A Quantitative Approach to Determination of NFPA

Reactivity Hazard Rating Parameters

T. C. Hofelich, B. A. Prine, and N. E. Scheffler
The Dow Chemical Company, Midland, MI 48667
7be National Fire Protection Association (NFPA) has
developed a system for labeling short-term acute hazards of materials infire, or emergency situations [lj. The
procedures for obtaining the hazard rating for health
and flammability are based upon measured quantities
&?/, but the basis for assigning reactivity ratings are
largely qualitative hl. 7bis paper proposes a quantitative approachfor assigning reactivity hazard ratings.

INTRODUCTION

NFPA rating symbols are widely used throughout the

chemical industry. They are typically found on storage
tanks and vessels and are frequently listed on supplier Material Safety Data Sheets. These numbers are also used in
the Dow Fire and Explosion Index (F&EI) calculation system D] to determine the material factors. The Dow F&EI
calculation system is widely used throughout the chemical
industry to rank relative hazards in chemical processing
systems. The results are used by the insurance industry to
determine rates and by chemical engineers to define plant
layouts. The assignment of correct reactivity rating values
has wide ranging implications.
NFPA reactivity rating number

The NFPA reactivity rating parameter is used to describe

more than one kind of reactivity potential (thermal stability, interaction with water and gas generation potential in
either of the preceding cases). The thermal stability guidelines are described both qualitatively and in a manner
employing differential scanning calorimetry (DSC) data [I].
The water reactivity potential is described in a strictly qualitative manner and so are the gas generation hazards. Each
of these aspects of reactivity shall be addressed in turn.

and rate of energy which could be released by a given

amount of material under a given set of conditions (e.g.,
temperature).
We introduce the term Instantaneous Power Density
(abbreviated IPD). The value is calculated as the zerothorder rate of energy release [in watts, per volume of material (in mL)]. The value may be estimated from combination of the estimated initial (i.e., zeroth order) rate of
decomposition of a material at a given temperature, the enthalpy released for that decomposition and the density of
the material. This paper summarizes how these parameters
are obtained from common laboratory measurements and
develops a correlation of IPD at 250C with reactivity rating
values for some commonly produced organic materials.

WATER REACTIVITY

Heat of mixing tests between a chemical and water can

provide a measure of how vigorous the reaction with water will be in a fire fighting scenario. There are two scenarios to consider here: a material that rapidly releases heat
on contact with water and a material that rapidly releases
heat and gas on contact with water, this latter case is not
considered here, but will be the subject of future research.
Proposed Rationale
A fire fighting situation is a highly dynamic scenario. A
fire that deals with uncontrolled chemicals starts with a situation involving concentrated chemical exposures and
moves to a scenario of chemicals diluted in an excess of
water. For water reactive chemicals, the greatest hazard is
in the early phases where the chemical is initially being
contacted with water. Hazard evaluations used in the development of these guidelines are based on 1:l mixtures of
a chemical with water.

THERMAL STABILITY

The guidelines currently suggest use of DSC detection

temperatures. This quantity alone is insufficient for the accurate appraisal of thermal hazards and may be a strong
function of the DSC operating parameters b].

Proposed Quantitation
It would be most desirable to develop a reactivity
parameter to reflect, as accurately as possible, the amount

Process Safety Progress (Vol.16, No.3)

EXPERIMENTAL/ CALCULATIONAL DETAILS

Kinetic Analysis for Correlating Reactivity Ratings

All of the DSC data obtained for this study were carried
out in flame-sealed glass capillaries under nitrogen atmosphere, as described in reference [ 71. Kinetic analysis of the
DSC curves was carried out as described in Hofelich et ul.
[S].
Fall, 1997 121

Details for Calculation of IPD

Rate = ConcorderX A,,, X eKEdRT

Instantaneous power density (IPD) is calculated as the

product of the enthalpy of decomposition/reaction and the
initial rate of reaction, determined at a specified temperature. This quantity represents the amount of heat energy
per unit time per unit volume (W/mL) that a material will
initially give at a specified temperature. The values which
make up the power density may be obtained from thermodynamic tables, calculations and/or experimental measurements. The values are most easily obtained from appropriate measurements using differential scanning
calorimetry [4] o r adiabatic reaction calorimetry Is]. This
rate expression represents the initial rate of reaction where
the decrease in concentration of the material as a result of
the decomposition/reaction has not progressed to a significant level ( < 5%). This allows one to use the initial concentration of the material in the simplified rate expression.
The initial rate of decomposition of the material at 250C
may be calculated using the following Arrhenius expression where R is the universal gas constant ( = 8.314J/(mol
K)) and T is taken as 523K:

--&($)

Order

1 -Order

(5)

The power density is given as the product of this decomposition arid the enthalpy of decomposition:

IPD = - H X Rate

W =J X g
UNITS: mL

Rate = 0

7g 9

1-Order

The power density is given as the product of this decomposition and the enthalpy of decomposition:
IPD= - A H X Rate

UNITS:

W
mL

-=-

JX
g
g
mLx s

IPD= -(-340)

X0.79

W
IPD= 2 7 0 ~
Correlation of IPD at 250C with Reactivity Rating

Rate = Concord" X A P R E
X eKEdRT
UNITS:

Order

mLXs

In order to clarify the calculation of instantaneous power

density, a sample calculation follows.
Differential scanning calorimetry was carried out followed by kinetic analysis of the curves. The following parameters were obtained for a material of interest:

Thirty materials were chosen from a set of the top 50

produced chemicals in the world. These materials were
chosen based upon availability of DSC and ARC information in our archives. A kinetic analysis of the calorimetric
traces yielded Arrhenius parameters and enthalpies of decomposition/reaction selected based upon the fitting technique described above. Upon inspection of all of the data
and attempts at correlation at several temperatures, we
found a reasonable correlation between reactivity rating
values and IPD at 250C. This temperature is not unreasonable if one considers the premise that reactivity rating Values are intended to be used for immediate, first response
by fire fighters. Table 1 shows the values of predicted vs.
currently assigned values for the NFPA Reactivity number.
Table 2 shows how IPD at 250C relates to the NFPA Reactivity Parameters.
Experimental Conditions for Water Reactivity

The Two Drop Calorimeter has been briefly described in

a previous publication [ 81. Experiments were typically
conducted using a 1:l ratio (v/v). Gas generation can be
monitored using this technique.

Enthalpy of decomposition ( A H ) :

- 340 J/g

Calculations for Water Reactivity

Arrhenius activation energy (Ea) :

152 kJ/mol

Arrhenius pre-exponential (A pRE) :

1.60 x 10+'5

Reaction order (n) :

The heat of mixing of a material with water (1:l

weightweight) is used directly in the calculation of the water reactivity parameter. The heats may be obtained as described in Hofelich et al. [S].Note is also made if any gas
is evolved upon mixing with water. The reactivity parameter is selected using Table 2.

Initial concentration of material,

or density of pure material (Conc.) :

0 3 0 g/mL

s-1

It is desired to estimate IPD at 250C. The initial rate of

decomposition of the material at 250C may be calculated

using the following Arrhenius expression where R is the
universal gas constant ( = 8.314 J/(mol K)):
122

Fall, 1997

RESULTS AND DISCUSSION

A summary plot of predicted NFPA reactivity rating value

vs. those listed in Tables 1 and 3 is shown in Figure 1. A
statistical analysis shows that for the 38 data points, the average difference was 0.17. The greatest outlier in the plot is
hydrogen peroxide (40-60%). Reference [I51lists the ma-

Process Safety Progress (Vol.16, No.3)

TABLE 1. Materials Used in Correlation

Material

IPD-250

Dioctyl Phthalate
Ethanolamine
Ethyl Alcohol
Isopropyl Alcohol
Methylene Chloride
Methyl Ethyl Ketone
Propylene Glycol
Acetone
Benzene
n-Butyl Alcohol
Ethyl Benzene
Ethylene Glycol
Phenol
Toluene
Bisphenol A
Maleic Anhydride
Acetic Acid
Cumene
DURSBAN*
Hydrogen Peroxide
(40 to 60%)
Methyl Methacrylate
1,3-Butadiene
Acrylonitrile
Ethylene
Styrene
DOWICIL** 75
Hydroxylamine
Chloropicrin
Cumene Hydroperoxide
Di-tert-butyl Peroxide

NFPA Prediction Scheme

Predict Current

+
+
+
+
+
+
+
+
+
+

O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE + 00
O.OOE 00
O.OOE 00
O.OOE 00
O.OOE 00
8.06E - 03
O.OOE 00
O.OOE 00
5.27E 00
6.OOE 02

+
+
+
+
+
+
+
+

+
+

3.48E 01
8.08E 00
1.62E - 01
8.20E - 02
5.73E 00
1.68E 02
2.43E 02
3.96E 02
1.64E 04
1.39E 04

+
+
+
+

+
+

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
3

0
0
0
0
0
0
0
0
0
0
0
0
0
0
1

2
1
1
1
1
3
3
3
4
4

2
2
2
2
2
2
3
3
4
4

Number of values =

38

Pt

...*

0.5

I
1.5

2.5

3.5

Current Ratting

1
1
1
1
1

5
5

20
18
16
14
12
10

8
6
4
2
0

-4

-3

-2

-1

Actual-Predict

FIGURE 2

IDURSBAN is a trademark of DowElanco.

**DOWCIL LS a trademark of the Dow Chemical Company.

terial with a reactivity rating of 1 while the IPDZ5,predicts

a reactivity rating value of 3. A summary of the errors is
shown in the histogram in Figure 2.
Potential problems, caveats, challenges
Thermal Stability

The use of IPD as a parameter to obtain reactivity values

has its strongest advantage in the fact that it is based upon

Histogram of errors from prediction of NFPA

reactivity numbers.

experimental data. These data may be obtained from a wide

variety of sources: chemical stability tests, thermodynamic
tables, DSC data, adiabatic or other calorimetric methods.
One potential problem is in the extrapolation of rate data.
it is most desired to determine rate parameters in the temperature region of interest, here, taken to be 250C. This
temperature region is easily studied using the DSC and ARC,
for example. If stability data are taken at other temperatures and extrapolated, one must be aware that a possible
change in mechanism may occur between the measured

TABLE 2. Reactivity Rating Parameters for Thermal Stability and Water Reactivity
Reactivity
Rating

Instantaneous
Power Density at 250C

1,000W/mL or greater
At or above 100 W/ml
and below 1,000W/mL
At or above 10 W/mL
and below 100 W/mL
At or above 0.01 W/mL
and below 10 W/mL
Below 0.01 W/mL

3
2
1

0
~~

Water Reactivity
Guidelines for Chemicals
Less Volatile than Water

Descriptor for
Water Reactivity

(not applicable)
> 2508 J/g (600 cal/g)

(not applicable)
Explosive

418 to 2508 J/g (100 to 600 cal/g)

Violent

125 to 418 J/g (30 to 100 cal/g)

Vigorous

< 125J/g (30 cal/g>

Non-reactive

Process Safety Progress (Vol.16, No.3)

Fall, 1997 123

~~

TABLE 3. Predicted vs. Actual NFPA Reactivity Numbers

for Water Reactivity
Chemical
~~~~

~~

Predicted

Actual

0
0

0
0

0
0

Diethanolamine/water
Phosphoric acid (75%)/water
Potassium hydroxide (45%)/water
Sodium hydroxide (40%)/water
Sodium hydroxide (50%)/water
Sulfuric acid/water
Phosphorous pentachloride/water
Thionyl chloride/water
Titanium tetrachloride/water
Triethyl aluminum/water

1
1
1
1
2

1
1
2
2
2
2

temperature and 250C. IPD values extrapolated from different mechanistic paths may not yield reasonable reactivity rating values and may give a false sense of safety. While
IPD at 250C appears to work reasonably well for estimating NFPA reactivity numbers, perhaps it would be best if
IPD at process temperatures be used in a general estimation of process hazard.
Another challenge appears in the form of considering all
of the energy which may be generated in a chemical decomposition. Many systems decompose not only with the
release of heat but also of gas which may perform pV
(pressure-volume) type work on the surroundings. This energy and its rate of release should also be taken into account and will be the subject of a future paper as work in
this area continues.
It should be noted that kinetic data are not always easy
to obtain. One must take care to critically review data from
reactions where kinetic complications are involved; e.g.,
autocatalysis or multiple reaction mechanisms. For kinetic
analysis results, a peer review by someone who is experienced in thermokinetic analysis is highly recommended.
Water reactivity

Guidelines to define relative amounts of hazards from

mixing with water are listed in Table 2. The rationale for
selecting the break points in Table 2 were as follows. Thirty
cal/g generate sufficient vapor pressure due to water in a
1:1 scenario. If the system is closed, mechanical problems
could ensue. One hundred cal/g will bring most 1:l scenarios to the point where water will start to boil. Four hundred cal/g will raise most scenarios to the point where all
of the water and many potential starting chemicals will be
completely vaporized. An additional 300 to 700 cal/g [ZO]
will almost certainly result in hypergolic ignition (that
would be 700 to 1100 cal/g when one half of the mixture
is water).
Water reactivity data from the Dow archives was compared to NFPA ratings. A summary of predicted NFPA reactivity rating value vs. those listed in reference [ I S ]is shown
in Table 3. Data for eight materials are plotted in Figure 1.
There was agreement on five of the eight. NFPA ratings do
not clearly address concentration effects in the definition of
their ratings and this leads to ambiguity when evaluating
data. Additionally, many of the water reactive materials
listed in NFPA (Appendix A) do form gases on contact with
water and how to address this still needs to be defined.
124 Fall, 1997

The potentials discussed above do not consider the formation of gases. Gases that form in a fire situation can be
condensable, non-condensable, water soluble, flammable
or oxidizing. The stoichiometry of the gas producing reactions will also have a bearing on the hazard development
scenario. Only reactions that produce gas immediately on
contact with water should be considered. These factors
need to be considered when assigning the reactivity rating
with adjustments being made for systems with unusual gas
hazards.

~~

~~

APPENDIX A CHEMICALS DESIGNATED AS WATER REACTIVE

BY NFPA
Chemical
Acetyl chloride
Ally1 trichlorosilane
Aluminum chloride
Amy1 trichlorosilane
Benzoyl chloride
Boron trifluoride etherate
Butyric anhydride
Calcium metal
Calcium carbide
Chlorosulfonicacid
Chromyl chloride
Diborane
Dichloroacetyl chloride
Diethyl aluminum chloride
Diethyl aluminum hydride
Diethylcarbamyl chloride
Diethyl telluride
Diethyl zinc
Diisobutyl aluminum hydride
Dichloroethyl aluminum
Ethyl aluminum sesquichloride
Fluorine
Gallium phosphide
Iron carbonyl
Isobutyric anhydride
Lithium metal
Methyldichlorosilane
Methylene diisocyanate
Methyl isocyanate
Methyl trichlorosilane
Phosphorous oxychloride
Phosphorous pentachloride
Phosphorous pentasulfide
Phosphorous tribromide
Phosphorous trichloride
Sodium hydride
Sulfur chloride
Tin tetrachloride
Titanium tetrqchloride
Trichlorosilane
Triethyl aluminum
Trimethyl aluminum
Vanadium tetrachloride
Vinyl trichlorosilane
Zirconium tetrachloride

Rating
2
2

2
2
1
1
1

2
2
2
2

3
1

3
3
2

3
3
3
3
3
4
2
1
1
2
2
1

3
2
2
2
2
2
2
2
2
1

2
2

3
3
2
2

Process safety Progress (~01.16,N0.3)

CONCLUSIONS

These two proposals can provide data based assessments to define NFPA reactivity hazard ratings for many
chemical systems and is an improvement over the current
art using DSC onset temperatures for thermal stability assessment. Further work is planned to extend the concepts
to consider gas-generating reactions, as well as looking into
ways IPD may be used in an overall, quantitative hazard
rating. The concepts described herein have been presented
to (March 1996) and accepted by the NFPA Technical
Committee on Classification and Properties of Hazardous
Chemical Data and will appear in the next publication of
NFPA-704.
ACKNOWLEDGMENTS

We wish to acknowledge helpful discussions from Bruce

Powers, Gary Phillips, Bill Heitzig, Larry Whiting, Holly
Ferguson and Joerg Steinmetzer.

LITERATURE CITED

1. Standard System for the Identqication of the Fire Hazards of Materials, National Fire Protection Association
(NFPA), Guideline 704 (1990).
2. National Fire Protection Associations List of Chemicals
Designated as Water Reactive (see reference 1).
3. Hofelich, T. C., and R. C. Thomas, International
Symposium on Runaway Reactions, American Institute
of Chemical Engineers, New York, p. 74 (1989).
4. ASTM Standard E698-79, Standard Test Method for Arrhenius Kinetic Constants for Thermally Unstable Materials, (1979).
5. Townsend, D., and J. TOU, Themzochim Acta, 37, 1
(1980).

Process Safety Progress (Vo1.16, No.3)

6. Laidler, K. J., Chemical Kinetics, McGraw-Hill (1965).

7 . Whiting, L. F., M. S. LaBean, and S. S. Eadie,
Evaluation of a Capillary Tube Sample Container for
Differential Scanning Calorimetry, 7&emzochemicu
Acta, 136 (1988).
8. Hofelich, T. C., D. J. F d p , and J. B. Powers, The
Determination of Compatibility via Thermal Analysis
and Mathematical Modeling, Process Safety Progress,
13,p. 277 (1994).
9. Dows Fire & Explosion Index Hazard Classqication
Guide, 7th ed., American Institute of Chemical Engineers, New York (1994).
10. Yoshida, T., Safety of Reactive Chemicals, Elsevier
Science Publishers, New York (1987).
11. Buback, M., Makromol. Cbem., 181, p. 373 (1980).
12. Latino,M. A., Procedure for Determining the Distribution Ranking Index, Proceedings of the 29th Annual Loss Prevention Symposium, American Institute of
Chemical Engineers, New York (1995).
13. Schumb, Walter C., Charles N. Satterfield, and
Ralph L. Wentworth, Hydrogen Peroxide, ACS
Monograph 128, Reinhold Pub. Corp., New York
(1955).
14. Schmidt, K. H., T. E. Lee, J. H. Mitchen, and E. E.
Spited, How to Cope with Aluminum Alkyls, H y
drocarbons Processing (November 1978).
15. Hazardous Chemicals Data, National Fire Protection
Association (NFPA) Guideline 49 (1994).
16. Guide to Fire Hazard Properfies of Flammable Liquids,
Gases, and Volatile Solids, National fire Protection Association (NFPA) Guideline 325 (1994).

Thispaper (50$ waspresented at the Fijth World Congress of Cbemical Engineering in Sun Diego, California on July 17, 1996.

Fall, 1997 125