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.

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.
AIChEs 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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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 2325, 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).

ble to all types of industrial facilities, from warehousing and

repackaging to blending and processing. If a large industrial
complex is being evaluated, it may be helpful to screen one
smaller facility at a time. Facilities should be separated
enough, by distance or otherwise, that reactive interactions
between them (e.g., by inadvertent mixing of materials or by
common drainage) is unlikely.

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. Some general indications that intentional chemistry
is being performed include:
the products have different chemical formulas, 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, or heat must be added
to the process.

Note that heat effects do not necessarily indicate that a

chemical reaction is taking place. Some physical processes,
such as mixing and dilution, can generate or absorb heat.
The occurrence of an exothermic reaction in normal operations can be taken as an indicator that some intentional
chemistry is taking place.
Endothermic reactions may not have obvious chemical
reactivity hazards, but should nevertheless be expected to
be associated with chemical reactivity hazards. Since energy is being put into the endothermic reaction system, the
final products will have a greater internal energy content
than the starting materials, so the products themselves may
pose a chemical reactivity hazard. In addition, the endothermic reaction may be reversible under certain conditions and thus may result in a potentially dangerous
exothermic reaction.
If the answer to Question 1 is clearly yes, skip to Question 5 to consider one special case of intentional chemistry
combustion systems. If the answer is a definite no, then
proceed to Question 2. (If you are uncertain whethear
chemical reactions are intended to take place, consult a
chemist or other expert.)

Table 1. Use a form such as this to document the screening of chemical reactivity hazards.
Facility:
Completed By:
Do the answers to the following questions indicate that
chemical reactivity hazard(s) are present?*
At this facility:
1. Is intentional chemistry performed?
2. Is there any mixing or combining of different substances?
3. Does any other physical processing of substances occur?
4. Are there any hazardous substances stored or handled?
5. Is combustion with air the only chemistry intended?
6. Is any heat generated during the mixing or physical
processing of substances?
7. Is any substance identified as spontaneously combustible?
8. Is any substance identified as peroxide forming?
9. Is any substance identified as water reactive?
10. Is any substance identified as an oxidizer?
11. Is any substance identified as self-reactive?
12. Can incompatible materials coming into contact cause
undesired consequences, based on the analysis below?
Scenario
1
2
3

Completion Date:
Approved By:
Yes No
Basis for Answer, 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, NR or ?

Information Sources, Comments

* Use Figure 2 with answers to Questions 112 to determine if the answer is Yes or No.
Does the contact/mixing occur at ambient temperature, atmospheric pressure, 12% oxygen atmosphere, and unconfined?
(IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY.)
R = Reactive (incompatible) under the stated scenario and conditions; NR = Non-reactive (compatible) under the stated scenario and conditions;
? = Unknown, assume incompatible until further information is obtained.

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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

No

Is
there any mixing
or combining of different
substances?

No

Are
there any
hazardous substances
stored or handled at
your facility?

Yes

Yes

Does
any other physical
processing of substances
occur at your
facility?

Yes

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.

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. 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.

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. You might encounter

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a situation where mixing or combining of substances is not

intended, but may occur from time to time, perhaps as an
unauthorized or unsupervised activity. For example, drain
cleaners, 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, or process steps that

were originally conducted separately might be combined for

reasons of efficiency or productivity. Judgment may be required to assess what might reasonably be expected to occur
some time during the life of the facility, based on what substances are accessible to workers or what has happened in the
past. 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, or are there no rules or little oversight of the
proper procedures? Adherence to rigorous management-ofchange procedures should help avoid these issues.
If the answer to Question 2 is clearly yes, skip to Question
6. If your answer is a definite no, proceed to Question 3. If you
are uncertain whether mixing or combining of different substances takes place or will take place at the facility, you should
conduct further analysis to determine a definite answer to this
question before going any further. This may involve systematically reviewing the facilitys operations and procedures, talking with operations and maintenance personnel, and discussing
with management what future activities can be anticipated.

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, but not
chemically, different from the starting material. Physical
processing pertains to facilities where different substances
are intentionally mixed, blended or combined together. It
also pertains to facilities where such processing as heating,
filtration, absorption, crushing, screening, drying, distillation, etc. is intentionally performed but no chemical reaction is ever intended or expected to occur as part of the operation. The product of the operation may be one or more
substances, solutions or mixtures that may have different
physical characteristics (appearance, phase, viscosity, etc.)
from the starting materials, but the same chemical substances are present. Transfer, handling, storage and repackaging of materials are not considered physical processing.
If the answer to Question 3 is clearly yes, skip to Question 6. If the answer is a definite no, proceed to Question 4.
If you are uncertain whether physical processing does or
will take place, a systematic review of the plants operations
and procedures, as well as discussions with management
about what future activities are anticipated, are needed.
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. In the U.S., MSDSs are required for each chemical
posing either a health hazard or a physical hazard. A physical
hazard is defined by the OSHA Hazard Communication Standard (4) as an element, chemical compound or mixture of el-

ements and/or compounds for which there is scientifically

valid evidence that it is a combustible liquid, a compressed
gas, an organic peroxide or an oxidizer, or is explosive,
flammable, pyrophoric, unstable (reactive), or water-reactive.
It should be noted that MSDSs are not required for all
chemical intermediates and byproducts. These materials
should also be considered in addition to raw materials and
products. Also, be aware that storage, 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.
Dangerous goods are defined in the context of recommended international hazardous material transportation
regulations. The United Nations Orange Book (5)
should be consulted for further information on the definition of dangerous goods for transportation purposes.
If the answer to Question 4 is clearly yes, or if you are unsure of the answer to this question, go to Question 7 to begin
a check for reactive materials and interactions. The answer to
Question 4 will be yes for most manufacturing facilities and
many industrial storage and warehousing facilities.
If you have arrived at Question 4 via the flowchart and
your answer to Question 4 is a definite no, then you are not
likely to have any chemical reactivity hazards at your facility. Consequently, a system to manage chemical reactivity
hazards is not likely to be warranted.

Question 5:
Is combustion with air
the only intended chemistry?
If intentional chemistry is performed, chemical reactivity hazards can be expected to exist. An exception is intentional, essentially complete combustion with air, such as
the burning of propane in a gas-fired heater. The burning of
ordinary flammable and combustible materials is not considered a chemical reactivity hazard, since combustion systems are relatively standardized and are already addressed
by various codes and standards.
Note that processes involving partial oxidation, such as
the conversion of ethylene to ethylene oxide, can pose significantly different hazards than the combustion systems
described above. Consequently, for processes involving
partial oxidation, the answer to Question 5 should be no.
If the answer to Question 5 is yes, proceed to Question
2. If intentional chemistry is practiced at the facility and
the answer to Question 5 is no, then chemical reactivity
hazards are almost certainly present and they will need to
be managed throughout the life of the facility.
Question 6:
Is heat generated during mixing
or physical processing of substances?
An important question to consider is whether, for example,
a mixture gets warm or hot upon combining the ingredients, or
would get warm or hot if cooling were lost. Heat can be gener-

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Risk Minimization

ated by heat of solution, heat of adsorption, mechanical energy

or other physical heat effects. Note that this is different from
adding heat during a mixing or physical processing operation
(such as by external steam heating), which is addressed by
Question 3. However, recognize that a change in physical condition may result in a change in reactivity, so that materials or
mixtures that were not apparently reactive at one temperature
can become dangerously reactive at another temperature.
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. Consequently, an unintended
chemical reaction may be initiated at the higher temperature
that may generate even more heat, evolve toxic or flammable
gases, or be explosive. The heat for getting to the secondary
unintended reactions might be added by non-chemical means.
If the answer to Question 6 is yes, then there is a significant likelihood that one or more chemical reactivity hazards
are present, and steps should be taken to identify and manage the hazards. If you are certain that no heat is generated,
proceed to Question 7. If you are uncertain as to whether
heat is generated, it may be possible to find out by heat balances or careful temperature measurements. 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.

Reactive materials and reactive interactions

Questions 712 pertain to all facilities that store, handle
or repackage any hazardous materials, as well as facilities
that produce and use hazardous materials. The questions
also pertain to operations involving mixing or physical
processing that do not generate heat. Questions 710 address substances that are reactive with air, water or ordinary combustibles materials that are almost certain to be
in close proximity to the reactive substances. Question 11
addresses self-reactive materials. Question 12 takes the
user through a series of steps for addressing reactive interactions, or chemical incompatibility.
Essential Practices for Managing
Chemical Reactivity Hazards
This article summarizes part of a new book
from AIChEs Center for Chemical Process
Safety, Essential Practices for Managing
Chemical Reactivity Hazards. The book includes many examples that accompany the
preliminary screening method, as well as
essential management practices for facilities where chemical reactivity hazards are
likely to exist. It also includes case histories, a full glossary,
and a CD-ROM with example company programs and other
valuable resources. This book, and numerous others on safety and risk management, are available from AIChE at 1-800AIChemE (1-800-242-4363) or www.aiche.org/publications.

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You may find it desirable to answer all of these questions for each facility being screened, and document the
answers to each question on the Table 1 form.

Question 7:
Is any substance identified
as spontaneously combustible?
This question pertains to substances that will readily
react with the oxygen in the atmosphere, igniting and burning even without an ignition source. Ignition may be immediate, or may result from a self-heating process that may
take minutes or hours (thus, some spontaneously combustible substances are known as self-heating).
Pyrophoric materials ignite spontaneously on short exposure to air under ordinary ambient conditions. (Some
materials that are considered pyrophoric require a minimum relative humidity in the atmosphere for spontaneous
ignition to occur.) The potential of pyrophoric materials to
exhibit this behavior is usually well known due to the extreme care required for their safe handling.
Pyrophoric and other spontaneously combustible substances will generally be identified as such on their product
literature, MSDSs or International Chemical
Safety Cards (ICSCs). If transported, these substances should be identified as DOT/UN Hazard
Class 4.2 materials for shipping purposes and labeled as spontaneously combustible. For pyrophoric substances, the NFPA diamond (6) for container or
vessel labeling has a red (top) quadrant with a rating of 4, indicating the highest severity of flammability hazard. It should
be noted that pyrophoric materials often exhibit one or more
other reactivity hazards as well, such as water reactivity.
A scenario that has resulted in many fires and explosions
in petroleum refineries involves iron sulfide. An impure, pyrophoric sulfide is formed when streams containing hydrogen sulfide or other volatile sulfur compounds are processed in ferrous equipment. Oxidation of moist iron sulfide
is highly exothermic. 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.
Many scenarios involving spontaneous combustion involve a combination of materials exposed to sufficient air,
often in an insulating situation that prevents heat from a
slow oxidation reaction from dissipating, which results in a
self-heating situation. Examples include the exposure of
activated carbon to a high concentration of organic vapors
and the contamination of cotton or cellulose materials with
oil. Such combination scenarios should be examined further and documented in Question 12.
Lists of pyrophoric materials that include less common
chemicals, including metals, can be found in Volume 2 of
Brethericks Handbook of Reactive Chemical Hazards (7).
Other spontaneously combustible substances are tabulated
by their proper shipping names and UN/NA numbers in the

U.S. Dept. of Transportation regulation 49 CFR 172.101.

If the answer to Question 7 is yes, then a chemical reactivity hazard is present that will need to be managed
throughout the life of the facility, as long as a spontaneously combustible material is stored or handled. If you are certain that no pyrophoric or other spontaneously combustible
materials are present, proceed to Question 8.

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,
which in turn might explosively decompose if concentrated. Peroxide formation, or peroxidation, usually happens
slowly over time, when a peroxide-forming liquid is stored
with limited access to air.
Substances that are peroxide-formers will often have an
inhibitor or stabilizer added to prevent peroxidation. They
are often not easily identifiable as peroxide formers using
MSDSs or ICSCs. Rather, they are frequently identified by
another characteristic, such as flammability, for storage and
shipping purposes. Examples of peroxide-formers include
1,3-butadiene, 1,1-dichloroethylene, isopropyl ether, and
alkali metals. Ref. 2 includes a tabulation of some chemical structures susceptible to peroxide formation.
If the answer to Question 8 is yes, then a chemical reactivity hazard is present that will need to be managed
throughout the life of the facility, as long as a peroxide-former is stored or handled. If you are certain that no peroxide-forming substances are present, proceed to Question 9.
If you are uncertain, consult a chemist or other expert.
Question 9:
Is any substance identified as water-reactive?
This question pertains to substances that will chemically
react with water, particularly at normal ambient conditions.
Some concentrated acids and bases can generate considerable heat of solution or heat of dilution when mixed with
water. However, this can be considered a physical effect
rather than a chemical reaction.
Water reactivity can be hazardous by one or more of
several mechanisms. The heat of reaction can cause thermal burns, ignite combustible materials, or initiate other
chemical reactions. Flammable, corrosive or toxic gases
are often formed as reaction products. The violence of
some reactions may disperse hazardous materials. Even
slow reactions can generate sufficient heat and off-gases to
overpressurize and rupture a closed container.
The potential hazards of most water-reactive materials are
generally well known because of the precautions required for
their safe handling. Substances that are water-reactive will
nearly always be identified as such on their MSDSs or ICSCs.
They may be identified as DOT/UN Hazard Class 4.3 materials for shipping purposes and labeled as dangerous when wet.
However, some water-reactive materials are classified other-

wise. Titanium tetrachloride, for example, is DOT/UN Hazard

Class 8 (corrosive material) for shipping purposes, and its
shipping label is likely to reflect both corrosive and poison
hazards. Acetic anhydride is likewise designated Class 8; it
may also be identified as a combustible liquid.
When the NFPA diamond used for container or vessel labeling has a white (bottom) quadrant that contains a W with a
line through it, the material will react violently
or explosively with water and a chemical reactivity hazard obviously exists. However, since
the purpose of the NFPA symbol is to alert
emergency responders to significant, immediate
water-reactivity hazards, even if the W is not present, the material may still be water-reactive but at a slower rate. For example, the reaction of an organic material with water may be
delayed because the reaction only occurs at the interface.
If the answer to Question 9 is yes, then a chemical reactivity hazard is present that will need to be managed
throughout the life of the facility, as long as a water-reactive material is stored or handled. If you are certain that no
water-reactive substances are present, go to Question 10. If
you are uncertain as to whether a material is water-reactive, a chemist or other expert should be consulted or a
simple test can be performed. For fire protection purposes,
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), using a two-drop mixing calorimeter (8).

Question 10:
Is any substance identified as an oxidizer?
This question pertains to any material that readily yields
oxygen or other oxidizing gas, or that readily reacts to promote or initiate combustion of combustible materials (9).
Thus, most oxidizers can be thought of as being reactive
with ordinary combustible liquids or solids, which are commonly used as process, packaging, general use or structural
materials. They can also react with many other substances.
Organic peroxides, included in the same general DOT/UN
Hazard Class (Class 5) as oxidizers, are considered self-reactive, so are addressed with Question 11 rather than here.
Oxidizers will nearly always be identified as such on their
MSDSs or ICSCs. They may be identified as DOT/UN Hazard Class 5.1 materials for shipping purposes and labeled as
oxidizers. However, some oxidizers are classified otherwise.
Chlorine, for example, is DOT/UN Class 2.3 (gases toxic by
inhalation) and labeled as poison gas for shipping purposes;
it may also be labeled as a corrosive material. Liquid oxygen
is Class 2.2 (nonflammable non-toxic compressed gases) but
should be labeled as nonflammable gas and oxidizer.
When the NFPA diamond has a white (bottom) quadrant containing OX, the material
possesses oxidizing properties. It may be either an oxidizer or an organic peroxide. In either case, it should be considered to pose a
chemical reactivity hazard.

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Inadvertent contact of oxidizers with reducing agents, including combustible materials, is the most significant thing
that can go wrong when handling oxidizing substances.
This contact will increase the burning rate of the combustible materials; it may also cause a fire to ignite without
any additional ignition source. Some oxidizers can also undergo self-sustained decomposition, vigorously or explosively, when contaminated or exposed to heat or shock.
NFPA 432 (10) can be consulted for typical organic peroxide formulations. Volume 2 of Brethericks Handbook of
Reactive Chemical Hazards (7) lists many structures and
individual chemical compounds having oxidizing properties.
If the answer to Question 10 is yes, a chemical reactivity
hazard is present that will need to be managed throughout the
life of the facility, as long as an oxidizer is stored or handled. If
you are certain that no oxidizers are present, proceed to Question 11. If you are uncertain, consult a chemist or other expert.

Question 11:
Is any substance identified as self-reactive?
This question pertains to substances that will energetically
self-react, often with accelerating or explosive rapidity. 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.
Self-reactive materials are generally identified as polymerizing, decomposing or unstable on their MSDSs or ICSCs.
Substances that are DOT/UN Class 1 (explosives) and Class
5.2 (organic peroxides) are likely to be self-reactive. However, 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. Many self-reactive materials are classified
in other categories; for example, most self-polymerizing materials are labeled as flammable gases or flammable liquids,
due to their flammability in addition to being reactive.
The NFPA diamond for self-reactive materials has a yellow
(right) quadrant with a rating between 1 (lowest) and 4 (highest). By the definitions in NFPA 704 (6), this indicates that the material poses an instability hazard. Having a non-zero NFPA instability rating is
a straightforward means of identifying self-reactive materials. NFPA 49 and NFPA 325 give instability ratings for many different industrial chemicals (11).
The common thread among self-reactive materials is that
they have more internal energy than their polymerization, decomposition or rearrangement products, so that energy is released when a self-reaction occurs. If this released energy is
not dissipated as fast as it is generated (such as by cooling),
this energy can go into preheating the unreacted material and
can cause the reaction rate to accelerate out of control.

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Some energy (i.e., the activation energy) is required to

start the self-reaction. For some highly reactive materials,
such as shock-sensitive explosives and organic peroxides,
mechanical shock, friction or a spark may be sufficient to
start a sustained decomposition reaction. However, for most
self-reactive materials, the energy input is in the form of
thermal energy (heat). For storage applications, 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), as described in NFPA 49 (12).
Annex E to NFPA 704 (6) gives a method for calculating
an instantaneous power density, defined as the product of
the enthalpy (heat) of the self-reaction and the initial rate of
reaction, determined at 250C (482F). 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 0.01 W/mL and no exotherm being exhibited by the material at temperatures at or below 500C
(932F) when tested by differential scanning calorimetry (11).
If the answer to Question 11 is yes, a chemical reactivity hazard is present that will need to be managed throughout the life of the facility, as long as a self-reactive material is stored or handled. If you are certain that no self-reactive substances are present, proceed to Question 12. If you
are uncertain as to whether a material is self-reactive, a
chemist or other expert should be consulted.

Question 12:
Can incompatible materials coming into
contact cause undesired consequences?
Up to this point, the chemical reactivity hazards of individual substances, either by themselves or in contact with
ubiquitous materials, have been considered. This last question addresses the potential for an unintended chemical reaction due to incompatible materials contacting each other.
Compatibility means the ability of materials to exist in contact without specified (usually hazardous) consequences
under a defined scenario. A scenario, in this context, is a detailed physical description of the process whereby a potential inadvertent combination of materials may occur (13).
Question 12 is especially pertinent to mixing and formulation facilities, where materials are being intentionally
combined. However, it can also apply to facilities involving storage, handling, repackaging or physical processing
where incompatible materials are present and have the potential for contacting each other, or the potential exists for
the wrong material to be unloaded into a storage tank or
otherwise introduced into a process.
Step 1: Decide on undesired consequences of concern.
The determination of whether materials are incompatible
depends on what you consider undesired consequences
in the context of your facilitys operation. A suggested
starting point is to consider the undesired consequences as
uncontrolled chemical reactions that can result in: the gen-

Table 2. Example of inadvertent mixing scenarios and compatibility findings.

Scenario
1 Mix 1 L of household ammonia cleaner
into 4 L of household chlorine bleach in
an open bucket, with intention of
immediate use
2 Inadvertently pump up to 1,400 kg
of 38C cyclohexane at 0.3 kg/s into
closed, temperature-controlled storage
tank of between 700 and 2,800 kg of
acrylic acid with 200 ppm MEHQ
inhibitor maintained 20C

Conditions Normal?
Yes

R, NR or ?
R

No

eration of toxic gas, corrosive gas or liquid, or flammable

gas; the formation of shock-sensitive or explosive material;
an explosion; the ignition of combustible material; the generation of sufficient off-gas to rupture a container or enclosure; sufficient heating of substances to initiate decomposition or a runaway reaction; or the reduction of thermal stability of a material to the point of initiating decomposition.
Step 2: Identify mixing scenarios. The next step is to identify specific scenarios by which materials could be combined.
Chemical compatibility depends heavily on the mixing scenario, which should consider at least the following (13):
materials that could be combined, including their compositions or concentrations
specific quantities of materials
storage temperatures
confinement (closed or open system)
atmosphere (air, nitrogen-inerted, oxygen-enriched)
maximum time the materials may be in contact.
Depending on the nature of the facility, many different
scenarios may be possible for the unintentional mixing or
combining of different substances. A few example causes
(starting points) for these scenarios include: a leaking liquid contacts an adjacent material or container; waste materials are combined in the plant sewer system; and a crossconnecting line is left open.
Note that measures can be taken to essentially eliminate
the potential for inadvertent mixing, such as by storage
segregation and elimination of cross-connections. If so,
then you may be able to significantly reduce the number of
potential scenarios that need to be evaluated.
Step 3: Document mixing scenario consequences. 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. In the
first column, describe what specific materials and quantities
could be combined, how they could be combined, and for
how long. In the second column, indicate whether ambient,
unconfined conditions apply (ambient temperature, atmospheric pressure, non-inerted and non-enriched atmosphere
with 21% oxygen, and no enclosure or confinement). Assume published compatibility data will be valid only if ambient, unconfined conditions apply, unless the data indicate
otherwise. In the third column, indicate whether for this
scenario under these conditions a chemical reaction will
occur that has the potential for any of your predetermined
undesired consequences. Document any comments and the
source of your information in the last column. This evaluation is illustrated in the examples shown in Table 2.

Information Sources, Comments

Based on sodium hypochlorite solution
MSDS; generates heat and toxic
vapors; can form explosive nitrogen
trichloride under certain conditions
Compatibility information only known
for ambient conditions; no reaction
with cyclohexane expected, 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, but this is often not
practical or possible. Small-scale laboratory tests can indicate whether a reaction is expected. However, be wary of
concluding that since no reaction is seen on a small scale, no
effects will be realized in an industrial facility. It is especially important to consider heat-transfer effects and scale-up issues when extrapolating small-scale results differences in
heat transfer, mixing and other scale-up effects can cause a
significant and potentially disastrous divergence between actual effects and those estimated from small-scale tests.
Lacking test results, the next best option is to check chemical-specific safety data, such as MSDSs or ICSCs for the
particular compounds and concentrations involved. Section
10 (dealing with stability and reactivity) of standard MSDSs
should contain information on incompatibilities with other
materials. Similar information should be in the chemical dangers section of ICSCs. However, these are rarely more than
lists of incompatible materials, and do not indicate expected
consequences. The listed incompatibilities should be considered as only applying to ambient conditions unless otherwise
stated. References such as Brethericks Handbook of Reactive Chemical Hazards (7) and NFPA 491, Hazardous
Chemical Reactions (11) summarize published literature on
incompatibilities. More detailed information may be given on
what to expect when materials are combined.
If chemical-specific information is not available, it might
be possible to predict the consequences by methods using
compatibility groups, based on chemicals with similar structures that are expected to have similar reactivity characteristics. One computerized tool that uses this approach is the
Chemical Reactivity Worksheet made available by the U.S.
National Oceanic and Atmospheric Administration (3). This
program includes over 6,000 chemicals, mixtures and solutions in its database. It also predicts chemical reaction consequences of combining two materials at a time (e.g., heat
generation by chemical reaction, may cause pressurization).
If any incompatibilities are found (R or ? in the third column of Table 2), the answer to Question 12 is yes. However, some judgment may be needed as to the likelihood of
each scenario occurring. For example, a scenario may be
judged not expected to occur any time during the life of the
facility. This could be noted in the Comments column along
with information supporting this judgment, and you may
decide to focus your management of chemical reactivity
hazards on hazards that are more likely to result in losses.
For facilities where many different materials are stored,

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Risk Minimization

processed or mixed, some companies use a matrix approach

to investigate all material combinations including contaminants, materials of construction, additives, catalysts, utilities
and common substances such as air and water. For larger or
more complex facilities, a systematic approach to identifying
incompatibility scenarios and analyzing their severities and
likelihoods may be warranted. A process hazard analysis
(PHA) approach, such as a hazard and operability (HAZOP)
study, can be an effective tool to facilitate such an effort.
If the answer to Question 12 is yes, then chemical reactivity hazards are present.
If you are certain that no incompatible materials have a
reasonable likelihood of contacting each other and causing
undesired consequences during the facilitys lifetime, stop

Literature Cited
1. U.S. Chemical Safety and Hazard Investigation Board, Hazard
Investigation, Improving Reactive Hazard Management, Report
No. 2001-01-H, NTIS No. PB2002-108705, U.S. CSB, Office of Investigations and Safety Programs, Washington, DC (Dec. 2002).
2. Johnson, R. W., et al., Essential Practices for Managing Chemical
Reactivity Hazards, AIChE Center for Chemical Process Safety,
New York, NY (2003).
3. U.S. National Oceanic and Atmospheric Administration, Chemical Reactivity Worksheet, version 1.5, available at http://response.restoration.noaa.gov/chemaids/react.html, U.S. NOAA, Office of Response and Restoration, Seattle, WA (2002).
4. U.S. Occupational Safety and Health Administration, Hazard
Communication Standard, 29 CFR 1910.1200 Paragraph (c), Definitions, U.S. Dept. of Labor, Occupational Safety and Health Administration, Washington, DC (Feb. 9, 1994).
5. United Nations, Recommendations on the Safe Transport of Dangerous Goods (Orange Book), United Nations, Geneva, Switzerland (2002).
6. National Fire Protection Association, Standard System for the
Identification of the Hazards of Materials for Emergency Response,
NFPA 704, National Fire Protection Association, Quincy, MA, (2001).
7. Urben, P. G., Ed., Brethericks Handbook of Reactive Chemical
Hazards, 6th ed., 2 vols., also available on CD-ROM as Brethericks Reactive Chemical Hazards Database Version 3.0 and online by subscription at www.chemweb.com, Butterworth-Heinemann, Oxford, UK (1999).
8. Hofelich, T. C., et al., Determination of Compatibility via Thermal
Analysis and Mathematical Modeling, Process Safety Progress, 13
(4), pp. 227233 (Oct. 1994).
9. National Fire Protection Association, Code for the Storage of
Liquid and Solid Oxidizers, NFPA 430, National Fire Protection
Association, Quincy, MA (2000).
10. National Fire Protection Association, Code for the Storage of
Organic Peroxide Formulations, NFPA 432, National Fire Protection Association, Quincy, MA (1997).
11. National Fire Protection Association, Fire Protection Guide to
Hazardous Materials, 13th ed., National Fire Protection Association, Quincy, MA (2002).
12. National Fire Protection Association, Hazardous Chemicals Data,
NFPA 49, National Fire Protection Association, Quincy, MA (2001).
13. ASTM International, Standard Guide for the Preparation of a Binary Chemical Compatibility Chart, ASTM E 2012-00, ASTM International, West Conshohocken, PA (2000).

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here. If the decision flow of the figure has been followed, the
preliminary screening method indicates that no significant
chemical reactivity hazards are expected at your facility.

Whats next?
If the preliminary screening indicates that chemical reactivity hazards exist, then a management system is needed to ensure the hazards are fully understood and reliably controlled.
Reference 2 outlines essential practices for identifying and
managing chemical reactivity hazards. These practices begin
with establishing an effective management system, followed
by collecting data, testing for reactivity where warranted, assessing and controlling risks, and documenting, communicating, investigating, auditing, training, and managing change.
The answers to the screening questions in this article
should not be thought of as unchangeable. Special care
needs to be taken whenever introducing new chemicals or
processes to a facility or when changing process conditions. Management controls need to be in place to prevent
unauthorized materials from being brought into a facility.
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.
Changes can also be documented that eliminate chemical reactivity hazards from your facility, such as discontinuing the storage and handling of a water-reactive material
or eliminating the potential for a reactive interaction. The
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result will be an inherently safer facility.
Related Course Offered by AIChE
Course #583: Identifying and Managing Chemical Reactiviy Hazards
Member fee: $995, Non-member fee: $1,155
Houston, TX
October 3031, 2003
For more information or to register, visit www.aiche.org/education
or call (800) 242-4363.
Onsite courses are also available.

ROBERT W. (BOB) JOHNSON is a process safety and risk management

consultant with Unwin Co. (Columbus, OH 43212; Phone: (614) 486-2245;
E-mail: rjohnson@unwin-co.com). He has helped clients with their technical
safety and risk analysis efforts for over 25 years. 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, and he teaches the
AIChE Continuing Education courses on process hazard analysis and
chemical reactivity hazards. He is a director of the AIChE Safety and Health
Division and chair of the 2004 Loss Prevention Symposium. He holds BS
and MS degrees in chemical engineering from Purdue Univ.
PETER N. LODAL is a senior technical associate and group leader of the Plant
Protection Technical Services group at Eastman Chemicals Tennessee
Operations site in Kingsport, TN (Phone: (423) 229-2675; Fax: (423) 2293949; E-mail: pnlodal@eastman.com). He has been with Eastman in various
process design and safety positions for more than 25 years. He is the chair of
the Center for Chemical Process Safety Reactive Chemicals Subcommittee,
and also chairs the Process Safety Subteam for the American Chemistry
Council (ACC). He is the author or co-author of more than 20 papers. He
holds BS and MS degrees in chemical engineering from Purdue Univ. and is
active as a director of his local AIChE section (East Tennessee).