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The desorption of linear alkenes with carbon numbers in the range from C6 to C14 from the molecular sieve adsorbent zeolite 5A has been studied by thermogravimetry. Such desorption exhibits three well-defined phases as observed for linear alkanes of a similar carbon number. The appearance of these desorption phases has been explained in terms of the interaction of alkene molecules with the zeolite cavities and the dependence of such interaction on the geometrical compatibility between the alkenes and the zeolite cavity.