Auto-catalytic decomposition reaction

The N2O decomposition reaction is especially interesting because under particular conditions the reaction can be induced to oscillate (see Fig. 4.28l l). If non-isothermal effects can be excluded, this implies the presence of an auto-catalytic elementary reaction step in the overall catalytic reaction cycle (see Chapter 8). In this case, the auto-catalysis results from N2O decomposition catalyzed by both mono-center and bi-center iron complexes. 

Modify the existing program to study adiabatic decomposition. Compare the results with those for an adiabatic decomposition of an auto-catalytic reaction. 

AP is stable at room temperature and it decomposes with a measurable rate at temperatures above 150 °C. Further, it undergoes decomposition due to auto-catalytic reaction of the following type at temperatures below 300 °C (Equation 4.22) ... 

This auto-catalytic reaction stops after about 30% decomposition. This is usually called low temperature decomposition (LTD) and it is believed that the electron transfer mechanism is operative in this region. At temperatures above 350 °C, high temperature decomposition (HTD) takes place usually by proton transfer mechanism and finally AP decomposes into NH3 and 4 (Equation 4.23) ... 

The reaction of 4-chloro-2-pentene with dibutyltin dilaurate, one of the first to be studied, provided some interesting observations. A plot of liberated chlorine vs. time (Figure 1) shows the reaction to be auto-catalytic. Investigation led to the discovery that dibutyltin dichloride, a product of the stabilization reaction, is a catalyst for the reaction (Figure 1). Further investigation revealed that at the outset all the reaction takes place by the unimolecular decomposition of the allylic chloride and that not until species with tin—chlorine bonds are present does this stabilizer undergo reaction with the allylic chloride. The reactive stabilizer in this instance is dibutyltin laurate chloride. Dibutyltin dilaurate does not react with the allylic chloride, and dibutyltin dichloride, which is very reactive,... 

The form of rate law and observed rate constants for the solution-phase thermal decomposition of hexamethylDewarbenzene-palladium chloride complex were found to depend on the history of the sample, the reaction being sometimes auto-catalytic and sometimes first-order. ... 

The thermal stabilizing properties of the electrode materials were foimd to be the result of reactions of the electrolyte or electrolyte decomposition products with the surface of the electrodes. Two primary mechanisms were proposed to be responsible for this stabilization. First, the electrode materials could react with the auto-catalytic species rapidly, preventing the exponential decomposition. Second, the surface species could Lewis basic species and reversibly bind the free PF5, preventing the electrolyte decomposition [32,34],... 

---