Enhancing selectivity is a key parameter in green chemistry. In this study, we have examined the liquid phase hydrogenation of alkynes over a palladium catalyst and used modifiers to enhance selectivity and activity. The reactions studied were the hydrogenation of 1-pentyne and 2-pentyne. Five modifiers were used, pentane nitrile and its respective amine, pentyl amine, 3-phenyl propionitrile and its respective amine, 3-phenyl propylamine and trans-cinnamonitrile. These modifiers were not hydrogenated under reaction conditions. It was possible to obtain high (>90%) selectivities to 1-pentene and cis-2-pentene at high conversion. The effect on rate was dependent upon the modifier and the alkyne. The effect of the modifier was the same whether added with or before the reactants. Competitive reactions confirmed that terminal alkynes and internal alkynes are hydrogenated on separate sites and do not interfere and that the modifier influences each separately. (C) 2010 Elsevier B. V. All rights reserved.