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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactions of PO_xCl_y~- Ions with H and H_2 from 298 to 500 K
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Reactions of PO_xCl_y~- Ions with H and H_2 from 298 to 500 K

机译：PO_xCl_y〜-离子与H和H_2在298至500 K之间的反应

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摘要

Rate constants and product branching ratios for PO_xCl_y~- ions reacting with H and H_2 were measured in a selected ion flow tube (SIFT) from 298 to 500 K.PO_2Cl~-,PO_2C1_2~-,POC1_2~-,and POC1_3~- were all unreactive with H_2,having a rate constant with an upper limit of <5X10~(-12) cm~3 s~(-1).PO_2C1_2~- did not react with H atoms either,having a similar rate constant limit of <5X10~(-12) cm~3 s~(-1).The rate constants for PO_2Cl~-,POC1_2~-,and POCl_3~- reacting with H showed no temperature dependence over the limited range of 298-500 K and were approximately 10-20% of the collision rate constant.Cl abstraction by H to form HCl was the predominant product channel for PO_2Cl~-,POCl_2~-,and POCl_3~-,with a small amount of Cl~- observed from POCl_2~-+H.Reactions of O_2 and O_3 with the POCl~- products ions from the reaction of POCl_2~-+H were observed to yield predominantly PO_3~- and PO_2~-,respectively.POCl~- reacted with O_2 and O_3 with rate constants of 8.9 +- 1.1X10~(-11) and 5.2+-3.3X10~(-10) cm~3 s~(-1),respectively.No associative electron detachment in the reactions with H atoms was observed with any of the reactant ions;however,detachment was observed with a PO~- secondary product ion at high H atom concentrations.Results of new G3 theoretical calculations of optimized geometries and energies for the products observed are discussed.
机译：在298至500 K的选定离子流管（SIFT）中测量与H和H_2反应的PO_xCl_y〜-离子的速率常数和产物支化比.PO_2Cl〜-，PO_2C1_2〜-，POC1_2〜-和POC1_3〜-为均与H_2不反应，速率常数上限为<5X10〜（-12）cm〜3 s〜（-1）.PO_2C1_2〜-也不与H原子反应，速率常数下限< 5X10〜（-12）cm〜3 s〜（-1）.PO_2Cl〜-，POC1_2〜-和POCl_3〜-与H反应的速率常数在298-500 K的有限范围内没有温度依赖性，并且为PO_2Cl〜-，POCl_2〜-和POCl_3〜-的主要产物通道是H提取氯形成HCl的主要产物通道，而从POCl_2〜-观察到少量的Cl〜-。观察到O_2和O_3与POCl_2〜-+ H反应生成的POCl〜-产物离子的反应主要产生PO_3〜-和PO_2〜-，POCl〜-与O_2和O_3的速率常数反应8.9 +-1.1X10〜（-11）和5.2 +-分别为3.3X10〜（-10）cm〜3 s〜（-1）。与任何一种反应物离子均未观察到与H原子反应的缔合电子脱离;但是，PO〜-副产物却观察到脱离讨论了新G3理论计算结果的优化几何结构和能量的理论结果。

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