Study of thermodynamic stabilities of polytypes of n-C36H74 by solubility measurements and incoherent inelastic neutron scattering

The thermodynamic properties of the two polytypes of n-hexatriacontane (n-C36H74), single-layered structure Mon and double-layered structure Orth II have been investigated by means of solubility measurements and incoherent inelastic neutron scattering. The solubility measurements reveal that Orth II is more stable than Mon by 1.2 kJ/mol because of the advantage of larger entropy. The neutron scattering measurements show that the vibrational modes of Orth II shift to the lower frequencies compared with those of Mon in the frequency region below 120 cm−1. The advantage of Orth II in vibrational entropy due to the low-frequency shifts is estimated to be 9.6 J K−1/mol at 288 K under the harmonic approximation, which nearly agrees with the entropy difference of 6.8 J K−1/mol between Mon and Orth II determined by solubility measurements. These results suggest that the difference in vibrational entropy due to low-frequency modes mainly contributes to the relative thermodynamic stabilities of polytypic structures...