|IUPAC Name:||propan-2-yl nitrate|
Isopropyl nitrate(CAS: 1712-64-7） appears as a clear colorless liquid with a pleasant odor. May spontaneously decompose and explode under prolonged exposure to fire or heat. Denser than water and insoluble in water. Vapors are heavier than air. Produces toxic oxides of nitrogen during combustion.
. Griffiths, J.F., Gilligan, M.F. and Gray, P., 1975.
Pyrolysis of isopropyl nitrate. I. Decomposition at low temperatures and pressures.
Abstract: Isopropyl nitrate was decomposed in a closed reactor at temperatures below 500 K and pressures up to 40 kN m−2. The reaction is first order with respect to isopropyl nitrate and the main products of the reaction are isopropyl nitrite, methyl nitrite, nitromethane, acetaldehyde, acetone, nitrogen oxides, and carbon dioxide. The addition of nitric oxide to decomposing isopropyl nitrate causes isopropyl nitrite and nitrogen dioxide to be formed exclusively in the earliest stages of reaction, although it does not alter perceptibly the overall rate and kinetics of reaction. The mechanism of decomposition may be rationalized in terms of an initial fission of the ON bond to yield an isopropoxyl radical and nitrogen dioxide. The isopropoxyl radical is able to decompose to a methyl radical and acetaldehyde. Each of these products then reacts further, in part to convert nitrogen dioxide to nitric oxide and then to form organic derivatives of nitric oxide. The overall behavior of the low-temperature decomposition of isopropyl nitrate resembles that of ethyl and n-propyl nitrates rather than that of t-butyl nitrate.
Combustion and Flame, 24, pp.11-19.
. Morin, J. and Bedjanian, Y., 2016.
Thermal decomposition of isopropyl nitrate: kinetics and products.
Abstract Abstract: Kinetics and products of the thermal decomposition of isopropyl nitrate (IPN, C3H7NO3) have been studied using a low pressure flow reactor combined with a quadrupole mass spectrometer. The rate constant of IPN decomposition was measured as a function of pressure (1–12.5 Torr of helium) and temperature in the range 473–658 K using two methods: from kinetics of nitrate loss and those of reaction product (CH3 radical) formation. The fit of the observed falloff curves with two parameter expression provided the following low and high pressure limits for the rate constant of IPN decomposition: k0 = 6.60 × 10–5exp(−15190/T) cm3 molecule–1 s–1 and k∞ = 1.05 × 1016 exp(−19850/T) s–1, respectively, which allows one to determine (via the above expression) the values of k1 (with 20% uncertainty) in the temperature and pressure range of the study. It was observed that thermal decomposition of IPN proceeds through initial breaking of the O–NO2 bond, leading to formation of NO2 and isopropoxy radical (CH3)2CHO, which rapidly decomposes forming CH3 and acetaldehyde as final products. The yields of NO2, CH3, and acetaldehyde upon decomposition of isopropyl nitrate were measured to be (0.98 ± 0.15), (0.96 ± 0.14), and (0.99 ± 0.15), respectively. In addition, the kinetic data were used to determine the O–NO2 bond dissociation energy in isopropyl nitrate, 38.2 ± 4.0 kcal mol–1.
The Journal of Physical Chemistry A, 120(41), pp.8037-8043.
. Beeley, P., Griffiths, J.F. and Gray, P., 1980.
Rapid compression studies on spontaneous ignition of isopropyl nitrate Part II: Rapid sampling, intermediate stages and reaction mechanisms.
Abstract: Rapid compression studies, which offer a means of studying gas reactions that proceed too fast for conventional techniques but too slowly for accurate shock tube work, require special techniques for quenching and sampling at millisecond or submillisecond intervals. These are developed and used here in a study of the intermediate products of the rapid decomposition of isopropyl nitrate (IPN). Satisfactory element balances are found. Product abundances are consistent with an initial formation of NO2 plus isoproxyl (iPrO) radicals that is followed by decomposition of iPrO to yield acetaldehyde and CH3. The principal features of the reaction mechanism for rapid decomposition are established and used as a basis to interpret the behavior during rapid oxidation. Studies on stoichiometrically similar mixtures of NO2 + CH3CHO contribute to these aspects. In decomposition, temperatures rise to around 600°K at the end of the compression stroke. Conditions then remain constant for nearly a hundredth of a second and 90% of the IPN has been consumed by the end of 8 ms. Dynamic absorption spectra show that NO2 is an important intermediate product during this period, although it is wholly consumed. The final products include substantial yields of CH2O, CH3CHO, and CH3NO2, and smaller amounts of CH3OH and CH3ONO. Carbon oxides are only minor products. Each rises smoothly in yield from the start. In oxidation, temperatures rise and IPN concentrations fall along paths at first identical to those of decomposition, and quite similar compositions of stable intermediate products are seen. But within a short interval (∼5 ms) there is a very marked change: temperatures now reach around 900°K due to self-heating, the intermediates are consumed in ignition, and CO2 becomes the predominant carbon-containing
Combustion and Flame, 39(3), pp.269-281.
. Fuller, M.E. and Goldsmith, C.F., 2019.
Shock Tube Laser Schlieren Study of the Pyrolysis of Isopropyl Nitrate.
Abstract Abstract: 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 × 1022T–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.
The Journal of Physical Chemistry A, 123(28), pp.5866-5876.
. Lewis, T.J., 1978.
Diffusion of isopropyl nitrate, acetone and water into nitrocellulose.
Abstract: The sorption kinetics of isopropyl nitrate, acetone and water into nitrocellulose films show marked differences from each other. The movement of water is essentially Fickian. That of acetone on all cycles and of isopropyl nitrate on the first cycle are characterized by a boundary between swollen and unswollen material moving at constant velocity into the film (Case II swelling). Sorption of isopropyl nitrate on all but the first cycle is characterized by a uniform concentration at all times throughout the expanding film (Case III swelling). Variations in the equilibrium sorption of isopropyl nitrate have been interpreted as indicating that the degree of crystallinity of the nitrocellulose fibres and films.
Polymer, 19(3), pp.285-290.