Risk Management for Hazardous Chemicals

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MATERIAL SAFETY DATA SHEET

CHEMICAL NAME

CRC PRESS/LEWIS PUBLISHERS DISCLAIMER: 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.

GERMANIUM
TETRAHYDRIDE

HAZARD WARNING INFORMATION

HEALTH

FIRE

REACTIVE

OTHER

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

Gas; Hydride

EPA Class

None

DOT Proper Shipping Name

Not Applicable

Chemical Abstract Service (CAS) Number

Germanium tetrahydride

7782-65-2

DOT Hazard Class and Label Requirements

DOT Emergency Guide Code

Poison Gas; Flammable Gas

DOT Identification Number

18
Chemical Formula

UN 2192

GeH4

Synonyms

Germanium hydride; germane; germanomethane; monogermanium tetrahydride.

SECTION II - HAZARDOUS INGREDIENTS AND IDENTITY INFORMATION

Hazardous Components (specific identity)

Germanium tetrahydride
(derivation from: Germanium is derived
from residues from refining of zinc and
other sources, by heating in the presence
of air and chlorine. It is also present in
some coals and can be recovered from
their ash).

1 ppm = 3.18 mg/m3

OSHA Exposure Criteria

NIOSH Exposure Criteria

PEL:
Not
Established

REL:
0.2 ppm
0.6 mg/m3

STEL:
Not
Established

STEL:
Not
Established

Immediately Dangerous
to Life and Health (IDLH)

ACGIH Exposure Criteria

TLV:
0.2 ppm
0.6 mg/m3
Not
Determined

STEL:
Not
Established

SECTION III - PHYSICAL AND CHEMICAL CHARACTERISTICS

Boiling Point
Vapor Pressure (atmospheres)

-126F (-88C)
>1 at 69F (20C)

Vapor Density (Air = 1)

Specific Gravity (H2O = 1)

2.65
Molecular Weight

76.6
Freezing Point

-267F (-165C)

Not Found
Solubility

Insoluble in water; slightly soluble in hot hydrochloric acid; soluble in liquid ammonia. Decomposes in
nitric acid.
Appearance and Odor

Colorless gas with a pungent odor. Normally shipped as a compressed gas.

SECTION IV - FIRE AND EXPLOSION HAZARD DATA

Flash Point (method used)

Explosive Limits in Air % by Volume

Not Applicable (gas)

NFPA Classification

LEL: Not Determined

UEL: Not Determined

Autoignition Temperature

Flammable Gas

Not Determined

Extinguishing Media

Stop flow of gas, if possible. Allow to burn, do not attempt to extinguish since combustion of germanium tetrahydride reduces the possibility of explosions due to the formation of unstable air mixtures.
Special Fire Fighting Procedures

Germanium tetrahydride is a dangerous fire and explosion hazard. The gas is pyrophoric and may spontaneously ignite in air. Poisonous gases are produced in fire. Wear self-contained breathing apparatus.
Use water spray to keep containers cool.
Unusual Fire and Explosion Hazards

Fire-exposed containers can explode violently in fire. They should be moved from fire areas if it can be
done without risk. Cooling water should be applied from a safe distance if possible.
1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

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SECTION V - REACTIVITY DATA

Conditions to Avoid

Germanium tetrahydride is a highly reactive gas and can ignite spontaneously on exposure to air. Avoid
contact with heat, air, ignition sources, and electrostatic sparks.

Stability
Stable

Unstable

None reported.

X
Hazardous
Polymerization
May Occur

Incompatibility (materials to avoid)

Will Not Occur

Conditions to Avoid

Under normal conditions of temperature and pressure, hazardous polymerization of germanium tetrahydride is not expected to occur.
Hazardous Decomposition or By-products

When germanium tetrahydride is involved in fire, it will emit toxic and acrid fumes and gases, including
germanium and highly explosive hydrogen gas.

SECTION VI - HEALTH HAZARD DATA

Inhalation?

Absorption (skin)?

Ingestion?

Primary Route(s) of Entry:

Health Hazards

INHALATION: Eye, nose, and throat irritant. Toxic effects include lachrymation, respiratory distress,
chest pain, possible seizures, and pulmonary edema (fluid in the lungs).
SKIN & EYES: Skin contact may cause irritation and burns (frostbite from the compressed gas). Eye
irritation is also likely to occur on contact with the gas.
INGESTION:

Not likely.

Carcinogenicity

NTP Listed?

Unknown Human
Unknown Animal

No

IARC Cancer Review Group?

OSHA Regulated?

Target Organs?

No

Respiratory system; liver;

kidneys; CNS; skin; eyes.

No

Medical Conditions Generally Aggravated by Exposure

Respiratory function impairments (bronchitis, asthma, etc.); Skin conditions (dermatitis).

Emergency and First-aid Procedures

Eye contact: Immediately flush large amounts of water for 15 minutes (minimum), occasionally lifting
eyelids, seek medical attention. Skin contact: Remove all contaminated clothing. Immediately wash
area with large amounts of soap and water. For inhalation: Remove the person from exposure. Provide
respiratory assistance and CPR. Transfer promptly to medical facility. Observation for 24 - 48 hours for
lung effects and seizures. If swallowed: Unlikely.

SECTION VII - PRECAUTIONS FOR SAFE HANDLING AND USE

Steps to be Taken in Case Material is Released or Spilled

Remove all ignition sources. Ventilate area. Leaking gas can ignite spontaneously. Evacuate nonessential personnel. Stop flow of gas. If the source of leak is a cylinder and cannot be stopped, clear
area and allow to empty. Have water source available to fight any surrounding fires. Stay clear and allow to burn until out. Emergency personnel must avoid contact with vapors and gases.
Preferred Waste Disposal Method

None specified in the references (incineration of a gas may be the only alternative).
Precautions to be Taken in Handling and Storage

Do not store in open air since violent and explosive fire may occur. Store in tightly closed containers in
a cool, dark, well-ventilated area away from sunlight. Keep away from ignition sources such as fire,
sparks, and flame.
Other Precautions and Warnings

Bulk storage of germanium tetrahydride is not recommended. Containers may explode in fire or under
conditions of extreme heat (do not store outdoors or in direct sunlight).

SECTION VIII - CONTROL MEASURES AND PERSONAL PROTECTIVE EQUIPMENT

Respiratory Protection (specify type)

PEL is low and difficult to monitor (0.2 ppm). Recommend using a powered supplied-air respirator with
full facepiece operated in pressure demand mode. Greater protection is obtained from a self-contained
breathing apparatus (SCBA) with full facepiece in pressure demand or other positive pressure mode.
Ventilation

Local exhaust or general mechanical systems recommended.

Protective Gloves

Impervious and Thermal Rubber

Eye Protection

Chemical Goggles and/or Face Mask

Other Protective Clothing

Protective 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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GERMANIUM TETRAHYDRIDE
GeH4

CAS: 7782-65-2

4
1

IDENTIFICATION AND TYPICAL USES

Germanium tetrahydride is a colorless gas with a pungent odor, normally shipped as a compressed gas. It is
used primarily as a doping agent for solid-state electronic components.

RISK ASSESSMENT: HEALTH

General Assessment
Germanium tetrahydride gas is a severe irritant of the
eyes, respiratory tract, and skin. As a gas, it is primarily toxic by inhalation. If the compressed gas
should contact the skin or eyes, burning and irritation
is likely to occur although absorption as an exposure
route has not been reported. Ingestion is not likely to
occur. There are no reports of carcinogenic, teratogenic, or mutagenic indications.
Inhalation of large concentrations causes dyspnea
(difficulty breathing), bronchospasm, chest pain, congestion, and pulmonary edema, which may be fatal.
Development of pulmonary edema may be delayed up
to 48 hours after exposure, thereby creating a false
sense of security with regard to health exposure risk.
There may also be seizures following exposure to
germanium tetrahydride gas. Germanium tetrahydride
is a hemolytic agent which means it can induce
hemolysis, a breakdown of the red blood cells with a
liberation of hemoglobin. Liver and kidney damage
are also possible (positive animal studies).

1 Acute Health Effects

The following acute (short-term) health effects may
occur immediately or shortly after exposure to germanium tetrahydride:
Skin:

Irritation and burning on contact with the cold

compressed gas.

Eye:

Burns which may cause damage to the eye and

surrounding tissues.

Lung: Irritation of the mouth, nose, and throat causing coughing and/or shortness of breath.
Higher exposures can lead to pulmonary
edema.
CNS:

Data on the acute effects of germanium tetrahydride on the central nervous system are inconclusive. However, animal studies have
shown some indication of seizure activity at
high concentrations.

0 Chronic Health Effects

The following chronic (long-term) health effects may
occur at some time after exposure to germanium tetrahydride and can last for months or even years:
Cancer Hazards: According to information presented
in the references, germanium tetrahydride has not
been adequately tested for its ability to cause cancer in
test animals.
Reproductive Hazards: There are no reports to support any claims of reproductive hazards following exposure to germanium tetrahydride.
Other Chronic Effects: Germanium tetrahydride is a
hemolytic agent and repeated or prolonged exposure
may damage the blood, liver, and kidneys.

Recommended Risk-Reduction Measures

Personnel should avoid direct contact with germanium
tetrahydride gas. Unless a less toxic chemical can be
substituted for a hazardous substance, engineering
controls are the most effective method of reducing
exposures. The best protection is to enclose operations and/or provide local exhaust ventilation at the
site of chemical release. Because germanium tetrahydride is a highly flammable and reactive gas, explosion-proof ventilation is required. 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 advisable whenever working with germanium tet-

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

rahydride. The exposure level is extremely low (0.2

ppm) and difficult to accurately monitor. The best
protection is obtained using a powered supplied-air
respirator operated in continuous flow mode or a selfcontained breathing apparatus (SCBA) with full facepiece in pressure demand mode. If a full facepiece is
not available, then chemical goggles should be worn
to protect the eyes. Whenever a chemical splash hazard exists, a face shield and a rubber apron should be
worn. To prevent hand and skin exposures, impervious, thermal protective gloves should be worn. 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 germanium
tetrahydride.
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 germanium tetrahydride is used or stored.
Before beginning employment and at regular intervals thereafter (e.g., annually), the following medical tests are recommended:

Lung function tests.

If symptoms develop or overexposure is suspected, the

following may be useful:

;
;

Consider chest X-ray after acute overexposure

(may be negative if taken immediately following
exposure due to delayed development of pulmonary edema).
Liver and kidney function tests.

Any evaluation should include a careful history of past

and present symptoms with an examination. Medical
tests that simply look for existing damage are not a
substitute for controlling exposures. Also, since
smoking can cause heart disease, lung cancer, emphysema, and other respiratory disorders, smokers exposed to germanium tetrahydride may experience
symptoms more rapidly than non-smokers under the
same conditions of exposure. Prudent risk management requires careful consideration of all possible risk
factors.
Other methods to reduce exposure to chemicals include:

Page: 4

;
;
;

;
;

Where possible, enclose operations and use local

exhaust ventilation at the site of chemical release.
If local exhaust ventilation or enclosure is not
used, respiratory protection should be mandatory.
Always ensure that proper protective clothing is
worn when using chemical substances.
Wash thoroughly immediately after exposure to
germanium tetrahydride and at the end of the
work shift or before eating, drinking, or smoking.
Work clothing contaminated with germanium tetrahydride should never be taken home for laundering (fire hazard). Only personnel trained in
the hazards of exposure should launder contaminated clothing.
Safety shower and eyewash stations should be
readily available in work areas where germanium
tetrahydride is used or stored.
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 germanium
tetrahydride should be communicated to all exposed and potentially exposed workers.

RISK ASSESSMENT: ENVIRONMENT

General Assessment
The environment is at risk of exposure during transportation, storage, disposal, or destruction of germanium tetrahydride. In almost every scenario, the threat
of environmental exposure is contingent upon the
proper handling of the chemical substance. Accidental
releases, large or small, can result in fire, explosion,
and possible contamination of the surrounding environmental mediums (primarily air, but water and soil
may also be contaminated depending upon the condition of the spill).
Germanium tetrahydride is considered to be a
dangerous, reactive, and explosive flammable gas. It
is pyrophoric, which means it can ignite spontaneously on exposure to air and burn vigorously. This
characteristic requires special consideration during
any emergency involving a leak or release of germanium tetrahydride gas.
Germanium tetrahydride can enter the environment through spills or leaks. Unchecked emissions
from industrial sources are also possible.

1 Acute Ecological Effects

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

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 germanium tetrahydride.
As a gas, germanium tetrahydride may not be expected to pose a serious threat to aquatic life. However, insufficient data are available to accurately
evaluate or predict the short-term effects of germanium tetrahydride exposure to 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 or predict the long-term (chronic) effects of germanium tetrahydride to aquatic life, plants, birds, or land animals.

6 Water Solubility
Germanium tetrahydride is insoluble in water. Concentrations of 1 milligram will not mix with a liter of
water.

 Persistence in the Environment

Germanium tetrahydride is non-persistent in water,
with a half-life of less than 2 days. The half-life of a
pollutant is the amount of time it takes for one half of
the chemical to be degraded. Virtually 100% of germanium tetrahydride will eventually end up in the air.

Page: 5

properly and quickly to any disaster thereby reducing

the potential risk to the environment and to personnel.
Storage of germanium tetrahydride should be segregated from sources of heat or ignition. Containers
should be air-tight and enclosed. Buildings designated for storage should be equipped with appropriate
explosion-proof design as well as the proper fire protection systems (alarms, sprinklers, emergency lighting, portable extinguishers).
If a spill or release 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 containment procedures.
When such spills occur, 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 germanium tetrahydride. If germanium
tetrahydride is spilled or leaked, the following steps
are recommended:

;
;
;
;

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.
Germanium tetrahydride is not expected to accumulate in the edible tissues of fish.

Recommended Risk-Reduction Measures

Proper training of all transporters will reduce the likelihood of a mishap or accident resulting in a leak or
release to the environment. The correct use of DOT
labeling (per the MSDS) on all containers, trucks, and
rail cars will enable emergency responders to react

Restrict persons not wearing protective clothing

from area of spill or leak until cleanup is complete and area can be opened for normal work.
Remove all ignition sources.
Ventilate area of spill or leak using maximum
explosion-proof equipment.
If possible, stop flow of leaking liquid or gas.
Gas will spontaneously ignite in contact with air.
Remove all combustible materials from the area
and have extinguishing equipment available. Use
water spray to knock down vapors. Once germanium tetrahydride gas is ignited, it may be best to
let it burn since combustion will reduce the likelihood of explosions of unstable germanium tetrahydride mixtures in air.
Keep germanium tetrahydride out of a confined
space, such as a sewer, because of the possibility
of explosion (unless the sewer is designed to prevent the buildup of explosive concentrations).

RISK ASSESSMENT: BUSINESS

General Assessment
Accidents or mishaps involving germanium tetrahydride can present a significant threat to business operations. The loss or damage of equipment or facilities can significantly affect fiscal viability. Lawsuits

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

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that may result from personnel injury, public exposures, and environmental contamination will also require a serious expenditure of resources. Media attention surrounding an injury, illness, 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 dealing with safety
or emergency response. A company official should be
pre-designated 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.

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1996 by CRC Press, Inc.