THE JOURNAL OF CHEMICAL PHYSICS VOLUME 48, NUMBER 1 1 JANUARY 1968

Chemistry of Detonations. II. Buffered Equilibria

:VIORTIMER J. KAMLET AND J. E. ABLARD
U. S. Naval Ordnance Laboratory, While Oak, Silver Spring, Maryland
(Received 19 June 1967)
At low loading densities, values of N, M, and Q calculated from the H
2
0-C0
2
"arbitrary" show poor
individual agreement with estimates of these quantities from the RUBY computer code. Nevertheless, when
substituted into the equation P=15.58 NM1/2Ql/2pO', they lead to detonation pressures which correspond
closely to RUBY predictions. That incorrect input information should yield results which are very nearly
"correct" is rationalized on the basis that the equilibria whose shifting engenders the changes in N, M, and
Q are "buffered" in the sense that "errors" in N are offset by compensating "errors" in M and Q. As a conse-
quence of the fact that most of the important equilibria in the detonation of C-H-N-O explosives are
buffered, calculated (and actual) mechanical properties of detonations appear to be extremely insensitive
to exact product compositions. A number of other interesting consequences of these buffered equilibria are
discussed.
1. INTRODUCTION
In Paper I of this series
l
it was suggested that deto-
nation pressures of C-R-N--O high explosives might
be estimated by means of the simple empirical equation
P=15.58iVM
l
/2Qj,f2po2 (P in kilobars), (1)
where iV is the number of moles of gaseous detonation
products per gram of explosive, M the average molecu-
lar weight of these gases, Q the chemical energy of the
detonation reaction ( - t:..Ho per gram of explosive), and
po the initial density. In a preliminary test of this rela-
tionship, iV
RUBY
, M
RUBY
, and QRUBY (the computer
estimates of these quantities) were substituted into
Eq. (1) for a number of typical organic explosives at
representative loading densities. That this led to val-
ues of Peale which differed only nominally from pressures
predicted by the RUBY and STRETCH BKW computer
codes
2
confirmed that, given "proper" values of iV, M,
and Q, the new equation leads to reasonable estimates
of P (Table III of Ref. 1).
It was then demonstrated that l\'"rh, ACrb, and Qurh,
as easily calculated from the H
2
0-C0
2
arbitrary as-
sumption of detonation product compositions, corre-
sponded reasonably closely (i.e., to within 5%) to
iV
RUBY
, M
RUBY
, and QRUBY at initial densities above
1.40 glcc, but that differences became significantly
larger at lower loading densities (Table V of Ref. 1).
The H
2
0-C0
2
arbitrary represents N
2
, H
2
0, and CO2
as being the only important gaseous products in the
detonation of most C-H-N-O explosives, with H20
having priority in formation over CO2
From these findings it was expected that, when used
1 M. J. Kamlet and S. J. Jacobs, J. Chern. Phys. 47, 23 (1967),
Part I, preceding paper.
'As used herein, the term RUBY includes the results of com-
putations at the Los Alamos Scientific Laboratory by the
STRETCH BKW computer code and at NOL by the Lawrence
Radiation Laboratory's RUBY code. For the purposes of present
discussions, these codes differ only in minor regards and, unless
otherwise specified, RUBY computations shall be considered as
based on Mader's most recent covolume factors and the "more
appropriate" of his dual K-W parameter sets (Ref. 11 of Part I),
with the heat of formation of solid carbon taken as zero. See
Part I for other leading references.
in combination with the arbitrary method of estimat-
ing N, M, and Q, Eq. (1) might allow rough predictions
of detonation pressures of experimental explosives at
or near their theoretical maximum densities. Such pre-
dictions would require as input information only the
elemental composition of a C-H-N-O explosive, its
loading density, and an estimate of its heat of forma-
tion, and would require no other calculational aids
than are available to the organic-synthesis chemist at
his desk. It was felt that the results would be meaning-
ful where arbitrary and RUBY values of N, M, and Q
did not differ markedly, i.e., only at Po> 1.40 g/cc.
When put to the test, however, the new method
showed both higher precision and broader scope than
anticipated. Comparisons between hand calculations
and machine computations (Table VI of Ref. 1) in-
volved 103 data sets for 27 compounds and compositions
at loading densities from 1.00 to 1.96 glee. They covered
the full gamut of N
urt
, Murb, Qarb, and Gurb (the weight
fraction of explosive going over to gaseous detonation
products) to be encountered among organic high explo-
sives. The results
3
showed good agreement between
P
eule
[Eq. (l)J and P
RUBY
at the higher densities as
was expected. At Po> 1.45 glee, differences averaged
1.6% and in only a single instance (of 66 data sets)
was the "error" greater than 5%.
II. THE SEEMING ANOMALY
36
Much to our surprise, however, it was also found
that, although agreement between Peale and PRUBY
was indeed slightly poorer at the lower loading densi-
ties, the differences were still quite small and no trend
could be discerned. At po=1.40 glee, differences aver-
aged 2.4% (12 data sets); at 1.20 glcc, differences
averaged 2.1% (12 data sets); at 1.00-1.13 glcc,
differences averaged 2.0% (13 data sets). Further,
in no case was the "error" as high as 5% at the lower
clensi ties.
'The values of P oalo included a "correction" step which in-
volved subtracting 6'/(, where Garb, the weight fraction of explosive
going over to gaseous products, was greater than 0.93. See Appen-
dix C to Part I.
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CHEMISTRY OF DETONATIONS. II
37
Such precision at 1.00 g/cc was most unexpected in
the light of our earlier observation that at this low
density N arb, M arb, and Qarb for underbalanced explo-
sives may differ by as much as 10-20% from the
corresponding RUBY values. With TNT at 1.00 g/cc
as an example:
N,ub=0.0253 moles gas/g explosive, NRUBy =0.0293,
difference = -13.7%,
M
arb
=28.52 g gas/mole gas, M
R
UBy=26.38,
difference = +8.2%,
Q arb = 1282 cal/ g, QRUBY = 1104,
difference = +13.9%, but
P
eale
=75.3 kbar, P RUlly =76.2,
difference = only -1.2%.
Similarly, with tetryl at 1.00 g/cc, N arb (0.0270) differs
fromN
RuBy
(0.0323) by -16.5%, but Peale (85.3kbar)
differs from P
RUBY
(87.1) by only -2.1%. With picric
acid at this density, N
arb
(0.0251) differs from NRUBY
(0.0317) by -20.8%; Peale (84.4 kbar) differs from
P
RUBY
(87.9) by only -4.0%.
The results may be summarized as follows. "Proper"
values of N, M, and Q in Eq. (1), e.g., RUBY values or
arbitrary values at the higher loading densities, lead
to detonation pressures which agree well with RUBY
predictions. At the lower densities the H
2
O-C02 arbi-
trary no longer provides "proper" estimates of N, M,
and Q. This apparently makes little difference as con-
cerns average agreement between Peale [Eq. (1) ] and
P
RUBY
, however, and we are faced with the seeming
anomaly that input information which is known to be
grossly "incorrect" leads to predictions from Eq. (1)
which are very nearly "correct."
The rationalization of this anomaly holds important
implications about effects of product compositions on
calculations from Eq. (1). To whatever extent Eq. (1)
successfully parallels RUBY and the Kistiakowsky-
Wilson equation of state, and to whatever extent the
latter in turn successfully describe actual phenomena,
these implications may also serve toward a better
understanding of properties of explosives in real deto-
nations and, eventually, certain types of damage effects.
III. BUFFERED EQUILIBRIA
It has been mentioned
l
that product compositions
in the Chapman-Jouguet condition and in the subse-
quent expansion of the detonation gases depend most
strongly on the two important equilibria
2

t::..Ho= -41.2 kcal, (2)
t::..Ho= -31.4 kcal, (3)
and that the H
2
0-C0
2
arbitrary is simply a concise
representation of the assumption that both equilibria
are predominantly to the right. From (H
2
0/H2) ratios
in RUBY print-outs, it was shown that the computer
predicts Equilibrium (3) to be far to the right for
C-H-N-O explosives at all loading densities under
consideration. The computer's (COdCO) ratios, on
the other hand, indicate that it finds Equilibrium (2)
to be predominantly to the right, i.e., (C0
2
/CO) > 15,
only at loading densities above 1.70 g/cc (see Table IV
of Ref. 1 for specific data). At Po<1.70 g/cc, RUBY
considers the 2 reaction to be in a regime
of shifting equilibrium, and the increasing values of
N
RUBY
as loading densities and detonation pressures
become lower are a reflection of RUBY'S predicting
greater amounts of carbon monoxide in accordance
with Le Chatelier's principle.
The resolution of the anomaly mentioned above has
as its crux the fact that Equilibrium (2), whose shift-
ing to the left at the lower densities engenders the
changes in NRUBY, MRUBY, and QRUBY, is "buffered"
in the following sense: The number of moles of detona-
tion gases per unit weight of explosive, their average
molecular weight, and the amount of chemical energy
which becomes available to heat and expand these
gases do not vary independently of one another. As
CO
2
and solid carbon are replaced by successively in-
creasing amounts of CO in the computer predictions
(or in actual detonation mixtures), an inevitable in-
crease in N
RUBY
(or actual N) is accompanied by
equally inevitable decreases of comparable magnitude
in RUBY'S (or actual) M and Q.
Since at any po, P from Eq. (1) depends not on N,
M, or Q alone, but on the quantity <:p which we define by
(4)
we encounter the phenomenon of compensating "errors"
which leads to an approximately "correct" result. In
the previously cited instance of TNT at 1.00 g/cc,
although arbitrary N, M, and Q differ from the cor-
responding RUBY values by -13.7%, +8.2%, and
+ 13.9%, respectively, <:Parb (4.838) differs from <:PRUBY
(4.998) by only -3.3%.
With the above as an example, we define a "buffered
equilibrium" as one wherein, although variation in con-
centrations of the component species engenders relatively
large changes in N, M, and Q, the individual effects
offset one another and lead to appreciably smaller changes
in <:P [Eq. (4) ] and hence in detonation properties.
In the same sense that the H
2
0-C0
2
arbitrary as-
sumption of detonation-product compositions repre-
sents Equilibria (2) and (3) as both lying far to the
right, an H
2
0-CO-C0
2
arbitrary concisely describes
the condition where Equilibrium (2) is predominantly
to the left and Equilibrium (3) predominantly to the
right. In contrast with the former arbitrary, which
has until now been used relatively infrequently,4 the
latter method of estimating product compositions has
4 A. Y. Apin, N. F. Velina, and Y. A. Lebedev, Zh. Prikl.
Mekhan. i Tekhn. Fiz. 1962, 96.
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38
M. J. KAMLET AND J. E. ABLARD
TABU: 1. "Buffered" equilibria. N, M, Q, and <p according to the various "Arbitraries."
===
Arbitrary 1: H
2
O-CO
2
, 2 CO->C02 +C, CO+H2->C+H,O
Arbitrary 2: H
2
O-CO-C0
2
, 2 CO<-C02+C, CO+ H2->C+ H2O
Arbitrary 3: CO-H,O-C0
2
, 2 CO<-CO,+C, CO+H,<-C+H2O
Explosive . b
Arb
Detonation products
(moles gas/mole explosive)
"Yarb M.,b Q.,b <Parh (I"/I" .. b-ll
BTNEU 4 N2, 3 H20, 5 C02 (12) 0.0311 32.18 1481 6.789
C.H6Ns0 13 2 4 N2, 3 H20, 5 C02 (12) 0.0311 32.18 1481 6.789 1.000
tJ.Hj=-72.7 3 4 N2, 3 H20, 5 C02 (12) 0.0311 32.18 1481 6.789 1.000
PETN 2 N2, 4 H20, 4 C02, 1 C (10) 0.0316 30.41 1525 6.805
C,HsN.012 2 2 N2, 4 H20, 2 CO, 3 Co, (11) 0.0348 28.73 1395 6.969 1.024
tJ.H,=-125.0 3 2 N2, 4 H20, 2 CO, 3 CO
2
(11) 0.0348 28.73 1395 6.969 1.024
RDX 3 N2, 3 H20, 1.5 CO2, 1.5 C (7.5) 0.0338 27.20 1481 6.783
C3H6N606 2 3 N2, 3 H20, 3 CO (9) 0.0405 24.66 1204 6.979 1.029
MI,=+14.7 3 3 N2, 3 H20, 3 CO (9) 0.0405 24.66 1204 6.979 1.029
Tetryl 1 2.5 N2, 2.5 H20, 2.75 CO
2
, 4.25 C (7.75) 0.0270 30.46 1420 5.615
C7H.N,Os 2 2.5 N
2
, 2.5 H20, 5.5 CO, 1.5 C (10.5) 0.0366 25.62 1025 5.931 1.056
Mlj =+4.7 3 2.5 N2, 7 CO, 1 H20, 1.5 H2 (12) 0.0418 23.93 861 6.000 1.069
TNT 1 1.51'\2,2.5 H20, 1. 75 Co., 5.25 C (5.75) 0.0253 28.52 1282 4.838
C7H.Na06 2 1.5 N2, 2.5 H20, 3.5 CO, 3.5 C (7.5) 0.0330 24.66 964 5.088 1.052
tJ.Hj=-17.8 3 1.5 N" 6 CO, 2.5 H2, 1 C (10) 0.0440 21.50 619 5.076 1.049
" For a glossary of compound names. see Appendix B of Ref. 1. b Heats of formation are in kilocalories per mole.
been a routine tool, preferred by many explosives
chemists for the calculation of "heats of detonation"
(H
2
0 gas) and explosion (H
2
0 liquid), and leads to
values of Q which tend to correspond most closely to
calorimetric measurements
5
(however, see below). Still
a third method, the CO-H
2
0-C0
2
arbitrary (which
is of interest only for underbalanced explosives wherein
free carbon remains available to participate in the
C+ H
2
0 reaction), represents the situation where Equi-
libria (2) and (3) are both far to the left and was
employed in some of the earlier calculations of detona-
tion properties from the K-W equation of state.
6

7
It is instructive to compare values of N, M, Q, and
eP as calculated from the three arbitraries. We may
thereby evaluate how these parameters are affected
by shifting from one extreme to the other each of the
equilibria which are believed to be important in the
detonation of organic explosives and the subsequent
expansion of the detonation gases. Comparisons are
given in Table I for five typical materials which cover
the full range of oxygen balances encountered among
conventional C-H-N-O explosives. BTNEU is bal-
anced exactly to CO
2
; PETN is balanced between CO
and CO
2
; RDX is CO balanced; tetryl and TNT are
increasingly underbalanced to CO.S
'D. Price, Chern. Rev. 59,801 (1959).
6 G. B. Kistiakowskyand E. B. Wilson, Jr., OSRD-114 (1941).
7 E. A. Christian and H. G. Snay, "Analysis of Experimental
Data on Detonation Velocities," U.S. Naval Ordnance Laboratory
Rept., NavOrd-1508 (1951).
S In speaking of "oxygen balances," reference is generally to the
H
2
0-CO-C0
2
arbitrary.
It is seen from Table I that Reactions (2) and (3)
satisfy the definition of "buffered equilibria" quite well
in that eP, and hence Peale [Eq. (1)J, are quite insensi-
tive to the equilibrium positions or the exact product
compositions for even the highly underbalanced explo-
sives. Although values of N differ by as much as 74%,
values of M by as much as 33%, and values of Q by
as much as 107% for individual explosives as these
equilibria are shifted from one set of extremes to the
other, values of eP [Eq. (4) ] show changes no greater
than 7%. Where these equilibria do not lie completely
to the extremes, as is more likely to be the case in
RUBY computations or in actual detonations, differ-
ences between eParb and cPRUBY or ePactua] should be even
smaller.
IV. CH
4
AS A POSSIBLE DETONATION PRODUCT
Another reaction involving carbon which is predicted
to be relatively unimportant by RUBY with its current
input data, but which deserves discussion, is
!::..Ho= -46.8 kcal. (5)
Equilibrium (5) is shifted toward CH
4
with decreas-
ing Po, but is predicted by RUBY to be far in the direc-
tion of H
2
0 at all densities under consideration. For
underbalanced explosives at 1.00 g/ cc, for example,
RUBY'S (H
2
0/CH
4
) ratios are typically between 100
and 300.
As is discussed in Appendix I, however, changes in
RUBY'S input information which are not unrealistic
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CHEMISTRY OF DETONATIONS. II
39
could cause methane to become a major rather than
a minor product at the lower loading densities. Such
input changes might involve assuming a positive heat
of formation for solid carbon and assigning to CH4 a
lower covolume factor (k
i
) in place of the value of 528
currently used by RUBY. A k
i
/M
i
=13.760.15 pro-
portionality was demonstrated for the "major" deto-
nation species in Paper I of this series,
1
and ki = 528
for CH4 does seem high in the light of this observation.
9
It is therefore also of value to consider the effect on cp
of shifting Equilibrium (5) completely to the left.
Taking the detonation products assumed for TNT
by Arbitrary 2 (Table I) and reacting the H
2
0 with
carbon to form CH4 and additional CO according to
Reaction (5), we get the new set of products: 1.5
moles N
2
, 5.83 moles CO, 1.17 moles CH
4
, and 0.17
moles H
2
0, for a total of 8.67 moles gas/mole TNT.
N becomes 0.0382, M becomes 26.18, Q becomes 725,
and cp becomes 5.263, an increase of 3.4% over the
value of cp predicted from Arbitrary 2. Again, in Reac-
tion (5), we encounter a buffered equilibrium wherein
shifts from one extreme to the other cause marked
changes in N, M, and Q, but only nominal changes in
cpo The same holds true if carbon and hydrogen from
Arbitrary 3 are reacted to form methane, or nitrogen
and hydrogen to form ammonia.
Indeed, since most of the equilibria which are be-
lieved to affect product compositions in actual detona-
tions appear to be buffered, we have found that taking
the elements of a C-H-N-O explosive and recombining
them to form any possible mixture of products from
among N
2
, CO, CO
2
, H
2
0, CH" NH
a
, H
2
, and HCN
generally leads to values of cp which differ between
extremes by no more than 8-10%. Examples which
are highly unlikely in terms of actual detonation mix-
tures, but are nevertheless illustrative, involve convert-
ing the elements of TNT to the following sets of prod-
ucts: (a) 3.0 moles HCN, 3.0 moles CO
2
, 0.5 moles CH"
0.5 g atoms C; (b) 1.67 moles NH
a
, 0.67 moles N
2
,
3 moles CO
2
, 4.0 g atoms C. In the former case cp = 4.684,
in the latter cp=4.775, which differ by -3.2% and
-1.3%, respectively, from the value used in the present
calculations.
The above observations regarding the sensitivity of
N, M, and Q and the relative insensitivity of cp to exact
compositions of products from individual explosives
lead to a variety of interesting observations. These
involve: (a) the present calculational method; (b) the
RUBY code and similar computer-based methods of cal-
culation; (c) effects of equilibria on actual detonation
properties and, eventually, on damage effects; and (d)
methods which are widely used to intercompare the
predicted performance of explosives.
9 Unlike the k. values for N2, CO, CO" and H
2
0, which have been
adjusted to accomodate experimental measurements, RUBY's
covolume factor for CH. remains the "geometrical" value based on
molecular dimensions as deduced from van der Waal's radii.
Assuming a ki of 220 for CH, (13.76X16) might prove no less
realistic. See Sec. III of Part I.
V. CONSEQUENCES OF BUFFERED EQUILIBRIA
IN THE DETONATION
A. Present Calculational Methods
It follows from the relative insensitivity of cp to
equilibrium positions that the present calculational
methods do not stand or fall with the validity of our
estimating N, M, and Q by means of the H20-C02
arbitrary. Using an H
2
0-CO-C0
2
or even a CO-H
2
0-
CO
2
decomposition scheme or any combination of these
to supply N, M, and Q for Eq. (1) would not have led
to values of Peale differing appreciably from those which
we have reported.
Since the H
2
0-C0
2
arbitrary was chosen in the pres-
ent study because it best reproduced RUBY'S estimates
of these quantities at the higher densities, the above
observation becomes important in reconciling the suc-
cess of the simplified calculations with our current belief
that the computer's predictions regarding the positions
of the various equilibria involving carbon are open to
serious question. RUBY'S computations are based on
the input assumption that carbon takes the form of
solid graphite with zero heat of formation.
2
It has
never been established that sufficient time is avail-
able in the C-J state for carbon to assume orientation
in an ordered crystal lattice of any appreciable size
and it seems fair to suggest that, lacking evidence in
this regard, the tJ.H,=O assumption must be considered
as suspect. Similar considerations have led to the use
of +15 kcaljg-atom as the heat of formation of carbon
in RUBy-type computations at the Lawrence Radiation
Laboratories of the University of California, this value
being considered the "heat of subdivision" of finely
divided graphite.
lO
As is discussed in the Appendix RUBY'S estimate of
the position of Equilibrium (5) is strongly influenced
by the input heat of formation of carbon; similar con-
siderations are likely to apply as regards Equilibria
(2) and (3). Thus, the possibility exists that RUBY'S
estimates of N, M, Q, and the various Ni bear little
relationship to the values of these quantities in actual
detonations.
It follows that the H
2
0-C0
2
arbitrary must be con-
sidered similarly suspect as regards estimates of actual
N, M, and Q. In consequence of the buffered equilibria,
however, this arbitrary may nevertheless be completely
adequate for the estimation of a c t u a l ~ cp, and hence
actual detonation pressures and velocities.
B. Computer-Based Methods of Calculation
We have already questioned RUBY'S input assump-
tions regarding the tJ.H
j
of carbon, the k
i
of the "minor"
10 Dr. E. Lee, Lawrence Radiation Laboratory (private
communication). The referee has pointed out to us that Mader
experimented with a positive AH, in the course of his BKW studies.
While using a positive AH, for carbon was a help in calculating
P and D, it caused troubles in calculations involving the isentropic
expansion of the detonation products, perhaps because it was not
allowed to change during this process.
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40 M. J. KAMLET AND J. E. ABLARD
detonation species, and the parameters in the K-W
equation (Appendix C of Ref. 1). Other of the input
data may be at least as suspect in that they are based
on inherently inexact measurements or involve extrap-
olations to pressures far beyond experimentally accessi-
ble ranges.
In seeming contradiction, however, RUBY does in
fact succeed in predicting detonation pressures over a
limited range of compositions and loading densities,
which accommodate the body of inherently inexact and
often contradictory measurements about as well as
might be expected of any computational method. Fur-
ther, the computer's estimates of detonation velocities
show reasonably good agreement with more accurate
experimental information over the same limited range
of compositions and densities.
Again we feel that a rationale for "correct" results
from "incorrect" input information may be found in
the phenomenon of compensating "errors" such as have
already been shown to minimize the effects of differ-
ences between arbitrary and RUBY N, M, and Q in
Eq. (1). It is no less likely that, even where the com-
puter grossly misjudges the N;'s, the buffered equilibria
may introduce mutual cancellations which also tend to
lessen the effects on RUBY'S pressure and velocity of
"errors" in the various quantities which interact to
produce these predictions in the computer's multi-
iterative machinations. Thus relatively large differ-
ences between RUBY values and actual values of pJ,
pg (or Vg), T, the tJ.H/s, Lx.k., CvdT, N, Q, EJ-Eo, ,,(,
etc., may offset one another and lead to values of PRUBY
and which are very nearly "correct." In conse-
quence, RUBY'S P and D predictions may parallel those
of Eq. (1) in being insensitive to exact product compo-
sitions and hence to inaccuracies in large segments of
the input information.
RUBY and Eq. (1) probably both reflect the fact that,
as is discussed in the next section, actual mechanical
properties of detonations are also insensitive to exact
product compositions. It is also possible that the suc-
cess of the K-W equation of state with other param-
eters and covolumes,2,7.11 other equations of state,12
and other computer-based methods over limited ranges
of explosive composition and density may be attributed
to similar buffering phenomena. A necessary corollary
is that, as has already been pointed out in part by
J ones,13 good agreement between predicted and expen-
mental P and D do not necessarily justify: Ca) the
form of the equation of state, (b) the equation-of-state
parameters except over limited ranges of composition,
(c) covolume factors of the detonation products, (d)
assumptions regarding the form and properties taken
11 R. D. Cowan and W. Fickett, J. Chern. Phys. 24, 932 (1956).
12 For a review of the various equations of state, see S. J.
Jacobs, ARS (Am. Rocket J. 30, 151 (1960). .
13 H. Jones, Third on Flame and Exploston Phenom-
ena (The Williams and Wilkins Co., Baltimore, 1949), pp. 590-
594.
by carbon and other solid products in the detonation,
(e) other input information, and (f) predictions of
other detonation properties which are not subject to
experimental verification.
C. Actual Mechanical Properties of the Detonation
From an analysis of computer results not unlike our
own, Johansson and Persson
I4
have recently suggested
that detonation pressures might vary with the square
of the loading density, i.e., for individual explosives
K=2.0, (6)
where A is a constant depending on the nature of the
explosive.
l
The proportionality was demonstrated for
five materials over the important range 1.0<po< 1.6
g/cc.
The results in Table VI and Fig. 1 of Ref. 1 confirm
quite clearly that the K-W equation with Mader's
parameters (as reflected in RUBy2) accommodates a
P=Ap02 relationship exceedingly well and extends the
applicable density range to 1.00-1.96 g/cc. Our many
comments regarding possible inadequacies of RUBY
should markedly weaken the significance of this ob-
servation, however, if based on the computer results
alone. The suggestion that the P_P02 relationship may
be real is therefore made primarily on the basis that,
as will be discussed in Paper III of this series,16 the
total body of available experimental information on
detonation pressures of C-H-N-O explosives also sup-
ports K=2.0 in Eq. (6).
For the purposes of the present discussion, however,
it does not matter what the exact value of K is, but
only that the same K in Eq. (6) should accommodate
the P vs po behavior of a wide variety of organic ex-
plosives. Again the total body of experimental informa-
tion indicates that such is indeed the case, and supports
the following reasoning.
Detonation pressures of CO
2
-balanced or overbal-
anced explosives, on the one hand, and highly under-
balanced explosives, on the other, show the same de-
pendence on Po. Since, according to the results of calori-
metric measurements (see next section), detonation
products of the former type of explosive are about the
same at all densities, while product compositions of
the latter type change markedly with po, it seems an
almost necessary corollary that pressures are relatively
slightly affected by shifting equilibria for the individ-
ual underbalanced explosives. An obvious implication
from these results is that equilibria in the detonation
are "buffered" in natural fact as well as in the calcu-
lations.
14 C. H. Johannson and P. A. Persson, Nature 212, 1230 (1966).
16 Our Eq. (1) is, of course, a more form of Eq.
where 4>=A/15.58, which allows an e,aslly
calculable 4> to include all C-H-N-Q explOSIves III a unItary
relationship.
16 M. J. Kamlet and C. Dickinson, J. Chern. Phys. 47, 43
(1967), Part III, next paper.
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CHEMISTRY OF DETOXATIONS. II 41
Detonation velocity measurements also support this
conclusion. In Part I we reported that the equation
A = 1.01, B= 1.30 (7)
allowed calculation of detonation velocities D which
agreed well with RUBY predictions. In still another paper
of this series we shall show that Eq. (7) also accommo-
dates a large body of ideal (infinite diameter) experi-
mental detonation-velocity results to within less than
1.5% average difference and less than 1.0% as a
90% confidence limit (26 explosives, Po from 0.95 to
1.90 glcc, more than 100 individual measurements).
That equilibria are buffered in actual detonations is
again a likely explanation for the fact that a single set
of A and B in Eq. (7) serves equally well for near-
CO
2
-balanced explosives and for hiahly underbalanced
explosives. b
Price has suggested" that an explosive's abilitv to
do some types of work is a simple function of its
detonation pressure. We shall offer supporting evidence
in this regard in a subsequent paper, since it follows
from Price's observation that the quantity cf>arb may
also provide the basis for predicting the relative
of C-H-N-O explosives to effect certain types of
ag: .. That such measures of performance (e.g., the
ablhty to push a plate or expand a cylinder) show the
same dependence on cf>arb for near-C0
2
-balanced and
highly underbalanced explosives again reflects the im-
of buffered Such buffering may
the effects of changmg product composition
at .least the early stages of the detonation gas expan-
SlOn m the same sense as has been demonstrated for
the C-J condition.
It seems necessary at this time to emphasize that
the above generalizations may pertain only as concerns
explosives and that diametrically opposed
concluslOns may apply to aluminized mixtures. Evi-
dence is available that kinetic factors (which extend
far beyond the time of the C-J condition), rather than
thermodynamic factors, govern the extent of utiliza-
tion of aluminum in the detonation. If, as seems reason-
able, the rates of the aluminum reactions are highly
temperature dependent, and if aluminum reacts at dif-
fer:nt rates H20, CO, and CO2, detonation prop-
ertIes of alunumzed explosives should depend very
strongly on exact equilibrium compositions of these
species in the C-J condition and in the early stages
of the gas expansion. For such reasons, Eqs. (1) and
(7) may be inapplicable for use with aluminized mix-
tures.
D. Some Comments Regarding "Heats of Detonation"
. Many explosives chemists have for many years con-
SIdered "heat of detonation" as the primary measure
of efft;ctiveness. "Figures of merit" of experimental
exploslVes have most often been expressed in terms of
Q/QTNT. It deserves comment that, as concerns "heats
of detonation," equilibria such as (2), (3), and (5)
engender two types of situationsP
On the one hand, a CO
2
-balanced explosive like
BTNEU produces no carbon to participate in such
equilibria and the "heat of detonation" mav be con-
sidered to be a reasonably constant prope;ty of the
explosive, relatively independent of the conditions
under which calculated or measured (Table I). An
underbalanced e?,plosive like TNT, on the other hand,
produces appreciable amounts of carbon in the detona-
tion state. At the successively lower pressures as the
gases expand, this carbon reacts first with CO
2
to form
CO [Equilibrium (2) ] and then with H
2
0 to form CO
a.nd H2 [Equilibri,:m (3) ] or CO and CH4 [Equilib-
num (5) J, successively greater amounts of detonation
energy being "soaked up" in these reactions. In conse-
quence, the "heat of detonation" of TNT becomes a
continuously varying property which can differ b\- as
much as 107% depending the initial density,' the
to which the gases haye expanded, ar:d the
condltlOns under which the equilibria "freeze." To a
greater or lesser extent, the latter considerations also
apply to any explosive with Garb < 1.00.
If R (C02/ Co) ratios come near to being cor-
rect, ArbItrary 1 (Table I) approximates the detona-
tio.n for high-density explosives at the C-J
pomt f.rom the correspondence with usual types
of calonmetnc measurements,5 it is likely that Arbi-
trary 2 represen ts a condition after the gases have
expanded to several (possibly 2-20) charge diameters.
Arbitrary 3 might correspond to a situation much far-
ther down the isentrope.
Using Q/QTNT from Table I as the basis for inter-
comparison, and depending on the arbitrary used to
compute the Q's, a "figure of merit" for BTNEU
might equally well be 1.15 (Arbitrary 1), 1.54 (Arbi-
trary 2), or 2.14 (Arbitrary 3). In the first case the
comparison would be at the top of the isentrope in
the second case a relatively short distance down'the
isentrope, the third case a relatively longer distance
down the lsentrope. From similar considerations it is
possible to take one's choice: PETN is 3% more
ful than BTNEU (Arbitrary 1) or BTNEU is 6%
more powerful than PETN (Arbitraries 2 or 3).
Even more important, however, a judicious choice
of sets of experimental conditions might provide evi-
dence for any such calculational intercomparison in
17 Very strict}y speaki?g, the term heat of detonation should refer
to the adjusted chemical energy difference between
the startl?g and the products formed in the C-J state.
The term of de!onation," which usually involves
at least some reeqUlhbratlOn dunng the expansion of the product
gases from the C-J state, is therefore almost necessarily a misno-
mer. same true .for .most other usages of the term by
explosl\:es IncludIng .ltS usages in the present paper. To
eml?haslze of termInology, "heat of detonation" is set
off In quotatIOn marks where appropriate. We are grateful to Dr
Donna Price for pointing this out. .
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42 M. J. K A M LET AND J. E. ;\ B L A R D
the form of accurately measured "calorimetric heats of
detonation." Such a choice might involve changes in
(calorimeter volume/explosive weight) ratios or, as
first shown by Sutton
18
and convincingly confirmed by
Apin and co-workers,4 varying charge densities or the
degree of confinement of the charge within the calo-
rimeter.
While such flexibility in calculation and measure-
ment of Q for underbalanced explosives conforms with
the general observation that different explosives are
indeed better for different applications, the "state of
the art" has not yet reached the stage where an appli-
cation and a calculational method based only on Q
can be unambiguously matched. For such reasons, we
feel that citing the "heat of detonation" (note quotes
I7
)
as a unique property of an under balanced explosive is
often apt to be misleading. Where "figures of merit"
are based on this property alone, intercomparisons of
explosives should be taken cum grana salis unless all
the assumptions in the calculations or the exact conditions
of the calorimetric measurements are clearly spelled out.
ACKNOWLEDGMENTS
The authors wish to thank Mr. H. Hurwitz of this
laboratory for making available to us unpublished RUBY
results upon which much of the above is based. We are
also particularly grateful to Dr. Donna Price and Dr.
S. J. Jacobs for their very substantial contributions to
the effort. The work was done under NOL Founda-
tional Research Task FR-44.
APPENDIX: EFFECT OF RUBY'S INPUT
INFORMATION ON THE POSITION IT
PREDICTS FOR EQUILIBRIUM (5)
Changes in the K-W parameters do not markedly
change the equilibrium position. Using TNT param-
eters in the STRETCH BKW code, Mader predicted an
(H
2
0/CH
4
) ratio of 178 for TNT at 1.00 g/cc. Using
the RDX parameter set in RUBY, Hurwitz at NOL
reported (H
2
0/CH
4
) = 144 for the same explosive at
the same density.2
In marked contrast, the equilibrium position is in-
fluenced strongly by input heats of formation and
covolume factors (k
i
). Following Le Chatelier's prin-
18 T. C. Sutton, Trans. Faraday Soc. 34, 992 (1938).
ciple, more negative heats of formation or, at the high
pressures encountered in detonations, lowered k/s for
individual species shift equilibria toward those species.
Less negative !::..H/s and higher k;'s shift equilibria
away.
Current RUBY computations at NOL, using 250 as
the k
i
for H
2
0, 390 for CO, and 528 for CH
4
, and
assuming zero heat of formation for solid carbon, pre-
dict (H
2
0/CH
4
) =445 for TNT at 1.47 g/ce. Hurwitz,19
using somewhat different values of (3 and K in earlier
RUBY computations at NOL (but which differences,
as mentioned above, should effect the equilibrium po-
sition relatively slightly) and taking the same k/s for
CO and CH
4
but 360 rather than 250 as the k
i
for
H
2
0, reported the following results for TNT at 1.47
g/cc: Assuming !::..Hj=O for solid carbon, (H
2
0/CH
4
) =
14.8; assuming !::..Hj =+15 kcal/g-atom for solid car-
bon, (H
2
0/CH
4
) =2.53.
Thus a 44% change in the k
i
of the single species
caused a 30-fold change in the product ratio. Assuming
a positive !::..Hj for carbon such as is currently preferred
by at least one highly knowledgeable group of research-
erslO caused a further sixfold change.
Similar effects are observed with RDX at 1.60
g/cc. Current STRETCH BKW computations predict
(H
2
0/CH
4
) = 1.08 X 10
4
Earlier RUBY computations
predicted (H
2
0/CH
4
) = 18.1 when !::..H
j
(carbon) was
taken as zero and 3.93 when !::..Hj (carbon) was taken
as + 15 kcal.
Correspondingly large shifts of Equilibrium (5) in
the direction of CH
4
would therefore not be unexpected
at densities as low as 1.00 g/ cc if a positive !::..H
f
were
assigned to carbon and if the ki for CH
4
were adjusted
downward in current RUBY computations.
9
Methane
could become a "major" rather than a "minor" deto-
nation product. The extreme sensitivity of product
compositions and the relative insensitivity of predicted
detonation properties to input information which is so
uncertain at the present "state of the art" should
emphasize the critical importance to RUBY of the fact
that equilibria are buffered. It should also emphasize
the potential pitfalls in performance predictions based
on "heat of detonation" alone, since the latter property
is highly dependent on exact product composition.
19 H. Hurwitz, "Calculation of Detonation Parameters with the
RUBY Code," U.S. Naval Ordnance Laboratory Rept., NOLTR
63-205 (1965).
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