Detailed chemical kinetic reaction mechanisms are developed for combustion of all nine isomers of heptane (C--H16), and these mechanisms are tested by simulating autoignition of each isomer under rapid compression machine conditions. The reaction mechanisms focus on the manner in which the molecular structure of each isomer determines the rates and product distributions of possible classes of reactions. The reaction pathways emphasize the importance of alkylperoxy radical isomerizations and addition reactions of molecular oxygen to alkyl and hydroperoxyalkyl radicals. A new reaction group has been added to past models, in which hydroperoxyalkyl radicals that originated with abstraction of an H atom from a tertiary site in the parent heptane molecule are assigned new reaction sequences involving additional internal H atom abstractions not previously allowed. This process accelerates autoignition in fuels with tertiary C-H bonds in the parent fuel. In addition, the rates of hydroperoxyalkylperoxy radical isomerization reactions have all been reduced so that they are now equal to rates of analogous alkylperoxy radical isomerizations, significantly improving agreement between computed and experimental ignition delay times in the rapid compression machine. Computed ignition delay times agree well with experimental results in the few cases where experiments have been carried out for specific heptane isomers, and predictive model calculations are reported for the remaining isomers. The computed results fall into three general groups; the first consists of the most reactive isomers, including n-heptane, 2-methyl hexane and 3-methyl hexane. The second group consists of the least reactive isomers, including 2,2-dimethyl pentane, 3,3-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane and 2,2,3-trimethyl butane. The remaining isomer, 3-ethyl pentane, was observed computationally to have an intermediate level of reactivity. These observations are generally consistent with knocking tendencies of these isomers, as measured by octane ratings, although the correlations are only approximate.

Detailed chemical kinetic reaction mechanisms are developed for all nine chemical isomers of heptane (C--H16), following techniques and models developed previously for other smaller alkane hydrocarbon species. These reaction mechanisms are tested at high temperatures by computing shock tube ignition delay times and at lower temperatures by simulating ignition in a rapid compression machine. Although the corresponding experiments have not been reported in the literature for most of these isomers of heptane, intercomparisons between the computed results for these isomers and comparisons with available experimental results for other alkane fuels are used to validate the reaction mechanisms as much as possible. Differences in the overall reaction rates of these fuels are discussed in terms of differences in their molecular structure and the resulting variations in rates of important elementary reactions. Reaction mechanisms in this study are works in progress and the results reported here are subject to change, based on model improvements and corrections of errors not yet discovered.

Previously we have reported on the combustion behavior of all nine isomers of heptane in a rapid compression machine (RCM) with stoichiometric fuel and ''air'' mixtures at a compressed gas pressure of 15 atm. The dependence of autoignition delay times on molecular structure was illustrated. Here, we report some additional experimental work that was performed in order to address unusual results regarding significant differences in the ignition delay times recorded at the same fuel and oxygen composition, but with different fractions of nitrogen and argon diluent gases. Moreover, we have begun to simulate these experiments with detailed chemical kinetic mechanisms. These mechanisms are based on previous studies of other alkane molecules, in particular, n-heptane and iso-octane. We have focused our attention on n-heptane in order to systematically redevelop the chemistry and thermochemistry for this C-- isomer with the intention of extending our greater knowledge gained to the other eight isomers. The addition of new reaction types, that were not included previously, has had a significant impact on the simulations, particularly at low temperatures.

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

Erstmals eine umfassende und einheitliche Wissensbasis und Grundlage für weiterführende Studien und Forschung im Bereich der Automobiltechnik. Die Encyclopedia of Automotive Engineering ist die erste umfassende und einheitliche Wissensbasis dieses Fachgebiets und legt den Grundstein für weitere Studien und tiefgreifende Forschung. Weitreichende Querverweise und Suchfunktionen ermöglichen erstmals den zentralen Zugriff auf Detailinformationen zu bewährten Branchenstandards und -verfahren. Zusammenhängende Konzepte und Techniken aus Spezialbereichen lassen sich so einfacher verstehen. Neben traditionellen Themen des Fachgebiets beschäftigt sich diese Enzyklopädie auch mit "grünen" Technologien, dem Übergang von der Mechanik zur Elektronik und den Möglichkeiten zur Herstellung sicherer, effizienterer Fahrzeuge unter weltweit unterschiedlichen wirtschaftlichen Rahmenbedingungen. Das Referenzwerk behandelt neun Hauptbereiche: (1) Motoren: Grundlagen; (2) Motoren: Design; (3) Hybrid- und Elektroantriebe; (4) Getriebe- und Antriebssysteme; (5) Chassis-Systeme; (6) Elektrische und elektronische Systeme; (7) Karosserie-Design; (8) Materialien und Fertigung; (9) Telematik. - Zuverlässige Darstellung einer Vielzahl von Spezialthemen aus dem Bereich der Automobiltechnik. - Zugängliches Nachschlagewerk für Jungingenieure und Studenten, die die technologischen Grundlagen besser verstehen und ihre Kenntnisse erweitern möchten. - Wertvolle Verweise auf Detailinformationen und Forschungsergebnisse aus der technischen Literatur. - Entwickelt in Zusammenarbeit mit der FISITA, der Dachorganisation nationaler Automobil-Ingenieur-Verbände aus 37 Ländern und Vertretung von über 185.000 Ingenieuren aus der Branche. - Erhältlich als stets aktuelle Online-Ressource mit umfassenden Suchfunktionen oder als Print-Ausgabe in sechs Bänden mit über 4.000 Seiten. Ein wichtiges Nachschlagewerk für Bibliotheken und Informationszentren in der Industrie, bei Forschungs- und Schulungseinrichtungen, Fachgesellschaften, Regierungsbehörden und allen Ingenieurstudiengängen. Richtet sich an Fachingenieure und Techniker aus der Industrie, Studenten höherer Semester und Studienabsolventen, Forscher, Dozenten und Ausbilder, Branchenanalysen und Forscher.

Practical fuels are a complex mixture of thousands of hydrocarbon compounds, making it challenging and difficult to study their combustion behavior. It's generally agreed that in order to study these complex practical fuels a much simpler approach of studying simple fuel surrogates containing limited number of components is more feasible. Ethanol and n-heptane have been studied as primary reference fuels in the surrogate study of gasoline and diesel over the past few decades. The objective of the following thesis has been to study the autoignition characteristics of ethanol and n-heptane and validate chemical kinetic mechanisms. The validation of a chemical kinetic mechanism provides a deeper insight into the combustion behavior of the fuels which can be further used to study advanced combustion concepts. Experiments have been conducted on the rapid compression machine (RCM) and validated against mechanisms from literature study. Rapid compression machines have been primarily used to study chemical kinetics at low to intermediate temperatures and high pressures for their accuracy and reproducibility. For the following study experiments span over a range of temperature (650-1000 K), pressure (10, 15 and 20 bar) and equivalence ratio ([phi]=0.3, 0.5, 1). Experimental data based on the adiabatic volumetric expansion approach have been modeled numerically using the Sandia SENKIN code in conjunction with CHEMKIN. Experiments have been primarily focused on validating kinetic mechanisms at low to intermediate temperatures and elevated pressures. Ignition delay time data from experiments have been deduced based on the pressure and time histories. A brute sensitivity and flux analysis has been performed to reveal the key sensitive reactions and the dominant reaction pathways followed under the present experimental conditions. Improvements have been suggested and discrepancies noted in order to develop a valid chemical kinetic mechanism. Under the present experimental conditions for the study of ethanol, reactions involving hydroperoxyl radicals, namely C2H5OH+HȮ2 and CH3CHO+ HȮ2 as well as the formation of H2O2 from HȮ2 radical and its subsequent decomposition have been found to be sensitive. Based on the following, improvements and developements have been suggested to increase the accuracy and predictability of the mechanisms studied. Ignition delay data from experiments have been compared against those obtained from the mechanism used in the study for n-heptane. Discrepancies have been found in the low temperature region, with the mechanism under predicting the first ignition delay. The causes for the discrepancy have been noted to be due to the NTC behaviour exhibited during the two stage ignition of n-heptane. At low temperatures the reaction pathway proceeded by chain branching mainly due to the ketohydroperoxide species reaction pathway has been analysed. As the temperature of the reaction increases the reaction pathway is dominated by the ȮOH species propagation resulting in the formation of conjugate olefins and [Beta]-decomposition products, a further investigation of which can help improve the predictability of the mechanism.

Autoignition of the five distinct isomers of hexane is studied experimentally under motored engine conditions and computationally using a detailed chemical kinetic reaction mechanism. Computed and experimental results are compared and used to help understand the chemical factors leading to engine knock in spark-ignited engines and the molecular structure factors contributing to octane rating for hydrocarbon fuels. The kinetic model reproduces observed variations in critical compression ratio with fuel structure, and it also provides intermediate and final product species concentrations in very dose agreement with observed results. In addition, the computed results provide insights into the kinetic origins of fuel octane sensitive.