Hoyermann, Karlheinz

[["dc.bibliographiccitation.firstpage","741"],["dc.bibliographiccitation.journal","ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS"],["dc.bibliographiccitation.lastpage","752"],["dc.bibliographiccitation.volume","214"],["dc.contributor.author","Hack, W."],["dc.contributor.author","Wagner, M."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.date.accessioned","2018-11-07T11:17:36Z"],["dc.date.available","2018-11-07T11:17:36Z"],["dc.date.issued","2000"],["dc.description.abstract","The reaction CHF((X) over tilde(1)A') + O-3 --> products (1) has been studied in an isothermal flow reactor in the temperature range from 235 K to 443 K and at a pressure of about p = 2 mbar under pseudo first order conditions, [O-3](0) >> [CHF](0). He was the main carrier gas. The CHF((X) over tilde) radical was produced in the reaction sequence CH3F + F --> CH2F + HF; CH2F + F --> CHF((X) over tilde) + HF and detected by laser induced fluorescence. For reaction (1) a value of the rate constant: k(1)(T) = (6.1+/-0.6) . 10(12)(T/298 K)(-0.6+/-0.4) [cm(3)/mol S] was obtained. No change in the rate constant was observed, substituting He by the quenchers N-2 or SF6. The reaction mechanism is discussed."],["dc.identifier.doi","10.1524/zpch.2000.214.6.741"],["dc.identifier.isi","000088100600003"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/54842"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Oldenbourg Verlag"],["dc.relation.issn","0942-9352"],["dc.title","The elementary reaction of CHF((X)over-tilde(1)A ') with ozone"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","95"],["dc.bibliographiccitation.journal","ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS"],["dc.bibliographiccitation.lastpage","112"],["dc.bibliographiccitation.volume","214"],["dc.contributor.author","Beiderhase, T."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Hack, W."],["dc.date.accessioned","2018-11-07T11:17:21Z"],["dc.date.available","2018-11-07T11:17:21Z"],["dc.date.issued","2000"],["dc.description.abstract","The reaction of CF(2)((X) over tilde) with O(3) has been investigated in a discharge flow reactor at room temperature and low pressure (p = 2.5 mbar). CF(2)((X) over tilde) was produced by a microwave discharge of a mixture of CF(2)Br(2)/He. The reactants and products were detected by mass spectrometers (MS), which were connected to the flow systems via a continuous molecular beam sampling system. The following primary products were observed (CF(2)O(3) (m/z = 98); CF(2)O (m/z = 47, 66); O(2) (m/z = 32)). The reaction mechanism: CF(2)((X) over tilde) + O(3) reversible arrow CF(2)O(3)(#) --> CF(2)O(3) -> CF(2)O + O(2) explains the observed primary products. The molecule with the empirical formula CF(2)O(3) has been observed directly by MS; the structure is discussed."],["dc.identifier.doi","10.1524/zpch.2000.214.1.095"],["dc.identifier.isi","000085326800008"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/54783"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Oldenbourg Verlag"],["dc.relation.issn","0942-9352"],["dc.title","Elementary reaction of CF2((X)over-tilde) with O(3): Primary products"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","625"],["dc.bibliographiccitation.journal","ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS"],["dc.bibliographiccitation.lastpage","641"],["dc.bibliographiccitation.volume","214"],["dc.contributor.author","Beiderhase, T."],["dc.contributor.author","Hack, W."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Olzmann, M."],["dc.date.accessioned","2018-11-07T11:17:32Z"],["dc.date.available","2018-11-07T11:17:32Z"],["dc.date.issued","2000"],["dc.description.abstract","Fluorinated hydrocarbon radical-radical reactions in the gas phase have been studied at low pressure (0.5 less than or equal to p/mbar less than or equal to 2) and low temperature (253 less than or equal to T/K less than or equal to 333) using the discharge flow reactor molecular beam sampling mass spectrometry (MS) technique. Stable and labile species have been detected by MS applying low energy electron impact as well as multiphoton ionisation. For the combination reaction (1) CH2F + CH2F --> products the rate coefficient k(1) = (7.0 +/- 0.8) . 10(12) (T/298)((-3.9+/-1.0)) cm(3)/mol . s was determined. At low pressure the HF elimination pathway (1b) (1b) CH2F + CH2F --> C2H3F + HF is the main channel (k(1b)/k(1) = (0.82 +/- 0.015)). For the CHF, radical self reaction (2) CHF2 + CHF2 --> products the rate coefficient was measured as k(2) = (1.7 +/- 0.5) . 10(13) exp((-555 +/- 89)/T) cm(3)/ mol . s. The stabilisation of C2H2F4 is the main reaction pathway (2a) (k(2a)/k(2) greater than or equal to 0.5), the HF elimination is of minor importance (k(2b)/k(2) = 0.2). No pressure dependence of k(1) and k(2) was observed in the limited pressure range."],["dc.identifier.doi","10.1524/zpch.2000.214.5.625"],["dc.identifier.isi","000087622100006"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/54830"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Oldenbourg Verlag"],["dc.relation.issn","0942-9352"],["dc.title","Gas-phase kinetics of the self reactions of the radicals CH2F and CHF2"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","732"],["dc.bibliographiccitation.issue","11"],["dc.bibliographiccitation.journal","International Journal of Chemical Kinetics"],["dc.bibliographiccitation.lastpage","740"],["dc.bibliographiccitation.volume","33"],["dc.contributor.author","Goos, E."],["dc.contributor.author","Hippler, H."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Jurges, B."],["dc.date.accessioned","2018-11-07T08:28:41Z"],["dc.date.available","2018-11-07T08:28:41Z"],["dc.date.issued","2001"],["dc.description.abstract","The methyl radical induced pyrolysis of isobutane has been studied in the temperature range of 800-950 K and at pressures of 80 and 130 mbar. We used Co-2-laser induced heating by fast vibrational-translational (V-T) energy transfer from SF6 to the reaction mixture, This is a convenient method to study homogeneous high temperature kinetics since the reactor walls remain cold. The radial temperature distribution in the reactor has been investigated by four different methods: stationary heat balance, optical absorption, pressure rise, and the temperature dependence of the rate of an isomerization reaction. Methyl radicals were produced in the presence of isobutane via the fast thermal decomposition of di-tert-butyl-peroxide and the products were analyzed using gas chromatography and mass spectroscopy. The main products of the overall reaction were propene (C3H6) and isobutene (i-C4H8), whereas ethene (C2H4), propane (C3H8), neo-pentane (neo-C5H12), and isopentane (i-C5H12) were minor products. The product distribution showed strong temperature dependence, The product yields and their temperature dependence were analyzed by a kinetic model developed for the high temperature oxidation of n-butane and the low temperature oxidation of n-pentane, and isopentane. We included a few missing reactions and slightly adjusted some rate constants to obtain a better agreement between the modeling and the experiments. The extended mechanism consists of 63 species and 171 reactions to be evaluated further in forthcoming experiments. (C) 2001 John Wiley & Sons, Inc."],["dc.identifier.doi","10.1002/kin.1070"],["dc.identifier.isi","000171483200011"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/16482"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","John Wiley & Sons Inc"],["dc.relation.issn","0538-8066"],["dc.title","Reactions of methyl radicals with isobutane at temperatures between 800 and 950 Kelvin"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","8954"],["dc.bibliographiccitation.issue","31"],["dc.bibliographiccitation.journal","Physical Chemistry Chemical Physics"],["dc.bibliographiccitation.lastpage","8968"],["dc.bibliographiccitation.volume","12"],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Maarfeld, Sven"],["dc.contributor.author","Nacke, Frank"],["dc.contributor.author","Nothdurft, Joerg"],["dc.contributor.author","Olzmann, Matthias"],["dc.contributor.author","Wehmeyer, Jens"],["dc.contributor.author","Welz, Oliver"],["dc.contributor.author","Zeuch, Thomas"],["dc.date.accessioned","2018-11-07T08:48:26Z"],["dc.date.available","2018-11-07T08:48:26Z"],["dc.date.issued","2010"],["dc.description.abstract","The kinetics of cycloalkyl + O reactions were studied with respect to their rate coefficients and the product branching ratios from the decomposition of the chemically activated cycloalkoxy radicals. Rate coefficients for the reactions of cyclohexyl (c-C6H11), cycloheptyl (c-C7H13) and cyclooctyl (c-C8H15) radicals with oxygen atoms were determined with an experimental setup consisting of a discharge flow reactor with molecular beam sampling and REMPI/TOF-MS detection. The following rate coefficients were obtained (units: cm(3)/mol(-1) s(-1)): k(c-C6H11 + O) = (1.33 +/- 0.24) x 10(14)(T/298 K)(0.11) (T = 250-600 K), k(c-C7H13 + O) = (1.85 +/- 0.25) x 10(14) (T = 298 K), k(c-C8H15 + O) = (1.56 +/- 0.20) x 10(14)(T/298 K)(0.66+/-0.15) (T = 268-363 K). Stable products were determined by quantitative FTIR spectroscopy. The decomposition of the cycloalkoxy radicals leads besides beta-C-H bond fission (yields: 24% for c-C6H11O, 20-25% for c-C8H15O) mainly to alkyl radicals by ring-opening via beta-C-C bond cleavage. These open-chain alkyl radicals further decompose mainly by beta-C-C bond scission. An increase of the total pressure from 4 mbar to 1 bar had no effect on the product distribution for the reaction c-C6H11 + O, whereas for the reaction c-C8H15 + O further decomposition of the ring-opening product is significantly suppressed at 1 bar. The experimental results on the channel branching and its pressure dependence were rationalized with the statistical rate theory. A comparison of the experimental and modeling results indicates a significant influence of hindered internal rotations (HIRs) on the reactions of the ring-opening products. The harmonic approximation to describe these modes was shown to be inadequate, while a treatment as one-dimensional HIRs led to a significantly improved agreement between experimental and modeling results. Implications of our findings for the formation of secondary organic aerosol and high-temperature combustion are discussed."],["dc.identifier.doi","10.1039/b925920a"],["dc.identifier.isi","000280514800032"],["dc.identifier.pmid","20520884"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/21207"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Royal Soc Chemistry"],["dc.relation.issn","1463-9076"],["dc.title","Rate coefficients for cycloalkyl plus O reactions and product branching in the decomposition of chemically activated cycloalkoxy radicals: an experimental and theoretical study"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","409"],["dc.bibliographiccitation.issue","4-5"],["dc.bibliographiccitation.journal","ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS"],["dc.bibliographiccitation.lastpage","426"],["dc.bibliographiccitation.volume","223"],["dc.contributor.author","Hold, M."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Morozov, I."],["dc.contributor.author","Zeuch, Thomas"],["dc.date.accessioned","2018-11-07T08:35:42Z"],["dc.date.available","2018-11-07T08:35:42Z"],["dc.date.issued","2009"],["dc.description.abstract","The primary product formation of the reactions CH2Cl + O and CHCl2 + O in the gas phase has been Studied around room temperature. The coupling of a conventional discharge flow reactor via a molecular sampling system to a mass spectrometer with electron impact ionization allowed the determination of labile and stable species (set-up A). The radicals are formed by H atom abstraction in the reactions CH3Cl + F and CH2Cl2 + F. The product analysis leads to the following branching fractions relative to precursor consumption: For CH2Cl + O, the channel HCHO + Cl yields 19 % and CO + HCl + H yields 43 %, the contributions of the labile species HCO is found but not quantified. For CHCl2 + O the channel CO + HCl + Cl yields 70 %, CICHO and the labile CICO are detected but not quantified. The comparison to CH3 + O shows the stepwise increase of channel fractions for the CO forming Mines by chlorination of the methyl radical. The rates of the reactions have been studied relative to CH3 + O and CH3OCH2 + O. Laser-induced multiphoton ionization combined with TOF mass spectrometry and molecular beam sampling front a flow reactor (set-up B) was used for the specific and sensitive detection of the CH2Cl, CHCl2, CH3, and CH3OCH2 radicals. The rate coefficient of the reactions CH2Cl + O was derived with reference to the reaction CH3OCH2 leading to k = (8.1 +/- 1.8) x 10(13) cm(3)/(mol.s) and for CHCl2 + O with reference to CH3 + O leading to k = (3.8 +/- 1.9) X 10(13) cm(3)/(mol.s). For CH3Cl + F and CH2Cl2 + F the rate coefficients have been determined with set-Lip A leading to k = (14.3 +/- 0.9)X 10(13) cm(3)/(mol.s) for CH3Cl + F and k = (8.4 +/- 3.8) X 10(13) cm(3)/(mol.s) for CH2Cl2 + F. Only a negligible temperature dependence in the temperature range from 250-360 K was observed for all reactions studied."],["dc.identifier.doi","10.1524/zpch.2009.6044"],["dc.identifier.isi","000268895100006"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/18136"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Oldenbourg Verlag"],["dc.relation.issn","0942-9352"],["dc.title","CH2Cl and CHCl2 Radical Chemistry: The Formation by the Reactions CH3Cl + F and CH2Cl2 + F and the Destruction by the Reactions CH2Cl + O and CHCl2 + O"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","271"],["dc.bibliographiccitation.lastpage","377"],["dc.contributor.author","Brandes, Elisabeth"],["dc.contributor.author","Dietlen, Siegmund"],["dc.contributor.author","Hieronymus, Hartmut"],["dc.contributor.author","Krause, Ulrich"],["dc.contributor.author","Plewinsky, Bodo"],["dc.contributor.author","Redeker, Tammo"],["dc.contributor.author","Schrder, Volkmar"],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.editor","Hattwig, Martin"],["dc.contributor.editor","Steen, Henrikus"],["dc.date.accessioned","2021-12-08T12:28:55Z"],["dc.date.available","2021-12-08T12:28:55Z"],["dc.date.issued","2004"],["dc.identifier.doi","10.1002/9783527612468.ch3"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/95888"],["dc.language.iso","en"],["dc.notes.intern","DOI-Import GROB-476"],["dc.publisher","Wiley-VCH Verlag GmbH & Co. KGaA"],["dc.publisher.place","Weinheim, Germany"],["dc.relation.eisbn","9783527612468"],["dc.relation.isbn","9783527307180"],["dc.relation.ispartof","Handbook of Explosion Prevention and Protection"],["dc.title","Properties of Reactive Gases and Vapours (Safety Characteristics)"],["dc.type","book_chapter"],["dc.type.internalPublication","yes"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","283"],["dc.bibliographiccitation.journal","Proceedings of the Combustion Institute"],["dc.bibliographiccitation.lastpage","291"],["dc.bibliographiccitation.volume","33"],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Olzmann, Matthias"],["dc.contributor.author","Welz, Oliver"],["dc.contributor.author","Zeuch, Thomas"],["dc.date.accessioned","2018-11-07T09:00:30Z"],["dc.date.available","2018-11-07T09:00:30Z"],["dc.date.issued","2011"],["dc.description.abstract","Reactions of hydrocarbon radicals with oxygen atoms are important in combustion, and both the rate coefficient and product branching have to be known for an accurate combustion modeling. In this work, the primary product formation in the reaction of the simplest open-chain secondary alkyl radical, iso-propyl (2-C3H7), with oxygen atoms in the gas phase was studied at room temperature and a pressure of 4 mbar. 2-C3H7 radicals were generated from diisopropylketone ((2-C3H7)(2)CO) and isopropyliodide (2-C3H7I), and O atoms were produced from SO2 by laser-flash photolysis at lambda = 193 nm, respectively. The reactants and products were detected by quantitative FTIR spectroscopy. The combined product analysis in the experiments with the different precursors leads to the following relative branching fractions: 2-C3H7 + O -> CH3CHO + CH3 (40%), CH3COCH3 + H (36%), C3H6 + OH (24%). The channel branching of the iso-propoxy (2-C3H7O) radical formed from the 2-C3H7 + O reaction was modeled using statistical rate theory with molecular and transition state data from G3MP2B3 calculations. The absolute rate of reaction was studied at room temperature and a pressure of 5.8 mbar. Laser-induced fluorescence (LIF) was used for the specific detection of the OH (v = 0,1) radicals, and the rate coefficient of the 2-C3H7 + O reaction was derived from the OH (v = 1) LIF-time profile leading to k(2-C3H7 + O) = (1.14 +/- 0.15) x 10(14) cm(3)/(mol.s) at 298 K. The OH-forming direct abstraction route and the channel to CH3CHO + CH3 may influence the flame speed of a propane flame. This is revealed, when the rate coefficient and channel branching of the 2-C3H7 + O reaction is incorporated in a suitable detailed reaction mechanism and target experiments are modeled in absence and presence of the title reaction. (C) 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved."],["dc.identifier.doi","10.1016/j.proci.2010.05.075"],["dc.identifier.isi","000285780200022"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/24179"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Elsevier Science Inc"],["dc.relation.issn","1540-7489"],["dc.title","The reaction of iso-propyl radicals with oxygen atoms: Rate coefficient, product branching, and relevance for combustion modeling"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","1977"],["dc.bibliographiccitation.issue","9"],["dc.bibliographiccitation.journal","Physical Chemistry Chemical Physics"],["dc.bibliographiccitation.lastpage","1984"],["dc.bibliographiccitation.volume","7"],["dc.contributor.author","Hack, W."],["dc.contributor.author","Hold, M."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Wehmeyer, Jens"],["dc.contributor.author","Zeuch, Thomas"],["dc.date.accessioned","2018-11-07T08:46:34Z"],["dc.date.available","2018-11-07T08:46:34Z"],["dc.date.issued","2005"],["dc.description.abstract","The primary products and the rate of the reaction of methyl radicals with oxygen atoms in the gas phase at room temperature have been studied using three different experimental arrangements: ( A) laser. ash photolysis to produce CH3 and O from the precursors CH3I and SO2 (the educts and the products were detected by quantitative FTIR spectroscopy); ( B) the coupling of a conventional discharge flow reactor via a molecular sampling system to a mass spectrometer with electron impact ionization, which allowed the determination of labile and stable species; ( C) laser induced multiphoton ionization combined with a TOF mass spectrometer-molecular beam sampling-flow reactor, which was used for the specific and sensitive detection of the CH3, CD3, C2H5 and C2D5 radicals and the determination of rate coefficients. The branching ratio of the reaction channels was determined by the experimental arrangements (A) and (B) leading to CH3 + O -> HCHO + H (55 +/- 5)% -> CO + H-2 + H (45 +/- 5)%. The rate coefficients of the normal and deuterated methyl and ethyl radicals with atomic oxygen showed no isotope effect: k(CD3 + O)/k(CH3 + O) = 0.99 +/- 0.12, k(C2D5 + O)/k(C2H5 + O) = 1.01 +/- 0.07 (statistical error, 95% confidence level). The absolute rate coefficient of the reaction CH3 + O was derived with reference to the reaction C2H5 + O (k 1.04 x 10(14) cm(3) mol(-1) s(-1)) leading to k(CH3 + O) = (7.6 +/- 1.4) x 10(13) cm(3) mol(-1) s(-1)."],["dc.identifier.doi","10.1039/b419137d"],["dc.identifier.isi","000228634500014"],["dc.identifier.pmid","19787902"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/20725"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Royal Soc Chemistry"],["dc.relation.issn","1463-9076"],["dc.title","Mechanism and rate of the reaction CH3+O- revisited"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]

[["dc.bibliographiccitation.firstpage","5127"],["dc.bibliographiccitation.issue","22"],["dc.bibliographiccitation.journal","Physical Chemistry Chemical Physics"],["dc.bibliographiccitation.lastpage","5132"],["dc.bibliographiccitation.volume","2"],["dc.contributor.author","Goos, E."],["dc.contributor.author","Hippler, H."],["dc.contributor.author","Hoyermann, Karlheinz"],["dc.contributor.author","Jurges, B."],["dc.date.accessioned","2018-11-07T11:14:11Z"],["dc.date.available","2018-11-07T11:14:11Z"],["dc.date.issued","2000"],["dc.description.abstract","The pyrolysis of n-butane, initiated by methyl radicals has been studied in the temperature range 750-1000 K and at pressures 0.08-0.13 bar in a quasi-wall-free reactor using laser heating by fast vibrational-translational (V-T) energy transfer. This is a convenient method to study homogeneous high-temperature kinetics since the reactor walls remain cold. The radial temperature distribution in the reactor has been investigated by four different methods: stationary heat balance, optical absorption, pressure rise, and the temperature dependence of the rate of an isomerization reaction. Methyl radicals were produced via the fast thermal dissociation of di-tert-butyl peroxide and product analysis was performed by the use of GC-MS. The main products of the overall reaction of the model system (n-C4H10+CH3) were C2H4, C3H6, C3H8, whereas 1-C4H8, n-C5H12, iso-C5H12 were minor components, all showing a strong dependence on temperature. The product distribution and the temperature dependence were analyzed by a kinetic model of 61 species and 164 reactions developed for the high-temperature butane and the low-temperature n-pentane oxidation. Good agreement was found between our experimental investigations and the modeling. However, we had to slightly adjust the rate constants for the reactions CH3+n-C4H10-->n-C4H9+CH4 (3) CH3+n-C4H10-->sec-C4H9+CH4 (4) At a temperature of 1000 K we found a larger branching ratio of k(3)/(k(3)+k(4))=1/3 compared to 1/8 as extrapolated from low-temperature data. The total rate coefficient was found to be (k(3)+k(4))=8x10(9) cm(3) mol(-1) s(-1) which is about 50% higher than the extrapolated values."],["dc.identifier.doi","10.1039/b005219l"],["dc.identifier.isi","000165154400018"],["dc.identifier.uri","https://resolver.sub.uni-goettingen.de/purl?gro-2/54072"],["dc.notes.status","zu prüfen"],["dc.notes.submitter","Najko"],["dc.publisher","Royal Soc Chemistry"],["dc.relation.issn","1463-9076"],["dc.title","Laser powered homogeneous pyrolysis of butane initiated by methyl radicals in a quasi-wall-free reactor at 750-1000 K"],["dc.type","journal_article"],["dc.type.internalPublication","yes"],["dc.type.peerReviewed","yes"],["dc.type.status","published"],["dspace.entity.type","Publication"]]