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Mechanistic details of the heterogeneous decomposition of ammonia on platinum

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100261a017· OSTI ID:6341641

Absolute reaction rates have been measured for the catalytic decomposition of NH/sub 3/ and ND/sub 3/ and for the NH/sub 3/ + D/sub 2/ exchange reaction over a polycrystalline platinum wire at pressures between 5 x 10/sup -7/ and 0.5 torr and temperatures between 400 and 1200 K in a continuous flow microreactor. At relatively low pressures and/or high temperatures, a primary isotope effect was observed for the decomposition of ND/sub 3/. Under these conditions, the order of the decomposition reaction is unity with respect to ammonia pressure with an apparent activation energy of 4.2 kcal/mol. As coverages increase, corresponding to relatively high pressures and/or low temperatures, the order of the decomposition reaction is zero with respect to ammonia, and the reaction rate becomes controlled by nitrogen desorption, with an activation energy of the decomposition reaction of 22 kcal/mol. The kinetics of the NH/sub 3/ + D/sub 2/ exchange reaction have been used, together with data concerning the adsorption-desorption parameters of NH/sub 3/, H/sub 2/, and N/sub 2/ as well as the reaction intermediates NH and NH/sub 2/, to develop a mechanistic model which describes the reaction rate over a wide range of experimental conditions. 35 references, 6 figures.

Research Organization:
California Institute of Technology, Pasadena
OSTI ID:
6341641
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:15; ISSN JPCHA
Country of Publication:
United States
Language:
English