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The chemisorption and transformation of n-hexane have been investigated over Pt black in the presence of hydrogen between 450 and 600 K. Direct gravimetric measurements have confirmed that only 3–8% of the total hydrocarbon coverage can be removed by evacuation or by purging the system with an inert gas. Hydrogenation experiments have been used to separate reactive and irreversibly bound hydrocarbons; their coverages have been measured as a function of temperature and partial pressure of hydrogen. The variation of the product selectivity with the partial pressure of hydrogen has been interpreted considering the effect of the irreversibly bound hydrocarbons on ensemble size and on availability of hydrogen.