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CHARACTERISTICS OF EXPLOSIVE REACTIONS IND

THEIR INITIATION AND PROPAGATION MECHANISMS

by Richard L. Ash, P.E.

An explosion, by definition, is a thermochemical process whereby


mixtures of gases, liquids, and solids react with the almost
instantaneous formation of gaseous pressures and near sudden heat
releases. There must be always a source of ignition, and the proper
temperature and pressure conditions must be present to initiate a
reaction. The chemical mixture used must be such that the overall
effects produced by the rearrangements between the various component
atoms contained within the molecular constituents will react exothermally.

There are two types of explosive reactions: deflagration and


detonation. The first is present initially in all explosive reactions,
with the second developing when conditions are suitable. To better
comprehend the reactions and their qualities it is necessary to first
consider the nature of initiation mechanisms and their propagation.

Initiation of a reaction is thermal in origin, beginning as a


combustion at minute explosion centers known as "hot spots." These
spots are formed by the application of heat, or pressure that de -
grades into heat, supplied by an initiating device. The hot spots
develop in. three possible ways: (1) the adiabatic compression of
tiny gas bubbles entrapped within an explosive mixture, (2) frictional
heating producedy the sliding of solid ingredient surfaces against
one another, and (3) viscous heating resulting from rapidly flowing
materials as they escape from between impacting surfaces. In many cases, there
may be combination effects; although in general, only the first
two methods of reaction initiation are considered to be common. The
hot spots are usually quite small, i.e., 10-3 to 10-5 cm in diameter, but
compared with molecular dimensions they would be quite large. If for
some reason these spots, or voids are not present, the result is that no
explosion may form, the explosive considered as being "dead-pressed."
To insure their presence in certain very dense explosives that will be
subjected to very high loading pressures, artificial voids (microballoons) may
be included in the mixture.

The initial combustion, or chemical reaction from which heat and


light are evolved, begins comparatively slowly. Following the ignition, a
certain time will be required to build up a critical concentration of
reactants called an induction lag or ignition time delay that will be
characteristic of each given mixture and set of environmental conditions. If
the explosive's ingredients are in liquid form and have low vapori -
zation temperatures, gaseous pressure and release of heat are relatively easy
to produce from the adiabatic compression of included gas pockets. In general,
the transition from liquid to the vapor phase is not difficult and effected
quite rapidly. For example, nitroglycerin requires heating to only 140F to
cause decomposition into intermediate gaseous products, with boiling occurring
at only 2930F. Similarly, certain petroleum
2.

distillates require very little compressional heating to ignite and


continue burning once their flash points are exceeded. An example would
be Diesel fuel oil that has a flash point of only 100 to 200F, depending on
its particular grade.

Solid ingredients require a longer induction period for decom-


position. If they are inorganic compounds, such as NaNO3 and CaCO3,
the crystals or grains first begin to swell and break up with the
addition of heat, prior to melting and subsequent decomposition.
Solid organic compounds, on the other hand, usually just melt prior
to the time decomposition will occur. In addition to the heat
effects on break-up and melting, solids permit the formation of hot
spots by frictional heating of rubbing solids as wel l as adiabatic
compression of included gas bubbles, if particles are set in motion
by impact or other form of pressure application. Localized surface
temperatures can reach very high values even under comparative gentle
conditions of sliding. The temperatures developed, however, would be limited
by the melting points and respective hardnesses of the rubbing solids. The
presence of gritty substances, which are hard and have
high melting points, tend to accelerate (or sensitize) the formation
of a reaction. This is because they produce high frictional heating and
particle degradation leading to rapid melting and 'decomposition of the
softer ingredients.

For the granular explosive compounds there is an initial decomposi -


tion of surface layers to form a melt, followed by the formation of
volatile intermediates. The initial decomposition is not normally
self-sustained because it is not highly exothermic. But the intermediate
products in the vapor phase frequently react with a large evolution of heat. If
the gases and heat liberated by the intermediates cannot
escape between the spaces left between and within the explosive grains,
pressure gradients develop to assist in the penetration of heat into
the solid surfaces. The relative rapidity at which the actions occur
will be controlled to a large degree by the sizing of the particles. The
finer the sizing of ingredients the more rapid would be the heating
and decomposition processes, both from the standpoint of a better distri-
bution of void spaces but also because of less mass through which
decomposition must penetrate.

If the rate of heat production exceeds that lost because of


convection and conduction, gas pressures will continue to grow. The
result causes combustion of material in contact with the ignition zone
to proceed at an increasing rate, further accelerating the generation
of heat with its attendant pressure rise. The reaction, thus, transcends from
a relatively slow-acting combustion initially into a rapidly-
progressing deflagration, or a relatively self-sustained and near-
spontaneous oxidation with high heat and pressure formation, that continues to
progress with increasing pressure intensities. As more and more hot
spots are formed because of divergence outward from the ignition source, the
individual pressure gradients from each reaction center soon
consolidate into a common zone or pressure front, which rapidly expands
throughout the entire mass of explosive mixture.
3.

If the rapidity of energy release continues to increase because of


rising pressures and temperatures, a low-order detonation soon results.
This is where compressional waves of small intensity are propagated in
the explosive at the velocity of sound, which increases with rising
temperature. Each explosion in turn transmits a small compressional
wave that advances through the material, which was already set in motion
forward and heated by its predecessors, and tends to overtake the latter
motion. As a consequence, the pressure and temperature gradients in the
wave front continually grow steeper with time and at an increasing velocity of
movement. When equilibrium conditions are reached for the particular
mixture, a fully-developed detonation is achieved, characterized by a
wave front (or shock) in which a finite effective pressure discontinuity
has developed in advance of the flame (or combustion) front and which moves
through the unreacted explosive material at a supersonic velocity. The
rate at which the detonation front moves through the explosive is the sum of
the velocities of sound through the material and of the respective
particle movements, or v e =v p + v i . The two pressures developed or that
from the compressive-wave shok front and that from the gases in the
explosion products that follow thereafter, are known as the Detonation
Pressure (Pd) and Explosion Pressure (Pe), respectively.
It follows, therefore, that several essential differences exist
between deflagration and detonation: namely, that the rate of re action of the
latter is supersonic with deflagration being much slower, and
that in detonation there is the propagation of a shock wave through an
explosive accompanied by a chemical reaction that furnishes energy to sustain
the shock wave advance in a stable manner, with formation of the final
gaseous products and their associated pressures following at some time later.
On the other hand, deflagration produces no shock wave and
only those pressures produced by the formation of gaseous products are
present.

Figure 1 illustrates a schematic diagram of a detonation reaction,


which has been stopped momentarily at the time the reaction has proceeded
half-way through a column charge of explosive. Initiation was begun at
the left end of the column, the reaction having moved or propagated
toward the right. It should be noted that the density of the unreacted
explosive increases near the detonation front because of the compression
action of the shock movement. The density of the explosive in the
detonation zone itself is even greater, approaching a value near 4/3 that
of the explosive's initial composition. However, providing there has been
no loss of explosion products into the surroundings, e.g., the mixture is
completely confined within an incompressible medium, then the density of the
products from the reaction must equal that of the initial unreacted explosive.
Therefore, it could be deduced that immediately behind the detonation zone
with its high density there will be a rarefraction zone, where the density
of material is less than that initially. The relationship between the
various densities along the explosive column would be as follows:
5<6 = 1<2<3<4, which describes the action of a dynamic impact or
impulse type of energy propagation. Any medium to which an explosive
detonation is applied, then, will experience a supersonic blow from the
5.

detonation front's pressure pulse, followed quickly thereafter by a prompt


release of pressure, and then followed shortly by a prompt build up of
pressure imparted by the explosion products that will be applied in a more or
less sustained manner. Deflagration produces only the last effect.

In detonation the primary reaction zone extends over a region


from the shock front where the initiation actually begins back to what is
called the Chapman-Jouget (C-J) Plane. The reaction-zone length will be
characteristic for each specific chemical composition and set of
environmental conditions. Changes in composition and the conditions under
which the explosive is used may extend or shorten its length. In many
commercial explosive mixtures, significant chemical reactions also can
occur behind the C-J Plane, such as for reactions from certain metallic
fuels that are difficult to oxidize completely and larger -sized
ingredients. The secondary reactions, however, can affect over -all
explosive performance but do not usually influence the stability of the
detonation front itself. For liquid ingredients, the shock front facilitates
propagation by breaking up the liquid into very small droplets, in
turn which are thrown into the reaction zone. Break-up into small fragments can
occur also for solid ingredients, resulting in the formation of fine
dust clouds. Both of those actions tend to intensify the rapidity of
reaction development by the formation of more surfaces being exposed to
chemical decomposition.

A number of factors can influence the specific mechanisms involved,


in turn which will control the rapidity at which the explosive reaction
can be developed and propagated. In the first instance, the explosive's
chemical composition as well as its physical make-up and intimacy and
uniformity of ingredient mixing must be proper. For example, the oxygen
balance may be such that only low heats of explosion are generated, and
lighter densities will invariably produce slower reactions. The same effect is
accomplished if coarser-grained ingredients are used in a mixture. Thus, even
though a theoretical velocity for a specific chemical mixture's
reaction can be estimated from common thermodynamic relationships, the
reaction velocity actually attained may be significantly lower. The result is
to lower the level of pressures that can be developed, and it is very
possible that a reaction has been sufficiently slowed that the shock front
characteristic of detonation may never form, resulting in the explosive
only deflagrating.

On the assumption that an explosive mixture has been properly


formulated and intimately mixed, there will be a theoretical ideal
detonation velocity for any one chemical composition and bulk density
combination. For example, the theoretical value for a 94/6 AN/FO mixture's
detonation velocity as a function of its density would be as follows:
Ve=3810 (0.392 + e) meters per sec, where e is expressed in gm/cc.
Converted to specific gravity and fps for velocity, the expression becomes .

ve = 12,500 (SGe) fps. The detonation pressure, on the other hand, is a


function of the explosive's density and the reaction velocity developed, or
Pd eve 2, which suggests that even though the density may not have been
changed, the pressures will not vary linearly but as the square of the
velocity actually attained. Thus, where the theoretical velocity may have

)
been determined to be 10,000 fps but only 5,000 fps was actually
attained, the resulting pressures produced would be not one-half but only one-
quarter of the maximum ideal value potentially available.

There are many reasons why the ideal theoretical values for ve
and the pressures developed for a specific chemical and density combination
may not be obtained under actual field blasting conditions. In the first place,
theoretical determinations are based on the assumption that adequate initiating
energy has been supplied. Thus, a low strength primer manifests itself by
causing a longer induction time lag and frequently by the
development of lower-than-ideal reaction velocity. In addition, the
explosive must be given infinite confinement, with no possibility for the
release of explosion products and heat loss. Another assumption made is that
the explosive's mass is unlimited, and there is no lateral restraint to the
passage of the detonation wave. It should be recognized, however, that those
conditions as required would be difficult to attain under
many circumstances encountered in field blasting.

Because the reaction products expand laterally, both the charge


diameter and its length must be large enough to not hamper movement of
the reaction. Both dimensions are related geometrically to the explosive's
characteristic reaction length. It has been shown that for most commercial
explosives, steady-state detonation requires a charge length from four to five
times the charge diameter as a minimum. Therefore, for explosives
with relatively long reaction lengths it is mandatory that they be used
in fairly large charge diameters and with lengths in excess of five times the
diameter used. If lesser diameters are employed, lower velocities can be
expected in decreasing order until that diameter is reached at which
no reaction is possible, termed the explosive's Critical Diameter, Dc.
Figure 2 illustrates the general characteristics of charge -diameter effects
on reaction velocities for several representative explosives. The curves shown
are idealized but obtained from actual experimental measurements.

It may be interesting to note that for many explosives, particularly the


blasting agents with relatively long reaction lengths, the increase of
velocity from the characteristic Dc to that charge diameter, De, where the
maximum value is attained and remains fairly stable, approaches the form of a
parabolic relationship. In other words, within the range of
charge diameters where velocity changes ve = f(De-Dc)n , where n is some
root power. For example, if an explosive had a Dc of 1 inch where ve = 0,
at a De of 2 inches the ve = 8,000 fps, at De = 4 inches the ve = 13,800
fps, and a De of 6 inches or larger gave a ve = 18,000 fps, then the
relationship between velocity and charge diameter within the range of
velocity change, or between 1 and 6 inches, would be simply ve = 8,000
(De - 1)1/2.

The effects on reactions caused by inadequate priming, loss of


confinement, too small a charge diameter, poor mixing, etc., usually are
apparent to the observer. In the first instance, poor performance is
evidenced by inadequate breakage of material blasted. Secondly, subnormal or
incomplete reactions result in the formation of intermediate reaction
products because final chemical and physical equilibrium conditions were not
obtained.
THE COMPOUNDING OF CHEMICAL EXPLOSIVES

By Richard L. Ash, P.E.

T h e d e s i g n o f a n e x p l o s i v e t h a t w i l l h a v e c e r t a i n s p e c i f i c q u a l ities
necessarily requires a more thorough understanding of expl osive
compounds and t heir r es pect i ve r eacti ons t han coul d be dis cuss ed here.
However, t he basic pri ncipl es and pr ocedur es ar e not diff i cult t o
understand. Users of explosives should be familiar with those
principles because the composition of a m ixture, along with the
environm e n t a l c o n d i t i o n s u n d e r w h i c h i t i s e m p l o y e d , i s di r e ct l y c o n t r o l l e d
by it en ergy pot e ntial, sensitivity, ability to be affected by moisture and
t e m p er at ur e, a n d ot h er s i g ni f i ca n t pr o p er t i es .

As a general rule explosives used for commercial or industrial


purposes require that they be reasonably safe to handle, yet sensitive
enough to i ns ur e pr oper executi on of their ener gy rel eas e. For all
practical purposes the energy release is almost instantaneous, with
the development of high pressures resulting from the evolution of
highl y-heated gas eous products. The process for most products can be
considered to be one of a very rapid oxidation in the form of combuStion.
Thus, most compounds contain an oxygen supplie r and a reducer, or a
combination of several chemicals which when used together provide those
same functions.

The highest energy release, or heat of explosion (Q e), generally


occurs when an oxygen balance exists, or when all of the available oxygen
from the supplier has been used by the reducers. The usual desired
products from an explosion include steam (H20), carbon dioxide (CO2),
free molecular nitrogen (N2), and inert non-poisonous solids like
Al O Na 0 and CaO. The formation of noxious or toxic gases is never
2 3' 2 ,

desirable, e.g., CO and NO. For example, the typical AN-FO balanced
mixture would be represented by the following chemical equation in
which 3 moles of ammonium nitrate (AN) are used for each mole of diesel
f u el oi l (FO), or

3NH 4NO3 + CH2 7H2O+ CO2+3N2

If aluminum were included in the mixture, in which 3 oxygen atoms


are needed for each 2 atoms of Al to produce A12O3, then to achieve a
balance, the follo wing equation would represent th e reaction:
6NH4NO3 + CH2+ 2AL

Estimating the heats of explosion will be discussed in a later section.

Mixture Proportioning

Usually explosive mixtures contain the elements of C, H, N, and O. In


addition, certain metals may be included such as Al, Ca, K, and Na.
Depending on the number of component ingredients, mixture compounding can
become very complex. However, a method is presented herein, where
each oxygen supplier is analyzed for its available oxygen and each
reducer is considered on the basis of how much oxygen is required to
provide a balanced product. This method has the advantages of being
direct and simplified. In this regard, Table 1 presents some of the
ingredients used in explosive mixtures and their respective explosion
characteristics. Those containing excess oxygen release ei ther O2, NO2, or NO, or some of
each. The reducers, by being deficient in
oxygen, do not form only N2 and CO2, instead they may also produce some
CO or C, or both. For example, if one considers ammonium nitrate (AN),
the products of H20, N2, and NO or NO, usually are formed. This means
par t of t he oxy g en is s ti l l r et ai n ed B y t he ni tr og e n i n t he f or m of N O
or NO which are toxic gases or fumes. However, for simple analysis
2'
it is more convenient to consider that only H20, N2 and 02 result.
T h e bas i c pr o c e d ur e i s t o f i r s t r e ar r a n g e t h e el e m e nt s i n a
compound's chemical formula so that all potential products can be
recognized more easily. Using ammonium nitrate as an example, the
method requires its formula be changed from NH4NO3 to N2H403. From the
latter form one sees that the products would be N, + 211,0 + 0 for each
mole of N H Similarly, a substance like TNT (trinitlroto uene),
403'
whose correct formula is C C (NO
6H2 H3 could be rearranged into the
form of C 7N3H506 2)3'
For simplicity, nowever, it might be desirabl e to
consider two moles of TNT, which yields 3N, + 511,0 + 7C0 7C. To
produce only CO.,, it follows that for the 14C a total of 28 oxygen atoms
is needed, of which actually only 7 are present. Thus, for two moles of
TNT, an oxygen deficiency of 21 atoms is present, or 101/2 atoms per single
mole. In summary, any compound can be analyzed for its ability to provide,
or require oxygen. Table 1 lists some of the properties and ideal
reaction products for cer tain ingredients frequently used in many
commercial explosive mixtures. I t wi l l b e n ot ed t h at dat a r ef er s t o
4 moles of each, the 4 representing the common number which provides no
fract i onal mol es in t he pr oducts. Thus, for the number of oxygen atoms
excess or deficient in any one of the compounds listed, one needs to
only divide the total as shown by 4.

It should be recognized that for compounding oxygen balanced


mixtures with more than two ingredients there can be many possible
combi nati ons. Each ingredi ent is used for one or mor e purposes as to
it s cont r i but i on t o war d t he mi xt ur e's bl as t i ng qual i t i es. In addition,
economics frequently have an important bearing on the relative qualities of
each ingredient to be used in any particular mixture. It is not the purpose
of this discussion, however, to detail the various processes
used in analyzing and designing the required mixture that will exhibit
certain properties.

T o ill ustr at e the general pr i nci ples outli ned pr evi ousl y, a s ample
explosive with specific ingredients can be designed if the relative
proportions of each are known. For exampl e, let it be assumed that it
is desired to compound a mixture containing equal parts (moles) of
nitrostarch, aluminum powder, and paraffin (CH2) with sufficient ammonium
nitrate to give a balanced mixtur e. From Table 1 we see that the
nitrostarch ( ) has a shortage of oxygen equal to 18 atoms per
4 moles, or 41/2C6N3H7011 Aluminum, if A1003 were to be
atoms per single mole.
formed, requires 11/2 atoms per mole. The paraffin (CH2T requires 3 atoms
of oxygen for each mole if CO2 and H20 are to be produced. On the other
3.

hand, ammonium nitrate (N2H403) has one excess oxygen atom for each
mole. Thus, if one mole each of nitrostarch, Al, and CH2 were used, one
can deduce the following oxygen balance equation:

+ Al + CH + XN
C6N3H7011 2 2H403

- 41 - 11 -- 3 + X= 0

where X = 9

Thus, for one mole each of the reducers 9 moles of AN must be used
to provide an oxygen balance, or

+ Al + CH + 9N2H403

C6N3H7011 2

To determine the moles of each product from the reaction, and it is


assumed only A1201, CO2, 11,)0, and N2 are formed, the first step is
to determine the total number of each element (Al, C, H, N, and 0)
contained in the original ingredien ts. By inspection, then, it can be
seen that there is but one Al, seven C's, forty -five H's, twenty-one
N ' s , a n d t hi r t y - e i g h t O ' s . Therefore, the products would be as follows:

21/A1203 + 7CO2 + 221/2120 + 101/21\12.

To check for total numbet of oxygen atoms, we find that it is correct, or

11/2 + 14 + 221/2 = 14 + 24 = 38.

Thus, rewriting the complete equation gives us the following:

C6N31 + Al + CH2 + 9N21403----,> 21/A1203 + 7CO2 + 221/2120 + 101/2N2


7011

If a 2000-lb batch of this particular mi xture wer e to be made,


it woul d be neces sary to det er mine the number of required pounds for each
ingredient. From Table 2 the respective molecular weights in gm of each are
given, or

297 + 27 + 14 + 9 (80) = 1058 gm total.

The respective weights of each ingredient in a ton batch then would be:
4.

lb.
Ni t r os t ar ch: 297
x 2000 = 562 28.1
1058

Aluminum: 27 x 2000 = 51 2.5


1058

P a r af f i n : 14 x 2000 = 25 1.3
1058

Amu. Nitrate: 720 x 2000 = 1362 68.1


1058
Total = 2000 100.0

The formation of poisonous fumes results when mixtures are not


balanced. For example, if one of the reducers were not included
in the above mixture, there would be an excess of oxygen provided
by the ammonium nitrate. Thus the nitrate ion would not be completely
reduced and NO or NO
or both, would be produced along with the N2.
2' 2
In the case where the nitrostarch was the ingredient not included,
a total of 4 1/2 oxygen excess atoms would be present. Thus, the
quantity of AN must be reduced from 9 to 4 1/2 moles to give an oxygen
balance. On the other hand, if it were only the paraffin that was
omitted, then the 9 moles of AN must be reduced by 3 moles to a
total of only 6 moles.

Conversely, if there is less than the required amount of oxygen


available, the result would be that there would be only, or some,
CO fromed rather than all CO Also some of the Al might not react
2'

but be left as a residue, or form an oxide other than A120 3. Where

there is considerable oxygen deficiency, a black residue or carbon


will always be found after blasting.
Potential Energy Determination

To estimate the total potential energy of an explosive mixture, it


is necessary to assume that the reac tion would be an adiabatic
exothermic process, in which all the heat given off is used to heat
the explosion products. It must be further assumed that the reaction
would be complete, or ideal. Because the pressures developed are
a direct function of the masses and volumes of the gases produced,
as well as the temperature to which they have been heated, it
follows that the explosives work potential would be directly re -
lated to the amount of heat released, or Qe.

The calculations required for determining Q for any explosive


mixture are generally quite simple. If the reaction were ideal,
then the heat of explosion would be merely the difference between the
total of the heats of formation for the reaction's products
(Q ) and the total for the ingredients, or reactants (Q ) Thus,
Q P= Q - Q or Q + Q = Q . The respective heats of formation
or var?ous EompouEds are gi en on Table 2.

For making calculations using heats of formation, one must


r ecogni z e fi rs t t hat no he at i s r equi r ed t o f or m any el em ent , i. e.,
-C, H, 11, 0 ,etc. If a compound, or ion, absorbs heat (endothermic)
when formed from its elements, it is the convention to consider the
compound as having a positive (+) heat of formation. I f h e a t i s
released (exothermic)when formed, the compound is said to have a
negative (-) heat of formation. In other words, the amount of
energy required to decompose a compound into its elements is exactly
equal to that amount liberated during the formation of that com -
pound from its elements, at the same temperature and pressure con -
d i t i o n s . To serve as common bases, standard pressure at sea level and a
temperature of 2980K are considered standard when listing
heats of formation in data tables. It will be noted from Table 2
that generally always the heats of formation for most compounds are
negative, or in other words, heat is released when they are formed.

The procedure for calculating the Q value for any explosive


can be illustrated by using as an exa mpla the mixture of nitrostarch,
Al, paraffin, and AN. The first step is to determine the equation
for the reaction, or

+ Al + CH + 9N
C6N3H7011 2 2H403

1/2A1203 + 7CO2 + 22-1/2 H2O + 10-"1/2N2.

Secondly, from Table 2 the respective heats of formation for the in -


gredients and explosion products are grouped according to the ex -
pression Qe = Q - Qr.
Thus, Q 1/2A1 + 7C0 + 22-1/2H + 10-1/2N
= 0
p 203 2 2 2'
and Q = 1/2(-399) + 7 (-94.1) + 22-1/2(-57.8) + 0,

Or Q = 2158.7 Kcal for 1058 gm.

Also, Qt = C6N3H7011 + Al + CH2 + 9N2H403,

and = -45.7 + 0 + (-7.0) + 9 (-87.3)


Qr
or Qr = -838.4 Kcal for 1058 gm.

Thus, Qe = (-2158.7) - (-838.4)

or Qe = -1320..3 Kcal for 1058 gm.

To convert Q t o ot h e r u n i t s , t h e r es p e c t i v e f a c t or s listed in
Table 2 can Be employed. For example,

Qe = (-1320.3) (1000) / (1058) = -1250.0 cal/gm,

or Qe = (-1250.0) (454) / (252) = -2250 Btu/lb

and Qe = (-1250.0) (1403) = -1,755,000 ft-lb/lb

The effects on heat potential when explosives are not balanced as


opposed to oxygen balanced mixtures are shown in Table 3. One need only to
consider that use of an internal combustion engine is
6.

actually utilizing a controlled explosion, which when starved for


oxygen always produces carbon monoxide, or CO. Methane gas, CH 4,
when mixed with the proper portion of air will explode when ignited, as
has been demonstrated by explosions in mining an d certain other
circumstances. There are also many instances where flour (C6111,105) ,
bituminous coal dust that is a mixture of many hydrocarbons, natural
gas, etc., have exploded and caused considerable damage. I t i s
not diffi cul t t o see, then, fr om T abl e 3 that the energy released
from explosive mixtures can be tremendous in magnitude. But if
properly controlled and understood, the energy can be put to con -
structive use.
TABLE 1

CHARACTERISTICS: OF. SOME:-INGREDIENTS. USED. IN: EXPLOSIVE: MIXTURES


Available
FFreezingreezing Explosion Oxygen

Compound Short Name , F Ideal Reaction Pro d u c t s Atoms


Temp., Temp.

4KC10 Chlorate 695 752 (Decompose) + 6 + 4KC1 12


3 02

4NaNO SN 585 712 (Decompose) 4N0 + + 2Na 10

3 3 0
02 2
4 AN 340 460 8 0 + 3 + 2NO 4
N2H403 H2 N2 2

NG 55 420 10H + +2N0 2


4 0 5 +12C
C3N3H509 2 N2 02
EGDN - 4 239 (Boi ls) + 8C0 0
4 8 0 4 +
C2N2H406 H2 N2 2
4CaCO Calcite. 4C0 + 4CaO
3 2
4 PETN 282 420 16H 0 + 8 +12C + 8C0 - 8
C5N4H8012* 2 N2 02

4 RDX 252 500 12H 0 +12N 2+ +12C0 -12


C3N6H606* 2
Nitrocellulose, 345
14H + 6C0 +18C0 -18
4 0 6 +
C6N3H7011 *Nitrostarch 212 (Decomp.) 250 2 N2 2

4 Picric Acid 255 610 6 0 + 6 +22C0 + 2C -26


C6N3N307 H2 N2

4 Tetryl 265 495 10H 0 +10N +22C0 +6C -34


C7N5H508 2 2

TNT 180 888 10H + +14C0 +14C -42


4 0 6
C7N3H506 2 N2
4 Cellulose, W o o d Pu l p , or S t a rc h 20H 0 +24C -48
C6H1005 2

4 DNT 158 752 (Decompose)12H20 + 4 + 4C0 +24C -52


C7N2N604 N2

4PbN Lead Azide 480 (Decomp.) 660 12N +


6 2

NOTE: * - These c ompoun d s are used in the water -we t co ndi ti on. PETN can be initiated

by a single #6 blasting cap with up to 35 per cent water content. Nitro-


cellulose and nitrostarch are very sensitive to initiation when dry.

4 e. Fa40
-4- C
1)0,tvaLy-. tn,
8.

TABLE 2
HEATS OF FORMATION FOR SELECTED
CHEMICAL COMPOUNDS
(Rf: Handbook of Chemistry and Physics, 48th Ed., 1967-68)
Qp or Qr
Compound Formula Form Mol. Wgt. Kcal/mole
A10 g 43.0 + 10.7
A 0 g 70.0 - 31.7
l2
Corundum A s 102.0 -399.1
l203
CaC1 s 111.1 -190.0

2
Calcite CaCO 3 s 100.00 -288.5
Lime Ca0 s 56.1 -151.9
Ca0 s 72.1 -158.3

2
Paraffin C s 14.0 - 7.0
H2
Formaldehyde C 0 g 30.0 - 27.7
H2
Formic acid C g 46.0 - 86.7
H202
Methyl alcohol C OH 1 32.0 - 57.0
H3
Nitromethane C N 1 61.0 - 21.3
H302
Methane C g 16.0 - 17.9
H4
Urea C O s 60.0 - 79.9
H4 N2
Acetylene C2H2 g 26.0 + 54.2
Oxalic acid C2H204 s 90.0 -197.6
Ethylene C2H4 g 28.0 + 12.5
Acetic acid C 0 1 60.0 -116.4
H4
Ethylene glycol C2H406N2 1 152.0 - 56.0
dinitrate
Ethyl alcohol OH 1 46.0 - 66.4
C2H5
Ethane C2H6 g 30.0 - 20.2
RDX C3H606N6 s 222.1 + 18.3
Propane C3H8 g 44.1 - 24.8
Glycerine C3H803 1 92.1 +159.7
TABLE 2 (cont.) 9.
Qp or Qr
Compound Formula Form Mol. Wet. Kcal/ mole

Nitroglycerine 1 227.1 - 82.7


C3H509N3
Butane g 59.0 - 29.8

C4H10
PETN s 316.1 -123.0
C5H8012N4
Pe n ta ne g 72.1 - 35.0
C5H12

Picric acid s 229.0 - 53.5


C6H307N3
Phenol 0 s 94.1 + 39.2
C6H6

Benzene g 84.1 + 19.8


C6H6
Nitrocellulose s 297.1 - 45.7
C6H7011N3
and Nitrostarch

Cellulose s 162.2 -170.5


C6H1005
Starch s 162.2 -205.2
C6H1005

Dextrose & Glucose s 180.2 +303.6


C6H1206
Hexane g 86.2 - 40.0
C6H14
Mannitol s 182.2 +317.3
C6H14

Trinitrotoluene s 227.1 - 13.0


C7H506N3
Tetryl s 287.2 + 9.3
C7H508N5

Dinitrotoluene s 182.1 - 6.9


C7H604N2

Toluene 1 92.2 + 12.0


C7H8
Heptane g 100.2 - 44.9
C7H16
Octane g 114.3 - 49.8
C8H18
Nonane g 128.3 - 54.7
C9H20

Nicotine 1 162.2 5.2


C10H14N2

Camphor 0 s 152.3 + 79.8


C10H16

Castor Oil 1 302.2 -


C11H10010

Su c ros e C s 342.4 +535.1

2H22011
CIO g 51.5 + 33.0

010 g 83.5 + 37.7


3

CO g 28.0 - 26.4

C g 44.0 - 94.1
O2
LO.

TABLE 2 (cont.)
Qp or Qr
Compound Formula Form Mol.Wgt. Kcal/ mole

alarese' (cont.) HH+ ion 1.0 + 52.1

OH ion 17.0 + 10.4

team H2O g 18.0 - 57.8

eroxide 1 34.0 - 47.1


H202

ydrochloric acid. HC1 1 36.5 - 40.0

arbonic acid C 1 62.0 -167.0


H2 O3

H g 58.0 + 70.3
N3

itric acid HNO 1 63.0 - 49.4

3
ercury fulminate HgC202N2 s 284.7 + 64.0

ylvite KC1 s 75.6 -104.2

otassium chlorate KC10 s 122.5 - 93.5

3
otassium perchlorate KC10 s 138.6 -103.6
4

alt peter KNO s 101.1 -117.8

3
austic potash KOH s 56.1 -111.8

0 s 94.2 - 86.4
K2

.rcanite S s 135.2 -342.7


K2 O4

ariclase Mg0 s 40.3 -143.8

alite NaC1 s 58.5 - 98.2

adium c h l o ra t e NaC10 s 106.5 - 85.7


3

Ddium perchlorate NaC10 s 122.5 - 92.2


4

Na2CO3 S 106.0 -270.3

ada Ni te r NaNO s 85.0 -101.5


3
austic soda NaOH s 40.0 -102.0

N 0 s 62.0 - 99.4
a2
+
N ion 14.0 + 85.1
11.

TABLE 2 (cont.)

Qp or Or
Compound Formula Form Mol.Wgt. Kcal/mole

Ammonia N g 17.0 - 11.0


H3

Sal ammoniac N C1 s 53.4 - 75.4


H4

Ammonium hydroxide N 0 1 35.1 - 87.6


H5

NO g 30.0 + 21.6

N g 46.0 + 8.1
O2

Ammonium nitrate s 80.1 - 87.3


N2H403

0 g 44.0 + 19.5
N2

N203 g 76.0 + 17.4

N204 g 92.0 + 2.3

N205 g 108.0 + 3.6


+ ion 16.0, + 59.2
0

Lead azide PbN s 291.3 +110.0

6
S g 64.1 - 71.0
O2

S g 80.1 - 95.1
O3

Quartz SiO s 60.1 -205.0


2

Zincite ZnO s 81.4 - 83.2

ATOMIC WEIGHTS

Al = 27.00, C = 1 2. 0 1 , Ca = 40.08, Cl = 35. 4 6 , H = 1.01,


Hg = 2 0 0 .6 1 , K = 39.09, Mg = 24.31, N = 14.00, Na = 23.00,

0 = 16.00, Pb = 2 0 7 .2 1 , S = 32.07, Si = 28.09, MI = 65.37

CONVERSION FACTORS

1 lb = 454 gm, 1 cal/gm = 1403 ft.-lb./lb., 1BTU = 252 cal


TABLE 3

HEATS OF EXPLOSION (Qe) FOR SELECTED

EXPLOSIVE COMPOUNDS AND MIXTURES

A. COMPOUNDS

Qe, Qe,
Formula Products cal/g m ft-lb/lb

:Salt peter)KNO3 K20,N0,02 +956 +1,334,950

:SN) NaNO3 +860 +1 , 2 06 , 58 0


N 0,N0,
a2 02
:AN) N2H403 H20,N2,NO2 -663 - 888,520

:NG) C 0, C .NO -1,468 -2,060,170


3N3H509 H2 N2' O2
:EGDN) C 0, C -1,620 -2,285,770
2N2H406 H2 N2' O2
CaCO CaO,CO2 4424 + 596,275

3
(PETN) C5N4H8012 0, C ,C0 -1,402 -1,967,570
H2 N2' O2
(RDX) C -1,220 -1,711,240
0, CO
3N6H606 H2 N2'
(NC&NS) C -1,402 -1,966,870
6N3H7011 0, C CO
H2 N2' O2'
(Tetryl) C7N5H508 H20,N2,CO,C -1,009 -1,415,210

(Picric Acid) C6N-H_ ,CO,C -779 -1,092,940


0,
iO7 H2 N2
(TNT) C7N3H506 0, ,CO,C -986 -1,383,220
H2 N2

(DNT) C7N2H604 H20,N2,CO,C -1,054 -1,478,480

(Cellulose) C6H1005 0,C -777 -1,089,710


H2

(Starch) C-H -517 -725 ,77 0


b 10-05 0,C
H2
(Lead ide) PbN2 ,Pb -370 -519 ,11 0
N2
(FO) CH2 H2 ,C -500 - 7 0 1 ,5 0 0

KC10 KC1,0 -87 - 1 2 2 ,4 8 0


3 2

B.MIXTURES

2CH + 30 (23/77) H20,CO2 -2,337 -3,278,950


2 2

2 + (27/73) C -2,139 -3,000,600


02 O2
13

B. MIXTURES

e
Formula Products cal./gm ft-lb/lb

C + 2AN (7/93) H20,N2CO2 -868 -1,217,800

C + 2AN (8/92) H20,N2 C0 -761 -1,067,960


H2

C + 3AN (6/94) H20,N2,CO2 -897 -1,257,790


H2

C + 5AN (3/97) H20,N2,CO2,NO -580 - 8 1 3 ,0 4 0


H2

Cellulose + 12AN (15/85) H2O, N C -911 -1,277,570


2, 02
2CH + 9AN + 2A1 (3 / 9 0 /7 ) H20,N2,CO2,A1203 -1,160 -1,626,920
2

.CH + 9AN + 4A1 (2/8 5/1 3) 11 20,N2,CO2,A1203 -1,398 -1,961,113


2
2CH + AN + 2SN (10/29/61) 0 C N 0 -693 -971,580
2 H2 N2' O2' a2

(2RATOL)53AN + 10TNT (65/35) 0 N CO C -500 - 7 0 1 ,5 0 0


H2 ' 2"

(.NAAATOL) 21AN + 2TNT (79/21) H20,N2,CO2 -1,310 -1,840,000

(TRITONAL) 10TNT + 21A1 (80/20) H20,N2,A1203,CO,C -3,938 -5,525,300

(PENTOLITE) 14TNT + lOPETN (50/50) H ,CO,C -998 -1,400,330


0,
2 N2
(CONP.B) 7OTNT + 100RDX + 103 Wax + 8 Polyisobutylene

H 0 N CO C -1,157 -1,623,270
2 ' 2"
(COMP.C-4) 100RDX + 28 Wax + 9 Polyisobutylene + 3 Sebacate

H 0 N C0 C -1,293 -1,814,080
2 ' 2"
C + 4NG (1/99) 0 C -1,598 -2,242,130
H2 N2' O2

Cellulose + 24NG (3/97) 0 C -1,595 -2,237,080


H2 N2' O2

Cellulose+12NG+6AN (5 / 8 1 /1 4 ) C -1,481 -2,077,420


H20'N2' O2

Cellulose+2NG+11AN (11/30/59) 0 C -1,124 -1,577,390


H2 N2, O2

Cellulose+4NG+4SN (12/ 64/ 24 ) 0 C N 0 -1,289 -1,807,770


H2 N2' O2' a2

N i t ro c e l l u l o s e +9 N G (13/87) 0 C -1,632 -2,290,000


H2 N2' O2

Cellulose + 2NG + 6AN +2SN (13/36/38/13)

H20,N2,CO2,Na20 -1,121 -1,572,623

CH + 20 (20/80) H20,CO2 -2,375 -3,332,130

4 2
CEZTAIN SEMXTED CHEMICAL COMPOUNDS

Nitrous Oxide NO Nitric Oxide - NO2


a

0 N \1 0

11204 Ammonium Nitrate - N2H403 r'l

14 Kt H 1,40

cyo'l 2

Formaldehyde - 0H20 Methyl Alcohol - 01130H.


or Okkee
C H., OH

Methane OH4 Ethylene - 0.2H4


H
-H
C, H
Hf H

Ethylene col. Dinttrate Ethyl Alcohol_ 0- I-1 OH5


G2
C142. N00 CH, OH or_02g60
1
H C3 N0z, C 14 2, 1-1

Ethane 021115 Ethylene, Glycol_ 02H02


C 1-4
1 Cgz, 014
C1-12.-1-4
15.
S
STRUCTURE DIAGRAMS FOR CERTAIN. SELECTED CHEMICAL COMPOUND

Nitroglycerine (NG) - 03)750


93

C1-12 0 NO,

CI 0 is404. NO2

Lsaao py1 Alcohol w 03117011. Propane - 03%

or G`H 0
c Ha.

Glycerine 03H803 Sutane C; H-


4 10

140

ct.t,og.
16.
STRUCTURE DIAGRAMS FOR CERTAIN SELECTED CHEMICAL COMPOUNDS

PETN (Pentaerythrite Tetranitrate))- 075118012114


NO2.

0420

Ni02 0442.0 C F1,0 NOz

c,4,0

Picric Acid - C 3.
6H 071
NO2

C C
a NO2.
c"
1\10a. 1-1

Benzene - 0 0 6

C C -1-4

\H

Obllulose (Similar to Starch)


0 1-1
H

t.; . ow ,c,

I
H o` CH
C11-4 204
17.
STRUCTURE DIAGRAMS FOR CERTAIN SELECTED CHEMICAL COMPOUNDS

Nitrocellulose (NO} - 0611101iN

C HO C HO H
NO z
C..

H
C
2.0
----
NO, Lo
Dextrose - C6H 06
12
H H DH 14
I I I I
C -7C CHO
I I I I
014
014 014 1-1
Glucose - H 0

6 1 2- 6
0
I 1-1 ON H I
C 1-17_014 C C C C. 014
I I I

H OH H OIH H

Mannitol (Manuite) - aH a

6 14 6
H H OH OH
i 1 i-t
C H 2.0 1-4 c_ G C WL0
I I L
01-1 H Fl
STRUCTURE DIAGRAMS FOR CERTAIN SELECTED CHEMICAL COMPOUNDS

Toluene (Methyl Benzene) - 07H8

Maltose - C. H
12 22 '11
0 0

Y C- C-C 0 1-1 01-1--C-


C I-Ipt-I 1 1
h I4 O - H 0 14

Sucrose - 12H2211

I 1
C1-12.014 cc 4,0 14
ci 14
0

C t42..01-1 94 Y I
61114 OH

Water - H20,

H.
PROPERTIES F FERTIO 1ZER AND KAMM PULS.

rip

FERTILIZER P ILL ' BLASTING RILL


C ATING 3-5% 1/2-1%

FAR H ESS VERY HA D SOFT

PHYSICAL FO M SOLID C YSTAL POROUS

FUEL OIL DISTRIBUTION SU F CE OILY THROUGHOUT FRILL

MINIMUM DIAMETE FO 2'/2 in.


UNCONFINE I DETONATION

4 in. C i NFINE R VELOCITY 6,000 FPS 11,000 FPS


Tank Jet Loading* Loading
pressure pressure rate density
psi psi lb/min 9/cc

SODIRIM. I i1=111.1

Pressure 10-60 15-70 0,80 0.85


vessel

40-80 7-10 0090-1.00

Combination 20 20-80 15-25 0.90 LOO


loader

*varies with hose diameter