Proc. Natl. Acad. Sci. USA Vol. 76, No. 9, pp.

4162-4164, September 1979

Chemistry

A theory of light-induced explosion

(effect of radiation/laser-induced explosion)

S. H. LIN*, W. B. RICHARDSON*t, AND H. EYRINGt

*Department of Chemistry, Arizona State University, Tempe, Arizona 85281; and *Department of Chemistry, University of Utah, Salt Lake City, Utah 84112

Contributed by Henry Eyring, December 7, 1978

ABSTRACT This paper presents a theoretical analysis, based on a simplified one-dimensional model, of the response of an explosive to a wide range of light intensities. A primary result has been the identification and development of a relationship among the important critical parameters. Numerical results illustrating the relationship among the critical light intensity, sample dimension, and ambient temperature have been obtained, with lead azide as the example.

1. Introduction A thermal explosion can occur when the rate of heat production by chemical reaction is greater than the rate of heat loss to the surroundings; under these conditions the reaction accelerates to a great speed and an explosion may occur (1). When an intense light impinges on the surface of an explosive material, the outcome is not at all certain. Recent experimental investigations (2, 3) have found that it is difficult to ignite a high explosive by using laser pulses of about 100 kW/cm2 average flux density and up to several seconds duration. Many crystalline materials decompose when irradiated with light of the appropriate wavelength. If the intensity is sufficiently high, some of the more sensitive compounds explode. Crystalline secondary explosives, which are mainly organic covalent compounds, do not explode even at energies of 2000 J; alkyl nitrate vapors, on the other hand, may be ignited by light (1). The ignition of crystalline materials by light gives useful information concerning the energy required for explosion. The absorption of light takes place in a layer close to the surface, and the crystal is not disturbed to any appreciable extent in a flash duration. The results obtained are also relevant to a discussion of the propagation of explosion and to detonation phenomena. Only a few materials have been studied in any detail. These include silver azide, thallous azide, silver nitride, nitrogen iodide, and lead styphnate and azide. The present paper gives a theoretical analysis based on a simplified one-dimensional model of the response of the explosive to a wide range of light densities. The objectives of the simple theory are to identify the important physical parameters of the problem and reveal any critical or threshold conditions that may exist. 2. Theory The general expression for the energy equation is given by
Cp

constant, and V2 the Laplacian operator. In the theory of thermal explosion it is postulated that the critical condition for inflammability is reached when the amount of heat developed by the chemical reaction is just equal to the amount lost to the surroundings. In other words, the conditions under which a stationary state is not possible will then give the critical conditions for explosion (1, 4). We then have XV2T = -Qnk. [2-2] It is assumed that the reaction is first order and that k = A exp(-E/RT), in which E is the activation energy, R is the gas constant, and A is the pre-exponential factor. If we let To represent the absolute ambient temperature, then Eq. 2-2 can be rewritten as (1, 5) V7 20 =-|QA E_ nA exp (
in which
E

exp(o),

[2-3]

[24] ~(T -TO). RTQ2 In this paper, we shall restrict ourselves to the planar case, in which the heat conduction depends on only one space coordinate x. We introduce the variable z x/r, in which r is the dimension of the vessel. It follows that (1, 5)
0=

do= -6 exp(O),
in which

[2-5]

E (nAr2 6=QX RTO2 exp -RTO)

To solve Eq. 2-5, we let

[2-6]
[2-7]

71 = exp(O), (

=dO

In terms of q and w, Eq. 2-5 becomes do do which can easily be solved as

[2-8]

-T = XV 2T + Qnk,

[2-1]

[2-9] (d+ D, inwhchD sth iterain ontat in which D is the integration constant. Solving the differential equation given by Eq. 2-9 yields
exp (-

=)-26 exp(0)
I

in which T is the temperature of the system, C the specific heat, p the density, X the thermal conductivity, Q the heat of reaction per mole, n the number of moles per unit volume, k the rate

2) + |exp(-0)-

exp c +

2 z)

[2-10]
in which C represents another integration constant. Eq. 2-10 can be rewritten as
t

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4162

Chemistry:

Lin et al.
-

Proc. Natl. Acad. Sci. USA 76 (1979)

4163

2exp (- 2 = D exp (C \2J D 2

+

)'1 /

Eliminating Wcrit from Eqs. 2-20 and 2-21 yields 1 (B41-1) 1

in which
2
4uB2
Vi

'

[2-22]

exp(C + 'p ).[2-11]

For the case of the light-induced explosion, we have the boundary conditions 0 = 0, z = 1 [2-12] and
-X-=aI, x = 0,
dx

B2= eu_( + V/u2)12 [2-231 In other words, to obtain Wvcrit we first calculate u for a given 6 and then substitute this u value into Eq. 2-20 to find Wcrit Alternatively, to find rcnt for a given O,, we differentiate Eq. 2-19 with respect to u and set db/du = 0 to yield
1
CL) 1

[2-13]

in which aI represents the absorbed light flux. In terms of 0 and z, Eq. 2-13 becomes da = _@0, z = ' [2-14] dz in which arIE [2-15] =

2 u2-o From Eq. 2-19 we have

O/U2-23crit

2-4

[2-24]

+ W + e-2 U\ +o ) 2-25] =\-6cit2 2e / WO I; From Eqs. 2-24 and 2-25, kcrit can easily be eliminated to
give

1
in which
U

@0

XRTO2

2 u2-w02 u
F

1-F

[2-26]

Using Eqs. 2-12 and 2-14, we find

2

2ep (-C -u + exp (c + u

exp(2C) (1 )
=

{Y VU+ Wo -.UIV
2
0 -go
U

12-16]

+ coo

and

2(

+ u)

in which u = vii. Eliminating C from Eqs. 2-16 and 2-17 yields u 2 = exp VU + 'i"' + exp (! Vu + o

(2-)

[2-18] or

U= exp(=)

V -. [2-19]

It is evident from the expressions for 6 and wo, that three of the important factors governing the growth of reaction to explosion are the heat of reaction Q, the light intensity I, and the length of the reacting system r. Eq. 2-19 can be used to obtain the maximum value of the parameter 6 (kcrit) or the parameter co (COcit) for which a solution of Eq. 2-5 is possible. For 6 > rcnt or coo > C0crit, a stationary temperature distribution ceases to be possible and this gives the critical condition for explosion. The critical temperature distribution Ocrit may also be calculated, giving the maximum dimensionless temperature above which an explosion results. The actual temperature may then be calculated from Eq. 24. In the above derivation the effect of the change in concentration of reactants during the induction period has not been taken into account, but it can easily be done. To find wor, we differentiate Eq. 2-19 with respect to u and set dcoo/du = 0 to yield
O crit

[2-27] In the following section, we shall numerically demonstrate the calculation of 6crit and Wcrit for a given wO and a given 6, respectively. The crit values will also be calculated. To show the application of the theoretical results, we shall apply them to the light-induced explosion of lead azide. 3. Numerical Calculations The numerical solutions of either the set of Eqs. 2-24 through 2-27 or 2-20 through 2-23 yield a one-to-one correspondence between the critical dimensionless quantities 6crit and wocnt Once these critical parameters are known, the solutions of Eqs. 2-17 and 2-11 give Ocrit = (E/RT02)(T - T0). The results are tabulated in Table 1, and it is evident that 6crit decreases rapidly with increasing (<crit, and hence with the light intensity I. Both 6 and cwo are defined in terms of a number of important physicochemical quantities and consequently there exists a wide latitude in choice of variables to be determined. The theory is strictly applicable to those compounds that do not melt prior to explosion because effects of phase transitions and convection have been excluded. A primary explosive such as lead azide satisfies the latter requirement (1) and it has been established (6, 7) that a photochemical ignition mechanism may be excluded under ordinary conditions. The thermal chemical properties (1, 6) and absorption spectrum (8, 9) of lead azide
Table 1. Relationships among critical parameters
bcrit
0.88 0.819 0.70 0.60 0.50 0.427 0.30 0.20 0.10 0.0168 0.01 0.001 0.000195
WO crit

Ocrit
1.19 1.28

0.1

2 u Wocrit Also from Eq. 2-19 we have

2

2
U2
2
-

[2-20]

0.319 0.542 0.795

1.0

e-u

U
crit

u
-TI

=
I

26

e -u

u -

U2-2 1 +I 26

[2-21]

1.45 2.0 2.86 5.00 5.60 8.19 10.00

1.50 1.71 1.95 2.15 2.61 3.12 3.98 6.08 6.67 9.25
11.0

4164

Chemistry:

Lin et al.

Proc. Natl. Acad. Sci. USA 76 (1979)

Table 3. Effect of activation energy on explosion parameters E, I, ti, EWAi) T., T" J cm-2 s-1 J cm-2 cal mold s 0C 0C
r =

are reasonably well established and the calculations discussed below were made using values of the density p = 3.62 g/cm3, thermal conductivity X = 4 X 10-4 cat g- K-' cm-', specific heat at constant pressure Cp = 0.117 cal g'1 K-', heat of reaction Q = 115,000 cal/mol, activation energy E = 37,000 cal/mol, and a value of 1014 s-l for the pre-exponential factor A (1 cal = 4.184 J). It is assumed that we are probing the sample with monochromatic light in a spectral region for which the fraction of light absorbed a may be set equal to 1. It is also implicitly assumed that we are employing light sources of such low intensity as to preclude sample ablation, etc. With the thermal parameters known and the characteristic film thickness r assigned, choice of a value for the critical value bcrit (hence uniquely determines the critical temperature To from Eq. 2-6. The critical temperature To is defined as the temperature at which the heat generated through self-heating equals that conducted away through the bulk of the sample. The temperature Tc at which the samples explode is then found from the tabulated values of 0crit and Eq. 2-4. Subsequently, the values of the critical light flux I are determined from Eq. 2-15. The results of a number of calculations utilizing various values of the film thickness r and WOcrit or bcrit are tabulated in Table 2. An estimate of the ideal ignition delay ti, defined as the time

30,000 40,000 50,000 30,000 40,000 50,000

0.1 cm, bcrit = 0.2, Wcrit ,=2.0 0.286 0.987 3.45 0.385 1.32 3.45 0.486 1.66 3.42
0.05 cm, 6crit = 0.2, Wcrit = 2.0 0.61 0.53 0.87 0.825 0.71 0.86 1.04 0.91 0.88

85 208 331 98 225 353

111 244 376

r =

126 263 402

required for the sample surface temperature to reach T> from To, is obtained from the relationship (6)
ti =

pCp RTC2 exp(E/RTc) QAEN

[3-1]

Table 2. Predicted relationships among c0,jat, critical light intensity, and ambient temperature I, J cm-2 r, E(Iti), Tow, Tc, J cm-2 0C s-1 cm 0C ti, s WOcrit
0.1

0 0.542 1.0 2.0 2.86 5.0 10.0

0 0.542

0.101 0.184 0.355 0.489 0.785 1.28 0.22 0.396 0.761 1.046 1.68 2.74 1.31 2.37 4.53 6.22 9.89 15.8
2.84 5.13 9.8 13.48 21.33 33.7

0.385 0.647 1.154 1.589 2.98 1.39 0.214 0.360 0.640 0.952 1.64 7.06

188 183 179 171 163 145 105

205 200 196 187 178 159 117 251 245 240 229 219 196 146

202 202 202 204 204 202 189

220 220 221 222 221 220 207 268 270 270 271 271 268 250

3.8 3.52 3.25 3.25 3.80 1.084 0.98 0.98 0.9 0.85 0.91 0.98 2.58 0.037 0.0367 0.0345 0.0345 0.0413 0.126
0.0095 0.00945 0.0089 0.0087 0.011 0.0345

0.05

1.0
2.0 2.86 5.0 10.0 0.01 0 0.542 1.0

in which N is Avogadro's number. It is of interest to note that for any fixed value of r, the sample thickness, the explosion temperature and ignition delay are substantially constant while the critical temperature To decreases rapidly with decreasing bcrit In addition, the well-known relationship between sample critical dimension and ease of ignition is seen to hold also for light-induced explosion; the required light intensities I increase rapidly for decreasing film thickness, although the total energy delivered is of course decreased (10). It should be noted that the last one or two sets of values listed in Table 2 (i.e., those for which w(Dcrit = 5 and 10) are in some cases of limited validity because of violations of the exponential approximation (Eq. 2-3). Additional numerical results were obtained by varying the reaction's activation energy E, which enters the defining equation for 6 in an exponential fashion. The results given in Table 3 were obtained by using the same thermal values as before for Pb(N3)2 except that E was varied widely. For fixed values of 6crit and wcrt) results for selected values of the sample thickness r are given and illustrate the dramatic effect of the value of the activation energy E upon the critical temperature To and the explosion temperature Tc.
The authors thank the U.S. Army Research Office (Grant DAHC 04-75-0019) for financial support of this work.
1. Bowden, F. P. & Yoffe, A. D. (1958) Fast Reactions in Solids (Butterworth, London), pp. 20-32. 2. Yang, L. C. & Menichelli, V. J. (1976) in Sixth Symposium on Detonation, August 1976, Publication A.C.R.-221 (Office of Naval Research, Arlington, VA), pp. 612-621. 3. Harrach, R. J. (1976) J. Appi. Phys. (1976) 47,2473-2482. 4. Frank-Kamenetskii, D. A. (1969) Diffusion and Heat Transfer in Chemical Kinetics (Plenum, New York), pp. 66-74. 5. Chambre, P. L. (1952) J. Chem. Phys. 20, 1795-1797. 6. Roth, J. (1964) J. Chem. Phys. 41, 1929-1936. 7. Blanchard, R. (1963) C. R. Hebd. Seances Acad. Sci. 256,
2550-2553. 8. Higgins, P. B. (1972) Appl. Opt. 11, 203-205. 9. Downs, D. S. & Christoe, C. W. (1975) J. Chem. Phys. 63, 3372-3373. 10. Murty Kanury, A. (1975) Introduction to Combustion Plenomena (Gordon & Breach, New York), pp. 111-136.

2.0
2.86 5.0 10.0
0.005

0.048 0.087 0.156 0.215

0.41

1.99
0.0252 0.048 0.087 0.117 0.235 1.116

0 0.542
1.0 2.0

2.86 5.0 10.0

273 267 261 249 239

214 160

292 295 294 295 295 291 271