The oxidation of ferrous perchlorate by molecular oxygen
The oxidation of ferrous perchlorate by molecular oxygen
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高氯酸亚铁被分子氧氧化
DOI：
10.1039/jr9540004349
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发表时间：
1954
期刊：
影响因子：
--
通讯作者：
P. George
中科院分区：
文献类型：
--
作者：
P. George
本文研究了在高氯酸溶液中，在25-40 ℃范围内，在不同pH值和离子强度（通过加入高氯酸钠调节）下，分子氧氧化亚铁离子的动力学。在大气压力下的空气和氧气，以及在100-130大气压下的氧气，使用特殊的装置，获得相同的动力学，即，总的三阶速度常数Kexp。根据经验方程HEQ，随着氢离子浓度的降低而略微增加。cc [H+]-w23;也随着离子强度的增加而略微增加。这些动力学依赖于有机杂质的耦合氧化或痕量金属催化的可能性被证明是非常不可能的。高氯酸铜对氧化反应有催化作用，但催化作用很小，当Cu ~（2+）浓度为0-15-0.20时，催化作用最大，而K_（1+）增加2.5倍。常见的电子转移和自由基机理不能解释这些动力学过程，而更倾向于下列机理：
The kinetics of the oxidation of ferrous ion by molecular oxygen, in perchloric acid solution, have been studied over a temperature range 25-40'at various pH's and ionic strengths (adjusted by addition of sodium perchlorate). With air and oxygen at atmospheric pressure, and oxygen at 100-130 atm., a special apparatus being used, thesame kinetics were obtained, viz., The overall third-order velocity constant Kexp. increased slightly with a decrease of hydrogen-ion concentration according to an empirical equation heq. cc [H+]-w23; also increases slightly as the ionic strength is increased. The possibility that these kinetics depend on either the coupled oxidation of organic impurities, or catalysis by trace metals, is shown to be very unlikely. Cupric perchlorate catalysed the oxidation, but the effect was small, becoming maximal at 0-15-0.20~-Cu2+ with a 2.5-fold increase in k,, The familiar electron-transfer and free-radical mechanism involving 0,-and HO, cannot account for these kinetics, which favour, instead, a mechanism of the type