The cool-flame combustion of decane

1982 ◽  
Vol 382 (1783) ◽  
pp. 429-440 ◽  
Keyword(s):  
Carbonyl Compounds ◽  
Hydrogen Bromide ◽  
Combustion Products ◽  
Cool Flame ◽  
Flame Combustion ◽  
Hydroperoxide Formation ◽  
Slow Combustion ◽  
Flame Region ◽  
Increasing Temperature ◽  
Oxidative Attack

Three approaches have been used to elucidate the mechanism of combustion of decane in the cool-flame region. First, measurements have been made of cool-flame and ignition parameters. These show a well defined change in activation energy at about 530 K. Second, analytical studies have been made of the effect of increasing temperature on the combustion products. These indicate that hydroperoxide formation ceases and that C 10 O-heterocycles become the predominant products at 500-530 K; the relative amounts of decanal and decanone do not however change. Finally, small amounts of hydrogen bromide have been added. These cause the complete conversion of hydroperoxides into decanones even at low temperatures; no lower carbonyl compounds are formed above 500 K. This work has led to two principal conclusions. One, which is shown by all three methods of study, is that the cool-flame combustion of decane involves two distinct mechanisms with a transition at 500-530 K. The other is that the selectivity of initial oxidative attack on decane remains low over the whole of the slow combustion and cool-flame regions between 440 and 680 K, suggesting that hydroxyl radicals are the main attacking species throughout.

The cool-flame oxidation of 3-methylpentane

1972 ◽  
Vol 329 (1579) ◽  
pp. 433-452 ◽  
Keyword(s):  
Hydrogen Transfer ◽  
Detailed Comparison ◽  
Combustion Products ◽  
Experimental Conditions ◽  
Cool Flame ◽  
Slow Combustion ◽  
Flame Region ◽  
The Difference ◽  
Increasing Temperature ◽  
Flame Oxidation

Kinetic and analytical studies of the gaseous oxidation of 3-methylpentane have been carried out both under slow combustion conditions and more especially in the cool-flame region. Analysis of the complex mixtures of in termediate products provides strong evidence for the occurrence of 3-methylpentylperoxy radical isomerization, which leads initially to the formation mainly of the corresponding β- and γ-hydroperoxyalkyl radicals. Detailed comparison of the yields of partial combustion products with those obtained from 3-ethylpentane under similar experimental conditions shows that formation of γ-hydro-peroxyalkyl radicals takes place less readily during the oxidation of 3-methylpentane due to the restricted number of modes of 1:6 hydrogen transfer. In consequence, this branched C 6 alkane gives smaller yields of the corresponding O -heterocycles but larger amounts of β-scission products. During the isomerization of 3-methylpentylperoxy radicals there is evidence for the occurrence of some alkyl group shifts. The results show that there is a somewhat greater tendency for m ethyl groups to migrate than there is for ethyl groups, the difference becoming more marked with increasing temperature.

The effect of hydrogen bromide on the products of the cool-flame combustion of n -pentane

1974 ◽  
Vol 341 (1625) ◽  
pp. 195-212 ◽  
Keyword(s):  
Initial Temperature ◽  
Hydrogen Bromide ◽  
Transient Temperature ◽  
Cool Flame ◽  
Flame Combustion ◽  
Cool Flames ◽  
Main Effect ◽  
Halogen Compound ◽  
Almost All ◽  
Uncatalysed Reaction

Detailed studies have been made of the products of the cool-flame combustion of n -pentane in the absence and presence of small concentrations (2-6 vol. %) of added hydrogen bromide. In the uncatalysed reaction, acetone and acetaldehyde are the principal products formed at low temperatures during the induction period preceding the first cool flame but increasing amounts of C 5 alkenes and O-heterocycles start to be formed as the initial temperature is increased. The main effect of hydrogen bromide is to increase dramatically the yields of C 5 ketones at the expense of almost all the other products. The results indicate that in the absence of the halogen compound the principal fate of the initially formed pentylperoxy radicals is isomerisation to hydroperoxypentyl radicals. At 250 °C, the latter radicals mainly add on further oxygen and are eventually converted to pentanedihydroperoxides; at higher temperatures, the hydroperoxypentyl radicals tend increasingly to decompose directly to give principally pentenes and C 5 O-heterocycles. Hydrogen bromide alters the mechanism operating with binary mixtures primarily by providing a source of readily abstractable hydrogen and thus enhancing the formation of pentenemonohydroperoxides. Control experiments on the homogeneous breakdown of pentane-2-monohydroperoxide show that the principal decomposition product is pentan-2-one and thus confirm the probable importance of pentanemonohydroperoxides as intermediates in the HBr-promoted reaction. Studies of the chemical changes accompanying the passage of cool flames show that these vary considerably with the prevailing conditions as well as with the number of previous cool flames which have propagated through the mixture. Hydrogen bromide causes well-defined differences in the nature and distribution of the products of the combustion of n -pentane, although these changes are not as great as those brought about by the passage of cool flames which generally lead to considerable transient temperature rises in the system.

Quantitative aspects of alkylperoxy radical isomerization during hydrocarbon combustion

1967 ◽  
Vol 300 (1463) ◽  
pp. 455-467 ◽  
Keyword(s):  
Oxygen Atom ◽  
Carbonyl Compounds ◽  
Hydrogen Abstraction ◽  
Carbon Number ◽  
Oxidation Mechanism ◽  
Intramolecular Rearrangement ◽  
Cool Flame ◽  
Hydrocarbon Combustion ◽  
Intramolecular Hydrogen ◽  
Oxidative Attack

Detailed studies of the distribution of the products formed in the different regimes of combustion of n -pentane indicate the importance in the overall oxidation mechanism of the isomerization of amylperoxy radicals. It has been shown that C 5 O -heterocycles and C 5 alkenes are formed as a result of the intramolecular rearrangement of such radicals but that O -heterocycles, carbonyl compounds and alkenes of carbon-number less than five are produced in other ways. The experimental results suggest that, under cool-flame conditions where the yields of C 5 O -heterocycles and C 5 alkenes are highest, between 40 and 50% of the initially formed amylperoxy radicals undergo isomerization followed either by O—O bond fission and cyclization or by C—O bond fission. Then nature and amounts of the various O -heterocyclic products formed from n -pentane enable deductions to be made firstly as to the extents of initial oxidative attack of the hydrocarbon at different skeletal positions and secondly as to the relative susceptibilities of the different C—H groups to intramolecular hydrogen abstraction by the outer oxygen atom of the amylperoxy radical.

Alkylperoxy radical rearrangements during the gaseous oxidation of isobutene

1963 ◽  
Vol 273 (1354) ◽  
pp. 427-434 ◽  
Keyword(s):  
Methyl Ethyl Ketone ◽  
Peroxy Radical ◽  
Methyl Ethyl ◽  
Isotopic Tracer ◽  
Cool Flame ◽  
Cool Flames ◽  
Tracer Techniques ◽  
Slow Combustion ◽  
Flame Region ◽  
Subsequent Decomposition

Isotopic tracer techniques have been used to elucidate the mechanism of production of ketones in the gaseous oxidation of isobutane. Both acetone and methyl ethyl ketone are formed from this hydrocarbon, the former predominating in the products of slow combustion and the latter in the products of cool flames. Addition of [1,3- 14 C] acetone to reacting isobutane + oxygen mixtures has established that none of the methyl ethyl ketone formed in the cool-flame region and only 25% of that formed during slow combustion arises from further reactions of acetone. The formation of methyl ethyl ketone probably involves predominantly rearrangement and subsequent decomposition of the tert .-butyl peroxy radical and this indeed appears to be the almost exclusive fate of this radical under cool-flame conditions.

The non-isothermal oxidation of 2-methylpentane. II. The chemistry of cool flames

1967 ◽  
Vol 298 (1453) ◽  
pp. 204-237 ◽  
Keyword(s):  
Flame Temperature ◽  
Complex Mixture ◽  
Isothermal Oxidation ◽  
Qualitative Description ◽  
Cool Flame ◽  
Slow Combustion ◽  
Aldehydes And Ketones ◽  
Flame Region ◽  
Alkylperoxy Radicals ◽  
Liquid Chromatographic

The products of all the modes of non-isothermal oxidation of 2-methylpentane by molecu­lar oxygen and of the attendant slow combustion reactions have been analysed by gas-liquid chromatographic and chemical methods. Oxidation in the cool-flame temperature range produces more than forty molecular species, including O -heterocycles, peroxides, alkenes and saturated and unsaturated aldehydes and ketones. A good qualitative description of the mode of formation of this complex mixture and of its variation with temperature is afforded by the alkylperoxy radical isomerization theory. This theory is developed semi-quantitatively and is in reasonable agreement with the quantitative experimental results. It is concluded that chain propagation in the cool-flame region occurs predominantly by attack on the fuel by hydroxyl radicals; the resulting oxidation is rapid and unselective. In contrast, at temperatures too low for cool-flame formation alkylperoxy radicals are the likely chain-propagating species, whereas at temperatures above the upper cool-flame limit hydroperoxy radicals probably propagate the chain. The mechanism of chain branch­ing is not clear but it is established that, in the cool-flame region, peroxidic compounds are involved.

Self-oscillations in the cool-flame combustion of a model n-heptane-isooctane mixture

1980 ◽  
Vol 14 (3) ◽  
pp. 335-339 ◽  
Author(s):  
Ya. Yu. Stepanskii ◽  
N. P. Evmenenko ◽  
G. S. Yablonskii ◽  
V. I. Bykov
Keyword(s):  
Cool Flame ◽  
Flame Combustion

Prediction of CO and NOx Pollutants in a Stratified Bluff Body Burner

2017 ◽  
Author(s):  
Pascal Gruhlke ◽  
Fabian Proch ◽  
Andreas M. Kempf ◽  
Enric Illana Mahiques ◽  
Stefan Dederichs ◽  
...  
Keyword(s):  
Nitric Oxide ◽  
Carbon Monoxide ◽  
Bluff Body ◽  
Combustion Products ◽  
Combustion Model ◽  
Wide Range ◽  
Flame Region ◽  
Numerical Grid ◽  
Nitric Oxide Emissions ◽  
Heavy Duty Gas Turbine

The major exhaust gas pollutants from heavy duty gas turbine engines are CO and NOx. The difficulty of predicting the concentration of these combustion products originates from their wide range of chemical time scales. In this paper, a combustion model that includes the prediction of the carbon monoxide and nitric oxide emissions is tested. Large eddy simulations (LES) are performed using a compressible code (OpenFOAM). A modified flamelet generated manifolds (FGM) approach is applied with a thickened flame approach (ATF) to resolve the flame on the numerical grid, with a flame sensor to ensure that the flame is only thickened in the flame region. For the prediction of the CO and NOx emissions, pollutant species transport equations and a second, CO based, progress variable are introduced for the flame burnout zone to account for slow chemistry effects. For the validation of the models, the Cambridge burner of Sweeney and Hochgreb [1, 2] is employed, as both carbon monoxide and nitric oxide [3] data is available.

scholarly journals Nitric Oxide Circumstances in Nitrogen-Oxide Seeded Low-Temperature Powling-Burner Flames

2017 ◽  
Vol 3 (3) ◽  
pp. 157
Author(s):  
M. Furutani ◽  
Y. Ohta ◽  
M. Nose
Keyword(s):  
Nitric Oxide ◽  
Low Temperature ◽  
Hydrogen Cyanide ◽  
Chemical Species ◽  
Nitrogen Monoxide ◽  
Cool Flame ◽  
Spectrum Measurement ◽  
Temperature Development ◽  
Flame Region ◽  
Blue Flame

<p>Flat low-temperature two-stage flames were established on a Powling burner using rich diethyl-ether/ air or n-heptane/air mixtures, and nitrogen monoxide NO was added into the fuel-air mixtures with a concentration of 240 ppm. The temperature development and chemical-species histories, especially of NO, nitrogen dioxide NO<sub>2</sub> and hydrogen cyanide HCN were examined associated with an emission-spectrum measurement from the low-temperature flames. Nitrogen monoxide was consumed in the cool-flame region, where NO was converted to the NO<sub>2</sub>. The NO<sub>2</sub> generated, however, fell suddenly in the cool-flame degenerate region, in which the HCN superseded. In the blue-flame region the NO came out again and developed accompanied with remained HCN in the post blue-flame region. The NO seeding into the mixture intensified the blue-flame luminescence probably due to the cyanide increase.</p>

scholarly journals Estimation of the combustion products from the cylinder of the petrol engine and its relation to "knock"

1935 ◽  
Vol 234 (744) ◽  
pp. 433-521 ◽  
Keyword(s):  
High Pressure ◽  
Experimental Evidence ◽  
Combustion Products ◽  
High Energy ◽  
High Pressure And Temperature ◽  
Engine Cylinder ◽  
Engine Knock ◽  
Slow Combustion ◽  
Set Up ◽  
Exhaust Valves

As a result of a variety of experiments it was suggested in 1928 that engine “knock” “appears to be due to inequality in the condition of the charge (in the engine cylinder) set up, particularly in regions of high pressure and temperature as in the neighbourhood of hot exhaust valves. This inequality provides regions of high energy containing molecules in high energy states where reaction can spread more quickly.” This view was a little vague, and was arrived at from indirect experimental evidence. It was with a view to obtaining more precise evidence that knock was occasioned in the flame as the result of processes of slow combustion occurring in the gaseous charge prior to its arrival that the present work was undertaken. Callendar and those working with him had simultaneously arrived at the conclusion that “knock” was occasioned in much the same manner, but they adopted the more definite view that peroxides of the hydrocarbons were formed and stored in the gas, and then suddenly detonated, so igniting a whole region of the gas simultaneously. This view had also been advanced by Moureu and Dufraisse.

scholarly journals The Toxicological Testing and Thermal Decomposition of Drive and Transport Belts Made of Thermoplastic Multilayer Polymer Materials

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2232 ◽  
Author(s):  
Piotr Krawiec ◽  
Łukasz Warguła ◽  
Daniel Małozięć ◽  
Piotr Kaczmarzyk ◽  
Anna Dziechciarz ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Degradation Kinetics ◽  
Combustion Products ◽  
Polymer Materials ◽  
Toxic Substances ◽  
Butadiene Rubber ◽  
Different Temperatures ◽  
Increasing Temperature ◽  
In Fire ◽  
Kinetics Of

The article presents the potential impact of flat drive and transport belts on people’s safety during a fire. The analysis distinguished belts made of classically used fabric–rubber composite materials reinforced with cord and currently used multilayer polymer composites. Moreover, the products’ multilayers during the thermal decomposition and combustion can be a source of emissions for unpredictable and toxic substances with different concentrations and compositions. In the evaluation of the compared belts, a testing methodology was used to determine the toxicometric indicators (WLC50SM) on the basis of which it was possible to determine the toxicity of thermal decomposition and combustion products in agreement with the standards in force in several countries of the EU and Russia. The analysis was carried out on the basis of the registration of emissions of chemical compounds during the thermal decomposition and combustion of polymer materials at three different temperatures. Moreover, the degradation kinetics of the polymeric belts by using the thermogravimetric (TGA) technique was evaluated. Test results have shown that products of thermal decomposition resulting from the neoprene (NE22), leder leder (LL2), thermoplastic connection (TC), and extra high top cower (XH) belts can be characterized as moderately toxic or toxic. Their toxicity significantly increases with the increasing temperature of thermal decomposition or combustion, especially above 450 °C. The results showed that the belts made of several layers of polyamide can be considered the least toxic in fire conditions. The TGA results showed that NBR/PA/PA/NBR belt made with two layers of polyamide and the acrylonitrile–butadiene rubber has the highest thermal stability in comparison to other belts.

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