Thermotropic phase transition temperatures, enthalpies and entropies of phase changes and odd-even alternation, in a homologous series of anhydrous lithium n-alkanoates, LiCnH2n-1O2 (LiC8-19 inclusive), have been investigated by differential scanning calorimetry (d.s.c.), hot stage polarizing microscopy and solid state C-13 NMR spectroscopy. The number of phases observed, between the room temperature microcrystalline solid and isotropic melt, shows a clear dependence on chain length. For LiC8-13, only one intermediate lamellar II crystalline phase is observed. For LiC14-19. a lamellar II and high temperature phase are evident. The high temperature phase is characterized by pre-melting and disordering of hydrocarbon chains as they change from nearly all-trans to one with increased gauche conformers. It is probably a solid rotator phase. Odd-even alternation in melting temperature, density and some thermodynamic data result from the relative distance between methyl groups, from opposite layers in a bi-layer. Molecular models indicate that the methyl groups in odd chains are more favourably orientated which lead to a more energetically favoured staggered conformer. As a consequence, the methyl groups, for odd chains, are in closer proximity than even chains. This subtle change in the molecular lattice could account for the presence of polymorphic structures on cooling from the melt. (C) 2010 Elsevier Ltd. All rights reserved.