Safety

Screening
Reactive Chemical
Hazards
Use these tools to identify
Yen-Shan Liu
William J. Rogers
potentially reactive chemical hazards
M. Sam Mannan and avoid the expense of
Mary Kay O'Connor Process Safety Center
Texas A&M Univ.
conducting numerous
detailed hazard assessments.

C
hemical reactivity can be viewed as a double-edged and reduce the high costs of detailed hazard assessment.
sword for the chemical industry. On the one hand, it Efficient screening techniques can be used to obtain the
allows materials to undergo desired reactions to requisite data in a short period of time with minimum
form products under moderate temperature and pressure. On resources. Knowledge of chemistry can be applied to extend
the other hand, a reactive hazard exists when changes in the data to systems for which data are unavailable. It is
chemical structure have the potential to generate heat, ener- important that this informaton be available during the process
gy and gaseous byproducts that cannot be safely absorbed
by the immediate surroundings (1). If the rate of energy
release is rapid enough and not adequately controlled, it
may also lead to uncontrolled catastrophic incidents caused How can additional information
be obtained? Tier III
by polymerization, decomposition, oxidation-reduction
(redox), acid-base reactions, or reactions with water. Testing methods for
hazardous substances and
The U.S. Chemical Safety and Hazard Investigation modeling of data
Board (CSB) examined 167 serious chemical incidents in
the U.S. from January 1980 to June 2001 that involved
uncontrolled chemical reactions. These incidents resulted
in 108 deaths and hundreds of millions of dollars in prop-
What can be done to reduce the risk?
erty damage. Furthermore, 24% of the incidents were Tier II
Quantifying reactivity hazards,
caused by inadequate hazard identification, even though decisions concerning safeguards
hazard information for over 90% of the incidents was
available in publicly accessible literature (2).
Most mid-size and large companies have a reactive-haz- Increasing
Cost
ard management program to assess potential reactive hazards
during storage, transport and processing of reactants, inter- Is there potential reactive chemistry?
mediates and products. The recommended procedure for Tier I
Rective chemical screening
evaluating and quantifying reactive hazards, shown in Figure and documentation
1 (3), is slow and resource-intensive, and in-house tests are
expensive and not practical. The use of appropriate screening
tools, however, can assure higher levels of process safety Figure 1. A three-tier process of increasing complexity and cost
is recommended for evaluating reactive hazards (3).

CEP May 2006 www.cepmagazine.org 41

Safety

Table 1. Toxic Catastrophe Prevention Act (TCPA)

Part D, Group I, List of individual reactive hazard substances (4).

CAS Threshold
design stage in order to develop a safer process. Substance Number Quantity, lb
This article presents several practical and efficient
screening tools, and examples that demonstrate the 1 Acetyl peroxide 110-22-5 2,500
2 Butyl hydroperoxide tertiary 75-91-2 2,500
effectiveness of using the tools separately and togeth-
3 Butyl hypochlorite tertiary None 2,500
er. The following screening methods are discussed: 4 Calcium dithionite or 15512-36-4 5,000
New Jerseys Toxic Catastrophe Prevention Act Calcium hydrosulfite
(TCPA), a state regulation that focuses on a substances 5 Chlorodinitrobenzenes 97-00-7 2,500
functional groups to identify reactive hazards (4) 6 Cumene hydroperoxide 80-15-9 2,500
The National Oceanic and Atmospheric 7 Dibenzoyl peroxide 94-36-0 2,500
Administrations (NOAA) Chemical Reactivity 8 Diethyl peroxide 628-37-5 2,500
9 Diisopropyl peroxydicarbonate 105-64-6 2,500
Worksheet, which has a large database of incompati-
10 Dinitro phenol, (dry or wet, 51-28-5 2,500
ble materials (5) less than 15% water as 2,4- )
Brethericks Handbook of Reactive Hazards, 11 Dinitro resourcinol (wetted 35860-81-6 2,500
which provides detailed information on reactive with not less than 15% water)
chemicals, including incident records (6) 12 Dipicryl sulfide 2217-06-3 2,500
Material Safety Data Sheets (MSDSs), which can 13 Di-tert-butyl peroxide 110-05-4 2,500
14 Divinyl acetylene 821-08-9 2,500
indicate such potential hazards as combustible liquid,
15 Ethyl nitrate 625-58-1 2,500
explosive, flammable, organic peroxide, oxidizer,
16 Ethyl nitrite (solutions) 109-95-5 2,500
pyrophoric, unstable (reactive) or water-reactive. 17 Isosorbide dinitrate 88-33-2 2,500
18 Magnesium diamide 7803-54-4 2,500
The Toxic Catastrophe Prevention Act 19 m-Dinitrobenzene 99-65-0 2,500
New Jerseys Toxic Catastrophe Prevention Act 20 Nitroglycerine (alcohol solution) 55-63-0 2,500
(TCPA) became effective in January 1986 with the goal 21 Nitromethane 75-52-5 2,500
of protecting the public from catastrophic releases of 22 o-Dinitrobenzene 528-29-0 2,500
extraordinarily hazardous substances (EHS). TCPA 23 p-Dinitrobenzene 100-25-4 2,500
24 Peracetic acid (greater than 56%) 79-21-0 2,500
requires owners or operators of facilities having EHS
25 Picric acid (wet, not less 88-89-1 2,500
above certain threshold quantities to anticipate the cir- than 10% water)
cumstances that could lead to incidental EHS release 26 Potassium dithionite or 14293-73-3 5,000
and take precautions to prevent such releases. The Potassium hydrosulfite
amended TCPA includes two additional categories of 27 Propargyl bromide (3-Bromopropyne) 106-96-7 2,500
reactive chemicals: Reactive Hazard Substances (RHS), 28 Silver picrate (wetted with not 146-84-9 2,500
less than 30% water)
the list of chemicals in Table 1; and Reactive Hazard 29 Sodium dithionite or 7775-14-6 5,000
Substance Mixtures (RHSM), as determined by the Sodium hydrosulfite
functional groups in Table 2. RHSMs include a reac- 30 Trinitro benzene as 1,3,5- (wetted 99-35-4 2,500
tant, product or byproduct that is a chemical substance with not less than 30% water)
listed in Table 1 or a mixture of substances having one
or more of the functional groups specified in Table 2. 2.3 psi was chosen because damage to nearby buildings and
The TNT equivalency equation is used to calculate other structures that was severe enough to cause serious per-
threshold quantities: sonal injuries has been documented at that overpressure. Since
the energy of explosion is not readily available, E is taken as
TQ = (D/24)3(1,024/E) (1) 100% and 28% of the heat of reaction of the RHS for intended
reactions and unintended reactions, respectively. If any of the
where TQ = threshold quantity of the RHS, lb; D = distance to intentional mixtures are products, byproducts or reactants con-
property line, ft; E = energy of explosion of the RHS; 24 = taining functional groups in Table 2, facility owners or opera-
scaled distance for the mass of TNT that results in a blast pres- tors are required to obtain heats of reaction (H). Table 3,
sure of 2.3 psi; and 1,024 = energy of explosion of TNT, cal/g. from the TCPA, presents data on threshold quantities for
The thresholds are based on the amounts of the RHS need- ranges of H, based on the TNT equivalency method.
ed to impact the public beyond an assumed property boundary Example 1: Bulk storage tank for cumene hydroperoxide.
of 328 ft (100 m) using an overpressure value of 2.3 psi. The Cumene hydroperoxide, an initiator in polymerization and
distance of 328 ft represents an average distance from the cov- catalytic cleavage in the manufacture of phenol and acetone,
ered process to the facilitys property line. The overpressure of is a well-known toxic chemical cited by the U.S. Dept. of

42 www.cepmagazine.org May 2006 CEP

 Table 2. Toxic Catastrophe Prevention Act (TCPA) Part D, Group II,
Functional groups that determine reactive hazard substance mixtures (4).

Groups Containing Carbon Groups Containing Nitrogen

1 -C-C- Acetylenic compounds 11 F-C-(NO2)2 Fluorodinitromethyl compounds

2 -C-C-M Metal acetylides 12 -N-M N-metal derivatives
3 -C-C-X Haloacetylene derivatives 13 -N=Hg+=N- Poly(dimercuryimmonium salts)
N=N Diazirines 14 -N-NO2- N-nitro compounds
\/
C 15 =N+-N-NO2 N-Azolium nitroimidates
4 -CN2 Diazo compounds 16 -C-N=N-C- Azo compounds
5 -C-N=O, -N-N=O Nitroso compounds 17 Ar-N=N-O-R Arenediazoates
6 -C-NO2, Ar-NO2, Nitroalkanes, C-nitro and 18 ArN=N-S-Ar Arenediazo aryl sulfides
Ar(NO2)n C(NO2)n, Nitroaryl and Polynitroaryl 19 Ar-N=N-O-N=N-Ar Bis(arenediazo) oxides
O2NC-CNO2 compounds
HC[OCH2C(NO2)3]3, Polynitroalkyl compounds 20 Ar-N=N-S-N=N-Ar Bis(arenediazo) sulfides
C[OCH2(NO2)3]4 Trinitroethyl orthoesters 21 C-N=N-N-C Trizenes
7 -C-O-N=O Acyl or alkyl nitrites l
R
8 -C-O-NO2 Acyl or alkyl nitrates (R=H, CN, OH, NO)
9 >C-C< 1,2-Epoxides 22 -N=N-N=N- High-nitrogen compounds
\/ -N=N-N=C- Tetrazoles
O
28 -N3 Azides (acyl, halogen, nonmetal, organic)
10 MC=NO Metal fulminates or aci-nitro salts,
C=N-O-M oximates 29 C-N2+-O- Arenediazonium oxides

40 -(CH-CH-)n- Polymerization alkene monomers 30 -C- N +S-

2 Diazonium sulfides and derivatives,
Xanthates
31 N+-HZ-, N+EOn- Hydrazinium salts, oxosalts of
Groups Containing Oxygen nitrogenous bases
23 -C-O-O-H, Alkylhydroperoxides, peroxyacids 32 -N+-OH Z- Hydroxylaminium salts
R-CO-O-OH 33 -C-N2+Z- Diazonium carboxylates or salts
24 -C-O-O-C-, Peroxides (cyclic, diacyl, dialkyl), 34 [NMetal]+Z- Amminemetal oxosalts
-CO-O-OR peroxyesters
35 Ar-Metal-X Halo-arylmetals, haloarenemetal
25 -O-O-M, EOO-, X-Ar-Metal p-complexes
MOO- Metal peroxides, peroxoacid salts
36 -N-X Halogen azides
26 -O-O-E Peroxoacids, peroxyesters XN3 N-halogen compounds
27 H3NCr-OO- Amminechromium peroxocomplexes -C-N-C- N-haloamides
ll l ll
39 -O-X Hypohalites O XO
XOn Halogen oxides 37 -N-F2 Difluoroamino compounds
-Cl-O3 Perchloryl compounds -C(NF)NF2 N,N,N-trifluoroalkylamidines
ClO2- Chlorite salts
R-O-Cl-O3 Alkyl perchlorates 38 N-O- N-O compounds
RN+H3ClO4- Aminium perchlorates
41 -(C-C-N-)n Polymerization amide monomers Abbreviations:
ll
O Ar = aromatic (benzene); M = metal; R = organic chain;
X = halogen; E = nonmetal; Z = anion; n = integer variable;
42 -(C-C-O-)n Polymerization ester monomers all other abbreviations are for the element symbols from
ll
O the periodic table of elements
43 S2O4= Dithionites

Table 3. Threshold quantities for reactive hazard

Transportation (DOT), New Jersey Dept. of Environmental substance mixtures based on heat of reaction (4).
Protection (DEP), U.S. Environmental Protection Agency
Heat of Reaction, cal/g Threshold Quantity, lb
(EPA), and National Fire Protection Association (NFPA).
100 H 200 13,100
Furthermore, it has caused many industrial thermal runway 200 H 300 8,700
incidents due to its intrinsically, highly unstable peroxy 300 H 400 6,500
function group (OO) (2, 6). 400 H 500 5,200
500 H 600 4,400
To avoid unexpected reactions, the amount of cumene 600 H 700 3,700
hydroperoxide in the storage tank should be maintained 700 H 800 3,300
below its threshold quantity of 2,500 lb (Table 1). The 800 H 900 2,900
900 H 1,000 2,600
threshold quantity is defined as the amount in a process at H 1,000 2,400

CEP May 2006 www.cepmagazine.org 43

Safety

Table 4. Compatibility chart for hydroxylamine and selected transition metals.

any time or the amount gener- Substance Hydroxylamine Iron Chromium Cobalt Copper Manganese
ated by a process within 1 h. Hydroxylamine 102,105,107 A6,B5,C1 A6,B5,C1 A6,B5,C1 B5,C1 B5,C1
Example 2: Distance to Iron A6,B5,C1 101,107,108 NR NR NR NR
overpressure endpoint for Chromium A6,B5,C1 NR 108 NR NR NR
styrene-acrylonitrile (SAN) Cobalt A6,B5,C1 NR NR 108 NR NR
copolymers. A RHSM and its Copper B5,C1 NR NR NR NR
threshold quantity can be decid- Manganese B5,C1 NR NR NR NR 108
ed based on its heat of combus- NR = No reaction
tion or decomposition. Styrene- A6 = Explosive due to vigorous reaction or reaction products may produce detonation
acrylonitrile (SAN) is made by B5 = Flammable gas generation
C1 = Heat generation by chemical reaction, may cause pressurization
the copolymerization of styrene 101 = Highly flammable 102 = Explosive 105 = Strong reducing agent
(H2C=CH-phenyl) and acry- 107 = Water-reactive 108 = Air-reactive
lonitrile (CH2=CHC=N), a
reaction that meets Table 2s criterion 40, polymerization are widely used in industry, with an annual manufacturing
alkene monomers. The heat of reaction for this intended capacity of around 800,000 tons worldwide. Since 1999,
copolymerization is 261 kcal/mol with a 70:30 feed- hydroxylamine was involved in two fatal explosive acci-
weight ratio of styrene and acrylonitrile. For a reactor filled dents in the U.S. and Japan, and has drawn significant
with 8,500 lb of SAN, the distance to the 2.3-psi overpres- attention in the field of process safety engineering. Due to
sure endpoint is estimated by rearranging Eq. 1: its chemical structure, H2N-OH, both the nitrogen and
oxygen atoms tend to donate their long pairs to transition
D = 24[8,500(261/1,024)]1/3 = 310.5 ft metals. As shown in Table 4, in the presence of transition
metals, hydroxylamine may ignite and a violent explosion
Equation 1 can be used to determine the threshold may occur due to an increase in pressure.
quantity of SAN: Users should be aware of the limitations of the NOAA
Reactivity Worksheet. The worksheet was originally devel-
TQ = (328/24)3(1,024/261) = 10,015 lb oped from A Method for Determining Hazardous Waste
Compatibility, a manual prepared by the Hazardous
The threshold quantity can also be estimated quickly from Materials Management Section of the California Dept. of
Table 3. The values in Table 3 are calculated using Eq. 1 Health Services for the EPA in 1980. Approximately 1,650
with the largest heat of reaction to incorporate worst-case chemicals were assigned to different reactive groups. Note
scenario analysis. For example, if the heat of reaction is 261 that a substance can belong to more than one reactive
kcal/mol, locate the appropriate row, 200 H 300, to group; for example, a metallic peroxide can belong to both
find that the threshold quantity is 8,700 lb. This value (8,700 the metal group and the peroxide group. NOAA expanded
lb) is calculated using Eq. 1 with H = 300 kcal/mol. the reactive groups and added many new substances, as
well as case histories and reactivity information. However,
NOAA Chemical Reactivity Worksheet due to the group-wise classification of reactive chemicals,
Approximately 36% of the incidents reported to the CSB determining the reactivities between hydroxylamine and dif-
were due to chemical incompatibility in the bulk storage, ferent transition metals is not conclusive.
handling and use of chemicals. The Chemical Reactivity Note that searching for a chemical by its Chemical
Worksheet provided by NOAA is a valuable screening tool Abstract Service Registry Number (CAS Number) is more
for identifying potential chemical incompatibilities using a efficient than searching by name. For example, searching
binary interactivity matrix. Free NOAA Chemical Reactivity simply for iron produced 41 results, while searching using
Worksheet software for both Windows and Macintosh is irons CAS Number, 1439-89-6, produced only one result.
available for download from the NOAA website (5).
The worksheet contains a database of more than 6,000 Brethericks Handbook of
common hazardous chemicals. Potential hazards can be iden- Reactive Chemical Hazards
tified if they are water-reactive, air-reactive, and incompatible Brethericks Handbook (6) has, for decades, been
in chemical mixtures. Polymerization, oxidization and de- regarded as a key reference work on reactive chemical
composition also are considered chemical reactive hazards. hazards. The fifth edition foreword by Trevor A. Kletz
Example 3: Chemical compatibilities of hydroxylamine notes, Those of us who have been working in the safety
with transition metals. Hydroxylamine-related products field for many years have seen the same accidents repeat

44 www.cepmagazine.org May 2006 CEP

themselves with distressing regularity. We welcome, there-
fore, every attempt to bring together scattered information
on any aspect of safety and make it readily available.
This two-volume handbook, now in its sixth edition,
contains hazard information for more than 5,000 elements,
compounds and mixtures. Chemicals can be identified by
their International Union of Pure and Applied Chemistry
(IUPAC) names, CAS Registry Numbers, empirical for-
mula, or structure formula. Volume 1 contains specific
chemicals (e.g., benzyl azide), while Volume 2 contains
general chemical categories (e.g., azides). A CD-ROM
version is also available, allowing users to modify the
results, customize the database sets, and bookmark entries.
Example 4: How to prevent possible hazards of zirconium
metal dust. Zirconium dust is highly combustible it ignites
at room temperature and has a great affinity for oxygen at
higher temperatures. According to Brethericks Handbook, 43
zirconium fire and explosion incidents have been reported;
most occurred under the conditions of pyrophoric finely
divided metal, moisture and friction, occasionally accompa-
nied by static sparks from polyethylene bags. The handbook
gives five suggestions for the safe handling of zirconium:
1. Exclude air or oxygen by blanketing with inert gases.
2. Exclude water, vapor other contaminants or oxidants.
3. Control particle size.
4. Limit the amount of powder handled.
5. Limit exposure of personnel.
Safe handling, transportation and storage information is
also provided for different types of zirconium mixture
powders to avoid ignition in air. Volume 2 of the hand-
book provides a thorough review of dust explosion inci-
dents with over 30 references.
Material Safety Data Sheets
The U.S. Occupational Safety and Health Admin-
istrations (OSHA) Hazard Communication Standard
requires companies that manufacture or distribute haz-
ardous chemicals to provide MSDSs to their customers.
The MSDS is an essential tool for identifying reactive
chemical hazards. If an MSDS is not available, it may be
obtainable from various MSDS websites, such as the
Cornell (http://msds.ehs.cornell.edu/msdssrch.asp) or
Sigma-Aldrich (www.sigmaaldrich.com) websites.
The required MSDS information can be in any format.
With approximately 650,000 hazardous chemical products
in the U.S., the accuracy and completeness of MSDSs
need to be improved. A study of 150 MSDSs found that
only 11% were correct in all the assessed areas, and 51%
had missing or incorrect information (7). Thus, the MSDS
should not be used as the primary source for identifying
reactive chemical hazards.
Additional screening resources
The following tools and resources are also useful for
identifying reactive chemical hazards:
Essential Practices for Managing Chemical Reactivity
Hazards (8) this free Center for Chemical Process Safety
(CCPS) Concept e-book is available free online through a
collaboration of CCPS, OSHA, EPA, the American
Chemistry Council (ACC), the Synthetic Organic Chemical
Manufacturers Association (SOCMA), and Knovel Corp.
Process Safety Beacon published by CCPS, this
free monthly electronic newsletter is reprinted in CEP each
month, and is also available in over a dozen languages
(www.aiche.org/ccps/publications/beacon/index.aspx)
The U.S. Coast Guards (USCG) Chemical Hazard
Response Information System (CHRIS) database
(www.chrismanual.com)
NFPAs Fire Protection Guide to Hazardous
Materials (www.nfpa.org)
Saxs Dangerous Properties of Industrial Materials,
11th ed., by Lewis, R. J., Wiley Interscience (2004).
Wileys Guide to Chemical Incompatibilities,
2nd ed., by Pohanish, R. P. and S. A. Greene, Wiley
Interscience (2003)
DS51E ASTM Computer Program for Chemical
Thermodynamic and Energy Release Evaluation
Version 8.0 (CHETAH) (www.astm.org).
Examining the 167 CSB incidents
Partial details of the 167 reactive chemical incidents
reviewed by the CSB are available in a spreadsheet on the
boards website (http://www.csb.gov). Information such as
company, location, chemicals and equipment is available. It
is difficult to verify whether all the incidents would be cov-
ered under TCPA due to a lack of sufficient information.
To study the efficacy of the TCPA lists as a guide to haz-
ard identification, the chemicals and functional groups in
Tables 1 and 2 were used as hazard indicators for both single
compounds and mixtures involved in the 167 CSB incidents.
It should be noted that we do not claim that such a regula-
tion would have prevented incidents. In addition, the list of
RHSM applies to intentional chemistry, and to be covered
under TCPA a facility has to exceed the threshold quantity in
Table 3. Nevertheless, this approach is justified since the
presence of functional groups is probably a reasonable indi-
cator of hazard, regardless of the nature of the process.
Of the 167 incidents, in 15 cases either the chemicals
were unknown or could not be determined, so 152 incidents
could be evaluated. Of these, the TCPA lists of RHS chemi-
cals and RHSM functional groups correctly identified the
hazards in 86 incidents. In 66 cases, the reactive hazard
potential was unrecognized based on these tables.
CEP May 2006 www.cepmagazine.org 45
Safety

Table 5. Cumulative results of four screening methods.

Combining the
Screening Cumulative Non- Cumulative
screening methods
Step Method Hazardous Hazardous hazardous Unrecognized Unknown Total Table 5 and Figure 2
present the results of apply-
1 TCPA 86 86 N/A 66 15 167
ing the four screening meth-
2 NOAA 37 123 5 24 15 167
3 Brethericks 17 140 N/A 12 15 167
ods sequentially to the 152
4 MSDS 6 146 2 4 15 167 incidents for which informa-
tion was available.
TCPA = Toxic Catastrophe Prevention Act lists of Reactive Hazard Substances and Reactive Hazard The TCPA and NOAA
Substance Mixtures (4) worksheets were used first
NOAA = National Oceanic and Atmospheric Administration Chemical Reactivity Worksheet (5) because they are available
Brethericks = Brethericks Handbook of Reactive Hazards (6)
free of charge and are easy
MSDS = Material Safety Data Sheets
to research. As noted, the
TCPA lists correctly identi-
fied the potential reactivity hazards for 86 of the incidents.
Hazardous Unrecognized
The NOAA worksheets identified the hazards for 37 of the
remaining 66 incidents.
Next, Brethericks Handbook was used to investigate
150 Brethericks MSDS 6 the reactivity problems of the 29 remaining incidents, of
12 MSDS 6
NOAA which it successfully screened 17.
Brethericks Brethericks
29 17 17 For the 12 remaining incidents, reactivity behavior was
identified for six from MSDS information.
The six incidents for which no reactivity problems were
Incidents

TCPA NOAA NOAA NOAA

100 66 37 37 37 indicated involved the following chemicals (the number in
parenthesis corresponds to the number in the CSB report):
light oils, hydrogen and catalysts (49)
chloralkyl phosphate (90)
sodium metabisulfite and acid (115)
TCPA TCPA TCPA TCPA methylacrylic acid (TMMA) (126)
50 86 86 86 86
aniline (141)
super phosphate acid (154).

0 YEN-SHAN LIU is pursuing her PhD at the Mary Kay OConnor Process
TCPA TCPA + TCPA + TCPA + Safety Center in the Dept. of Chemical Engineering at Texas A&M
NOAA NOAA + NOAA + Univ. (E-mail: ysliu@tamu.edu). Her research focuses on developing
Brethericks Brethericks an advanced nanocalorimetry system for process safety, homeland
+ MSDS security and rapid material characterizations. She obtained her BS in
chemical engineering from Mississippi State Univ.
Figure 2. Cumulative results of the sequential application of the WILLIAM J. ROGERS is laboratory director of the Mary Kay OConnor Process
four screening methods to 167 incidents investigated by the CSB. Safety Center and a research scientist at Texas A&M Univ. (Phone: (979)
845-3330; E-mail: wjrogers@tamu.edu). His research interests include
thermal behavior of chemical processes, reaction system hazard
characterization, experimental design, and computational chemistry for
When the NOAA Reactivity Worksheet was applied to
property and chemical behavior estimations. He holds a PhD in physical
the 167 CSB incidents, 105 incidents were identified as chemistry from Ohio State Univ.
hazardous, 10 as non-hazardous, and 52 as unknown or M. SAM MANNAN is a professor of chemical engineering and director of
the Mary Kay OConnor Process Safety Center at Texas A&M Univ.
unrecognized, according to the following definitions:
(College Station, TX 77843-3122; Phone: (979) 862-3985; Fax: (979)
hazardous: potential reactive chemical hazards 845-6446; E-mail: mannan@tamu.edu; Website: http://process-
non-hazardous: not potential reactive chemical hazards safety.tamu.edu). An internationally recognized expert on process
safety and risk assessment, his research interests include hazard
unknown: insufficient information
assessment and risk analysis, modeling of flammable and toxic gas
unrecognized: chemicals not in the database cloud dispersion, inherently safer design, resilient engineered
A spreadsheet containing the detailed analyses is avail- systems, reactive chemicals and runaway reactions, aerosols, and
abnormal situation management.
able from the authors on request.

46 www.cepmagazine.org May 2006 CEP

Concluding thoughts
Lessons learned from past incidents can
be used to prevent similar events from
happening in the future. However, a key
issue in managing hazardous chemicals is
the use of a more-comprehensive screen-
ing methodology for complex reactions
and processes.
The TCPA and NOAA information can
provide fast and reliable screening of
potentially hazardous chemicals, but those
databases contain only widely used chemi-
cals. Brethericks Handbook has detailed
information for reactive hazards and
records of past incidents involving the
chemicals, while MSDSs contains impor-
tant, but not detailed, information.
A combination of these screening meth-
ods can improve process safety while
avoiding the expense of detailed
hazard assessments. CEP
www.cepmagazine.org or Circle No.122
Literature Cited
1. Bretherick, L., and P. G. Urben, Brethericks Handbook of Reactive
Chemical Hazards, 6th ed., Butterworth-Heinemann, Jordan Hill, Oxford
(1999).
2. U.S. Chemical Safety and Hazard Investigation Board (CSB), Improving
Reactive Hazards, CSB, Washington, DC, available at www.csb.gov/reports
(2002).
3. Saraf, S. R., Molecular Characterization of Energetic Materials, PhD dis-
sertaton, Texas A&M Univ., College Station, TX (2003).
4. New Jersey Dept. of Environmental Protection, Toxic Catastrophe
Prevention Act (TCPA), N.J.A.C. 7:31: Consolidated Rule Document, avail-
able at www.nj.gov/dep/rpp/download/conrulerev5a.pdf (revised Apr. 26,
2004).
5. National Oceanic and Atmospheric Administration (NOAA), Chemical
Reactive Worksheet, NOAA, Washington, DC, available at
http://response.restoration.noaa.gov/chemaids/react.html.
6. Urben, P. G., Brethericks Reactive Cehmical Hazards Database, Version
3.0 CD-ROM edition, Butterworth-Heinemann, Jordan Hill, Oxford (1999).
7. Kolp, P., et al., Assessment of the Accuracy of Material Safety Data
Sheets, American Industrial Hygiene Association Journal, 56 (2), pp.
178183 (1995).
8. Johnson, R. W., et al., Essential Practices for Managing Chemical
Reactivity Hazards. Wiley-Interscience, electronic copy available free of
charge at http://info.knovel.com/ccps/ (2003).
CEP May 2006 www.cepmagazine.org 47