Combustion and Flame 149 (2007) 162172 www.elsevier.

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Laminar burning velocities of lean hydrogenair mixtures at pressures up to 1.0 MPa

D. Bradley a, , M. Lawes a , Kexin Liu a , S. Verhelst b , R. Woolley a
a School of Mechanical Engineering, University of Leeds, Leeds LS2 9JT, UK b Department of Flow, Heat and Combustion Mechanics, Ghent University, Sint-Pietersnieuwstraat 41, B-9000 Ghent, Belgium

Received 11 September 2006; received in revised form 24 November 2006; accepted 5 December 2006 Available online 15 February 2007

Abstract Values of laminar burning velocity, ul , and the associated strain rate Markstein number, Masr , of H2 air mixtures have been obtained from measurements of ame speeds in a spherical explosion bomb with central ignition. Pressures ranged from 0.1 to 1.0 MPa, with values of equivalence ratio between 0.3 and 1.0. Many of the ames soon became unstable, with an accelerating ame speed, due to DarrieusLandau and thermodiffusive instabilities. This effect increased with pressure. The ame wrinkling arising from the instabilities enhanced the ame speed. A method is described for allowing for this effect, based on measurements of the ame radii at which the instabilities increased the ame speed. This enabled ul and Masr to be obtained, devoid of the effects of instabilities. With increasing pressure, the time interval between the end of the ignition spark and the onset of ame instability, during which stable stretched ame propagation occurred, became increasingly small and very high camera speeds were necessary for accurate measurement. Eventually this time interval became so short that rst Masr and then ul could not be measured. Such ame instabilities throw into question the utility of ul for high pressure, very unstable, ames. The measured values of ul are compared with those predicted by detailed chemical kinetic models of one-dimensional ames. 2007 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: Combustion instability; Explosions; Premixed laminar ames; Burning velocity

1. Introduction The measurement of laminar burning velocities and the associated Markstein numbers presents several problems at high pressure, because the ames are more prone to DarrieusLandau and thermodiffusive instabilities. The instabilities produce severe ame wrinkling, with an associated increase in burning velocity. The ame stretch rate, , is given by
* Corresponding author. Fax: +44 113 343 2150.

E-mail address: d.bradley@leeds.ac.uk (D. Bradley).

(1/A)(dA/dt), where A is the ame surface area and t is time. It comprises contributions from the aerodynamic strain rate, s , and the ame curvature, c . Instabilities are suppressed by sufciently high values of . These are attained in the early stage of explosive ame propagation from a point source and by ow divergence in counterow burners [1]. However, by denition, a laminar burning velocity, ul , must be a value at zero ame stretch rate. This can be found for stable ames by plotting the measured ame speed against the ame stretch rate and extrapolating the speed, to obtain the value at zero stretch rate.

0010-2180/$ see front matter 2007 The Combustion Institute. Published by Elsevier Inc. All rights reserved. doi:10.1016/j.combustame.2006.12.002

D. Bradley et al. / Combustion and Flame 149 (2007) 162172 Table 1 Measurements, in chronological order, of ul for H2 air at pressures above 0.1 MPa Ref. [10] [11] [12] [9] p (MPa) Up to 0.7 0.02 to 2.5 0.2, 0.3, 0.4 0.5, 1.0 T (K) 300 to 550 291 to 500 298 300, 365 1.0 0.5 to 4 0.45 to 4 0.3 to 1.0 Apparatus Bomb, pressure measurement Bomb, pressure measurement Spherical bomb, shadowgraph Spherical bomb schlieren Allowance for stretch No No Yes No

163

Allowance for instability No No No No

This approach is not possible when a ame has become unstable. In spherical explosions ames become unstable at a critical value of the Peclet number, Pecl , the critical ame radius normalized by the ame thickness. More fundamentally, this occurs when the dimensionless stretch rate falls below its critical stabilizing value. In such cases, unstable ame speeds might be measured and an allowance made for the instabilities. The resulting near-linear plot of corrected ame speed against ame stretch rate can yield a stretch-free, stable, laminar burning velocity. This approach has been used for unstable explosion ames at high pressure [2] to yield laminar burning velocities of i-octaneair mixtures. Throughout this paper the term laminar burning velocity will imply a stretchfree, stable, laminar ame. Computationally, ame instabilities usually are avoided by the somewhat articial assumption of a one-dimensional, planar ame. With this assumption, the accuracy of the predicted burning velocities depends on the accuracy of the molecular transport coefcients, the realism of the chemical kinetic reaction scheme, and the accuracy of the rate constants. Here, a key problem, particularly at high pressure, is the dependence of the rate constants for three body reactions upon the nature of the third body, M. In the case of hydrogen, this is well exemplied by the importance of the rate of reaction [3,4], H + O2 + M HO2 + M, relative to that of the chain branching reaction, H + O2 OH + O. (2) (1)

The rate constant for the reaction of Eq. (2) is known with quite good accuracy, but with regard to Eq. (1), there is uncertainty about both the rate constant and the collision efciencies of different third bodies [5]. All of these problems come to the fore with lean hydrogenair mixtures at high pressure. The low, and often negative, values of the Markstein numbers make the ames particularly unstable. Even at

atmospheric pressure, cellular ames have been observed when equivalence ratios, , fell below about 0.79 [6]. These early measurements generally took no account of ame stretch. More recent measurements of laminar burning velocities of hydrogenair mixtures at atmospheric pressure over a range of values of , in explosion bombs [79] and in counterow burners [1], have been made in stable regimes, with allowance for the effects of ame stretch rate to obtain ul . Measurements at higher pressures, all in explosion bombs, are summarized in Table 1. Milton and Keck [10] and Iijima and Takeno [11] correlated laminar burning velocities of H2 air ames over the range of their measurements from a zero-dimensional analysis of the pressure history during bomb explosions. Aung et al. [12] reported burning velocities of stable ames for quite lean mixtures up to 0.4 MPa, while Verhelst et al. [9] observed more marked inuences of instabilities and gave values of burning velocity at particular radii. No attempts were made to allow for the effects of ame instabilities. Since the pioneering introduction of kinetic modeling to describe experimental ames at 0.1 MPa by Dixon-Lewis and Williams [13], there have been many computations of H2 air laminar burning velocities. These have been based on detailed chemical kinetic modeling, and several are summarized in Table 2. Combustion at higher pressures was modeled by Warnatz [14], Dixon-Lewis [15], and Marinov et al. [16,17]. None of these approaches involved modeling of instabilities. Different weakly stretched ames were studied computationally by Sun et al. [18], based on the detailed chemical kinetics of Kim et al. [19]. Laminar burning velocities and Markstein numbers were obtained at pressures of 0.06, 0.1, and up to 0.5 MPa. When consideration was given to ame stretch rates, it was found that the burned gas Markstein length, Lb , based on ame speed, S, was negative at all pressures for the leaner mixtures. The value of Lb became positive for = 0.7, 0.9, and 1.3 for p = 0.06, 0.1, and 0.5 MPa, respectively.

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Table 2 Contributions to chemical kinetic modeling of ul for hydrogenair mixtures Ref. [13] [14] [15] [16] [17] [18] p range (MPa) 0.1 0.001 to 2.0 0.002 to 2 0.1 0.1 to 7 0.06, 0.1, 0.5 T range (K) 336 2001100 160 to 700 298, 9801176 900 300 0.1883H2 , 0.7656N2 , 0.046O2 0.6 to 5.6 0.3 to 5.6 0.15 to 6.0 0.4 to 0.6 0.6 to 5.0 Allowance for stretch No No No No No Yes

The present paper describes measurements of laminar burning velocities at constant pressure during the early stages of combustion in a spherical explosion bomb with central ignition. Measurements were made up to 1.0 MPa at values of between 0.3 and 1.0, and most of the ames were unstable. Allowance was made for instabilities to obtain values of ul , as in [2], and these are compared with some recent modeled predictions. Values of the Markstein number for strain rate, Masr [20], and of Pecl also were found. 2. Experimental methods The hydrogenair mixtures were exploded in a spherical stainless steel bomb equipped with three pairs of orthogonal windows of diameter 150 mm, described in [21]. The internal radius of the bomb, R, and that of a sphere with the same internal volume as the bomb, R0 , were 190 and 192.78 mm, respectively. Four peripheral fans close to the wall of the bomb, driven by electric motors, initially mixed the reactants. An electric heater at the wall provided up to 6 kW for preheating the vessel and mixture up to 365 K. Gas temperatures were obtained from a sheathed chromelalumel thermocouple. Pressures were measured during the explosion with a Kistler pressure transducer. A central spark plug was used with ignition energies of about 26 mJ, supplied from a 12-V transistorized automotive ignition coil. Flame images were captured by schlieren cine photography to obtain ame speeds and by shadowgraphy to obtain values of Pecl . A Photron APX RS digital camera at various resolutions and frame rates, depending on the burning rate of the mixture, was employed. In general, at 0.5 MPa the camera speed was 25,000 frames/s and with 256 256 pixels the resolution was 0.172 mm/pixel. At 1.0 MPa the speed was 30,000 frames/s and the resolution was 0.174 mm/pixel. Flame speeds, Sn = dr/dt, were calculated from the mean ame radii, r, obtained from measurements of the ame projected area. Shown in Fig. 1 are the variations of the measured ame speed, Sn , with ame radius, r, for explosions
Fig. 1. Measured ame speeds, Sn , at different ame radii for three pressures, = 0.4, T = 365 K.

at an equivalence ratio, , of 0.4, a temperature of 365 K, and pressures, p, of 0.1, 0.5, and 1.0 MPa. The most stable ame was that at 0.1 MPa. In the early stage of ame propagation the value of Sn decreased and the schlieren ame photographs showed no evidence of cellularity. However, at the instants indicated by the asterisks, the structure became fully cellular; Sn started to increase and continued to do so. This instant dened the critical radius, rcl . When normalized by the ame thickness, l , this gave the critical Peclet number, Pecl , for the given conditions. It was assumed that l was given by /ul . The oscillations in the values of Sn arose from acoustic waves traveling across the explosion bomb. The DarrieusLandau and thermodiffusive instabilities, which give rise to the cellularity, occur within a peninsula of instability and these are analyzed semitheoretically. The limits of this are dened by upper and lower limiting wavenumbers, diagrammatically plotted against Pe in Fig. 2. The framework for the construction of the instability peninsula is the linear instability theory of Bechtold and Matalon [22], which generally applies for a strain rate Markstein number, Masr > 3. During a spherical explosion Pe increases and the onset of instabilities, with full ame cellularity, occurs at Pecl , also shown in the gure. The value of Pecl depends upon the strength of both

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with and without instabilities, Sn and S, respectively, is equal to the ratio of the surface areas. Hence at Pe, F = (Sn /S)Pe = (f ns /nl )Pe .
1/3

(5)

Fig. 2. Instability peninsula, with limiting wavenumbers.

the DarrieusLandau and thermodiffusive contributions. The smallest unstable wave numbers, nl , are associated with the largest unstable wavelength, which is of the order Pe. The largest theoretical unstable wave numbers are ns and are associated with the smallest unstable wavelength. Wavelengths between these limits are unstable. The wave numbers, n, are related to dimensionless wavelengths by n = 2 Pe/, (3)

The value of F increases with the range of unstable wavelengths. The procedure adopted was to nd the ame speed enhancement factor, F , at different values of Pe, from the values of nl and f ns , the latter found from Eq. (4), and divide the measured unstable ame speed, Sn , by F . This gave the ame speed S that would have obtained in the absence of instabilities. Many of the measurements were for values of Masr < 3, with the majority of the values negative. For these, a different procedure was adopted. In such instances it had been observed that the wavelength of a single unstable localized cell, s , just prior to its ssioning into the smallest stable cells was close to that of the ame kernel at Pecl [24]. From Eq. (3), this leads to f nscl = nlcl = 2 Pecl /s . Combination of this with the differential of Eq. (3) gives [2] (df ns /dPe) = 2/s = nlcl /Pecl . (6)

where is the wavelength normalized by l . In practice, full cellularity develops at higher values of Pecl than predicted by the theory and, as in [23], allowance is made for this by replacing theoretical values of Pecl with those observed experimentally. A value for the largest wavenumber then is found by multiplying the theoretical value by a numerical constant less than unity, f , and, at the measured Pecl , equating this product to the theoretical value of nlcl , to give f nscl = nlcl . Here the subscript cl indicates the conditions at Pecl . For Pe > Pecl the theory shows ns to increase close to linearly with Pe. This linearity is maintained for the modied wave number, f ns , shown in Fig. 2. This larger unstable wave number at Pe is given by [23] f ns = f nscl + (Pe Pecl )(df ns /dPe). (4)

A maximum limit to this gradient and, consequently, to the lowest value of the smallest unstable wavelength, s , is set by the condition that the dimensional wavelength cannot be less than the ame thickness l , s = 1. This condition is approached for the more negative values of Masr , but experimental evidence [24] suggests a lower limit of about 50 for such very unstable ames, and this value is assumed. From Eqs. (4) and (6) and the equality f nscl = nlcl , it follows that f ns = (Pe/Pecl )nlcl . From Eqs. (5) and (7), Pe nlcl 1/3 (8) . Pecl nl Values of nlcl and nl could be estimated from the theory of [22] and F was found from Eq. (8) at different measured radii. This enabled S to be found for the different measured ame speeds, Sn . In the absence of instabilities, as the spherical ame propagates its ame speed, S, changes, to an extent that partially depends upon the selected ame isotherm. The changes arise from the combined effects of a decreasing proportion of unreacted mixture within the ame thickness, and the effects of the ame stretch rate, = (2/r)(dr/dt). At the smaller values of the inuence of unreacted mixture within the ame thickness is negligible and the linear relationship F= Ss S = Lb (9) (7)

The theory shows the range of unstable wavelengths to increase as Masr decreases and, usually, as the ratio of unburned to burned gas density, u /b , increases. From Eq. (3), (df ns /dPe) = 2/s , where s is the actual smallest unstable wavelength, which is independent of Pe. Fractal considerations [23] suggest a ratio of the fractal surface area with a resolution of the inner cutoff to that with a resolution of the outer cutoff of (f ns /nl )1/3 . The ratio, F , of ame speeds

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ul unr = Ks Masr + Kc Macr . ul

(10)

Here Ks and Kc are Karlovitz stretch factors for aerodynamic strain rate and ame curvature. They are the product of the respective stretch rate term and the chemical time l /ul , while Masr and Macr are the associated Markstein numbers. The rst term on the right is usually the dominant one. Values of unr are found from S, after removing any unburned gas entrainment effects, u and b [20,21]. The Markstein length for the strain rate is found from u /b and Lb , as described in [20], and, when normalized by the ame thickness, /ul , this yields Masr .
Fig. 3. Variations of ame speeds, S and Sn , with ame stretch rate, = (2/r)S, for 0.1 MPa, = 0.4, T = 365 K.

3. Experimental results The respective plots of Sn and S against , for the higher pressure conditions of 0.5 and 1.0 MPa in Fig. 1, are shown in Figs. 4 and 5. These ames were much more unstable, with stable regimes that were less extensive than that exhibited in Fig. 3

applies, with = (2/r)S. The expression yields values of both the burned gas Markstein length, Lb , and the linearly extrapolated unstretched ame speed, Ss , at = 0 (r = ). These values are independent of the isotherm chosen for the measurement of the ame speed [20]. The combustion is at constant pressure and the laminar burning velocity, ul , is found from the expression ul = Ss (b /u ) [20,21]. Plots of S against are shown in Fig. 3 by the circle symbols, for the explosion ame at 0.1 MPa of Fig. 1. The stretch rate decreases as the radius increases. The open circle symbols dene the early, stable propagation, when the stable ame speed S is equal to the measured ame speed, Sn . The unstable values of Sn are shown by the dotted curve in Fig. 3. The lled circle symbols give values of S derived from Sn by making allowance for the instability, as described above. In this instance, the stable ame regime is fairly extensive and the open circle symbols are probably sufcient to dene the linear regime for the plot of S against . This straight line is shown by the full line in Fig. 3, which is extrapolated to = 0. This value of S at zero stretch rate yielded ul . The slope of the linear extrapolation line gave the ame speed Markstein length Lb . The lled circle points, obtained from the unstable values of Sn , are quite close to the extrapolated full line. However, the best straight line through all the points, open and lled, is the broken line, which gives slightly different values of ul and Lb . It is both convenient and practical to dene a stretched burning velocity, unr , that expresses solely the rate at which burned gas is formed and excludes the changing rate of entrainment of unburned gas into the ame thickness. The effect upon unr of the contributions to the ame stretch rate from the aerodynamic strain rate and the ame curvature is given by

Fig. 4. Variations of ame speeds, S and Sn , with ame stretch rate, = (2/r)S, for 0.5 MPa, = 0.4, T = 365 K.

Fig. 5. Variations of ame speeds, S and Sn , with ame stretch rate, = (2/r)S, for 1.0 MPa, = 0.4, T = 365 K.

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Fig. 6. High-speed shadowgraphs of developing ame cellularity, p = 0.5 MPa, T = 365 K, = 0.6. Time interval between frames 0.04 ms. The ame begins to accelerate due to the cellularity at frame (h).

and with fewer experimental points. There is consequently more reliance in Figs. 4 and 5 upon the linear extrapolation of the derived values of S against to obtain the stretch-free value of S and hence ul . The bold lines are the best straight lines and, when extrapolated to zero, they yield values of ul . The procedures described above were repeated for equivalence ratios between 0.30 and 1.0, at pressures up to 1.0 MPa. Usually there were three explosions at each value of and it was possible to derive realistic error bands for the mean values of ul . The principal experimental problem lay in the accurate determination of the low values of rcl in highly unstable ames. This required maximum framing rates and careful scrutiny of developing cellularity in ame images. The problem is illustrated by the high-speed shadowgraphs in Fig. 6, obtained at a frame speed of 25,000 fps. The spark plug, with a central electrode and a curved electrode (white) to the right, is at bottom left in each frame. The ame front is white, and cellularity creates the mottled appearance of the ame surface. Frames (a) and (b) are 0.04 ms apart and are without any cellularity. This subsequently develops, to the point at which the ame begins to accelerate due to cellularity, at frame (h). The ame ac-

Fig. 7. Full curves: measured critical radii, rcl , for 365 K, p = 0.5, and 1.0 MPa. Broken curve from [25] at 300 K and p = 0.5 MPa.

celeration continues on the subsequent frames. The value of rcl is 3.36 0.53 mm, l , given by /ul , is 5.68 103 mm, and Pecl is 537. Shown in Fig. 7 by the full lines are two sets of values of rcl at 365 K, for 0.5 and 1.0 MPa. The broken line gives the experimental values of Law et al. [25] for 300 K and 0.5 MPa, which are in good agreement with the present values. There is little time between

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Fig. 8. Experimental values of Pecl up to = 1.0, at 0.1, 0.5, and 1.0 MPa, T = 365 K.

Fig. 10. Present experimental values of ul for different for p = 0.1, 0.5, and 1.0 MPa, T = 365 K.

Fig. 9. Experimental values of Masr up to = 1.0, at 0.1, 0.5, and 1.0 MPa, T = 365 K.

the end of the spark and the development of cellularity for stable stretched ame propagation. Experimental values of Pecl for the different values of at 365 K and pressures of 0.1, 0.5, and 1.0 MPa are given, with uncertainty bars, in Fig. 8. Clearly, the onset of instabilities occurs at values of Pecl that decrease as the pressure increases. With the rather large values of F in the unstable regime, it is not surprising that there is signicant scatter, observable in Figs. 35, in the corresponding values of S. This leads to uncertainty in the slope of the linear plot of S against and, consequently, in ul and Masr . In the cases of explosions at 1.0 MPa, for > 0.6 this, combined with the very short time interval between the end of sparking and the development of cellularity, made accurate measurement of Lb and Masr impossible. Very high initial values of Sn were probably due to the inuence of the spark. Values of Masr , also with uncertainty bars, derived from Lb by the procedures described in [20], are given in Fig. 9 for values of up to 1.0 at 365 K and pressures of 0.1 and 0.5, but only up to = 0.6 at 1.0 MPa. At

Fig. 11. Laminar burning velocities, ul , for different , p = 0.1 MPa, T = 300 K. Circle and cross symbols: current experimental values (with error bands). Triangle and square symbols: values of three other experimentalists. Broken curves show values computed from schemes in [5,26].

0.1 MPa, values of Masr became positive at values of greater than 0.6. At 0.5 and 1.0 MPa, the presented values of Masr are always negative, with large uncertainties in some of the values. The corresponding values of ul , up to = 1.0, at the same three pressures and 365 K are given in Fig. 10. A decrease in ul with increase in pressure is apparent, although the error bands of this parameter also increase with pressure. It is informative to compare measurements of ul with those made by other researchers over the predominantly stable regimes at 0.1 MPa and 300 K, for values of up to 1.0. Fig. 11 shows the present values of ul and the experimental values of Egolfopoulos and Law [1], Aung et al. [7], and Dowdy et al. [8]. The open circle symbols indicate values measured in the stable regime and the diagonal cross symbols indicate values obtained from combination of this regime

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Fig. 12. Variations of ame speeds, S and Sn , with ame stretch rate, = (2/r)S, for 0.1 MPa, = 0.4, T = 300 K.

Fig. 13. Modeled values of ul from [5,26] compared with present experimental values, p = 0.5 MPa, T = 365 K. Error bands are for experiments.

with the corrected unstable regime. Error bands are indicated for these latter values, which tend to be at the upper limit of the other experimental values. Fig. 11 also includes two sets of computed values, indicated by the broken curves. These are derived from the present authors applications of a onedimensional chemical kinetics code. This involved the H2 O2 kinetic schemes of both Konnov [5] and Conaire et al. [26], both with 21 reactions and 10 species. The latter scheme was based on the latest version available from the Lawrence Livermore National Laboratory Web site [27]. The chemical kinetic code was that of release 3 of the Chem1D code, developed at Eindhoven by de Goey and co-workers [28,29]. This includes an exact solution of multicomponent transport, based on the EGlib library [30]. It can be seen that the values obtained with the two schemes are in good agreement with each other at this pressure, but they tend to be somewhat lower than the experimental values, particularly at the leaner conditions. Lowering the temperature from 365 to 300 K makes the ame more stable. This is evident from a comparison of Fig. 3, for 365 K, with Fig. 12, for 300 K. At the lower temperature the mixture is stable down to a lower ame stretch rate.

Fig. 14. Modeled values of ul from [5,26] compared with present experimental values, p = 1.0 MPa, T = 365 K. Error bands are for experiments.

4. Discussion Values of ul computed from the kinetic schemes of both Konnov [5] and Conaire et al. [26] are compared with the present measured values, over the full range of , in Fig. 13 for 0.5 MPa and in Fig. 14 for 1.0 MPa. The error bands are for the experimental values, and the uncertainties are quite large at the higher pressure. The experimental values are closer to the values computed with the Konnov scheme, but tend to be increasingly high as the pressure increases,

although the stoichiometric values are closer. Estimations of the error bands in computed values of ul that arise from uncertainties in the values of the many rate constants of the complex kinetic schemes are nontrivial [31] and were not attempted. However, to obtain some understanding of the effect of such uncertainties, the effects on the value of ul of changes in the values of the key rate constant, k2 , for the important reaction, Eq. (2), were computed. In his reaction scheme, Konnov proposed a value of k2 = 9.75 1013 exp(14,850/RT ) (units: cm2 mol s cal K) [5]. Konnov attributed an uncertainty factor, UF, of 1.6 to this reaction. Shown in Table 3 are the values of ul computed with Konnovs scheme for a stoichiometric mixture at 0.1, 0.5, and 1.0 MPa. Computations are for three values of the rate constant: a low value equal to k2 /1.6, the original value of k2 , and a high value of 1.6k2 . All other rate constants remain at the values ascribed to them by Konnov. No converged solution could be obtained for ul with the

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Table 3 Computed values of ul between upper and lower limits of rate constant for Eq. (2) in reaction scheme [5] Rate constant k2 /1.6 k2 1.6k2 Pressure 0.1 MPa 2.63 m/s 2.87 m/s 3.04 m/s 0.5 MPa 2.19 m/s 2.52 m/s 2.79 m/s 1.0 MPa 2.16 m/s 2.46 m/s

Note. = 1.0, at three pressures and 365 K, k2 = 9.75 1013 exp(14,850/RT ) (units: cm3 mol s cal K) [5].

Fig. 16. Present values of Pecl at different Masr . Full line is Eq. (11).

Fig. 15. Exponent n for inverse pressure dependency of ul at different , T = 365 K. Present experimental values and modeled values from [5,26]. Error bands are for experiments.

smallest value of the rate constant at 1.0 MPa. However, at 0.5 MPa, reducing the rate constant decreased ul by 13%, while increasing it increased ul by 11%. This uncertainty in the value of ul is comparable to that in the experimental values. On the assumption that there is an inverse dependence of ul upon pressure, which can be expressed by ul being proportional to p n , the experimental values of n at the different values of are given, with experimental error bars, in Fig. 15. The scheme of Konnov [5] gives values of n that are quite close to the experimental values, though smaller than them, over the full range of values of . At low values of the scheme of Conaire et al. [26] gives signicantly lower values of n. It can be seen from Figs. 8 and 9 that the error bands on both Pecl and Masr increase with pressure. On the basis of experimental results over a range of conditions, Gu et al. [32] have correlated Pecl in terms of Masr by Pecl = 177Masr + 2177 for values of Masr between 5 and 10. (11) This relationship is shown by the straight line in Fig. 16. The gure also shows the experimental points

from the present work. It can be seen that Eq. (11) is only a very approximate guide to the present values, with their large error bands. In [22] the value of l was given by (/u cp ul ). It follows that the ratio of l given by the expression involving kinematic viscosity to that involving thermal diffusivity is the Prandtl number, Pr. Because Pr is usually about 0.7, values of Pe based on the expression for kinematic viscosity are somewhat higher than those based on that for thermal diffusivity. However, such simplistic expressions for l can be no more than a very approximate guide to the ame thickness that is signicant. The direct measurement of the thickness is advocated in [25]. The presented data raise some wider issues concerning the use of the laminar burning velocity as a parameter at high pressure, when laminar ames are unstable. Figs. 35 show that as the pressure increases, ever fewer experimental points can be measured in the stable ame regime. At 1.0 MPa in Fig. 5 only three data points could be obtained, even with a high camera frame speed of 30,000 fps. The error in the experimentally derived value of Masr is increased with so few points. The derived values of ul also are increasingly dependent on large corrections to the measured unstable ame speeds to obtain instabilityfree ame speeds, S, as the pressure increases. The corrections depend upon the inevitable assumptions in the linear-instability theory and the application of fractals to ame speeds, as well as upon the uncertainties in measured values of Pecl . Where values of ul , corrected in this way, could be compared with reliable measured values obtained by other means, the agreement was good, but caution is required as the correction increases. Questions about the accuracy of the corrections raise the further point that, if there is no measurable stable regime and no meaningful value of ul , what purpose is served by trying to derive virtual values of this parameter, either by the present experimen-

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tal approach or by chemical kinetic computations of imaginary stable ames? In practice, the problem may not be so severe, because instabilities are suppressed in increasingly turbulent ames [33].

Eindhoven (TU/e) for permission to use the Chem1D code and their assistance with the calculations.

References 5. Conclusions Burning velocities have been measured for equivalence ratios between 0.3 and 1.0, at pressures between 0.1 and 1.0 MPa. This has only been possible by making a semitheoretical allowance for the pronounced effects of DarrieusLandau and thermodiffusive instabilities. The starting point for such an allowance, or correction for instabilities, was the accurate measurement of the critical radius, rcl , at which the ame speed increased due to ame instabilities. This enabled the critical Peclet number, Pecl , to be found, together with inner and outer cutoff wavelengths of instability. Measurements of ame speed within the stretched stable regime of ame propagation, between the end of sparking and the onset of unstable propagation, enabled the Markstein number for strain rate, Masr , to be found. Values of these parameters are reported, as well as those for ul . All these measurements required high speed photography, with camera frame speeds of up to 30,000 fps. As the pressure increased, the enhancement of ame speed due to instabilities occurred earlier in the ame propagation, making accurate allowance for the instabilities correspondingly more important. With increasing pressure, the decreasing time for stable ame propagation between the end of sparking and the development of cellularity eventually made accurate measurement of Masr impossible. As the interval became even shorter, the measurement of ul became unreliable, throwing into question the utility of this parameter for high pressure, unstable, ames. The measured values of ul were somewhat higher than those predicted by recent chemical kinetic models, but error bars are possibly comparable at high pressures for the two sets of values. The pressure exponent for the effect of pressure on ul was fairly close to that predicted by the kinetic scheme of Konnov. An earlier prediction of the relationship between Pecl and Masr proved to be an approximate guide to the present experimental results, but there were large error bands on the values.
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Acknowledgments EPSRC is thanked for its support of the research. The authors also thank Prof. Dr. de Goey, Dr. ir. Somers, and ing. Hermanns from the Combustion Technology section at the Technical University of

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