A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O2 through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO2 from RO2 is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O2QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

This thesis investigates the combustion chemistry of cyclohexane, methylcyclohexane, and ethylcyclohexane on the basis of state-of-the-art synchrotron radiation photoionization mass spectrometry experiments, quantum chemistry calculations, and extensive kinetic modeling. It explores the initial decomposition mechanism and distribution of the intermediates, proposes a novel formation mechanism of aromatics, and develops a detailed kinetic model to predict the three cycloalkanes’ combustion properties under a wide range of conditions. Accordingly, the thesis provides an essential basis for studying much more complex cycloalkanes in transport fuels and has applications in engine and fuel design, as well as emission control.

The Oxidation of Cyclohexane focuses on the processes, methodologies, reactions, and approaches involved in the oxidation of cyclohexane. The publication first offers information on the theory of slow chain oxidations and the products of liquid-phase cyclohexane oxidation. Discussions focus on the applicability of the stationary state method to liquid-phase oxidation reactions; mechanism of liquid hydrocarbon chain oxidation; kinetic equations for product accumulation in degenerate branching chain reactions; and changes of the volume of the liquid phase due to oxidation product formation. The text then ponders on experimental apparatus for the study of the liquid-phase oxidation of cyclohexane, including prevention of cyclohexane losses in the waste gases, explosion danger and problems of safety, and characteristics of gas sampling in cyclohexane oxidation apparatus. The manuscript takes a look at the kinetics of uncatalyzed cyclohexane oxidation and kinetics of cyclohexane oxidation in continuous flow systems. Topics include effect of temperature on the relative yield of cyclohexane oxidation products; kinetics of cyclohexane oxidation in a glass reactor; rate of oxygen absorption and accumulation of reaction products; ideal displacement reactor; and determination of diffusion factor. The publication is a dependable reference for readers interested in the oxidation of cyclohexane.

Mathematical Modelling of Gas-Phase Complex Reaction Systems: Pyrolysis and Combustion, Volume 45, gives an overview of the different steps involved in the development and application of detailed kinetic mechanisms, mainly relating to pyrolysis and combustion processes. The book is divided into two parts that cover the chemistry and kinetic models and then the numerical and statistical methods. It offers a comprehensive coverage of the theory and tools needed, along with the steps necessary for practical and industrial applications. - Details thermochemical properties and "ab initio" calculations of elementary reaction rates - Details kinetic mechanisms of pyrolysis and combustion processes - Explains experimental data for improving reaction models and for kinetic mechanisms assessment - Describes surrogate fuels and molecular reconstruction of hydrocarbon liquid mixtures - Describes pollutant formation in combustion systems - Solves and validates the kinetic mechanisms using numerical and statistical methods - Outlines optimal design of industrial burners and optimization and dynamic control of pyrolysis furnaces - Outlines large eddy simulation of turbulent reacting flows

Gasoline consists of many different classes of hydrocarbons, such as paraffins, olefins, aromatics, and cycloalkanes. In this study, a surrogate gasoline reaction mechanism is developed, and it has one representative fuel constituent from each of these classes. These selected constituents are iso-octane, n-heptane, 1-pentene, toluene, and methyl-cyclohexane. The mechanism was developed in a step-wise fashion, adding submechanisms to treat each fuel component. Reactions important for low temperature oxidation (