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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Kinetic Analysis of the Effect of O_2 on the Reactions of Atomic Bromine with Some Hydrocarbons and Ethers
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A Kinetic Analysis of the Effect of O_2 on the Reactions of Atomic Bromine with Some Hydrocarbons and Ethers

机译：O_2对原子溴与某些烃类和醚类反应的动力学分析

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The kinetics of the reactions of atomic bromine with ethene,2-methylpropane,dimethyl ether,and diethyl ether have been studied at 298 K in a 70-L photochemical reaction chamber with the relative rate method.Chemical analysis was by gas chromatography with a flame ionization detector.The effects of bromine and oxygen partial pressure and of the choice of reference reactant on the numerical values of the rate constants obtained have been evaluated.The results are analyzed to obtain limiting values of the rate constant ratio that are independent of the concentration of O_2 and do not depend on the mechanism used to represent the overall reaction.The following rate constants were obtained at 298 K by using the well-established rate constant for the reaction of Br with 2-methylpropane as the primary reference:Br+(CH_3)_2O,k_298=9.43X10~5 L mol~(-1)s~(-1)(+-)2%;Br+(C_2H_5)_2O,k_(298)=1-41X10~7 L mor~(-1)s~(-1)(+-)6%.With the rate constants for Br+(CH_3)_2O as a secondary reference value,the rate constant at 298 K for Br+(C_2H5)_2O was 1.27X10~7 L mol~(-1)s~(-1)(+-)8% calculated at a limiting high concentration of O_2.When Br+(C_2H_5)_2O was measured relative to Br + C_2H_4,the rate constant at 298 K,calculated for limiting high concentrations of O_2,ranged from 4.7X10~7 to 1.2X10~7 L mol~(-1)s~(-1)depending on the rate constant chosen for the reference reaction.The sensitivity to oxygen concentration of the rate constant for the reaction of Br with ethene depends on the concentration of Br_2 used as the photolytic source of atomic bromine.When the reaction of Br with an organic reactant is sensitive to the presence of oxygen,measurements at O_2 concentrations much larger than those in synthetic air may be required to obtain reliable rate constants for the initial reaction of Br with the organic reactant.
机译：在70 L光化学反应室中，采用相对速率法研究了原子溴与乙烯，2-甲基丙烷，二甲醚和二乙醚的反应动力学，在298 K下进行了化学分析。评估了溴和氧分压以及参考反应物的选择对所获得的速率常数数值的影响。分析结果以获得速率常数比率的极限值，该极限值与浓度无关不依赖于O_2的反应速率，并且不依赖于代表整体反应的机理。通过使用公认的Br与2-甲基丙烷反应的速率常数作为主要参考，在298 K下获得以下速率常数：Br +（CH_3 ）_2O，k_298 = 9.43X10〜5 L mol〜（-1）s〜（-1）（+-）2％; Br +（C_2H_5）_2O，k_（298）= 1-41X10〜7 L mor〜（- 1）s〜（-1）（+-）6％。以Br +（CH_3）_2O的速率常数作为第二参考值，在极限高浓度O_2下，Br +（C_2H5）_2O在298 K处的常数为1.27X10〜7 L mol〜（-1）s〜（-1）（+-）8％.Br +（C_2H_5）_2O相对于Br + C_2H_4进行测量，在298 K处的速率常数，针对极限高浓度O_2计算得出，范围为4.7X10〜7至1.2X10〜7 L mol〜（-1）s〜（-1），具体取决于为参考反应选择的速率常数.Br与乙烯反应的速率常数对氧浓度的敏感性取决于用作原子溴光解源的Br_2的浓度。当Br与有机反应物的反应敏感时对于氧气的存在，可能需要在O_2浓度下进行的测量要比在合成空气中的测量大得多，以便获得可靠的速率常数，以用于Br与有机反应物的初始反应。

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