The Rotational Isomeric State description of the conformational behaviour of hydrocarbon chains and their Knight’s Gambit Lattice representation are shown to provide the same picture of the orientational order of an isolated chain tethered to an impenetrable interface. The experimental order parameter profile can be reproduced both by subjecting the chain to a mean field potential and by confining it within a cylinder with rigid walls. The chain undertakes conformations containing loops and this is enhanced by the introduction of a cis double bond in the middle of the chain. A hydrocarbon chain containing a bulky pentagon corresponding to a nitroxide group, exhibits sowewhat higher order parameters, particularly for those atoms close to the label. This finding indicates that the low orientational order reported by fatty acids labelled at the 12 positions, reflects interactions of the spin label with the surrounding rather than an intrinsic change in the conformational behaviour.