A pyrolysis mechanism for ammonia

International Journal of Chemical Kinetics - Tập 22 Số 5 - Trang 513-535 - 1990
David F. Davidson1, Katharina Kohse‐Höinghaus1,2, Albert Y. Chang1, Ronald K. Hanson1
1High Temperature Gasdynamics Laboratory, Department of Mechanical Engineering Stanford University, Stanford, California 94305
2On leave from DFVLR, Institut für Psysikalische Chemie der Verbrennnung, D-7000 Stuttgart, W. Germany.

Tóm tắt

AbstractThe mechanism of NH3 pyrolysis was investigated over a wide range of conditions behind reflected shock waves. Quantitative time‐history measurements of the species NH and NH2 were made using narrow‐linewidth laser absorption. These records were used to establish an improved model mechanism for ammonia pyrolysis. The risetime and peak concentrations of NH and NH2 in this experimental database have also been summarized graphically.Rate coefficients for several reactions which influence the NH and NH2 profiles were fitted in the temperature range 2200 K to 2800 K. The reaction and the corresponding best fit rate coefficients are as follows: with a rate coefficient of 4.0 × 1013 exp(−3650/RT) cm3 mol−1 s−1, with a rate coefficient of 1.5 × 1015T−0.5 cm3 mol−1 s−1 and with a rate coefficient of 5.0 × 1013 exp(−10000/RT) cm3 mol−1 s−1. The uncertainty in rate coefficient magnitude in each case is estimated to be ±50%. The temperature dependences of these rate coefficients are based on previous estimates.The experimental data from four earlier measurements of the dissociation reaction were reanalyzed in light of recent data for the rate of NH3 + H → NH21 + H2, and an improved rate coefficient of 2.2 × 1016 exp(−93470/RT) cm3 mol−1 s−1 in the temperature range 1740 to 3300 K was obtained. The uncertainty in the rate coefficient magnitude is estimated to be ± 15%.

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Tài liệu tham khảo

T. R.Roose Ph.D. Thesis Stanford University 1981.

10.1139/v79-112

K.HolzrichterandH. Gg.Wagner 18th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1981.

M.YumuraandT.Asaba 18th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1981.

10.1002/kin.550170308

10.1063/1.454162

10.1063/1.451073

10.1016/0022-4073(89)90084-8

10.1002/kin.550211107

10.1016/0022-4073(89)90103-9

10.1016/0022-4073(89)90073-3

J. A.MillerandC. T.Bowman Progress Energy Combust. Sci. in press (1988).

10.1016/0010-2180(81)90008-0

10.1080/00102208208923595

10.1080/00102208308923691

10.1016/0010-2180(86)90018-0

10.1002/kin.550190406

10.1016/0010-2180(84)90007-5

10.1002/kin.550160609

T. R.Roose R. K.Hanson andC. H.Kruger 11th Intl. Symposium on Shock Tubes and Waves University Washington 245 (1977).

10.1002/kin.550160603

10.1080/00102208408923833

P.Dransfeld W.Hack H.Kurzke F.Temps andH. Gg.Wagner 20th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1984.

10.1002/kin.550120702

N.Fujii H.Miyama M.Koshi andT.Asaba 18th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1981.

M.YumuraandT.Asaba 14th Intl. Symposium on Shock Tube and Waves Sydney 1983.

10.1021/j100339a009

10.1364/AO.26.000885

10.1063/1.455815

D. F.DavidsonandR. K.Hanson Int. J. Chem. Kinet. in press 1990.

R. J.Kee J. A.Miller andT. H.Jefferson CHEMKIN; A General Purpose Problem Independent Transportable Fortran Chemical Kinetics Code Package Sandia National Lab. Report No. SAND80‐8003 1980.

A. E.Lutz R. J.Kee andJ. A.Miller SENKIN; A Fortran Program for Predicting Homogeneous Gas Phase Chemical Kinetics with Sensitivity Analysis Sand 87‐8248 Sandia Nat. Lab. Livermore 1988.

R. J.Kee F. M.Rupley andJ. A.Miller The CHEMKIN Thermodynamic Database Sandia Nat. Lab. Report No. SAND87‐8215 1987.

Hanson R. K., 1985, Combustion Chemistry

Bahn G. S., 1968, Reaction Rate Compilation for H‐O‐N System

10.1063/1.1727340

10.1021/j100847a044

C.Morley 18th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1981.

10.1021/j100467a001

10.1021/j150667a043

A. M.Dean J. E.Hardy andR. K.Lyon 19th Symp. (Int.) on Combustion The Combustion Institute Pittsburgh 1982.

10.1016/0022-2852(88)90048-3

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International Journal of Chemical Kinetics

Tập 22 Số 5

513-535

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