1. Chemical storage B.Brazier 2010

2. BACKGROUND Fire and explosion are only two of the many hazards. Fire and explosion are only two of the many hazards. Over 500 chemical-storage incidents were over the past 5 years. Over 500 chemical-storage incidents were over the past 5 years. These incidents occurred due to unsafe chemical storage practices. These incidents occurred due to unsafe chemical storage practices. B.Brazier 2010

3. Storage-related incidents Principal causes: Principal causes: 1. Improper or non-existent labeling of chemicals in storage. 1. Improper or non-existent labeling of chemicals in storage. 2. Storage of chemicals beyond the recommended shelf-life. 2. Storage of chemicals beyond the recommended shelf-life. 3. Degradation of chemical storage containers. ("Polyethylene Bottles Containing Corrosive Chemicals May Deteriorate With Prolonged Use," 3. Degradation of chemical storage containers. ("Polyethylene Bottles Containing Corrosive Chemicals May Deteriorate With Prolonged Use," B.Brazier 2010

4. IMPROPER LABELING Small amounts of "left-over" chemicals had accumulated over several years. Small amounts of "left-over" chemicals had accumulated over several years. The chemicals were prepared for recycling or disposal by removing the chemicals from their individual containers and putting them into a plastic bucket. The chemicals were prepared for recycling or disposal by removing the chemicals from their individual containers and putting them into a plastic bucket. Powder that was thought to be a base material was poured from an unlabeled jar into the bucket, resulting in spontaneous ignition. Powder that was thought to be a base material was poured from an unlabeled jar into the bucket, resulting in spontaneous ignition. The building then had to be evacuated, and the fire department was summoned to put out the fire. The building then had to be evacuated, and the fire department was summoned to put out the fire. Analysis performed by the laboratory later revealed that the powder was maleic anhydride, Analysis performed by the laboratory later revealed that the powder was maleic anhydride, B.Brazier 2010

5. EXTENDED TIME IN STORAGE Unrefrigerated ether cannot be stored safely for over 6 months because peroxides, which are shock-sensitive, can form and cause an explosion. Unrefrigerated ether cannot be stored safely for over 6 months because peroxides, which are shock-sensitive, can form and cause an explosion. The building that housed the 18 ether containers had to be evacuated, and barricades had to be assembled to protect flammable inventory. The building that housed the 18 ether containers had to be evacuated, and barricades had to be assembled to protect flammable inventory. The peroxides were then neutralized with ferrous sulphate, and all 21 containers were removed. The peroxides were then neutralized with ferrous sulphate, and all 21 containers were removed. Periodic inspection and removal of outdated chemicals in storage would have prevented the incident. Periodic inspection and removal of outdated chemicals in storage would have prevented the incident. B.Brazier 2010

6. Storage rules 1. Label all chemicals. The name and address of the manufacturer or other responsible party must be listed on the label. Chemicals with a shelf life should be labeled with the date received. 2. Store chemicals in the locations recommended (i.e., where the temperature range, vibration, or the amount of light does not exceed the manufacturer's recommendations). Make sure that chemicals that are stored together are compatible. B.Brazier 2010

7. Storage rules 3. Inspect annually all chemicals in stock and storage. 4. Hazardous chemicals should be inspected every 6 months. 5. Some hazardous chemicals may require more frequent inspections. 6. Any outdated materials should be properly disposed of or replaced if necessary B.Brazier 2010

8. Rules 7. Keep only enough inventory necessary for uninterrupted operation. 8. Chemical inventory should be maintained at a minimum to reduce fire, exposure, and disposal hazards 9. Rotate new shipments of chemicals with existing stock so that the oldest stock is available first. B.Brazier 2010

9. Storing Acids Store large bottles of acids on low shelf or in acid cabinets. Store large bottles of acids on low shelf or in acid cabinets. Segregate oxidizing acids from organic acids, flammables and combustible materials. Segregate oxidizing acids from organic acids, flammables and combustible materials. Segregate acids from bases and active metals such as sodium, potassium, etc. Segregate acids from bases and active metals such as sodium, potassium, etc. Use bottle carrier for transporting acid bottles. Use bottle carrier for transporting acid bottles. Have spill control pillows or acid neutralizers available in case of spill. Have spill control pillows or acid neutralizers available in case of spill. B.Brazier 2010

10. Strong Oxidizing Acids Chromic Acid Chromic Acid Nitric Acid Nitric Acid Hydrobromic Acid Hydrobromic Acid Perchloric Acid Perchloric Acid Iodic Acid Iodic Acid Sulfuric Acid Sulfuric Acid B.Brazier 2010

11. Organic Acids Acetic Acid Acetic Acid Phenol Phenol Benzoic Acid Benzoic Acid Trichloracetic Acid Trichloracetic Acid B.Brazier 2010

12. Storing Bases Segregate bases from acids Segregate bases from acids Store solutions of inorganic hydroxides in polyethylene containers. Store solutions of inorganic hydroxides in polyethylene containers. Have spill control pillows or caustic neutralizers available for spills. Have spill control pillows or caustic neutralizers available for spills. B.Brazier 2010

13. Bases Ammonium Hydroxide Ammonium Hydroxide Calcium Hydroxide Calcium Hydroxide Bicarbonates Bicarbonates Potassium Hydroxide Potassium Hydroxide Carbonates Carbonates Sodium Hydroxide Sodium Hydroxide B.Brazier 2010

14. Flammable Store in approved safety cans or cabinets Store in approved safety cans or cabinets Segregate from oxidizing acids and oxidizers. Segregate from oxidizing acids and oxidizers. Keep away from any source of ignition: flames, heat or sparks. Keep away from any source of ignition: flames, heat or sparks. Know where fire fighting equipment is stored and how to use. Know where fire fighting equipment is stored and how to use. If volatile flammable liquids are stored in a refrigerator it must be in an explosion-proof (lab-safe) refrigerator. If volatile flammable liquids are stored in a refrigerator it must be in an explosion-proof (lab-safe) refrigerator. B.Brazier 2010

15. Flammable Solids Benzoyl peroxide Benzoyl peroxide Phosphorous, yellow Phosphorous, yellow Calcium Carbide Calcium Carbide Picric Acids Picric Acids B.Brazier 2010

16. Flammable Gases Acetylene Acetylene Ethylene Oxide Ethylene Oxide Ammonia Ammonia Formaldehyde Formaldehyde Butane Butane Hydrogen Hydrogen Carbon Monoxide Carbon Monoxide Hydrogen Sulfide Ethane Methane Ethyl Chloride Propane Ethylene Propylene B.Brazier 2010

17. Storage of Oxidizers Store in a cool, dry place. Store in a cool, dry place. Keep away from flammable and combustible materials, such as paper or wood. Keep away from flammable and combustible materials, such as paper or wood. Keep away from reducing agents such as zinc, alkaline metals, formic acid. Keep away from reducing agents such as zinc, alkaline metals, formic acid. B.Brazier 2010

18. Oxidizers - Solids Ammonium Dichromate Ammonium Dichromate Nitrates Nitrates Ammonium Perchlorate Ammonium Perchlorate Ammonium Persulfate Ammonium Persulfate Benzoyl Peroxide Benzoyl Peroxide Bromates Bromates Calcium Hypochlorite Calcium Hypochlorite Chlorates Chlorates Chromium Trioxide Chromium Trioxide Ferric Trioxide Ferric Trioxide Ferric Chloride Ferric Chloride Hypochlorite Hypochlorite Iodine Iodine Permanganic Acid Periodic Acid Potassium Dichromate Potassium Ferricyanide Potassium Permanganate Potassium Persulfate Peroxides, Salts of Sodium Chlorite, Sodium DichromateIodates Sodium Nitrate Sodium Perborate B.Brazier 2010

19. Pyrophoric Substances: These ignite spontaneously on contact with air. Store in a cool, dry place. These ignite spontaneously on contact with air. Store in a cool, dry place. Boron Cadmium Calcium Chromium* Cobalt* DiboraneTitanium* Dichloroborane 2-Furaldehyde Iron* Lead* Manganese* Nickel* Cobalt* Phosphorous, Sodium Yellow* Zinc* B.Brazier 2010

20. Light Sensitive Chemicals Avoid exposure to light & Store in amber bottles in a cool, dry place. Avoid exposure to light & Store in amber bottles in a cool, dry place. Bromine Oleic Acid Ethyl Ether Potassium Ferricyanide Ferric Ammonium Citrate Silver salts Hydrobromic Acid Sodium Iodide Mercuric Salts Mercurous Nitrate B.Brazier 2010

21. Carcinogens Label all containers as Cancer Suspect Agents. Label all containers as Cancer Suspect Agents. Store according to hazardous nature of chemicals, e.g., flammable, corrosive. Store according to hazardous nature of chemicals, e.g., flammable, corrosive. When necessary, store securely. When necessary, store securely. B.Brazier 2010

22. Carcinogens Antimony compounds Antimony compounds Acrylonitrile Acrylonitrile Arsenic compounds Arsenic compounds Benzene Benzene Benzidine Benzidine Chloroform Chloroform Beryllium Beryllium Dimethyl Sulfate Dimethyl Sulfate Cadmium compounds Dioxane Chromates,Salts of Ethylene Dibromide Beta-Naphthylamine Hydrazine Vinyl Chloride Nickel Carbonyl B.Brazier 2010

23. Chemical Segregation and Storage Groups Stanford Storage Group Classification System Stanford Storage Group Classification System used to segregate chemicals stored in the laboratory. used to segregate chemicals stored in the laboratory. It is based on physical and chemical reactivity information found in the MSDS or other references. It is based on physical and chemical reactivity information found in the MSDS or other references. B.Brazier 2010

24. Storage Groups Storage Groups are groups of chemicals that will not react violently if mixed together. Storage Groups are groups of chemicals that will not react violently if mixed together. Stanford has about 10,000 unique chemicals classified according this system in the SCIMS Database. Stanford has about 10,000 unique chemicals classified according this system in the SCIMS Database. The Stanford Storage Group system was developed for laboratory scale storage The Stanford Storage Group system was developed for laboratory scale storage B.Brazier 2010

25. STANFORD COMPATIBLE STORAGE GROUP CODES A letter designation is given to each compatible group of materials. A letter designation is given to each compatible group of materials. For example, "A" represents "compatible organic bases, flammables and poisons". For example, "A" represents "compatible organic bases, flammables and poisons". "G" is "not intrinsically reactive, flammable or combustible". "G" is "not intrinsically reactive, flammable or combustible". A chemical that is incompatible with other chemicals in all of the other Storage Groups must be placed in Storage Group "X". Storage Group "X" chemicals must be segregated from all other chemicals. A chemical that is incompatible with other chemicals in all of the other Storage Groups must be placed in Storage Group "X". Storage Group "X" chemicals must be segregated from all other chemicals. If the information is not available, then Storage Group "U" will be assigned. If the information is not available, then Storage Group "U" will be assigned. B.Brazier 2010

28. SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPS Segregate chemicals in a compatible fashion according to the compatible Storage Groups. Segregate chemicals in a compatible fashion according to the compatible Storage Groups. If a particular item does not yet have a storage group designated, the researcher must use his best judgement on how best to store the material. If a particular item does not yet have a storage group designated, the researcher must use his best judgement on how best to store the material. Keep the different storage groups in separate cabinets, if possible. Keep the different storage groups in separate cabinets, if possible. B.Brazier 2010

29. SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPS In areas that contain items from more than one storage group, there is no need to store them alphabetically by storage group (i.e. A then B then C). The letters are just an arbitrary convention. In areas that contain items from more than one storage group, there is no need to store them alphabetically by storage group (i.e. A then B then C). The letters are just an arbitrary convention. B.Brazier 2010

30. SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPS If you must store items from more than one storage group on the same shelf, they must have separate secondary containment for each group. If you must store items from more than one storage group on the same shelf, they must have separate secondary containment for each group. For example: For example: –Acetic acid (Storage group "D", organic acid) –Hydrochloric acid (Storage group "F", inorganic acid) –Nitric acid (Storage group "E", oxidizing) These all acids but they are incompatible and must be stored in separate secondary containment and on separate shelves within the same cabinet. These all acids but they are incompatible and must be stored in separate secondary containment and on separate shelves within the same cabinet. B.Brazier 2010

31. SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPS B.Brazier 2010

32. SEGREGATE CHEMICALS BY COMPATIBLE STORAGE GROUPS B.Brazier 2010

33. Store in same cabinet If you must store items from many storage groups in the same cabinet with more than one shelf, If you must store items from many storage groups in the same cabinet with more than one shelf, put storage group "B" and "X" on the top shelf. put storage group "B" and "X" on the top shelf. This will prevent other chemicals from dripping on them. This will prevent other chemicals from dripping on them. B.Brazier 2010

35. Flammable liquid storage If the total quantity of flammable liquids exceeds 5 Lt, they must be stored in a flammable liquid storage cabinet except when in active use. If the total quantity of flammable liquids exceeds 5 Lt, they must be stored in a flammable liquid storage cabinet except when in active use. B.Brazier 2010

36. OTHER STORAGE CONSIDERATIONS: Long-term storage on bench tops or in fume hoods is discouraged. Long-term storage on bench tops or in fume hoods is discouraged. All containers MUST remain closed except when actively adding or removing materials. Do not store funnels in open containers. All containers MUST remain closed except when actively adding or removing materials. Do not store funnels in open containers. Never store hazardous materials next to or above sinks. This includes dark rooms with waste fixer stored adjacent to open floor drains. Never store hazardous materials next to or above sinks. This includes dark rooms with waste fixer stored adjacent to open floor drains. B.Brazier 2010

37. OTHER STORAGE CONSIDERATIONS: Store solids above liquids. Store solids above liquids. Avoid exposing stored chemicals to building heat or to direct sunlight. Avoid exposing stored chemicals to building heat or to direct sunlight. All chemical storage shelving must have lips and seismic restraints. All chemical storage shelving must have lips and seismic restraints. Use explosion-proof refrigerators when storing flammables in a refrigerator. Use explosion-proof refrigerators when storing flammables in a refrigerator. B.Brazier 2010