Risk Minimization

Screen Your
Facilities for Chemical
Reactivity Hazards
Use this straightforward approach
to check which of your sites are
likely to have chemical reactivity
hazards that need to be managed.

Robert W. Johnson
Unwin Co.
Peter N. Lodal
Eastman Chemical Co.

T

HE U.S. CHEMICAL SAFETY AND
Hazard Investigation Board (CSB) recently released an investigation report on chemical reactivity hazards at U.S. facilities (1). The CSB analyzed 167
incidents that occurred between 1980 and 2001 involving
uncontrolled chemical reactions. These incidents resulted
in 108 fatalities, numerous injuries, and significant on-site
and off-site property damage; because the data are admittedly incomplete, the true impact of chemical reactivity
incidents is expected to be higher. In a vast majority of the
incidents studied, the information needed to properly assess the hazards was known prior to the event.
A chemical reactivity hazard is a situation with the
potential for an uncontrolled chemical reaction that can
result directly or indirectly in serious harm to people,
property or the environment (2). Reactivity is the tendency of substances to undergo chemical change (3); it
encompasses several more-specific types of hazards,
such as instability and water reactivity.
AIChE’s Center for Chemical Process Safety
(CCPS) recently formed a committee of reactive-chemistry experts that developed a simple screening tool to
help companies and facilities identify where chemical
reactivity hazards are likely to be found. This article
summarizes the essentials of that screening method.

Preliminary screening for reactivity hazards
The preliminary screening method is based on a series
of twelve questions that are intended to help you quickly
decide whether chemical reactivity hazards are likely to be

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August 2003

CEP

present at a given facility. If chemical reactivity hazards
are indicated, then management practices (as discussed at
the end of this article and in Ref. 2) are warranted.
A form such as Table 1 can be used to document answers to the screening questions and the conclusions
that are drawn. The flowchart in the figure shows how
these questions are related to one another.
Who should do the screening? The questions may
be examined either individually or by a group. A team
approach, involving several people with different knowledge and functional perspectives, is typically preferred.
Those involved need some knowledge of chemistry to
properly understand the questions and their application.
What kinds of facilities should be screened? The
preliminary screening method is intended to be applicaManaging Chemical Reactivity Hazards
and High Energy Release Events
The 18th Annual CCPS International Conference and
Workshop — this year with the theme “Managing
Chemical Reactivity Hazards and High Energy Release
Events” — will be held September 23–25, 2003, at the
Marriott Camelback Inn Resort in Scottsdale, AZ. The
meeting features sessions on: regulatory issues; management systems; calorimetry tools; inherent safety;
high energy release events; relief system design; transportation and storage; calorimetry/testing; and case
histories. For details on the program, exhibiting, or
sponsoring, or to register, visit www.aiche.org/ccps/icw
or call 1-800-AIChemE (1-800-242-4363).

Is any substance identified as spontaneously combustible? 8. Since energy is being put into the endothermic reaction system. by inadvertent mixing of materials or by common drainage) is unlikely.org 51 . assume incompatible until further information is obtained. Is any substance identified as self-reactive? 12. and unconfined? (IF NOT. † Does the contact/mixing occur at ambient temperature. If the answer is a definite no. skip to Question 5 to consider one special case of intentional chemistry — combustion systems. Is any substance identified as peroxide forming? 9. In addition. Is there any mixing or combining of different substances? 3. by distance or otherwise. atmospheric pressure. Is any substance identified as water reactive? 10. then proceed to Question 2. the endothermic reaction may be reversible under certain conditions and thus may result in a potentially dangerous exothermic reaction.ble to all types of industrial facilities. based on the analysis below? Scenario 1 2 3 Completion Date: Approved By: Yes No Basis for Answer. ? = Unknown. the final products will have a greater internal energy content than the starting materials.. CEP August 2003 www. it may be helpful to screen one smaller “facility” at a time. Are there any hazardous substances stored or handled? 5. Does any other physical processing of substances occur? 4. NR or ?‡ Information Sources.) ‡ R = Reactive (incompatible) under the stated scenario and conditions. such as mixing and dilution. Some general indications that intentional chemistry is being performed include: • the products have different chemical formulas. Some physical processes. NR = Non-reactive (compatible) under the stated scenario and conditions. Is any substance identified as an oxidizer? 11. Is any heat generated during the mixing or physical processing of substances? 7. If the answer to Question 1 is clearly yes. Comments * Use Figure 2 with answers to Questions 1–12 to determine if the answer is Yes or No.) Table 1. or heat must be added to the process. Question 1: Is intentional chemistry performed at the facility? Intentional chemistry means processing of substances in such a way that a chemical reaction is intended to take place. DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY. 12% oxygen atmosphere. Facility: Completed By: Do the answers to the following questions indicate that chemical reactivity hazard(s) are present?* At this facility: 1. “Facilities” should be separated enough. (If you are uncertain whethear chemical reactions are intended to take place. If a large industrial complex is being evaluated. from warehousing and repackaging to blending and processing. can generate or absorb heat. Can incompatible materials coming into contact cause undesired consequences. consult a chemist or other expert. Endothermic reactions may not have obvious chemical reactivity hazards. Is combustion with air the only chemistry intended? 6. Comments Yes Yes Yes Yes Yes Yes No No No No No No NA NA NA NA NA NA Yes Yes Yes Yes Yes Yes No No No No No No NA NA NA NA NA NA Conditions Normal?† R. Use a form such as this to document the screening of chemical reactivity hazards. so the products themselves may pose a chemical reactivity hazard.cepmagazine. structures or Chemical Abstract numbers than the starting materials • a gaseous product is given off or a solid residue is formed that is different from any of the constituents or solvents in a starting mixture • a catalyst or initiator is added to the starting mixture • heat is generated by the process. Note that heat effects do not necessarily indicate that a chemical reaction is taking place.g. but should nevertheless be expected to be associated with chemical reactivity hazards. The occurrence of an exothermic reaction in normal operations can be taken as an indicator that some intentional chemistry is taking place. Is intentional chemistry performed? 2. that reactive interactions between them (e.

Risk Minimization Question 1 Is intentional chemistry performed at your facility? START Yes 5 Is combustion with air the only chemistry intended at your facility? No See text information on each numbered question 2 No Is there any mixing or combining of different substances? No 4 Are there any hazardous substances stored or handled at your facility? Yes Yes 3 Does any other physical processing of substances occur at your facility? Yes 6 No 7 Is any heat generated during the mixing or physical processing of substances? Is any substance identified as spontaneously combustible? Yes No Yes Yes No No Is any substance identified as peroxide forming? 8 Yes Chemical reactivity hazards likely to be present that will need to be managed throughout the life of the facility. Question 2: Is there any mixing or combining of different substances? Mixing or combining of substances can range from a large-scale formulation process to an individual procedure for dissolving one substance in another.org August 2003 CEP a situation where mixing or combining of substances is not intended. cleaning solutions or agricultural products might be combined because one product does not appear to work or in an attempt to make a more potent agent. For example. You might encounter 52 www. Follow this flowchart to determine if chemical Can incompatible materials coming into contact cause undesired consequences? Yes reactivity hazards are likely to exist at a facility. or process steps that . perhaps as an unauthorized or unsupervised activity. but may occur from time to time. No 9 Is any substance identified as water reactive? END Chemical reactivity hazards not likely to be present Yes No 10 Is any substance identified as an oxidizer? Yes No 11 Is any substance identified as self-reactive? No Yes • Polymerizing • Decomposing • Rearranging 12 No ■ Figure.cepmagazine. drain cleaners.

distillation. An exception is intentional. The product of the operation may be one or more substances.S. etc. The answer to Question 4 will be yes for most manufacturing facilities and many industrial storage and warehousing facilities. but not chemically. If the answer to Question 2 is clearly yes. such as the conversion of ethylene to ethylene oxide. based on what substances are accessible to workers or what has happened in the past. If you have arrived at Question 4 via the flowchart and your answer to Question 4 is a definite no. MSDSs are required for each chemical posing either a health hazard or a physical hazard. It also pertains to facilities where such processing as heating. for example. be aware that storage. a compressed gas. Judgment may be required to assess what might reasonably be expected to occur some time during the life of the facility. Question 5: Is combustion with air the only intended chemistry? If intentional chemistry is performed. is intentionally performed but no chemical reaction is ever intended or expected to occur as part of the operation. chemical reactivity hazards can be expected to exist. or water-reactive. If the answer is a definite no. If you are uncertain whether physical processing does or will take place. flammable. crushing. pyrophoric. an organic peroxide or an oxidizer. different from the starting material. or would get warm or hot if cooling were lost. and discussing with management what future activities can be anticipated. a mixture gets warm or hot upon combining the ingredients. proceed to Question 4. In the U. If intentional chemistry is practiced at the facility and the answer to Question 5 is no. unstable (reactive). Heat can be gener- CEP August 2003 www. If your answer is a definite no. a system to manage chemical reactivity hazards is not likely to be warranted. or is explosive. or are there no rules or little oversight of the proper procedures? Adherence to rigorous management-ofchange procedures should help avoid these issues. for processes involving partial oxidation.org 53 . This may involve systematically reviewing the facility’s operations and procedures. proceed to Question 3. One factor to be considered when making this judgment is the operating discipline at the facility — are rules against unauthorized combining of materials and solutions always strictly enforced. then chemical reactivity hazards are almost certainly present and they will need to be managed throughout the life of the facility. The burning of ordinary flammable and combustible materials is not considered a chemical reactivity hazard. but the same chemical substances are present. you should conduct further analysis to determine a definite answer to this question before going any further. drying. essentially complete combustion with air. A physical hazard is defined by the OSHA Hazard Communication Standard (4) as an element. It should be noted that MSDSs are not required for all chemical intermediates and byproducts. If the answer to Question 3 is clearly yes. handling or processing at higher temperatures or pressures may initiate an uncontrolled reaction in a material or mixture that is apparently unreactive closer to ambient conditions. or if you are unsure of the answer to this question. Consequently. If the answer to Question 4 is clearly yes. blended or combined together. then you are not likely to have any chemical reactivity hazards at your facility. screening. Question 6: Is heat generated during mixing or physical processing of substances? An important question to consider is whether. chemical compound or mixture of el- ements and/or compounds for which there is scientifically valid evidence that it is a combustible liquid. solutions or mixtures that may have different physical characteristics (appearance. storage and repackaging of materials are not considered physical processing.were originally conducted separately might be combined for reasons of efficiency or productivity. as well as discussions with management about what future activities are anticipated. filtration. such as the burning of propane in a gas-fired heater. viscosity. skip to Question 6.cepmagazine. can pose significantly different hazards than the combustion systems described above. are needed. skip to Question 6. Note that processes involving partial oxidation. Consequently. proceed to Question 2. absorption. Transfer. The United Nations’ “Orange Book” (5) should be consulted for further information on the definition of dangerous goods for transportation purposes. etc. a systematic review of the plant’s operations and procedures. If you are uncertain whether mixing or combining of different substances takes place or will take place at the facility. phase. These materials should also be considered in addition to raw materials and products. go to Question 7 to begin a check for reactive materials and interactions. “Dangerous goods” are defined in the context of recommended international hazardous material transportation regulations. handling. If the answer to Question 5 is yes. Question 4: Are any hazardous substances stored or handled at the site? Hazardous materials and dangerous goods are those substances for which material safety data sheets (MSDSs) are required. Question 3: Does any other physical processing of substances occur? Physical processing is any modifying of substances such that the resulting product or products are physically. since combustion systems are relatively standardized and are already addressed by various codes and standards.. the answer to Question 5 should be no. Physical processing pertains to facilities where different substances are intentionally mixed. Also.) from the starting materials. talking with operations and maintenance personnel.

pyrophoric sulfide is formed when streams containing hydrogen sulfide or other volatile sulfur compounds are processed in ferrous equipment. Question 12 takes the user through a series of steps for addressing reactive interactions. If transported. If the answer to Question 6 is yes. If you are certain that no heat is generated. or chemical incompatibility. Lists of pyrophoric materials that include less common chemicals. A more definitive answer can be determined by conducting calorimetric tests that are representative of the full range of material compositions that will be encountered in the facility. Note that this is different from adding heat during a mixing or physical processing operation (such as by external steam heating). Ignition may be immediate. It also includes case histories. Other spontaneously combustible substances are tabulated by their proper shipping names and UN/NA numbers in the . it may be possible to find out by heat balances or careful temperature measurements. “Essential Practices for Managing Chemical Reactivity Hazards” This article summarizes part of a new book from AIChE’s Center for Chemical Process Safety. igniting and burning even without an ignition source.org/publications.) The potential of pyrophoric materials to exhibit this behavior is usually well known due to the extreme care required for their safe handling. (Some materials that are considered pyrophoric require a minimum relative humidity in the atmosphere for spontaneous ignition to occur. mechanical energy or other physical heat effects. as well as facilities that produce and use hazardous materials.Risk Minimization ated by heat of solution. Questions 7–10 address substances that are reactive with air.cepmagazine. and steps should be taken to identify and manage the hazards. which is addressed by Question 3. Many scenarios involving spontaneous combustion involve a combination of materials exposed to sufficient air. the NFPA diamond (6) for container or vessel labeling has a red (top) quadrant with a rating of 4. Reactive materials and reactive interactions Questions 7–12 pertain to all facilities that store. If you are uncertain as to whether heat is generated. heat of adsorption. Question 11 addresses self-reactive materials. which results in a self-heating situation. and document the answers to each question on the Table 1 form.aiche. or may result from a self-heating process that may take minutes or hours (thus. including metals. It should be noted that pyrophoric materials often exhibit one or more other reactivity hazards as well. proceed to Question 7. such as water reactivity. This book. as well as essential management practices for facilities where chemical reactivity hazards are likely to exist. 54 www. However.” The book includes many examples that accompany the preliminary screening method. can be found in Volume 2 of “Bretherick’s Handbook of Reactive Chemical Hazards” (7). handle or repackage any hazardous materials. and numerous others on safety and risk management. recognize that a change in physical condition may result in a change in reactivity. “Essential Practices for Managing Chemical Reactivity Hazards. Pyrophoric and other spontaneously combustible substances will generally be identified as such on their product literature. A scenario that has resulted in many fires and explosions in petroleum refineries involves iron sulfide. Opening sulfide-containing equipment without adequate purging can result in rapid self-heating and ignition of the iron sulfide. which can then ignite other residual flammable gases or liquids in the equipment. or be explosive. indicating the highest severity of flammability hazard. The heat for getting to the secondary unintended reactions might be added by non-chemical means. a full glossary. For pyrophoric substances. some spontaneously combustible substances are known as self-heating). Such combination scenarios should be examined further and documented in Question 12.org August 2003 CEP You may find it desirable to answer all of these questions for each facility being screened. evolve toxic or flammable gases. The questions also pertain to operations involving mixing or physical processing that do not generate heat. often in an insulating situation that prevents heat from a slow oxidation reaction from dissipating. MSDSs or International Chemical Safety Cards (ICSCs). An impure.2 materials for shipping purposes and labeled as spontaneously combustible. Consequently. Oxidation of moist iron sulfide is highly exothermic. and a CD-ROM with example company programs and other valuable resources. are available from AIChE at 1-800AIChemE (1-800-242-4363) or www. Pyrophoric materials ignite spontaneously on short exposure to air under ordinary ambient conditions. these substances should be identified as DOT/UN Hazard Class 4. then there is a significant likelihood that one or more chemical reactivity hazards are present. Abnormal situations can occur in which too much heat is generated (or too little cooling occurs) and a substance or mixture gets hotter than intended. an unintended chemical reaction may be initiated at the higher temperature that may generate even more heat. so that materials or mixtures that were not apparently reactive at one temperature can become dangerously reactive at another temperature. Examples include the exposure of activated carbon to a high concentration of organic vapors and the contamination of cotton or cellulose materials with oil. water or ordinary combustibles — materials that are almost certain to be in close proximity to the reactive substances. Question 7: Is any substance identified as spontaneously combustible? This question pertains to substances that will readily react with the oxygen in the atmosphere.

If you are certain that no peroxide-forming substances are present. the reaction of an organic material with water may be delayed because the reaction only occurs at the interface.U. when a peroxide-forming liquid is stored with limited access to air.101. They may be identified as DOT/UN Hazard Class 4. However. When the NFPA diamond has a white (bottom) quadrant containing OX. However. Oxidizers will nearly always be identified as such on their MSDSs or ICSCs. Water reactivity can be hazardous by one or more of several mechanisms. Dept. Examples of peroxide-formers include 1. is DOT/UN Hazard Class 8 (corrosive material) for shipping purposes. Organic peroxides.2 (nonflammable non-toxic compressed gases) but should be labeled as nonflammable gas and oxidizer. some oxidizers are classified otherwise. as long as a spontaneously combustible material is stored or handled. then a chemical reactivity hazard is present that will need to be managed throughout the life of the facility. even if the W is not present. Ref. Question 10: Is any substance identified as an oxidizer? This question pertains to any material that readily yields oxygen or other oxidizing gas.cepmagazine. When the NFPA diamond used for container or vessel labeling has a white (bottom) quadrant that contains a W with a line through it. and alkali metals. Substances that are peroxide-formers will often have an inhibitor or stabilizer added to prevent peroxidation. using a two-drop mixing calorimeter (8). They are often not easily identifiable as peroxide formers using MSDSs or ICSCs. of Transportation regulation 49 CFR 172. If you are certain that no pyrophoric or other spontaneously combustible materials are present. proceed to Question 9. is DOT/UN Class 2. immediate water-reactivity hazards. this can be considered a physical effect rather than a chemical reaction. Liquid oxygen is Class 2. as long as a peroxide-former is stored or handled. consult a chemist or other expert. the material may still be water-reactive but at a slower rate. However. If the answer to Question 9 is yes. Some concentrated acids and bases can generate considerable heat of solution or heat of dilution when mixed with water. it may also be identified as a combustible liquid. proceed to Question 8. particularly at normal ambient conditions. In either case. They can also react with many other substances. Substances that are water-reactive will nearly always be identified as such on their MSDSs or ICSCs.3 materials for shipping purposes and labeled as dangerous when wet. it may also be labeled as a corrosive material. for example. general use or structural materials. Flammable.1-dichloroethylene. Acetic anhydride is likewise designated Class 8. the material will react violently or explosively with water and a chemical reactivity hazard obviously exists. If the answer to Question 8 is yes. for example. they are frequently identified by another characteristic. The potential hazards of most water-reactive materials are generally well known because of the precautions required for their safe handling. Peroxide formation. for storage and shipping purposes. Chlorine. Question 9: Is any substance identified as water-reactive? This question pertains to substances that will chemically react with water. the material possesses oxidizing properties.org 55 . so are addressed with Question 11 rather than here. Even slow reactions can generate sufficient heat and off-gases to overpressurize and rupture a closed container. then a chemical reactivity hazard is present that will need to be managed throughout the life of the facility. which in turn might explosively decompose if concentrated. usually happens slowly over time. Thus. and its shipping label is likely to reflect both corrosive and poison hazards.3 (gases toxic by inhalation) and labeled as poison gas for shipping purposes. are considered self-reactive. which are commonly used as process. ignite combustible materials. some water-reactive materials are classified other- wise.S. or initiate other chemical reactions. most oxidizers can be thought of as being reactive with ordinary combustible liquids or solids. or that readily reacts to promote or initiate combustion of combustible materials (9). However. If you are certain that no water-reactive substances are present. CEP August 2003 www. packaging. go to Question 10. For example.1 materials for shipping purposes and labeled as oxidizers. Titanium tetrachloride. as long as a water-reactive material is stored or handled. Question 8: Is any substance identified as peroxide-forming? This question pertains to substances that will react with the oxygen in the atmosphere to form unstable peroxides. included in the same general DOT/UN Hazard Class (Class 5) as oxidizers. a chemist or other expert should be consulted or a simple test can be performed. isopropyl ether. The violence of some reactions may disperse hazardous materials. The heat of reaction can cause thermal burns. If you are uncertain. It may be either an oxidizer or an organic peroxide. For fire protection purposes. If the answer to Question 7 is yes. If you are uncertain as to whether a material is water-reactive. corrosive or toxic gases are often formed as reaction products. 2 includes a tabulation of some chemical structures susceptible to peroxide formation. Rather. such as flammability. They may be identified as DOT/UN Hazard Class 5.3-butadiene. or peroxidation. it should be considered to pose a chemical reactivity hazard. since the purpose of the NFPA symbol is to alert emergency responders to significant. 1. a material is considered water-reactive if a gas or at least 30 cal/g of heat is generated when it is mixed with water (6). then a chemical reactivity hazard is present that will need to be managed throughout the life of the facility.

Question 12: Can incompatible materials coming into contact cause undesired consequences? Up to this point. This contact will increase the burning rate of the combustible materials. vigorously or explosively. Many self-reactive materials are classified in other categories. For some highly reactive materials. However. 56 www. most self-polymerizing materials are labeled as flammable gases or flammable liquids. If this released energy is not dissipated as fast as it is generated (such as by cooling). including combustible materials. handling.2 (organic peroxides) are likely to be self-reactive. it can also apply to facilities involving storage. so that energy is released when a self-reaction occurs. a chemical reactivity hazard is present that will need to be managed throughout the life of the facility. decomposing or unstable on their MSDSs or ICSCs. when contaminated or exposed to heat or shock. Two criteria that are considered to reflect an NFPA instability rating of zero and the absence of a self-reactivity hazard are an instantaneous power density value below 0. If you are uncertain. By the definitions in NFPA 704 (6). the energy input is in the form of thermal energy (heat). NFPA 49 and NFPA 325 give instability ratings for many different industrial chemicals (11).e. Annex E to NFPA 704 (6) gives a method for calculating an “instantaneous power density. the critical temperature at which the thermal energy is sufficient to start an uncontrolled reaction in a particular storage configuration for a specified time is known as the self-accelerating decomposition temperature (SADT). a chemist or other expert should be consulted. friction or a spark may be sufficient to start a sustained decomposition reaction. the chemical reactivity hazards of individual substances. The common thread among self-reactive materials is that they have more internal energy than their polymerization. repackaging or physical processing where incompatible materials are present and have the potential for contacting each other. is the most significant thing that can go wrong when handling oxidizing substances. as described in NFPA 49 (12). often with accelerating or explosive rapidity.” defined as the product of the enthalpy (heat) of the self-reaction and the initial rate of reaction. a chemical reactivity hazard is present that will need to be managed throughout the life of the facility. it may also cause a fire to ignite without any additional ignition source. Having a non-zero NFPA instability rating is a straightforward means of identifying self-reactive materials. Some oxidizers can also undergo self-sustained decomposition. such as shock-sensitive explosives and organic peroxides. proceed to Question 12. due to their flammability in addition to being reactive. If the answer to Question 10 is yes. determined at 250°C (482°F). mechanical shock. proceed to Question 11. If the answer to Question 11 is yes. decomposition or rearrangement products. or the potential exists for the wrong material to be unloaded into a storage tank or otherwise introduced into a process. some organic peroxide formulations — Class V formulations according to NFPA 432 (10) — burn with even less intensity than ordinary combustibles and present no chemical reactivity hazard. A scenario. where materials are being intentionally combined. The NFPA diamond for self-reactive materials has a yellow (right) quadrant with a rating between 1 (lowest) and 4 (highest). However. NFPA 432 (10) can be consulted for typical organic peroxide formulations. either by themselves or in contact with ubiquitous materials.org August 2003 CEP Some energy (i. this indicates that the material poses an instability hazard. However. is a detailed physical description of the process whereby a potential inadvertent combination of materials may occur (13).. consult a chemist or other expert. the activation energy) is required to start the self-reaction. have been considered.Risk Minimization Inadvertent contact of oxidizers with reducing agents. as long as an oxidizer is stored or handled. Question 11: Is any substance identified as self-reactive? This question pertains to substances that will energetically self-react. Step 1: Decide on undesired consequences of concern. Volume 2 of “Bretherick’s Handbook of Reactive Chemical Hazards” (7) lists many structures and individual chemical compounds having oxidizing properties. for example. If you are certain that no oxidizers are present. this energy can go into preheating the unreacted material and can cause the reaction rate to accelerate out of control. For storage applications. If you are uncertain as to whether a material is self-reactive. in this context. as long as a self-reactive material is stored or handled. Question 12 is especially pertinent to mixing and formulation facilities. The determination of whether materials are incompatible depends on what you consider “undesired consequences” in the context of your facility’s operation. This last question addresses the potential for an unintended chemical reaction due to incompatible materials contacting each other. If you are certain that no self-reactive substances are present. Substances that are DOT/UN Class 1 (explosives) and Class 5. Self-reactive materials are generally identified as polymerizing. A suggested starting point is to consider the undesired consequences as uncontrolled chemical reactions that can result in: the gen- .01 W/mL and no exotherm being exhibited by the material at temperatures at or below 500°C (932°F) when tested by differential scanning calorimetry (11). for most self-reactive materials. These substances have various chemical structures that make them susceptible to at least one of three forms of self-reaction: • polymerization • decomposition • rearrangement Some substances such as ethylene oxide can self-react in more than one way. Compatibility means the ability of materials to exist in contact without specified (usually hazardous) consequences under a defined scenario.cepmagazine.

with intention of immediate use 2 Inadvertently pump up to 1.S. temperature-controlled storage tank of between 700 and 2. an explosion. mixtures and solutions in its database. non-inerted and non-enriched atmosphere with 21% oxygen. the formation of shock-sensitive or explosive material.800 kg of acrylic acid with 200 ppm MEHQ inhibitor maintained 20°C Conditions Normal? Yes R. NR or ? R No ? eration of toxic gas. and no enclosure or confinement). For example. Small-scale laboratory tests can indicate whether a reaction is expected. a scenario may be judged not expected to occur any time during the life of the facility. Information Sources. which should consider at least the following (13): • materials that could be combined. generates heat and toxic vapors. atmospheric pressure. based on chemicals with similar structures that are expected to have similar reactivity characteristics. CEP August 2003 www. Assume published compatibility data will be valid only if ambient. the next best option is to check chemical-specific safety data.Table 2.400 kg of 38°C cyclohexane at 0. Lacking test results. Note that measures can be taken to essentially eliminate the potential for inadvertent mixing. Similar information should be in the chemical dangers section of ICSCs. “heat generation by chemical reaction. including their compositions or concentrations • specific quantities of materials • storage temperatures • confinement (closed or open system) • atmosphere (air. Step 3: Document mixing scenario consequences. References such as “Bretherick’s Handbook of Reactive Chemical Hazards” (7) and NFPA 491. nitrogen-inerted. and for how long. unconfined conditions apply (ambient temperature. the ignition of combustible material. the generation of sufficient off-gas to rupture a container or enclosure. Document any comments and the source of your information in the last column.3 kg/s into closed. This could be noted in the Comments column along with information supporting this judgment. sufficient heating of substances to initiate decomposition or a runaway reaction. may cause pressurization”). Section 10 (dealing with stability and reactivity) of standard MSDSs should contain information on incompatibilities with other materials. but may be hot enough to increase dimer formation and possibly initiate at initiate polymerization The best data to use for determining whether an incompatibility exists will obviously be from testing the actual scenarios and conditions that are identified. If any incompatibilities are found (R or ? in the third column of Table 2). can form explosive nitrogen trichloride under certain conditions Compatibility information only known for ambient conditions. The next step is to identify specific scenarios by which materials could be combined.000 chemicals. “Hazardous Chemical Reactions” (11) summarize published literature on incompatibilities. it might be possible to predict the consequences by methods using compatibility groups. these are rarely more than lists of incompatible materials. In the second column. It also predicts chemical reaction consequences of combining two materials at a time (e. describe what specific materials and quantities could be combined.. Step 2: Identify mixing scenarios. This program includes over 6. For facilities where many different materials are stored. and a crossconnecting line is left open. no reaction with cyclohexane expected. More detailed information may be given on what to expect when materials are combined. In the first column. Example of inadvertent mixing scenarios and compatibility findings. then you may be able to significantly reduce the number of potential scenarios that need to be evaluated. no effects will be realized in an industrial facility. and you may decide to focus your management of chemical reactivity hazards on hazards that are more likely to result in losses. be wary of concluding that since no reaction is seen on a small scale. unconfined conditions apply. If so. many different scenarios may be possible for the unintentional mixing or combining of different substances. some judgment may be needed as to the likelihood of each scenario occurring. oxygen-enriched) • maximum time the materials may be in contact. Depending on the nature of the facility. A table such as the bottom part of Table 1 can be set up to identify and document the identified scenarios and whether an incompatibility hazard exists for each scenario.org 57 . Chemical compatibility depends heavily on the mixing scenario. However. However. and do not indicate expected consequences. Scenario 1 Mix 1 L of household ammonia cleaner into 4 L of household chlorine bleach in an open bucket. waste materials are combined in the plant sewer system. such as MSDSs or ICSCs for the particular compounds and concentrations involved. unless the data indicate otherwise. corrosive gas or liquid. In the third column. Comments Based on sodium hypochlorite solution MSDS. If chemical-specific information is not available. indicate whether for this scenario under these conditions a chemical reaction will occur that has the potential for any of your predetermined undesired consequences. the answer to Question 12 is yes.cepmagazine. how they could be combined. or flammable gas. The listed incompatibilities should be considered as only applying to ambient conditions unless otherwise stated. mixing and other scale-up effects can cause a significant and potentially disastrous divergence between actual effects and those estimated from small-scale tests. It is especially important to consider heat-transfer effects and scale-up issues when extrapolating small-scale results — differences in heat transfer. but this is often not practical or possible. This evaluation is illustrated in the examples shown in Table 2. A few example causes (starting points) for these scenarios include: a leaking liquid contacts an adjacent material or container. such as by storage segregation and elimination of cross-connections. or the reduction of thermal stability of a material to the point of initiating decomposition. indicate whether ambient. National Oceanic and Atmospheric Administration (3). One computerized tool that uses this approach is the Chemical Reactivity Worksheet made available by the U.g. However.

restoration. Hofelich.org August 2003 CEP here.1200 Paragraph (c). stop Literature Cited 1. Ed. NOAA.com.” 13th ed. National Fire Protection Association..” version 1. He is the author or co-author of more than 20 papers. He holds BS and MS degrees in chemical engineering from Purdue Univ. MA (2000). and documenting.cepmagazine.. 58 www. UK (1999). 1994). 10. National Fire Protection Association. C. 2.org/education or call (800) 242-4363. training. “Recommendations on the Safe Transport of Dangerous Goods” (“Orange Book”). et al. Washington.. and managing change.. Urben. auditing.. OH 43212. MA (2002). “Fire Protection Guide to Hazardous Materials. some companies use a matrix approach to investigate all material combinations — including contaminants. Quincy. Related Course Offered by AIChE Course #583: Identifying and Managing Chemical Reactiviy Hazards Member fee: $995. U. If you are certain that no incompatible materials have a reasonable likelihood of contacting each other and causing undesired consequences during the facility’s lifetime. For larger or more complex facilities.S. 13.S. NTIS No. (BOB) JOHNSON is a process safety and risk management consultant with Unwin Co. 6. “Hazard Communication Standard. “Determination of Compatibility via Thermal Analysis and Mathematical Modeling.Risk Minimization processed or mixed. He is the chair of the Center for Chemical Process Safety’ Reactive Chemicals Subcommittee. T. These practices begin with establishing an effective management system. Geneva.” Report No. 9. Definitions. U. (2001). Phone: (614) 486-2245.155 Houston. 227–233 (Oct. DC (Dec. “Bretherick’s Handbook of Reactive Chemical Hazards. TN (Phone: (423) 229-2675.S. R. 2002). Switzerland (2002).S. E-mail: pnlodal@eastman. materials of construction. “Standard System for the Identification of the Hazards of Materials for Emergency Response.” AIChE Center for Chemical Process Safety.” ASTM E 2012-00. G... et al. then chemical reactivity hazards are present. 4. 2 vols. 8. the preliminary screening method indicates that no significant chemical reactivity hazards are expected at your facility. He was the primary author of the AIChE Center for Chemical Process Safety books “Guidelines for Safe Storage and Handling of Reactive Materials” and “Essential Practices for Managing Chemical Reactivity Hazards. U. He holds BS and MS degrees in chemical engineering from Purdue Univ. Non-member fee: $1. Seattle.5. “Chemical Reactivity Worksheet. The screening method can be revisited for each new chemical discovered or being considered to see whether chemical reactivity hazards are likely to be introduced that must be managed and controlled on an ongoing basis. What’s next? If the preliminary screening indicates that chemical reactivity hazards exist. PA (2000).com). then a management system is needed to ensure the hazards are fully understood and reliably controlled. visit www. 2003 For more information or to register. followed by collecting data. Dept. New York.. Office of Investigations and Safety Programs. NY (2003).. Management controls need to be in place to prevent unauthorized materials from being brought into a facility. . WA (2002). National Oceanic and Atmospheric Administration. 1994). such as a hazard and operability (HAZOP) study. Quincy. Chemical Safety and Hazard Investigation Board.html. U. A process hazard analysis (PHA) approach. 2001-01-H.” 29 CFR 1910. and is active as a director of his local AIChE section (East Tennessee). also available on CD-ROM as “Bretherick’s Reactive Chemical Hazards Database – Version 3. MA.” and he teaches the AIChE Continuing Education courses on process hazard analysis and chemical reactivity hazards. He has been with Eastman in various process design and safety positions for more than 25 years. ASTM International. 5. National Fire Protection Association. available at http://response. “Hazardous Chemicals Data. and also chairs the Process Safety Subteam for the American Chemistry Council (ACC). U.aiche. assessing and controlling risks. If the decision flow of the figure has been followed. P. MA (1997). investigating. Washington. Improving Reactive Hazard Management. 13 (4). a systematic approach to identifying incompatibility scenarios and analyzing their severities and likelihoods may be warranted. The answers to the screening questions in this article should not be thought of as unchangeable. 12. National Fire Protection Association. National Fire Protection Association. PB2002-108705. Fax: (423) 2293949. National Fire Protection Association. 3. Quincy. National Fire Protection Association. Office of Response and Restoration.” Process Safety Progress. pp. Quincy. “Essential Practices for Managing Chemical Reactivity Hazards.” NFPA 430. ROBERT W. communicating. Butterworth-Heinemann. Quincy. “Standard Guide for the Preparation of a Binary Chemical Compatibility Chart. (Columbus.S. “Hazard Investigation.” 6th ed. CSB. MA (2001). PETER N. National Fire Protection Association. Occupational Safety and Health Administration. The CEP result will be an inherently safer facility. West Conshohocken.noaa. utilities and common substances such as air and water. He is a director of the AIChE Safety and Health Division and chair of the 2004 Loss Prevention Symposium. DC (Feb. 11.” NFPA 704. E-mail: rjohnson@unwin-co.” NFPA 49. TX October 30–31.chemweb. LODAL is a senior technical associate and group leader of the Plant Protection Technical Services group at Eastman Chemical’s Tennessee Operations site in Kingsport. such as discontinuing the storage and handling of a water-reactive material or eliminating the potential for a reactive interaction. W. “Code for the Storage of Liquid and Solid Oxidizers. testing for reactivity where warranted. can be an effective tool to facilitate such an effort.” NFPA 432. National Fire Protection Association. If the answer to Question 12 is yes. United Nations. He has helped clients with their technical safety and risk analysis efforts for over 25 years. “Code for the Storage of Organic Peroxide Formulations. ASTM International. catalysts. National Fire Protection Association. of Labor. Johnson.S. additives. Onsite courses are also available.com). Oxford.0” and online by subscription at www. U. Special care needs to be taken whenever introducing new chemicals or processes to a facility or when changing process conditions. Occupational Safety and Health Administration.gov/chemaids/react. Reference 2 outlines essential practices for identifying and managing chemical reactivity hazards. Changes can also be documented that eliminate chemical reactivity hazards from your facility. United Nations. 7. 9.