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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Oxidation of Nitrite by Peroxynitrous Acid
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Oxidation of Nitrite by Peroxynitrous Acid

机译：过氧亚硝酸氧化亚硝酸盐

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摘要

The kinetics of the oxidation of nitrite to nitrate by peroxynitrous acid at pH 5.2 is best described by the rate law k_(obs) = k_(iso) + k'[NO_2~-] + k"[NO_2~-]~2, in which the peroxynitrous acid isomerization rate constant k_(iso) = (1.10 ± 0.05) s~(-1), k' = (3.2 ± 0.1) M~(-1) s~(-1), and k" = (4.2 ± 0.3) M~(-2)s~(-1), at 25 ℃. The ternary reaction may involve initial formation of an adduct between nitrite and peroxynitrite, followed by reaction with a second nitrite to form two nitrite and a nitrate. Ab initio calculations indicated that there is only a small intrinsic barrier to the net transfer of HO~+ from peroxynitrous acid to the nitrogen atom of nitrite. A similar transfer to either of the two oxygens of nitrite produces the reactants, and would not lead to an increase in the rate of disappearance of peroxynitrous acid, as observed. The low rate constant is most likely due to stringent orientational constraints. Formal transfer of HO~+ to ~(15)NO_2~- results in formation of ~(15)NO_3~-, as experimentally observe. HO~+ transfer is common the the chemistry of peracids, a family of compounds to which peroxynitrous acid belongs.
机译：用速率定律k_（obs）= k_（iso）+ k'[NO_2〜-] + k“ [NO_2〜-]〜2，可以最好地描述过氧亚硝酸在pH 5.2下将亚硝酸盐氧化成硝酸盐的动力学，其中过氧亚硝酸异构化速率常数k_（iso）=（1.10±0.05）s〜（-1），k'=（3.2±0.1）M〜（-1）s〜（-1），k“ = 25℃时为（4.2±0.3）M〜（-2）s〜（-1）。三元反应可涉及在亚硝酸盐和过氧亚硝酸盐之间最初形成加合物，然后与第二亚硝酸盐反应形成两个亚硝酸盐和硝酸盐。从头算计算表明，HO〜+从过氧亚硝酸到亚硝酸根氮原子的净转移只有很小的内在障碍。如所观察到的，类似地转移至亚硝酸盐的两个氧之一产生反应物，并且不会导致过氧亚硝酸的消失速率增加。低速率常数很可能归因于严格的方向约束。实验观察到，HO〜+正式转移至〜（15）NO_2〜-导致〜（15）NO_3〜-的形成。 HO +转移在过酸的化学过程中很常见，过酸是过氧亚硝酸所属的一类化合物。

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