Effects of nitric oxide on the thermal decomposition of methyl nitrite: Overall kinetics and rate constants for the HNO + HNO and HNO + 2NO reactions

1992 ◽  
Vol 24 (8) ◽  
pp. 743-760 ◽  
Author(s):  
Y. He ◽  
M. C. Lin
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Rate Constants ◽  
Methyl Nitrite ◽  
Overall Kinetics

A Shock Tube Study of the Thermal Decomposition of Nitric Oxide

1975 ◽  
Vol 10 (3-4) ◽  
pp. 155-162 ◽  
Author(s):  
QUAC LE TRUNG ◽  
DONALD MACKAY ◽  
AKIRA HIRATA ◽  
OLEV TRASS
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Shock Tube ◽  
Tube Study

Influence of Nitric Oxide on the Thermal Decomposition of Dimethyl Ether. Gaseous Catalysis

Nature ◽  
1936 ◽  
Vol 138 (3491) ◽  
pp. 546-547 ◽  
Author(s):  
P. F. GAY ◽  
MORRIS W. TRAVERS
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Dimethyl Ether

Substituent effects of rate constants for thermal [4π + 2π] cycloreversion of spiro-fused β-lactam oxadiazolines

1993 ◽  
Vol 71 (6) ◽  
pp. 907-911 ◽  
Author(s):  
Michel Zoghbi ◽  
John Warkentin
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Rate Constants ◽  
Transition States ◽  
Substituent Effects ◽  
Ground States ◽  
Phenyl Substituent ◽  
First Order ◽  
Average Value ◽  
Carbonyl Ylide

Twelve Δ3-1,3,4-oxadiazolines in which C-2 is also C-4 of a β-lactam moiety (spiro-fused β-lactam oxadiazoline system) were thermolyzed as solutions in benzene. Substituents in the β-lactam portion affect the rate constant for thermal decomposition of the oxadiazolines to N2, acetone, and a β-lactam-4-ylidene. The total spread of first-order rate constants at 100 °C was 47-fold and the average value was 6.7 × 10−4 s−1. A phenyl substituent at N-1 or at C-3 was found to be rate enhancing, relative to methyl. At C-3, H and Cl were also rate enhancing, relative to methyl. The data are interpreted in terms of the differential effects of substituents on the stabilities of the ground states, and on the stabilities of corresponding transition states for concerted, suprafacial, [4π + 2π] cycloreversion. The first products, presumably formed irreversibly, are N2 and a carbonyl ylide. The latter subsequently fragments to form acetone (quantitative) and a β-lactam-4-ylidene.

Stationary flames of methyl nitrate and methyl nitrite

1955 ◽  
Vol 232 (1190) ◽  
pp. 389-403 ◽  
Keyword(s):  
Nitric Oxide ◽  
Atmospheric Pressure ◽  
Burning Velocity ◽  
Vapour Phase ◽  
Main Reaction ◽  
Methyl Nitrite ◽  
Nitrate Esters ◽  
Methyl Nitrate ◽  
Low Pressures ◽  
Ethyl Nitrite

Methyl nitrate (CH 3 ONO 2 ) is the most explosive of the nitrate esters, and previous studies have been confined mainly to the slow thermal decomposition, and to the vapour phase explosion at low pressures in closed vessels. A stationary decomposition flame has now been maintained and studied spectrographically. A t low pressures the zones of reaction are clearly separated. From the early stages of the flame strong formaldehyde bands are emitted. This decomposition flame has been successfully simulated in artificial mixtures of methyl nitrite with oxygen. The results obtained are in accord with the preliminary fission of the nitrate molecule in the pre-heat zone of the flame: CH 3 ONO 2 →CH 3 O + NO 2 . The combustion flame of m ethyl nitrate with oxygen, nitric oxide and nitrogen dioxide has also been examined at low pressures. At atmospheric pressure, m ethyl nitrite (CH 3 ONO) has been found to support a decomposition flame of very small burning velocity. However, the combustion of m ethyl nitrite with oxygen at atmospheric pressure is an extremely fast and vigorous flame. It has been observed in both pre-mixed and diffusion systems and information about the changes occurring in it have been obtained by absorption and emission spectroscopy. All the experimental results may be interpreted in terms of two general principles: the reluctance of nitric oxide to react except at high temperatures and pressures and the frequent occurrence in flames of extensive pyrolytic reactions before the main reaction zone is reached.

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