Pre-reforming of propane was studied over an industrial nickel-chromium catalyst under pressures of 1 and 5 bar, at a low steam to carbon molar ratio of 1, in the temperature range of 220–380 °C and at flow rates of 4000 and 12,000 h−1. It was shown that propane conversion proceeded more efficiently at low pressure (1 atm) and temperatures above 350 °C. A genetic algorithm was applied to search for kinetic parameters better fitting experimental results in such a wide range of experimental conditions. Power law and Langmuir–Hinshelwood kinetics were considered. It was shown that only Langmuir–Hinshelwood type kinetics correctly described the experimental data and could be used to simulate the process of propane pre-reforming and predict propane conversion under the given reaction conditions. The significance of Langmuir–Hinshelwood kinetics increases under high pressure and temperatures below 350 °C.
The mechanism of the photooxidation of aromatic azides containing a substituent at one of the ortho positions (2,4-dimethoxyphenyl azide (1a) and 2-methyl-4-[(2E)-1-methylbut-2-en-1-yl]phenyl azide (1b)) was studied in acetonitrile. The electronic spectra and the kinetic regularities of the consumption of corresponding nitroso oxides, which are the reaction intermediates, were investigated by flash photolysis. Owing to the one-and-a-half order of the C-N and N-O bonds and asymmetric molecule structure these nitroso oxides exist as four conformers (cis/syn, cis/anti, trans/syn, and trans/anti). The conformers differ in the spectral properties and in the reactivity in various irreversible transformations. The only product, (2Z,4E)-4-methoxy-6-oxohepta-2,4-dienenitrile oxide (7a), was observed during photooxidation of 1a, whereas transformations of the nitroso oxide isomers derived from 1b led to a set of stable products: the cis/anti isomer was transformed into (3,4,7-trimethyl-3a,4-dihydro-2,1-benzisoxazol-5(3H)-ylidene)ethanal (10), the trans isomers recombined forming the corresponding nitro and nitroso compounds, and the most reactive cis/syn isomer was transformed into ortho-nitrosobenzyl alcohol 11. The last was oxidized slowly to the corresponding benzaldehyde 12. Interaction of 11 and 12 led to the formation of (Z)-1,2-bis(2-formyl-4-((2E)-1-methylbut-2-en-1-yl)phenyl)diazene-1-oxide (13). The DFT simulation and kinetic modeling of the nitroso oxide transformations as well as the product analysis allowed revealing the fine details of the mechanism of decay for these species.
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