On the isobaric thermal expansivity of liquids.

The temperature and pressure dependence of isobaric thermal expansivity, α(p), in liquids is discussed in this paper. Reported literature data allow general trends in this property that are consistent with experimental evidence to be established. Thus, a negative pressure dependence is to be expected except around the critical point. On the other hand, α(p) exhibits broad regions of negative and positive temperature dependence in the (T, p) plane depending on the nature of the particular liquid. These trends are rationalized here in terms of various molecular-based equations of state. The analysis of the Lennard-Jones, hard sphere square well and restricted primitive model equations allows understanding the differences in the α(p) behavior between liquids of diverse chemical nature (polar, nonpolar, and ionic): broader regions of negative temperature and positive pressure dependencies are obtained for liquids characterized by larger ranges of the interparticle potential. Also, using the statistical associating fluid theory (SAFT) allowed the behavior of more complex systems (basically, those potentially involving chain and association effects) to be described. The effect of chain length is rather simple: increasing it is apparently equivalent to raise the interaction range. By contrast, association presents a quite complex effect on α(p), which comes from a balance between the dispersive and associative parts of the interaction potential. Thus, if SAFT parameters are adjusted to obtain low association ability, α(p) is affected by each mechanism at clearly separate regions, one at low temperature, due to association, and the other to dispersive forces, which has its origin in fluctuations related with vapor-liquid transition.