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

Hydrogen peroxide thermochemical oscillator as driver for primordial RNA replication

This paper presents and tests a previously unrecognised mechanism for driving a replicating molecular system on the prebiotic earth. It is proposed that cell-free RNA replication in the primordial soup may have been driven by self-sustained oscillatory thermochemical reactions. To test this hypothesis a well-characterised hydrogen peroxide oscillator was chosen as the driver and complementary RNA strands with known association and melting kinetics were used as the substrate. An open flow system model for the self-consistent, coupled evolution of the temperature and concentrations in a simple autocatalytic scheme is solved numerically, and it is shown that thermochemical cycling drives replication of the RNA strands. For the (justifiably realistic) values of parameters chosen for the simulated example system, the mean amount of replicant produced at steady state is 6.56 times the input amount, given a constant supply of substrate species. The spontaneous onset of sustained thermochemical oscillations via slowly drifting parameters is demonstrated, and a scheme is given for prebiotic production of complementary RNA strands on rock surfaces.Comment: Submitted 14 Nov 2013 to J. Roy. Soc. Interface, accepted in final form 25 Feb 2014. An article on this paper appears on https://theconversation.com/au. A new recipe for primordial soup on the pre-biotic earth may help answer questions about the origin of life, and explain why new life does not emerge from non-living precursors on the modern eart

Thermodynamics of the deposition of complex waxes and asphaltenes in crude oil

Peer reviewedPublisher PD

Combustion of biomass as a global carbon sink

This commentary article highlights the important role of black carbon produced from biomass burning in the global carbon cycle. Consideration of the fundamental chemistry and thermokinetics of cellulose thermal decomposition suggests that suppression of biomass burning or biasing burning practices to produce soot-free flames must inevitably transfer more carbon to the atmosphere. A simple order-of-magnitude quantitative analysis indicates that black carbon may be a significant carbon reservoir that persists over geological time scales

Strong "quantum" chaos in the global ballooning mode spectrum of three-dimensional plasmas

The spectrum of ideal magnetohydrodynamic (MHD) pressure-driven (ballooning) modes in strongly nonaxisymmetric toroidal systems is difficult to analyze numerically owing to the singular nature of ideal MHD caused by lack of an inherent scale length. In this paper, ideal MHD is regularized by using a k-space cutoff, making the ray tracing for the WKB ballooning formalism a chaotic Hamiltonian billiard problem. The minimum width of the toroidal Fourier spectrum needed for resolving toroidally localized ballooning modes with a global eigenvalue code is estimated from the Weyl formula. This phase-space-volume estimation method is applied to two stellarator cases