2008 SACHE Faculty Workshop

Chemical
Reactivity
Hazards:
2005 SACHE Faculty Workshop

Chemical
foresee
Reactivity
avoid
Hazards:
control
Introduction

The worst process industry disasters worldwide

have involved uncontrolled chemical reactions
Thesis: Chemical reactivity hazards must be
anticipated and recognized before controls can
be engineered
Reactivity hazards that are eliminated will not
need engineering and administrative controls
SACHE has many products that can help
educate engineers to understand and safeguard
against uncontrolled reactions
Syllabus

Course Texts
Pretest
Key Concepts 1
Midterm Exam
Key Concepts 2
Open-Book Final

Extra-Credit Activities
Course
Texts
 Texts
CCPS Safety Alert 2001.
Reactive Material Hazards: What You Need to Know.
New York: AIChE. 10 pages.

Download for free at

http://www.aiche.org/CCPS/Resources/SafetyAlerts/index.aspx
 Texts
Johnson, Rudy, Unwin 2003.
Essential Practices for Managing Chemical Reactivity Hazards.
New York: AIChE. 193 p.

Register for free access at www.knovel.com/ccps

 Texts
CCPS 1995.
Guidelines for Chemical Reactivity Evaluation and Application to Process Design.
New York: AIChE. 210 p.

AIChE members can access for free at www.knovel.com

 Texts
CCPS 1995.
Guidelines for Safe Storage and Handling of Reactive Materials.
New York: AIChE. 364 p.

AIChE members can access for free at www.knovel.com

 Texts
CCPS 1999.
Guidelines for
Process Safety in
Batch Reaction Systems.
New York: AIChE. 171 p.

Available from www.wiley.com

 Texts
Hazard Investigation 2002.
Improving Reactive Hazard Management.
Washington, D.C.: U.S. Chemical Safety and Hazard Investigation Board. 150 p.

Download for free at www.csb.gov

 Texts
HarsBook: A technical guide for the assessment of thermal hazards in
highly reactive chemical systems.
HarsNet Thematic Network on Hazard Assessment of Highly Reactive Systems. 143 p.

Download for free at www.harsnet.net

 Texts
P.G. Urben (ed.) 2006. Brethericks Handbook of Reactive Chemical
Hazards (2 vols).
Academic Press. 2,680 pages

~$400 from Amazon.com; also available electronically

 Software
CCPS 2006. Chemical Reactivity Training CD-ROM.
New York: AIChE.

$265.50 from wiley.com; free to all SACHE members

Pretest
Pretest

Q1 On the NFPA diamond, which

color(s) or position(s) are
associated with chemical
reactivity hazards?

0
4 3
WW
OX
OX
Pretest

A1 Flammability

0
Toxicity
4 3 Instability
WW
OX
OX
Special Hazards
Pretest

Q2 Your new research calls for the piloting of a

process involving acetone cyanohydrin.
What should you do first?
Pretest

A2 First, find out the inherent hazards

of acetone cyanohydrin.

C4H7NO
Pretest

A2 First, find out the inherent hazards

of acetone cyanohydrin.

CH3
C O + HCN
CH3
Pretest

A2 First, find out the inherent hazards

of acetone cyanohydrin.

CH3 OH
C
CH3 C N
 Acetone Cyanohydrin
NFPA 49
Severe health hazard; combustible;
readily decomposes, producing
HCN; no special hazards;
reacts with acids, alkalis,
oxidizing materials,
reducing agents

2
3 1
 Acetone Cyanohydrin
International Chemical Safety Card
Extremely toxic, Class IIIB combustible,
unstable at elevated temp,
decomposes in water

1
4 2
Acetone Cyanohydrin
WISER (http://wiser.nlm.nih.gov)
HIGHLY FLAMMABLE: Easily ignited by heat, sparks or flames
DO NOT GET WATER on spilled substance or inside containers

2
4 2
Acetone Cyanohydrin

DOT
Class 6.1 Poisonous material
Acetone Cyanohydrin

DOT Emergency Response Guidebook 2004

A water-reactive material that
produces large amounts of HCN
when spilled in water
Acetone Cyanohydrin

NOAA Chemical Reactivity Worksheet

Chemical Profile Special Hazards
Water-Reactive
Readily decomposes to acetone and poisonous hydrogen cyanide gas No rapid reaction with Air
on contact with water, acids (sulfuric acid) or when exposed to
heat. Should be kept cool and slightly acidic (pH 4-5) [Sax, 2nd Air and Water Reactions
ed., 1965, p. 388]. Slowly dissociates to acetone, a flammable Soluble in water. Readily decomposes on
liquid, and hydrogen cyanide, a flammable poisonous gas, under contact with water to form acetone and
poisonous hydrogen cyanide.
normal storage and transportation conditions. Rate of
dissociation increased by contact with alkalis and/or heat. General Description

A colorless liquid. Flash point 165F. Lethal by

inhalation and highly toxic or lethal by skin
absorption. Density 7.8 lb / gal (less dense than
water). Vapors heavier than air. Produces toxic
oxides of nitrogen during combustion ( AAR, 1999).
Acetone Cyanohydrin

NIOSH Pocket Guide to Chemical Hazards

Incompatibilities & Reactivities:
Sulfuric acid, caustics
Note: Slowly decomposes to acetone & HCN at room temperatures; rate is
accelerated by an increase in pH, water content, or temperature.
Acetone Cyanohydrin

CHRIS
Acetone Cyanohydrin

CHRIS
Acetone Cyanohydrin
SIDS: Stability in Water

60
50
T (min)

40
30
20
10
0
4.5 5 5.5 6 6.5 7 7.5
pH
Acetone Cyanohydrin

Conclusions
Extremely toxic; must keep contained
and avoid all contact
Combustible; must avoid flame, ignition
Dissociates to produce highly toxic and
flammable gases; dissociation increases
with heat, moisture, alkalinity
Must prevent spills into drains, etc.
Must avoid incompatible materials
Key Concepts
Key Concepts

From 2005 SACHE module on

Chemical Reactivity Hazards
(etc.)
The NOAA Chemical Reactivity
Worksheet predicts the results of
mixing any binary combination of
the 6,080 chemicals in the CAMEO
database, including many
common mixtures and solutions.

For each substance, a general

description and chemical profile
are given, along with special
hazards such as air and water
reactivity.
CRWorksheet Limitations

Only binary combinations considered

Consequences predicted only for
ambient temperature, atmospheric
pressure
Possible effects of confinement,
catalysts, contaminants, or materials of
construction not included
Reaction products not predicted, though
flammable or toxic gas generation may
be suggested
Preliminary
Screen for
Chemical
Reactivity
Hazards

Summary
Flowchart
Source: Johnson et al. 2003
Incident

April 21, 1995

5 worker
fatalities
~300
evacuated
Facility
destroyed
Surrounding
businesses
damaged Ed Hill, The Bergen Record
Used with permission
 WHY?
Those hazards that are not eliminated or
reduced to insignificance must be managed
throughout the lifetime of the facility,
to avoid uncontrolled chemical reactions that
can result directly or indirectly in serious
harm to people, property or the environment.
 Inherently Cleaner, Safer Plants

Inherently Environ-
Pollution Waste
Cleaner mental
Prevention Management
Processes Restoration

POTENTIAL RELEASE AFTERMATH

Processes
Recovery
Mitigation Prevention Safer
Accident
Inherently
Safe Operation
(with respect to Chemical Reactivity Hazards)

Contain and control all chemical reactivity

hazards throughout entire facility lifetime
Reduce hazards or design safeguards
such that even if hazard containment or
control were lost, no injuries, property
damage, environmental damage or
business interruption would occur
Eliminate chemical reactivity hazards
Inherently Safer Strategies

MINIMIZE

SUBSTITUTE

MODERATE

SIMPLIFY
Foresee, Avoid, Control

Anticipate chemical reactivity hazards

Identify all reactive materials and
all possible reactive interactions
Do whatever it takes to fully understand
intended and unintended reactions
Boundaries of safe operation
Calculations, literature, testing, experts
Design and operate to avoid unintended
reactions and control intended reactions
 Section 4.1
START Develop/Document System to Manage Chemical Reactivity
Hazards

Managing 4.2 4.9 4.10

Collect Reactivity Investigate Review, Audit,
Chemical Hazard Information Chemical
Reactivity
Manage Change,
Improve Hazard

Reactivity
4.3 Incidents Management
Identify Chemical Practices/Program
Reactivity Hazards
Hazards 4.4
Test for Chemical IMPLEMENT; OPERATE FACILITY
NO
Reactivity
Sufficient
information to evaluate 4.8
hazard?
Communicate and Train on
Chemical Reactivity Hazards
YES

4.5 4.6 4.7

Assess Chemical Identify Process Document Chemical Reactivity
Reactivity Risks Controls and Risk Risks and Management Decisions
Management Options
 4.2 4.9 4.10
Collect Reactivity Investigate Review, Audit,
Hazard Information Chemical Manage Change,
Identify, Reactivity Improve Hazard
4.3
Characterize Identify Chemical
Incidents Management
Practices/Program
Hazards Reactivity Hazards
4.4
NO Test for Chemical IMPLEMENT; OPERATE FACILITY
Reactivity
Sufficient
information to evaluate 4.8
hazard?
Communicate and Train on
YES
Chemical Reactivity Hazards

4.5 4.6 4.7

Assess Chemical Identify Process Document Chemical Reactivity
Reactivity Risks Controls and Risk Risks and Management Decisions
Management Options
Chemical Reaction Hazard Identification
D.C. Hendershot 2002. A Checklist for Inherently Safer
Chemical Reaction Process Design and Operation.
CCPS International Symposium on Risk, Reliability and
Security.
Reaction Hazard Identification

1 Know the heat of reaction for the

intended and other potential chemical
reactions.
There are a number of techniques for measuring or
estimating heat of reaction, including various
calorimeters, plant heat and energy balances for
processes already in operation, analogy with similar
chemistry (confirmed by a chemist who is familiar with
the chemistry), literature resources, supplier contacts,
and thermodynamic estimation techniques. You should
identify all potential reactions that could occur in the
reaction mixture and understand the heat of reaction of
these reactions.
Reaction Hazard Identification

2 Calculate the maximum adiabatic

temperature for the reaction mixture.
Use the measured or estimated heat of reaction,
assume no heat removal, and that 100% of the
reactants actually react. Compare this temperature to
the boiling point of the reaction mixture. If the
maximum adiabatic reaction temperature exceeds the
reaction mixture boiling point, the reaction is capable
of generating pressure in a closed vessel and you will
have to evaluate safeguards to prevent uncontrolled
reaction and consider the need for emergency
pressure relief systems.
Reaction Hazard Identification

3 Determine the stability of all individual

components of the reaction mixture at
the maximum adiabatic reaction
temperature.
This might be done through literature searching,
supplier contacts, or experimentation. Note that this
does not ensure the stability of the reaction mixture
because it does not account for any reaction among
components, or decomposition promoted by
combinations of components. It will tell you if any of
the individual components of the reaction mixture can
decompose at temperatures which are theoretically
attainable.
Reaction Hazard Identification

3 (continued)
If any components can decompose at the maximum
adiabatic reaction temperature, you will have to
under-stand the nature of this decomposition and
evaluate the need for safeguards including emergency
pressure relief systems.
Reaction Hazard Identification

4 Understand the stability of the reaction

mixture at the maximum adiabatic
reaction temperature.
Are there any chemical reactions, other than the
intended reaction, which can occur at the maximum
adiabatic reaction temperature? Consider possible
decomposition reactions, particularly those which
generate gaseous products. These are a particular
concern because a small mass of reacting condensed
liquid can generate a very large volume of gas from the
reaction products, resulting in rapid pressure
generation in a closed vessel.
Reaction Hazard Identification

4 (continued)
Again, if this is possible, you will have to understand
how these reactions will impact the need for safeguards,
including emergency pressure relief systems.
Understanding the stability of a mixture of components
may require laboratory testing.
Reaction Hazard Identification

5 Determine the heat addition and heat

removal capabilities of the pilot plant
or production reactor.
Dont forget to consider the reactor agitator as a
source of energy about 2550 Btu/hour/horsepower.
Understand the impact of variation in conditions on
heat transfer capability. Consider factors such as
reactor fill level, agitation, fouling of internal and
external heat transfer surfaces, variation in the
temperature of heating and cooling media, variation in
flow rate of heating and cooling fluids.
Reaction Hazard Identification

6 Identify potential reaction contaminants.

In particular, consider possible contaminants which are
ubiquitous in a plant environment, such as air, water,
rust, oil and grease. Think about possible catalytic
effects of trace metal ions such as sodium, calcium, and
others commonly present in process water. These may
also be left behind from cleaning operations such as
cleaning equipment with aqueous sodium hydroxide.
Determine if these materials will catalyze any
decomposition or other reactions, either at normal
conditions or at the maximum adiabatic reaction
temperature.
Reaction Hazard Identification

7 Consider the impact of possible deviations

from intended reactant charges and
operating conditions.
For example, is a double charge of one of the reactants a
possible deviation, and, if so, what is the impact? This kind of
deviation might affect the chemistry which occurs in the
reactor for example, the excess material charged may react
with the product of the intended reaction or with a reaction
solvent. The resulting unanticipated chemical reactions could
be energetic, generate gases, or produce unstable products.
Consider the impact of loss of cooling, agitation, and
temperature control, insufficient solvent or fluidizing media,
and reverse flow into feed piping or storage tanks.
Reaction Hazard Identification

8 Identify all heat sources connected to

the reaction vessel and determine their
maximum temperature.
Assume all control systems on the reactor heating
systems fail to the maximum temperature. If this
temperature is higher than the maximum adiabatic
reaction temperature, review the stability and
reactivity information with respect to the maximum
temperature to which the reactor contents could be
heated by the vessel heat sources.
Reaction Hazard Identification

9 Determine the minimum temperature to

which the reactor cooling sources
could cool the reaction mixture.
Consider potential hazards resulting from too much
cooling, such as freezing of reaction mixture
components, fouling of heat transfer surfaces, increase
in reaction mixture viscosity reducing mixing and heat
transfer, precipitation of dissolved solids from the
reaction mixture, and a reduced rate of reaction
resulting in a hazardous accumulation of unreacted
material.
Reaction Hazard Identification

10 Consider the impact of higher

temperature gradients in plant scale
equipment compared to a laboratory or
pilot plant reactor.
Agitation is almost certain to be less effective in a plant
reactor, and the temperature of the reaction mixture
near heat transfer surfaces may be higher (for systems
being heated) or lower (for systems being cooled) than
the bulk mixture temperature. For exothermic
reactions, the temperature may also be higher near the
point of introduction of reactants because of poor
mixing and localized reaction at the point of reactant
contact.
Reaction Hazard Identification

10 (continued)
The location of the reactor temperature sensor relative
to the agitator, and to heating and cooling surfaces may
impact its ability to provide good information about the
actual average reactor temperature. These problems will
be more severe for very viscous systems, or if the
reaction mixture includes solids which can foul
temperature measurement devices or heat transfer
surfaces. Either a local high temperature or a local low
temperature could cause a problem. A high temperature,
for example, near a heating surface, could result in a
different chemical reaction or decomposition at the
higher temperature.
Reaction Hazard Identification

10 (continued)
A low temperature near a cooling coil could result in
slower reaction and a buildup of unreacted material,
increasing the potential chemical energy of reaction
available in the reactor. If this material is subsequently
reacted because of an increase in temperature or other
change in reactor conditions, there is a possibility of an
uncontrolled reaction due to the unexpectedly high
quantity of unreacted material available.
Reaction Hazard Identification

11 Understand the rate of all chemical

reactions.
It is not necessary to develop complete kinetic
models with rate constants and other details, but
you should understand how fast reactants are
consumed and generally how the rate of reaction
increases with temperature. Thermal hazard
calorimetry testing can provide useful kinetic data.
Reaction Hazard Identification

12 Consider possible vapor phase

reactions.
These might include combustion reactions, other vapor
phase reactions such as the reaction of organic vapors
with a chlorine atmosphere, and vapor phase
decomposition of materials such as ethylene oxide or
organic peroxide.
Reaction Hazard Identification

13 Understand the hazards of the products of

both intended and unintended reactions.
For example, does the intended reaction, or a possible
unintended reaction, form viscous materials, solids, gases,
corrosive products, highly toxic products, or materials which
will swell or degrade gaskets, pipe linings, or other polymer
components of a system? If you find an unexpected material
in reaction equipment, determine what it is and what impact
it might have on system hazards. For example, in an
oxidation reactor, solids were known to be present, but
nobody knew what they were. It turned out that the solids
were pyrophoric, and they caused a fire in the reactor.
Reaction Hazard Identification

14 Consider doing a Chemical Interaction

Matrix and/or a Chemistry Hazard
Analysis.
These techniques can be applied at any stage in the
process life cycle, from early research through an
operating plant (Mosley et al. 2000). They are intended
to provide a systematic method to identify chemical
interaction hazards and hazards resulting from
deviations from intended operating conditions.
ASTM E 2012-00
Standard Guide for the Preparation of a
Binary Chemical Compatibility Chart

Scenario-based
 Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2 INFORMATION SOURCES; COMMENTS
NORMAL? or ?
1 Mix one liter of household ammonia Yes R Based on sodium hypochlorite solution
cleaner into four liters of household chlorine MSDS. Generates heat and toxic
bleach in an open bucket, with intention of vapors; can form explosive nitrogen
immediate use trichloride under certain conditions
2 Inadvertently pump up to 1400 kg of 38C No ? Compatibility information only known for
cyclohexane at 0.3 kg/s into closed, ambient conditions; no reaction with
temperature-controlled storage tank of cyclohexane expected, but may be hot
between 700 and 2800 kg of acrylic acid with enough to increase dimer formation and
200 ppm MEHQ inhibitor, maintained at 20C possibly initiate polymerization
1
Does the contact/mixing occur at ambient temperature, atmospheric pressure, 21% oxygen atmosphere, and
unconfined? (IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY)
2
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

Johnson and Lodal, "Screen Your Facilities for

Chemical Reactivity Hazards," CEP, Aug. 2003
 Inadvertent Mixing Scenarios

SCENARIO
2 Inadvertently pump up to 1400 kg of 38C
cyclohexane at 0.3 kg/s into closed,
2 Inadvertently pump up to 1400 kg of 38C
cyclohexane at 0.3 kg/s into closed,
temperature-controlled storage tank of
temperature-controlled
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
storage tank of
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
 Inadvertent Mixing Scenarios

SCENARIO CONDITIONS
1
NORMAL?

2 Inadvertently pump up to 1400 kg of 38C

cyclohexane at 0.3 kg/s into closed,
No
temperature-controlled storage tank of
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
1
Does the contact/mixing occur at ambient temperature, atmospheric pressure,
21% oxygen atmosphere, and unconfined? (IF NOT, DO NOT ASSUME THAT
PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY)
 Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2
NORMAL? or ?

2 Inadvertently pump up to 1400 kg of 38C

cyclohexane at 0.3 kg/s into closed,
No
?
temperature-controlled storage tank of
between 700 and 2800 kg of acrylic acid with
200 ppm MEHQ inhibitor, maintained at 20C
2
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
 Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2 INFORMATION SOURCES; COMMENTS
or ?
Compatibility information only known for
NORMAL?

2 Inadvertently pump up to 1400 kg ofambient

38C conditions;
No ? no reaction
Compatibility with
information only known for
cyclohexane at 0.3 kg/s into closed, ambient conditions; no reaction with
temperature-controlled storage tank ofcyclohexane expected, but expected,
cyclohexane may be hot
but may be hot
between 700 and 2800 kg of acrylic acid with enough to increase dimer formation and
200 ppm MEHQ inhibitor, maintained enough
at 20C to increase dimer formation
possibly initiate polymerization and

possibly initiate polymerization

 Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2 INFORMATION SOURCES; COMMENTS
NORMAL? or ?

2 Inadvertently pump up to 1400 kg of 38C No ? Compatibility information only known for

cyclohexane at 0.3 kg/s into closed, ambient conditions; no reaction with
temperature-controlled storage tank of cyclohexane expected, but may be hot
between 700 and 2800 kg of acrylic acid with enough to increase dimer formation and
200 ppm MEHQ inhibitor, maintained at 20C possibly initiate polymerization

G.W. Boicourt, Experimental Safety: What You

Need for Effective Process Safety
Evaluation, Proceed. 30th Annual Loss Prev.
 Inadvertent Mixing Scenarios
CONDITIONS R, NR
SCENARIO 1 2 INFORMATION SOURCES; COMMENTS
NORMAL? or ?

2 Inadvertently pump up to 1400 kg of 38C No ? Compatibility information only known for

cyclohexane at 0.3 kg/s into closed, ambient conditions; no reaction with
temperature-controlled storage tank of cyclohexane expected, but may be hot
between 700 and 2800 kg of acrylic acid with enough to increase dimer formation and
200 ppm MEHQ inhibitor, maintained at 20C possibly initiate polymerization

GuideWord/ Severit
Cause Freq Consequences
Deviation On Off
AS WELL AS Connecting valve Containment rupture
Cyclohexane left open explosion
Added Fire
Toxic reaction products
release
 Chemistry Hazard Analysis Scenarios
Guideword Deviation Consequences Comments/Actions
No No Catalyst C No reaction when Reactants A Develop kinetic and
added and B are mixed; if Catalyst C thermodynamic data on
is added after the entire charge this reaction
of Reactants A and B has been
completed, a rapid and violent
reaction can occur
More High Side reactions have been Investigate the
temperature; observed in similar systems behavior of the reaction
greater than above 70C, and may also at elevated temperature
70C occur with this chemistry
As well as Rust, as well The effect of contamination Determine the effect of
as normal with iron or rust is unknown iron/rust contamination
materials

Mosley, Ness, and Hendershot, "Screen Reactive

Chemical Hazards Early in Process Development," CEP,
 4.2 4.9 4.10
Collect Reactivity Investigate Review, Audit,
Hazard Information Chemical Manage Change,
Reactivity Improve Hazard
4.3 Incidents Management
Identify Chemical Practices/Program
Reactivity Hazards
4.4
NO Test for Chemical IMPLEMENT; OPERATE FACILITY
Reactivity
Sufficient
information to evaluate 4.8
hazard?
Communicate and Train on
YES
Chemical Reactivity Hazards

PHAs; Ensure Risk Control

4.5 4.6 4.7
Assess Chemical Identify Process Document Chemical Reactivity
Reactivity Risks Controls and Risk Risks and Management Decisions
Management Options
 Intentional Chemistry
Unintentional Chemistry
Materials Reactive with Ubiquitous
Substances
Spontaneously Combustible
Peroxide Forming
Water Reactive
Oxidizing
Chemical Self-Reactive Materials
Reactivity Polymerizing
Hazards Decomposing
Rearranging
Reactive Interactions
Incompatibilities
Abnormal Conditions

Identify,
characterize
hazards
 Normal Situation - Reactives
Reactive materials contained
Reactive interactions (incompatibilities) avoided
Intended reactions controlled

Chemical
Reactivity
Hazards
Potential Loss Event
Impacts
People
Property
Environment
 Abnormal Situation - Reactives
Loss of containment
Reactive interaction (incompatibility)
Loss of reaction control

Chemical
se

Reactivity
au

Hazards
C

Deviation
Chemical Reactivity: Loss Events

Johnson and Unwin, Addressing Chemical Reactivity

Hazards in Process Hazard Analysis, 18th Annual
International CCPS Conference, NY: AIChE, Sept. 2003.

Loss Event
Fire
Explosion
Release
Loss Events Associated with Reactivity
Hazards
Hazard Type Typical Uncontrolled Chemical Reaction Consequences

Intentional Containment rupture explosion (uncontrolled reaction resulting in

Chemistry liquid/vapor heating or gas generation inside inadequately relieved
vessel or enclosure that is incapable of withstanding peak pressure)
Fire (e.g., excess heating or loss of cooling in unconfined
configuration allows autoignition temperature to be attained)
Toxic reaction products release (e.g., off-gas treatment system fails)

Spontaneously Containment rupture explosion (self-ignition of vapor, dust or mist

Combustible inside inadequately relieved vessel or enclosure that is incapable of
Materials withstanding peak pressure)
Fire (e.g., self-ignition of flash fire, jet fire, pool fire, pile fire, or
building fire)
Toxic combustion gases release

Peroxide Condensed-phase explosion (e.g., explosive decomposition of

Formers unstable peroxide initiated by heat, friction, spark, or mechanical
shock)
Fire (e.g., follow-on effects from condensed-phase explosion, such as
flammable liquid containment rupture and ignition)
Hazard Type Typical Uncontrolled Chemical Reaction Consequences

Water- Explosively violent reaction (e.g., reaction of sodium with water)

Reactive Containment rupture explosion (reaction with water resulting in
Materials liquid/vapor heating or gas generation inside inadequately relieved
vessel or enclosure that is incapable of withstanding peak pressure, or
flammable vapors generated by reaction with water ignited inside
inadequately relieved vessel or enclosure that is incapable of
withstanding peak pressure)
Flash fire (e.g., ignition of unconfined flammable vapors generated
by reaction with water)
Toxic vapor release (toxic vapors generated by reaction with water,
or decomposition reaction initiated by heat of reaction with water)

Oxidizers Fire (initiated or accelerated by presence of oxidizer)

Condensed-phase explosion (initiation of detonable mixture of
oxidizer with reducing substance)
Containment rupture explosion (ignition or spontaneous ignition of
oxidation reaction inside inadequately relieved vessel or enclosure that
is incapable of withstanding peak pressure)
Toxic combustion gases release
Note that many oxidizers are subject to decomposition, so also have
possible Self-Reactive Material consequences
Hazard Type Typical Uncontrolled Chemical Reaction Consequences

Self-Reactive Condensed-phase explosion (e.g., heat, friction, spark, or mechanical

Materials shock initiation of decomposition proceeding at detonation velocity)
(Polymerizing, Containment rupture explosion (e.g., by self-reaction resulting in
Decomposing, liquid/vapor heating, gas generation, or evolution and ignition of
Rearranging) flammable vapors inside inadequately relieved vessel or enclosure that
is incapable of withstanding peak pressure)
Toxic vapor release (e.g., from toxic decomposition products or heat
from self-reaction resulting in vaporization of toxic component)
Flash fire (e.g., by ignition of flammable off-gases)
Pile fire (e.g., by self-heating to autoignition temperature)

Incompatible Condensed-phase explosion (e.g., by initiation of detonable mixture)

Materials Containment rupture explosion (e.g., by liquid/vapor heating, gas
generation, or evolution and ignition of flammable vapors inside
inadequately relieved vessel or enclosure that is incapable of
withstanding peak pressure)
Toxic vapor release (e.g., from toxic reaction products or from
heating and vaporization of toxic component)
Flash fire (e.g., by ignition of flammable off-gases)
Hazardous material spill (e.g., loss of containment due to reaction
with wrong material of construction)
 Extra-
Credit
Activities
SACHE Case Histories

Batch Polystyrene Reactor Runaway

The Bhopal Disaster
Methacrylic Acid Tankcar Explosion -video
Explosion and Fire Caused By a Runaway
Decomposition
Rupture of a Nitroaniline Reactor
Seveso Accidental Release
Mini Case Histories
SACHE Reactivity Products

Hazards Awareness and Reduction

An Introduction to Reactive and
Explosive Materials (video)
Acrylic Monomers Handling
The Hazards of Hydroxylamine
Chemical Reactivity Hazards (web-based)
Introduction to Inherently Safer Design
SACHE Reactivity Products

Emergency Relief Systems

Design for Overpressure and
Underpressure Protection
Unit Operations Laboratory Experiment
for Runaway Reactions and Vent Sizing
Relief System Design for Single- and
Two-Phase Flow
Runaway Reactions -- Experimental
Characterization and Vent Sizing
RMR

Reactivity Management Roundtable

Kickoff Meeting
Las Vegas, Nevada
October 23, 2003

Most Recent Activities

NOAA CRW updating
Warehousing matrix
TurboTax-type chemical
reactivity hazard identification
DIERS Users Group

AIChE Design Institute for Emergency

Relief Systems
DIERS Users Group Meetings

See
http://www.diers.net/diersweb/home.aspx for
schedule and information
DIERS Conference

3rd International Symposium on

Runaway Reactions and
Pressure Relief Design
Cincinnati, Ohio
October 31 - November 4, 2005
Held in conjunction with
2005 AIChE Annual Meeting
DIERS Conference Topics

1 Theoretical and Experimental Reactivity

Screening

2 Best Practices and Standards for Managing

Chemical Reactivity

ERS Design for Reactive Systems

3 Computational Methods
4 Experimental Methods
5 Fire Exposure

6 Effluent Handling Design for Reactive Systems

Loss Prevention Symposium

43rd Annual Loss Prevention Symposium

Tampa, Florida
April 27-29, 2009
Fires, Explosions and Reactive Hazards
Case Histories and Lessons Learned
Continuing Education Courses

AIChE / ASME on-site: Identifying and

Managing Chemical Reactivity Hazards
Mary Kay OConnor Process Safety Ctr
2008 SACHE Faculty Workshop

Chemical
Reactivity
Hazards
Contact Information

Robert W. Johnson
Unwin Company
1920 Northwest Blvd, Suite 201
Columbus, OH 43212-1197 USA

(614) 486-2245
rjohnson@unwin-co.com
www.unwin-co.com