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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetic and product study of the gas-phase reactions of OH radicals, NO3 radicals, and O-3 with (C2H5O)(2)P(S)CH3 and (C2H5O)(3)PS
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Kinetic and product study of the gas-phase reactions of OH radicals, NO3 radicals, and O-3 with (C2H5O)(2)P(S)CH3 and (C2H5O)(3)PS

机译：OH自由基，NO3自由基和O-3与（C2H5O）（2）P（S）CH3和（C2H5O）（3）PS的气相反应的动力学和产物研究

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Rate constants for the reactions of OH radicals and NO3 radicals with O,O-diethyl methylphosphonothioate [( C2H5O)(2)P( S) CH3; DEMPT] and O,O,O-triethyl phosphorothioate [( C2H5O)(3)PS; TEPT] have been measured using relative rate methods at atmospheric pressure of air over the temperature range 296-348 K for the OH radical reactions and at 296 ( 2 K for the NO3 radical reactions. At 296 ( 2 K, the rate constants obtained for the OH radical reactions ( in units of 10(-11) cm(3) molecule(-1) s(-1)) were 20.4 +/- 0.8 and 7.92 +/- 0.27 for DEMPT and TEPT, respectively, and those for the NO3 radical reactions ( in units of 10(-15) cm(3) molecule(-1) s(-1)) were 2.01 +/- 0.20 and 1.03 +/- 0.10, respectively. Upper limits to the rate constants for the reactions of O-3 with DEMPT and TEPT of < 6 x 10(-20) cm(3) molecule(-1) s(-1) were determined in each case. Rate constants for the OH radical reactions, measured relative to k( OH + alpha-pinene)) 1.21 x 10(-11) e(436/T) cm(3) molecule(-1) s(-1), resulted in the Arrhenius expressions k( OH + DEMPT)) 1.08 x 10(-11) e(( 871 +/- 25))/T cm(3) molecule(-1) s(-1) and k( OH + TEPT)) 8.21 x 10(-13) e(( 1353 +/- 49))/T cm(3) molecule(-1) s(-1) over the temperature range 296-348 K, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the reference rate constant. Diethyl methylphosphonate was identified and quantified from the OH radical and NO3 radical reactions with DEMPT, with formation yields of 21 +/- 4%, independent of temperature, from the OH radical reaction and 62 +/- 11% from the NO3 radical reaction at 296 +/- 2 K. Similarly, triethyl phosphate was identified and quantified from the OH radical and NO3 radical reactions with TEPT, with formation yields of 56 +/- 9%, independent of temperature, from the OH radical reaction and 78 +/- 15% from the NO3 radical reaction at 296 +/- 2 K.
机译：OH和NO3自由基与O，O-二乙基甲基硫代膦酸酯[（C2H5O）（2）P（S）CH3; DEMPT]和O，O，O-三乙基硫代磷酸酯[（C2H5O）（3）PS; [TEPT]是使用相对速率方法在大气中的大气压下进行的OH自由基反应的温度范围为296-348 K，在296（2 K的NO3自由基反应温度下）。在296（2 K时，对于OH自由基反应（以10（-11）cm（3）分子（-1）s（-1）为单位）对于DEMPT和TEPT分别为20.4 +/- 0.8和7.92 +/- 0.27 NO3自由基反应（以10（-15）cm（3）分子（-1）s（-1）为单位）分别为2.01 +/- 0.20和1.03 +/- 0.10。分别确定O-3与DEMPT和TEPT <6 x 10（-20）cm（3）分子（-1）s（-1）的反应OH自由基反应的速率常数，相对于k（OH +α-pine烯）1.21 x 10（-11）e（436 / T）cm（3）分子（-1）s（-1），导致Arrhenius表达式k（OH + DEMPT））1.08 x 10（-11）e（（871 +/- 25））/ T cm（3）分子（-1）s（-1）和k（OH + TEPT））8.21 x 10（-13）e（（ 1353 +/- 49））/ T cm（3）分子（ -1）s（-1）在296-348 K的温度范围内，其中指示的误差是两个最小二乘方标准偏差，并且不包括参考速率常数的不确定性。通过与DEMPT的OH自由基和NO3自由基反应鉴定并定量了甲基膦酸二乙酯，OH自由基反应的生成产率为21 +/- 4％，与温度无关，而NO3自由基反应的生成产率为62 +/- 11％ 296 +/- 2K。类似地，从TEPT的OH自由基和NO3自由基反应中鉴定和定量了磷酸三乙酯，OH自由基反应的形成产率为56 +/- 9％，与温度无关，而OHPT反应为78 + / -在296 +/- 2 K时从NO3自由基反应产生的15％。

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