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A Review of ASTM CHETAH 7.0 Hazard Evaluation Criteria
Summary
ASTM Committee E-27 has recently released Version 7.0 of the well- known CHETAH hazard
evaluation program. This is the first revision since Version 4.4, Second Edition was published in
1990. In this paper, we review CHETAHs hazard criteria and point out conceptual deficiencies
in criteria 2, 3, 4, 5, and 6.
Introduction
CHETAH incorporates very convenient means for using the Benson group contribution system
to estimate, from chemical structure alone, thermochemical data such as heat capacity, ideal gas
entropy, heat of formation, equilibrium constants and heats of combustion for a multitude of
compounds. The program is also very valuable in estimating the value of these themochemical
data for balanced reactions. It permits, as well, calculation of flammability limits for selected
gas mixtures.
In addition to the above features, CHETAH provides means for classifying chemical compositions
with respect to their potential for violent (explosive) self-reaction. In carrying out this function
CHETAH calculates the value of six hazard evaluation criteria, as follows:
[1600(2X + Y =2 Z)]
O B = (1)
M w
Where X is the number of atoms of carbon, Y is the number of atoms of hydrogen , Z is the
number of atoms of oxygen and M w is the molecular weight.
In the CHETAH manual the oxygen balance concept is attributed to W.C. Lothrup and C.R.
Handrick [1]. G. R. Handrick [2] and others report that oxygen balance was recognized in the
1930s; possibly much earlier. It was and remains a standard parameter in explosives design.
Lothrop and Handrick demonstrated a strong correlation between effective oxygen balance and
explosive performance for several classes of C H N O explosives. They neither recommended
nor mentioned use of oxygen balance as a hazard evaluation criterion. The five ranges of self-
reactivity hazard referred to in CHETAH Criterion 3 are not taken from Lothrop and Handrick.
OB as calculated in CHETAH by means of Equation 1 and evaluated according to the CHETAH
scheme is an unsatisfactory measure of reactivity hazard. For example, molecular oxygen is placed
at the boundary between the High and Medium hazard regions. Ozone is assigned exactly
the same ranking as molecular oxygen. Most commercial explosive compositions are ranked,
correctly, as oxygen balanced and of High hazard potential. But, water, carbon dioxide, and
a great many other inert compounds are also oxygen balanced and are assigned High hazard
rankings.
As it is based only on the empirical formula, the OB parameter is blind to isomerism, assigning
identical rankings to cyanates and fulminates, to inert glycolic acid and isomeric, explosive
peroxyacetic acid. Similar examples abound [3].
OB is obviously unsuitable for evaluating oxygen-free energetic compounds such as explosive
nitrides, azides, acetylene and acetylides, diazo compounds and others, but the OB formula
nevertheless produces values, and assigns explosive compounds of these classes incorrect Low
hazard rankings. This deficiency is of limited practical importance because few compounds of
the classes noted above can be evaluated in CHETAH.
Lothrop and Handrick were careful to distinguish between total oxygen content and effective
oxygen. It is only the latter, such as oxygen loosely bound in nitrate, nitro, peroxide, and similar
groups that can contribute to hazard potential. CHETAH fails to make this distinction.
CHETAH 7.0 carries a disclaimer stating: Experience has shown that the Oxygen Balance
criterion is useful only for C H N O compounds .... Nevertheless, the program produces an
oxygen balance value for every compound evaluated and this value is presumably included in
the calculation of Criterion 5, Overall Energy Release. In spite of the disclaimer noted above,
CHETAH 7 can produce faulty hazard rankings for C H N O compounds. Lothrop and Handrick
offer information on this point ([1], page 432). Here, Lothrop and Handrick discuss the influence
of what they termed auxoplosive groups as follows: As examples of such groups, one may take
hydroxyl, carbonyl, chloride ... etc. Not infrequently the presence of such groups affects oxygen
4
2
10M W
y= (2)
n
where y is (presumably) the ERE value, M is the Maximum Heat of Decomposition (Criterion
1), W is the weight of the composition 3 in grams and n is the number of atoms in the composition.
Squaring the value for enthalpy of decomposition stretches out the scale but, by itself, changes no
relative rankings. The factor W/n increases ERE values for compositions containing heavy atoms
and decreases ERE values for compositions containing much hydrogen. The practical effect is to
increase the relative hazard ranking of compounds containing heavy atoms.
Criterion 1 and Criterion 4 cannot both be generally valid.
Benson groups and 475 gas-phase molecules in the main CHETAH 7.0 data bank. In most cases,
evaluation of Criterion 6 is impossible for lack of data and the program returns the message
Cannot Be Determined.
On page 19 of the CHETAH 7.0 manual it is stated that, If the threshold plosive density (0.265)
is not exceeded, the program will print a statement Cannot Be Determined. In other words,
the same message is used to cover both situations noted above, although the value of the plosive
density has, in fact, been calculated and ranked in the latter case. This procedure emasculates
the plosive density system described in [4] by discarding all negative (non-plosive) rankings. In
fact, the plosive density system as described in this publication produces many false negatives,
i.e., it ranks many explosive compounds as non-explosive.
If the CHETAH 7.0 plosive density calculation produces a positive (plosive) ranking, the value is
reported, accompanied by the statement: ATTENTION! The Plosive Density Method is showing
a result of PLOSIVE and is known to be the most reliable method for classifying materials as
to their ability to decompose with violence. This statement is not universally true. Figure 1,
attached, is a copy of a CHETAH 7.0 calculation on nitric acid. Note that the user is influenced
to accept the Criterion 6 plosive ranking, even in the face of clear evidence (in Criterion 1) that
nitric acid is not subject to spontaneous exothermic decomposition and is not explosive. This is
not a singular case.
Criterion 6 also fails to correctly model systems consisting of a strong oxidizer such as nitric
acid, strong hydrogen peroxide, etc., and combustible matter. All such systems are characterized
by a maximum in the hazard potential at some critical ratio of oxidizer to fuel. Recognition of
this fact is vital to the safe handling of strong oxidizing agents. But, the plosive density system
downgrades the hazard ranking in direct proportion to the fuel added, completely missing one of
the valuable generalizations in chemical reactivity hazard management.
The plosive density system is based upon a radical view of explosive phenomena. No known
physical entities correspond to the terms plosophoric, auxoplosive, and the like. There are
only metastable compositions capable of rapid (explosive) spontaneous reaction. The assignment
of reactive hazard potential is the proper domain of thermochemistry and reaction kinetics, al-
though much remains to be done before hazard ranking from structure is practical and highly
dependable.
Conclusions
References
[1] W. C. Lothrop and G. R. Handrick. The relationship between performance and constitution
of pure organic explosive compounds. Chemical Reviews, 44:419445, 1949.
[3] E. S. Shanley and G. A. Melhem. The oxygen balance for thermal hazards assessment.
Process Safety Progress, 14(1):2931, 1995.
[4] W. H. Seaton. Group contribution method for predicting the potential of a chemical compo-
sition to cause an explosion. J. Chem. Educ., 66(5):A137A140, 1989.
REFERENCES 7
Combustion Products (chosen for Fuel Value and Net Heat of Combustion):
moles state species
.50000 ref-gas 1007 N2
.50000 gas 4306 H2O water
Figure 2: CHETAH 7 hazard evaluation and ranking for nitric acid (continued)
Notes:
#1 This evaluation was developed to classify a composition as able or
not able to decompose with violence, if subjected to the proper conditions