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The adsorption of CO on a clean Pd(lll) surface has been studied by means of low energy electron diffraction (LEED), contact potential measurements and flash desorption. At coverages ㊀ between 1/3 and 1/2 ordered adsorption phases are observed for which structure models are derived. The maximum increase of the work function Δϕ is about 1 eV; Δϕ is proportional to ㊀. Adsorption isotherms have been measured between 100 and 300 °C and the isosteric heat of adsorption Ead has been determined as a function of ㊀. Ead is constant (34 kcal/mole) up to ㊀ = 1/3 and then decreases owing to structural influences and intermolecular interactions.