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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Pulse Radiolysis Investigations on Acidic Aquenous Solutions of Benzene: Formation of Radical Cations
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Pulse Radiolysis Investigations on Acidic Aquenous Solutions of Benzene: Formation of Radical Cations

机译:苯的酸性水溶液的脉冲辐射分解研究:自由基阳离子的形成

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摘要

The transient optical absorption bands (#lambda#_(max) = 310, 350-500 nm, k = 5.6 * 10~9 dm~3 mol~(-1)s~(-1)) formed on pulse radiolysis of an acidic (HClO_4 = 7.8 mol dm~(-3)) aqueous solution of benzene are assigned to the solute radical cation formed on acid-catalyzed dehydration of the OH adduct. The solute radical cation is able to undergo an electron transfer reaction with Br~- with a bimolecular rate constant of 8 * 10~9 dm~3 mol~(-1)s~(-1). On the other hand, the OH adduct (#lambda#_(max) = 310 nm) was oxidized by Fe(CN)_6~(3-) with a bimolecular rate constant of 6.6 * 10~7 dm~3 mol~(-1) s~(-1). The radical cation of benzene is a strong one-electron oxidant with oxidation potential in the range 2.1-2.4 V vs NHE.
机译:瞬态光吸收带(#lambda #_(max)= 310,350-500 nm,k = 5.6 * 10〜9 dm〜3 mol〜(-1)s〜(-1))在对样品进行脉冲辐解时形成将酸性(HClO_4 = 7.8 mol dm〜(-3))苯水溶液分配给在酸催化下OH加合物脱水形成的溶质自由基阳离子。溶质自由基阳离子能够与Br〜-进行电子转移反应,其双分子速率常数为8 * 10〜9 dm〜3 mol〜(-1)s〜(-1)。另一方面,OH加合物(#lambda #_(max)= 310 nm)被Fe(CN)_6〜(3-)氧化,双分子速率常数为6.6 * 10〜7 dm〜3 mol〜( -1)s〜(-1)。苯的自由基阳离子是一种强的单电子氧化剂,相对于NHE而言,氧化电位在2.1-2.4 V范围内。

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