolysis 
 
Chlorine trifluoride hydrolyzes rapidly with moistureto form mostly hydrogen fluoride along with hydro-gen chloride, chlorine monofluoride, and a varietyof oxyhalogen compounds. The oxyhalogens mayinclude chlorine dioxide, chlorous acid, chlorineoxyfluoride and oxygen difluoride.
Table 1
Physical and Chemical Properties 
Molecular Weight 92.447Boiling Point (1 atm) 11.75ºC (53.15ºF)Melting Point
-
76.32ºC (
-
105.38ºF)Gas Density (21.1°C) 3.913 kg/m
3
(0.2443 lb/ft
3
)Specific Volume (21.1°C) 0.2556 m
3
 /kg (4.094 ft
3
 /lb)Specific Gravity (air = 1) 3.260 Vapor Pressure (21.1°C) 1.55 kg/cm
2
(21.5 psia)Critical Temperature 153ºC (308ºF)Critical Pressure 57 atm (308 psia) Appearance Gas/colorlessLiquid/pale greenSolid/white
Odor varies with hydrolysis products; low concentrations are described as bleach-like while higherconcentrations are described as acidic or suffocating.
Figure 1
Vapor and Liquid Release on Raw Chicken 
 
Table 2 
Exposure Levels for Chlorine Trifluoride 
LC 
(50) 
299 ppm for 1 hour rat (death due to respiratoryfailure)
OSHA PEL 
0.1 ppm Ceiling
ACGIH TLV 
0.1 ppm Ceiling
NIOSH IDLH 
20 ppm
AIHA ERPGs 
ERPG-1 = 0.1 ppmERPG-2 = 1 ppmERPG-3 = 10 ppm
Proposed AEGL Values for Chlorine Trifluoride 
Classification 10-min 30-min 1-hour 4-hour 8-hour 
 AEGL-1 0.7 ppm 0.7 ppm 0.35 ppm 0.09 ppm 0.04 ppm AEGL-2 6.2 ppm 6.2 ppm 3.1 ppm 0.77 ppm 0.39 ppm AEGL-3 81 ppm 27 ppm 14 ppm 3.4 ppm 1.7 ppm
Exposure Levels for Hydrogen Fluoride 
LC 
(50) 
966 ppm for 1 hour rat
OSHA PEL 
3 ppm TWA 
ACGIH TLV 
3 ppm Ceiling
NIOSH IDLH 
30 ppm
Proposed AEGL Values for Hydrogen Fluoride 
Classification 10-min 30-min 1-hour 4-hour 8-hour 
 AEGL-1 2 ppm 2 ppm 2 ppm 1 ppm 1 ppm AEGL-2 95 ppm 34 ppm 24 ppm 12 ppm 8.6 ppm AEGL-3 170 ppm 62 ppm 44 ppm 22 ppm 15 ppm
Fire Potential 
Chlorine trifluoride is a strong oxidizer that canessentially decrease the ignition temperature ofpotential fuels, including materials of construc-tion (e.g., metals) for ClF
3
systems. Furthermore,because of chlorine trifluoride’s extreme reactiv-ity, there is a high potential for contamination toserve as an ignition source. Friction between twomaterials can generate fine particles (contami-nants), which may ignite from the heat generated.Contaminants in chlorine trifluoride systems poten-tially can burn with sufficient heat to propagate theignition to system components.Due to this fire potential, Air Products conductedextensive exposure tests on a variety of materialsused in personal protective equipment, operatingsystems, building materials, and materials thatchlorine trifluoride might contact in the event of arelease. These materials were tested for exposureto both vapor and liquid phases of chlorine trifluo-ride. Throughout the tests, materials that did notreact with ClF
3
were immediately compromised bythe presence of contamination (see Figure 2).
Containers 
Chlorine trifluoride is shipped as a liquefiedcompressed gas under its own vapor pressure of1.44 atm @ 21.1ºC (21.5 psia @ 70ºF). Althoughtransportation regulations permit the use of low-pressure cylinders (working pressure <40 atm or600 psig), Air Products only uses high-pressurecylinders that provide an added measure of safetydue to their increased ruggedness.
Cylinders 
 A typical cylinder is a hollow tube with a closedbase that permits the container to stand upright.The opposite end is tapered to a small openingthat is threaded to accommodate the installationof a valve. A threaded neck ring is attached to thethreaded end to allow a protective cylinder valvecap to be installed.Carbon steel is the primary material of construc-tion for chlorine trifluoride. Air Products speciallyselects cylinders for their internal finish, internallyblasts them to remove any residual scale and slag,and cleans them to oxidizer service requirements.Pressure relief devices are not permitted on chlo-rine trifluoride cylinders.For more information on the safe handling of cylin-ders, see Air Products’ Safetygram-10, “Handling,Storage, and Use of Compressed Gas Cylinders.”
Figure 2 
Vapor CIF 
Exposure to Polyethylene Tubing, Clean and Used 

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