Technical Performance Chemicals Product Information Hydrazine Product Stewardship SAFETY AND HANDLING OF HYDRAZINE SOLUTIONS Hydrazine is a versatile chemical, used in many in- oxygen. Therefore, some loss of hydrazine can occur if dustrial applications such as the production of chemical solutions are stored under conditions that permit entry of blowing agents, pharmaceutical and agricultural interme- air. diates, urethane coatings and in boiler water treatment. Hydrazine solutions are stable under normal storage Like any chemical, hydrazine should be handled carefully. conditions if contact with air, oxidizing or catalytic agents In order to aid in properly handling and storing hydra- and impurities is avoided. Decomposition of hydrazine is zine, the following is presented to assure the customers caused by elevated temperatures and/or the presence of safety. catalytic surfaces or ionic impurities. When hydrazine decomposes under these circumstances, the products Why Aqueous Hydrazine? formed are either nitrogen and ammonia, or nitrogen, Hydrazine (N H ) is generally sold in solution rather ammonia and hydrogen, depending on the catalyst. In con- than anhydrous form.2 4 This reduces the hazards associated tact with air, the reaction products are nitrogen, ammonia with handling, storage and processing of the anhydrous and water. form. Hydrazine solutions are commercially available from Hydrazine in the vapor state is subject to auto-de- Arch Chemicals in a range of concentrations suitable for composition from catalytic effects or high energy excita- most applications. This brochure provides the basic in- tion, such as an electric discharge or spark. In the case of formation to enable a potential user to evaluate the com- pure or concentrated hydrazine vapor, the rate of auto- mercial aspects of handling, storing and using hydrazine decomposition is rapid enough to cause an explosion. Thus, solutions. the upper explosive limit of hydrazine is defined as 100% N H . However, the rate of auto-decomposition is retarded 2 4 Properties of Aqueous Hydrazine when hydrazine vapors are diluted with substances which absorb a part of the energy Water vapor mixed with hy- Chemical Properties drazine has such a retarding effect. Other vapor diluents The most active chemical properties of hydrazine are such as heptane also have a retarding effect. If a vapor its basicity, its readiness to react with oxidants, and its diluent is used, care must be taken to ensure that reactions reactivity with organic compounds, which are evidenced between hydrazine and the diluent, or the decomposition by the large number of derivatives reported in trade jour- products of either, do not increase the hazard of an explo- nals and patent literature. Books on this subject have also sion. been published. As a base, hydrazine is weaker than ammonia. How- Although hydrazine may exist as the monohydrate in ever, you can prepare more concentrated solutions of aque- water solutions, all of the hydrazine is readily available ous hydrazine than you can of ammonia. Since hydrazine for chemical reaction. solutions behave as fairly caustic liquids, appropriate pre- cautions should be taken. Care should also be taken when Physical Properties neutralizing hydrazine solutions with strong acids. Pure hydrazine is a colorless, highly polar liquid with a slight ammonia-like odor. It is miscible with water in all Hydrazine solutions will attack rubber and cork and proportions and these solutions are highly alkaline the more slowly leach silica from glass vessels if stored in them for important properties of commonly available hydrazine periods of years. solutions are listed in our Technical Data Sheet on Hydra- A powerful reducing agent, hydrazine reacts with a zine. variety of oxidants including many metal oxides, certain metal salts in their aqueous solutions, and atmospheric 6-21V18/99 1999 Arch Chemicals, Inc. Arch Chemicals, Inc. Technical Performance Chemicals Product Information Hydrazine Hazards of as might be induced by flame or spark. Hydrazine Solutions Hydrazine is a strong reducing agent, as well as a Certain precautions must be observed in handling base. Therefore, it should not be stored near organic ma- hydrazine solutions. These precautions require recogni- terials, oxidizing agents or acids. These include sawdust, tion of (1) the toxic and corrosive characteristics of hy- rags, hydrogen peroxide, sodium hypochlorite solution drazine, (2) its ease of oxidation, and (3) the need to avoid (bleach), halogens such as chlorine, fluorine, and bromine; conditions which can lead to rapid decomposition. and fuming nitric acid. Contact with metal oxides such as iron, copper, lead, manganese and molybdenum should be Toxicity avoided. Contact with any of these oxidizing agents can Hydrazine can he absorbed into the body in harmful result in immediate ignition followed by an explosion due or fatal amounts by ingestion, skin contact, or inhalation. to rapid gas formation. Mixtures of hydrazine vapor in Contact with the skin, eyes and respiratory tract can cause air are flammable between the limits of 4.7% and 100% severe irritation and/or burns. Hydrazine may cause der- hydrazine by volume. mal sensitization. The flammability of hydrazine vapor is decreased by Exposure to large single doses, or small repeated doses the use of any of several diluents. Nitrogen is generally of hydrazine may cause death, temporary blindness, diz- recommended due to ready availability lack of reactivity ziness, nausea, cyanosis, and damage to internal organs. and cost. The lower explosive limit of a hydrazine-nitro- Damage may occur to the central nervous system and/or gen-air mixture is a straight-line function between 4.7% to such organs as the liver, kidneys, lungs, and those or- for air and 38% for nitrogen at 109oC to 112oC (228oF to gans that form the blood. Hydrazine has been shown to 234oF). Exposure of all hydrazine solutions to direct sun- cause cancer in laboratory animals. It is considered a sus- light or to high temperatures should be avoided. pect carcinogen in humans. High concentrations of hy- drazine have caused embryo lethality and fetal malforma- Personnel Protection tion in laboratory animals. Persons handling aqueous solutions should wear pro- For complete, up-to-date information, obtain and read tective equipment: apron or protective suit, chemical safety the current Material Safety Data Sheet for the hydrazine goggles and/or face shield, and butyl rubber gloves and product used. To order an MSDS, contact Arch Chemi- boots . Butyl rubber is the material of choice when han- cals at the address listed on the back cover of this bro- dling hydrazine. Other compatible materials for protec- chure. tive clothing include: Neoprene1, nitrile rubber and poly- vinyl chloride. Fire Protective clothing and equipment should be worn when- It has been determined by using ASTM procedures ever the potential exists for contact with hydrazine. This that aqueous solutions below 40% N H have no flash or 2 4 includes: fire point. However, as the concentration of hydrazine in- 1. Opening drum plugs or tank truck manway covers. creases, the flash point decreases from about 113oC 2. Connecting and disconnecting lines. (235oF) at 40% concentration to about 52oC (126oF) for 3. Placing pumps into drums. anhydrous hydrazine. 4. Operating manual pumps. Since hydrazine is miscible with water, the use of water 5. Starting and stopping electrical pumps where the in fighting a fire involving hydrazine not only cools the switches are near the pumps. flame but also dilutes the hydrazine to a point where it 6. Breaking hydrazine piping, even if previously decon- will no longer support combustion. taminated. Hydrazine in liquid form, even anhydrous hydrazine, 7. Flushing out empty drums. is very stable and insensitive to shock. However, hydra- zine vapors can present a hazard and precautions must be taken to avoid their auto- or catalytic decomposition, such 1 Trademark of E.I. du Pont de Nemours, Inc. Arch Chemicals, Inc. 2 Technical Performance Chemicals Product Information Hydrazine Workers should change into clean working clothes each day. If hydrazine is spilled or splashed on articles of cloth- Inhalation: Remove victim to fresh air. Call a physician ing, they should be removed immediately and laundered immediately before reuse. Leather shoes should not be worn when han- For complete, up-to-date information, obtain and read dling hydrazine since hydrazine cannot be removed from the current Material Safety Data Sheet for the hydrazine leather. If hydrazine should be spilled on leather shoes, product being used. To order an MSDS, call 1-800-511- remove them immediately and discard. MSDS. Dilute aqueous solutions of hydrazine are capable of releasing hydrazine vapors to the surrounding atmosphere. Spill and Leak Procedures Because of the toxicity of hydrazine vapors, care should Wear a NIOSH approved full-face positive-pressure be taken to assure adequate local exhaust ventilation when- supplied-air respirator or self-contained breathing appa- ever hydrazine is handled in open containers. ratus. Follow OSHA regulations for respirator use (See Ventilation in areas where hydrazine is handled should Title 29, Section 1910. 134 Code of Federal Regulations). be adequate to limit the vapor concentration of hydrazine Wear chemical safety goggles, butyl rubber gloves, boots to values below the current Occupational Safety and Health and slicker suit. Administration (OSHA) Permissible Exposure Limit Remove all sources