高铁酸盐（VI）和高铁酸盐（V）对苯酚的氧化作用：脉冲辐解和停流研究
The oxidation of phenol by ferrate(VI) and ferrate(V). A pulse radiolysis and stopped-flow study.
作者信息
Rush J D, Cyr J E, Zhao Z, Bielski B H
机构信息
Chemistry Department, Brookhaven National Laboratory, Upton, N.Y. 11973-5000, USA.
出版信息
Free Radic Res. 1995 Apr;22(4):349-60. doi: 10.3109/10715769509145647.
Potassium ferrate, K2FeO4, is found to oxidize phenol in aqueous solution (5.5 < or = pH < or = 10) by a process which is second order in both reactants; -d[FeVI]/dt=k1[FeVI][phenol], k1 = 10(7)M-1s-1. Product analysis by HPLC showed a mixture of hydroxylated products, principally paraquinone, and biphenols that indicate that oxidation of phenol occurs by both one-electron and two-electron pathways. The two-electron oxidant, producing both para- and ortho-hydroxylated phenols is considered to be ferrate(V) which is itself produced by the initial one-electron reduction of ferrate(VI). The rate of ferrate(V) reaction with phenol was determined by pre-mix stopped flow pulse-radiolysis and found to be k7 = (3.8 +/- 0.4) x 10(5)M-1s-1.
高铁酸钾（K₂FeO₄）被发现可在水溶液（5.5 ≤ pH ≤ 10）中氧化苯酚，该过程对两种反应物均为二级反应；-d[Fe⁶⁺]/dt = k₁[Fe⁶⁺][苯酚]，k₁ = 10⁷ M⁻¹ s⁻¹。通过高效液相色谱法进行的产物分析表明，产物为羟基化产物的混合物，主要是对苯醌和联苯酚，这表明苯酚的氧化通过单电子和双电子途径发生。产生对羟基和邻羟基苯酚的双电子氧化剂被认为是高铁酸根（V），它本身是由高铁酸根（VI）的初始单电子还原产生的。通过预混合停流脉冲辐解测定了高铁酸根（V）与苯酚的反应速率，发现k₇ = (3.8 ± 0.4) × 10⁵ M⁻¹ s⁻¹。
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