Chemicals have the ability to react when exposed to other chemicals or certain physical conditions. The reactive properties of chemicals vary widely and they play a vital role in the production of many chemical, material, pharmaceutical, and food products we use daily. When chemical reactions are not properly managed, they can have harmful, or even catastrophic consequences, such as toxic fumes, fires, and explosions. These reactions may result in death and injury to people, damage to physical property, and severe effects on the environment. Process Safety Management is used to prevent and mitigate chemical reactivity hazards.

This page was developed as a product of OSHA's former Alliances with The Dow Chemical Company, the Chemical Reactivity Hazards Management Signatories and the Process Safety Signatories.

Chemical reactivity hazards are addressed in specific standards for the general and construction industries.

Standards

This section highlights OSHA standards, preambles to final rules (background to final rules), directives (instructions for compliance officers), and other federal standards related to chemical reactivity hazards.

Note: Twenty-five states, Puerto Rico and the Virgin Islands have OSHA-approved State Plans and have adopted their own standards and enforcement policies. For the most part, these States adopt standards that are identical to Federal OSHA. However, some States may have adopted different standards applicable to this topic or may have different enforcement policies.

OSHA

General Industry (29 CFR 1910)

• 1910 Subpart H, Hazardous materials [related topic page]
  • 1910.106, Flammable and combustible liquids
  • 1910.119, Process safety management of highly hazardous chemicals [related topic page]
    • Appendix A, List of highly hazardous chemicals, toxics and reactives (Mandatory)
    • Appendix B, Block flow diagram and simplified process flow diagram (Non-mandatory)
    • Appendix C, Compliance guidelines and recommendations for process safety management (Non-mandatory)
    • Appendix D, Sources of further information (Non-mandatory)
  • 1910 Subpart L, Fire protection [related topic page]
    • 1910.156, Fire brigades
  • 1910 Subpart Z, Toxic and hazardous substances [related topic page]
    • 1910.1200, Hazard communication [related topic page]
    • 1910.1450, Occupational exposure to hazardous chemicals in laboratories

Construction Industry (29 CFR 1926)

• 1926 Subpart D, Occupational health and environmental controls
  • 1926.59, Hazard communication
  • 1926.64, Process safety management of highly hazardous chemicals
    • Appendix A, List of highly hazardous chemicals, toxics and reactives (Mandatory)
    • Appendix B, Block flow diagram and simplified process flow diagram (Non-mandatory)
    • Appendix C, Compliance guidelines and recommendations for process safety management (Non-mandatory)
    • Appendix D, Sources of further information (Non-mandatory)

Preambles to Final Rules

• Process Safety Management (1992)
  
  
• Search all available preambles to final rules.

Directives

• Inspection Procedures for the Hazard Communication Standard. CPL 02-02-038 [CPL 2-2.38D], (1998, March 20). Establishes policies and provides clarifications to ensure uniform enforcement of the Hazard Communication Standard (HCS).
  
  
• Process Safety Management (PSM) of Highly Hazardous Chemicals – Compliance Guidelines and Enforcement Procedures. CPL 02-02-045 [CPL 2-2.45A CH-1], (1994, September 13). Contains page changes to Instruction CPL 2-2.45A, which established uniform policies, procedures, standard clarifications, and compliance guidance for enforcement of the standard for PSM of Highly Hazardous Chemicals, 29 CFR 1910.119, and amendments to the standard for Explosives and Blasting Agents, 29 CFR 1910.109. (Note: Some original CPL and audit guidelines are not included in this document).
  
  
• OSHA Response to Significant Events of Potentially Catastrophic Consequences. CPL 02-00-094 [CPL 2.94], (1991, July 22). It is OSHA policy to respond as quickly as possible to significant events which may affect the health or safety of employees including chemical incidents.
  
  
• Search all available directives.

Other Federal

Department of Transportation (DOT)

• 49 CFR 105-177, Subtitle B--Other Regulations Relating to Transportation

Environmental Protection Agency (EPA)

• 40 CFR 68, Protection of the Environment: Chemical Accident Prevention Provisions. Includes a list of regulated substances and thresholds, the petition process for adding or deleting substances to/from the list of regulated substances, the requirements for owners or operators of stationary sources concerning the prevention of accidental releases, and approved state accidental release prevention programs.

Hazard Recognition

Chemical reactivity hazards present serious, sometimes catastrophic danger to workers when the hazard is not thoroughly understood and controlled. Hazardous releases have resulted in fires, explosions, toxic, and/or high-energy events when chemical reactions have gone astray. Conducting safe chemical reactions is key to the chemical manufacturing industry and vitally important to employee health and safety. The following references aid in recognizing chemical reactivity hazards.

• Identifying Chemical Reactivity Hazards: Preliminary Screening Method [409 KB PDF, 5 pages]. Environmental Protection Agency (EPA) Alert. Identifies the Center for Chemical Process Safety (CCPS) preliminary screening method as a tool to help small and medium size facilities identify where chemical reactivity hazards are likely to occur and may be applicable to a wide range of activities including warehousing, repackaging, blending, mixing, and processing.
  
  
• Guidelines for Chemical Reactivity Evaluation and Application to Process Design. American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS), (1995). Provides principles and strategies for the evaluation of chemical reactions, and for using this information in process design and management.
  
  
• Guidelines for Safe Storage and Handling of Reactive Materials. American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS), (1995). Offers guidelines that can significantly reduce the risk or mitigate the severity of accidents associated with storing and handling reactive materials.
  
  
• PSM of Highly Hazardous Chemicals [63 KB PDF^*, 2 pages]. OSHA Fact Sheet, (2002). Discusses OSHA standard 29 CFR 1910.119 including its content, why it is necessary, and what industries are covered by the standard.
  
  
• Chemical Safety Program. Department of Energy (DOE), Office of Health, Safety, and Security, Chemical Safety Program, (2007). Provides a forum for the exchange of best practices, lessons learned, and guidance in the area of chemical management.
  
  
• Chemical Accidents from Electric Power Outages [165 KB PDF, 5 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Alert EPA 550-F-01-010, (2001, September). Discusses how power outages and restarts could potentially trigger a serious chemical accident.
  
  
• Safe Storage and Handling of Swimming Pool Chemicals [103 KB PDF, 7 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Alert EPA 550-F-01-003, (2001, March). Discusses how pool chemicals may become a hazard when they become wetted by a small quantity of water or when they are improperly mixed, such as with other chemicals or reactive materials.
  
  
• Process Safety Management. OSHA Publication 3132, (2000). Also available as a 199 KB PDF, 59 pages. Summarizes the OSHA final process safety management (PSM) standard which applies to manufacturing industries including those pertaining to chemicals, transportation equipment, and fabricated metal products.
  
  
• Use Multiple Data Sources for Safer Emergency Response [161 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Alert EPA-F-99-006, (1999, June). States that a critical consideration when choosing a response strategy is the safety of emergency responders. Adequate information about on-site chemicals can make a difference when choosing a safe response strategy.
  
  
• Urben, P.G., ed. Bretherick's Handbook of Reactive Chemical Hazards. 6th ed. St. Louis, MO: Elsevier Science and Technology Books, 2000. Includes every chemical for which documented information on reactive hazards has been identified. Covers more than 5,000 elements and compounds, along with secondary entries involving two or more compounds, and features extensive cross-referencing, which links similar compounds of incidents not obviously related.
  
  
• Dangerously Reactive Liquids and Solids and Their Hazards. Canadian Centre for Occupational Health and Safety (CCOHS). Answers questions about properties and hazards of dangerously reactive chemicals.
  
  
• Fire Hazard From Carbon Adsorption Deodorizing Systems [252 KB PDF, 3 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Alert EPA 550-F-97-002e, (1997, May). Discusses how activated carbon systems used to adsorb vapors for control of offensive odors may pose a fire hazard when used for certain types of substances, if proper procedures are not followed.
  
  
• Water-Reactive Chemicals, Hazardous Materials Not Covered Under 29 CFR 1910.119. OSHA Hazard Information Bulletin (HIB), (1996). Highlights a potentially serious hazard regarding materials not covered by the process safety management (PSM) standard, 29 CFR 1910.119.
  
  
• Safe Disposal of Vented Reacting Fluids [2 MB PDF, 142 pages]. Health & Safety Executive (HSE) Contract Research Report No. 100/1996, (1996). Discusses the subject of relief for runaway reactions.

Incident Investigation Reports

• Accident Investigation Search. OSHA. Enables the user to search the text of Accident Investigation Summaries (OSHA-170 form) for words that may be contained in the text of the abstract or accident description.
  
  
• U.S. Chemical Safety Board (CSB). An independent federal agency whose mission is to prevent industrial chemical accidents and save lives.
  • Completed Investigations. Lists completed hazard investigation reports.
    • Hazard Investigation: Improving Reactive Hazard Management [310 KB PDF, 150 pages]. Examines chemical process safety in the United States - specifically, hazardous chemical reactivity. Conducted data analysis evaluating the number, impact, profile, and causes of reactive incidents.
      
• How to Prevent Runaway Reactions - Case Study: Phenol-Formaldehyde Reaction Hazards [130 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Case Study EPA 550-F99-004, (1999, August). Aims to increase awareness of possible hazards connected with exothermic reactions.
  
  
• Prevention of Reactive Chemical Explosions - Case Study: Waste Fuel/Oxidizer Reaction Hazards [220 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Chemical Safety Case Study EPA-550-F00-001, (2000, April). Describes the hazards associated with blending waste fuels and reactive chemicals and to offer recommendations to reduce the potential for accidents.
  
  
• BPS, Inc.; West Helena, Arkansas [7 MB PDF, 83 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) EPA/OSHA Joint Chemical Accident Investigation Report EPA 550-R-99-003, (1999, April). Describes an accident investigation carried out by the EPA and OSHA. It describes the accident, determines the root causes and contributing factors, and identifies findings and recommendations.
  
  
• Napp Technologies, Inc.; Lodi, New Jersey [2 MB PDF, 84 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Expert Review of Joint EPA/OSHA Chemical Accident Investigation Report EPA-550-F99-004, (1999, March). Describes an accident investigation carried out by the EPA and OSHA. It describes the accident, determines the root causes and contributing factors, and identifies findings and recommendations.
  
  
• Terra Industries, Inc., Nitrogen Fertilizer Facility; Port Neal, Iowa [3 MB PDF, 114 pages]. Environmental Protection Agency (EPA) Chemical Accident Investigation Report. Contains conclusions reached by the EPA chemical accident investigation team regarding the cause of the explosion at the Terra Industries, Inc., Port Neal Complex that occurred on December 13, 1994, and recommendations for preventing future similar occurrences in ammonium nitrate facilities.

Hazard Evaluation

Determining the potential for interactions is not always easy. The key to evaluating chemical reactivity hazards is to first determine what chemicals exist in the workplace, and then determine which chemicals are reactive with other materials. The following references aid in evaluating reactive interactions and their potential hazards.

• Chemical Reactivity Worksheet. National Ocean Service, National Oceanic and Atmospheric Administration (NOAA), Office of Response and Restoration. It can be used to find out about the reactivity of substances or mixtures of substances.

References

• Process Safety Progress 21.4(2002, December).
  • Kao, C, et al. "An Index-Based Method for Assessing Exothermic Runaway Risk." Pages 294-304. Proposes a simplified mathematical and tabular method for assessing the risk of exothermic runaway reactions, based on the calculated hazard index.
    
• Lewis, Richard J., Sr. Sax's Dangerous Properties of Industrial Materials. 11th Edition, New York: John Wiley and Sons, 2005. Provides information on the hazards of substances used in industry. Includes toxicological, fire, reactivity, explosive potential, and regulatory information.
  
  
• Urben, P.G. Ed. Bretherick's Handbook of Reactive Chemical Hazards. 6th ed. St. Louis, MO: Elsevier Science and Technology Books, 2000. Includes every chemical for which documented information on reactive hazards has been identified. Covers more than 5,000 elements and compounds, along with secondary entries involving two or more compounds, and features extensive cross-referencing, which links similar compounds of incidents not obviously related.
  
  
• American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS) Guideline Series:
  • Guidelines for Chemical Reactivity Evaluation and Application to Process Design. New York: Wiley-AIChE, 2004. Provides principles and strategies for the evaluation of chemical reactions, and for using this information in process design and management.
  • Guidelines for Hazard Evaluation Procedures - With Worked Examples. 2nd ed. New York: Wiley-AIChE, 1992. Provides process engineers with up-to-date on the effective methodologies that process safety demands.
  • Guidelines for Safe Warehousing of Chemicals. New York: Wiley-AIChE, 1998. Presents performance-based approaches to such hazards as health effects, environmental pollution, fire, and explosion that provides practical means to minimize the risk of these hazards to employees, the surrounding population, the environment, property, and business operations.
  • Guidelines for Safe Storage and Handling of Reactive Materials. New York: Wiley-AIChE, 1995. Presents critical guidelines that can significantly reduce the risk or mitigate the severity of accidents associated with storing and handling reactive materials.

Control and Prevention

The following references provide information about the control and prevention of chemical reactivity hazards, including laboratory safeguards.

• Managing Chemical Reactivity Hazards [103 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention (CEPPO) Chemical Safety Alert, EPA 550-F-04-005, (2005, February). Introduces facilities to the methodology for chemical reactivity hazard management as developed by the Center for Chemical Process Safety (CCPS).
  
  
• New Measures Adopted to Prevent Chemical Accidents for Improved Community Safety. New Jersey Department of Environmental Protection (NJDEP) News Release, (2003, August 5). Announces the expansion of New Jersey's Toxic Catastrophe Prevention Act (TCPA) program to provide greater protection for residents living near industrial facilities.
  
  
• Prevention of Reactive Chemical Explosions Case Study: Waste Fuel/Oxidizer Reaction Hazards [220 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO) Case Study, EPA 550-F00-001, (2000, April). Involves waste fuel/oxidizer reaction hazards. Raises awareness about the hazards associated with blending waste fuels and reactive chemicals and to offer recommendations to reduce the potential for accidents.
  
  
• How to Prevent Runaway Reactions Case Study: Phenol-Formaldehyde Reaction Hazards [130 KB PDF, 6 pages]. Environmental Protection Agency (EPA), Chemical Emergency Preparedness and Prevention Office (CEPPO), EPA 550-F99-004, (1999, August). Includes phenol-formaldehyde reaction hazards. Increases awareness of possible hazards associated with exothermic reactions. Highlights the hazards associated with this and similar cases and provides recommendations to reduce those hazards.
  
  
• Guidelines for Process Safety in Batch Reaction Systems. American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS). New York: Wiley-AIChE; 1999. Identifies the singular concerns of batch reaction systems including potential sources of unsafe conditions. Provides a "how-to" guide for the practicing engineer in dealing with them by applying appropriate practices to prevent accidents.
  
  
• Guidelines for Safe Storage and Handling of Reactive Materials. American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS). New York: Wiley-AIChE; 1995. Offers guidelines that can significantly reduce the risk or mitigate the severity of accidents associated with storing and handling reactive materials.
  
  
• Remediation Technology Screening Matrix (RTSM) and Reference Guide, Version 4.0. US Department of Defense (DoD) and other Federal Agencies participating in the Federal Remediation Technologies Roundtable (FRTR), (2002, January).
  • Chemical Reduction/Oxidization. Describes the unique hazards associated with reduction/oxidization including physical, chemical, radiological, and biological hazards. Also offers effective control methods.
    
• For additional information, see OSHA's Safety and Health Topics Pages on:
  • Hazard Communication
  • Hazardous and Toxic Substances
  • Laboratories
  • Process Safety Management

Additional Information

Related Safety and Health Topics Pages

• Ammonia Refrigeration

Training

• OSHA Training Institute (OTI) Course Catalog Search. Provides a keyword search and catalog listing of available courses.
  
  
• Construction Industry Safety and Health Outreach Program. OSHA, (1996, May). Contains a process safety management section in Subpart D, Occupational Health and Environmental Controls.
  • Process Safety Management of Highly Hazardous Chemicals (1926.64). Summarizes the OSHA final PSM standard.
    
• Education and Training. American Institute of Chemical Engineers (AIChE). Lists several courses on plant design, operations, and process safety.
  
  
• Education. Mary Kay O'Connor Process Safety Center, (2003). Also available as a 521 KB PDF, 26 pages. Offers a variety of process safety courses, which are also offered on-site and can be tailored to specific needs. Courses include reactive hazards identification, experimental and theoretical assessment methods, and hazards management.

Other Resources

General

• Process Safety Incident Database (PSID). American Institute of Chemical Engineers (AIChE), Center for Chemical Process Safety (CCPS). Provides participants access to the database and giving each the benefit of the collected experiences. The CCPS facilitated the development of the PSID to collect and share incident information and experiences.
  
  
• Center for Chemical Process Safety (CCPS). American Institute of Chemical Engineers (AIChE). Brings together manufacturers, insurers, government, academia, and expert consultants to lead the way in improving manufacturing process safety. Conferences, courses, and publications on process safety are available.
  
  
• Explore Our Emergency Management Programs. Environmental Protection Agency (EPA). Provides national leadership, issuing regulations, developing technical guidance and assists Local Emergency Planning Committees (LEPC) and State Emergency Response Commission (SERC) Contacts to develop their own unique emergency planning systems.
  


• Committee E27 on Hazard Potential of Chemicals. American Society for Testing and Materials (ASTM). Develops test methods and standards related to the potential of chemicals to produce hazards such as ignition and energy release.
  
  
• Design Institute for Emergency Relief Systems (DIERS). American Institute of Chemical Engineers (AIChE). Works to reduce the frequency, severity and consequences of pressure producing accidents, and to develop new techniques which will improve the design of emergency relief systems. This user group consists of 160 companies.
  
  
• U.S. Chemical Safety Board (CSB). An independent federal agency established to promote the prevention of major chemical accidents at fixed facilities. It produces accident and hazard investigation reports, conducts research, and advises industry, labor, and government.
  
  
• Material Safety Data Sheet (MSDS) Form. OSHA, (1985, September). May be used to comply with OSHA's Hazard Communication Standard, 29 CFR 1910.1200.

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