4.03 CHEMICAL STORAGE PROGRAM

This program contains requirements for practices designed and implemented to protect University employees, students, visitors and the environment from the risks of hazardous chemicals that are stored on University property.

A. SCOPE

This program is applicable to all University students, faculty and staff that are required by the nature of their job to handle hazardous chemicals.

B. DEFINITIONS

Flammable chemicals - Solid, liquid or gaseous chemicals that readily catch fire and burn in the presence of oxygen.

CLASSIFICATION TERM FLASH POINT TEMPERATURE

Flammable Liquid Class I Below 100°F (37.8°C)

Flammable Liquid Class I A Below 73ºF (22.8ºC) and Boiling Point below 100ºF (37.8ºC)

Flammable Liquid Class I B Below 73ºF (22.8ºC ) and Boiling Point at or above 100ºF (37.8ºC)

Flammable Liquid Class I C Below 100ºF (37.8ºC) and Boiling Point at or above 73ºF (22.8ºC)

Combustible chemicals - Solid, liquid or gaseous materials that burn in the presence of oxygen.

CLASSIFICATION TERM FLASH POINT TEMPERATURE

Combustible Liquid Class II Below 140ºF (60ºC) or at or above 100ºF (37.8ºC)

Combustible Liquid Class III At or above 140ºF (60ºC)

Combustible Liquid Class III A Below 200ºF (93.4ºC) or at or above 140ºF (60ºC)

Combustible Liquid Class III B At or above 200°F (93.4ºC)

NOTE: Ignitable liquids, regulated as wastes by the Environmental Protection Agency (EPA) under the Resource Conservation and Recovery Act, include Class I flammable liquids and Class II combustible liquids.

Corrosive chemicals - Any solid, liquid or gaseous chemicals that burn, irritate or destructively attack organic tissues, most commonly the skin.

Material Safety Data Sheet (MSDS) - Written or printed material prepared by the manufacturer of a hazardous chemical that contains information about the hazards of the chemical and the appropriate work practices required for use.

NFPA-approved - Approved by the National Fire Protection Association.

Oxidizing chemicals - Any solid, liquid or gaseous chemicals that may cause or enhance the combustion of other materials or readily react to oxidize combustible materials, generally by yielding oxygen or some other oxidizing gas.

Pyrophoric chemicals - Any liquid or solid chemicals that will ignite spontaneously in air below 130ºF (54.4ºC).

Reactive chemicals - Any solid, liquid or gaseous chemicals that react violently with water, or are normally unstable and readily undergo violent changes without detonating, or form potentially explosive mixtures with water, or generate toxic gases when mixed with water or corrosive chemicals, or are capable of detonation or an explosive reaction.

Toxic chemicals - Any solid, liquid or gaseous chemicals that can cause damage to living tissue, impairment of the central nervous system, severe illness or in extreme cases, death when ingested, inhaled or absorbed by the skin.

C. GENERAL STORAGE REQUIREMENTS FOR ALL CHEMICALS

1. Label all chemical containers appropriately. If transferring chemicals out of their original container to another container or if the original container label is illegible, follow the chemical labeling guidelines as detailed in UNM's Hazard Communication Program.

2. Be knowledgable of the procedures contained in SHEA's Chemical Spill Response Program to prepare yourself and others in the event that any chemical container leaks or is spilled.

3. Follow all precautions regarding the storage of incompatible chemicals. Consult the label and Material Safety Data Sheet (MSDS) for each chemical to ensure that you are familiar with the chemical and how it should be handled, stored and disposed. Separate all chemicals into compatible groups and store alphabetically within stored groups. (See Section I and Section J for two charts concerning incompatibilities and compatibilities of various chemical groups.)

4. Provide a definite storage place for each chemical and return the chemical to that same location after each use.

5. Avoid storing chemicals in laboratory fume hoods or on benchtops, except for those chemicals intended to be used by the end of the day.

Store volatile toxic chemicals and odorous chemicals in a ventilated cabinet, if possible. The cabinet's associated electrical components must be explosion-proof if flammable materials are being ventilated. If located in a laboratory, locate the cabinet near the fume hood. Store other chemicals inside a closable cabinet or on a shelf that has a lip to prevent containers from sliding off in the event of a fire or other serious accident.

Do not expose stored chemicals to heat, direct sunlight or freezing conditions.

Store all containers of liquids on compatible plastic trays that are capable of holding the contents of the container if it leaks, or at least 10% of the total volume stored within the tray. Store liquids on lower shelves, if possible.

9. Seal all chemical containers well to minimize the escape of flammable, corrosive, irritating or toxic vapors or gases.

10. Ventilation is required for chemicals that may release dangerous or damaging quantities of vapors or gases which may be flammable, corrosive, irritating or toxic.

11. For every chemical storage area, there should be evacuation and emergency procedures to be followed and fire extinguishers available in the case of personal exposure or a leak, spill or fire within the room.

D. STORAGE REQUIREMENTS FOR FLAMMABLE AND COMBUSTIBLE CHEMICALS

1. The storage area should be separated and protected so that a fire or spill in the storage area is not likely to spread beyond the storage area.

2. If containers of flammable and combustible liquids are larger than five (5) gallons in size, special provisions are necessary to prevent liquid from flowing out of the storage area in the event of a spill or leak. Contact SHEA at 277-2753 for further details.

3. When possible, store quantities of flammable liquids greater than one (1) gallon in NFPA-approved safety cans. Store all flammable liquids and solids in NFPA-approved storage cabinets. SHEA will provide these cabinets to you at no cost.

4. Do not store flammable chemicals in any refrigerator unless it has been designed for that purpose. Ordinary refrigerators contain spark sources that can ignite flammable vapors. If refrigerated storage is needed inside of a flammable storage room, an explosion-proof refrigerator must be used. Use chemical storage refrigerators only for storing chemicals, never food or drink. Label these refrigerators with the following signage:

NO FOOD OR DRINK TO BE STORED IN THIS REFRIGERATOR

Maximum Container Sizes for Flammable and Combustible Liquids

The following container sizes, in liters, are the maximum allowable unless otherwise specified:

Flammable Liquids Combustible Liquids

Container Class IA Class IB Class IC Class II Class IIIA

Glass 0.5 1 4 4 4

Metal or approved plastic 4 20 20 20 20

Safety cans 7.5 0 20 20 20

NOTE: Glass containers as large as one (1) gallon can be used, if needed, and if the required purity would be adversely affected by storage in a metal or approved plastic container, or if the liquid would cause excessive corrosion or degradation of a metal or approved plastic container.

6. Storage Limits for Flammable and Combustible Liquids

The following limits apply to all Class B Occupancies with sprinkler systems and is the maximum allowable. Contact SHEA for clarification if you have questions.

Liquid Class Flash Point (o F) Amount Allowable (per 100 sq. ft.)

Class I Flammable Below 100º 4 gallons

Class II Combustible 100º - 139º 4 gallons

Class IIIA Combustible 140º - 200º 12 gallons

Class IIIB Combustible Above 200º Unlimited

7. Safety Equipment for Storage of Flammable Liquids

Safety Cans: Safety cans are containers that have built-in safety features for protecting flammable liquids from exposure to a fire situation. In a fire situation, a safety can is exposed to extremely high temperatures. This heat is transmitted to the contents, which in turn boil and produce a large vapor pressure. Every safety can is fitted with a spring-loaded cap that vents these vapors safely without bursting the can. The other safety feature of a safety can is the flame arrestor that consists of a cylindrical wire screen. Vapors emitted from a safety can will ignite when exposed to the flames of a fire. Since flames usually flash back to the source of liquid, the flame arrestor serves as a heat dissipator. The temperature in the space above the liquids in a safety can is lowered below the ignition temperature and ignition of the contents is eliminated.

Flammable Liquid Storage Cabinets: Flammable liquid storage cabinets are designed to maintain the temperature at the top of the cabinet interior below 325ºF when subjected to a 10-minute fire test. Cabinets built to withstand the temperature rating during the 10-minute fire test are acceptable by OSHA standards if: (a) the maximum capacity of Class I and II liquids is not more than 60 gallons (or more than 120 gallons for Class II liquids); and (b) the cabinet is labeled with conspicuous lettering, such as Flammable-Keep Fire Away. All storage cabinets must have self-closing doors that will close the latch automatically when released. These doors must not be blocked open.

Special Refrigerators: Special refrigerators that can safely store flammable liquids have a spark-free interior such that all wiring and thermostat controls have been removed from the interior. Two types of these refrigerators are commercially available: a "flammable liquid storage" model and an "explosion-proof" model. A "flammable liquid storage" model is normally used in a non-explosive area where no flammable vapors are present. Such a refrigerator is normally powered through a standard three-wire cord plugged into an electrical outlet. An "explosion-proof" refrigerator is required when the area in which the refrigerator will be located has the potential for ignition of flammable vapors. An explosion-proof refrigerator is supplied with a "pigtail" cord that must be wired directly to a power source using metal conduit as specified by local electrical codes. Choosing the appropriate refrigerator will depend on the area in which it will be located.

8. Flammable and Combustible Liquid Storage Rooms

a. Large quantities of liquids that need to be stored in specially designed storage rooms include those with flash point temperatures at or below 200ºF (93.4ºC) and include all liquids identified as flammable liquids, ignitable liquids or combustible liquids in Class II or IIIA.

b. An inside storage room that does not exceed 150 sq. ft. in floor area is permitted to contain up to two (2) gallons per sq. ft. of floor area within the room, if the room is separated from the building by construction having at least one (1) hour fire resistance, and all openings between the room and the building are protected by assemblies having a one (1) hour fire-resistance rating. If it is desirable to increase the allowable storage capacity of such a room, the capacity can be increased to five (5) gallons per sq. ft. by providing the room with an automatic fire extinguishing system.

c. An inside storage room needs to be ventilated to prevent possible accumulation of flammable concentrations of vapors from container leaks and spills. Recommended ventilation is from floor level with a capacity of one (1) cubic foot per minute of exhaust for each square foot of floor area in the room, with a minimum exhaust of 150 cubic foot per minute.

d. If there is dispensing in the room, there should be provisions for ventilating the dispensing operation close to the points at which vapors are being emitted.

e. If storage room containers of flammable and combustible liquids are larger than five (5) gallons in size, it is necessary to provide barriers to prevent spills in the room from migrating outside the room. If these containers hold Class I or Class II liquids, curbs or ramps are needed as barriers.

f. Wiring and electrical fixtures located inside storage rooms must be suitable for the hazards. Explosion-proof (National Electric Code Class I, Division 2) electrical equipment is required for prevention of explosions if large quantities of flammable liquids (Class I) are being stored or dispensed. If only combustible liquids are being stored or dispensed, general use wire is acceptable.

g. If an inside storage room has an exterior wall, it is classified by the NFPA flammable and combustible liquids code as a "cut-off room" for which there are two additional requirements: (a) Exterior walls are required to provide ready accessibility for fire fighting; and (b) if Class IA or Class IB liquids are dispensed or if Class IA liquids are stored in containers larger than one (1) gallon, the exterior wall or roof is required by the NFPA to be designed to provide explosion venting.

h. There is no need for explosion venting in a small room used only for storage or in a room used for dispensing if adequate ventilation is provided.

E. STORAGE REQUIREMENTS FOR REACTIVE CHEMICALS

1. Consider the storage requirements of each reactive chemical prior to purchasing.

2. Consult the label and MSDS in making decisions about storage of reactive chemicals.

3. Use and store only the quantities of material you will need for immediate use.

4. Cyanides and sulfides should be stored in a location separate from acids or protected from contact with acids.

5. All acids should be stored separately from all alkaline materials (bases).

6. Date all highly reactive materials as soon as received and make sure the label states:

DANGER! HIGHLY REACTIVE MATERIAL

7. Do not open a container of highly reactive material that is past its expiration date. Call SHEA at 277-2753 for assistance.

8. Dispose of highly reactive material through SHEA prior to the expiration date.

9. Segregate the following materials:

• oxidizing agents from reducing agents and combustibles
• powerful reducing agents from readily reducible substrates
• pyrophoric compounds from flammables
• perchloric acid from reducing agents and combustibles

10. Store reactive liquids in trays constructed of compatible materials which are large enough to contain the contents of the bottles. Store perchloric acid bottles in glass or ceramic trays.
11. Store materials that react vigorously with water away from any possible contact with water. If chemicals are to be stored that are reactive if exposed to the air or water, they can safely be stored in sprinklered areas where sprinkler discharge would serve to prevent rupture of the outer container.
12. Temperature control or refrigeration must be provided, as needed, for chemicals that deteriorate or react if their temperatures exceed safe limits recommended by the manufacturer or person synthesizing the chemical. Store thermally unstable materials in a refrigerator with the following safety features: all spark-producing controls are on the outside, a magnetic locked door, an alarm to warn when the temperature is too high.
13. Assign responsibility for the storage areas utilized for highly reactive materials to one (1) primary person and a backup person. Review this responsibility at least twice yearly.
14. Some highly reactive shock/heat sensitive materials are:

Ammonium perchlorate Dibenzoyl peroxide

Ammonium permanganate Diisopropyl peroxydicarbonate

Anhydrous perchloric acid Dinitrobenzene (ortho)

Butyl hydroperoxide Ethyl methyl ketone peroxide

Butyl perbenzoate Ethyl nitrate

t-Butyl peroxyacetate Hydroxylamine

t-Butyl peroxypivalate Peroxyacetic acid

1-Chloro-2,4-dinitrobenzene Picric acid (<10% water content)

Cumene hydroperoxide Trinitrobenzene

Diacetyl peroxide Trinitrotoluene

F. STORAGE REQUIREMENTS FOR OXIDIZERS

Oxidizing agents such as chlorates, perchlorates, peroxides, nitric acid, nitrates, nitrites and permanganates represent a significant hazard because of their propensity under certain conditions to undergo vigorous reactions when they come into contact with easily oxidized material such as metal powders and organic materials like wood, paper and other combustible material. Mineral acids such as perchloric acid, sulfuric acid and nitric acid, as well as other oxidizers, should be stored separate from flammables and combustibles, by separate rooms, cabinets or break resistant containers. If large bottles must be stored in proximity of combustible materials, acid resistant trays must be used to prevent the oxidation of wood or corrosion of metal shelves.

1. Class I Oxidizer

Class I oxidizers will cause an increase of the burning rate of combustible material with which it comes in contact. Some examples are:

Hydrogen peroxide (8-28%) Magnesium perchlorate

Nitric acid (70% or less) Silver nitrate

Perchloric acid solutions (less than 60% wt/wt)

2. Class II Oxidizer

Class II oxidizers will cause an increase of the burning rate or may cause spontaneous ignition of combustible material with which it comes in contact. Some examples are:

Calcium hypochlorite (50% or less wt/wt) Chromic acid

Hydrogen peroxide (28-52% wt/wt) Sodium peroxide

Contact SHEA if quantities are stored in excess of 1,000 lbs.

3. Class III Oxidizers

Class III oxidizers will cause a severe increase in the burning rate of combustible material with which they come in contact, or will undergo vigorous self-sustained decomposition when catalyzed or exposed to heat. Regulated quantities are permitted to be stored only on the ground floor of a building with no basement. Some examples are:

Ammonium dichromate Perchloric acid solutions (60-73%)

Hydrogen peroxide (52-91% wt/wt) Sodium chlorate

Contact SHEA if quantities are stored in excess of 200 lbs.

4. Class IV Oxidizer

Class IV oxidizers can undergo an explosive reaction when catalyzed or exposed to heat, shock, or friction. Regulated quantities are permitted to be stored only in detached storage. Storage areas for Class IV oxidizers must be provided with a means to vent fumes in any type of emergency. Some examples are:

Ammonium perchlorate Perchloric acid solutions

Ammonium permanganate (greater than 72.5%)

Hydrogen peroxide (greater than 91% wt/wt) Potassium superoxide

Contact SHEA if quantities are stored in excess of 10 lbs.

G. STORAGE REQUIREMENTS FOR TOXIC CHEMICALS

1. Store chemicals known to be highly toxic, including carcinogens, in ventilated storage in unbreakable, chemically resistant secondary containers.

Keep quantities on hand at an absolute minimum.

Label storage areas with appropriate warning signs, such as:

CAUTION! REPRODUCTIVE TOXIN STORAGE

-or-

CAUTION! CANCER-SUSPECT AGENT STORAGE

and limit access to these areas.

2. Storage areas for pesticides and other toxic chemicals should be secured when the storage areas are not supervised by a responsible person so that unauthorized personnel are kept out.

8. STORAGE REQUIREMENTS FOR PEROXIDIZABLE CHEMICALS
9. Some chemicals can form significant quantities of unstable peroxides after prolonged exposure to air and light. Certain peroxides may detonate with extreme violence when they become concentrated by evaporation or distillation, when combined with other compunds to yield a detonable mixture or when simply disturbed by unusual heat, shock or friction.

   1. The following is a representative list of those compounds which form peroxides:

10. PEROXIDE HAZARD IN STORAGE. These compounds form peroxides that may explode even without being concentrated.

Isopropyl ether Divinyl ether Potassium metal

Potassium amide Sodium amide (sodamide) Vinylidene chloride

II. PEROXIDE HAZARD ON CONCENTRATION. These compounds may form peroxides as a result of distillation or most likely evaporation.

Dioxane Ethyl ether

Tetrahydrofuran Acetal

Cumene Cyclohexane

Dicyclopentadiene Diacetylene

Furan Ethylene glycol dimethyl ether

Methylcyclopentane Methyl acetylene

Tetrahydronaphthalene Vinyl ethers

III. HAZARDS DUE TO PEROXIDE INITIATION OF POLYMERIZATION. When stored as a liquid, the peroxide forming potential increases and certain of these monomers, especially butadiene, chloroprene and tetrafluoroethylene, should be considered as a peroxide hazard in storage.

Butadiene Chlorobutadiene (Chloroprene) Vinyl pyridine

Chlorotrifluoroethylene Styrene

Tetrafluoroethylene Vinyl acetate

Vinyl acetylene Vinyl chloride

Storage and handling procedures:

Each person responsible for a laboratory must develop and maintain an inventory of the peroxidizable materials in the laboratory. The inventory should be reviewed every three (3) months, at which time samples from List I, three (3) months or older, and List II and List III samples twelve (12) months or older would either be tested for peroxides or disposed of through SHEA. Quantities of peroxidizable compounds should be purchased according to short-term needs to ensure that peroxide buildup, which may accompany long-term storage, is minimized. Purchase in container sizes corresponding to use requirements to minimize exposure to air from multiple openings of the container.

3. Use the following labeling formats for all peroxide-forming liquids:

All peroxidizable compounds should be stored away from heat and light. Sunlight is an especially good promoter of peroxidation. Protection from physical damage and ignition sources during storage is also essential. Particular care should be given to ensure tight closure on storage containers. Loose or leaky closures may permit evaporation of storage material, leaving a hazardous concentration of peroxides in the container. Most common container materials, such as steel, stainless steel, copper, nickel, aluminum, baked phenolic linings and ceramics, are suitable for containers; however, they must be clean and free of metal oxides because iron or copper oxides may actually promote peroxide formation.

The use of oxidation inhibitors is especially important in the safe handling of peroxidizable materials. Hydroquinone, alkyl phenols, aromatic amines or similar materials are recommended by the manufacturers as being effective in preventing peroxide formation during storage. Compounds that are suspected of having very high peroxide levels because of visual observation of unusual viscosity or crystal formation or because of age should be considered extremely dangerous. The precautions taken for disposal of these materials should be the same as for any material that can be detonated by friction or shock. IT IS OF THE UTMOST IMPORTANCE THAT THE CONTAINER NOT BE OPENED. The act of opening the container COULD DETONATE PEROXIDE CRYSTALS under the container cap or other closure. Peroxidization in a chemical process may not only be a serious hazard because of the explosion potential, but may also affect lower yield and produce unwanted impurities.

I. CHEMICAL INCOMPATIBILITY CHART

NUMBER CHEMICAL GROUP DO NOT STORE WITH GROUP

NUMBERS

1 Inorganic Acids 2-8, 10, 11, 13, 14, 16-19, 21-23

2 Organic Acids 1, 3, 4, 7, 14, 16-19, 22

3 Caustics 1, 2, 5, 7, 8, 13-18, 20, 22, 23

4 Amines and alkanolamines 1, 2, 5, 7, 8, 13-18, 23

5 Halogenated compounds 1, 3, 4, 11, 14, 17

6 Alcohols, glycols, glycol ethers 1, 7, 14, 16, 20, 23

7 Aldehydes 1-4, 6, 8, 15-17, 19, 20, 23

8 Ketones 1, 3, 4, 7, 19, 20

9 Saturated hydrocarbons 20

10 Aromatic hydrocarbons 1, 20

11 Olefins 1, 5, 20

12 Petroleum oils 20

13 Esters 1, 3, 4, 19, 20

14 Monomers, polymerizable esters 1-6, 15, 16, 19-21, 23

15 Phenols 3, 4, 7, 14, 16, 19, 20

16 Alkylene oxides 1-4, 6, 7, 14, 15, 17-19, 23

17 Cyanohydrins 1-5, 7, 16, 19, 23

18 Nitriles 1-4, 16, 23

19 Ammonia 1-2, 7, 8, 13-17, 20, 23

20 Halogens 3, 6-15, 19, 21, 22

21 Ethers 1, 14, 20

22 Elemental phosphorus 1-3, 20

23 Acid anhydrides 1, 3, 4, 6, 7, 14, 16-19

J. CHEMICAL COMPATIBILITY CHART

RELATED AND COMPATIBLE STORAGE GROUPS

ORGANIC FAMILY

Acids, anhydrides, peracids

Alcohols, glycols, amines, amides, imines, imides

Hydrocarbons, esters, aldehydes

Ethers, ketones, ketenes, halogenated hydrocarbons, ethylene oxide

Epoxy compounds, isocyanates

Peroxides, hydroperoxides, azides

Sulfides, polysulfides, sulfoxides, nitrites

Phenols, cresols

INORGANIC FAMILY

Metals, hydrides

Halides, sulfates, sulfites, thiosulfates, phosphates, halogens

Amides, nitrates (except ammonium nitrates, azides

Hydroxides, oxides, silicates, carbonates, carbon

Sulfides, selenides, phosphides, carbides, nitrides

Chlorates, perchlorates, perchloric acid, chlorites, hypochlorites, peroxides, hydrogen peroxide

Arsenates, cyanides, cyanates

Borates, chromates, manganates, permanganates

Nitric acid, other inorganic acids

Sulfur, phosphorus, arsenic, phosphorus pentoxide