This PhD thesis is an analysis of the chemical kinetics and oxidation behavior of fuel components via experiments and correlations. First, a number of experimental studies of the reactivity of OH radicals with unsaturated hydrocarbons are performed at temperatures ranging from 294 to 1400 K by OH absorption and laser induced fluorescence techniques in two different reactors: shock tube and flow reactor. It is found that OH has a tendency to add to the unsaturated CC bond, forming a relatively stable adduct. The thermal stability of these adducts is vital for a better understanding of the kinetics of olefins, poly-olefins, alkynes and other unsaturated components in real and surrogate fuel blends. In this work, the reaction rate coefficient of the reaction of hydroxyl radical with many olefins (butenes, pentenes, hexenes), di-olefins (butadienes, and pentadienes) and allyl radical are measured. A strong competition between H-abstraction and OH-addition pathways is seen particularly in the intermediate temperature window of ~ 400 to 900 K. All of these measured elementary reactions give new insights into the chemical kinetics of fuels and allow modelers to improve the predictive capability of their models. Second, measurements of the ignition delay times of propene, isobutene, 2-methylhexane and 2-methylbutanol in air are performed using a high-pressure shock tube. Details about multi-stage ignition and ignition delay dependence on various thermodynamic properties is investigated for these four hydrocarbons. We followed this with a correlation study of ignition delay times of fuel blends and real fuel streams. The main requirement of these correlations is that these should be predictive enough to compete with the predictive capabilities of detailed chemical kinetic models but at a much reduced computational cost. The obtained correlation scheme does not only predict ignition timing during CFD simulations but also other combustion properties such as low-temperature heat release timing and resulting temperature and pressure increases due to cool flame. A discussion on the weak dependence of high-temperature ignition delay times on the composition of real fuels is also presented, where universal Arrhenius type expressions of ignition delay times of gasoline, diesel and jet fuels are given.
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