Low effective activation energies for oxygen release from metal oxides: evidence for mass-transfer limits at high heating rates.

Oxygen release from metal oxides at high temperatures is relevant to many thermally activated chemical processes, including chemical-looping combustion, solar thermochemical cycles and energetic thermite reactions. In this study, we evaluated the thermal decomposition of nanosized metal oxides under rapid heating (~10(5) K s(-1)) with time-resolved mass spectrometry. We found that the effective activation-energy values that were obtained using the Flynn-Wall-Ozawa isoconversional method are much lower than the values found at low heating rates, indicating that oxygen transport might be rate-determining at a high heating rate.

[1]  M. Zachariah,et al.  Nanothermite reactions: Is gas phase oxygen generation from the oxygen carrier an essential prerequisite to ignition? , 2013 .

[2]  M. Zachariah,et al.  Time-Resolved Mass Spectrometry of Nano-Al and Nano-Al/CuO Thermite under Rapid Heating: A Mechanistic Study , 2012 .

[3]  A. Lyngfelt,et al.  Oxygen Release and Oxidation Rates of MgAl2O4-Supported CuO Oxygen Carrier for Chemical-Looping Combustion with Oxygen Uncoupling (CLOU) , 2012 .

[4]  C. Detavernier,et al.  Structural and Kinetic Study of the Reduction of CuO–CeO2/Al2O3 by Time-Resolved X-ray Diffraction , 2012, Catalysis Letters.

[5]  A. Navrotsky.  Nanoscale effects on thermodynamics and phase equilibria in oxide systems. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[6]  R. Cavicchi,et al.  Rapid-heating of energetic materials using a micro-differential scanning calorimeter , 2011 .

[7]  A. Navrotsky,et al.  Nanophase Transition Metal Oxides Show Large Thermodynamically Driven Shifts in Oxidation-Reduction Equilibria , 2010, Science.

[8]  M. Zachariah,et al.  Time-Resolved Mass Spectrometry of the Exothermic Reaction between Nanoaluminum and Metal Oxides: The Role of Oxygen Release , 2010 .

[9]  M. Zachariah,et al.  Diffusive vs Explosive Reaction at the Nanoscale , 2010 .

[10]  Robert L. White.  Isoconversion effective activation energies derived from repetitive injection fast gas chromatography/mass spectrometry , 2009 .

[11]  Young Kook Lee,et al.  Effect of Heating Rate on the Activation Energy for Crystallization of Amorphous Ge2Sb2Te5 Thin Film , 2009 .

[12]  E. Dreizin,et al.  Metal-based reactive nanomaterials , 2009 .

[13]  Z. Guo,et al.  Oxidation investigation of nickel nanoparticles. , 2008, Physical chemistry chemical physics : PCCP.

[14]  Robert L. White,et al.  Isoconversion Effective Activation Energy Profiles by Variable Temperature Diffuse Reflection Infrared Spectroscopy , 2008, Applied spectroscopy.

[15]  E. Dreizin,et al.  Experimental methodology and heat transfer model for identification of ignition kinetics of powdered fuels , 2006 .

[16]  Nicolas Sbirrazzuoli,et al.  Isoconversional Kinetic Analysis of Thermally Stimulated Processes in Polymers , 2006 .

[17]  N. Kanari,et al.  Kinetics of reduction of iron oxides by H2: Part I: Low temperature reduction of hematite , 2006 .

[18]  A. Steinfeld.  Solar thermochemical production of hydrogen--a review , 2005 .

[19]  Robert L. White,et al.  Infrared and mass spectrometry studies of the thermal decomposition of a nitro‐aromatic polymer , 2005 .

[20]  A. Lyngfelt,et al.  Comparison of iron-, nickel-, copper- and manganese-based oxygen carriers for chemical-looping combustion , 2004 .

[21]  E. Wimmer,et al.  Ab initio thermodynamics of oxide surfaces: O 2 on Fe 2 O 3 (0001) , 2004 .

[22]  J. Hanson,et al.  Reduction of CuO and Cu2O with H2: H embedding and kinetic effects in the formation of suboxides. , 2003, Journal of the American Chemical Society.

[23]  Peter Saunders,et al.  Physical basis of interpolation equations for radiation thermometry , 2003 .

[24]  Atsushi Tsutsumi,et al.  Effect of heating rate on steam gasification of biomass. 1. Reactivity of char , 2003 .

[25]  S. Vyazovkin.  Reply to “What is meant by the term ‘variable activation energy’ when applied in the kinetics analyses of solid state decompositions (crystolysis reactions)?” , 2003 .

[26]  Peter R.N. Childs,et al.  Practical Temperature Measurement , 2001 .

[27]  Sergey Vyazovkin,et al.  Kinetic concepts of thermally stimulated reactions in solids: A view from a historical perspective , 2000 .

[28]  Li Yue,et al.  The decomposition kinetics of nanocrystalline calcite , 1999 .

[29]  Robert L. White,et al.  Species-specific isoconversion effective activation energies derived by thermogravimetry–mass spectrometry , 1998 .

[30]  A. Małecki,et al.  The influence of oxygen pressure on the kinetics of the thermal decomposition of Co3O4 , 1994 .

[31]  V. V. Bogdanova,et al.  Thermolysis kinetics of polypropylene on rapid heating , 1993 .

[32]  T. Ozawa.  Estimation of activation energy by isoconversion methods , 1992 .

[33]  J. Mayer,et al.  Oxidation and reduction of copper oxide thin films , 1991 .

[34]  Li,et al.  Oxygen-diffusion-induced phase boundary migration in copper oxide thin films. , 1989, Physical review. B, Condensed matter.

[35]  Charles G Hill,et al.  Introduction to Chemical Engineering Kinetics & Reactor Design , 1977 .

[36]  Y. Tolmachev,et al.  Thermal Decomposition of Solid Metal Oxides , 1975 .

[37]  David T. Y. Chen.  Effect of heating rate on activation energies derived by a dynamic kinetic method , 1975 .

[38]  Joseph H. Flynn,et al.  General Treatment of the Thermogravimetry of Polymers. , 1966, Journal of research of the National Bureau of Standards. Section A, Physics and chemistry.

[39]  T. Ozawa.  A New Method of Analyzing Thermogravimetric Data , 1965 .

[40]  C. D. Doyle.  Estimating isothermal life from thermogravimetric data , 1962 .

[41]  W. Moore,et al.  The Diffusion of Copper in Cuprous Oxide , 1951 .

[42]  F. Smyth,et al.  THE SYSTEM COPPER: CUPRIC OXIDE: OXYGEN. , 1921 .

[43]  K. Fezzaa,et al.  Reactive sintering: An important component in the combustion of nanocomposite thermites , 2012 .

[44]  M. Zachariah,et al.  T-Jump/time-of-flight mass spectrometry for time-resolved analysis of energetic materials. , 2009, Rapid communications in mass spectrometry : RCM.

[45]  M. E. Brown,et al.  Thermal decomposition of ionic solids , 1999 .

[46]  P. A. Barnes,et al.  New approach to the investigation of mechanisms and apparent activation energies for the reduction of metal oxides using constant reaction rate temperature-programmed reduction , 1999 .

[47]  S. Vyazovkin,et al.  Kinetics in solids. , 1997, Annual review of physical chemistry.

[48]  M. Maciejewski.  Somewhere between fiction and reality , 1992 .

[49]  J. Nowotny,et al.  Non-stoichiometric compounds : surfaces, grain boundaries, and structural defects , 1989 .

[50]  Mohamed A. Fahim,et al.  Chemical energy storage by the reaction cycle CuO/Cu2O , 1989 .