Exact Free Radical Kinetics related to Atmospheric reactions among Minor Constituents.

研究同位素对化学反应速率和产物的影响，对于提高化学家对化学反应的详细性质的理解一直是有用的。虽然化学家一直在研究同位素效应，但其他科学家一直在使用这些测量方法来帮助他们解释自然系统（如古气候学）的同位素组成。海洋环流、大气化学转化机制、火成岩地质测温和太阳系演化历史等方面的研究，并在此基础上，探讨了几种测定化学反应速率常数的方法，以及如何测定同位素之间的微小差异。进行了以下研究。(1)光电离质谱仪的灵敏度提高到100倍。(2)测定了甲基自由基与氧反应速率的同位素效应。(2)测定了甲基自由基与氧反应速率的同位素效应。(3)测定了含硫自由基与R02自由基反应的速率常数。

The study of isotope effects on the rates and products of chemical processes has long been useful in increasing chemists understanding of the detailed nature of chemical reactions. While chemists have been studying isotope effects, other scientists have been using these measurements to aid in their interpretation of observations of isotopic composition of 'natural systems such as paleoclimatology,. oceanic circulation, atmospheric chemical transformation mechanisms, igneous rock geothermometry and the, evolutionary historyy of the solar system.On the basic of above background, several methods how to measure the exact rate constants of chemical reactions, and how to measure the small difference to the rate constants between isotopes of molecules were investigated in the present study. The following studies were carried out.(1) Sensitivity of photoionization mass spectrometer was improved to factor 100.(2) Isotope effects for the rates of reaction of methyl radicals with oxygen were determined.(2) Isotope effects for the rates of reaction of methyl radicals with oxygen were determined.(3) Rate constants for reactions of sulfur containing radicals with R02 radicals were determined.