The objective of this research is to elucidate the role of various chemical additives on ethanol synthesis over Rh- and Ni-based catalysts. Chemical additives used for this study will include S, P, Ag, Cu, Mn, and Na which have different electronegativeities. The effect of additives on the surface state of the catalysts, heat of adsorption of reactant molecules, reaction intermediates, reaction pathways, reaction kinetics, and product distributions is/will be investigated by a series of experimental studies of NO adsorption, reactive probing, steady state rate measurement, and transient kinetic study. CO insertion is known to be a key step to the formation of acetaldehyde and ethanol from CO hydrogenation. Reaction of ethylene with syngas is used as a probe to determine CO insertion capabilities of metal catalysts. During the sixth quarter of the project, the mechanism of CO insertion on Ni/SiO{sub 2} was investigated by in-situ infrared spectroscopy. Ni/SiO{sub 2}, a methanation catalyst, has been shown to exhibit CO insertion activity. In situ infrared studies of CO/H{sub 2} and C{sub 2}H{sub 4}/CO/H{sub 2} reactions show that the carbonylation of Ni/SiO{sub 2} to Ni(CO){sub 4} leads to an inhibition of methanation in CO hydrogenation but an enhancement of formation of propionaldehyde in …