ROLE OF A PEROXIDE INTERMEDIATE IN THE CHEMI-LUMINESCENCE OF LUMINOL - A MECHANISTIC STUDY
ROLE OF A PEROXIDE INTERMEDIATE IN THE CHEMI-LUMINESCENCE OF LUMINOL - A MECHANISTIC STUDY
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DOI：
10.1021/ja00538a022
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
LIND, JS
中科院分区：
文献类型：
--
作者：
MERENYI, G;LIND, JS
通过在含H_202但不含氧的碱性水溶液中同时产生鲁米诺自由基和超氧阴离子02‘·，可以在不同的pH值下测量过氧化氢加合物形成的速率常数。测定了加合物的分解速率常数。后一反应被证明是激发态产生的一个速率决定的动力学步骤。其速率常数强烈依赖于pH。在基本不发光的pH 7.7时，其值为(2±0.5)×10~3 S~(-1)，而在pH为11.0时，其值为(1.8±0.3)×10~5 S_1。认为过氧化氢和碱(过氧化氢)沿着不同的化学途径反应，产生不同的最终产物。只有碱的分解才会产生光。本文提出了一个总体的反应方案。用间接测量的方法测得化学发光量子产率为？0.1。
By simultaneous generation of the luminol radical and the superoxide radical anion 02 ‘· in an alkaline aqueous solution containing H202 but no oxygen, it was possible to measure at different pH values the rate constant for the formation of the peroxide adduct. The rate constant for the decomposition of the adduct was also determined. The latter reaction is shown to be a rate-determing kinetic step in the production of the excited state. Its rate constant is strongly pH dependent. At pH 7.7, where essentially no light is produced, its value is (2±0.5) X 103 s" 1, while at pH 11.0 the value (1.8±0.3) X105 s_1 is obtained. It is suggested that the acid (hydroperoxide) and the base (peroxide) react along different chemical pathways yielding different end products. Only the decomposition of the base results in light generation. An overall reaction scheme is proposed. In an indirect measurementthe chemiluminescence quantum yield is determined to be^ 0.1.