On the influence of the position of the double bond on the low-temperature chemistry of hexenes

摘要

The chemistry of oxidation and autoignition of 1-, 2-, and 3-hexene has been studied after rapid compression between 630 and 850 K for stoichiometric mixtures with "air." The phenomenology of autoignition has been recognized, and intermediate products formed before autoignition have been identified and analyzed. They mainly comprise of hexadienes, O-heterocycles, and aldehydes. There are many common products, because some of the intermediate alkenyl or alkenylperoxy radicals are delocalized. Saturated O-heterocycles are specific products formed by addition of HO_2 to the double bond. Unsaturated O-heterocycles are products typical of the long alkenyl chain. Saturated and unsaturated lower aldehydes are the products of OH addition to the double bond of hexenes and hexadienes. The relative abundance of the intermediates enables a better insight into the competition between the reactivity of the double bond and the reactivity of the alkenyl chain. According to the position of the double bond, the behavior of 3-hexene is dominated by the properties of the double bond whereas the behavior of 1-hexene is dominated by the properties of the alkenyl chain. The reactivity of the alkenyl chain is related to the type and number of C-H bonds, the ability of stabilized radicals to react, and the cyclic strain of the transition state of isomerization reactions. Therefore, 1-hexene reacts much more with the typical features of alkanes like a two-stage ignition with a cool flame and a negative temperature coefficient. 3-Hexene does not have typical features and 2-hexene has an intermediate behavior.