A detailed chemical kinetic reaction mechanism is used to study the oxidation of n-heptane under several classes of conditions. Experimental results from ignition behind reflected shock waves and in a rapid compression machine were used to develop and validate the reaction mechanism at relatively high temperatures, while data from a continuously stirred tank reactor (cstr) were used to refine the low temperature portions of the reaction mechanism. In addition to the detailed kinetic modeling, a global or lumped kinetic mechanism was used to study the same experimental results. The lumped model was able to identify key reactions and reaction paths that were most sensitive in each experimental regime and provide important guidance for the detailed modeling effort. In each set of experiments, a region of negative temperature coefficient (NTC) was observed. Variation in pressure from 5 to 40 bars were found to change the temperature range over which the NTC region occurred. Both the lumped and detailed kinetic models reproduced the measured results in each type of experiments, including the features of the NTC region, and the specific elementary reactions and reaction paths responsible for this behavior were identified and rate expressions for these reactions were determined.

Combustion has played a central role in the development of our civilization which it maintains today as its predominant source of energy. The aim of this book is to provide an understanding of both fundamental and applied aspects of low-temperature combustion chemistry and autoignition. The topic is rooted in classical observational science and has grown, through an increasing understanding of the linkage of the phenomenology to coupled chemical reactions, to quite profound advances in the chemical kinetics of both complex and elementary reactions. The driving force has been both the intrinsic interest of an old and intriguing phenomenon and the centrality of its applications to our economic prosperity. The volume provides a coherent view of the subject while, at the same time, each chapter is self-contained.

The primary reference fuels n-heptane and iso-octane and their mixtures are used as a measure of the tendency of a given automotive fuel to cause knocking or pre-ignition in an internal combustion engine. Consequently, many experimental studies have been performed on these hydrocarbons in an attempt to better understand their oxidation. Shock tube studies at high temperature and pressure have been performed. Low temperature studies, in which species concentration profiles of primary, intermediate and final products, have been carried out using jet stirred flow reactors. In addition, experiments have been performed in CFR engines and fundamental features of n-heptane autoignition have been observed using a rapid compression machine. A detailed chemical kinetic reaction mechanism is employed here to study the oxidation of both fuels. Computed results are compared with experimental data obtained in the High Pressure Turbulent Flow Reactor at Princeton University.

This book provides a comprehensive overview of the application of liquid biofuels to internal combustion (IC) engines. Biofuels are one of the most promising renewable and sustainable energy sources. Particularly, liquid biofuels obtained from biomass could become a valid alternative to the use of fossil fuels in the light of increasingly stringent environmental constraints. In this book, the discussion is limited to liquid biofuels obtained from triglycerides and lignocellulose among the many different kinds of biomass. Several liquid biofuels from triglycerides, straight vegetable oil, biodiesel produced from inedible vegetable oil, hydrotreated vegetable oil, and pyrolytic oil have been selected for discussion, as well as biofuels from lignocellulose bio-oil, alcohols such as methanol, ethanol and butanol, and biomass-to-liquids diesel. This book includes three chapters on the application of methanol, ethanol and butanol to advanced compression ignition (CI) engines such as LTC, HCCI, RCCI and DF modes. Further, the application of other higher alcohols and other drop-in fuels such as DMF, MF, MTHF, and GVL are also discussed. The book will be a valuable resource for graduate students, researchers and engine designers who are interested in the application of alcohols and other biofuels in advanced CI engines, and also useful for alternative energy planners selecting biofuels for CI engines in the future.

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

Controlled fires are beneficial for the generation of heat and power while uncontrolled fires, like fire incidents and wildfires, are detrimental and can cause enormous material damage and human suffering. This edited book presents the state-of-the-art of modeling and numerical simulation of the important transport phenomena in fires. It describes how computational procedures can be used in analysis and design of fire protection and fire safety. Computational fluid dynamics, turbulence modeling, combustion, soot formation, thermal radiation modeling are demonstrated and applied to pool fires, flame spread, wildfires, fires in buildings and other examples.

Organic Reaction Mechanisms 2014, the 50th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2014. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular Rearrangements An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation. This volume includes a 5-year cumulative index.