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Risk Management for Hazardous Chemicals

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MATERIAL SAFETY DATA SHEET


CHEMICAL NAME

CRC PRESS/LEWIS PUBLISHERS DISCLAIMER:

NITROGEN TRIFLUORIDE

THE INFORMATION AND RECOMMENDATIONS


PRESENTED HEREIN ARE BASED ON SOURCES BELIEVED TO BE RELIABLE. CRC MAKES NO REPRESENTATION ON ITS
COMPLETENESS OR ACCURACY. IT IS THE RESPONSIBILITY OF THE USER TO DETERMINE THE CHEMICAL'S SUITABILITY
FOR ITS INTENDED USE, THE CHEMICAL'S SAFE USE, AND THE CHEMICAL'S PROPER DISPOSAL. NO REPRESENTATIONS
AND/OR WARRANTIES, EITHER EXPRESSED OR IMPLIED, OF THE MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE, OR OF ANY OTHER NATURE, ARE MADE WITH RESPECT TO THE INFORMATION PROVIDED IN THIS MSDS OR
TO THE CHEMICAL TO WHICH INFORMATION MAY REFER. CRC NEITHER ASSUMES NOR AUTHORIZES ANY OTHER
PERSON TO ASSUME FOR IT, ANY OTHER ADDITIONAL RESPONSIBILITY OR LIABILITY FOR THE USE OF, OR RELIANCE
UPON, THIS INFORMATION.

HAZARD WARNING INFORMATION


HEALTH

FIRE

REACTIVE

OTHER

OX

DEGREE OF HAZARD
0 = Minimum Hazard
1 = Slight Hazard
2 = Moderate Hazard
3 = Serious Hazard
4 = Severe Hazard

COLOR CODING

OTHER CODES

HEALTH = BLUE
FIRE = RED
REACTIVITY = YELLOW
OTHER = WHITE

OX = Oxidizer
ACID = Acid
ALK = Alkali
COR = Corrosive
W = Use No Water

SECTION I - GENERAL INFORMATION


Characterization

RCRA Number

EPA Class

Gas

D003

DOT Proper Shipping Name

Characteristic (R) Waste

Chemical Abstract Service (CAS) Number

Nitrogen Tetroxide

7783-54-2

DOT Hazard Class and Label Requirements

DOT Emergency Guide Code

Nonflammable Gas; Oxidizer


DOT Identification Number

15
Molecular Formula

UN 2451

NF3

Synonyms

Nitrogen fluoride; trifluoramine; trifluorammonia; perfluorammonia.

SECTION II - HAZARDOUS INGREDIENTS AND IDENTITY INFORMATION


Hazardous Components (specific identity)

Nitrogen trifluoride:

(derivation:
By electrolysis of ammonium acid fluoride or low-temperature reaction of nitrogen and fluorine in the presence of
electrical discharge).

1 ppm = 2.95 mg/m3

OSHA Exposure Criteria

NIOSH Exposure Criteria

PEL (8-hour):
10 ppm
29 mg/m3

REL (10-hour):
10 ppm
29 mg/m3

STEL:
Not
Established

STEL:
Not
Established

Immediately Dangerous to Life


and Health (IDLH)

ACGIH Exposure Criteria

TLV:
10 ppm
29 mg/m3
1000 ppm
STEL:
Not
Established

SECTION III - PHYSICAL AND CHEMICAL CHARACTERISTICS


Boiling Point

-200F (-129C)
Vapor Pressure (atmospheres)

Specific Gravity (H2O = 1)

2.46 (Gas)
Molecular Weight (atomic weight)

>1 at 68F (20C)


Vapor Density (Air = 1)

71.0
Freezing Point

1.537 at -200F (-129C)

-340F (-206C)

Solubility

Very slightly soluble in cold water.


Appearance and Odor

Colorless gas with a slight moldy odor. Usually shipped as a non-liquefied compressed gas.

SECTION IV - FIRE AND EXPLOSION HAZARD DATA


Flash Point (method used)

Not Applicable
NFPA Classification

Non-Flammable Gas

Explosive Limits in Air % by Volume

LEL: Not Applicable

UEL: Not Applicable

Autoignition Temperature

Not Applicable

Extinguishing Media

Will not burn but will enhance the burning of other materials. Use agent suitable to surrounding fire, except for water (water, heat, and nitrogen trifluoride may cause an explosion). Do NOT use Halon 130.
Special Fire Fighting Procedures

Poisonous gases are produced in fire. Wear full protective clothing and (SCBA). Move container from fire
area if it can be done without risk. Cool exposed containers with direct water spray (do NOT allow water
to get inside containers. Do NOT release runoff from control measures to sewers and waterways.
Unusual Fire and Explosion Hazards

Containers may explode in fire. Fight fire from a distance or with unmanned hose holders, if possible.
Stay away from ends of tanks. Use extreme caution if nitrogen trifluoride is in or near a fire.

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

Page: 2

SECTION V - REACTIVITY DATA


Conditions to Avoid

Nitrogen trifluoride is normally stable in closed containers under routine conditions of handling and storage, but can explode under pressure. Avoid contact with incompatibles, heat, and organic materials.

Stability
Stable

Unstable

Incompatible ammonia, carbon monoxide, methane, hydrogen sulfide, diborane, tetrafluorohydrazine, hydrogen, ethylene, chlorine dioxide, charcoal, oil, grease, and oxidizable materials.

Conditions to Avoid

Hazardous
Polymerization
May Occur

Incompatibility (materials to avoid)

Under normal conditions of temperature and pressure, hazardous polymerization of nitrogen trifluoride is
not expected to occur.

Will Not Occur

Hazardous Decomposition or By-products

When heated to decomposition, nitrogen trifluoride emits highly toxic fluorine fumes.

SECTION VI - HEALTH HAZARD DATA


Inhalation?

Primary Route(s) of Entry:

Absorption (skin/eye)?

Ingestion?

Health Hazards

INHALATION: The gas causes the development of methemoglobinemia which can significantly impair the
blood's ability to transport oxygen to the cells, causing a lack of oxygenated tissues. This
may cause symptoms such as cyanosis, dizziness, weakness, and severe headache. It
may also lead to hemolysis, anemia, and altered kidney functions.
SKIN & EYES: A severe eye and skin irritant. Sudden bursts of the compressed liquid may cause frostbite and associated tissue destruction. Skin and eye contact can cause burns.
INGESTION:

Unlikely, but possible. May cause burns to the mouth and throat.

Carcinogenicity

NTP Listed?

Unknown Human
Unknown Animal

No

IARC Cancer Review Group?

OSHA Regulated?

Target Organs?

No

29 CFR 1910.1000
Table Z-1

Blood, liver, kidneys, central nervous system.

Medical Conditions Generally Aggravated by Exposure

Chronic respiratory problems (bronchitis, asthma) may be aggravated.


Emergency and First-aid Procedures

Eye contact: Do not allow victim to keep eyes tightly shut. Flush immediately with water for 15 minutes
(minimum). Skin contact: Wash with large amounts of tepid water for a minimum of 15 minutes. Do NOT
use dry heat or rub the affected area. For inhalation: Remove the person from exposure. Provide respiratory assistance and CPR. Transfer to medical facility. If swallowed: Not likely since nitrogen trifluoride is a
gas above 70F (21C). Do NOT induce vomiting. Contact poison control center for assistance.

SECTION VII - PRECAUTIONS FOR SAFE HANDLING AND USE


Steps to be Taken in Case Material is Released or Spilled

Wear self-contained breathing apparatus (SCBA). Stop flow of gas. Restrict those not wearing protective
equipment and who are not involved in cleanup from entering area. Avoid skin contact. Ventilate area of
spill. If gas cannot be stopped, remove leaking container to safe area outdoors and allow to empty.
Preferred Waste Disposal Method

No citation.
Precautions to be Taken in Handling and Storage

Store in tightly closed, insulated, steel containers or cylinders in a cool, well-ventilated area away from
heat. Protect containers from physical damage. Regularly inspect for leaks, cracks, or faulty valves.
Other Precautions and Warnings

Use external or detached storage. Ensure cylinders are stored upright and properly secured at all times.

SECTION VIII - CONTROL MEASURES AND PERSONAL PROTECTIVE EQUIPMENT


Respiratory Protection (specify type)

Use a NIOSH/MSHA-approved air-purifying gas-cartridge respirator, or a supplied-air respirator, or a selfcontained breathing apparatus (SCBA) with full facepiece operated in positive pressure mode.
Ventilation

Local exhaust (preferred) at site of chemical work or general ventilation.


Protective Gloves

Impervious Gloves

Eye Protection

Chemical Goggles and Face Mask

Other Protective Clothing

Protective Uniform or Apron

Work/Hygiene Practices

Always wash hands thoroughly after using chemical; never bring food, drink, or smoking materials into
vicinity of chemicals.

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

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NITROGEN TRIFLUORIDE
NF3

CAS: 7783-54-2

0
1

1
ox

IDENTIFICATION AND TYPICAL USES


Nitrogen trifluoride as a colorless gas with a slight,
moldy odor. It is normally shipped as a non-liquefied
compressed gas. It is used as an oxidizing agent in
high energy fuels or for chemical synthesis, and as a
dry etchant gas.

from nitrogen trifluoride during the metabolic process


which may indicate a possibility of fluoride buildup
over time and may result in the mottling of teeth and
in unspecified skeletal changes.

1 Acute Health Effects


The following acute (short-term) health effects may
occur immediately or shortly after exposure to nitrogen trifluoride:

RISK ASSESSMENT: HEALTH


General Assessment
Nitrogen trifluoride is a severe irritant to the eyes,
nose, and throat. As a gas, it can primarily enter the
body through inhalation. While skin absorption is not
likely, skin contact can result in serious tissue damage
as a direct result of the cold temperatures of the compressed gas or cryogenic liquid. Ingestion is not a
probable route of exposure under most circumstances.
There are no data regarding any carcinogenic,
mutagenic, or teratogenic potential on long-term exposure.
Inhalation of nitrogen trifluoride can cause severe
irritation to the eyes, nose, and throat. The primary
systemic effect of exposure to nitrogen trifluoride vapors is the development of methemoglobinemia which
can significantly interfere with the blood's ability to
transport oxygen to the body's cells. This causes a
lack of oxygenated blood in the tissues. Symptoms
include cyanosis with blue lips, nose, ears, fingers,
toes, and facial skin due to this lack of oxygen. There
can also be dizziness, weakness, severe headache,
hemolysis (damage) of the red blood cells, leading to
anemia and possible alterations in kidney function.
Skin contact with compressed liquid nitrogen
trifluoride can cause characteristic burns due to frostbite. Eye contact causes irritation, watering, inflammation of the lids, burns to the cornea, and (possibly)
severe lesions.
Human exposure data are limited. However, animal studies indicate that the fluoride ion is not released

Skin:

Severe irritation with localized tissue damage


and possible burns due to the cold temperature
of the compressed gas.

Eye:

Conjunctival irritation and possible damage to


the cornea and loss of vision.

Lung: Irritation to respiratory tract causing shortness


of breath and cough. The gas causes the development of methemoglobin which significantly impairs the blood's ability to effectively
transport oxygen. This can lead to anemia and
cyanosis.

0 Chronic Health Effects


The following chronic (long-term) health effects may
occur at some time after exposure to nitrogen trifluoride and can last for months or even years:
Cancer Hazards: According to information presented
in the references, nitrogen trifluoride has not been
adequately tested for its ability to cause cancer in test
animals.
Reproductive Hazard: According to the references,
nitrogen trifluoride has not been tested for its ability to
adversely affect reproduction in test animals.
Other Chronic Effects: Long-term exposures to low
concentrations may result in damage to tooth enamel
and could lead to unspecified skeletal changes.

Recommended Risk-Reduction Measures

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

Nitrogen trifluoride is a very toxic substance. Personnel should avoid direct contact with nitrogen trifluoride. If a less toxic material or compound cannot be
substituted for nitrogen trifluoride, then engineering
controls are the most effective method of reducing
exposure risk. The best protection is to enclose operations and/or provide local exhaust ventilation at the
site of nitrogen trifluoride release. While not always
operationally feasible, isolating operations can also
reduce exposure. Using respiratory protection is less
effective than the controls mentioned above, but is still
required whenever working with or around nitrogen
trifluoride. The permissible exposure limit of 10 ppm
(8-hour TWA) can be reached relatively quickly, even
under normal operating conditions. Prudent risk management requires proper consideration and implementation of an appropriate respiratory protection program
(per OSHA 29 CFR 1910.134). While a gas-cartridge
air-purifying respirator will certainly suffice for low or
transient exposures over the PEL, the best protection is
obtained using an MSHA/NIOSH-approved suppliedair respirator or a self-contained breathing apparatus
(SCBA) with full facepiece and operated in pressure
demand mode. If a full facepiece is not available, then
chemical goggles should be worn to protect the eyes.
A face shield should also be considered. To prevent
hand and skin exposures, gloves should be used.
Glove manufacturers should be contacted and permeation studies obtained before final glove selections are
made.
Administrative controls should also be in place to
minimize the potential for human exposures. These
may include written procedures or policies which
specify the methods and techniques that will be practiced whenever personnel are to work with nitrogen
trifluoride.
All personnel should receive training on the use,
hazards, protective measures, emergency actions, and
other precautions per 29 CFR 1910.1200 (Hazard
Communication) prior to the first assignment in an
area where nitrogen trifluoride is used or stored.
If symptoms develop or overexposure is suspected, the following may be useful:
; Complete blood count (CBC) with tests for electrolytes and arterial blood gases.
; Monitor methemoglobin levels. Methylene blue
therapy may be indicated if levels exceed 60%.
It should be noted that medical tests that simply look
for existing damage are not a substitute for controlling
exposures. Medical histories are extremely important
when assessing exposure risk. Also, smoking not only

Page: 4

causes heart disease, lung cancer, emphysema, and


other respiratory ailments, it also decreases the blood's
ability to effectively transport oxygen by increasing
the carboxyhemoglobin content of the blood. Therefore, smokers exposed to nitrogen trifluoride may experience symptoms more rapidly than non-smokers
under the same conditions of exposure. Smokers
should therefore avoid unprotected contact with this
chemical. Prudent risk management requires proper
consideration of all possible factors that may be causing the appearance of exposure symptoms among
workers.
Other methods to reduce exposure include:
;

Always ensure that proper protective clothing is


worn when using chemical substances, and that
personnel are trained on its use, care, and maintenance.

Wash thoroughly immediately after exposure to


nitrogen trifluoride and at the end of the work
shift or before eating, drinking, or smoking.

Hazard warning information should be posted in


the work area. In addition, as part of an on-going
education and training program, all information
on the health and safety hazards of nitrogen
trifluoride should be communicated to exposed
workers.

Eye wash stations should be provided in the immediate work area for emergency use. If there is
a possibility of skin exposure to compressed nitrogen trifluoride gas, emergency shower facilities should also be provided.

Workers whose clothing has been contaminated


by nitrogen trifluoride should change into clean
clothes before leaving work. Contaminated work
clothing should be laundered only by individuals
who have been informed of the hazards of exposure to chemical substances such as nitrogen
trifluoride.

RISK ASSESSMENT: ENVIRONMENT


General Assessment
The environment is always at some risk of exposure
during transportation, storage, disposal, or destruction
of nitrogen trifluoride. In almost every scenario, the
threat of environmental exposure is contingent upon
the proper handling of the chemical substance. As a
gas, it primarily affects the air. However, depending
upon the nature and conditions of the release, accidental spills, large or small, can result in contamina-

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

tion of the other surrounding environmental mediums


(water and soil).
Nitrogen trifluoride is a non-flammable gas.
However, as an oxidizer it can greatly accelerate the
burning of ordinary combustible materials such as
wood and paper. It can also react explosively in contact with a number of commonly encountered materials, including oil, grease, oxidizable materials, ammonia, carbon monoxide, methane, and even water. In
contact with water or water vapor, reactions may be
violent and explosive. Caution is always required in
handling, storage, transportation, and disposal of nitrogen trifluoride. Emergency responders should be
made aware of the presence of nitrogen trifluoride at
any emergency response situation.
Nitrogen trifluoride may enter the environment
through industrial discharges and from spills.

1 Acute Ecological Effects


Acute (short-term) toxic effects may include the death
of animals, birds, or fish and death or low growth rate
in plants. Acute effects are seen 2 to 4 days after animals or plants are exposed to nitrogen trifluoride.
Insufficient data are available to evaluate or predict the acute (short-term) effects of nitrogen trifluoride on aquatic life, plants, birds, or land animals.

0 Chronic Ecological Effects


Chronic (long-term) toxic effects may include shortened life span, reproductive problems, lower fertility,
and changes in appearance or behavior in exposed
animals. These effects can be seen long after first exposure(s) to toxic chemicals.
Insufficient data are available to evaluate the
chronic (long-term) effects of nitrogen trifluoride on
aquatic life, plants, birds, or land animals.

6 Water Solubility
Nitrogen trifluoride is slightly soluble in water. Concentrations of 1 to 100 milligrams may mix with a liter
of water (there may be a violent reaction, depending
upon the concentration of nitrogen trifluoride present).

 Persistence in the Environment


Nitrogen trifluoride will react with water in the aquatic
environment and therefore may be only slightly persistent in water, with a half-life between 2 and 20
days. The half-life of a pollutant is the amount of time
it takes for one-half of the chemical to be degraded.

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As a gas, virtually 100% of nitrogen trifluoride will


eventually end up in the air.

O Bioaccumulation in Aquatic Organisms


Some substances increase in concentration, or bioaccumulate, in living organisms as they breathe contaminated air, drink contaminated water, or eat contaminated food. These chemicals can become concentrated in the tissues and internal organs of animals
as well as humans.
The concentration of nitrogen trifluoride found in
fish tissues is expected to be somewhat lower than the
average concentration of nitrogen trifluoride in the
water from which the fish was taken.

Recommended Risk-Reduction Measures


Proper training of all transporters will reduce the likelihood of a mishap or accident resulting in a leak or
spill of nitrogen trifluoride into the environment. Labels on all containers, trucks, and rail cars must meet
DOT requirements and accurately reflect their contents
to enable emergency responders to react properly and
quickly to any disaster thereby reducing the potential
risk to the environment and to personnel.
Storage of nitrogen trifluoride should be segregated from other chemicals to minimize the risk of
cross-contamination. Nitrogen trifluoride must be
stored to avoid contact with incompatible materials
since violent reactions can occur. Containers should
be protected from physical damage and stored to avoid
contact with heat. If a spill or leak to the environment
has occurred, fire department, emergency response
and/or hazardous materials spill personnel should be
notified immediately. Cleanup should be attempted
only by those trained in proper spill containment procedures. Contaminated soils should be removed for
incineration and replaced with clean soil.
If nitrogen trifluoride should contact the water table, aquifer, or navigable waterway, time is of the essence. Because it will decompose to nitric acid in
water, total remediation may not be possible. The local and/or state emergency response authorities must
be notified. A comprehensive emergency response or
disaster preparedness/recovery plan should be in place
prior to any operations involving the use, transportation, storage, or disposal of nitrogen trifluoride.
If nitrogen trifluoride is spilled or leaked, the following specific steps are recommended:
; Restrict persons not wearing protective clothing
from area of spill or leak until cleanup is complete. Avoid skin and eye contact.

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

If applicable, stop flow of leaking liquid or gas.


If leak source is a cylinder and the leak cannot be
stopped in place, remove leaking cylinder to a
safe place in the open air, and repair or allow
cylinder to empty.

Ventilate area of spill or leak.

It may be necessary to dispose of nitrogen trifluoride as a hazardous waste. The responsible state
agency or the regional office of the federal Environmental Protection Agency (EPA) should be
contacted for specific recommendations.

Page: 6
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Calabrese, E. J. 1994. Biological Effects of Low Level Exposures. New
York: CRC Press/Lewis Publishers.
Cockerman, L. G., B. S. Shane. 1994. Basic Environmental Toxicology.
New York: CRC Press/Lewis Publishers.
Cothern, C. R. 1995. Handbook for Environmental Risk Decisionmaking.
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Fodden, C. R., and J. L. Weddell. 1992. Hazardous Materials Emergency
Action Data. New York: CRC Press/Lewis Publishers.

RISK ASSESSMENT: BUSINESS


General Assessment
Accidents or mishaps involving nitrogen trifluoride
can present a serious threat to business operations.
The loss or damage of equipment or facilities can significantly affect fiscal viability. Lawsuits that may
result from personnel illness, injury/death, public exposures, and/or environmental contamination will require a serious expenditure of resources. Media attention surrounding an injury, death, or environmental
damage can also result in a loss of profits and loss of
current as well as future business.

Recommended Risk-Reduction Measures


Company attorneys, safety and health professionals,
and environmental specialists should be involved in
the development of any procedures for responding to
chemical incidents. A company official should be predesignated as a public relations officer with specific
training in dealing with the press. Corporate plans and
policies should be developed, approved, and implemented long before any need for such arises.

Forseberg, K., and L. H. Keith. 1993. Chemical; Protective Clothing


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Gardner, R. W. 1994. Chemical Intolerance.
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CRC

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Hodgson, E., R. B. Mailman, and Janice E. Chambers. 1988. Dictionary
of Toxicology. London: The MacMillian Company.
Hosty, J. W., and P. Foster. 1990. A Practical Guide to Chemical Spill
Response. New York: Van Nostrand Reinhold.
Howard, P. H. 1995. Handbook of Environmental Fate and Exposures
Data for Organic Chemicals, Vol. I-IV. New York: CRC
Press/Lewis Publishers.
Jones, F. E. 1994. Toxic Organic Vapors in the Workplace. New York:
CRC Press/Lewis Publishers.
Kamrin, M. A. 1988. Toxicology: A Primer on Principles and Applications. Chelsea, Michigan: Lewis Publishers.
Keith, L. H. and M. M. Walker. 1995. Handbook of Air Toxics. New
York: CRC Press/Lewis Publishers.
Lauwerys, R. R., P. Hoet. 1993. Industrial Chemical Exposure. New
York: CRC Press/Lewis Publishers.

REFERENCES
Ahlbom, A. 1993. Biostatistics for Epidemiologists. New York: CRC
Press/Lewis Publishers.
American Conference of Governmental Industrial Hygienists. 1988.
Documentation of the Threshold Limit Values and Biological Exposure Indices, 5th Edition (with updates). Cincinnati: ACGIH
Anthony, C. P., and N. J. Kolthoff. 1971. Textbook of Anatomy and
Physiology. St. Louis: C. V. Mosby Company.
Brusick, D. J. 1994. Methods for Genetic Risk Assessment. New York:
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Lewis, .J., Sr. 1993. Hawley's Condensed Chemical Dictionary, 12th


Edition. New York: Van Nostrand Reinhold.
Lewis, . J., Sr. 1992. Sax's Dangerous Properties of Industrial Materials,
Volumes 1, 2, and 3, 8th Edition. New York: Van Nostrand Reinhold.
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New York: CRC Press/Lewis Publishers.
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1996 by CRC Press, Inc.

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