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A previous study of the desorption of straight-chain alkanes [H(CH2)NH, N = 5−60] from the surface of graphite has revealed that the measured desorption barriers, , have a nonlinear dependence on the chain length (Paserba, K. R.; Gellman, A. J. Phys. Rev. Lett. 2001, 86 (19), 4338). A model is proposed for the mechanism of oligomer desorption that accounts for the chain length dependence of the through consideration of both the energy and entropy of oligomers interacting with a surface. The segments of the oligomer are identified with individual backbone bonds such that an alkane with N carbon atoms has I = N − 1 segments. The oligomer segments are rapidly attaching to and detaching from the surface such that the various partially detached oligomers are in equilibrium with one another and can be classified by the number of detached segments i. Equilibrium among the partially detached oligomers is dictated by their relative free energies ΔAi, which are dependent on the numbers of detached segments. The ene...

Kinetics and Mechanism of Oligomer Desorption from Surfaces: n-Alkanes on Graphite