1 Appendix A SAFE STORAGE OF LABORATORY CHEMICALS The purpose of this section is to identify and classify hazardous chemicals that are commonly used in a research environment. Once identified, each laboratory must establish a site-specific policy to provide for the proper storage, handling and use of these chemicals. Storage Practices Accidents resulting from poor storage techniques are preventable. Many storage requirements presently recommended have been learned through adverse experiences and incorporated into regulations. Certain of these regulations, specifically those related to storage and handling of carcinogens, are not to be ignored. The specific Safety Data Sheet (SDS) should be consulted before use and when questions arise concerning chemical properties and associated hazards. Use of appropriate storage cabinets, for each type of hazardous chemical, can significantly reduce risks, whereas inappropriate cabinets mask and therefore increase the dangers. Wooden storage cabinets for acids are safer and more durable than metal cabinets, unless a metal cabinet is specially treated with a corrosion-resistant coating. Likewise, specially designed fireproof metal cabinets are preferable for storage of flammable materials, since they can maintain flammable liquids below vaporization temperatures, even in a fire. Steel cabinets common in most labs are highly inappropriate for storage of flammables since they allow heat from a fire to be quickly transferred to the cabinet shelves. This results in rapid vaporization of the flammable liquid, bottle breakage and accelerated fire spreading. Basic Rules for hazardous chemical storage Date all chemical on receipt Maintain an inventory that is verified annually Establish a separate and secure storage area for chemicals Do not store chemicals in fume hoods or work areas. Label storage areas and cabinets to identify the hazardous materials stored within. Properly identify all unlabeled products before storing. Never store chemical in a standard refrigerator. Chemicals should not be stored on the floor. Liquid chemicals should not be stored above eye level. Any shelving within the storage area should be firmly secured to the floor and wall. Island shelf assemblies should be avoided unless they are secured to the ceiling. Lips on storage shelves are recommended to prevent bottles from being knocked off. Wooden shelves are best suited for general storage since they are less effective heat conductors, but metal shelves should be used for flammables to reduce fire hazards. Chemical storage under, over or near a sink should be avoided since many chemicals are affected by moisture. Chemical storage should be away from heavily traveled areas. All storage cabinets or closets should be closed when not in use. Stored chemicals should be cool, dry and have caps and lids tightly closed; none of the chemical should be on the outside of the container.
2 Stored chemical should be arranged in compatible families rather than in alphabetical order. Extremely hazardous chemicals should be purchased in as small a quantities as possible. Post emergency telephone numbers in the chemical storage areas. TYPES OF CHEMICALS STORAGE Alphabetical storage Probably the most common chemical storage practice is that of storing chemicals in alphabetical order. When chemicals are stored alphabetically there is still a great potential of incompatible substance coming in contact. Problems associated with Alphabetical Chemical Storage Acetic acid + Acetaldehydes o Small amounts of acetic acid will cause acetaldehyde to polymerize releasing large amounts of heat. Acetic anhydride + Acetaldehyde o Condensation reactions can be violent explosive Acrolein + Ammonia, aqueous o Extremely violent polymerization reaction of Acrolein and any alkali or amine Aluminum metal + Ammonium nitrate o Potential for explosion Aluminum metal + Antimony Trichloride o Aluminum metal burns in the presence of antimony trichloride vapor Aluminum metal + any Bromates, Chlorate or Iodates Finely divided aluminum plus these compounds produces the potential for explosion that is detonated by heat, friction or light Aluminum chloride-self reacting o Upon prolonged storage, explosion occurs when container is opened Ammonium nitrate + Acetic acid o Mixture will ignite especially if acid is concentrated Cupric sulfide + Cadmium chlorate o Explodes on contact Hydrogen peroxide + Ferrous sulfide o Vigorous reaction, highly exothermic Lead Perchlorate + Methanol o Explosive mixture if agitated Maleic anhydride + Magnesium hydroxide o Potentially explosive reaction Mercury Nitrate + Methanol o Mixture has potential of forming Mercury Fulminate, an explosive Nitric acid + Nitrobenzene o Mixtures of nitric acid and nitrobenzene can detonate Potassium cyanide + Potassium nitrite o Potentially explosive mixture if heated Silver + Tartaric acid o Explosive mixture
3 Silver Oxide + Sulfur o Potentially explosive mixture Sodium + Selenium o Reaction attended by burning Sodium + Silver Bromide, Silver Chloride, Silver Fluoride or Silver Fluoride o Forms impact-sensitive systems Sodium + Stannic Halides o Forms impact-sensitive systems Sodium cyanide + Sulfuric acid o Release of HCN gas, death Categorical Storage The ten most common chemical groups are flammables, oxidizers, reducers, concentrated acids, concentrated bases, water reactive, extreme toxics, peroxide-formers, pyrophoric and gas cylinders. The first five groups are kept separated to avoid accidental contact with an incompatible material that could result in a violent or explosive reaction. Water reactive materials are isolated to lessen the probability of their involvement in a fire situation. Extreme toxics and carcinogens are segregated to provide some degree of control over their distribution in the event of an accidental spill. Peroxide-formers and pyrophoric materials should be stored in a cool, dark environment. Any attempt at segregating hazard chemicals is better than no separation at all and the resulting potential for contact between incompatible substances is greatly reduced. However, undesirable contacts are still possible and a more complete categorical storage system needs to be done. Segregation based on Incompatibility The following table shows chemicals broken into a storage scheme of 24 segregated groups. Group 1: INORGANIC ACIDS Chlorosulfonic acid Hydrofluoric acid Hydrogen fluoride Sulfuric acid Group 2: ORGANIC ACID Acetic acid Formic acid Group 3: CAUSTICS (BASIC) Sodium hydroxide Group 4: AMINE AND ALKANOLAMINES Aminoethylethanolamine Diethanolamine Dimethylamine Hydrochloric acid Hydrogen chloride Nitric Acid Phosphoric acid Butyric acid Propionic acid Ammonium hydroxide solution Aniline Diethylamine Ethylenediamine
4 2-Methyl-5-ethylpyridine Pyridine Triethylamine Monoethanolamine Triethanolamine Triethylenetetramine Group 5: HALOGENATED COMPOUNDS Allyl chloride Carbon Tetrachloride Chlorobenzene Chloroform Methylene Chloride Monochlorodifluoromethane 1, 2,4-Trichlorobenzene 1,1,1-Trichloroethane Trichloroethylene Trichlorofluoromethane Group 6: ALCOHOLS, GLYCOLS AND GLYCOL ETHER 1,4-Butanediol Diacetone alcohol Ethyl alcohol Ethylene glycol Iso-amyl alcohol Methyl alcohol Nonanol Propanols Group 7: ALDEHYDES Acetaldehyde Butylaldehyde Formaldehyde Para-formaldehyde Group 8: KETONES Acetone Di-isobutyl ketone Mesityl oxide Group 9: SATURATED HYDROCARBONS Butane Ethane Hexane Methane Paraffins Pentane Butanols Diethylene glycol Ethyl butanol Furfuryl alcohol Iso-octyl alcohol Methyl amyl alcohol Octanol Propylene glycol Acrolein Crotonaldehyde Furfural Propionaldehyde Acetonphenone Isophorone Methyl ethyl ketone Cyclohexane Heptane Iso-butane Nonane Paraffin wax Petroleum ether Group 10: AROMATIC HYDROCARBONS Benzene Dodecyl benzene Naphtha Toluene Cumene Ethyl benzene Naphthalene ylene
5 Group 11: OLEFINS Butylenes 1-Dodecene 1-Heptene 1-Tridecene 1-Decene Ethylene 1-Hexene Turpentine Group 12: PETROLEUM OILS Asphalt Jet fuels Oils Gasoline Kerosene Mineral Oils Group 13: ESTERS Amyl acetate Castor oil Dimethyl sulfate Ethyl acetate Group 14: MONOMERS AND POLYMERIZABLE ESTERS Acrylic acid Butadiene Ethyl acrylate Isoprene Group 15: PHENOLS Carbolic acid Cresols Group 16: ALKYLENE OIDES Ethylene oxide Group 17: CYANOHYDRINS Acetone cyanohydrins Group 18: NITRILES Acetonitrile Butyl acetates Cottonseed oil Dioctyl adipate Methyl acetate Acrylonitrile Butyl acrylate Isodecyl acrylate Methyl acrylate Creosote Phenol Propylene oxide Ethylene cyanohydrins Adiponitrile Group 19: AMMONIA/AMMONIUM HYDROIDE Group 20: Group 21: Group 22: HALOGENS ETHERS (including THF) PHOSPHOROUS, ELEMENTAL Group 23: SULFUR, MOLTEN
6 Group 24: ACID ANHYDRIDE Acetic anhydride Propionic anhydride
7 Appendix B CHEMICAL HAZARDS Chemicals are considered hazardous if they pose either a PHYSICAL or HEALTH hazards to workers exposed to them. PHYSICAL HAZARDS include: Fire or explosions Sudden releases of pressure (for example what happens when a tank of compressed gas is punctured) and: Reactivity (if a chemical can burn, explode or release dangerous gases after contact with water, air or other chemicals). HEALTH HAZARDS are illnesses or other health problems that could develop as a result of exposure to a hazardous chemical. Health hazards could be as minor as a headache or mild skin irritation or as major as cancer (or in rare cases, death) HAZARD TYPES CORROSIVE those substances that by direct chemical action, are injurious to body tissue or corrosive to metal. Corrosive injury may be to a minor degree (irritation) or actual physical disruption of the body tissues. COMMON CORROSIVE LIQUIDS INORGANIC ACIDS ORGANIC ACIDS OTHER INORGANICS Chlorosulfonic Acetic Bromine Chromic Butyric Phosphorous Trichloride Hydrochloric Chloroacetic Silicon Tetrachloride Nitric Formic Sulfuryl Chloride Sulfuric Thionyl Chloride Peroxides CAUSTIC SOLUTIONS ORGANIC SOLVENTS OTHER ORGANICS Ammonia Dichlorethylene Acetic Anhydride Sodium Hydroxide Ethylene Chlorohydrin Liquefied Phenol Potassium Hydroxide Perchloroethylene Triethanolamine Methyl Ethyl Ketone 2-Aminoethanol Gasoline HAZARDS AND PRECAUTIONARY MEASURES Everyone knows mineral acids can cause burns. Few persons realize the extent to which they can damage body tissue. The concentration and duration of exposure control the degree of injury. The primary modes of exposure of corrosive liquids are the skin and eyes.
Concentrated alkaline solutions have a more corrosive effect on tissue than most strong acids. Initial contact may not be painful. Strong alkalis gelatinize tissue thereby producing deep painful penetrating burns. Even relatively dilute alkaline solutions can dissolve skin fats, soften the epidermis and sensitize the skin to other chemicals. In the eyes, caustics are extremely destructive and more difficult to remove than acids. In fact, isotonic solutions of sodium hydroxide (2%) can cause irreparable damage to the eye within three minutes. Concentrated solutions, 50% or greater can cause irreparable damage within fifteen seconds. 8 Always wear adequate protective equipment (gloves, goggles, face shield, etc.). If the danger of inhaling corrosive fumes exits, use the proper ventilation equipment or wear suitable respiratory protection. Immediate first aid must include flushing with large amounts of cool water for a minimum of 15 minutes followed by medical attention. Do not rub the skin. If caustic material gets into the eye, it is imperative that the eyes are washed out immediately with water for a minimum of 15 minutes before leaving the area to seek medical attention. Seconds count! CORROSIVE SOLIDS The effects of corrosive solids are largely dependent on their solubility in skin, respiratory moisture and on the duration of contact. Some compounds do have a specific ability to penetrate the skin. Besides the corrosive properties of solids, the heat of the solution is often an important factor in damaging tissues. COMMON CORROSIVE SOLIDS ALKALIS ORGANIC ACIDS METAL SALTS Calcium oxide Oxalic Tin (IV) chloride Sodium Calcium hydroxide Phenol Phosphorous pentoxide Potassium Cement Salicylic Potassium chromate Lithium Sodium Hydroxide Trichloroacetic Mercury (II) chloride Phosphorous Sodium peroxide Iodine Sodium phosphate HAZARDS AND PRECAUTIONARY MEASURES As with liquids, adequate protective equipment should be worn. Of primary importance is the use of adequate respiratory protection. Protective equipment for the skin and eyes is necessary. Full eye protection is particularly important. All gases and vapors from corrosive liquids or solids cause severe eye irritation or damage. Skin and eyes contacted by corrosive gases and vapors should be washed off thoroughly as suggested for liquids. A good exhaust system is highly recommended for those areas where corrosive gases may be encountered. Immediate medical attention should be sought when exposure occurs. First aid must include flushing with large amounts of cool water for a minimum of 15 minutes.
9 FLAMMABLE CHEMICALS Flammable Liquids-any liquid having a flashpoint below 100 o F except a mixture having components with flash points of 100 o F. Flammable solvents are the most common source of fire. NECESSARY COMPONENTS FOR INITIATING FIRE FUELS OIDIZERS IGNITION SOURCES Flammable Liquids Gases Acetone Oxygen Sparks Alcohol Fluorine Flames Hexane Nitrous Oxide Static Electricity Ether Oxygen Difluoride Heat Toluene Ozone Electrical Flammable Solids Liquids Plastics Hydrogen Peroxide 30% Cigarettes Fibers Nitric Acid Light Bulbs Wood/Paper Perchloric Acid Heaters Dusts Bromine Lightning Pyrophoric Metals Catalytic Surfaces Flammable Gases Solids Acetylene Metallic Lasers Propane Perchlorates Self Heating Carbon Monoxide Metallic Peroxides Hydrogen Ammonium Nitrate Ethylene Oxide Ammonium Nitrite COMMON CONTROL MEASURES DO NOT store more that a total of 5 gallons of solvents in glass in a laboratory. Transfer solvents in a working fume hood. Eliminate all sources of ignition before transferring/working with flammable solvents. Store solvents in a cool area, maximum temperature of 80 o F. Transport solvents in metal or other protective containers. Flammable solids are solids that can cause fire through friction, absorption of moisture, spontaneous chemical change, or retained heat from manufacturing or processing. Flammable solids can ignite readily and burn so vigorously and persistently creating a serious hazard
10 Flammable solids can form explosive mixtures in the atmosphere and react in much the same way as flammable gases. Dust accumulated on surfaces and can be fanned into the air by a fire, air jet or even an improperly chosen fire extinguisher. Dangers from flammable solids (dust) can be minimized by: Using dust tight containers. Using adequate ventilation. Using proper fire extinguishers. Isolation from ignition sources REACTIVE CHEMICALS Reactive chemicals -substances that causes violent reactions liberating heat and/or gases too rapidly to be safely dissipated by the surroundings. Reactive chemicals can be categorized into two groups: Unstable Compounds Unstable Mixtures UNSTABLE COMPOUNDS a. Explosives Explosives are substances that decompose with violent rapidity releasing large quantities of gases and heat. The process of explosion causes the rapid expansion of surrounding air accompanied by burning gases and flying objects. This process is usually destructive to both life and property. High explosives detonate at rates up to four miles per second, while low explosives detonate at rates of only thousands of feet per second. COMMON EPLOSIVE COMPOUNDS Acetylenic Compounds Acetylene Copper (I) Acetylide Ethoxyacetylene Propylene Sodium Azide Azides Compounds Benzenesulphonyl azide Carbonyl Diazide Silver Azide Lead (II) Azide Azo Compounds Chlorite/Chlorate/Perchlorate Compounds Diazirine Silver Chlorite Azomethane Silver Chlorate Diazomethane Sodium Perchlorate Magnesium Perchlorate Fulminates Nitro Compounds/Nitrate Esters Silver Fulminate Nitromethane Mercury (II) Fulminate Nitroglycerine Sodium Fulminate Nitrocellulose Copper (II) Fulminate Trinitrotoluene
11 Picrates Peroxides Picric Acid Diacetyl Peroxide Lead Picrate Zinc Peroxide Dimethyl Peroxide Polymerizable Compounds Acrylic Acid Styrene Ethylene Vinyl Chloride Butadiene Cyclopentadiene UNSTABLE MITURES a. Explosives 1. Nitroglycerine and Ammonium Nitrate 2. Nitroglycerine and Potassium Nitrate b. Water-Reactive Chemicals Compounds that are water reactive should not be stored where automatic sprinkler systems are installed. No water should service the storage area. The storage area should be placarded with DO NOT USE WATER signs. They should be properly desiccated whenever possible. Store in a cool, waterproof area. WATER REACTIVE COMPOUNDS Alkali Metals Organometallic Compounds Halides Hydrides Peroxides Carbides Oxides Phosphides Anhydrides Lithium, Sodium Tetramethylaluminum Acetyl chloride, Titanium tetrachloride Diborane, Sodium hydride Sodium peroxide Calcium carbide Sodium oxide Aluminum phosphide Acetic anhydride c. Peroxidizable Chemicals Peroxidizable chemicals are those chemicals that are susceptible to dangerous decomposition. Since these chemicals are packaged in an air atmosphere, peroxides can form even though the container has not been opened. Peroxidizable chemicals should be dated upon receipt. Containers, which show signs of iron or copper oxide should be handled with extra precautions since many metal oxide promote peroxide formation.
12 Peroxide-Forming Compounds Hazard on Storage Hazard on Concentration Peroxide Initiation of Polymerizations Discard within 3 months of opening Discard within 6 months opening Discard within 1 year of Opening Isopropyl Ether Ethyl Ether Styrene Divinyl Acetylene Tetrahydrofuran Butadiene Vinylidene Chloride Dioxane Tetrafluorethylene Potassium Metal Acetal Chlorotrifluoroethylene Sodium Amide Vinyl Ethers Vinyl Acetylene 2-Butanol Vinyl Acetate 2-Propanol Vinyl Pyridine Cyclohexene Chloroprene Cumene Methylcyclopentane Methyl Acetylene Diacetylene Dicyclopentadiene Air Sensitive Compounds Air sensitive compounds are those that react spontaneously with the oxygen in the air. These compounds usually are pyrophoric they burst into flames on contact with air. AIR SENSITIVE COMPOUNDS Metallic dust (zinc, nickel, titanium) Alkali metals (cesium, potassium) Hydrides (barium hydride) Others (sodium amide, sodium and many organometallics) Pyrophoric metals such as finely divided nickel and titanium should be stored in metal containers with some moisture. Other solids are frequently stored under an inert gas or liquid. Strong Oxidizing Agents and Strong Reducing Agents Oxidizers are chemicals, other than blasting agents or explosives, which initiates or promotes combustion in other materials causing fire through the release of oxygen or other gases. An oxidizing agent is a chemical that gives off free oxygen in a chemical reaction. STRONG OIDIZERS Fluorine Ozone Chlorine Persulfates Peroxides Peroxy Acids Perchlorates Dichromates
13 Permanganates Hypochlorites Nitrates Nitrites Nitrous Oxide Liquid Oxygen Liquid Air Chlorosulfonic acid Nitromethane Chorates Reducing Agents are an agent that cause reduction and is oxidized. STRONG REDUCERS Finely divided metals Hydrazine Hydrides Hydrogen Aniline Sodium Lithium Potassium Butadiene Acetylides All oxidizers carry the special NFPA symbol OY. Reducers carry no special warning. PRECAUTIONARY MEASURES Isolate reactive chemicals. Store compounds of the same class together, away from other classes. For water-sensitive chemicals, do not allow water in the storage area, or water type fire extinguisher and sprinklers Store reactive chemicals in a cool, dry area, protect from sunlight, and label with out-of-date dates Protect reactive chemicals from shock. Store away from flammable and toxic materials. Wear adequate personal protective equipment. Train workers thoroughly in the hazards of the chemicals they are working with. Have antidotes, neutralizers, fire-fighting equipment, etc., close at hand in case of emergency. COMMON REACTIVE CHEMICALS Ammonium Nitrate Benzoyl Peroxide Tert-Butyl Hydroperoxide Calcium Hydride Chromium Nitrate Diborane Dimethyl Phosphine p-dinitrobenzene Hydrazine Hydrate Magnesium Perchlorate Nitromethane p-nitrotoluene Ammonium Perchlorate 2-Butanone Peroxide tert-butyl Peroxide Cesium Chromium Trioxide Diethylaluminum Hydride m-dinitrobenzene Hydrazine Hydrogen Peroxide (concentrated) Mercury (I) Perchlorate o-nitrotoluene Peroxides
14 Phosphorous (red) Potassium Picric Acid Trinitrotoluene Shock Sensitive Chemicals Shock sensitive refers to the susceptibility of the chemical to rapidly decompose or explode when struck, vibrated or otherwise agitated. Some chemicals become increasingly shock sensitive with age. Write the date received and date opened on all containers of shock sensitive chemicals. Unless the manufacturer added an inhibitor, closed containers of shock sensitive materials should be discarded after 1 year. Open containers of shock sensitive chemicals should be discarded within 6 months of opening. The label and SDS will indicate if a chemical is shock sensitive. SHOCK SENSITIVE CHEMICALS Acetylides of heavy metals Mercury Tartrate Aluminum ophorite explosive Mononitrotoluene Amatol Nitrated Carbohydrate Ammonal Nitrated Glucoside Ammonium Nitrate Nitrated Polyhydric Alcohol Ammonium Perchlorate Nitrogen Trichloride Ammonium Picrate Nitrogen Tri-Iodide Ammonium Salt Lattice Nitroglycerine Butyl Tetryl Nitroglycide Calcium Nitrate Nitroglycol Copper Acetylide Nitroguanidine Cyanuric trazide Nitroparaffins Cyclotrimethylenetrinitramine Nitronium perchlorate Cyclotetramethylenetranitramine Nitrourea Dinitroethyleneurea Organic Amine Nitrate Dinitroglycerine Organic Nitrosamines Dinitrophenol Organic Peroxides Dinitrophenolates Picramic acid Dinitrophenyl hydrazine Picramide Dinitrotoluene Picratol Dipicyl sulfone Picric acid Dipicrylamine Picryl Chloride Erythritol tetranitrate Picryl Fluoride Fulminate of Mercury Polynitro aliphatic compounds Fulminate of Silver Potassium nitroaminotetrazole Fulminating Gold Silver acetylide Fulminating Mercury Silver Azide Fulminating Platinum Silver Styphnate Fulminating Silver Silver Tetrazene Gelatinized Nitrocellulose Sudatol Guanyl nitrosamino guanyltetrazene Sodium Amatol Guanyl Nitrosaminoguanylidene Sodium Dinitro-o-cresolate Germane Sodium Nitrate-potassium
15 Hexanite Explosive Mixtures Sodium picramate Hexanitrodiphenylamine Tetrazene Hexogen Tetranitrocarbazole Hydrazinium Nitrate Tetrytol Hydrazoic acid Trimonite Heavy Metal Azides Trinitroanisole Lead Azides Trinitrobenzene Lead Mannite Trinitrobenzoic acid Lead Mononitroresocinate Trinitrocresol Lead Picrate Trinitro-m-cresol Lead Salts Trimethylolethane Lead Styphnate Trinitronaphthalene Magnesium ophorite Trinitrophenetol Mannitol Hexanitrate Trinitrophloroglucinol Mercury Oxalate Trinitroresorcinol Tritonal Urea Nitrate TOIC CHEMICALS/CARCINOGENS Toxic chemicals are any chemical which when inhaled, ingested or absorbed may cause damage or disturbance to function. Toxic substances may cause injury by damaging biological structure and/or disturbing body function. 1. Damage can be LOCAL and/or SYSTEMIC. Local toxicity-is the effect of a substance on the body area that has been exposed to the substance. Exposure may be through direct contact, inhalation, ingestion or penetration. Systemic toxicity-is the effect of a substance on body tissues after absorption into the bloodstream. Absorption may take place through the skin, stomach or lungs. 1. Damage can be ACUTE and/or CHRONIC. Acute toxicity is defined as that effect manifested on short exposure on single contact, ingestion or inhalation. Chronic toxicity is defined as that effect observed when a toxicant acts on body tissues over a long period of time, days to years. A person suffering from chronic toxicity may not observe effects until an advanced stage is reached and permanent damage have been done. PARAMETERS THAT AFFECT TOICITY Routes of entry- Contact the skin, eye, respiratory tract and/or digestive system. Physical Condition Are you ill? Has your body been damaged by a previous assault? Dose How much of the chemical assaulted your system? Duration How long were you exposed to the chemical? Sensitivity How sensitive are you to the chemical? Combined Effects What other chemicals were you exposed to? Stress Were you under any physical or mental stress during or after the exposure.
Others Sex, race, heredity, temperature, altitude and a host of additional parameters sometimes affect toxicity. 16 COMMON MODES OF ENTRY FOR TOIC CHEMICALS SKIN Skin is the most frequently exposed body tissue to poisons. The most common result is irritation. Many toxic chemicals, however, are rapidly absorbed through the skin and may cause systemic effects. Toxic contamination of the clothing and shoes increases the hazard because of the localization of toxic concentration. Pain sensations do not necessarily accompany an assault on the skin. NOSE (Inhalation) The internal surface area of the lungs is estimated to be greater than 100 m 2, thus allowing rapid absorption of poisons into the bloodstream. Absorption rate and activity are related the more active the person, the faster the absorption. Many toxic chemicals reveal their presence by giving sensory warnings, such as pain or smell. These sensory effects can be useful because immediate action can be taken. However, the sense of smell may become aware of danger after the fact, or may not respond at all. Olfactory fatigue may prevent detection of toxic materials. Sensory warning is a useful backup, but should not be relied on as a fast line of defense. EYES Very few substances are safe when in contact with the eye. The sensitivity of the eye to chemicals is such that irritation, pain, impairment of vision or even blindness can result. INGESTION The act of taking food, medicines, etc into the body via the mouth. INJECTION Purposeful injection of poisons can occur through mechanical injury--a cut. PREVENTIVE MEASURES Unless you know definitely that a substance in not toxic, treat it as though it is. Cover exposed areas of skin (wear gloves, aprons, caps, etc.). Wear appropriate personal protective equipment for the compound Change protective garments as required. Keep food out of the lab. Do not use lab glassware for food or drink. Keep antidotes for common poisons on hand. Train all personnel thoroughly. SOME COMMON POISON CHEMICALS Acetaldehyde Acrylamide Barium & Barium Cmpds 1,3-Butanediene Cadmium & Cadmium Cmpds Carbon Tetrachloride Chloroform DDT 1,4-Dichlorobenzene 1,2-Dichloroethane Dichloromethane 1,1-Dimethylhydrazine Eprichlorohydrin Ethyl Acetate 1,4-Dioxane Formaldehyde Ethylene Oxide Lead & Lead Cmpds Mercury & Mercury Cmpds. Silver
17 Appendix C Chemical Incompatibilities and their Consequences Product Incompatibilities Interaction Hazard Flammables Acetone Chloroform Explosion Hydrogen Peroxide Severe Explosion Benzene Perchlorates Explosions Sodium Air Spontaneous fire Water Spontaneous fire Bleach Explosion Sulfur Sulfur dust in air Explosion Bromates and Chlorates Explosion Calcium hypochlorite Explosion Charcoal Spontaneous fire Tin Vigorous reaction Corrosive Nitric acid Acetic acid Explosion Ammonia Spontaneous fire Cyanides Explosion Perchloric acid Cellulose, paper, wood fiber Violent explosion Charcoal Violent explosion Picric acid Bases Explosive salt Concrete Explosive salt Poisons Cyanides Chlorates Violent explosion Nitrites Violent explosion Nitrites Aluminum Explosion Esters Explosion Phosphorous Explosion Carcinogens Arsenic Bromates, chromates Explosion Chlorine Spontaneous fire Potassium nitrate Explosion Nickel Ammonium nitrate Explosion Oxidizers Chlorates Organic matter, cellulose, charcoal, Spontaneous fire to violent explosions cotton, paper wood Dioxides Nitrates Oxides Permanganates Perchlorates Peroxides
18 Incompatibilities for Flammable and Combustible Chemicals Extremely Flammable Materials (FP < 100F o, BP<100F o ) Chemical Flash Point (F o ) Boiling Point (F o ) Incompatible Interaction Hazards Substances Acetaldehyde -40 68 Acetic acid Explosion Air Explosion Alcohols Violent reaction Ammonia Violent reaction Bromine, chlorine, Violent reaction fluorine Sodium hydroxide Violent reaction Diethyl ether -49 94 Air & aging Explosion (peroxides) Chromic acid Violent reaction Perchloric acid Violent reaction Sodium peroxide Spontaneous fire Hydrogen Gas -76 Acetaldehyde Violent reaction sulfide Copper powder Red-hot reaction Lead dioxide Spontaneous fire Nitric acid Incandescent reaction Vinyl chloride -108-7 Air & aging Unstable (explosion) (polyperoxide) Nitric acid Temperature & pressure increase
19 Flammable Materials (FP <100 F o, BP < 100F o ) Chemical Flash Point (F o ) Boiling Point (F o ) Incompatible Substances Interaction Hazards Acetone 15 133 Chloroform Explosion Chromic Anhydride Explosion (acid) Hydrogen peroxide Explosion Potassium t-butoxide Spontaneous fire Benzene 12 176 Chlorine Explosion Chromic anhydride Spontaneous fire (acid) Sodium peroxide Spontaneous fire Carbon disulfide -22 115 Aluminum powdered Spontaneous fire Azides (lead, Violent explosion potassium, sodium) Chlorine Explosion Potassium Violent explosion Zinc Incandescent reaction Isopropyl alcohol 53 180 Sulfuric acid Temperature & pressure increase Potassium t-butoxide Spontaneous fire Combustible Materials (FP 100-200 F o ) Chemical Flash Point (F o ) Boiling Point (F o ) Incompatible Substances Interaction Hazard Aniline 158 364 Nitric acid Spontaneous fire Sodium Spontaneous fire peroxide Formalin (37% 122-185 214 Nitrogen Explosive (>180 o C) formaldehyde) dioxide Formic acid 156 213 Furfuryl alcohol Explosive Hydrogen Possible explosion peroxide Nitroethane 106 237 Hydroxides Explosive salts Inorganic bases Explosive salts Phenol 173 360 Calcium hypochlorite (bleach) Spontaneous fire
20 Incompatibilities for Acids Chemical Incompatible Substances Interaction Hazard Acetic acid Acetaldehyde Temperature & pressure increase Ammonia Carcinogen Ammonium nitrate Spontaneous fire Hydrogen peroxide Explosion Potassium hydroxide Violent reaction Chlorine Alcohols Violently explosive Aluminum Spontaneous fire Ammonia Explosion Turpentine Spontaneous fire Dimethyl sulfate Ammonium hydroxide Violent reaction Hydrochloric acid Acetic anhydride Temperature & pressure increase Ammonium hydroxide Temperature & pressure increase Perchloric acid Violent reaction Sodium hydroxide Temperature & pressure increase Sodium/calcium cyanide Highly poisonous cyanide gas Vinyl acetate Temperature & pressure increase Hydrofluoric acid Ammonium hydroxide Temperature & pressure increase Calcium oxide Violent reaction Sodium Explosion Vinyl acetate Temperature & pressure increase Nitric acid Acetylene Explosion Alcohols Highly explosive esters Cyclohexanone Violent reaction Organic matter Spontaneous fire Sodium Spontaneous fire Sulfuric acid Acrylonitrile Vigorous exothermic reaction Chlorate Explosion Iron Explosion Potassium permanganate Explosion Water Violent eruption
21 Incompatibilities for Alkalis Chemical Incompatible Substances Interaction Hazard Ammonium hydroxide Dimethyl sulfate Violent reaction Fluorine Spontaneous fire Silver nitrate Explosion Sulfuric acid Temperature & pressure increase Calcium carbide Hydrogen chloride Incandescent reaction Magnesium Incandescent reaction Sodium peroxide Spontaneous fire Sulfur Incandescent reaction Water Spontaneous fire Calcium hydroxide Nitroethane Explosion Nitromethane Explosion Nitropropane Explosion Phosphorous Spontaneous fire Calcium oxide Hydrofluoric acid Violent reaction (Quicklime) Phosphorous pentoxide Violent reaction Water Increase in temperature Potassium hydroxide Acetic acid Violent reaction Phosphorus Spontaneous fire Tetrahydrofuran Explosion Water Violent reaction Sodium hydroxide Acetic anhydride Temperature & pressure increase (Lye, caustic soda) Nitroethane Explosion Aluminum Violent reaction Sulfuric acid Temperature & pressure increase Water Spontaneous fire
22 Incompatibilities for Oxidizers Chemical Incompatible Substances Interaction Hazards Ammonium dichromate Self-reactive Incandescent reaction Ammonium perchlorate Self-reactive Explosion (when heated) Carbon Mild explosion Metals Explosion Organic matter Explosion Calcium hypochlorite Amines Explosion (Bleach) Carbon Tetrachloride Explosion Oil or grease Violent reaction Phenol Spontaneous fire Turpentine Explosion Fluorine Ammonium hydroxide Fire & explosion Cellulose Violent explosion Hydrocarbons Violent explosions Polyethylene Fire/violent reaction Sulfur Fire Hydrogen Peroxide Acetic acid Explosion Cellulose Spontaneous fire Charcoal Spontaneous fire Iron Violent reaction Mercuric oxide Violent reaction Potassium nitrite Ammonium sulfate Spontaneous fire Boron Explosion Potassium permanganate Acetic acid Explosion Hydrogen peroxide Violent reaction/fire Metals (antimony, arsenic & Explosion titanium) Phosphorus Explosion Sulfuric acid Explosion Perchloric acid Self-reactive Explosion (spontaneous) Acetic acid Explosion Alcohols Violent reaction Diethyl ether Violent explosion Paper Violent explosion Wood Violent explosion Sodium nitrate Antimony Explosion Cyanides Explosion Sodium peroxide Acetic acid Explosion Benzene Spontaneous fire Charcoal Fire/explosion Diethyl ether Spontaneous fire Phosphorous Fire/explosion
23 Incompatibilities for Explosive/Reactive Chemicals Class 4 ---materials that readily undergo explosion at normal temperatures and pressures or from some kind of shock (mechanical or thermal) Chemical Incompatible Substances Interaction Hazard Benzoyl peroxide Self reactive Explosion (spontaneous) Methyl methacrylate Spontaneous fire Organic matter Explosion Nitrotoluene Sulfuric acid Explosion Peracetic acid Self reactive Explosion Acetic anhydride Explosion Olefins Vigor exothermic reaction Organic matter Explosion Class 3---materials that react explosively with water or are capable of exploding when heated under pressure. Chemical Incompatible Substances Interaction Hazard Acetylene Bromine Explosion Chlorine Explosion Copper Explosion Mercuric nitrate Explosion Sodium hydride Vigorous reaction Ethylene oxide Acid & bases Increase in temperature Alcohols Explosion Ammonia Explosion Iron oxide Violent reaction Potassium Violent reaction Nitroethane Calcium hydroxide Explosion Hydrocarbons Explosion Other hydroxides Explosion Potassium/sodium hydroxide Explosion Class 2---materials that react violently with water or undergo a violent chemical change but do not explode Chemical Incompatible Substances Interaction Hazard Acetaldehyde Air Explosion Alcohols Violent reaction Ammonia Violent reaction Acrylonitrile Strong acid Vigorous exothermic reaction Bromine Explosion Potassium hydroxide Violent reaction Sulfuric acid Vigorous exothermic reaction Calcium Acids Violent reactions Air Spontaneous fire Oxygen Spontaneous fire Sulfur Explosion Water Spontaneous fire Calcium hypochlorite Charcoal Explosion (when heated) Ethyl alcohol Violent explosion Hydrochloric acid Chlorine gas (poison, corrosive) Iron oxide (rust) Explosion Turpentine Explosion
24 Appendix D Chemical Classification & Safety Signs The National Fire Protection Association (NFPA) uses a symbol system designated as a diamond-shaped label containing four differently colored squares. A number (0-4) or an abbreviation is added to each square indicating the order of hazard severity--the higher the number, the greater the hazard. Flammable Materials (Red background) SPECIFIC HAZARDS (White background) Oxidizer O Acid ACID Alkali ALK Corrosive CORR No Water--W Flammability is the measure of how easily a gas, liquid or solid will ignite and how quickly the flame, once started, will spread. Flammable liquids themselves are not flammable; rather, the vapors from the liquids are combustible. The flash point of a material is the temperature at which a liquid (or volatile solid) gives off vapor in quantities significant enough to form an ignitable mixture with air. Given an external source of ignition (spark or flame), a material can ignite at temperatures at or above its flash point. Pyrophoric materials can ignite spontaneously with no external source of ignition.
25 Health Hazards (Blue background) A carcinogen is an agent capable of causing cancer. Long-term exposure to carcinogenic substances can result in cancers of various types. A number of substances have been found to be capable of producing cancer following exposure by inhalation, ingestion or skin contact. Mutagens are chemical and physical agents that induce mutations in DNA and in living cells. This affects the genetic system in such a way as to cause cancer or hereditary changes in chromosomes. Individuals exposed to chemicals with mutagenic properties may develop genetic damage to the extent that future offspring will be affected. Teratogens are chemical and physical agents that interfere with normal embryonic development. Teratogens differ from mutagens in that there must be a developing fetus. Damage to the fetus (embryo) is most likely to occur early in pregnancy, during the first 8-10 weeks. Teratogens may produce congenital malformations or death of the fetus without damage to the pregnant woman. Reactivity (yellow background) Explosive materials are chemicals that cause sudden, almost instantaneous release of large or small amounts of pressure, gas and heat when subjected to sudden shock, pressure or high temperatures. Specific Hazards (white background) Corrosive materials can burn, irritate or destructively attack living tissue. Materials with corrosive properties can be either acidic (low ph) or alkaline (high ph). An oxidizing agent is a chemical used to provide oxygen for chemical reactions. Oxidizers spontaneously evolve oxygen at room or slightly elevated temperatures and can explode violently when shocked or heated. Because oxidizing agents are unpredictable, they represent a particularly hazardous threat.
26 Appendix E GENERAL EMERGENCY/FIRE/SPILL PROCEDURES Before starting any new work, personnel should be aware of any possible hazards that could occur in his/her specific work place. They should be familiar with all emergency procedures and the location of all emergency equipment available in case of trouble. The following emergency procedures are recommended in the event of fire, spills, explosions, etc.: 1. Alert others in the area of the problem. Evacuate and secure the area. Post a clear warning sign near the area. 2. Assist the injured. Remove the injured from the area only if they are in danger of further harm. If they are not in danger, leave them until trained personnel arrive. 3. Contact the needed emergency personnel (fire, medical, etc.). Contact the Safety & Environmental Compliance Department at 6-7070. If you call 911, you must also contact the University Police (6-6213)so they will be aware of the problem. 4. Start emergency first aid of the injured (CPR, decontamination of victims, etc) 5. If available, use outside vented chemical fume hood to remove fumes from the area. You may need to contact the Central Utilities Department (6-7048) on main campus or your facilities maintenance department, as they may need to shut off the air handlers to prevent the spread of fumes throughout the building 6. Begin decontamination only after the area has been secured and any victims have been removed. Only trained personnel should conduct decontamination and clean up 7. Above all, DO NOT BECOME A VICTIM YOURSELF. If you are not equipped or trained to respond to an incident, go find someone who is. You must protect yourself. FIRE Respond to fire alarms by immediately evacuating your area by the shortest possible route. Ensure that all persons in your area have heard the alarm. If you discover a fire or any other emergency situation: RESCUE Remove all persons from the immediate fire scene or room. ALERT Activate the nearest fire alarm pull station, dial 6-6312 (University Police) and 9-911 (Mobile Fire-Rescue). CONFINE Confine the fire area by closing doors to room or areas. ETINGUISH Extinguish a small fire by using a portable fire extinguisher or use to escape from a larger fire. Evacuate and meet at your building s pre-designated meeting location a minimum of 100 feet away from the building. Stay out of the way of the Fire Department and on-coming traffic.
27 CHEMICAL SPILLS Chemical spills will inevitably occur and staff should be properly trained to recognize the hazards associated with the spill, minimize the spill within their ability and notify proper response personnel when necessary. Initial response to a chemical spill should include: General plan of action during a chemical spill: Don t panic Alert other people of the problem and evacuate to a place of safety. If time allows and a chemical fume hood is available, open the face completely and turn on to help ventilate the area. If windows are available, open them. Contact University Police (6-6312) for help in securing the area. Contact SECompliance Department (6-7070). Remove any injured person to fresh air and begin decontamination on them and yourself if necessary. Remove any contaminated clothing. Flush skin and eyes for a minimum of 15 minutes. Use soap for final cleaning of the skin. If flammable vapors are involved, do not operate electrical switches except to turn off motorized equipment. Try to turn off or remove any heat sources. Check SDS for proper procedures before starting any clean up procedures. Do not touch the spill without protective gloves and clothing. If the spill does not present an immediate danger to life and health, try to control the spread or volume of the spill. Try not to allow the material to escape into the floor drains. NEVER assume gases or vapors do not exist or are harmless because of a lack of smell. Many chemicals anesthetize the nose and the sense of smell is eliminated. The following procedures shall be followed in the event of any chemical exposure to the eyes or skin: Chemical Splash to the Eyes Get to the eyewash or any source of water immediately and flush eyes out thoroughly with copious amounts of cool water for a minimum of 15 minutes. Hold the eyes open to wash thoroughly behind the eyelid In the absence of an eyewash fountain, place the injured person on his/her back and gently pour water into the eye. The injured eye must be held open. Continue washing for a minimum of 15 minutes. Immediately seek medical attention. Chemical Splash to Skin or Clothing Get to a safety shower as soon as possible Quickly remove all contaminated clothing WHILE USING THE SHOWER. Flood the affected body in cool water for a minimum of 15 minutes. Immediately seek medical attention.
28 General Purpose laboratory Spill kit should include: 1. Plastic bucket with sealable lid 2. Plastic dustpan and brush 3. Heavy gauge polyethylene bags with closure (twist ties, cables ties, etc) 4. Chemical resistant gloves (nitrile, at minimum) 5. Safety goggles or face shield 6. Splash-proof coverall or apron and shoe protectors 7. Inert absorbent materials kitty litter, vermiculite, etc. 8. Paper towels or rags 9. ph indicator paper 10. Neutralizing agents for acid such as sodium bicarbonate (baking soda) or sodium carbonate (soda ash) 11. Neutralizing agents for bases such as boric acid or citric acid LIQUID CHEMICAL SPILLS 1. Alert other persons to the spill and the need to evacuate the area. 2. Determine the degree of hazard before attempting clean up and take the necessary preventive measures (i.e., protective equipment, eye protection, etc.) 3. Confine or contain spill to smallest area possible. 4. Wear personal protective equipment, goggles, face shield and gloves appropriate for the situation. 5. For small quantities of ACIDS, use a neutralizing agent or absorbent mixture (i.e., soda ash, sodium bicarbonate, or diatomaceous earth). For BASES, Citric acid or boric acid can be used. Check area with ph indicating paper to insure complete neutralization. NOTE: If acids/bases have been absorbed, but not neutralized, they still pose a danger of burns to the skin and eyes. HANDLE WITH CAUTION. Do not use acids to neutralize base spills (or vice versa), as the reaction can be violent. 6. For small quantities of FLAMMABLE/COMBUSTIBLE LIQUIDS, a commercially purchased Spill Pillow (specifically designed for solvents) can be used. Absorbent materials, such as vermiculite or kitty litter, can be used, but fumes can still volatilize from these materials. 7. For small quantities of other materials, absorb the materials with a non-reactive materials (i.e., vermiculite, clay, dry sand or towels) 8. Non-reactive absorbents, such as oil dry, vermiculite or commercially available absorbent pads should be available for liquid spills. NOTE: Paper towels may be used for incidental spills and for final wipe-up operations, but caution should be exercised. Some chemicals may cause ignition through reactions with the toweling causing a fire. 9. Mop up the spill. Wring the mop out into a pail equipped with rollers. DO NOT use your hands. 10. Carefully pick up any broken glass using mechanical means such as tongs or broom and dustpan. 11. Carefully pick up and clean any cartons, bottles or equipment that may have been splashed and contaminated. 12. If absorbent has been used to clean up flammable or volatile chemicals, it must be stored in a well-ventilated area, away from sources of heat or ignition. 13. Double bag contaminated clean up materials and seal. These materials must be disposed of as hazardous waste.
14. When clean up operations are complete, wash hands with soap and water for at least 1 minute. Check any nondisposable personal protective equipment (boots, respirators) for contamination. Clean and dry completely prior to placing back in storage. 29 SOLID CHEMICAL SPILLS 1. Alert other persons to the spill and the need to evacuate the area. 2. Determine the degree of hazard before attempting clean up and take the necessary preventive measures (i.e., protective equipment, eye protection, etc.). 3. Generally, solids of low toxicity can be swept up into a dustpan and placed into a container compatible with the chemical. Damp toweling should be used to pick up and transfer materials of a higher toxicity level to a compatible waste container. Make sure the material is not water sensitive before using this procedure. 4. Dispose of residue as hazardous waste, remembering brooms, dustpans and other items may require disposal as hazardous waste also. 5. Double bag contaminated clean up materials and seal. 6. When clean up operations are complete, wash hands with soap and water for at least 1 minute. Check any nondisposable personal protective equipment (boots, respirators) for contamination. Clean and dry completely prior to placing back in storage. NOTE: Highly reactive solids, such as alkali metals, are best reclaimed by using tongs. SPILLS OF HIGHLY TOIC OR CARCINOGENIC CHEMICALS Principal Investigators in charge of laboratories where HIGHLY TOIC and/or CARCINOGENIC chemicals are used are responsible for developing and implementing SPECIFIC decontamination, clean up and disposal procedures for such chemicals and for ensuring that all personnel under their charge, who are required to work with such chemicals, know and can execute these specific procedures should the need arise. ELEMENTAL MERCURY SPILLS When spilled, mercury often fragments into small beads that can bounce and roll far from the initial spill location. Mercury spills can be avoided by using supplies and equipment that don t contain mercury. All labs and facilities where mercury is used should have a mercury spill kit in case of spill. Mercury spill kits are commercially available and usually contain treated sponges, gloves, shoes coverings, a small, plastic dustpan and scraper and plastic bags and spill clean up material. When a spill of elemental mercury occurs: 1. Alert others in the area that a spill has occurred. 2. Isolate the area to prevent people from entering the spill area and spreading the contamination. 3. Determine whether the spill is a simple or complex spill A simple spill is one caused by a laboratory thermometer or other small device where all the mercury is accessible on a non-porous surface. A complex spill is one that involves more than 10 milliliters, is located on a porous surface (carpet, etc) or is widely spread. 4. Prior to starting clean-up procedures, remove all gold or silver jewelry. 5. Wear a pair of chemical resistant gloves (nitrile or silver shield), a lab coat and eye protection.
6. Starting at the outside perimeter and using a non-sparking scraper, push the scattered mercury droplets together into larger droplets. 7. Aspirate the larger mercury droplets and place them into a zip-lock bag or screw top container. A disposable syringe or hand-held mercury vacuum can be used to aspirate the mercury droplets. Commercially available mercury absorbent materials (Hg-Sorb) should be used to accumulate small particles of mercury. 8. DO NOT USE A REGULAR VACUUM AS THIS DISPERSES DROPLETS, INCREASES THE AIRBORNE LEVEL OF MERCURY VAPOR AND CONTAMINTES THE EQUIPMENT USED. 9. Use a flashlight to illuminate smaller beads of mercury. Mercury droplets can be pinhead size or smaller. Re-clean the spill area and perimeter if necessary. Pay close attention to cracks and crevices that may hide small beads of mercury. 10. Place any materials used for the cleanup procedures into a plastic bag for disposal. 11. Call Safety & Environmental Compliance Department (6-7070) for final disposal 30 DO NOT MI CLEAN UP MATERIALS WITH ANY FREE MERCURY YOU MAY HAVE COLLECTED. HYDROFLUORIC ACID Hydrofluoric acid (HF) has a number of chemical, physical and toxicological properties, which make handling this material especially hazardous. Anhydrous HF is a clear, colorless, fuming, corrosive liquid. HF is also available in the gaseous state. All forms including the solution or the vapor can cause severe burns to tissue. Using Hydrofluoric Acid Safely: 1. NEVER USE HF WHEN WORKING ALONE AFTER HOURS. 2. All lab personnel, not just those who will be using HF, must receive training pertaining to the dangers associated with HF and the emergency procedures in the event of an exposure or spill. A Material Safety Data Sheet (SDS) on HF should always be kept in the immediate work area where HF is used. 3. HF emergency procedures should be posted where laboratory workers can see them. 4. A sign should be posted to alert people that HF work is in progress. 5. HF should only be used in areas of adequate ventilation to minimize the possible inhalation of vapors. 6. Always use chemical goggles together with a face shield when handling HF. Safety glasses, with side shields, do not provide adequate eye protection. 7. Wear a long-sleeved buttoned lab coat with a chemical splash apron (nitrile, neoprene or Viton), pants and closed toe shoes. Never where shorts or open-toed shoes when handling HF or other corrosive chemicals. 8. Wear heavyweight Viton, nitrile, or neoprene when working with HF. DO NOT USE LATE GLOVES: THEY ARE NOT EFFECTIVE AGAINIST HF. Always consult the manufacturers glove selection guide when selecting a glove for HF. 9. Since HF is extremely corrosive and rapidly damages tissue, operational eyewash should be present in the laboratory where HF is being used. An operational safety shower (tested monthly) must be near by and accessible. The eyewash/safety shower should be used for a minimum of 5 minutes to rinse the exposed area and then treatment of skin with Calcium Gluconate gel should be initiated. 10. Calcium Gluconate gel: Calcium Gluconate gel is a topical antidote for HF skin exposure. Keep calcium Gluconate gel nearby whenever you are working with HF. Calcium Gluconate has a limited shelf life and should be stored in a refrigerator if possible and replaced with a fresh supply after its expiration date has passed. Use gloves to apply the gel to any exposed area.