Autocatalytic Decompositions

FIGURE 2.2. Types of Explosions. [ A thermally driven (self-healing) B chemically driven (e.g., inhibitor depletion, melting with decomposition, autocatalytic decomposition)). 

Hansen L D, Eatough D J, Lewis E A and Bergstrom R G 1990 Calorimetric measurements on materials undergoing autocatalytic decomposition Can. J. Chem. 68 2111-14... 

Pentaeiythritol Tetranitrate. Specification-grade pentaerythritol tetranitrate (PETN) can be stored up to 18 months at 65°C without significant deterioration. However, many materials have been found to be incompatible with PETN and the presence of as Htfle as 0.01% occluded acid or alkah greatly accelerates decomposition. The decomposition of PETN is autocatalytic with reported kinetic constants oi E = 196.6 kJ/mol (47 kcal/mol) and Z = 6.31 x 10 . The decomposition products of PETN at 210°C in wt % are 47.7 NO, 21.0 CO, 11.8 NO2, 9.5 N2O, 6.3 CO2, 2.0 H2, and 1.6... 

The problems of monomer recovery, reaction medium viscosity, and control of reaction heat are effectively dealt with by the process design of Montedison Fibre (53). This process produces polymer of exceptionally high density, so although the polymer is stiU swollen with monomer, the medium viscosity remains low because the amount of monomer absorbed in the porous areas of the polymer particles is greatly reduced. The process is carried out in a CSTR with a residence time, such that the product k jd x. Q is greater than or equal to 1. is the initiator decomposition rate constant. This condition controls the autocatalytic nature of the reaction because the catalyst and residence time combination assures that the catalyst is almost totally expended in the reactor. 

The potassium permanganate crystals are dried at atmospheric pressure below 150°C, cooled, and packaged. Care is taken to prevent heating the product above 200°C during drying to avoid autocatalytic exothermic decomposition of the product. 

Thermal stabihty of the foaming agent in the presence of high temperature steam is essential. Alkylaromatic sulfonates possess superior chemical stabihty at elevated temperatures (205,206). However, alpha-olefin sulfonates have sufficient chemical stabihty to justify their use at steam temperatures characteristic of most U.S. steamflood operations. Decomposition is a desulfonation process which is first order in both surfactant and acid concentrations (206). Because acid is generated in the decomposition, the process is autocatalytic. However, reservoir rock has a substantial buffering effect. 

Thermal Decomposition of GIO2. Chloiine dioxide decomposition in the gas phase is chaiacteiized by a slow induction period followed by a rapid autocatalytic phase that may be explosive if the initial concentration is above a partial pressure of 10.1 kPa (76 mm Hg) (27). Mechanistic investigations indicate that the intermediates formed include the unstable chlorine oxide, CI2O2. The presence of water vapor tends to extend the duration of the induction period, presumably by reaction with this intermediate. When water vapor concentration and temperature are both high, the decomposition of chlorine dioxide can proceed smoothly rather than explosively. Apparently under these conditions, all decomposition takes place in the induction period, and water vapor inhibits the autocatalytic phase altogether. The products of chlorine dioxide decomposition in the gas phase include chlorine, oxygen, HCl, HCIO, and HCIO. The ratios of products formed during decomposition depend on the concentration of water vapor and temperature (27). 

Organic Solids A few organic compounds decompose before melting, mostly nitrogen compounds azides, diazo compounds, and nitramines. The processes are exothermic, classed as explosions, and may follow an autocatalytic law. Temperature ranges of decomposition are mostly 100 to 200°C (212 to 392°F). Only spotty results have been obtained, with no coherent pattern. The decomposition of malonic acid has been measured for both the solid and the supercooled liquid. The first-order specific rates at 126.3°C (259.3°F) were 0.00025/min for solid and 0.00207 for liquid, a ratio of 8 at II0.8°C (23I.4°F), the values were 0.000021 and 0.00047, a ratio of 39. The decomposition of oxalic acid (m.p. I89°C) obeyed a zero-order law at 130 to I70°C (266 to 338°F). 

It is appropriate to start with BaN6 since this compound has been studied particularly intensively and has been regarded as a model in the development of the theory of kinetics of decompositions of solids. The sigmoid a—time curves for BaN6 pyrolyses, Fig. 15, are typical examples of solid state autocatalytic behaviour. 

Torkar et al. [702,706—708] identified nucleation as an autocatalytic process at the (hk0) planes of hexagonal platelets of NaN3. The decelera-tory reaction fitted the first-order equation [eqn. (15)]. Values of E tended to be irreproducible for the pure salt E was about 180 kJ mole 1 but this was reduced to about half by doping. This influence of an additive and the observed similarities in magnitudes of E for decomposition and for diffusion were interpreted as indicating that growth of nuclei was controlled by a diffusion process. 

Systems for consideration under this heading are conveniently classified into two groups, distinguished by the relationship existing between the reactant and the additive considered, which may be (i) a product of the decomposition process or (ii) a substance chemically different from all the participating phases. In certain important respects, reactions of type (i) may be regarded as specific instances of the autocatalytic behaviour characteristic of the reactant-derived product in many nucleation and... 

Several alkali chlorates and perchlorates undergo fusion during the onset of decomposition, the autocatalytic character of reaction then being attributable to the greater rate of reaction in the melt. Khorunzhii and II in [849], from work on the reactions of Na+ and K+ salts of chloric and perchloric acids, conclude that surface and grain boundary diffusion exert an essential role in decomposition rate control. 

As the reaction proceeds higher sulfanes and finally Ss are formed. The reaction is autocatalytic which makes any kinetic analysis difficult. The authors discussed a number of reaction mechanisms which are, however, obsolete by today s standards. Also, the reported Arrhenius activation energy of 107 17 kJ mol is questionable since it was derived from the study of the decomposition of a mixture of disulfane and higher sulfanes. Nevertheless, the observed autocatalytic behavior may be explained by the easier ho-molytic SS bond dissociation of the higher sulfanes formed as intermediate products compared to the SS bond of disulfane (see above). The free radicals formed may then attack the disulfane molecule with formation of H2S on the one hand and higher and higher sulfanes on the other hand from which eventually an Ss molecule is split off. 

Quite complex kinetic behavior has been identified on some surfaces. For instance, on Ir(100), the TPD data from NO-saturated surfaces display two N2 desorption peaks, one at 346 K from the decomposition of bridge-bonded NO, and a second at 475 K from the decomposition of atop-bonded NO molecules [13], Interestingly, the first feature is quite narrow, indicating an autocatalytic process for which the parallel formation of N20 appears to be the crucial step. An additional complication arises from the fact that this Ir(100) surface undergoes a (1x5) reconstruction, and that NO adsorbed on the metastable unreconstructed (lxl) phase leads to N2 desorption at lower temperatures. In another example, on the reconstructed hexagonal Pt(100) surface, when a mixed NO + CO adsorbed layer is heated, a so-called surface explosion is observed where the reaction products (N2, C02 and N20) desorb simultaneously in the form of sharp peaks with half-widths of only 7 to 20 K. The shape of the TPD spectra suggests again an autocatalytic mechanism [14],... 

Couttenye, R.A., De Vila, M.H. and Suib, S.L. (2005) Decomposition of methane with an autocatalytically reduced nickel catalyst Journal ofCatalysis, 233,317-326. 

Many methods have been proposed and are used to study the thermal stability of propellants and to ensure the absence of possible autocatalysed decompositions during storage. None are sufficiently reliable to merit individual description. In practice, stabilisers are added, the usual being diphenylamine for nitrocellulose powders and symmetrical diethyl diphenyl urea (carbamate or centralite) for double base propellants. Provided a reasonable proportion of stabiliser remains, the propellant can be assumed to be free from the possibility of autocatalytic decomposition. The best test of stability is therefore a chemical determination of the stabiliser present. 

Violently explosive decomposition at the start of distillation at 165°C/33 mbar of a 2 kg sample was attributed to autocatalytic decomposition which can occur at 125°C in small samples. Increased lability of the 2-chloro substituent when hydrochloride formation has occurred is postulated as a possible cause. Caution on heating any halogenated amine is advised. 

A melting point sample exploded at 150°C. Larger quantities showed signs of autocatalytic decomposition from -30°C. This presumably involves release of strain in the aziridine ring. 

Though regarded as one of the more stable peroxides, it becomes shock-sensitive on heating, and self-accelerating decomposition sets in at 49° C [1]. One of the recently calculated values of 46 and 42°C for induction periods of 7 and 60 days, respectively, for critical ignition temperatures is closely similar to that (4577 days) previously recorded. Autocatalytic combustion of the polymerisation initiator is exhibited. Although not ordinarily shock sensitive, it responds to a detonator [2],... 

It is still unclear what kind of radiation sources can lead to asymmetric reactions. Jeremy Bailey from the Anglo-Australian Observatory in Epping, Australia, investigated which astronomical objects could be considered radiation sources (Bailey et al., 1998 Bailey, 2001). It was possible in laboratory experiments to generate a small enantiomeric excess of some amino acids by using circularly polarized UV light (Norden, 1977). This asymmetric photolysis involves photochemical decomposition of both d- and L- enantiomers, but at different rates, so the more stable form tends to survive. This process must be subject to autocatalytic multiplication. 

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