You are on page 1of 7

Department of Physical Chemistry 4-12 Regina Elisabeta Blvd, District 3, Bucharest phone: +40-21-3143508; fax: +40-21-3159249 ISSN: 1844-0401

ARS DOCENDI PUBLISHING HOUSE Sos. Panduri 90, District 5 Bucharest phone/fax: +40-21-4102575 e-mail: arsdocendi@yahoo.com

OVERALL ACTIVATION ENERGY OF PROPANE-AIR COMBUSTION IN LAMINAR FLAMES
Venera Brînzea , Domnina Răzuş , Maria Mîţu  and D. Oancea 
abstract: The overall activation energy of propane oxidation in laminar flames was evaluated from normal burning velocities characteristic for the flame propagation in preheated or diluted propane-air mixtures, using various correlations between the normal burning velocity and the average flame temperature. The burning velocities were obtained both from experimental measurements on spherically propagating flames and from detailed kinetic modeling of flame propagation. The experiments used a near-stoichiometric propane-air mixture ([C3H8] = 4.08 vol.%) and were made in a spherical closed vessel, at various initial temperatures (298-423 K). The modeling was made by means of INSFLA package, based on a comprehensive mechanism valid for gas-phase oxidation of C1-C4 hydrocarbons (53 chemical species and 592 elementary reactions). key words: laminar flames; spherical vessel; propane; overall activation energy.

received: May 06, 2009

accepted: May 20, 2009

Introduction
The modern society depends in a large extent on the energy obtained from the controlled combustion of the fossil fuels. An important part of the necessary energy, both for industry and for domestic use, is obtained from combustion of gases, usually hydrocarbons. In certain conditions, the combustion of hydrocarbons can take place as an explosion, whose evolution is due to a fast energy release, accumulating in the system due to a slow dissipation rate. The problem of gaseous explosive mixtures of fuels with air, in particular of hydrocarbons, raises the interest towards the safe storage, processing and transport of gases or flammable liquids, especially in the chemical and petrochemical industry. Fundamental research in this field is focused on theoretical aspects of kinetics and thermodynamics of combustion reactions in different conditions (deflagration or detonation; isobaric or isochoric propagation etc) [1÷6].



“Ilie Murgulescu” Institute of Physical Chemistry, 202 Spl. Independentei, 060021, Bucharest, Romania corresponding author e-mail: venerab@icf.ro Department of Physical Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., 030018, Bucharest, Romania

Analele Universităţii din Bucureşti – Chimie, Anul XVIII (serie nouă), vol. I, pag. 35 – 41 © 2009 Analele Universităţii din Bucureşti

The overall activation energy and the overall reaction order are required as input data for Computational Fluid Dynamics modeling of flame propagation in closed and vented vessels and for design of venting systems [7]. with central ignition.heating resistors 9 . 1. maintained at (25 ± 10C) by a water jacket.7’ . The combustion vessel is equipped with an ionization probe for monitoring the flame front position.thermal isolation 5 . electrically heated. its temperature was adjusted (± 1 0C) using an AEM 1RT96 controller and monitored by a K-type thermocouple. OANCEA The objective of the present paper is to evaluate the overall activation energy of propane gas-phase oxidation in flames. Data acquisition was made at 5000 signals per second using an acquisition card Tektronix type AA1. BRINZEA  D. For this purpose. using the normal burning velocity of propane-air – a characteristic parameter of propagation process. RAZUS  M. The pressure evolution during explosion was measured with a piezoelectric pressure transducer type Kistler 601A mounted in a special adapter. characterizing the dependency of normal burning velocity on temperature of fuel-air mixture. 1. The overall activation energy is an important parameter. 1 Combustion vessel.pressure transducer 4.52 L).36 V.5 mm was located in the geometrical centre of the spherical vessel. The piezoelectric pressure transducer was connected to a Charge Amplifier type Kistler 5001SN whose signals were recorded with an acquisition data system TestLabTM Tektronix 2505.2 . The spark gap of constant width 3.8 . Experimental procedure Experiments were made in a thermostated spherical closed vessel (V = 0.electrodes 3 .thermocouple 7.thermometer 6 . Ignition was made with inductivecapacitive sparks produced between stainless steel electrodes. . valid over a restricted range of pressure and temperature. the experimental and computed burning velocities of a near-stoichiometric propane-air mixture with variable initial temperature are examined in correlation with the average flame front temperatures. It is obtained by assuming a simple one-step kinetics of fuel oxidation. directly influenced by the reaction rate in the flame front. The scheme of the combustion vessel is given in Fig. MITU  D.admission / evacuation valve Fig.

14]: ln Su Const. The 4. Other details were previously given [8. based upon a comprehensive reaction scheme [12]. Results and discussions The normal burning velocity was evaluated either from pressure-time records.74 T f T0 (2) where: T0 is the initial temperature and Tf is the maximum temperature in the flame front. A premixed laminar free flame was considered. The runs were performed for a near-stoichiometric propane-air mixture ([C3H8] = 4.calc) at various initial temperatures together with the maximum temperatures in the flame front and average flame temperatures are given. 2 the experimental and computed normal burning velocities of the nearstoichiometric propane-air mixture are plotted versus the reciprocal average flame temperature. determined from computed temperature profiles. 592 elementary reactions). T f is the average flame temperature and R is the universal gas constant.9]. Computing program The normal burning velocities of propane-air mixture were computed by means of the program INSFLA. In Table 1 the experimental and computed normal burning velocities (Su. developed by Warnatz and coworkers [10] for kinetic modeling of fuelair flames in various conditions. at a total pressure of 4 bar and used 48 h after mixing. The overall activation energy of flame propagation Ea of preheated propane-air mixtures was calculated according to a modified Arrhenius type equation [13.99%) (SIAD Italy) was used without further purification.08 vol. Propane (99.%) and mixtures diluted with N2 or CO2 at initial pressure p0 = 1 bar and various initial temperatures T0 within 298-420 K. The average flame temperature can be expressed as [15]: Tf T0 0.exp and Su. assuming radiative energy losses and a mechanism CH4-C4 (53 chemical species. the combustion vessel was evacuated down to 0.% C3H8-air mixture was obtained in a 10 L storage cylinder using the partial pressures method. to become quiescent and thermally equilibrated. Ea 2 RT f (1) where: Su is the normal burning velocity.5 mbar and the explosive mixture was admitted and allowed 30 min. or from computations. obtained in a closed spherical vessel with central ignition using the cubic law of pressure rise versus time in the early stage of propagation (p0 ≤ p ≤ 2p0) [11]. In Fig.OVERALL ACTIVATION ENERGY OF PROPANE-AIR COMBUSTION 37 Before each test.08 vol. The linear plots have close values of their slopes and the corresponding overall .

as seen from Table 2.550 0. OANCEA activation energies agree well with literature data referring to a stoichiometric propane-air mixture.86 47.62 Tf (K) 2302.72 61.555 0.09 24.32 26.2 2380.535 0.540 0. The calculated overall activation energies (Ea = 705 kJ/mol from experimental values of Su .10 42. Ea = 365 kJ/mol Computed Su.calc (cm/s) 35. BRINZEA  D.8 1825.9 3.0 3. (1) instead of average flame temperature.2 1842.3 1811. present data and data from literature [Reference] Present data Kuehl [16] Hill [17] Zhao [18] Metghalchi [19] Equivalence ratio 1.7 3.565 1000K / T f Fig.s ) -1 0.75 50.12 56. MITU  D.53 Su.4 2339.00 Ea 2 RT f Ea (kJ/mol) 365 487 432 451 401 22. maximum temperatures in the flame front and average flame temperatures of a 4.8 3.560 0.% C3H8-air.00 1.8 Tf (K) 1781.98 29.6 3.13 The overall activation energy of flame propagation for the examined C 3H8-air mixture was obtained also using the maximum temperature in the flame front Tf in eq. together with experimental and computed burning velocities.530 Experimental Su. 2 Normal burning velocity variation with average flame temperature Table 2 Activation energies calculated with eq.0 2352.02 27.5 0.58 66.2 4.8 4. RAZUS  M.exp (cm/s) 38.5 2331. Table 1 Normal burning velocities.08 vol.8 1871.38 V. (1).545 0.1 4.23 69.00 1. Ea = 435 kJ/mol ln(Su/cm. at p0 = 1 bar T0 (K) 298 333 363 393 423 Su.01 1.86 53.3 4.00 1.

90 0.23 30.80 0.90 0.13 32.85 0.54 2.47 24. Ea 2 RT f (3) where: n is the overall reaction order.54 13.28 19.62 35. (3) against the reciprocal value of average flame temperature.95 0. The results obtained from the slopes of linear correlations (3) are: Ea = 171 kJ/mol for C3H8-air-N2 mixture and Ea = 182 kJ/mol for C3H8-air-CO2 mixture. the stoichiometric propane-air mixtures diluted with N2 or CO2 were examined. Their normal burning velocities calculated by means of INSFLA program were correlated with the average flame temperatures. at ambient initial conditions Inert [Inert] (vol. characterized by the average flame temperature.05 1785 1730 1669 1555 1453 1263 1785 1696 1581 1464 1340 1226 In Fig. (3) are given in Table 3. Closer values of overall activation energies for the two systems: Ea = 177 kJ/mol (C3H8-air-N2) and Ea = 186 kJ/mol (C3H8-air-CO2 mixture) were obtained assuming a lower value for the overall .70 1. assuming that the overall reaction order is 2.OVERALL ACTIVATION ENERGY OF PROPANE-AIR COMBUSTION 39 and Ea = 782 kJ/mol from computed Su) are quite high as compared to that obtained using the average flame temperature. when the normal burning velocities are examined against average flame temperature using fuel-air mixtures at constant initial temperature (usually T0 = 298 K). 3 the plots of the left member of eq.00 0.13 26.16 15.85 0. In the present case. as already reported for C3H6-air mixtures [20]. because the combustion reaction occurs only in a restricted zone of the flame front.18 6.00 0. Y is the mole fraction of reactive components (fuel + oxidant) in the examined mixture. for both stoichiometric systems C3H8-air-N2 and C3H8-air-CO2. those calculated by means of average flame temperature are more reliable.61 2. for a stoichiometric propane-air mixture diluted with N2 and CO2 are given. diluted with various amounts of an inert component.95 0.80 0. Table 3 Burning velocities and flame temperatures of propane-air-inert mixtures. Data used in eq. using the relationship [15]: ln Su 1 ln T f 2 n ln Y 2 Const.75 Tf (K) 2307 2233 2150 1997 1859 1602 2307 2187 2032 1874 1706 1552 Tf Su (cm/s) 35. From the two sets of values.%) 0 5 N2 10 15 20 30 0 5 CO2 10 15 20 25 Y 1. An alternative way to determine the activation energies of flame propagation is the dilution method.

0 4.e. n = 1. Our data are in good agreement with those reported by Munteanu et al.s )-1/2ln(Tf/K)-n/2lnY C3H8-air-N2 C3H8-air-CO2 7. [21]: Ea = 170 kJ/mol from quenching distances of C3H8-air-inert mixtures. A good agreement was found between the overall activation energy computed from experimental values of burning velocities and those from computed burning velocities.%) propane-air mixture by means of preheating method examining the normal burning velocity in correlation either with the average flame temperature T f or with the maximum temperature in the flame front Tf.5 0.0 6. Such deviations were found earlier for C 3H6-air mixtures [23]. These differences can be attributed to the active role of the studied additives. The overall activation energies for stoichiometric C3H8-air-N2 and C3H8-air-CO2 mixtures were also obtained by means of dilution method.85 -1 1000 K/ T f Fig. . The overall activation energy obtained by means of preheating method (Ea = 365 kJ/mol for C3H8-air mixture) is approximately double in comparison with the overall activation energies obtained by means of dilution method (Ea = 171 kJ/mol for C3H8-air-N2 mixture and Ea = 182 kJ/mol for C3H8-air-CO2 mixture) due probably to the active role played by the additives in the process of flame propagation.70 0.5 6.75 0. MITU  D. as reported by Chang and coworkers [22]. Examination of the induction periods for self-ignition of propane in air delivered close values of the overall activation energy: Ea = 196 kJ/mol. The values are also in good agreement with literature data.80 0. Conclusions The overall activation energy of propane oxidation in a flame was obtained for a nearstoichiometric (4.08 vol.60 0.55 0.5.0 7.0 5.40 V. i.65 0. 3 Linear correlations describing eq. 8. (3) A systematic difference between the overall activation energies from preheating method and dilution method is obtained.5 ln(Su/cm. BRINZEA  D.5 5. OANCEA reaction order. RAZUS  M.

(2007) Fuel 86. 7... J.W. D. R. D. Flame 38. and Razus. D. 22.. (2009) J. D. J. Green. C. R.. Razus. G. 52. New York and London. and Winship. Bjerketvedt. 45. Razus. London and Oxford. 18. A. Z. 334-42. A. Oancea. G. (2004) Combust. (1988) Combust. Mater. J. D. Kuehl. J.. Warnatz. 1248-52. Oancea. R. Munteanu. V. B. Thompson. Oancea. N. Roumaine Chim.L. Bucuresti.) on Combustion. and Tech. Loss Prev.. Maas. M. Biet. Dewael.) on Combustion.. (2004) Combust.. Process Ind.Chimie XIV(I-II). Sajus. 17. 165. D. 15. M. V. C..I. C. and Oancea. Sale.D. 83-7. 13. 19. (2001) Combustion..C. 510-21.S. and Churchill. Metghalchi. 5. V.L. and Vlachos. A. Hill.. Sci. Razus. (1991) Intern. Cathonnet. 209-14. 197-209. Seydi. 143-54. Burre. Berlin. 12(3). D. K. vol.I.. 1-150. and Hertzberg. Baltimore. I. Norton.Chem. (1997) J. Razus. Thomas. 8. van Tiggelen. and Dryer. I. Brinzea. J.. and Babushok. (2008) 13th International Conference on Physical Chemistry – ROMPHYSCHEM 13. Sci.. (1977) Combust.Timisoara. (2005) Anal. V. 97–107. D. Kazakov. V.G. and Tech. (2005) Combust. . (1980) Combust. 4. Dagaut. Flame 138. D.. K.R. 14. G. Code ID_458. UK. M. D. and van Wingerden... Heidelberg and New York. 319-30.. B.J. J. U. Paris. D. D. Inst. D. D.OVERALL ACTIVATION ENERGY OF PROPANE-AIR COMBUSTION 41 Acknowledgement: The results reported in the present contribution were partly financed by Research Grant IDEI. 10. 9. P. and Keck.L. 3-rd Ed. L. 92-6.Loss Prev.Bucuresti. S.K. (2000) J.. C. 6. de Soete. 24-9. M. 16. Brinzea. 1865-72.. REFERENCES 1... D. J. Burger.. Flame 7.(Intern. J. Bakke. Ed. and van Tiggelen. 7-30. and Oancea. 2. A. 20. (1960) AIChE Journal 6. Branzea V. J. and Oancea.. and Vovelle. Flames and Explosion of Gases. Movileanu. Flame 142. Hazard. 12. and Oancea.West. Movileanu. Mitu. Zhao.Process Ind. F. C.Univ. R. D. 60. Razus. Technip. 13. D. 19. Razus. 3. 437-55. Explosion and Shock Waves 13. and Boettner. and Dibble. p. Mater.L. (1968) Oxidations et Combustions. and Movileanu. 1705-23. (2000) Rev.. The Combust. P. (1963) Combust.(Intern. 51. A. (2006) J. Lewis. R. and von Elbe. D. Chang. (1962) 8th Symp. 3-rd Ed.. 23. (1958) 7th Symp. Babkin. Cashdollar. Academic Press. J. and Hung. Chemical Kinetics 23. Li. P. Gealer. The Combustion Institute. 176. 11.. and van Tiggelen. 431-5. V. Hazard. Zlochower. M. (1987) Combustion. awarded to “Ilie Murgulescu” Institute of Physical Chemistry. Delfau. and Ionescu. (2003) Ann. 239-46. Brinzea...Univ. F. 21. Mitu. Springer Verlag. 327-40. Balaceanu. J.