Time-Resolved Photothermal Grating Calorimetry for Investigating Kinetics of Free-Radical Chain Reactions

1995 ◽  
Vol 67 (2) ◽  
pp. 365-373 ◽  
Author(s):  
R. T. Cambron ◽  
J. M. Harris
1969 ◽  
Vol 6 (5) ◽  
pp. 466-473
Author(s):  
Donald H. Martin ◽  
Robert B. Taylor ◽  
Ffrancon Williams

Part I. Comparison of nitric oxide and propylene as inhibitors The reduction by propylene of the rate of pressure increase in the decomposition of propaldehyde at 550° has been shown by chemical analysis to represent a true inhibition of the reaction, and not to be due n an important degree to an induced polymerization of the propylene. With propaldehyde and with diethyl ether the limiting values to which the decomposition rates are reduced by nitric oxide and by propylene respectively are the same, although much more propylene is required to produce a given degree of inhibition. From this it is concluded that the limiting rates are more probably those of independent non-chain processes, than those characteristic of stationary states where the inhibitor starts and stops chains with equal efficiency.


2020 ◽  
Vol 117 (9) ◽  
pp. 4486-4490 ◽  
Author(s):  
Meirong Zeng ◽  
Nadja Heine ◽  
Kevin R. Wilson

Autoxidation is an autocatalytic free-radical chain reaction responsible for the oxidative destruction of organic molecules in biological cells, foods, plastics, petrochemicals, fuels, and the environment. In cellular membranes, lipid autoxidation (peroxidation) is linked with oxidative stress, age-related diseases, and cancers. The established mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy–hydroperoxide-mediated free-radical chain reactions. For a series of model unsaturated lipids, we present evidence for an autoxidation mechanism, initiated by hydroxyl radical (OH) addition to C=C bonds and propagated by chain reactions involving Criegee intermediates (CIs). This mechanism leads to unexpectedly rapid autoxidation even in the presence of water, implying that as reactive intermediates, CI could play a much more prominent role in chemistries beyond the atmosphere.


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