ABSOLUTE RATE CONSTANTS FOR HYDROCARBON AUTOXIDATION .6. ALKYL AROMATIC AND OLEFINIC HYDROCARBONS
ABSOLUTE RATE CONSTANTS FOR HYDROCARBON AUTOXIDATION .6. ALKYL AROMATIC AND OLEFINIC HYDROCARBONS
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DOI：
10.1139/v67-132
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发表时间：
1967-01-01
影响因子：
1.1
通讯作者：
INGOLD, JA
中科院分区：
文献类型：
--
作者：
HOWARD, JA;INGOLD, JA
测定了大量碳氢化合物在30℃下自氧化的绝对速率常数。链扩展和链终止速率常数取决于烃类的结构和携带链的过氧自由基的结构。除空间位阻的影响外，氢原子萃取速率常数按伯<仲<叔的顺序增大；对于失去一个仲氢原子的化合物，速率常数的增大顺序为：未活化<单π-电子系统活化的非环<单π-电子系统活化的环< Π-system活化的环<两π-电子系统活化的非环<两π-电子系统活化的环。两个过氧自由基自反应终止链的速率常数一般按照叔过氧自由基<无环烯丙基-无环-二环-二环-苯基-二环-叔过氧自由基<伯过氧自由基<氢过氧自由基的顺序递增。
Absolute rate constants have been measured for the autoxidation of a large number of hydrocarbons at 30 °C. The chain-propagating and chain-terminating rate constants depend on the structure of the hydrocarbon and also on the structure of the chain-carrying peroxy radical. With certain notable exceptions which are mainly due to steric hindrance, the rate constants for hydrogen-atom abstraction increase in the order primary < secondary < tertiary; and, for compounds losing a secondary hydrogen atom, the rate constants increase in the order unactivated < acyclic activated by a single π-electron system < cyclic activated by a single Π-system < acyclic activated by two π-systems < cyclic activated by two π-systems. The rate constants for chain termination by the self-reaction of two peroxy radicals generally increase in the order tertiary peroxy radicals < acyclic allylic secondarycyclic secondaryacyclic benzylic secondary < primary peroxy radicals < hydroperoxy radicals.