2.4 – Chemical Procurement, Distribution, and Storage

2.4.1 Procurement

Before a new substance that is known or suspected to be hazardous is received, those who will handle it should know information on proper handling, storage, and disposal. It is the responsibility of the supervisor to ensure that the laboratory facilities in which the substance will be handled are adequate and that those who will handle the substance have received the proper training. The necessary information on proper handling of hazardous substances can be obtained from the Safety data sheets, which are provided by the vendor. Because storage in laboratories is restricted to small containers, order small-container lots to avoid hazards associated with repackaging. No container should be accepted without an adequate identifying label as outlined in Section 1.5.2.2 of this manual.

2.4.2 Distribution

When hand-carrying open containers of hazardous chemicals or unopened containers with corrosive or highly acutely or chronically toxic chemicals, place the container in a secondary container or use a bump bucket. Rubberized buckets are commercially available and provide secondary containment as well as “bump” protection. If several bottles must be moved at once, the bottles should be transported on a small cart with a substantial rim to prevent slippage from the cart. Wherever available, a freight elevator should be used to transport chemicals from one floor to another.

2.4.3 – Chemical Storage in the Laboratory

Carefully read the label before storing a hazardous chemical. The SDS will provide any special storage information as well as information on incompatibilities. Do not store un-segregated chemicals in alphabetical order. Do not store incompatible chemicals in close proximity to each other.

Separate compatible hazardous chemicals in storage as follows (from National Research Council, Division on Earth and Life Studies, Board on Chemical Sciences and Technology, Committee on Prudent Practices in the Laboratory: An Update, National Academies Press, 2011):

A: Organic Bases
B: Pyrophoric and Water-Reactive Materials
C: Inorganic Bases
D: Organic Acids
E: Oxidizers Including Peroxides
F: Inorganic Acids not Including Oxidizers or Combustibles
G: Not Intrinsically Reactive or Flammable or Combustible
L: Nonreactive Flammables and Combustibles, Including Solvents
X: Incompatible with All Other Storage Groups

Gases:

  • toxic
  • oxidizers and inert
  • flammable

Once separated into the above hazard classes, chemicals may be stored alphabetically using the following rules:

For systems named with simple substituents:

  • multiplier prefixes (di-, tri-, tetra-, etc.) are ignored
    Example: triethylamine is alphabetized under “e”
  • prefixes sec- and tert- are ignored
    Example: tert-butanol is alphabetized under “b”
  • the prefixes iso-, cyclo-, and neo- are alphabetized
    Example: isobutanol is alphabetized under “i”

For systems named with complex substituents:

  • any terms used in brackets are alphabetized
    Example: 4-(1,1-dimethylethyl)-5-ethylnonane is alphabetized under “d”
  • substituents on nitrogen are designated as “N-” and the “N-” is ignored
    Example: N-methyl-3-phenyloctan-2-amine is alphabetized under “m”

Use approved storage containers and safety cans for flammable liquids. It is preferable to store flammable chemicals in flammable storage cabinets. Flammable chemicals requiring refrigeration should be stored only in the refrigerators and freezers specifically designed for flammable storage.

A good place to store hazardous chemicals is in a cabinet under the hood (most labs have separate flammable and acid cabinets under the hoods). Chemicals of different classes can be segregated in trays. Do not store chemicals on bench tops or in hoods. Liquids (particularly corrosives or solvents) should not be stored above eye level.

Use secondary containers (one inside the other) for especially hazardous chemicals (carcinogens, etc.). Use spill trays under containers of strong reagents.

Avoid exposure of chemicals while in storage to heat sources (especially open flames) and direct sunlight.

Conduct periodic inventories of chemicals stored in the laboratory (annually) and dispose of old or unwanted chemicals promptly in accordance with the facilities hazardous chemical waste program.

Assure all containers are properly labeled.

2.4.3.1 – Chemical Storage: Chemical Stability

Stability refers to the susceptibility of a chemical to dangerous decomposition. The label and SDS will indicate if a chemical is unstable.

Special note: peroxide former’s – Ethers, liquid paraffin’s, and olefins form peroxides on exposure to air and light. Peroxides are extremely sensitive to shock, sparks, or other forms of accidental ignition (even more sensitive than primary explosives such as TNT). Since these chemicals are packaged in an air atmosphere, peroxides can form even though the containers have not been opened. Unless an inhibitor was added by the manufacturer, sealed containers of ethers should be discarded after one (1) year. Opened containers of ethers should also be discarded within one (1) year of opening. All such containers should be dated upon receipt and upon opening.

See Section 3.2, Highly Reactive Chemicals and High Energy Oxidizers for additional information and examples of materials, which may form explosive peroxides.

For additional information on chemical stability, contact your supervisor or the Director of EHS.

2.4.3.2 – Chemical Storage: Incompatible Chemicals

Certain hazardous chemicals should not be mixed or stored with other chemicals because a severe reaction can take place or an extremely toxic reaction product can result. The label and SDS will contain information on incompatibilities. The following table contains examples of incompatible chemicals:

CHEMICALKEEP OUT OF CONTACT WITH:
Acetic AcidChromic acid, nitric acid hydroxyl compounds, ethylene glycol, perchloric acid, peroxides, permanganates
AcetoneConcentrated nitric and sulfuric acid mixtures
AcetyleneChlorine, bromine, copper, fluorine, silver, mercury
Alkali MetalsWater, carbon tetrachloride or other chlorinated hydrocarbons, carbon dioxide, the halogens
AmmoniaMercury, chlorine, calcium hypochlorite, iodine, bromine, hydrofluoric acid
AmmoniumAcids, metal powders, flammable liquids, chlorates, nitrites, Nitrate sulfur, finely divided organic or combustible materials
AnilineNitric acid, hydrogen peroxide
Arsenical MaterialsAny reducing agent
AzidesAcids
BromineAmmonia, acetylene, butadiene, butane, methane, propane (or other petroleum gases), hydrogen, sodium carbide, turpentine, benzene, finely divided metals
Calcium OxideWater
Carbon (activated)Calcium hypo chlorite, all oxidizing agents.
Carbon-TetrachlorideSodium
ChloratesAmmonium salts, acids, metal powders, sulfur, finely divided organic or combustible materials
Chromic AcidAcetic acid, naphthalene, camphor, glycerin, turpentine, alcohol, flammable liquids in general
ChlorineAmmonia, acetylene, butadiene, butane, methane, propane (or other petroleum gases), hydrogen, sodium carbide, turpentine, benzene, finely divided metals
Chlorine DioxideAmmonia, methane, phosphine, hydrogen sulfide
CopperAcetylene, hydrogen peroxide
CumeneHydroperoxide Acids, organic or inorganic
CyanidesAcids
Flammable liquidsAmmonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens
HydrocarbonsFluorine, chlorine, bromine, chromic acid, sodium peroxide
Hydrocyanic AcidNitric acid, alkali
Hydrofluoric AcidAmmonia, aqueous or anhydrous
Hydrogen PeroxideCopper, chromium, iron, most metals or their salts, alcohol’s, acetone, organic materials, aniline, nitromethane, flammable liquids, and oxidizing gases
Hydrogen sulfideFuming nitric acid, oxidizing gases, acetylene, ammonia (aqueous or anhydrous), hydrogen
HypochloritesAcids, activated carbon
IodineAcetylene, ammonia (aqueous or anhydrous), hydrogen
MercuryAcetylene, fulminic acid, ammonia
NitratesSulfuric acid
Nitric AcidAcetic acid, aniline, chromic acid, hydrocyanic acid, hydrogen sulfide, flammable liquids, flammable gases
NitritesAcids
NitroparaffinsInorganic bases, amines
Oxalic AcidSilver, mercury
OxygenOils, grease, hydrogen; flammable liquids, solids, or gases
Perchloric AcidAcetic anhydride, bismuth and its alloys, alcohol, paper, wood
Peroxides (organic)Acids (organic or mineral), avoid friction, store cold
Phosphorus (white)Air, oxygen, alkalies, reducing agents
PotassiumCarbon tetrachloride, carbon dioxide, water
Potassium ChlorateSulfuric and other acids
Potassium PermanganateGlycerin, ethylene glycol, benzaldehyde, sulfuric acid
SelenidesReducing agents
SilverAcetylene, oxalic acid, tartaric acid, ammonium compounds
SodiumCarbon tetrachloride, carbon dioxide, water
Sodium nitriteAmmonium nitrate and other ammonium salts
Sodium PeroxideEthyl or methyl alcohol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural
SulfidesAcids
Sulfuric AcidPotassium chlorate, potassium perchlorate, potassium permanganate (or compounds with similar light metals, such as sodium, lithium, etc.)
TelluridesReducing agents
(From Manufacturing Chemists’ Association, Guide for Safety in the Chemical Laboratory, pp. 215-217.)
2.4.3.3 – Chemical Storage in Cold Rooms and Refrigerators

The cold rooms in Hall-Atwater and Shanklin Laboratories are not to be used to store or perform experiments with hazardous organic or volatile chemicals. Cold rooms provide little or no fresh air exchange and tend to condense volatile chemicals out on the walls, ceilings and benches. These chemicals can build up in the atmosphere within the room and cause serious health problems.

Fire/Explosion proof refrigerators should be used to store volatile organic chemicals. Every bottle placed into a refrigerator should have a tight cap and should be Para filmed or placed into a plastic bag. A quick check has revealed that caps on chemical bottles tend to loosen when they sit for a long time at low temperatures. Lab refrigerator failures are often caused by severe corrosion due to leaking chemical bottles.

Any experiments that you feel must be carried out at sub-ambient temperatures should be discussed with the Director of EHS. Alternative methods or engineered solutions should be considered.