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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Peroxynitrate is formed rapidly during decomposition of peroxynitrite at neutral pH
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Peroxynitrate is formed rapidly during decomposition of peroxynitrite at neutral pH

机译：过氧亚硝酸盐在中性pH分解过程中迅速形成过氧硝酸盐

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The decomposition of peroxynitrite near neutral pH leads ultimately to the formation of dioxygen and nitrite via an intermediate with an absorbance maximum at 284 nm. The intermediate oxidises I~- with a rate constant of (78 ± 8) × 10 M~(-1)s~(-1) and decays near pH 7 with a rate constant of (0.58 ± 0.02) s~(-1) at 22 °C, but is longer-lived at lower pH. On the basis of experiments performed with a tandem-quenching flow reactor, we tentatively identify this intermediate as peroxynitric acid, formed during the proposed reaction sequence ONOOH + ONOO~- → NO_2~- + O_2NOO~- + H~+ → 2 NO_2~- + O_2. These products are those expected from a peracid. The rate constant for the first reaction is ca. 3 × 10~4 M~(-1) s~(-1). Part of the dioxygen formed is in the ~1Δg state (S. Miyamoto, G. E. Ronsein, T. C. Corréa, G. R. Martinez, M. H. G. Medeiros and P. Di Mascio, Dalton Trans., 2009, DOI: 10.1039/b905560f). The decay of peroxynitrous acid at concentrations higher than 0.1 mM near neutral pH is best described by the simultaneous process of isomerisation (k = 1.2 s~(-1)) and decomposition to peroxynitrate. The rate of formation and the amount of peroxynitrate formed are much larger than can be accounted for by homolysis reactions.
机译：接近中性pH的过氧亚硝酸盐的分解最终通过在284 nm处具有最大吸光度的中间物形成双氧和亚硝酸盐。中间物以速率常数（78±8）×10 M〜（-1）s〜（-1）氧化I〜-并在pH 7附近以速率常数（0.58±0.02）s〜（-1）降解）在22°C下，但在较低的pH值下寿命更长。根据串联骤冷反应器进行的实验，我们初步确定该中间体为过氧硝酸，在提出的反应顺序ONOOH + ONOO〜-→NO_2〜-+ O_2NOO〜-+ H〜+→2 NO_2〜中形成。 -+ O_2。这些产品是过酸所期望的产品。第一反应的速率常数为约。 3×10〜4 M〜（-1）秒〜（-1）。形成的部分双氧的一部分处于〜1Δg状态（S. Miyamoto，G.E. Ronsein，T.C.Corréa，G.R.Martinez，M.H. G. Medeiros和P.Di Mascio，Dalton Trans。，2009，DOI：10.1039 / b905560f）。过氧亚硝酸在接近中性pH值时浓度高于0.1 mM时的衰减最好通过异构化（k = 1.2 s〜（-1））和分解为过氧硝酸盐的同时过程来描述。形成速度和形成的过氧硝酸盐的量比均质反应所能解释的要大得多。

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