Journal of Physical Chemistry, Vol.100, No.46, 18177-18182, 1996
Isotope-Exchange Reaction of Formate with Molecular-Hydrogen on Ni(110) by IRAS
Kinetics of the CH/CD isotope exchange reaction of formate (HCOO(a)/DCOO(a)) on Ni(110) with gaseous D-2/H-2 was investigated below the decomposition temperature (360 K) by infrared reflection absorption spectroscopy (IRAS). The apparent activation energies of HCOO(a) --> DCOO (a) and DCOO(a) --> HCOO(a) reactions were derived as 52 +/- 5 and 58 +/- 5 kJ . mol(-1), respectively. A half-order dependence of the reaction rate on hydrogen pressure was observed, suggesting that the rate-determining step was the reaction of the adsorbed formate with reversibly adsorbed hydrogen atom. The reaction of HCOO(a) with D-2 was 2.1 +/- 0.3 times faster than that of DCOO(a) with H-2 at 300 K, and the origin of the isotope effect is discussed.
Keywords:ELECTRON-ENERGY LOSS;FORMIC-ACID;CHEMISORBED FORMATE;DECOMPOSITION;SURFACE;SPECTROSCOPY;ADSORPTION;RU(001);CU(110);DEHYDROGENATION