THE KINETICS OF THE THERMAL DECOMPOSITIONS OF THE LOWER PARAFFINS: V. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF n-BUTANE

1940 ◽  
Vol 18b (1) ◽  
pp. 1-11 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins

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.

The rates of the nitric oxide-inhibited decompositions of hydrocarbons in the series propane to n -decane (which according to the results of Part I represent the chain-free molecular reactions) have been measured over a range of pressures. As inferred from the 'apparent chain length' the molecular rearrangement process increases in importance relatively to the chain reaction with the ascent of the series, and, for a given hydrocarbon, with increasing pressure. For each hydrocarbon, the order of reaction varies between the first and the second. The results are not consistent with a constant order of 1.5 as has been suggested. Nor is the pressure dependence consistent with the uniform transition from second order to first predicted for unimolecular reactions dependent upon a single mode of activation by collision. There appears to be a contribution to the overall reaction from processes which remain of second order up to high pressures. The decomposition rate for a given hydrocarbon pressure tends to a limit as the series is ascended, for reasons which are discussed.


1940 ◽  
Vol 18b (11) ◽  
pp. 351-357 ◽  
Author(s):  
E. W. R. Steacie ◽  
Gerald Shane

An investigation has been made of the nitric oxide inhibited thermal decomposition of ethane. Apparent chain lengths of 2.4 to 5 are found at temperatures from 640° to 565 °C. The activation energy of the inhibited reaction is found to be 77.3 Kcal. The results are discussed and it is concluded that the thermal decomposition of ethane proceeds mainly by a rearrangement mechanism and that free-radical chain mechanisms for the ethane decomposition are untenable.


1940 ◽  
Vol 18b (7) ◽  
pp. 203-216 ◽  
Author(s):  
E. W. R. Steacie ◽  
Gerald Shane

The kinetics of the thermal decomposition of ethane have been investigated by the static method in the temperature range 565° to 640 °C. The reaction was found to be uninfluenced by surface. The rate of the reaction can be expressed by[Formula: see text]The products of the reaction are ethylene, hydrogen, and a small amount of methane and probably higher hydrocarbons.The reaction is discussed from the point of view of free radical mechanisms, and it is suggested that the results cast serious doubt on the validity of the Rice-Herzfeld mechanism and its modification by Küchler and Theile.


Author(s):  
A. G. Zhukova ◽  
L. G. Gorokhova ◽  
A. S. Kazitskaya ◽  
T. K. Yadykina ◽  
N. N. Mikhailova ◽  
...  

Introduction. Fluorine compounds in small doses, but with prolonged exposure, cause various disorders in organs at the cellular and molecular levels. Activation of free-radical processes plays an important role in the damaging eff ect of fl uorides. Th erefore, one of the most eff ective ways to limit fl uorine-induced damage is to directly aff ect free-radical processes using herbal preparations with antioxidant properties.The aim of the study is to study the eff ect of a dihydroquercetin-based drug on the activity of free radical processes in brain tissue under subchronic exposure to sodium fl uoride (NaF).Materials and methods. Th e work was performed on white male laboratory rats weighing 200-250 g. Th e rats were divided into 3 groups: 1 — control; 2 — rats with chronic exposure to sodium fl uoride (NaF) for 9 weeks; 3 — rats receiving a NAF solution with simultaneous administration of a complex drug based on dihydroquercetin at a dose of 3 mg/kg in 1% starch gel for 3, 6 and 9 weeks. The activity of free radical oxidation and antioxidant defense enzymes — superoxide dismutase (SOD) and catalase-was determined in the cerebral cortex. Th e level of expression of hypoxia-induced transcription factor HIF — 1A and inducible forms of proteins HSP72 and HSP32 were determined in the cytosolic fraction of brain tissue.Results. In the early stages of subchronic fl uoride exposure (1-3 weeks), the expression of protective proteins HIF-1α, HSP72, HSP32 and catalase was shown in the rat cortex, as a result of which the activity of free-radical processes was maintained at the control level. An increase in the timing of fl uoride intake to 9 weeks led to a decrease in antioxidant protection and signifi cant activation of free radical oxidation in brain tissue. Daily administration of a complex drug with dihydroquercetin for 3, 6 and 9 weeks to rats with subchronic fl uoride exposure led to a decrease in the severity of pro- and antioxidant balance disorders in the cerebral cortex. At the same time, the greatest protective eff ect of dihydroquercetin with fl uoride exposure was manifested by the 9th week of its administration.Conclusions. When subchronic intake of fl uorides in the body, the drug based on dihydroquercetin has a neuroprotective eff ect, which is manifested by an increase in the activity of antioxidant enzymes of fr ee radical oxidation and catalase and the resistance of the cortex to induced fr ee radical oxidation.


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