Thermal decomposition of peroxyacetyl nitrate and reactions of acetyl peroxy radicals with nitric oxide and nitrogen dioxide over the temperature range 283-313 K

A detailed investigation of the inhibition by nitric oxide of the thermal decomposition of n-butane has been carried out over the temperature range 500° to 550 °C.In all cases it was found that inhibition decreased with increasing butane concentration. This suggests that radical recombination occurs in the normal decomposition by ternary collisions with butane molecules acting as third bodies.The activation energies of the normal and inhibited reactions have been determined. For high pressures the two values are in good agreement, viz., 58,200 and 57,200 cal. per mole respectively. The products of the inhibited reaction were also found to be the same as those of the normal reaction.It is concluded that free radical processes predominate, involving comparatively short chains.

Download Full-text

KINETICS AND MECHANISMS OF THE THERMAL DECOMPOSITION OF PROPIONALDEHYDE: PART II. THE REACTION IN THE PRESENCE OF NITRIC OXIDE

Canadian Journal of Chemistry ◽

10.1139/v65-031 ◽

1965 ◽

Vol 43 (1) ◽

pp. 278-289 ◽

Cited By ~ 4

Author(s):

K. J. Laidler ◽

M. Eusuf

Keyword(s):

Nitric Oxide ◽

Thermal Decomposition ◽

Relative Rate ◽

Temperature Range ◽

Presence And Absence

The decomposition of propionaldehyde in the presence of various amounts of nitric oxide has been studied in the temperature range 520–560 °C and at propionaldehyde pressures from 30 to 300 mm Hg. The reaction is inhibited by small amounts of nitric oxide, and larger amounts give rise to strong catalysis. The order of the maximally inhibited reaction is 1.5 and the degree of inhibition decreases with an increase of propionaldehyde pressure. In the catalytic region the order of the overall reaction is 1.25 with respect to propionaldehyde, and the relative rate (the ratio of rates in the presence and absence of nitric oxide) is independent of propionaldehyde pressure. The overall rate in the catalytic region can be expressed as[Formula: see text]the unit of concentration being mole per cc. A mechanism in which nitric oxide initiates chains by the reaction C2H5CHO + NO → C2H5CO + HNO, propagates them by C2H5NO + C2H5CHO → C2H6 + C2H5CO + NO, and terminates them by C2H5 + C2H5NO → C4H10 + NO and C2H6 + C2H4 + NO and C2H5NO + C2H5NO → C4H10 + 2NO or C2H6 + C2H4 + 2NO is proposed and is shown to be consistent with the results.

Download Full-text

Promotion of the Oxidation of Nitric Oxide and Hydrocarbon by the Thermal Decomposition of Peroxyacetyl Nitrate (PAN) at Night

Chemistry Letters ◽

10.1246/cl.1994.251 ◽

1994 ◽

Vol 23 (2) ◽

pp. 251-254

Author(s):

Issei Iwamoto ◽

Hitoshi Tanihara ◽

Masaaki Kawahara ◽

Soichi Otsuka ◽

Kazuhiko Sakamoto

Keyword(s):

Nitric Oxide ◽

Thermal Decomposition ◽

Peroxyacetyl Nitrate

Download Full-text

KINETICS AND MECHANISMS OF THE PYROLYSIS OF DIMETHYL ETHER: II. THE REACTION INHIBITED BY NITRIC OXIDE AND PROPYLENE

Canadian Journal of Chemistry ◽

10.1139/v63-292 ◽

1963 ◽

Vol 41 (8) ◽

pp. 1993-2008 ◽

Cited By ~ 13

Author(s):

D. J. McKenney ◽

B. W. Wojciechowski ◽

K. J. Laidler

Keyword(s):

Nitric Oxide ◽

Thermal Decomposition ◽

Dimethyl Ether ◽

Chain Process ◽

Maximal Inhibition ◽

First Order ◽

Temperature Range ◽

Maximum Inhibition ◽

A Chain

The thermal decomposition of dimethyl ether, inhibited by nitric oxide and by propylene, was studied in the temperature range of 500 to 600 °C. About 1.5 mm of nitric oxide gave maximal inhibition, the rate then being approximately 8% of the uninhibited rate. With propylene, approximately 70 mm gave maximal inhibition, the rate being slightly higher than that using nitric oxide (~12.5% of the uninhibited rate). In both cases the degree of inhibition was independent of the ether pressure. In the maximally inhibited regions both reactions are three-halves order with respect to ether pressure. As the pressure of nitric oxide was increased beyond 10–15 mm, the overall rate increased, and in this region the reaction is first order with respect to both nitric oxide and ether. A 50:50 mixture of CH3OCH3 and CD3OCD3, with enough NO to ensure maximum inhibition, was pyrolyzed. Even at very low percentage decomposition the CD3H/CD4 ratio was approximately the same as that in the uninhibited decomposition, proving that the inhibited reaction is largely a chain process. Detailed inhibition mechanisms are proposed in which the inhibitor is involved both in initiation and termination reactions.

Download Full-text