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A Review of ASTM CHETAH 7.0 Hazard Evaluation Criteria

E. S. Shanley and G. A. Melhem


Arthur D. Little, Inc., Cambridge, Massachusetts 02140

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:

Criterion 1 Maximum Heat Of Decomposition

Criterion 2 Fuel Value minus Heat of Decomposition

Criterion 3 Oxygen Balance

Criterion 4 CHETAH ERE Criterion

Criterion 5 Over-all Energy Release Potential


2
Criterion 6 Net Plosive Density

Each of these is discussed below.


1
This paper appeared in Journal of Loss Prevention in the Process Industries, Vol 8., No. 5, Page 261-264
2
This is the term used by CHETAH to express the result of a hazard evaluation calculation
2

Criterion 1. Maximum Enthalpy Of Decomposition


The CHETAH program provides very convenient means to estimate the heat of formation for the
ideal gas phase of any composition that can be modeled in the Benson group-additivity system.
Using this value and the empirical formula, the program sorts through its data bank to find and
report the combination of products yielding, at STP, the maximum enthalpy change. The value
of this enthalpy change, in kcal/gram or kJ/gram, constitutes Criterion 1.
Criterion 1 provides very significant guidance regarding self- reactivity hazard. It is intuitively
plausible and empirically established that a high (negative) value of this parameter is usually
associated with highly self-reactive compositions, while a low (negative) value usually indicates
little or no self-reactivity hazard. CHETAH 7.0 uses a value of -3.0 kJ/gram as a cutoff point,
classifying compositions with values more negative than this as possible reactivity hazards and
compositions with less negative values as posing less self-reactivity hazard.
Although Criterion 1 is widely understood and used, it has predictable limitations associated with
attempting to place an artificial boundary on a continuum of properties. In the physical world,
there is no sharp transition between dangerously self-reactive compounds and compounds with
low self-reactivity hazard. Many compounds exhibiting enthalpy changes more negative than
-3.0 kJ/gram have no known impact sensitivity, and vice versa. In addition, compounds with
similar energy release values may display a wide range of sensitivity to initiation, blurring the
distinction between safe and hazardous compounds. The five additional CHETAH hazard
ranking criteria are presumably intended to improve resolving power.

Criterion 2. Fuel Value minus Enthalpy of Decomposition


Criterion 2. is based upon the idea that heat of combustion constitutes a measure of the absolute
maximum heat available from any substance. A small difference between heat of combustion
and the enthalpy change during self-reaction, together with a high (negative) value of enthalpy
change during self-reaction, is taken to indicate high hazard potential.
This criterion provides hazard ranking values identical to those of Criterion 1 in the case of
oxygen-balanced and oxygen-rich compositions, as well as for most non-redox, energetic com-
positions such as explosive azides, nitrides, and the like. It down-rates the hazard potential of
fuel-rich compositions in proportion to the heat of combustion of the decomposition products in
excess oxygen. In this sense, Criterion 2. seems to rank fuel-rich compositions relative to their
own, hypothetical, oxygen-balanced counterparts, rather than to other fuel-rich compositions.
There is no obvious reason why the heat of combustion of self-reactivity products should be
relevant to hazard evaluation. Criterion 2 seems to provide little hazard information in addition
to that provided by Criterion 1.
3

Criterion 3. Oxygen Balance


Oxygen Balance (OB) is evaluated by the use of Equation 1.

[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

balance in a favorable manner, and it is of interest to see whether a concurrent improvement in


power is produced. ... With hardly an exception auxoplosive groups are shown to be detrimental
to power whether or not they appear to improve oxygen balance .
Oxygen Balance as calculated by CHETAH appears to be an unsuitable criterion for hazard
ranking.

Criterion 4. CHETAH ERE (Energy Release Evaluation) Cri-


terion
In CHETAH 7.0 this criterion is defined by the equation:

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.

Criterion 5. Overall Energy Release Potential


In the CHETAH 7.0 manual it is stated that, This criterion combines the four individual criteria
and the number of peroxide bonds into a single High or Low rating. ... The weights assigned
to the individual criteria were arrived at using sophisticated pattern recognition techniques ....
Regardless of its sophistication, no mathematical manipulation can compensate for conceptual
deficiencies in the means used to generate the input data.

Criterion 6. Net Plosive Density


The Plosophoric Density system is described in an article by W.H. Seaton [4]. This system
is limited by a vocabulary of only about 45 Plosophore groups and six whole molecules,
mostly nitrate and peroxide compositions. This is to be compared with some 600 conventional
3
ERE and other CHETAH criteria can be applied to compositions such as oxidant-fuel mixtures (compositions)
as well as to specific chemical compounds
5

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

We find serious conceptual deficiencies in CHETAHs hazard ranking criteria 2, 3, 4, 5, and


6. Although hazard evaluation is a central feature of CHETAH, this seems to be the weakest
feature of an otherwise unique and valuable program. Better guidance might be provided by
fewer criteria that relied less on correlative methods.
REFERENCES 6

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.

[2] G. R. Handrick. Personal communication. 1994.

[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

Figure 1: CHETAH 7 hazard evaluation and ranking for nitric acid

- - - - ASTM PROGRAM CHETAH 7.0 (REVISED 24-Jan-94) - - - -


COMMITTEE E-27 CHEMICAL THERMODYNAMICS AND ENERGY HAZARD APPRAISAL PROGRAM
RUN DATE: 15-DEC-94
ENERGY RELEASE EVALUATION

Title: NITRIC ACID


Compound Name: NITRIC ACID Moles: 1.0000
Formula: HNO3
Molecular Weight: 63.0129 State: Gas Grams: 63.013

Heat of Formation at 25 C: -32.10 kcal/mol


Group Count Description
4302 1 HNO3 nitric acid

HEAT OF COMBUSTION SECTION: mass basis mole basis


Fuel Value (Net Heat of Combustion) = 0.05 kcal/g = 3.20 kcal/mol
= 0.21 kJ/g = 13.39 kJ/mol
= 91.41 Btu/lb

Combustion Products (chosen for Fuel Value and Net Heat of Combustion):
moles state species
.50000 ref-gas 1007 N2
.50000 gas 4306 H2O water

PLOSIVE HAZARD CLASSIFICATION SECTION:


For items marked with #, see footnotes below. Plosive Hazard *
Classification (#1)
Maximum Heat of Decomposition (#2) = 0.0000 kcal/g LOW
Fuel Value - Heat of Decomposition = 0.0508 kcal/g LOW
Oxygen Balance (#3) = 63.48 percent HIGH
CHETAH ERE Criterion 4 = 0.0000 kcal2/mol LOW
Total Number of Peroxide Bonds = 0
Over-all Energy Release Potential = 0.1852 LOW

Net Plosive Density (#4) = 0.5205 PLOSIVE


REFERENCES 8

Figure 2: CHETAH 7 hazard evaluation and ranking for nitric acid (continued)

* ATTENTION! The Plosive Density Method is showing a result of PLOSIVE and


it is known to be the most reliable method for classifying materials as
to their ability to decompose with violence.

* WARNING: THESE RATINGS ONLY APPLY TO HAZARDS ASSOCIATED WITH STRONG


MECHANICAL SHOCK. THIS DOES NOT IMPLY THE ABSENCE OF OTHER HAZARDS.

Decomposition Products (chosen to maximize heat of decomposition):


moles state species
1.0000 gas 4302 HNO3 nitric acid

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

Information on the interpretation of the hazard classification criteria


used by CHETAH may be found in the CHETAH documentation (ASTM publication
DS-51A) and in J. Chem. Ed. v66, A137 (1989).
#2 For decomposition products shown.
#3 Experience has shown that the oxygen balance criterion is useful
only for compounds composed of the elements C, H, N, and O.
#4 Sum of auxoplosive and plosophoric weights per gram of mixture.