Sieck L Wayne, Searles S K, Ausloos P
Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234.
J Res Natl Bur Stand A Phys Chem. 1971 May-Jun;75A(3):147-153. doi: 10.6028/jres.075A.015.
The photoionization of C and C alkanes has been investigated at 106.7 and 104.8 nm in a mass spectrometer specifically designed for the investigation of ion-molecule reactions occurring at thermal kinetic energies. Absolute rate constants are reported for the reactions of various fragment ions with the corresponding parent molecule. The rate constants found for reactions of ions with -CH, -CH, -CH, and -CH were found to be 3.3, 4.4, 4.7, and 5.2 × 10 cm/molecule-second respectively. The ions were also found to be highly reactive, exhibiting rate constants of 3.6 and 3.8 × 10 cm/molecule-second in reactions with -CH and -CH. The rate constants for reaction of with -CH, -CH, -CH, and -CH were found to be 4.9, 4.9, 7.6, and 7.9 × 10 cm/molecule-second, respectively. Butene ions are less reactive by an order of magnitude. The results are compared with complementary data derived from electron impact experiments, and the relationship between the structure and reactivity of the various ions is discussed.
在一台专门设计用于研究热动能下离子 - 分子反应的质谱仪中，已对碳和碳烷烃在106.7纳米和104.8纳米处的光电离进行了研究。报告了各种碎片离子与相应母体分子反应的绝对速率常数。发现离子与 -CH、-CH、-CH和 -CH反应的速率常数分别为3.3、4.4、4.7和5.2×10厘米²/分子·秒。还发现离子具有高反应活性，在与 -CH和 -CH的反应中表现出的速率常数分别为3.6和3.8×10厘米²/分子·秒。与 -CH、-CH、-CH和 -CH反应的速率常数分别为4.9、4.9、7.6和7.9×10厘米²/分子·秒。丁烯离子的反应活性低一个数量级。将结果与从电子轰击实验获得的补充数据进行了比较，并讨论了各种离子的结构与反应活性之间的关系。
