화학공학소재연구정보센터
Journal of Chemical Physics, Vol.105, No.1, 271-278, 1996
Trapping-Mediated Dissociative Chemisorption of C3H8 and C3D8 on Ir(110)
We have employed molecular beam techniques to investigate the molecular trapping and trapping-mediated dissociative chemisorption of C3H8 and C3D8 on Ir(110) at low beam translational energies, E(i) less than or equal to 5 kcal/mol, and surface temperatures, T-s, from 85 to 1200 K. For T-s=85 K, C3H8 is molecularly adsorbed on Ir(110) with a trapping probability, xi equal to 0.94 at E(i)=1.6 kcal/mol and xi=0.86 at E(i)=5 kcal/mol. At E(i)=1.9 kcal/mol and T-s=85 K, xi of C3D8 is equal to 0.93. From 150 g to approximately 700 K, the initial probabilities of dissociative chemisorption of propane decrease with increasing T-s. For T-s from 700 to 1200 K, however, the initial probability of dissociative chemisorption maintains the essentially constant value of 0.16. These observations are explained within the context of a kinetic model which includes both C-H (C-D) and C-C bond cleavage. Below 450 K propane chemisorption on Ir(110) arises essentially solely from C-H (C-D) bond cleavage, an unactivated mechanism (with respect to a gas-phase energy zero) for this system, which accounts for the decrease in initial probabilities of chemisorption with increasing T-s. With increasing T-s, however, C-C bond cleavage, the activation energy of which is greater than the desorption energy of physically adsorbed propane, increasingly contributes to the measured probability of dissociative chemisorption. The activation energies, referenced to the bottom of the physically adsorbed molecular well, for C-H and C-C bond cleavage for C3H8 on Ir(110) are found to be E(r,CH) 5.3 +/- 0.3 kcal/mol and E(r,CC)=9.9 +/- 0.6 kcal/mol, respectively. The activation energies for C-D and C-C bond cleavage for C3D8 on Ir(110) are 6.3 +/-0.3 kcal/mol and 10.5+/-0.6 kcal/mol, respectively. The desorption activation energy of propane from Ir(110) is approximately 9.5 kcal/mol. These activation energies are compared to activation energies determined recently for ethane and propane adsorption on Ir(111), Ru(001), and Pt(110)-(1X2), and ethane activation on Ir(110).