Safe

Storage
of
Hazardous
Chemicals

University of California, Berkeley

Office of Environment, Health & Safety
 Contents
Page

Introduction 1

1.0 Take Inventory of Your Chemicals 2

2.0 Label Your Chemicals 3

3.0 Segregate Incompatibles 4

3.1 Common Incompatibles 6

4.0 Basic Storage Requirements 8

5.0 Chemical Storage Guide: Individual

Hazards and Mixed Hazards 10

5.1 Flammables and Combustibles 11

5.2 Corrosives 14

5.3 Toxics 16

5.4 Highly Toxics 17

5.5 Oxidizers 19

5.6 Compressed Gases 21

5.7 Cryogens 23

5.8 Pyrophorics (Air Reactives) 25

5.9 Water Reactives 26

5.10 Explosive and Potentially Explosive 27

5.11 Peroxide Forming Chemicals 31

Illustrations by Oruc Cakmakli
Introduction

The safe storage of hazardous chemicals is an essential part of

an environmental, health, and safety program. Chemical
storage facilities must meet certain minimum standards to
satisfy diverse regulations, such as those of Cal/OSHA, the
local sanitary district, and the California Fire Code. This manual
provides guidelines to help you meet these standards.

In addition, laboratories and work areas on campus must

observe several requirements that incorporate safe storage:
• Keeping an up-to-date chemical inventory
• Maintaining a chemical hygiene plan and documenting staff
training
• Conducting annual self-inspections
EH&S provides more information on the above programs at
its website www.ehs.berkeley.edu.

The five sections of this brochure cover the main elements of a

safe chemical storage program:

Section Information

1 How to Maintain an Accurate Inventory of

Hazardous Chemicals

2 Proper Chemical Labeling

3 Segregating Incompatible Chemicals

4 Providing Basic Storage Needs

5 Storing Chemicals according to their

Hazardous Characteristic

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1.0 Take Inventory of Your Chemicals

Safe storage begins with an up-to-date inventory of hazardous

chemicals that can be used to apprise personnel of the dan-
gers in a laboratory, shop, or work area. An accurate inventory
is also necessary if emergency responders are to respond effec-
tively to a fire or chemical release in the area. The campus can
be fined if it does not provide an inventory to emergency re-
sponse personnel and appropriate regulatory agencies.

The Office of Environment, Health & Safety (EH&S) coordinates

the collection of chemical inventories for the campus. Submit
your inventory to EH&S annually. Also submit one whenever
the maximum amount listed for a particular chemical changes by
more than 50 percent or you obtain a chemical that was previously
not reported. Immediately notify EH&S if a laboratory or other
area has been cleaned out or a new laboratory has started up or
moved.

The annual review of your chemical inventory is a prime oppor-

tunity to clean out unwanted chemicals. Your unwanted chemi-
cals will either be picked up and disposed of or collected for re-
use through the campus Chemical Exchange Program
(CHEX). Visit the EH&S
website (www.ehs.berkeley.edu)
for Fact Sheets about CHEX
and disposal of unwanted
hazardous materials.

Keep an extra copy of your

inventory handy at a central
location.

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-2-
2.0 Label Your Chemicals

All hazardous chemicals must be clearly labeled for the benefit

of current users, emergency personnel, and future users.
Unknown chemicals can be expensive to dispose of. Make sure
all labels are legible and in good condition. Repair or replace
damaged or missing labels.

Manufacturers’ Labels
Cal/OSHA requires that manufacturers provide labels with
the following information:

• contents of the container

• physical and health hazard information
• name, address, and emergency phone number of the
manufacturer or other responsible party

Original manufacturers’ labels must not be removed or defaced.

Material Safety Data Sheets (MSDSs) must be accessible to anyone
working with these chemicals. Electronic format MSDSs are
available from the EH&S website at www.ehs.berkeley.edu. The
MSDS may also provide useful storage information.

Your Own Labels

Hazardous chemicals that are not in the manufacturer’s original
container (e.g., working solutions
prepared in the lab) must, at a
minimum, be labeled with the
contents of the container. If the
contents are hazardous, attach a label
indicating the hazard to warn
individuals in the work area. It is not
necessary to label containers that
will be used temporarily (during one
work shift) and are under your
immediate control. Label your chemicals.
-3-
3.0 Segregate Incompatibles

Chemical Families
Materials should always be segregated and stored according
to their chemical family or hazard classification. Do not store
chemicals alphabetically unless they are compatible! The
most common hazard classes include:

• flammables/combustibles
• corrosive acids
• corrosive bases
• toxics
• highly toxics
• oxidizers
• compressed gases
• cryogens
• pyrophorics
• water reactives
• explosives

Accidental contact between incompatible chemicals can result

in a fire, an explosion, the formation of highly toxic and/or
flammable substances, or other potentially harmful reactions:

Oxidizers mixed with flammable solvents can cause a fire.

Acids mixed with metal dust can produce flammable
hydrogen gas.
Alphabetical storage can bring incompatibles together. For
example, if chromic acid (an oxidizing acid) and chromium
powder (a combustible metal) were stored together and an
accident broke their containers, the chemicals could mix
and react with explosive violence.

Segregate Families
Each chemical family should be separated from all other
chemical families by an approved non-combustible partition
or by a distance of twenty feet. Ideally, each hazard class would
-4-
be kept in a cabinet or on a shelf segregated from other hazard
classes. Incompatible chemicals within the same hazard class
should also be separated from one another. For example, both
nitric and perchloric acids are incompatible with organic acids
(such as acetic acid) and should not be stored together.

Most labs have limited space, but the following priorities may
help you decide how to store the chemicals.

• Do not store chemicals alphabetically unless they are

compatible.
• Store flammable liquids in approved safety containers in
flammable storage cabinets. Do not store anything but
flammable or combustible liquids in these cabinets.
• Segregate acids from bases.
• Segregate most organic acids from mineral acids.
•Keep oxidizers away from other chemicals, especially
flammables or combustibles.
• Keep corrosives away from substances that they may react
with and release corrosive, toxic, or flammable vapors.

Multiple Hazard Classes

Many chemicals belong to more than one chemical family or
hazard class. In such cases, all storage rules must be strictly
observed. For example, acetic acid is both a corrosive acid and
a combustible liquid. It must be stored away from corrosive
bases, such as sodium hydroxide, and also from oxidizing
acids, such as nitric acid.

For More Information

For more specific information, use the storage guidelines that
follow. You can obtain labels and material safety data sheets
(MSDSs) from the manufacturer, your department, or EH&S.
MSDSs provide information on chemical compatibility.

-5-
3.1 Common Incompatibles

Do not store these chemicals in close proximity to each other.

In an earthquake, fire, or other spill, they could mix and react
violently and/or release poisonous gas.

Laboratory Material Incompatible with

Alkali metals like calcium, water, carbon dioxide, carbon tetrachlo-
potassium, and sodium ride, other chlorinated hydrocarbons
chromic acid, nitric acid, hydroxyl-
Acetic Acid
containing compounds, ethylene gly-
col, perchloric acid, peroxides, per-
manganates
Acetone concentrated sulfuric or nitric acid
mixtures
Acetylene copper (tubing), halogens, silver,
mercury, and their compounds

Ammonia, Anhydrous mercury, halogens, calcium

hypochlorite, hydrogen fluoride

Ammonium Nitrate acids, metal powders, flammable

liquids, chlorates, nitrates, sulfur,
finely divided organics or
combustibles

Aniline nitric acid, hydrogen peroxide

Bromine ammonia, acetylene, butadiene,

butane, hydrogen, sodium carbide,
turpentine, finely divided metals

Chlorates ammonium salts, acids, metal

powders, sulfur, carbon, finely
divided organics, combustibles

Chromic Acid acetic acid, naphthalene, camphor,

alcohol, glycerine, turpentine, other
flammable liquids or combustible
materials
-6-
Chlorine ammonia, acetylene, butadiene,
benzene, other petroleum fractions,
hydrogen, sodium carbide,
turpentine, finely divided powdered
metals
Cyanides acids

Hydrogen Peroxide copper, chromium, iron, most metals

or their respective salts, flammable
liquids or combustible materials,
aniline, nitro-methane
Hydrogen Sulfide nitric acid, oxidizing gases

Hydrocarbons halogens, chromic acid, sodium

(general) peroxide

Iodine acetylene, ammonia, chlorine

F
Mercury acetylene, ammonia, lithium

Nitric Acid acetic, chromic, and hydrocyanic

acids, aniline, carbon, hydrogen
sulfide, flammable material, readily
nitrated substances
Oxygen oils, grease, hydrogen; flammable
materials

Oxalic Acid silver, mercury, chlorites, strong

oxidizers

Perchloric Acid acetic anhydride, bismuth and its

alloys, alcohol, paper, wood, other
organic materials

Potassium glycerine, ethylene glycol,

Permanganate benzaldehyde, sulfuric acid

Sodium Peroxide any oxidizable substances

Sulfuric Acid chlorates, perchlorates,

permanganates
-7-
4.0 Basic Storage Requirements

The following basic storage requirements apply to all hazardous

chemicals. Refer to the “Chemical Storage Guide” sections of
this brochure for additional requirements that apply to chemicals
in a specific hazard class (e.g., flammables and corrosives).

Storage Area Requirements

✔ Label storage areas according to the type of chemical
family or hazard classification found there.

✔ Inspect storage areas at least annually, as required by Cal/

OSHA.

✔ Keep aisles, hallways, doorways, exits, and entryways clear.

✔ Keep storage areas well lit, appropriately ventilated, and at

a consistent, cool temperature.

✔ Eliminate ignition sources such as open flames, heat sources,

or direct sunlight.

✔ Keep emergency equipment such as fire extinguishers handy

and in good working order.

✔ Confine chemical storage areas so that leaks or spills are

controlled. Prevent chemicals from running down sink, floor,
or storm water drains. Clean up spills and drips immediately.

Storage Don’ts
✖ Don’t store chemicals in a sink or fume hood, except for
certain toxic gases that are so dangerous they can only be stored
in a gas cabinet or fume hood.

✖ Don’t store chemicals on dirt or grass, near a creek or storm

drain entrance, where they could contaminate the environment.

✖ Don’t store chemicals on the floor, window ledges, or balconies.

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Storage Cabinets
Use only approved storage cabinets. Never alter a flammable
storage cabinet unless directed to do so by EH&S.

Label cabinets with the hazard class of the chemicals.

Storage Shelves
Shelves should be level, stable, and secured to the wall or
another stable surface.

In case of an earthquake, shelves should have raised edges or

rim guards (minimum height of 2 inches) to prevent containers
from falling. Use bungee cords for added security.

Shelves should be kept free of chemical contamination and dust.

Shelves should be located away from direct sun, flame, and

heat sources.

Containers should not protrude over shelf edges.

Store large bottles/containers no higher than 2 feet from the

floor. Store corrosives on lower shelves.

Storage Containers
Keep containers closed unless you are dispensing a chemical
or adding to the container. Never store a container open with
a funnel in it.

Provide secondary containment for liquids in containers larger

than 1 gallon in size. Dishpans or polyethylene trays work well.

Use approved containers for flammable solvents.

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5.0 Chemical Storage Guide:
Individual Hazards and Mixed Hazards

Sections 5.1 through 5.11 provide basic storage guidelines for

the most common hazard classes. Each section describes the
characteristics of the hazard class (consistent with California
Fire Code). It includes common examples of laboratory and
non-laboratory chemicals and provides basic storage require-
ments and precautions. Note: These examples do not consti-
tute a full list, and the laboratory/non-laboratory classifica-
tions may not strictly apply.

Please note that many chemicals have multiple hazard classi-

fications. Consequently, you may need to consult several stor-
age guideline sections to determine how to store a hazardous
chemical safely. For example, acetic acid is a corrosive acid and
also a combustible liquid. Therefore, you need to follow sec-
tion 5.1 (flammables and combustibles) and section 5.2 (corro-
sives). You may also call EH&S for help.

Federal and state regulations may require a Risk Management

Plan for certain highly hazardous chemicals, depending on the
amount stored. EH&S periodically reviews your chemical in-
ventory and will notify you if there is a concern. It is a prudent
practice to maintain the lowest possible quantities of highly
hazardous chemicals.

The capital letters in parenthesis used in sections 5.1– 5.11 that

follow the chemical examples indicate that the chemical has
an additional hazardous characteristic other than the one being
discussed. Refer to the appropriate storage guideline section
in this brochure for information and follow its directives as
well.

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NFPA Chemical Hazard Identification System

Each hazard class section on the following pages includes two chemical
examples illustrated with National Fire Protection Association (NFPA)
diamond symbols that rate the degree of health, flammability, reactivity,
and special hazards of the chemicals discussed. Hazards are rated from 0
for minimal hazard to 4 for severe hazard .

The degree of hazard is often dependent upon the physical state of the
chemical as well. For example, a flammable gas will pose a more significant
immediate safety threat upon release than a liquid that has the same flash
point.

Flammability
(Red)
Health Reactivity
(Blue) (Yellow)

Special
(White)

The NFPA Health Hazard rates the effect of short-term exposure to a

chemical by physical contact, eye and skin absorption, or inhalation. A
highly toxic chemical with a health hazard rating of 4 could be lethal on
very short exposure.

The NFPA Flammability Hazard rates the ease with which a chemical will
ignite from exposure to a spark, open flame, or high temperature. A
flammable or pyrophoric chemical with a flammability rating of 4 could
readily ignite at room temperature.

The NFPA Reactivity Hazard rates a chemical’s thermal instability, potential

for hazardous reaction with water, or sensitivity to friction or shock. A highly
unstable chemical, such as an explosive with a reactivity rating of 4, could
readily detonate if exposed to localized thermal or mechanical shock at
normal temperatures and pressures.

The NFPA Special Hazards include W (to indicate a water reactive chemical
that could react violently or explosively upon contact with water) and OX
(to indicate an oxidizer that could ignite combustible or flammable material
upon contact).
-11-
5.1 Flammables and Combustibles

Characteristics
These chemicals are easily ignited
and may present a serious fire and
explosion hazard. Flammable liquids
have a flash point below 100°F.
Combustible liquids have a flash
point of 100°F to 200°F. Flammable
solids have an ignition temperature
below 212°F. Flammable solids include finely divided solid
materials which, when dispersed in air, could ignite. Other classes
of chemicals with a high fire hazard include oxidizers (section
5.5), pyrophoric chemicals (section 5.8), and water reactive
chemicals (section 5.9).

Laboratory Chemicals
Flammable Solids Flammable Liquids
naphthalene (HT) alcohols - methanol,
finely divided metal ethanol
(e.g., aluminum, esters - ethyl acetate
cadmium, ethers - diethyl ether
chromium, ketones - acetone,
cyclohexane
titanium, zinc) (P)

Flammable Gases Combustible Liquids

hydrogen acetic acid (CA)
methane cumene
phenol (CA, T)
propionic acid (CA)

4 1
1 1 1 0

ethyl ether glycerine

--12-
Non-Laboratory Chemicals
Flammable Solids Flammable Liquids
moth balls (HT) gasoline
(containing naphthalene) lighter fluid
calcium carbide (WR) paint thinner
Flammable Gases Combustible Liquids
acetylene antifreeze
diesel fuel
engine oil

Additional hazardous characteristics: CA–Corrosive acid; HT–Highly

toxic; P–Pyrophoric; T–Toxic; WR–Water reactive

Storage Limits
California Fire Code regulations limit the quantity of flammable
liquids stored in research and teaching laboratories on the
Berkeley campus.

Quantity Limits outside Flammable Storage Cabinets

A maximum of ten (10) gallons of flammable liquids may be
stored outside a flammable storage cabinet.

Quantity Limits within Flammable Storage Cabinets

Flammable liquids stored in approved cabinets within
laboratories or classrooms shall not exceed sixty (60) gallons.

Maximum Container Capacity

• The capacity of glass containers shall not exceed one (1)
gallon.
• The capacity of all other containers (including safety cans)
shall not exceed two (2) gallons.

See the Fact Sheet on the storage of flammable liquids at

www.ehs.berkeley.edu. If you need additional information, please
contact the Campus Fire Marshal at 642-4409.

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Storage Precautions for Flammables and
Combustibles
Keep flammables away from all ignition sources: open flames,
hot surfaces, direct sunlight, spark sources.

Store flammables separate from other hazard classes, especially

oxidizers and toxics.

Separate flammable gases from oxidizing gases with an

approved non-combustible partition or by a distance of 20 feet.

Store flammable liquids in approved safety containers or

cabinets.

In instances where static electricity may accumulate and ignite

flammable vapors, ground and bond flammable liquid containers.

Keep a fire extinguisher (appropriate for the hazard) readily available

and make sure anyone who may need to use it is properly trained.
Keep flammable liquids that require cold storage in laboratory-
safe flammable material refrigerators or freezers to avoid
ignition of the materials by sparks or static electricity. See
the Fact Sheet about storage of hazardous materials in freezers
and refrigerators at
www.ehs.berkeley.edu.

Retrofitting non-
laboratory-safe
refrigerators for use
with flammables is
prohibited.

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5.2 Corrosives

Characteristics
Strong acids and bases can destroy
human tissue and corrode metals.
Acids and bases are incompatible with
one another and may react with many
other hazard classes.

Laboratory Chemicals
Acids Bases
Organic Acids ammonium hydroxide (T)
acetic acid (C) calcium hydroxide
citric acid ( C ) potassium hydroxide (T, WR)
formic acid (C, T) sodium hydroxide (T, WR)
oxalic acid (T) tri-sodium phosphate (T)

Inorganic Oxidizing Acids

chromic acid (O, T) 0 0
nitric acid (HT, O)
4 0 3 1
perchloric acid (O, PEC)
sulfuric acid (O, T, WR) OX W

Inorganic Non-Oxidizing Acids nitric acid sodium hydroxide

hydrochloric acid
phosphoric acid

Non-Laboratory Chemicals
Acids Bases
muriatic acid (contains drain declogger (containing
hydrochloric acid) sodium hydroxide)
wall cleaner (containing tri-
sodium phosphate)

Additional hazardous characteristics: C–Combustible liquid or solid;

HT–Highly toxic; O–Oxidizer; PEC–Potentially explosive chemical;
T–Toxic; WR–Water reactive

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Storage Precautions for Corrosives
Segregate acids from bases. Segregate inorganic oxidizing acids
(e.g., nitric acid) from organic acids (e.g., acetic acid),
flammables, and combustibles.

Segregate acids from chemicals that could generate toxic gases

upon contact (e.g., sodium cyanide and iron sulfide).

Segregate acids from water reactive metals such as sodium,

potassium, and magnesium.
Use tight-fitting goggles, gloves, and closed-toe shoes while
handling corrosives.

Store solutions of inorganic hydroxides in

polyethylene containers.

Store corrosives on lower shelves, at least

below eye level and in compatible
secondary containers.

Do not store corrosives on metal shelves.

Although ventilation helps, chemicals will
still corrode the shelves. Store containers
in plastic tubs or trays as secondary
containment.

If you notice powder deposits, discoloration, and crystallization

around the cap of a container, particularly an oxidizing acid,
contact EH&S immediately. The material may be potentially
explosive.

Follow the special handling and use procedures for

hydrofluoric acid (See the Fact Sheet about hydrofluoric acid
at www.ehs.berkeley.edu). Keep calcium gluconate available as
an antidote.

Have spill control pillows or neutralizing agents available in case

of a spill. These may be purchased from safety supply companies.
-16-
5.3 Toxics
Characteristics
Overexposure to toxic chemicals can
cause injury or death. Toxics are
chemicals with a lethal dose (LD50) of
more than 50 and less than 500
milligrams per kilogram body weight
or a lethal concentration (LC50) in air of
more than 200 and less than 1,000 parts
per million.

Laboratory Chemicals
Solids Liquids Gases
acrylamide aniline (C) ammonia
cadmium chloride chlordane hydrogen fluoride (CA)
potassium fluoride (CA) phenol (C, CA) vinyl bromide

Non-Laboratory Chemicals 4
Solids Liquids 0
3
diazinon copper sulfate
Additional hazardous characteristics: C–
Combustible liquid ; CA–Corrosive acid hydrogen sulfide
Storage Precautions for Toxics

Segregate toxics from other hazard classes and 2

store in a cool, well ventilated area, away from 3 0
light and heat.
phenol
Containers should be tightly sealed to
minimize exposure to personnel and
contamination of other chemicals.

Manage toxic gases, highly toxic gases, and pyrophoric gases

in accordance with the campus Toxic Gas Program
requirements. Contact EH&S for specifics, or print out the Fact
Sheet about the campus Toxic Gas Program at
www.ehs.berkeley.edu.
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5.4 Highly Toxics
Characteristics
These chemicals can cause serious
injury or death at low concentrations.
Highly toxics are chemicals with a
lethal dose (LD50) of less than or equal
to 50 milligrams per kilogram body
weight or a lethal concentration (LC50)
in air of less than or equal to 200 parts
per million.

Laboratory Chemicals
Solids Liquids Gases
arsenic salts acrolein diborane (P, WR)
calcium cyanide hydrocyanic fluorine (CA, O, WR)
organic mercury acid (CA, F) nitrogen dioxide (O)
compounds nicotine (C)

4 0
4 3 4 1
W diborane potassium dichromate

Additional hazardous characteristics: C–Combustible; CA–Corrosive

acid; F–Flammable; O–Oxidizer; P–Pyrophoric; WR–Water reactive

Storage Precautions for Highly Toxics

Maintain the lowest possible quantities of highly toxics.

Segregate highly toxic chemicals from other hazard classes and

store in an area that is cool, well ventilated, and away from
light and heat.

Use highly toxic chemicals in a designated area or laboratory.

Highly toxic chemicals that produce fumes or dust should
always be handled within a chemical fume hood.

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The California Fire Code limits the aggregate amount of highly
toxic solids and liquids to 10 pounds per laboratory or storage
area.

The California Fire Code limits the amount of highly toxic

gases to 20 cubic feet per laboratory or storage area.

Manage toxic gases, highly toxic gases, or pyrophoric gases in

accordance with the campus Toxic Gas Program requirements.
See the Fact Sheet about the campus Toxic Gas Program at
www.ehs.berkeley.edu. Contact EH&S for specifics.

Containers should be tightly sealed to minimize exposure to

personnel and avoid contamination from other chemicals.

Do not eat, drink, or apply cosmetics where highly toxic chemi-

cals are handled.

Handle highly toxic chemicals in a chemical fume hood.

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5.5 Oxidizers

Characteristics
Oxidizers are a fire hazard. They will
readily decompose under certain
conditions to yield oxygen or react to
promote or initiate the combustion
of flammable or combustible
materials.

Laboratory Chemicals

Solids Liquids Gases

ammonium nitrate bromine chlorine (HT)
calcium nitrate (T) chromic acid (CA, T) fluorine (CA, HT, WR)
hydrogen peroxide nitrogen dioxide (HT)
potassium chlorate
nitric acid (CA, HT) oxygen
potassium nitrate
perchloric acid ozone (HT)
sodium dichromate (HT)
(CA, PEC)
sodium nitrate
sulfuric acid (CA, T, WR)

Non-Laboratory Chemicals
Solids Liquids Gases
fertilizers (e.g., bleaching agents oxygen
ammonium nitrate) (e.g., hydrogen chlorine (T)
pool chemicals peroxide,
(e.g., bromine sodium
tablets) hypochlorite)

0 0
1 0 3 2
W
OX OX

silver nitrate sulfuric acid

Additional hazardous characteristics: CA–Corrosive acid; T–Toxic; HT–

Highly toxic; PEC–Potentially explosive chemical; WR–Water reactive

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Storage Precautions for Oxidizers

Segregate oxidizers from flammable and combustible materials

(paper, wood). See Flammables and Combustibles (section 5.1).

Segregate oxidizers from reducing agents (zinc, alkaline metals,

formic acid).

Segregate inorganic oxidizers from organic peroxides.

Take care not to contaminate oxidizers. Some oxidizers, such

as perchloric acid, can become explosive mixtures if
contaminated with trace amounts of organic materials or
metals. See Explosive and Potentially Explosive Chemicals
(section 5.10).

Store in a cool, dry place. Do not store under sink.

Remember that perchloric acid, nitric acid, and hydrogen

peroxide are oxidizers and must not be stored on wooden
shelves or in cardboard boxes.

Do not store oxidizers on wood shelves. A leak could start a fire.

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5.6 Compressed Gases

Characteristics
What all compressed gases have in
common is the large amount of energy
stored in the cylinder from the compression
of the gas. Dropping or knocking over a
COMPRESSED cylinder can cause the energy to be
GAS rapidly released. It may even propel a
cylinder like a rocket. Additional
hazards can arise from the toxicity,
flammability, corrosivity, or reactivity
of the gas.
Laboratory Chemicals
0
argon hydrogen (F)
4 0
butane (F) methane (F)
carbon monoxide (T) nitrogen OX
chlorine (T,O)
ethylene (F) chlorine

Non-Laboratory Chemicals
acetylene (F) 4
compressed air 1 3
oxygen (O)
Additional hazardous characteristics:
F–Flammable;T–Toxic; O–Oxidizer acetylene

Storage Precautions for Compressed Gases

Segregate incompatible gases as you would other incompatible

chemicals.

Limit the quantity of compressed gas cylinders on site to what

will be used within a reasonable period of time.

Store cylinders upright.

-22-
Secure cyclinders so they will not fall during an earthquake.

An acceptable means includes using two non-combustible

restraints, such as chains, one restraint located approximately
one-third of the cylinder length from the top, and the other
restraint one-third from the bottom.

Keep cylinders away from heat and open flames.

Leave the valve protection cap on the cylinder unless it is in use.

Never store cylinders in walk-in freezers. The confined space

with no ventilation poses a potential hazard.

If you suspect that a cylinder is leaking, do not attempt to sniff

the leak out. Apply a soap solution to the cylinder and locate
the leak by noting where the bubbles appear.

Toxic gases, highly toxic gases, and pyrophoric gases must be

managed in accordance with the campus toxic gas program
requirements. See the Fact Sheet about the campus Toxic Gas
Program at www.ehs.berkeley.edu. Contact EH&S for details
about ventilation and quantity limitations.

Secure gas cylinders adequately.

-23-
5.7 Cryogens

Characteristics
These materials are extremely cold
(-100°C to -270°C). Upon contact with
cryogenic materials, living tissue can
freeze and become brittle enough to
CRYOGENS
shatter. Additional hazards include rapid
pressure buildup, oxygen enrichment,
and asphyxiation. Rapid pressure
buildup could lead to an explosion
if cryogen is improperly contained. Cryogenic liquids and gases
have many properties and hazardous characteristics in
common with compressed gases.

Laboratory Chemicals
liquid argon liquid hydrogen (F)
liquid carbon monoxide (F, T) liquid methane (F)
liquid ethylene (F) liquid nitrogen
liquid fluorine (CA, HT, O, WR) liquid oxygen (O)
liquid helium

0 0
3 0 3 0
OX

liquid nitrogen liquid oxygen

Additional hazardous characteristics: CA–Corrosive acid; F–

Flammable; HT–Highly toxic; O–Oxidizer; T–Toxic; WR–Water reactive

Storage Precautions for Cryogens

Store and handle in a well-ventilated area. When liquid

cryogens are converted to the gaseous phase, they may create
an oxygen deficiency. Do not use cryogens in small enclosed
spaces.
-24-
Use only approved storage vessels (i.e., thermos-like evacuated,
double-walled containers) with pressure-relief mechanisms.
Non-approved vessels may explode.

Secure containers so they will not tip over or obstruct an aisle,

hallway, or corridor during an earthquake.

Liquid nitrogen and liquid helium are capable of liquefying

oxygen from air. This form of oxygen enrichment can become
a strong fire or explosion hazard.

Use appropriate protective equipment for handling cryogens:

insulated holders for carrying vessels; eye protection, goggles,
or face shields; and aprons. Use cryogenic gloves or leather
gloves when handling supercold surfaces.

Wear cryogenic or leather gloves when handling supercold surfaces.

-25-
5.8 Pyrophorics (Air Reactives)

Characteristics
Substances that ignite spontaneously
upon contact with air.
SPONTANEOUSLY
COMBUSTIBLE

Laboratory Chemicals
Solids Liquid Gases
sodium (WR) aluminum diborane (HT, WR)
finely divided metal borohydride (CB,WR) phosphine (HT, WR)
(e.g., aluminum, diethylzinc (WR) silane (WR)
chromium, zinc)
4 3
2 3 2 2
W zinc
silane

Additional hazardous characteristics: CB–Corrosive base; HT–Highly

toxic; WR–Water reactive

Storage Precautions for Pyrophorics

Store in a cool, dry place. Prevent contact with air.

Take extreme care to prevent containers of pyrophorics from

leaking or breaking. For additional protection, consider
keeping the chemicals in the manufacturer’s original shipping
package (i.e., surrounded by vermiculite inside a metal can).

Many pyrophorics are also water reactives (section 5.9).

Manage pyrophoric gases, toxic gases, and highly toxic gases,

in accordance with the campus Toxic Gas Program
requirements. See the Fact Sheet about the campus Toxic Gas
Program at www.ehs.berkeley.edu. Contact EH&S for specifics.
-26-
5.9 Water Reactives

Characteristics
These substances often react
violently with water and may ignite
DANGEROUSWHEN
WET
or generate toxic, flammable, or
corrosive gases.

Laboratory Chemicals
Solids Liquids
aluminum chloride (anhydrous) acetyl chloride (CA, F)
calcium carbide (F) chlorosulfonic acid (CA, HT)
magnesium (F) stannic chloride (CA)
phosphorus pentatchloride (CA, HT) thionyl chloride (CA)
sodium (P)

2 0
2 3 3 2
W W

antimony potassium hydroxide

Additional hazardous characteristics: CA–Corrosive acid; F–Flammable;

HT–Highly toxic; P–Pyrophoric

Storage Precautions for Water Reactives

Store in a cool, dry

place.

Keep away from water.

In case of fire, do not use

water. Use a dry
Keep water reactives in a dry environment.
chemical extinguisher.
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5.10 Explosive and Potentially Explosive
Chemicals

Characteristics
Explosive chemicals can rapidly
release tremendous amounts of
destructive energy. Explosive
chemicals can cause death, serious
injury, or severe property damage.
Heat, shock, friction, or even static
electricity can initiate explosions of
these chemicals. The family includes pure chemicals (e.g., TNT)
and mixtures (e.g., ammonium nitrate/fuel mixtures).

In addition to explosive chemicals, which constitute a

known high hazard, there are chemicals that may become
explosive, depending on how they are handled. This
category is commonly referred to as potentially explosive
chemicals and includes:

• pure chemicals or mixtures that may become explosive

through contamination (e.g., perchloric acid contaminated
with organic compounds or metals); and

• pure chemicals or mixtures that may degrade over time and

become explosive (e.g., hydrated picric acid, which
becomes explosive upon drying). This category also
includes certain alcohols and ethers that may accumulate
explosive levels of peroxides by interacting with air. See
Peroxide Forming Chemicals (section 5.11).

For more extensive information regarding potentially explo-

sive chemicals, please see the ”Guidelines for Explosive and
Potentially Explosive Chemicals Safe Storage and Handling”
available through the EH&S office or visit the website:
www.ehs.berkeley.edu.
-28-
Primary Classes of Explosive Chemicals
(with examples)

Nitrogen-Oxygen Chemicals
(e.g., Nitrates, Nitro)
ethylidene dinitrate
picric acid (dry)
thallium aci-phenylnitromethanide
trinitrotoluene (TNT)

Oxides, Peroxides, and Related Chemicals 4

(See Peroxide Forming Chemicals.) 3 4
benzoyl peroxide (97%) (dry)
bis (1-chloroethylthallium chloride) oxide

Nitrogen-Rich Chemicals picric acid (dry)

(e.g., Azo-, Diazo, Triazo, Tetrazole)
aluminum azide
5-aminotetrazole
1-bromoaziridine
chromyl azide chloride
diethyl diazomalonate
hydrogen azide (>17%) 4
lead azide 2 4
mercury (I&II) azide
molybdenum diazide tetrachloride
sodium diazomethanide
tetrazole trinitrotoluene
1,2,3-triazole

Perchlorate Chemicals
ammonium perchlorate
ethyl perchlorate (the most explosive chemical known)
hexyl perchlorate

Acetylenic Chemicals
n-chloro-3-aminopropyne
propiolic acid
3-propynethiol
4- sodium hexakis(propynyl)ferrate

-29-
Examples of Potentially Explosive Chemicals
(which are normally stable)

• Organic chemicals, such as ethers, that form peroxides

through exposure to air or light (See Peroxide Forming
Chemicals, section 5.11.)

• Hydrated picric acid that becomes dry

• Sodium amide that reacts with air or moisture

• Certain alkyl nitrates (e.g., butyl nitrate or propyl nitrate)

that become contaminated with nitrogen oxides

• Certain normally stable perchlorates (e.g., pyridium perchlo-

rate or tetraethylammonium perchlorate) that become un-
stable at elevated temperatures

Storage Precautions for Explosive and

Potentially Explosive Chemicals

Identify all explosive and potentially explosive chemicals in

your inventory.

For chemicals that may degrade to become potentially

explosive, record the opening date and discard date directly
onto the container or onto a potentially explosive chemical
warning label (available from EH&S).

Keep explosive chemicals away from all ignition sources: open

flames, hot surfaces, direct sunlight, spark sources.

Store explosive chemicals in an explosive magazine and inspect

areas weekly to comply with the California Fire Code. (Contact
EH&S for assistance.)

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Consider designating a special area to store and use potentially
explosive chemicals.

Make sure everyone who uses explosive or potentially

explosive chemicals is thoroughly trained in safe storage
methods, conditions to avoid (e.g., contamination), the hazards
of the chemical, and disposal procedures.

Contact EH&S immediately if you suspect a material may have

become explosive. Post warning signs so others do not handle
or disturb the material.

Note: Most explosions occur while purifying or distilling

mixtures. Therefore, use extreme caution before
concentrating or purifying any mixture that may contain an
explosive chemical (e.g., a peroxide forming chemical or
perchlorate).

Contact EH&S to discuss your storage and handling of

explosive and potentially explosive chemicals.

-31-
5.11 Peroxide Forming Chemicals

Characteristics
Over a period of time, these
chemicals can form peroxides that
may explode when the cap is
PEROXIDE removed or when they are
FORMING concentrated during laboratory
activities. It is important to note on
the container the date the chemical
arrived in the laboratory, when it was opened, when it should
be tested for peroxide concentration, and when it should be
discarded. Dispose of the chemical before the discard date
indicated on the container or follow the guidelines below.

Dispose of within 24 Hours: 2

acrylic acid (uninhibited) 3 2
butadiene (uninhibited)

acrylic acid
Test or Dispose of within 3 Months:
butadiene (inhibited)
chloroprene
divinylacetylene
isopropyl ether

Test or Dispose of within 12 Months:

acetaldehyde
acrolein
benzyl ether
4
2-butanol
cyclohexanol 2 1
diethyl ether
ethyl vinyl ether
2-hexanol diethyl ether
3-methyl-1-butanol
tetrahydrofuran

-32-
Storage and Disposal of Peroxide Forming
Chemicals

By the expiration date, the owner/user should either dispose

of the chemical or test it for peroxide content. Dispose of any
chemicals found to have a peroxide concentration greater than
or equal to 100 parts per million. (Call EH&S for assistance.)
Materials that have lasted beyond the recommended shelf life
but have been tested and show no detectable peroxides, or
whose peroxide concentrations are less than 100 ppm, may be
retained but should be tested at frequent intervals. Test all
peroxide forming chemicals prior to distillation, regardless
of age.

Important note: Never test containers of unknown age or

origin. Old bottles are likely to contain concentrated
peroxides, and peroxides may have crystallized in the cap
threads, which can present a serious hazard when the bottle
is opened for testing.

Contact EH&S for help with managing older containers and

for additional guidelines on the
safe storage and handling of
peroxide forming chemicals.

-33-
Storage Precautions for Peroxide Forming
Chemicals

Identify all peroxide forming chemicals in your inventory.

Write the opening date and discard date on the containers of

chemicals that may degrade to become potentially explosive.

Store in airtight containers in a dark, cool, and dry place.

Never store peroxide formers in a freezer because a change

from a solid to a liquid can cause detonation.

Discard or test peroxide forming chemicals before the

expiration date printed on the container label. Contact EH&S
for disposal information.

If precipitate appears in an organic chemical that may form an

explosive peroxide (e.g., crystals around the neck or cap of
bottle), or if an oily layer appears, do not move it. Contact EH&S
immediately.

Inspect peroxide-forming chemicals often for evidence of

contamination, degradation, or any change from normal
physical or chemical characteristics. Contact EH&S
immediately if you suspect a material may have become
explosive. Post warning signs so others do not handle or
disturb the material.

Note: Most explosions occur while purifying or distilling

mixtures. Therefore, use extreme caution before
concentrating or purifying any mixture that may contain an
explosive chemical (e.g., a peroxide or perchlorate).
For more extensive information regarding potentially explo-
sive chemicals, please see the "Guidelines for Explosive and
Potentially Explosive Chemicals Safe Storage and Handling"
available through the EH&S office or visit the website:
www.ehs.berkeley.edu.
-34-
 General Assistance
Office of Environment, Health & Safety 642-3073

Emergency Phone Numbers

Life-threatening Emergency or
Imminent Hazard to the Environment 911

Chemical or Biological Spill EH&S 642-3073

Radioactive Materials Spill ORS 642-8414

Off-hours/Weekend Spills UCPD 642-6760

Physical-Plant Campus Services (24 hours) 642-6556

Department Contacts
Name Phone Number

Department Safety Coordinator

Building Coordinator

Lab or Shop Emergency Contact

Published by the Office of Environment,

Health & Safety, April 2001