Thermal oscillations in the decomposition of organic peroxides: Identification of a hazard, utilization, and suppression

The purpose of this research is to identify and characterize oscillatory thermal instability in organic peroxides that are used in vast quantities in industry and misused by terrorists. The explosive thermal decompositions of lauroyl peroxide, methyl ethyl ketone peroxide, and triacetone triperoxide are investigated computationally, using a continuous stirred tank reactor model and literature values of the kinetic and thermal parameters. Mathematical stability analysis is used to identify and track the oscillatory instability, which may be violent. In the mild oscillatory regime it is shown that, in principle, the oscillatory thermal signal may be used in microcalorimetry to detect and identify explosives. Stabilization of peroxide thermal decomposition via Endex coupling is investigated. It is usually assumed that initiation of explosive thermal decomposition occurs via classical (Semenov) ignition at a turning point or saddle-node bifurcation, but this work shows that oscillatory ignition is also characteristic of thermoreactive liquids and that Semenov theory and purely steady state analyses are inadequate for identifying a thermal hazard in such systems

Oscillatory thermal instability and the Bhopal disaster

A stability analysis is presented of the hydrolysis of methyl isocyanate (MIC) using a homogeneous flow reactor paradigm. The results simulate the thermal runaway that occurred inside the storage tank of MIC at the Bhopal Union Carbide plant in December 1984. The stability properties of the model indicate that the thermal runaway may have been due to a large amplitude, hard thermal oscillation initiated at a subcritical Hopf bifurcation. This type of thermal misbehavior cannot be predicted using conventional thermal diagrams, and may be typical of liquid thermoreactive systems.Comment: 12 pages, 5 figures. Submitted to Process Safety and Environmental Protection 08 July 2010. A belated submission from work that should have been written up and published years ag

Theoretical Modeling of the Thermal State of Accreting White Dwarfs Undergoing Classical Novae

White dwarfs experience a thermal renaissance when they receive mass from a stellar companion in a binary. For accretion rates < 10^-8 Msun/yr, the freshly accumulated hydrogen/helium envelope ignites in a thermally unstable manner that results in a classical novae (CN) outburst and ejection of material. We have undertaken a theoretical study of the impact of the accumulating envelope on the thermal state of the underlying white dwarf (WD). This has allowed us to find the equilibrium WD core temperatures (T_c), the classical nova ignition masses (M_ign) and the thermal luminosities for WDs accreting at rates of 10^-11 - 10^-8 Msun/yr. These accretion rates are most appropriate to WDs in cataclysmic variables (CVs) of P_orb <~ 7 hr, many of which accrete sporadically as dwarf novae. We have included ^3He in the accreted material at levels appropriate for CVs and find that it significantly modifies the CN ignition mass. We compare our results with several others from the CN literature and find that the inclusion of ^3He leads to lower M_ign for >~ 10^-10 Msun/yr, and that for below this the particular author's assumption concerning T_c, which we calculate consistently, is a determining factor. Initial comparisons of our CN ignition masses with measured ejected masses find reasonable agreement and point to ejection of material comparable to that accreted.Comment: 14 pages, 11 figures; uses emulateapj; accepted by the Astrophysical Journal; revised for clarity, added short discussion of diffusio

Modification of classical electron transport due to collisions between electrons and fast ions

A Fokker-Planck model for the interaction of fast ions with the thermal electrons in a quasi-neutral plasma is developed. When the fast ion population has a net flux (i.e. the distribution of the fast ions is anisotropic in velocity space) the electron distribution function is significantly perturbed from Maxwellian by collisions with the fast ions, even if the fast ion density is orders of magnitude smaller than the electron density. The Fokker-Planck model is used to derive classical electron transport equations (a generalized Ohm's law and a heat flow equation) that include the effects of the electron-fast ion collisions. It is found that these collisions result in a current term in the transport equations which can be significant even when total current is zero. The new transport equations are analyzed in the context of a number of scenarios including $\alpha$ particle heating in ICF and MIF plasmas and ion beam heating of dense plasmas