Kinetics of the R + NO2 reactions (R = i-C3H7, n-C3H7, s-C4H9, and t-C4H9) in the temperature range 201-489 K.
Kinetics of the R + NO2 reactions (R = i-C3H7, n-C3H7, s-C4H9, and t-C4H9) in the temperature range 201-489 K.
复制标题
R NO2 反应（R = i-C3H7、n-C3H7、s-C4H9 和 t-C4H9）在 201-489 K 温度范围内的动力学。
DOI：
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发表时间：
2010
影响因子：
2.9
通讯作者：
R. Timonen
中科院分区：
文献类型：
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作者：
M. Rissanen;Suula L Arppe;A. Eskola;Matti Tammi;R. Timonen
在直接时间分辨实验中测量了四种烷基自由基与NO（2）反应的双分子速率系数。反应在伪一级反应条件下进行了研究，在一个温度控制的管式流动反应器耦合到激光光解/光电离质谱仪（LP-PIMS）。在实验范围内，测得的反应速率系数与氦浴气体压力无关，并表现出负的温度依赖性。对于i-C（3）H（7）+ NO（2）和t-C（4）H（9）+ NO（2）反应，纵坐标（反应速率系数的对数）对横坐标（1/T或log（T））的依赖关系是非线性的。所获得的结果（单位：cm（3）s（-1））可以用以下公式表示：k（n-C（3）H（7）+ NO（2））=（（4.34 +/- 0.08）x 10（-11））（T/300 K）（-0.14+/-0.08）（203-473 K，1-7 Torr），k（i-C（3）H（7）+ NO（2））=（（3.66 +/- 2.54）x 10（-12））exp（656 +/- 201 K/T）（T/300 K）（1.26+/-0.68）（220-489 K，1-11 Torr），k（s-C（4）H（9）+ NO（2））=（（4.99 +/- 0.16）x 10（-11））（T/300 K）（-1.74+/-0.12）（241-485 K，2 - 12 Torr）和k（t-C（4）H（9）+ NO（2））=（（8.64 +/- 4.61）x 10（-12））exp（413 +/- 154 K/T）（T/300 K）（0.51+/-0.55）（201-480 K，2-11 Torr），其中显示的不确定度仅指从拟合程序中获得的1个标准偏差。测定的双分子速率系数的估计总不确定度约为+/-20%。
The bimolecular rate coefficients of four alkyl radical reactions with NO(2) have been measured in direct time-resolved experiments. Reactions were studied under pseudo-first-order conditions in a temperature-controlled tubular flow reactor coupled to a laser photolysis/photoionization mass spectrometer (LP-PIMS). The measured reaction rate coefficients are independent of helium bath gas pressure within the experimental ranges covered and exhibit negative temperature dependence. For i-C(3)H(7) + NO(2) and t-C(4)H(9) + NO(2) reactions, the dependence of ordinate (logarithm of reaction rate coefficients) on abscissa (1/T or log(T)) was nonlinear. The obtained results (in cm(3) s(-1)) can be expressed by the following equations: k(n-C(3)H(7) + NO(2)) = ((4.34 +/- 0.08) x 10(-11)) (T/300 K)(-0.14+/-0.08) (203-473 K, 1-7 Torr), k(i-C(3)H(7) + NO(2)) = ((3.66 +/- 2.54) x 10(-12)) exp(656 +/- 201 K/T)(T/300 K)(1.26+/-0.68) (220-489 K, 1-11 Torr), k(s-C(4)H(9) + NO(2)) = ((4.99 +/- 0.16) x 10(-11))(T/300 K)(-1.74+/-0.12) (241-485 K, 2 - 12 Torr) and k(t-C(4)H(9) + NO(2)) = ((8.64 +/- 4.61) x 10(-12)) exp(413 +/- 154 K/T)(T/300 K)(0.51+/-0.55) (201-480 K, 2-11 Torr), where the uncertainties shown refer only to the 1 standard deviations obtained from the fitting procedure. The estimated overall uncertainty in the determined bimolecular rate coefficients is about +/-20%.