Safetygram #39
Chlorine Trifluoride
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).
Introduction
est in the use of ClF3 for organic synthesis work
Chlorine trifluoride (ClF3) is a toxic, corrosive, very
increased although the material was eventually
reactive liquefied compressed gas packaged in
considered to be too reactive for practical use
cylinders as a liquid under its own vapor pressure
and mostly abandoned for these applications.2
of 1.55 kg/cm2 at 21掳C (22 psia at 70掳F). ClF3 is
Synthesis reactions proved difficult to control and
a very useful chemical in operations requiring a
usually led to a wide variety of reaction by-
high-energy fluorinating agent or incendiary mate-
products that were hazardous.
rial, especially since it can be handled at room
temperatures. However, those same factors that
Many fluorinating compounds were evaluated as
make it quite useful also contribute to several high
potent oxidizers for liquid-fueled rockets in the late
hazard potentials for the product.
1940s through the early 1950s to overcome the
storage and handling disadvantages of liquid F2.
Air Products has been the primary manufacturer
ClF3 was first tested in the U.S. in 1948 on a liquid
and distributor of ClF3 in North America for the past
propellant rocket motor using hydrazine as the
35 years, and the compound represents one of the
fuel. Additional testing yielded favorable results.
highest-reactivity products that Air Products cur-
However, all rocket materials of construction
rently manufactures or handles worldwide.
(including metals and seals) that could contact ClF3
Lessons from History had to be scrupulously selected, cleaned, and pas-
sivated to prevent the components from burning
Fluorine (F2) has been recognized as the most during reaction.3 ClF3 was also recognized as an
powerful oxidizing agent of all known elements. extremely hazardous propellant due to its re-
Due to difficulties handling F2 in its most reactive activity, toxicity, and toxic by-products of
state (liquid), substitutes were evaluated in the fluorination.
late 1920s to find similarly reactive compounds
with easier handling. Ruff and Krug successfully During the liquid rocket propellant era, a major
isolated ClF3 in 1930 after experimental tests with incident involving ClF3 occurred the first time a
chlorine monofluoride suggested the presence of a one-ton steel container was loaded with liquid ClF3
higher fluoride species.1 Liquid ClF3 is considered for bulk shipment. The container had been cooled
more reactive than vapor-phase F2 reactions since with dry ice to perform the liquid transfer and help
more moles of fluorinating agent are present per make the product safer to handle, since the ClF3
unit area of reactant surfaces. Also, liquid ClF3 vapor pressure would only be about 0.007 kg/cm2
may demonstrate even higher reactivity in certain (0.1 psia) in the subcooled state. However, the dry
circumstances than liquid F2 because the F2 liquid ice bath embrittled the steel container wall, which
temperature is cryogenic, thus reducing its activity split while it was being maneuvered onto a dolly,
potential. instantaneously releasing 907 kg (2,000 lb) of cold
ClF3 liquid onto the building floor. The ClF3 dis-
German interest in ClF3 during World War II solved the 30 cm (12 inch) thick concrete floor and
prompted the first industrial bulk production another 90 cm (36 inches) of gravel underneath
capability for the material. The Germans produced the spill. The fumes that were generated (chlorine
ClF3 in tonnage quantities for military use in trifluoride, hydrogen fluoride, chlorine, hydrogen
flamethrowers due the liquid鈥檚 extreme hypergolic chloride, etc.) severely corroded everything that
nature with fuels (self-igniting) and as a general was exposed.3 One eyewitness described the inci-
incendiary material. Following the war, inter- dent by stating, 鈥淭he concrete was on fire!鈥?
In the 1990s the semiconductor industry began
Table 1
using ClF3 in the cleaning process for certain
chemical vapor deposition (CVD) tool chambers. Physical and Chemical Properties
In situ cleaning of the tool was desirable because
Molecular Weight 92.447
the solid residues on the chamber interior were
removed from the walls without dismantling the Boiling Point (1 atm) 11.75潞C (53.15潞F)
tool or risking personnel exposure to the hazardous
Melting Point -76.32潞C (-105.38潞F)
residues or cleaning agents. It also yielded quicker
turnaround time for the tool to resume wafer
Gas Density (21.1掳C) 3.913 kg/m3 (0.2443 lb/ft3)
processing. The high reactivity of ClF3 allowed the
operation to be accomplished at relatively low Specific Volume (21.1掳C) 0.2556 m3/kg (4.094 ft3/lb)
temperatures, without requiring plasma or high
Specific Gravity (air = 1) 3.260
temperature heating to dissociate it for use during
the cleaning process. The use of vapor-phase ClF3 Vapor Pressure (21.1掳C) 1.55 kg/cm2 (21.5 psia)
for CVD chamber cleaning has demonstrated the
Critical Temperature 153潞C (308潞F)
ability to prolong chamber component life through
the lack of high temperature, plasma use, and tool Critical Pressure 57 atm (308 psia)
dismantling requirements.
Appearance Gas/colorless
Because the use of ClF3 in semiconductor appli- Liquid/pale green
Solid/white
cations had increased due to its excellent per-
formance in tool chamber cleaning, Air Products
Odor varies with hydrolysis products; low concentrations are described as bleach-like while higher
decided to empirically test the reactivity of ClF3 concentrations are described as acidic or suffocating.
with materials of construction, personal protec-
tive equipment, contaminants commonly found
Figure 1
in systems and equipment, and other materials
that may come into contact with the product. This
Vapor and Liquid Release on Raw Chicken
Safetygram discusses the results of these tests
and provides current recommendations to those
who are manufacturing, handling, and performing
emergency response with chlorine trifluoride.
Safety Considerations
Health
Chlorine trifluoride is toxic by itself and also reacts
with moisture to form a variety of other toxic and
corrosive materials, including hydrofluoric acid.
When the product escapes into the environment,
it hydrolyzes with the moisture in the air or, in
the case of human contact, with the moisture in
the human body. Direct contact with ClF3 vapor
may know in advance what is required to address Reactivity
or liquid can result in a thermal burn in addition
these exposures in the way of supplies and treat-
to the chemical burns produced by the hydrolysis
ment. It should be noted that hydrofluoric acid
products. See Figure 1 to see the result of direct Chlorine trifluoride is hypergolic (will initiate the
exposure requires immediate specific and special-
product contact with a piece of raw chicken being combustion of many materials without an ignition
ized medical treatment. Not only can this strong
used to simulate flesh. source) with many materials. It is extremely re-
acid cause burns, but also the fluoride ion can be active with most inorganic and organic materials.
Since hydrogen fluoride is the major product of quickly absorbed through the skin, attack under- These reactions can be very violent or in some
hydrolysis, the health hazards associated with lying tissues, and be absorbed into the blood- cases explosive. Therefore, all materials that come
hydrofluoric acid (HF) can be considered as pri- stream. If inhaled in high concentrations, HF can into contact with chlorine trifluoride must be
mary health hazards for ClF3. Medical treatment cause obstruction of the airway and acute pulmo- evaluated.
for hydrofluoric acid exposures is very specialized. nary edema.
Air Products鈥? Safetygram-29, 鈥淭reatment Protocol Hydrolysis
Table 2 gives the exposure levels for chlorine tri-
for Hydrofluoric Acid Burns,鈥? provides detailed Chlorine trifluoride hydrolyzes rapidly with moisture
fluoride and hydrogen fluoride.
information on the health effects and treatment to form mostly hydrogen fluoride along with hydro-
for HF. All users of ClF3 should use copies of this gen chloride, chlorine monofluoride, and a variety
Safetygram to educate their employees, emer- of oxyhalogen compounds. The oxyhalogens may
gency people and local medical providers so they include chlorine dioxide, chlorous acid, chlorine
oxyfluoride and oxygen difluoride.
Fire Potential
Table 2
Chlorine trifluoride is a strong oxidizer that can
Exposure Levels for Chlorine Trifluoride essentially decrease the ignition temperature of
potential fuels, including materials of construc-
LC(50) 299 ppm for 1 hour rat (death due to respiratory
tion (e.g., metals) for ClF3 systems. Furthermore,
failure)
because of chlorine trifluoride鈥檚 extreme reactiv-
OSHA PEL ity, there is a high potential for contamination to
0.1 ppm Ceiling
serve as an ignition source. Friction between two
ACGIH TLV 0.1 ppm Ceiling
materials can generate fine particles (contami-
nants), which may ignite from the heat generated.
NIOSH IDLH 20 ppm
Contaminants in chlorine trifluoride systems poten-
AIHA ERPGs ERPG-1 = 0.1 ppm tially can burn with sufficient heat to propagate the
ERPG-2 = 1 ppm
ignition to system components.
ERPG-3 = 10 ppm
Due to this fire potential, Air Products conducted
Proposed AEGL Values for Chlorine Trifluoride
extensive exposure tests on a variety of materials
Classification 10-min 30-min 1-hour 4-hour 8-hour used in personal protective equipment, operating
systems, building materials, and materials that
AEGL-1 0.7 ppm 0.7 ppm 0.35 ppm 0.09 ppm 0.04 ppm
chlorine trifluoride might contact in the event of a
release. These materials were tested for exposure
AEGL-2 6.2 ppm 6.2 ppm 3.1 ppm 0.77 ppm 0.39 ppm
to both vapor and liquid phases of chlorine trifluo-
AEGL-3 81 ppm 27 ppm 14 ppm 3.4 ppm 1.7 ppm ride. Throughout the tests, materials that did not
react with ClF3 were immediately compromised by
Exposure Levels for Hydrogen Fluoride
the presence of contamination (see Figure 2).
LC(50) 966 ppm for 1 hour rat
Containers
OSHA PEL 3 ppm TWA
Chlorine trifluoride is shipped as a liquefied
ACGIH TLV 3 ppm Ceiling
compressed gas under its own vapor pressure of
NIOSH IDLH 1.44 atm @ 21.1潞C (21.5 psia @ 70潞F). Although
30 ppm
transportation regulations permit the use of low-
Proposed AEGL Values for Hydrogen Fluoride pressure cylinders (working pressure <40 atm or
600 psig), Air Products only uses high-pressure
Classification 10-min 30-min 1-hour 4-hour 8-hour
cylinders that provide an added measure of safety
AEGL-1 2 ppm 2 ppm 2 ppm 1 ppm 1 ppm due to their increased ruggedness.
AEGL-2 95 ppm 34 ppm 24 ppm 12 ppm 8.6 ppm
Cylinders
AEGL-3 170 ppm 62 ppm 44 ppm 22 ppm 15 ppm
A typical cylinder is a hollow tube with a closed
base that permits the container to stand upright.
The opposite end is tapered to a small opening
Figure 2
that is threaded to accommodate the installation
Vapor CIF3 Exposure to Polyethylene Tubing, Clean and Used of a valve. A threaded neck ring is attached to the
threaded end to allow a protective cylinder valve
cap to be installed.
Carbon steel is the primary material of construc-
tion for chlorine trifluoride. Air Products specially
selects cylinders for their internal finish, internally
blasts 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鈥? Safetygram-10, 鈥淗andling,
Storage, and Use of Compressed Gas Cylinders.鈥?
Figure 3 Figure 4
Manual Diaphragm Valve Pneumatic Diaphragm Valve
Lock Plug
(Alumite)
Ceodeux Monel 400 Spring
Springs
Loaded Diaphragm Valve for
Handwheel Nut
Chlorine Trifluoride Service
Piston
Handwheel (SS303)
CGA 72B
Actuator
Gland Nut 1.125-14NGO
(303 SS) Assembly
RH-EXT
4.76鈥? (Alumite)
O-Ring
(121 mm) (PTFE Coated)
Outlet Cap Stem
Upper Spindle
Assembly (SS303)
(303 SS)
Disk
(Duroplast)
Push Button Body
(303 SS)
Washer (SS316)
(TFE)
3/4鈥? Diaphragm
14 NGT
Diaphragm (303 SS)
(Ni 200)
Lower Spindle
(Ni 200)
Gasket
Spring
(Monel K500)
Sleeve Washer
Washer
Gland Nut (SS304) (SS631)
(Monel 400)
(SS304)
Body
(Monel 400)
Packing
(PTFE)
CGA 670
Screw
(SS304)
O-Ring
(NBR)
Insert Button Diaphragms (4)
(PCTFE) (SS403) (Ni Alloy)
Valves and Connections Table 3
Valves Valve Connections
USA
Containers in chlorine trifluoride service are CGA 670 728 Ultra High Integrity (DISS) Connection has been adopted by ISO.
equipped with one of several different valves. CP
UK BS 6
Grade cylinders are valved with an aluminum silica
bronze wrench-operated valve while Electronic France NF P
Grade cylinders are equipped with either a Monel
Japan JIS A (22 R)
spring-loaded diaphragm valve or a stainless steel
pneumatic diaphragm valve designed specifically
for chlorine trifluoride service. Cutaway drawings
Cylinder Storage and Handling Storage
and valve details are available in the Air Products
Safetygram-23, 鈥淐ylinder Valves,鈥? for the wrench-
Cylinders of chlorine trifluoride and other com- Cylinders should be secured in an upright position
operated valve. The spring-loaded diaphragm
pressed gases should be stored and handled in and stored in a well-ventilated area protected from
and pneumatic diaphragm valves are of unique
accordance with Compressed Gas Association the weather. The storage area should be secure
designs. Cutaway pictures of these valves appear
Pamphlet P-1, 鈥淪afe Handling of Compressed with limited access. The toxicity, reactivity and cor-
in Figures 3 and 4.
Gases in Containers.鈥? For more information, refer rosivity of ClF3 requires area monitoring for leakage
Valve Connections to Air Products鈥? Safetygram-10, 鈥淗andling, Storage, where the material is stored and used. Storage
and Use of Compressed Gas Cylinders.鈥? area temperatures should not exceed 125掳F (52掳C)
Valve connections for chlorine trifluoride vary by and should be free from combustible materials
country. Table 3 lists some of the connection stan- International or local regulations may require and ignition sources. Storage should be away
dards used in various countries. additional safeguards for storage or use. from heavily traveled areas and emergency exits.
Personnel must know and understand the Avoid areas where salt or other corrosive materi-
For more information on cylinder valve con- properties, proper uses, and safety precautions als are present to prevent cylinder deterioration.
nections, refer to Air Products鈥? Safetygram-31, for the specific product before using the product Valve protection caps and valve outlet seals must
鈥淐ylinder Valve Outlet Connections.鈥? or associated equipment. remain on cylinders when not connected for use.
When returning a cylinder to storage, the valve
outlet seal must be installed leak-tight. Separate
System Design, Preparation and
full and empty cylinders. Avoid excess inventory Most non-fluorinated elastomers show little or no
and storage time. Visually inspect stored cylinders resistance to ClF3. Others like NeopreneTM, rubber,
Operation
on a routine basis, at least weekly, for any indica- polyethylene and PVC have shown resistance
tion of leakage or other problems. Use a first-in, during short exposures but are very susceptible to
Chlorine trifluoride is a strongly oxidizing, toxic,
first-out inventory system, and keep up to date any contamination鈥攖he reaction of ClF3 with the
corrosive liquefied gas at typical storage tempera-
inventory records. The use of 鈥淔ULL,鈥? 鈥淚N USE,鈥? contaminant rapidly propagates to the elastomer.
tures. It is normally packaged in specially cleaned
and 鈥淓MPTY鈥? tags is highly recommended. Some and prepared carbon steel or stainless steel cyl-
Sealants and Lubricants
locales require special planning when storage of inders and is used as a vapor to limit its potential
ClF3 exceeds a specific amount. Before purchasing reactivity with system components and other TFE tape is the most common sealant used on
ClF3, contact the local authorities to determine the materials. Unless special precautions are taken, threaded connections in chlorine trifluoride service.
requirements for the storage of this material. ClF3 ClF3 should only be removed from cylinders as a It is important when assembling these connections
is typically stored in areas specifically designed for vapor. Care must be taken to prevent its condensa- not to expose the tape directly to the flow path. To
ClF3. Storage areas must be posted with the proper tion in piping or other equipment. avoid this, it is recommended the first thread be
signage, such as NFPA 704 ratings.
left uncovered.
Materials of Construction
Handling and Use
Lubricants of any kind should be avoided, if pos-
Metals
sible. If a lubricant must be used, a perfluorinated
Use only in well-ventilated areas designated for
type specially manufactured for use with fluorine
Most metals are compatible with chlorine trifluo-
ClF3. Use a suitable handcart designed for cylinder
products is required. Hydrocarbon-based lubricants
ride at ambient pressure and temperatures, pro-
movement. Do not drag, roll or slide cylinders.
must never be used in chlorine trifluoride service,
vided the metal is oxygen-cleaned and passivated
Never attempt to lift a cylinder by its cap. Secure
and even approved perfluorinated lubricants must
prior to exposure. Passivation allows the formation
cylinders at all times during storage, transport and
never be exposed to liquid ClF3.
of a thin metal fluoride surface that is resistant to
use. Use a pressure-reducing regulator or separate
further reaction with ClF3, and more importantly,
control valve to discharge gas from the cylinder.
System Preparation
allows a controlled reaction with any remaining
Never apply flame or local heat to any part of a
contaminants left behind by imperfect cleaning.
cylinder. Do not allow any part of the cylinder to Due to the potential for ignition, systems used for
It is this protective metal fluoride layer that helps
exceed 125掳F (52掳C). High temperature may cause chlorine trifluoride must be very carefully cleaned
determine a metal鈥檚 suitability for ClF3 service.
damage to the cylinder. If user experiences any to remove readily oxidized impurities and scru-
Some metals, such as molybdenum, titanium and
difficulty operating the cylinder valve, discontinue pulously maintained to prevent contamination.
tungsten, form fluorides that are relatively volatile.
use and contact the supplier. Use an adjustable Cleaning agents must be thoroughly removed
This makes these metals unsuitable for service
strap wrench to remove overly tight cylinder caps. prior to introducing ClF3 into systems (normally
with this product because the metal fluoride gradu-
To prevent accidental opening of the cylinder valve, by extensive purging with high-purity nitrogen or
ally volatizes off the surface, exposing new metal
never insert anything into the cap holes to assist in other inert gas), as these agents can also become
to the gas. This results in excessive erosion of the
cap removal. fuels in the presence of ClF3. Heating of system
metal. components during purging should be considered
Ensure that the cylinder valve is properly closed,
to ensure removal of low-volatility cleaning agents.
Carbon steel, copper and stainless steel are
the valve outlet seal has been reinstalled leak-
acceptable at ambient temperatures. Brass is rap-
tight, and the valve protection cap is installed To minimize potential problems, users should
idly dezincified by hydrogen fluoride; therefore any
before returning to storage, moving or shipping the avoid excessive use of mechanical connections
moisture contamination or leak of product to the
cylinder. (to limit potential leakage sites) and elastomers
atmosphere will form hydrogen fluoride and rapidly (to limit potential reactivity and contamination) in
Disposal attack the brass. If the potential for elevated tem- ClF3 systems. Similarly, system valves incorpo-
peratures exist, Monel and nickel are the metals of rating metal seats should be used if possible to
Return unused product to the supplier for proper
choice. Material selection becomes more critical reduce the chance of ignition of elastomer seats.
disposal. In process applications, gaseous chlorine
in systems using ClF3 in the liquid phase, as more Chlorine trifluoride systems should be passivated
trifluoride can be disposed of in either liquid or dry
oxidizer is available to contribute to a reaction. before use with increasing concentrations of ClF3,
scrubbers. Dry scrubbers work well under normal
fluorine, or a fluorine mixture. The system should
operating conditions for small quantities of ClF3 Elastomers
be observed during passivation for unexpected
but are not recommended for large or emergency
Only fluorinated elastomers should be used in chlo- overheating of any components that would indicate
releases unless specifically designed. Scrubbers
excessive reaction with the components.
rine trifluoride systems, and only if a metal cannot
must be designed to withstand the heat generated
be substituted. Cleanliness of these materials is
in the event of a large release. For normal opera-
System Operations
critical, as any contamination can quickly compro-
tion, it is recommended an inert gas be used as a
mise the material. It is recommended that elas-
diluent prior to product being introduced to scrub- Employees working with ClF3 should be specially
tomers not be used in service where they will be
ber. This will help disperse the heat of reaction. trained to ensure they understand the system
exposed to the liquid phase, since even these elas- requirements and the physical and exposure haz-
Wet scrubbers typically use caustic solutions, such
tomers may deteriorate rapidly and possibly ignite
as potassium or sodium hydroxide, as the scrub- ards of ClF3 and its reaction products.
at elevated temperature (130掳C). Elastomers are
bing medium. Wet scrubbers handle the heat of
more difficult to clean for oxidizer service because Chlorine trifluoride systems must be kept dry to
reaction better, as well as neutralize the products
they can absorb the solvents or detergents used
of reaction. Disposal of liquid chlorine trifluoride is minimize corrosion and contamination from acids
to clean them; therefore, all elastomers should be
extremely hazardous and is not recommended. that will form on contact of ClF3 with moisture.
degassed after cleaning in a vacuum oven.
When not in use, equipment should be depressur-
Figure 5
ized and purged with dry inert gas. For extended
out-of-service periods, equipment should be kept Vapor Pressure of Chlorine Trifluoride
sealed under positive pressure with dry inert gas.
As with any hazardous gas cylinder, operators 60.00
should confirm the cylinder valve is firmly closed 50.00
before loosening the valve outlet seal to connect
40.00
Pressure (psia)
a cylinder to the system. The outlet seal should
be loosened slowly to limit the release rate of any 30.00
ClF3 that may have leaked into the valve outlet. The 20.00
same procedure should be used to disconnect the
10.00
cylinder from the system, and the pigtail must be
vented and purged thoroughly before loosening the 0.00
-110 -90 -70 -50 -30 -10 10 30 50 70 90 110 130
connection.
Temperature (F)
When connecting new ClF3 cylinders, care is
needed to prevent contamination of the valve outlet
connection, especially if a gasketed connection is
used. New gaskets must be thoroughly degreased Prior to any maintenance, including supply cylinder Figure 6
and dried prior to installation unless specially changes, special care must be taken to ensure no
cleaned and packaged gaskets are used directly NFPA Hazard Diamond for
hazardous quantity of ClF3 remains in the equip-
Chlorine Trifluoride
from the manufacturer. New cleanroom gloves or ment. Thorough purging with inert gas should
equally clean alternatives should be used to install always be done after the ClF3 cylinder valve is
replacement gaskets. Similar precautions must be firmly closed. If there is any suspicion of con-
taken when changing other system components to densed ClF3 in the system, the process should be
0
avoid introduction of easily ignited contaminants. heated and (ideally) evacuated to confirm no ClF3
remains before the system is opened.
When ClF3 supply cylinders are initially opened,
4 0
National and Regional Code
the operator should always be prepared to quickly
Requirements
reclose the valve should any evidence of reaction,
W
overheating, or leaks develop. If any uncertainty
ClF3 is a challenging material to properly manage
exists about the cleanliness of system compo-
OX
from a code compliance and usage standpoint. This
nents, the cylinder valve should only be opened
is because ClF3 possesses both physical hazards
to introduce a minimal amount of ClF3 vapor and
(very strong oxidizer and very reactive) and health
then immediately closed. This will limit the amount
hazards (toxic and corrosive). The physical hazards
of ClF3 available to sustain ignition if a problem
of ClF3 often cause local authorities to require the
develops.
source containers be positioned remotely from the and code requirements are adequately addressed.
It is very important that chlorine trifluoride system consumer鈥檚 main facility or occupants. However, One method to effectively manage ClF3 hazards is
pressures be kept well below the ClF3 vapor pres- the low vapor pressure of the product at room through the use of properly designed and facili-
sure at the temperature of the coolest component temperature provides challenges to distribute the tated gas cabinets that are specially engineered to
in the process. This will prevent the condensation vapor any significant distance. house ClF3 cylinders and distribution control piping
of the ClF3 vapors in trhe system (see Figure 5). and components.
ClF3 is classified as a 鈥淗azardous Production
This is primarily to avoid the heightened reactiv-
Gas Cabinet Supply Safety
Material鈥? (HPM) per regional Code definition based
ity of liquid-phase ClF3 in the system and to allow
Considerations
on its NFPA 704 ratings (Figure 6).
proper flow control. Use of an absolute pressure
regulator is recommended whenever possible to
An HPM is a solid, liquid, or gas associated with When chlorine trifluoride is used in microelectron-
control system pressure below the ClF3 condensa-
semiconductor manufacturing that has a degree of ics facilities, consideration should be given to the
tion pressure.
hazard rating in health, flammability, or reactivity following gas cabinet system design elements:
With its relatively high boiling point, chlorine trifluo- of Class 3 or 4 as ranked by NFPA criteria. Also, an
鈥? Automatic sprinkler protection is not recom-
HPM requires that the material be used directly in
ride vapor pressure is low at typical use tempera-
mended for ClF3 gas cabinets due to the potential
tures, which can result in unacceptably low system research, laboratory, or production processes that
for violent reaction with leaking ClF3 (supported
have as their end product materials that are not
pressure and flow rates, especially from cylinders
in 1997 by a major industrial insurance compa-
with little remaining inventory. If the supply cylinder hazardous (e.g., integrated circuits).
ny鈥檚 specific recommendations regarding ClF3
is heated to permit higher flows, it is even more
The physical hazards of ClF3 often result in the gas cabinets for the semiconductor industry).4
critical to protect against condensation in cooler
local code authority establishment of low threshold
downstream components. System heating can also 鈥? Pneumatically operated cylinder valves should
or exempt quantities for the material. However,
be considered to prevent condensation; maintain- be considered to allow automatic and immediate
proper facilitation and usage of ClF3 does provide a
ing uniform heating throughout the system can be supply shutdown should there be a downstream
safe supply and distribution system if the hazards
difficult. incident.
ER Notes
Figure 7
鈥? PPE that comes into contact with liquid
Vapor CIF3 Exposure to Nitrile Glove, Clean and Oil-Contaminated
may ignite.
鈥? Always assume that at least the outer gloves
have been exposed to HF; exposure can cause
burns.
鈥? Knowing the limitations of PPE in emergency
operations, responders should think about how
they may come in contact with the material and
minimize their exposure.
Figure 7 demonstrates the importance of clean
PPE. Upon exposure to a stream of ClF3 vapor, the
new glove exhibits no reaction. The same glove,
contaminated with a small amount of oil, instantly
bursts into flame.
First Aid
Table 4
Transportation Information As described under the 鈥淗ealth鈥? section of this
Safetygram, chlorine trifluoride is highly toxic and
Shipping Name: Chlorine Trifluoride
also reacts with moisture to form a variety of
toxic and corrosive materials, including hydro-
Hazard Class: 2.3
fluoric acid. Medical treatment for hydrofluoric
Shipping Label: Toxic Gas, Oxidizer, Corrosive acid exposures is very specialized. Air Products鈥?
Safetygram-29, 鈥淭reatment Protocol for Hydro-
Identification Number: UN 1749
fluoric Acid Burns,鈥? provides detailed information
Description: Chlorine Trifluoride, 2.3, UN1749 on the health effects and treatment for hydrogen
fluoride. All users of chlorine trifluoride should use
When shipping via common carrier, all cylinders must be secured in an upright position and be located at the rear
copies of Safetygram-29 to educate their employ-
of the trailer. Never load additional freight on top of the cylinders. For small cylinders, special shipping pallets are
ees, emergency people and local medical providers
mandatory.
so they may know in advance what is required to
address these exposures in the way of supplies
in emergency situations to minimize the chance
鈥? A gas detector should be located in the cabinet
and treatment.
of reaction of the product contaminants on PPE.
to monitor and cause an automatic shutdown
Because the possibility of a reaction exists and the
alarm on either hydrogen fluoride or chlorine
Emergency Response
external PPE may melt if exposed to heat, natural
dioxide indication.
fiber clothing should be worn under the PPE to
For small vapor leaks, shut off gas flow by closing
鈥? A heat or smoke detector should be located in minimize any melted material binding to the skin.
cylinder valve, using the appropriate PPE. Purge
the gas cabinet to monitor and cause an auto-
the residual vapor to a scrubber, using an inert gas.
Cylinder Handling
matic shutdown alarm on an internal or external
Repair the leak. Be sure to thoroughly inspect the
fire condition.
area surrounding the leak for any signs of corro-
Leather gloves, safety glasses with side shields
sion, which may require replacement of that part of
and safety shoes are recommended.
鈥? The delivery pipe or tubing should be coaxial
the system. After the repair, the system must again
(double contained) with a monitoring alarm for
Operations be passivated.
loss of primary containment.
Polycarbonate faceshield over safety glasses, PVC
Personal Protective Equipment For leaks at the cylinder or through the valve,
splash suit, inner gloves smooth leather, outer isolate the cylinder and contact the Air Products
(PPE) gloves 17-mil nitrile is recommended. All personal Emergency Response System at:
protective equipment MUST be clean and dry. 800-523-9374 (in North America)
General Rules
or
Emergency Use
Because PPE may be compromised by the pres- +01-610-481-7711 (all other locations)
ence of dirt or water, PPE used in normal opera- Self-contained breathing apparatus (SCBA), totally
In the case of a large vapor release or small liquid
tions must be clean and free of contamination. In encapsulating chemical protective suit (TECP), nat-
spill, immediately evacuate the area. If possible,
emergency situations where the product is leaking ural fiber clothing only to be worn under the PPE,
without risk and while wearing appropriate PPE,
and response time is critical, the PPE must be as smooth leather inner gloves and 17 mil nitrile outer
stop flow of gas. Do not attempt any remediation!
clean as possible to prevent reaction with the prod- gloves are recommended. Gloves and splash suit
Call the Air Products Emergency Response System
uct. Therefore, only new gloves and acid-splash MUST be new. Earplugs should also be considered
immediately.
suits or totally encapsulating suits should be used due to the possibility of a loud, vigorous reaction.
In the unlikely event of a large liquid spill, evacuate 1. Advances in Fluorine Chemistry, Volume 1,
the area and immediately contact the Air Products Butterworth鈥檚 Scientific Publication, 1960.
Emergency Response System. Do not attempt any
2. Handling Hazardous Materials, Technology
remediation!
Survey SP-5032, Washington, D.C.: National
Aeronautics and Space Administration,
Warning: Any attempt to neutralize a liquid spill
Technology Utilization Division.
may result in an explosion.
3. Clark, John D., Ignition! An Informal History of
Liquid Rocket Propellants, New Brunswick, NJ:
Rutgers University Press.
4. Loss Prevention Data 7-7, Semiconductor
Fabrication Facilities 17-12, Factory Mutual
Engineering Corp., 1997.
Emergency Response System Product Safety Information
鈥? Call: +1-800-523-9374 鈥? For MSDS, Safetygrams,
(Continental U.S. and Puerto Rico) and Product Safety Information
www.airproducts.com/productsafety
鈥? Call: +1-610-481-7711 (other locations)
鈥? 24 hours a day, 7 days a week
鈥? For assistance involving Air Products and
Chemicals, Inc. products
Information Sources
Technical Information Center
鈥? Compressed Gas Association (CGA)
鈥? Call: +1-800-752-1597 (U.S.)
www.cganet.com
鈥? Call: +1-610-481-8565 (other locations)
鈥? European Industrial Gases Association (EIGA)
鈥? Fax: +1-610-481-8690 www.eiga.org
鈥? E-mail: gasinfo@apci.com 鈥? Japanese Industrial Gases Association (JIGA)
www.jiga.gr.jp/english
鈥? Monday鈥揊riday, 8:00 a.m.鈥?5:00 p.m. EST
鈥? American Chemistry Council
www.americanchemistry.com
For More Information
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漏 Air Products and Chemicals, Inc., 2004 (24184) 900-04-123-US-Feb07
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