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.

The oxidation of hexane in the cool-flame region

1952 ◽  
Vol 212 (1110) ◽  
pp. 311-330 ◽  
Keyword(s):  
Atmospheric Pressure ◽  
Chemical Nature ◽  
Complex Mixture ◽  
Cyclic Ethers ◽  
Reaction Products ◽  
Cool Flame ◽  
Oxidation Of Methane ◽  
Cool Flames ◽  
Flame Region ◽  
Considerable Support

The chemical nature of the cool flame of hexane at 300°C, maintained stationary in a flow system at atmospheric pressure, has been investigated. The relative intensities of cool flames obtained from mixtures of differing composition have been measured, using a photomultiplier cell, and correlated with analyses made of the complex mixture of reaction products. The stationary two-stage flames which may be obtained at either higher oxygen concentrations or higher pressures than the cool flame are also described, and investigated similarly. The results are examined in the light of a theory of combustion of the higher hydrocarbons via aldehydes and hydroxyl radicals, which is an extension of a mechanism derived for the oxidation of methane. This receives considerable support, particularly from the identification of the complete homologous series of saturated aldehydes which can result from the hexane molecule. Associated with these reactions are others due to the greater stability of peroxide radicals at 300°C than at the higher temperatures of methane oxidation. Thus the building up of a partial pressure of hydroperoxide sufficient to ignite in the presence of oxygen may initiate the cool flame, and considerable amounts of cyclic ethers have been found which probably had a peroxidic precursor.

The non-isothermal oxidation of 2 -methylpentane. - III. The reaction at high pressure

1969 ◽  
Vol 313 (1513) ◽  
pp. 261-297 ◽  
Keyword(s):  
High Temperatures ◽  
Isothermal Oxidation ◽  
Gas Liquid Chromatography ◽  
Labile Hydrogen ◽  
Chain Process ◽  
Unimolecular Decomposition ◽  
Hydrogen Atoms ◽  
Radical Chain ◽  
Cool Flame ◽  
Alkylperoxy Radicals

The non-isothermal oxidation of 2-methylpentane has been studied at pressures of 1-4 MN m -2 and temperatures of 440 to 660 °C in an arrested-piston rapid-compression machine. The variations with pressure and temperature of the induction periods leading to cool-flame reaction and hot ignition have been determined, and the products of the reaction have been analysed by gas-liquid chromatography. At high temperatures and pressures the cool-flame reaction occurs by a free-radical chain process in which homogeneous isomerization and subsequent decomposition of alkylperoxy radicals propagate the chain. The resulting propa­gation cycle is substantially the same as that which has been established at lower tempera­tures and subatmospheric pressures. At high temperatures and pressures the reaction is, however, even more unselective, and oxidation of β -hydroperoxyalkyl radicals competes more successfully with their unimolecular decomposition, thus leading to the formation of β -ketoaldehydes. These compounds, together with the conjugated unsaturated carbonyl compounds, account quantitatively for the absorption of ultraviolet light by reacting 2-methylpentane/air mixtures. The mechanism of chain branching in the cool-flame reaction probably involves the pyrolysis of hydroperoxides. In the second stage of two-stage ignition, the propagation cycle is the same as that occurring in the cool flame but the important difference is that the cool flame has formed substantial concentrations of compounds with labile hydrogen atoms; these react readily with alkylperoxy radicals to form hydroperoxides, the pyrolysis of which again branches the chain.

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.

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 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 non-isothermal oxidation of 2-methylpentane I. The properties of cool flames

1966 ◽  
Vol 293 (1434) ◽  
pp. 378-394 ◽  
Keyword(s):  
High Pressure ◽  
Pressure Rise ◽  
Isothermal Oxidation ◽  
Temperature Sensitive ◽  
Gaseous Mixtures ◽  
Cool Flame ◽  
Cool Flames ◽  
Slow Combustion ◽  
Subsequent Passage ◽  
Limiting Pressure

The conditions of pressure and temperature under which gaseous mixtures of 2-methylpentane with oxygen react non-iso thermally have been established. At temperatures greater than 307 °C, 1:2 fuel-oxygen mixtures of sufficiently high pressure ignite by a one-stage mechanism. At lower temperatures, the limiting pressure for ignition decreases and the resulting ignition is a two stage phenomenon, the passage of a cool flame preceding that of the hot flame. At similar temperatures but lower pressures, multiple and single cool flames propagate but do not lead to ignition. Correlation of the intensities of and rates of pressure rise due to cool flames with the limiting conditions for low temperature ignition has shown that cool flames affect profoundly the subsequent passage of a hot flame and that this effect is not purely thermal. The complexity of the limiting pressure/temperature relationship for cool flame propagation shows that the transition from slow combustion to cool flame is dependent upon several temperature-sensitive branching reactions. Moreover, the formation of periodic cool flames would appear to necessitate the participation, even under given conditions of pressure and temperature, of more than one branching agent.

The cool-flame oxidation of 3-ethylpentane

1971 ◽  
Vol 325 (1563) ◽  
pp. 469-492 ◽  
Keyword(s):  
Carbon Number ◽  
Sole Source ◽  
Initial Reaction ◽  
Cool Flame ◽  
Cool Flames ◽  
Lower Molecular Mass ◽  
Flame Region ◽  
Group Migration ◽  
Flame Oxidation ◽  
Alkylperoxy Radicals

Detailed studies have been carried out of the combustion of 3-ethylpentane with special reference to the chemical changes taking place in the cool-flame region, where at least 74 individual products are formed. At ca . 300 °C, the first products to appear are 3-ethylpent-1-ene and 3-ethylpent-2-ene, C 7 O -heterocycles and alkenes of carbon number less than seven; the rates of consumption of 3-ethylpentane and of formation of all products increase dramatically just before propagation of the first cool-flame but do not vary appreciably when subsequent cool-flames pass. As the temperature is raised to ca . 400 °C, the quantities of 3-ethylpentane consumed and of lower molecular mass products formed increase markedly while the amounts of most C 7 products decrease. Consideration of the analytical results indicates that alkylperoxy radical isomerization plays an important part in the primary chain-propagation cycle both in and out of the cool-flame region and at temperatures as high as 400 °C. It appears that the initial reaction of alkyl radicals with oxygen takes place, largely, if not exclusively, by direct addition to form alkylperoxy radicals. Different modes of isomerization of these radicals leads to the wide variety of products found and decomposition of the a-hydroperoxyalkyl radicals by direct loss of HO 2 is probably the sole source of the conjugate alkenes. The results also provide the first recorded evidence of ethyl group migration during alkylperoxy radical isomerization.

A mathematical model of the cool-flame oxidation of acetaldehyde

1971 ◽  
Vol 322 (1550) ◽  
pp. 377-403 ◽  
Keyword(s):  
Mathematical Model ◽  
Negative Temperature ◽  
Isothermal Oxidation ◽  
Limited Range ◽  
Detailed Model ◽  
Cool Flame ◽  
Induction Periods ◽  
Cool Flames ◽  
Satisfactory Account ◽  
Flame Oxidation

A detailed mathematical model of the non-isothermal oxidation of acetaldehyde has been found to give a realistic simulation of (i) single and multiple cool flames, their limits, amplitudes and induction periods; (ii) two-stage ignition; and (iii) the negative temperature coefficient for the maximum rate of slow combustion. A simplified form of the model, valid over a limited range of conditions, has been subjected to mathematical analysis to provide interpretations of the effects simulated by the detailed model. It is concluded that cool flames are thermokinetic effects often, but not exclusively, of an oscillatory nature, and that a satisfactory account of cool-flame phenomena must necessarily take reactant consumption into account.

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 Validation of Emission Spectroscopy Gas Temperature Measurements Using a Standard Flame Traceable to the International Temperature Scale of 1990 (ITS-90)

2019 ◽  
Vol 40 (11) ◽  
Author(s):  
Gavin Sutton ◽  
Alexander Fateev ◽  
Miguel A. Rodríguez-Conejo ◽  
Juan Meléndez ◽  
Guillermo Guarnizo
Keyword(s):  
Emission Spectroscopy ◽  
Internal Combustion Engines ◽  
Gas Flow ◽  
Rayleigh Scattering ◽  
Flame Temperature ◽  
Emission Spectra ◽  
Diagnostic Techniques ◽  
Gas Temperature ◽  
Flame Region ◽  
Ftir Spectrometer

Abstract Accurate measurement of post-flame temperatures can significantly improve combustion efficiency and reduce harmful emissions, for example, during the development phase of new internal combustion engines and gas turbine combustors. Non-perturbing optical diagnostic techniques are capable of measuring temperatures in such environments but are often technically complex and validation is challenging, with correspondingly large uncertainties, often as large as 2 % to 5 % of temperature. This work aims to reduce these uncertainties by developing a portable flame temperature standard, calibrated via the Rayleigh scattering thermometry technique, traceable to ITS-90, with an uncertainty of 0.5 % of temperature (k = 1). By suitable burner selection and accurate gas flow control, a stable, square, flat flame with uniform post-flame species and temperature is realised. Following development, the standard flame is used to validate two IR emission spectroscopy systems, both measuring the line-integrated emission spectra in the post-flame region. The first utilises a Hyperspectral imaging FTIR spectrometer capable of measuring 2D species and temperature maps and the second, a high-precision single line-of-sight FTIR spectrometer. In the central post-flame region, the agreement between the Rayleigh and FTIR temperatures is within the combined measurement uncertainties and amounts to 1 % (k = 1) of temperature.

Sign in / Sign up

Export Citation Format

Share Document