Shock Tube Laser Schlieren Study of the Pyrolysis of Isopropyl Nitrate

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2019-07, Vol.123 (28), p.5866-5876
• Main Authors: Fuller, Mark E, Goldsmith, C. Franklin
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b03325

The decomposition of isopropyl nitrate was measured behind incident shock waves using laser schlieren densitometry in a diaphragmless shock tube. Experiments were conducted over the temperature range of 700–1000 K and at pressures of 71, 126, and 240 Torr. Electronic structure theory and RRKM Master Equation methods were used to predict the decomposition kinetics. RRKM/ME parameters were optimized against the experimental data to provide an accurate prediction over a broader range of conditions. The initial decomposition i-C3H7ONO2 ⇌ i-C3H7O + NO2 has a high-pressure limit rate coefficient of 5.70 × 1022 T –1.80 exp­[−21287.5/T] s–1. A new chemical kinetic mechanism was developed to model the chemistry after the initial dissociation. A new shock tube module was developed for Cantera, which allows for arbitrarily large mechanisms in the simulation of laser schlieren experiments. The present work is in good agreement with previous experimental studies.