%0 Journal Article %1 Nehse1996 %A Nehse, Maria %A Warnat, Jürgen %A Chevalier, Christophe %D 1996 %J Symposium (International) on Combustion %K automatic kinetic mechanism modeling reaction %N 1 %P 773 - 780 %R 10.1016/S0082-0784(96)80286-4 %T Kinetic modeling of the oxidation of large aliphatic hydrocarbons %U http://www.sciencedirect.com/science/article/pii/S0082078496802864 %V 26 %X Because of the complexity of low-temperature oxidation, a detailed reaction scheme of higher hydrocarbons (which are components of practical fuels) typically involves several hundred chemical species taking part in thousands of elementary reactions. Nevertheless, only a very limited number of different reaction types is appearing, for example, alkane thermal decomposition, H-atom abstraction to form an alkyl radical, alkyl radical isomerization, and β decomposition of the alkyl radical for the high-temperature range and a few additional reaction types at low temperature. A ŁISP\ program developed for the automatic generation of reaction mechanisms is able to produce mechanisms for the oxidation of aliphatic hydrocarbons. In contrast to earlier attempts described in the literature, a rather complete description of the aldehyde oxidation is included. The transition between low-and high-temperature range with a negative temperature dependence is well reproduced. With the help of newly available experiments for n-decane, the reaction mechanisms for n-heptane, and n-decane are validated for a wide range of pressures, temperatures, and equivalence ratios, covering conditions dictated by potential applications. This is a severe test case, because calculated ignition-delay times are very sensitive with respect to the quality of the reaction mechanism used. Additional sensitivity analysis based on the ØH\ concentration, shows the principal rate-determining reactions. However, more kinetic data for high hydrocarbons and oxygenated species are necessary to validate the reaction mechanism, especially with respect to chain-length dependencies of rate coefficients and the behavior of fuels with multiple C-C bonds. Furthermore, some results on flame velocity are given for n-heptane.

@article{Nehse1996, abstract = {Because of the complexity of low-temperature oxidation, a detailed reaction scheme of higher hydrocarbons (which are components of practical fuels) typically involves several hundred chemical species taking part in thousands of elementary reactions. Nevertheless, only a very limited number of different reaction types is appearing, for example, alkane thermal decomposition, H-atom abstraction to form an alkyl radical, alkyl radical isomerization, and β decomposition of the alkyl radical for the high-temperature range and a few additional reaction types at low temperature. A \{LISP\} program developed for the automatic generation of reaction mechanisms is able to produce mechanisms for the oxidation of aliphatic hydrocarbons. In contrast to earlier attempts described in the literature, a rather complete description of the aldehyde oxidation is included. The transition between low-and high-temperature range with a negative temperature dependence is well reproduced. With the help of newly available experiments for n-decane, the reaction mechanisms for n-heptane, and n-decane are validated for a wide range of pressures, temperatures, and equivalence ratios, covering conditions dictated by potential applications. This is a severe test case, because calculated ignition-delay times are very sensitive with respect to the quality of the reaction mechanism used. Additional sensitivity analysis based on the \{OH\} concentration, shows the principal rate-determining reactions. However, more kinetic data for high hydrocarbons and oxygenated species are necessary to validate the reaction mechanism, especially with respect to chain-length dependencies of rate coefficients and the behavior of fuels with multiple C-C bonds. Furthermore, some results on flame velocity are given for n-heptane. }, added-at = {2013-12-24T18:29:02.000+0100}, author = {Nehse, Maria and Warnat, Jürgen and Chevalier, Christophe}, biburl = {https://www.bibsonomy.org/bibtex/2aa28676fec83d0c46380a95b527b073e/rlanger}, description = {Kinetic modeling of the oxidation of large aliphatic hydrocarbons}, doi = {10.1016/S0082-0784(96)80286-4}, interhash = {3a14e414bd86acc38c057a394169c171}, intrahash = {aa28676fec83d0c46380a95b527b073e}, issn = {0082-0784}, journal = {Symposium (International) on Combustion }, keywords = {automatic kinetic mechanism modeling reaction}, number = 1, pages = {773 - 780}, timestamp = {2014-01-10T20:17:37.000+0100}, title = {Kinetic modeling of the oxidation of large aliphatic hydrocarbons }, url = {http://www.sciencedirect.com/science/article/pii/S0082078496802864}, volume = 26, year = 1996 }