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INTRODUCTION
WATER REACTIVITY
THERMAL STABILITY
Proposed Quantitation
It would be most desirable to develop a reactivity
parameter to reflect, as accurately as possible, the amount
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
--&($)
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
Enthalpy of decomposition ( A H ) :
- 340 J/g
152 kJ/mol
1.60 x 10+'5
0 3 0 g/mL
s-1
Fall, 1997
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
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
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
Violent
Vigorous
Non-reactive
~~
~~
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
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.
~~
~~
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
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
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).
Thispaper (50$ waspresented at the Fijth World Congress of Cbemical Engineering in Sun Diego, California on July 17, 1996.