DESIGN OF EXPLOSIVE

COMMERCIAL COMPOSICIONS.

1
OXYGEN BALANCE

Most commercial explosives are

designed to have approximately a zero
oxigen balance. That is the primary
constituent elements, H, N, O, C, in
the explosive are so proportioned that
in the gases resulting from detonation
all the O2 reacts to form water, the
combined N2 is relased to form
molecular N2, and the C reacts to form
carbon dioxide (CO2).
2
If there is only enough O2 present in
the explosive to form water and Co2,
then the explosive is said to be
oxygen balanced. If it has a
deficiency it has a negative oxygen
balance, and if an excess, it has a
positive O2 balance.

3
 When a balanced explosive contains no
other elements with an affinity for
oxygen, the zero oxygen balance may be
expressed mathematically as follows:

OB = O0 2CO2 H2O = O ------- (1)

In this equation O0 is the number of gram

atoms of these elements (usually 100 Grs.)
of explosive and the H2O and CO2 are
moles yielded per unit weight of explosive.
4
 This my be expressed in the more general
form for any explosive containing C, H, N
and O only, as follows:

OB = O0 2C0 H0 -------------(2)

Where:
O0, C0 and H0 represent the number of gram atoms
of these elements per unit weight of the explosive.
O0 is corrected for the amount combined with
elements to form solid products such as CaO and
Na2O where such elements are present.
5
 CONSIDER AN/FO AT ZERO
OXYGEN BALANCE.

3NH4NO3 + CH2 3N2 + H2O +CO2 + Q3 KCal/Mole.

N2 28 C -
12
H4 - 4 H2 - 2
O3 48
80
14

3 x 80 = 240 6
Mixture is:

FO: 14 x 100 % FO = 5.6 % FO 6%

254

AN: 240 x 100 % AN = 94.4 % AN 94%

254

7
Mixture of AN/FO to be used is: 94/6 by
weight the energy output can now be
calculated:

Q3 = HP HR (3)
Examples:
Try to find the explosion heat of the following explosive
mixtures:

AN/FO: 98/2
2. AN: 80%
FO: 5%
AL: 15% 8
 ALUMINUM INCREASES
THE ENERGY
2 Al + 3NH4NO3 3N2 + 6H2O + Al2O3 + 1.65 KCal/gr.

EH = 1.65 KCal/gr.

Also: 2 Al + NO3NH4 N2 + H2 + Al2O3 + 2.3 KCal/gr.

EH = 2.3 KCal/gr.

On average there is a 2% energy increase for each

1% Al added up to a maximum of 15% aluminum
addition.
9
Strength
Theoretical
relative to
AN/FO

1.6

1.5

1.4
Actual

1.3

1.2

1.1

5 10 15 20 25 30
% Al 10
The effect of adding aluminum (-30 mesh
to AN/FO).

Where is the cut off?

13-15% Al addition is normal limit used in
the field.

11
 The
Thermohydrodynamic
Theory.

12
 THE DETONATION PROCESS
OR DETONATION STATE.
INTRODUCTION.
The pressure, temperature and density of the gases
in the shock wave, as well as its velocity are
parameters which may express numerically part of
the physical mechanism of detonation of high
explosives and which may be calculated by means
of the thermohydrodynamic theory together with
basic thermochemical and thermodynamic
equations.
One distinguishing feature of the shock wave is the
very sharp rise in pressure at the head of the
wave. 13
FIG. 1 PROFILE OF PRESSURES

Rarefaction
P2

P3

Reaction zone

14
 FIG. 2: DETONATION SCHEME

Shock front
D

P2V2T2 P1V1T1
P3V3T3 W Explosive

Explosion Detonation Chemical reaction
state Head or
state Solid
explosive

15
FIG. 3: VELOCITY IN A STATIC COORDINATE
SYSTEM.

W | | D D = V.O.D

W = Velocity of the particles of the gases.

FIG. 4: VELOCITIES IN A DYNAMIC

COORDINATE SYSTEM.
D-W = U2 | | D=U1

16
The derivation of the equations of the
thermohydrodynamic theory is a simple but
ingenious application of the principles of
conservation of mass, momentum and energy to
the conditions in front of and in a plane shock
wave.

From figure 2; we can see that the amount

(mass) of material caming into the schock front
per unit cross-Setional area per unit time will be
equal to its velocity times its density and this
must be equal to the mass leaving the
detonation front to the left.
17
The explosive is moving into the detonation front
with a velocity U1 = -D. The gases moving to the
left move with a velocity U2.

Then according to the law of conservation of

mass we will have:

U1 1 U 2 2 (1)

Or:

U1 U2

V1 V2
18
Where:

1 = Density of explosive
2 = Density of gases behind shock front
V2 = Specific volume of explosive gases = 1/ 2
V1 =Specific volume of explosive = 1/ 1
U1 = Absolute velocity of explosive
U2 = Absolute velocity of explosive in the
detonation state.

19
The momentum of corresponding masses in front
of and behind the shock front is made up of the
mass time, its velocity plus the momentum of the
individual molecules which cause the pressure in
each zone.

This law of conservation of momentum yields:

2 2
U U
1
P1 P2 (2)
2
V1 V2

20
The total energy is made up of intermal energy, E,
kinetic energy of a mass of explosives; or gases in
the wave front and the energy of compression of
explosives and gases, respectively. Thus the
application of the law of conservation of energy
yields for a unit mass:

2 2
E1 + U1 + P1 V1 = E2 + U2 + P 2 V2 -------------
(3)
2 2

21
From (1) and (3)

*
P2 P1
U1 D V1 (4)
V1 V2

22
E E2 E1 1 / 2( P2 P1 )(V1 V2 ) (5)
**

P2 P1
W U1 U 2 (V1 V2 ) (6)
V1 V2

T2

E E2 E1
T1
cvdt cv (T2 T1 ) (7)

23
 Or:

E E2 E1 cv(T2 T1 ) Q2 (8)

Q2 = Chemical energy Q released in the

reaction zone.

24
Equation 4 gives the velocity of detonation in
terms of pressures and specific volumes. Although
V1 is known, and P1 = 0, P2 and V2 must de
calculated from thermochemical relations and an
appropriate equation of state for the gases in the
detonation wave.

It is interesting to note that in the shock wave

V2 is smaller than V1 or P2 > P1.

25
 EQUATIONS OF STATE
With explosives the primary interest is centered upon an
equation of state for the gases which are produced by
the detonation, and this equation, if it defines with
sufficient accuracy the pressure volume temperature
relations at high temperatures and pressures, may be
employed to aid in the solution of the two states of
interest.

The equation of state for ideal gases:

pv = nRT ------------- (9)

26
Has been found to be applicable to gases at
only moderate pressures, and may be applied
to a reasonably close approximation to
conditions in rocket combustion chambers. In
a detonation wave and in the gases which
occupy a borehole after the detonation has
passed through the explosive column, the
pressures are of the order of 104 atmospheres
or more. In this case the actual volume of the
molecules must be accounted for; which the
ideal equation of state does not take into
consideration. One equation which has been
employed to correct for the fact that molecules
have finite size is van der Waals: 27
 (p + a)(v - b) = NRT ----- (10)

The factor b is a constant covolume factor

representing a correction which is about four
times the actual volume of the molecules.
The second correction factor a/v2 was
proposed to allow for the attraction between
the molecules. While this equation is useful
to account for the behavior of gases at
intermediate pressures, it is not readily
applicable to explosion conditions.

28
A virial equation of state is employed by Taylors
and is written in the form:

pv b b02 b03 b04

1 0.625 2 0.2869 3 01928 (11)
nRT v v v 4

Where b and b0 are constants depending on the

composition of the gases. A more generalized form of an
equation of state may be written as follows, or expanded
as a series2:

pv = nRT --------- (12)

29
Where:
= cx ------- (13)

C
T
X K (V ) (14)
V

30
and the parameter c is assumed to take on
values within a limited range.
One of equations most tractable to systematized
calculations is a modified form of Abels
equation of state which has been employed
successfully by both Brown3 and Cook4:

p(v - ) = nRT ------------------ (15)

31
The term is a covolume and is employed by Cook
as a function of the specific volume of the gases v.
He found upon computing the values of covolume
for a large number of explosives from measured
detonation velocities that the relationship between
and v are as shown in a curve and a table
respectively. These experimentally determined
values can then be employed to calculate the ideal
detonation velocities of other explosives by a
procedure which is the inverse of that used in
determining the relationship between specific
volume and covolume.

32
 Fig. g) The relationship bettween and v for high explosives

1.0
Pv = nRT + (v)p
lit/kg

.8

.6
O LEAD AZIDE O 60% STRAIGHT
O MERCURY FULMINATE DYNAMITE
O Pb(NO3)2 - 70, TNT 30 EXPLOSIVE A*
O PETN EPLOSIV B**
X CYCLONITE 0 EXPLOSIVE C*
.4 O PICRIC ACID O TNT
+ TECTRYL 0 AMMONIUM
PICATRE
0 EXPLOSIVE D*
* COMMERCIAL EXPLOSIVES

.2

0
0 .2 .4 .6 .8 1.0 1.2 1.4
V lit/kg
33
 THERMOCHEMISTRY AND MATERIAL
BALANCE

The chemical reaction accompanying a detonation wave is

always exothermic in character and from established principles
of thermochemistry the heat of any given reaction is equal to
the heat of formation of the products of the reaction minus the
heat of formation of the reactants. Thus, before the heat of
reaction may be calculated the composition of the explosive
must be known as well as the composition of the products of
the reaction. The composition of an explosive is usually known,
and hence, a very large portion of explosive calculation
problems is concerned with the determination of the products
of reaction.
34
For an oxygen balanced explosive which has a
positive oxygen balance the products can be easily
calculated, but for those with a negative oxygen
balance the calculations are quite complex because
chemical equilibria must be taken into account.

An explosive is usually composed of the elements H,

N, C and O with minor amount of other elements.
Thus, a generalized form a material balance equation
for an explosive rection may be written in the
following form:
35
Ha Nb Cc Od xN2 + yH2O + zCO2 + - - - - -+ Q3 --- (16)

That is, in one hundred grams of explosive there

are a, b, c and d gram atoms of the four
elements. The total number of gram atoms of
these elements must be the same in both sides
of equation 16.

Many commercial explosives are designed with

zero oxygen balance.

36
That is, the constituent elements
hydrogen, nitrogen, carbon and oxygen are
so proportioned that in the gases resulting
from the detonation all af the hydrogen
combines to form H2O (vapor), the
combined nitrogen is released to form
molecular nitrogen (N2) and the carbon
reacts to become carbon dioxide (Co2). If
there is just enough oxygen present to
form H2O and carbon dioxide (H2O) then
the explosive is said to be oxygen
balanced. If it has a deficiency it has a
negative oxygen balance, and if an excess
it has a positive oxygen balance.
37
 A deficiency will result in the formation of
carbon monoxide (CO) and other compounds,
the amounts present being dependent on the
temperature and chemical equilibrium
constants. Either an excess or deficiency of
oxygen will usualy yield a lower heat of
reaction than a balanced composition.

Where an explosive does not contain other

elements such as Na and Ca, which have a high
affinity for oxygen, the oxygen balance equation
may be written as follows:
38
 OB = O0 2CO2 H2O ----(17)

Or it may be expressed in a more general form:

OB = O0 C0 H0 ------ (18)

39
 THERMODYNAMICS

INasmuch as heat capacities of the products of

a detonation determine the temperature of the
gases and consequently play a dominant role in
detonation pressure and velocity calculation it is
necessary to define terms. The ideal heat
capacity at constant volume Cv is a function of
temperature. Hence, for a single gas reactions
other than in the detonation zone the final
temperature may be calculate by:

40
 T2

Q3 Cv dT
T1

However, to facilitate calculations an average

heat capacity Cv is defined as follows

T2

C v (T2 T1 ) Cv dT (19b)
T1

41
The detonation process can be considered
to be adiabatic with a good degree of
accuracy. From the laws of
thermodynamics it is known a that a
change in internal energy of gases is given
by :

dE dq dw - - - - (19)

42
Where q is heat and w is work.

Since there is no change dq in an adiabatic

process then we can write:

dE - dw - pdv - -- (20)

Also dE is a total differential and is a function of

p, v and T. Hence

E E
dv dT

dE (21)
v T T v 43
These expressions may be further utilized as follows
for an adiabatic process:

dE pdv 0 (22)
Since

E
Cv
T v
44
 E
Cv T s T p (dv) s (23)
v

The subscript s indicating constant entropy

(adiabatic conditions).

Differentiation of p(v - ) = nRT (eqn. 16) yields

pdv vdp dp pd
dT (24)
nR
45
Substitution in equation (23) yields, using
subscript 2 to indicate detonation conditions

p2 p2
(25)
v2 s v2

Where:

nR Cv

E nR

v v C p (26)
Cv 2 s 2 T v 2

46
The last term on the right side of (26) is small
and can be neglected.

The term under the radical sign in equation (4)

can also be written for the assumed adiabatic
detonation conditions as follows:

p2
D v1 (27)
v2 s
47
Hence, the detonation velocity is determined from
(25) and (27) as:

v p2 2
D 2 1
(28)
v2

or, from (15), substituting for p2,

v nRT2 2
D 2 1
(29)
v2 2

48
Also, since p2 > p1 for condensed explosives,
equations (25) and

p2 p2 p1 p2
(30)
v2 s v1 v2 v1 v2

also give

v2
(31)
v1 v 2
49
 An expression for can then be found from (29)
and (31)

1nRT2
1
2
v1 v1 1
(32)
2
D

From an equation before mentioned

1
nRT2 2
W (33)

50
And also:

nRT2
E2 E1 (34)
2

From (34) and (8) an expresion for the explosion

temperature may be derived:

C v (T3 T1 ) Q3 (35)
51
In the above equations Cv is the ideal heat
capacity of the gaseous products of
detonations and Cv is the average heat capacity
of the gases and solids produced.

The calculation of the explosion state

temperature does not involve detonation
parameters and it may be written.

T2
Q2 T1 C v
(36)
C v 12 nR
52
Or:

Q3
T3 T1 (37)
Cv

53
 CALCULATION OF DETONATION
PARAMETERS
ALGORITHM
The detonation state parameters from and
oxygen balanced explosive may be calculated
as follows:

1. Given: Explosive composition and density.

2. Calculate gram atoms per 100 grs of explosive
of H, N, O and C.
54
3. Subtract the amount of O required to form
oxides of Na, Al or Ca (i.e, Na2O, Al2O3 or
CaO) if they are present.
4. Assume a detonation temperature T2 in K.
5. Assume a value of V2, which may be
approximated from the equation:

v2 v1 0.72 0.1( 1 0.9) (38)

55
6. Write an equation for reaction:

C x H y O2 NU Ca, etc H 2O XCo2 N 2 solid
y u
oxides Q3
2 2

Note 1. For an oxygen balanced explosive there

will be just enough O2 to balance the equation.

7. Calculate from equation (26) for gases only.

must also satisty the equation (31)
CV can be obtained from tables. 56
8. Check temperature T2 by equation (33) using
both solids and gases.
9. Adjust T2, , and V2 until equations (6), (7)
(10) can be satisfied.
10. Calculate detonation pressure from equation
of state using R = 0.08207
liter Atm/Mol/K.
11. Calculate detonation velocity from (29)

57
 v nRT2 2
D 2 1

v2 2

With R = 8.315 joules/Mol/K.

58
A) CALCULATION OF EXPLOSION STATE PARAMETERS

For calculations of explosion state parameters, it is

assumed that the explosion products occupy the
volume of the BoreHole at the density of the
explosive or
(1 = 3 or V1 = V3 ).

The temperature in this case is calculated from:

Q3
T3 T1 (39)
ni C v 59
Detailed procedure is as follows:

1. Repeat steps (1) to (3) for detonation state.

2. Assume a temperature T3.
3. Calculate average heat capacity of products.
4. Iterate with equation (39) until calculated
temperature agress with assumed
5. temperature.
6. Calculate explosion pressure (p3).

60
 AVAILABLE ENERGY

The energy available from explosives to do blasting

work may be accurately found by the work equation
for an adiabatic explosion process, where vi is the
specitic volume at atmospheric pressure:

vf

AE
vi
pdv

61
This integral can be evaluated by using either
the detonation or explosion state conditions
as the initial conditions and assuming that the
explosion products are constant in
composition during expansion.

However, the process of calculating is

somewhat tedious, and for most commercial
explosives the available work may by
approximated by the heat of explosion Q3.
AE Q3
62
An the other hand, when using explosives
in the field an optimum amount of the heat
of explosion can be utilized if the blastholes
are properly stemmed and if the explosive
completly fills the cavity at its normal
absolute density , that is, if it has a loading
density of one. Poor stemming, improper
loading or cracks in the rock mass will
seriously decrease the efficiency of the
available energy at the detonation and
explosion states.

63
 A traves de la humildad por aprender
se alcanza el xito. Aplique la tecnologia
de lo obvio y supere el sindrome del
producto terminado.

Dr. Carlos Agreda T

Profesor
Lima, 20 de abril del 2006 64