A model of elementary chemistry and fluid mechanics in the combustion of hydrogen on platinum surfaces

Abstract Using computational methods, we consider the catalyzed combustion of lean hydrogenoxygen mixtures in a stagnation flow over a platinum surface and in a flat-plate boundary layer. The analysis includes elementary chemistry in the gas phase as well as on the surface. The stagnation flow is modeled using a similarity transformation that leads to a one-dimensional boundary-value problem, whereas the flat-plate boundary layer is modeled by the use of the boundary-layer assumption. Predictions of each model are compared with experimental measurements of (a) catalytic ignition and combustion of hydrogenoxygen mixtures at low pressure (100 millitorr) and (b) OH concentration profiles in catalytically supported combustion at atmospheric pressure. The article proposes reaction mechanisms and interprets the catalytic behavior in terms of the chemistry models.

[1]  D. Collins,et al.  A photoemission and thermal desorption study of carbon monoxide and oxygen adsorbed on platinum , 1976 .

[2]  T. Germer,et al.  Direct characterization of the hydroxyl intermediate during reduction of oxygen on Pt(111) by time-resolved electron energy loss spectroscopy , 1989 .

[3]  G. Ertl,et al.  A molecular beam study of the adsorption and desorption of oxygen from a Pt(111) surface , 1981 .

[4]  F. Netzer,et al.  The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100) , 1975 .

[5]  K. Schwaha,et al.  The adsorption of oxygen on the stepped Pt(S)-[9(111) × (111)] face , 1977 .

[6]  B. Hellsing,et al.  Kinetic model and experimental results for H2O and OH production rates on Pt , 1987 .

[7]  Irving Langmuir,et al.  The mechanism of the catalytic action of platinum in the reactions 2Co + O2= 2Co2 and 2H2+ O2= 2H2O , 1922 .

[8]  E. Fridell,et al.  An experimental study of the kinetics of OH and H2O formation on Pt in the H2 + O2 reaction , 1989 .

[9]  B. Gurney,et al.  Synthesis of OH from reaction of O and H on the Rh(100) surface , 1987 .

[10]  L. Pfefferle,et al.  Catalysis in Combustion , 1987 .

[11]  Robert J. Kee,et al.  A Mathematical Model of Silicon Chemical Vapor Deposition Further Refinements and the Effects of Thermal Diffusion , 1986 .

[12]  Robert J. Kee,et al.  A Mathematical Model of the Coupled Fluid Mechanics and Chemical Kinetics in a Chemical Vapor Deposition Reactor , 1984 .

[13]  M. Hoffbauer,et al.  Dynamics of OH desorption from single crystal Pt(111) and polycrystalline Pt foil surfaces , 1987 .

[14]  J. Gland Molecular and atomic adsorption of oxygen on the Pt(111) and Pt(S)-12(111) × (111) surfaces , 1980 .

[15]  B. E. Nieuwenhuys,et al.  Influence of the surface structure on the adsorption of hydrogen on platinum, as studied by field emission probe-hole microscopy , 1976 .

[16]  J. Yates,et al.  Kinetics and energetics of oxygen adsorption on Pt(111) and Pt(112)- A comparison of flat and stepped surfaces , 1988 .

[17]  Robert J. Kee,et al.  A Mathematical Model of the Fluid Mechanics and Gas‐Phase Chemistry in a Rotating Disk Chemical Vapor Deposition Reactor , 1989 .

[18]  G. Ertl,et al.  Preexponential factors for hydrogen desorption from single crystal metal surfaces , 1979 .

[19]  B. Hellsing,et al.  Kinetic model study of OH desorption during H2O production on Pt , 1988 .

[20]  L. Schmidt,et al.  Steps in the reaction hydrogen + oxygen .dblharw. water on platinum(111): laser-induced thermal desorption at low temperature , 1992 .

[21]  J. Völter,et al.  Adsorption von Wasserstoff an platin: I. Adsorbierte menge, kinetik der ad- und desorption , 1972 .

[22]  R. Rye,et al.  Flash desorption and equilibration of H2 and D2 on single crystal surfaces of platinum , 1974 .

[23]  R. C. Weast CRC Handbook of Chemistry and Physics , 1973 .

[24]  V. Zhdanov Some aspects of the kinetics of the hydrogen-oxygen reaction over the Pt(111) surface , 1986 .

[25]  P. J. Richards,et al.  The heat of adsorption of hydrogen on platinum , 1974 .

[26]  G. Fisher,et al.  The interaction of water with the Pt(111) surface , 1980 .

[27]  G. Ertl,et al.  Adsorption of hydrogen on a Pt(111) surface , 1976 .

[28]  Y. Peng,et al.  The Adsorption, Desorption, and Exchange Reactions of Oxygen, Hydrogen, and Water on Platinum Surfaces. I. Oxygen Interaction , 1974 .

[29]  R. Madix,et al.  On the H2D2 exchange on stepped platinum surfaces , 1976 .

[30]  R. Schefer,et al.  Catalyzed combustion of H2/air mixtures in a flat plate boundary layer: II. Numerical model , 1982 .

[31]  H. Bonzel,et al.  On the kinetics of oxygen adsorption on a Pt(111) surface , 1973 .

[32]  Robert J. Kee,et al.  A Model of Silicon Carbide Chemical Vapor Deposition , 1991 .

[33]  L. Schmidt,et al.  Adsorption and desorption of NO, CO and H2 on Pt(111): Laser-induced thermal desorption studies , 1986 .

[34]  A. B. Anton,et al.  THE MECHANISM AND KINETICS OF WATER FORMATION ON PT(111) , 1990 .

[35]  B. Koel,et al.  Study of high coverages of atomic oxygen on the Pt(111) surface , 1989 .

[36]  R. Greif,et al.  A Numerical Model of the Flow and Heat Transfer in a Rotating Disk Chemical Vapor Deposition Reactor , 1987 .

[37]  B. Poelsema,et al.  Temperature dependency of the initial sticking probability of H2 and CO on Pt(111) , 1985 .

[38]  Robert J. Kee,et al.  Surface chemkin: A general formalism and software for analyzing heterogeneous chemical kinetics at a gas‐surface interface , 1991 .

[39]  G. Selwyn,et al.  Temperature effect on the removal of hydroxyl radicals by a polycrystalline platinum surface , 1983 .

[40]  P. J. Richards,et al.  Hydrogen isotope chemisorption and equilibration on platinum , 1974 .

[41]  Forman A. Williams,et al.  Catalytic combustion of hydrogen-air mixtures in stagnation flows , 1993 .

[42]  F. Netzer,et al.  Adsorption studies on a stepped Pt(111) surface: O2, CO, C2H4, C2N2 , 1978 .

[43]  W. R. Williams,et al.  Steps in the reaction hydrogen + oxygen .dblharw. water on platinum: hydroxy desorption at high temperatures , 1992 .

[44]  W. Lisowski Kinetics of hydrogen adsorption and desorption on thin platinum films , 1988 .

[45]  L. Schmidt,et al.  binding states of CO and H2 on clean and oxidized (111)Pt , 1977 .

[46]  James A. Miller,et al.  Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels , 1992 .

[47]  V. Korchak,et al.  The adsorption of oxygen on a stepped platinum single crystal surface , 1978 .

[48]  B. Poelsema,et al.  A molecular beam study of the interaction between hydrogen and the Pt(111) surface , 1989 .

[49]  J. White,et al.  The decomposition of H2O on oxygen-covered pt(111): Thermal and vibrational excitation effects , 1984 .