The thermal chemistry of a number of C-4 hydrocarbons (1,3-butadiene, 1-bromo-3-butene, 1-bromo-2-butene, trans-2-butene, cis-2-butene, 1-butene, 2-iodobutane, 1-iodobutane, and butane) was investigated on clean and hydrogen- and deuterium-predosed Pt(111) single-crystal surfaces by temperature-programmed desorption and reflection-absorption infrared spectroscopy. A combination of rapid beta-hydride eliminations from alkyls to olefins and the reverse insertions of those olefins into metal-hydrogen bonds explains the hydrogenation, dehydrogenation, and H-D exchange products that desorb from the surface. A preference for hydrogenation at the end carbons and dehydrogenation from the inner carbons also explains the extent of the isotope exchange and the preferential isomerization of 1-butene to 2-butene observed on this Pt(111) surface. The reactions of more dehydrogenated C-4 species is also discussed.