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首页> 外文期刊>Environmental Science & Technology >Prometryne Oxidation by Sodium Hypochlorite in Aqueous Solution: Kinetics and Mechanism
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Prometryne Oxidation by Sodium Hypochlorite in Aqueous Solution: Kinetics and Mechanism

机译：次氯酸钠在水溶液中氧化异丙基萘的动力学和机理

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摘要

The reaction of the herbicide prometryne S-CH_3) with sodium hypochlorite has been investigated from the kinetic and mechanistic stand point. Under the fixed experimental conditions: pH = 7, T= 25℃, [NaClO]/[substrate] = (10~(-3) M)/(10~(-5) M), prometryne oxidation takes place according to the following pathway: R-S-CH_3 (P) → R-SO-CH_3 (a) → R-SO_2-CH_3 (b) → R-O-SO_2-CH_3 (x) → R-OH (c), where R stands for C_9H_(16)N_5 i.e., the substituted triazine ring of prometryne and (x) is an unexpected intermediate never previously detected nor identified. After having synthesized the pure intermediates (a), (b), and (x), the values of the pseudo-first-order kinetic constants of the first three steps were experimentally obtained: [k_1 = (0.64 ± 0.03) s~(-1), K_2 = (1.81 ± 0.05) x 10~(-3) s~(-1), K_3 = (1.50 ± 0.03) x 10~(-4) s~(-1)]. As for k)4, its value [(2.5 ± 0.2) x 10~(-5) s~(-1)] has been calculated indirectly on the basis of the kinetic theory concerning consecutive reactions. All the steps were pseudo-first-order reactions with respect to their specific substrate. The effect of pH on the hydrolysis of (b) [(b) → (c)], in the absence of NaCIO, has been also assessed to better elucidate the mechanism of the overall pathway.
机译：从动力学和机理的观点出发，研究了除草剂pro去氢萘啶酮S-CH_3与次氯酸钠的反应。在固定的实验条件下：pH = 7，T = 25℃，[NaClO] / [底物] =（10〜（-3）M）/（10〜（-5）M），pro烯氧化根据遵循的路径：RS-CH_3（P）→R-SO-CH_3（a）→R-SO_2-CH_3（b）→RO-SO_2-CH_3（x）→R-OH（c），其中R代表C_9H_（ 16）N_5，即pro萘啶和（x）的取代三嗪环是未曾发现或鉴定的意外中间体。合成了纯中间体（a），（b）和（x）之后，通过实验获得了前三个步骤的拟一级动力学常数值：[k_1 =（0.64±0.03）s〜（ -1），K_2 =（1.81±0.05）x 10〜（-3）s〜（-1），K_3 =（1.50±0.03）x 10〜（-4）s〜（-1）]。对于k）4，其值[（2.5±0.2）x 10〜（-5）s〜（-1）]是根据有关连续反应的动力学理论间接计算的。所有步骤都是针对其特定底物的伪一级反应。在不存在NaCl的情况下，还评估了pH对（b）[（b）→（c）]水解的影响，以更好地阐明整个途径的机理。

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