Abstract
Phenomena inherent in degenerate branched and completely branched chain reactions are considered from a unified viewpoint. In the case of degenerate branched chain reactions, such phenomena include a negative temperature coefficient, cool flames, and oscillations arising in slow combustion of hydrocarbons. Another phenomenon (intermittent flames) is inherent only in completely branched chain reaction of low-temperature combustion of hydrogen at reduced pressures in the presence of SO2 additives. These kinetic manifestations of chain branching processes are characterized by a variety of elementary reactions with participation of intermediate compounds and free radicals with different structures. A specific kinetic feature of reactions of both types is simultaneous participation of the active center responsible for chain branching in the branched reaction and in the reaction of propagation of an ordinary chain.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
H. Davy, “Some New Experiments and Observations on the Combustion of Gaseous Mixtures, with an Account of a Method of Preserving a Continued Light in Mixtures of in Flammable Gases and Air without Flame,” Philos. Trans. Roy. Soc., London 107, 77–86 (1817).
D. M. Newitt and L. S. Thornes, “The Oxidation of Propane. The Products of the Slow Oxidation at Atmospheric and Reduced Pressures,” J. Chem. Soc., 1656 (1937).
J. H. Knox and R. G. W. Norrish, “Cool Flame Phenomena in the Oxidation of Ethane,” Trans. Faraday Soc. 50, 928–933 (1954).
R. A. Fish, “The Cool Flames of Hydrocarbons,” Angev. Chem. Int. Ed. Eng. 7 (1), 45–60 (1968).
C. H. Yang and B. F. Gray, “Slow Oxidation of Hydrocarbons and Cool Flames,” J. Phys. Chem. 73 (10), 3395–3406 (1969).
J. F. Griffiths, “Negative Temperature-Coefficient of Reaction Rate during Hydrocarbon Oxidation,” J. Chem. Soc. D, No. 9, 483b–484 (1969).
V. Ya. Shtern, Mechanism of Gas-Phase Oxidation of Hydrocarbons (Izd. Akad. Nauk SSSR, Moscow, 1960) [in Russian].
H. Pearlman, “Multiple Cool Flames in Static, Unstirred Reactors under Reduced-Gravity and Terrestrial Conditions,” Combust. Flame 148, 208–284 (2007).
D. B. Lenhert, D. L. Miller, N. P. Cernansky, and K. G. Ovens, “The Oxidation of Gasoline Surrogate in the Negative Temperature Coefficient Region,” Combust. Flame 156, 549–564 (2009).
G. Vanhove, G. Petit, and R. Minettyi, “Experimental Study of the Kinetic Interactions in the Low-Temperature Autoignition of Hydrocarbon Binary Mixture and Surrogate Fuel,” Combust. Flame 145 (4), 521–532 (2006).
W. J. Pitz and Ch. Mueller, “Recent Progress in the Development of Diesel Surrogate Fuels,” Prog. Energy Combust. Sci. 37 (3), 330–350 (2011).
O. Herbient, W. J. Pitz, and Ch. Westbrook, “Detailed Chemical Kinetic Mechanism for the Oxidation of Biodiesel Fuels Blend Surrogate,” Combust. Flame 157, 893–908 (2010).
G. Mittal and C.-J. Sung, “Autoignition of Methylciclohexane at Elevated Pressures,” Combust. Flame 156, 1852–1855 (2009).
Yu. Zhang and A. L. Boehman, “Oxidation of 1-Butanol and Mixture of n-Heptan/1-Butanol in Motored Engine,” Combust. Flame 157, 1816–1824 (2010).
S. Saxena and I. D. Bedoya, “Fundamental Phenomena Affecting Low Temperature Combustion and HCCI Engines, High Load Limits and Strategies for Extending these Limits,” Prog. Energy Combust. Sci. 39 (5), 457–488 (2013).
W. J. Pitz and Ch. Westbrook, “Chemical Kinetics of the High Pressure Oxidation of n-Butane and its Relation to Engine Knock,” Combust. Flame 63, 113–133 (1986).
A. A. Mantashyan and A. Zh. Mikaelyan, “Stable and Pulsed Low-Temperature Chain Flames of Hydrogen in the Presence of SO2,” Khim. Zh. Armenii 59 (2), 8–17 (2006).
A. A. Mantashyan, E. M. Makaryan, A. M. Avetisyan, et al., “Effect of SO2 on the Chain Reaction of Hydrogen Oxidation: Intermittent Flames,” Fiz. Goreniya Vzryva 50 (1), 3–12 (2014) [Combust., Explos., Shock Waves 50 (1), 1–9 (2014)].
A. A. Mantashyan, E. M. Makaryan, A. M. Avetisyan, et al., “Specific Features of Low-Temperature Combustion of Hydrogen–Oxygen Mixtures Containing SO2. Intermittent Flames,” Khim. Zh. Armenii 67 (1), 1–17 (2014).
A. A. Mantashyan and A. B. Nalbandyan, “New Ways of Studying Gas-Phase Reactions by the Method of the Electron Paramagnetic Resonance,” Zh. Fiz. Khimii 46, 3030 (1972).
A. B. Nalbandyan and A. A. Mantashyan, Elementary Processes in Slow Gas-Phase Reactions (Izd. Akad. Nauk Arm. SSR, Erevan, 1975) [in Russian].
P. S. Gukasyan, A. A. Mantashyan, and R. A. Sayadyan, “Detection of High Concentrations of Radicals in the Zone of the Cold Flame in the Reaction of the Oxidation of Propane,” Fiz. Goreniya Vzryva 12 (5), 789–792 (1976) [Combust., Explos., ShockWaves 12 (5), 706–708 (1976)].
A. A. Mantashyan and P. S. Gukasyan, “Temperature Dependence of the Radical Concentration in Reactions of Cool Flame Oxidation of Propane,” Dokl. Akad. Nauk SSSR 234 (2), 379–382 (1977).
A. A. Mantashyan, P. S. Gookasyan, and R. H. Sayadyan, “Mechanism of Cool Flame Propane Oxidation,” React. Kinet. Catal. Lett. 11 (3), 225–228 (1979).
A. A. Mantashyan, “Cool Flame and Oscillations in Hydrocarbon Oxidation,” in Twenty Fifth Symposium (Int.) on Combustion (Combust. Inst., Pittsburgh, 1994), pp. 927–932.
T. R. Simonyan and A. A. Mantashyan, “Investigation of Heat-Ups with the Cold-Flame Oxidation of Butane,” Fiz. Goreniya Vzryva 15 (2), 165–166 (1979) [Combust., Explos., Shock Waves 15 (2), 257–258 (1979)].
T. R. Simonyan and A. A. Mantashyan, “ESR Studies on Stabilized Cool Flame of Propilene,” React. Kinet. Catal. Lett. 17 (3/4), 319–322 (1981).
N. N. Semenov, On Some Problems of Chemical Kinetics and Reactivity (Izd. Akad. Nauk SSSR, Moscow, 1958) [in Russian].
A. A. Mantashyan, G. L. Grigoryan, A. S. Saakyan, and A. B. Nalbandyan, “Negative Temperature Coefficient of the Propane Oxidation Reaction Rate,” Dokl. Akad. Nauk SSSR 204 (6), 1392–1394 (1972).
D. L. Baulch, C. J. Cobos, R. A. Cox, et al., “Evaluated Kinetic Data for Combustion Modeling Supplement I,” J. Phys. Chem. Ref. Data 23, 847 (1994).
B. H. Bonner and C. F. H. Tipper, “Cool-Flame Combustion of Hydrocarbons,” in Tenth Symposium (Int.) on Combustion (Combust. Inst., Pittsburgh, 1965), pp. 145–150.
A. A. Mantashyan and Sh. E. Shaginyan, “Cool Flame Oxidation of Cyclohexane. Parametric Characteristics,” Khim. Zh. Armenii 60 (4), 843–852 (2007).
A. A. Mantashan and S. E. Shaginyan, “Phenomenological Characteristics of Cool-Flame Oxidation of Cyclohexane,” Fiz. Goreniya Vzryva 44 (1), 26–28 (2008) [Combust., Explos., Shock Waves 44 (1), 22–24 (2008)].
A. A. Mantashyan and Sh. E. Shaginyan, “Temperature Dependence of Flammability Limits in Terms of Pressure and Induction Period of Cool Flames of Cyclohexane,” Khim. Zh. Armenii 60 (5), 906–912 (2007).
Sh. E. Shaginyan and A. A. Mantashyan, “Kinetic Specific Features of Cool Flame Oxidation of Cyclohexane,” Khim. Zh. Armenii 61 (2), 167–178 (2008).
Sh. E. Shaginyan, “Effect of Acetaldehyde and Propionic Aldehyde on Cool Flames of Cyclohexane,” Khim. Zh. Armenii 61 (2), 145–152 (2008).
S. G. Bernatosyan and A. A. Mantashyan, “Oscillatory Oxidation of Propane in a Flow-Type Reactor,” Arm. Khim. Zh. 36 (1), 34–40 (1983).
A. A. Mantashyan, S. G. Bernatosyan, and T. R. Simonyan, “Cool Flame Oscillations in Hydrocarbon Oxidation,” Oxidation Commun. 5 (1/2), 207–223 (1983).
A. A. Mantashyan, “Adjoint Processes of Chemical Conversion of Sulphur Dioxide under the Action of Gas-Phase Chain Reactions,” Zh. Fiz. Khim. 89 (1), 43–49 (2015).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A.A. Mantashyan.
Published in Fizika Goreniya i Vzryva, Vol. 52, No. 2, pp. 3–17, March–April, 2016.
Rights and permissions
About this article
Cite this article
Mantashyan, A.A. Kinetic manifestations of low-temperature combustion of hydrocarbons and hydrogen: Cool and intermittent flames. Combust Explos Shock Waves 52, 125–138 (2016). https://doi.org/10.1134/S0010508216020015
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0010508216020015