Abstract

In the conductive theory of thermal explosion, an exothermic system is considered to be an ignition hazard only if the numerical value of the dimensionless group δ = Qσa 0 2A exp (− E/RT a κ(RT a 2/E) exceeds a critical value. [Here Q is the exothermicity, σ the density, a 0 the half-width, A exp(− E RT a ) the rate constant at ambient temperature, and κ the thermal conductivity.] This classical approach implicitly assumes that the material is initially assembled at or near to ambient temperature. Such initial conditions represent only a subclass of the whole problem. In some situations of technical importance the reactant may be initially considerably above T a . The present paper considers the temperature evolution in bodies subject to Frank-Kamenetskii boundary conditions but which are assembled with a positive, uniform temperature-excess. It is shown that in the usual exponential approximation, any system with δ ⩽ δ cr has a critical initial temperature, above which thermal runaway occurs. Exact numerical results for the critical conditions are presented for the three class A geometries (infinite slab, infinite cylinder, and sphere). Very accurate analytical approximations are also provided. For an Arrhenius rate-law, ignition cannot occur in this way for very low δ < δ ex, where δ ex ∼ O[ exp(−ϵ − 1 2 )] and ϵ = RT a E . A comparison is made between the predictions of this model and the critical conditions observed in an actual, practical example; the spontaneous ignition of piles of bagasse (extracted sugar cane) for which δ ≈ 0.02 ⪡ δ cr.

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