The Interfacial Kinetics of the Reaction of CO2 with Nickel. Part I: The 14CO2-CO Exchange Reaction and the Influence of Sulfur
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The rate of dissociation of CO2 on nickel has been studied by means of the 14CO2-CO exchange reaction. For pure polycrystalline nickel between 500 and 1240°C the forward rate constant, in mole cm−2 s−1 atm−1, is given by:
This is shown to be closely consistent with ideal chemisorption kinetics. Lower apparent rate constants when Ni3S2 is added to the surface or at bulk saturation with sulfur are consistent with a surface blockage mechanism by chemisorbed sulfur which shows a Langmuir adsorption isotherm. The adsorption coefficient of sulfur, in at. pet−1, is deduced to be given by the equation:
$$\ln k_f = - 7300/T - 2.57.$$
Results from associated Auger electron spectroscopic studies are in good accord with an ideal Langmuir adsorption isotherm for sulfur on polycrystalline nickel.
$$\ln K_s = 29,100/T - 15.82.$$
KeywordsMetallurgical Transaction Kcal Mole Apparent Rate Constant Dibutyl Phthalate Peak Height Ratio
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