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National University, Seoul, Korea, September 1-3, 2010.
Modification of BKW EOS Introducing Density-Dependent Molecular Covolumes Concept M. Suceska1,a, H. G. Ang1,b and H. Y. Chan1,c
Energetics Research Institute, Nanyang Technological University, 50 Nanyang Avenue, Block N1-B4a-02, Singapore 639798, Singapore
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Keywords: BKW equation of state, covolume, detonation, detonation properties
Abstract. One of the most important tasks of thermochemical codes for the calculation of detonation properties is the accurate description of the state of gaseous products within a rather wide range of pressures and temperatures – from several hundreds of kbar and several thousands of K to atmospheric pressure and temperature. Due to its simplicity and convenience, the BeckerKistiakowski-Wilson (BKW) equation of state is used in many practical applications in the explosives field, despite its lack of rigorous theoretical background. The BKW EOS gives good agreement between calculated and experimentally obtained detonation parameters for many standard high explosives having densities in the range 1.2 – 2 g/cm3. However, it fails to predict accurately detonation properties at lower densities. To overcome this problem, we introduced the concept of density dependent molecular covolumes in the BKW EOS instead of invariant. The applicability of the approach is verified by comparing experimental and calculated values of detonation parameters for a series of explosives having different formulations and densities. It was found that by applying this approach the accuracy of the calculations for lower densities can be significantly improved. Introduction Thermochemical codes use thermodynamics to solve simultaneously state variables and chemical composition of detonation products, and hence obtain a prediction of explosive performance. This problem is relatively straightforward, given that the equation of state of the gaseous and solid products is known . One of the most difficult parts of this problem is accurately describing the equations of state of the gases. Various gaseous equations of state (EOS) have been proposed until now to describe behavior of the detonation products gases at extremely high pressures and temperatures. Some of them are: Becker-Kistiakowski-Wilson (BKW) EOS , Johnes-Cowperthwaite- Zwisler (JCZ) EOS , modified Van der Waals EOS, , modified virial EOS (VLW EOS) , etc. The semiempirical Becker-Kistiakowski-Wilson (BKW) EOS is one of the most extensively used :
pV = 1 + x ⋅ exp( β x ) ; RT K Where: x = ., and K = κ ∑ xi k i ; ( xi = ni / ∑ ni ). V (T + θ ) α (1) (2)
where p is the pressure, V is the molar gas volume and R is the gas constant. α, β, κ and Θ are adjustable parameters, xi is the mole fraction of products species, and ki are covolumes. The BKW has a long and venerable history in the explosives field, despite the fact that it does not have a rigorous theoretical background. However, as shown by Mader , it is based upon a
care should be taken when considering the covolume in BKW EOS.8 1850 BKWG 0. and temperatures reported by Hobbs and Bear . The term covolume is somewhat a misnomer.403 10. There have been a number of different parameter sets proposed for the BKW EOS. and density at CJ point increase with density decrease (Fig. The BKWC set gives better prediction for detonation velocities at lower densities. 6].e. has the smallest value of β (β = 0. in the low density limit it can be related to the virial coefficients. Some sets of constants used in BKW EOS Constants α β κ θ BKW-TNT 0. i.5 0. κ. September 1-3. while Baer and Hobbs  proposed the BKWS parameter set on the basis of a large product species calibration. has the largest value of constant β (β = 0.1 6620 BKWC 0. pressures. 1). 2010.5 0. . BKWC and BKWG.International Symposium on Explosion. while the BKWG set. By successive iterations on β and κ one may reproduce detonation velocity and pressure of a single explosive at different densities. multiplied by 10.46 [2. BKW-TNT set for high carbon explosives and BKW-RDX set for high oxygen explosives. pressure. The calculation has shown that the differences between calculated and experimental detonation velocities. As the result of the optimisation they proposed the BKWC parameter set (Table 1). at explosives densities above 1 g/cm3 (the error is almost in the range of experimental errors). The calculations are performed using two different sets of constants.096). from 10 to 400 kbars. However. which is calibrated to give good . The BKWG set. In the high density limit. Since there is no general relation between the molecular volume and the virial coefficient. β.  proposed the BKWR set. Korea. i. Calculated temperature is affected most dramatically by changing θ. the covolumes cannot be uniquely identified with a physical molecular property.54 0.86 5441 Results and Discussion We have carried out an extensive analysis in order to check the accuracy of the predicted detonation parameters by BKW EOS over a broad pressure range. Both sets give satisfactory agreement at pressures above 100 kbar.298 13.403).096 17. the parameters α.5 0.56 4950 BKWS 0. however it gives consistently lower values of detonation pressure and density at C-J point (ρCJ). Seoul National University.15 400 BKWR 0. which is the standard set used in EXPLO5 code.46 was introduced by Mader  so as to make the CO covolume agree with the value used initially by Cowan and Fickett. Fried et al. Typically. The covolume in BKW EOS is defined as the volume (in Ǻ3) occupied by a molecule rotating about its center of mass. Finger et al.09585 12. using van der Waal radii. Mader  used two BKW sets of parameters.5 0. Fried et al. The constant 10. It is best to think of covolumes as effective interaction parameters that lie somewhere between the molecular volume and virial limits . Table 1.685 400 BKW-RDX 0.5 0. θ and ki are adjusted to fit measured detonation properties. which is the standard set used in Cheetah thermochemical code. density at C-J point.176 11. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium). repulsive potential applied to the virial EOS.181 14.e. To obtain more reliable data we plotted experimental detonation velocities and pressures against the density of explosives. and then used in the analysis calculated data from the best fit.  employed a modern stochastic optimisation algorithm to find the global parameters set and covolumes that best match available experimental data. The BKWC. Seoul. the covolume acts as an effective molecular volume multiplied by a stiffness factor. For the analysis we used experimental detonation velocity. As noted by L.
To decrease the covolume we introduced the so-called covolume correction factor (kf): K0 = k f ⋅ K .2). a smaller value of β.International Symposium on Explosion. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium). p. However. Our approach is based on the following consideration: The reason for the larger deviation from experimental data at lower densities lies in the fact that BKW EOS predicts higher values of pressures. β. b) The constant α is taken to be 0. Therefore. in turn. nor stochastic optimization procedures (BKWC parameters set) gives completely satisfactory results within broad pressure limits. the covolumes of other products are taken from Hobbs and Bear  and Fried et al. . p. gives very good prediction at high densities but larger errors at lower densities. give consistently lower values of ρCJ. associated with overestimated values of the repulsive forces. Difference between experimental and calculated detonation velocities vs. c) The constants β and κ are adjusted by successive iteration to give the best agreement for D. ρCJ at higher densities. pressure (a) and density of explosives (b). which is. Korea. 1. and κ. On the other hand. agreement for D. The analysis also shows that neither traditional adjustment of constants and covolumes in BKW EOS. 2010.0) and BKWG sets (EXPLO5) The analysis shows that a larger value of constant β and lower value of constant κ can improve accuracy of prediction of detonation velocities at lower densities. Seoul. d) The constant θ is adjusted to reproduce experimental detonation temperatures for a given set of α. and ρCJ at higher densities. predicted detonation pressures and velocities are still much higher. September 1-3. but the error significantly increases at lower densities. a high value of β and a low value of κ. (3) where K0 is corrected total covolume. and a correspondingly adjusted value of κ. in an attempt to find an alternative way to improve the accuracy. Fig. while the density of detonation products at C-J point is much lower than experimentally obtained. we come up with a solution that is based on a variable covolume concept. Seoul National University. can give better agreement for all detonation parameters at higher densities. To adjust the constants and covolume correction factors we applied the following procedure: a) Geometrical covolumes of main detonation products reported by Mader  are used. the use of smaller values of the covolumes seemed to be a logical solution to the problem.5. At lower densities. . and K is total covolume of gaseous products calculated from geometrical covolumes of individual products K = κ ∑ xi k i (Eq. Since the covolume is a measure of the repulsive forces. calculated using BKWC (Cheetah 2.
PETN. The values of β. the intermolecular distance becomes smaller. However at lower densities. κ. September 1-3. At densities above 1. Fig.e. 2010. β=0. kf is constant for a given density of explosive (i. pressures above 100 kbar kf is close to unity. The K0=kf(ρ)·K correction also yields good results. Another approach is to use kf to be dependent on the density of the gaseous detonation products. At lower densities. detail analysis has shown that this type of correction gives slightly lower values of p and ρCJ at lower densities of explosives The proposed concept of variable covolume can be seen in the following way.68 ⋅ρ 0) BKWG set of constants Constants: α=0. As density increases. i. which means that the covolume does not change significantly. it changes with the density of the gaseous detonation products. kf approaches zero. The results show that the covolume correction K0=kf(ρ0)·K gives exceptionally good agreement between experimental and calculated values for all detonation parameters – the error is almost in the range of experimental uncertainty.e. which means that the value of covolume also approaches zero. and NM). one was to use kf to be dependent on the density of the explosive. while in the latter approach. For the implementation of covolume corrections into EXPLO5 code. e) Then. Seoul. TETRYL.5 g/cm3 . Covolume correction factor vs. κ=21. the distance between molecules is relatively big and . All calculations are done using a modified version of EXPLO5 software .07 ρ 2. Korea. the covolume correction factor (kf) is adjusted to give the best agreement for D. θ obtained by the above mentioned procedure are given in Table 1.209 + 1. and the repulsive forces between the molecules become more significant. Seoul National University.89 g/cm3) using values of kf given by Eqs. it does not change with the density of gaseous detonation products). The volume of the molecules themselves becomes a higher fraction of the total volume. HMX. are given in Fig. The calculated values of kf as a function of density of explosive and pressure at CJ point. we calculated detonation parameters for 32 different densities (between 0.43 ) Using several standard CHNO explosives (TNT.25 and 1. 2. TNM. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium).06(1 − exp(−1.43 ) (0.72 + ρ 2.5. θ=4950 (4) (5) k f (ρ ) = (0. for each of the tested explosives.057. RDX.International Symposium on Explosion. 2 shows that kf decreases with density of explosive and pressure at CJ point. which are better than the original BKWC and BKWG constants sets. 2. p. 4 and 5. In the first approach. density of explosive and pressure at CJ point Fig. we applied two approaches. It was found by nonlinear regression analysis that these dependences can be described by the following equations: k f ( ρ 0 ) = 1. Summarised results of the comparison of experimental and calculated values of some detonation parameters are given in Table 2. NGL. However.
these two “covolumes” are inversely proportional.CJ ratio and K0. At the same time.23 1. In the BKW EOS the covolume (the effective molecular volume multiplied by 10. there is a good correlation between the reciprocal Van der Waals covolume (1/b) and corrected BKW covolume (K0).CJ = M/ρCJ).58 5.50 2. and temperature. as well as between the b/Vm.07 4. Seoul National University.66 1. uncorrected BKW covolume (K) remains almost constant with density of gaseous products.307 6. and T calculated by EXPLO5. Also.14 2.CJ).536 p [kbar] -0.41 4. As shown in Fig.CJ are experimentally obtained values of detonation pressure and molar volume of gaseous products at CJ point (Vm. the results shows the variable covolume can satisfactorily reproduce experimental detonation .307 D [m/s] 0.66 5. Error in predicted detonation properties Parameters set BKWG set with the covolume correction: K0=kf(ρ0) .461 -2.31 9.68 3. 3.70 4. their volumes become negligible compared to the total volume of the gas.46) is the numerator. Table 2. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium). At lower pressures the b/Vm.842 -1. as well as the ratio between the covolume and volume occupied by gas (b/Vm.224 -1. Fig. Hence.  applied a similar concept to the Van der Waals equation of state. we assumed that the covolume in BKW EOS is an arbitrary function of density – since density decreases the covolume in BKW EOS should decrease too since the repulsive intermolecular forces reduce.95 2. We compared the covolumes in BKW EOS and the covolume in the Van der Waals EOS (b). September 1-3. Following this principle.976 9. In the calculation we used only the repulsive term in the Van der Waals EOS: p= RT .CJ ratio decreases approaching zero. volume.CJ − b) (6) where p is experimentally obtained value of detonation pressure and Vm.982 -2. but in different way compared to the BKW EOS. and used this approach to calculate detonation properties of explosives.International Symposium on Explosion.90 2. (EXPLO5) BKWG set.485 0. Thus. 2010.488 1. The decrease of covolume in the BKW EOS actually equates to a reduction of the intermolecular potential – it results in a lowering of the pressure at the same composition. Korea. approaching zero at p→0. as well as the covolume and repulsive forces. (EXPLO5) BKWC set (Cheetah 2.418 Note: The error expressed in percents.336 2. with the covolume correction: K0=kf(ρ). This above analysis supports the concept of variable BKW EOS covolume. respectively . It should be mentioned that the covolume in the Van der Waals EOS accounts for the repulsive forces between gas molecules.0) BKWG set (EXPLO5) Statistic parameters MV [%] RMS [%] MV [%] RMS [%] MV [%] RMS [%] MV [%] RMS [%] ρCJ [g/cm3] 0. Seoul.28 14.56 4. The authors supposed that the covolume of gaseous products in the Van der Waals EOS is a monotonically decreasing function of density (pressure). and in the van der Waals EOS the covolume (volume occupied by molecules themselves) is the denominator.22 3.514 T [K] 1. the intermolecular forces become insignificant.377 2. At the same. RMS is the root mean square Recently Kopyshev et al.177 -3.281 -0. 3 shows that above 150 kbar the volume of molecules themselves occupies more than 80% of total volume. Consequently the repulsive forces and covolume in BKW EOS are are very high. MV is the mean value of error. (Vm .
Explosion. M. . Arlington VA. The verification of the concept was done comparing experimental and calculated detonation parameters for 32 CHNO explosives having different densities and compositions. W. Hayes. The effect of elemental composition on detonation behaviour of explosives. Office of Naval Research. Horning. Cheetah 2. H. 4. M. CRC Press. References 1. M. P. L. Guidry. W. No. Office of Naval Research. Vol. J. 42.52. Seoul National University. 162. M. Equatin of state of explosion products on the basis of a modified Van der Waals model. Energetic Materials Center. M. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium). 3. V. September 1-3. H. Xiong. Vol. C. 1976. can be significantly improved using density dependent covolumes instead of invariant covolumes. Correlation between Van der Waals covolume and BKW EOS covolume (uncorrected covolume calculated using BKWG set of constants) Conclusions The results of this work have shown that the accuracy of prediction of detonation properties at lower explosive densities. B. No. Sixth Symposium (International) on Detonation. Science in China Series B: Chemistry. XinPing. Cowperthwaite. The concept of variable covolume in BKW EOS. Lee. is based on the fact that the covolume is a measure of the interaction forces between the products species – thus.H. H.5 (2009) 605-608. C. Sixth Symposium (International) on Detonation. L. Fig. 1998. Boca Raton. 2008. B. 6. 2. The JCZ equation of state of detonation products and their incorporation into the TIGER code“.1 (2006) 76-87. first of all verification of its applicability to explosives composition other than CHNO and optimisation of the covolume-density relationship. 1976. Lawrence Livermore National Laboratory. XiaoHua. as presented in this paper. Korea. 710. Bi. ACR-221. Helm. The best results for were obtained using covolume corrections factor dependent on explosive densities. 2010. E. Numerical modeling of explosives and propellants. Medvedev. p. F. A. Additional work is required for further verification of the concept. since density decreases the interaction forces (and therefore covolume) decreases too. Zwisler. Kopyshev. Finger.0 User's Manual. Kahara. Souers. p. 3. Howard. 5.International Symposium on Explosion. L. R. W. ACR-221. Seoul. Fried. using BKW EOS. Combustion. parameters over a broad pressure range – better than the most frequently used BKW EOS parameters sets. E. Mader. Arlington VA. VLW equation of state of detonation products. and Shock Waves. McGuire. P.
July 12 . Calibrating the BKW-EOS with a large product species data base and measured C-J properties. Vols. Bear. 465-466 (2004) 325-330. MA. R. L. Hobbs. 409. 2010. Seoul. . M. Calculation of Detonation Parameters by EXPLO5 Computer Program. September 1-3.16 1993. Boston. M. Shock wave and High-energy reaction Phenomena 2010 (3rd ESHP Symposium). 7. Korea.International Symposium on Explosion. Materials Science Forum . Suceska. M. p. Seoul National University. ONR 3339512. Tenth Symposium (International) on Detonation. 8.
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