Unraveling order and entropy with modern quasi-chemical models

Abstract

In this work, the derivation of a general expression for the residual entropy for quasi-chemical models – including modern COSMO-RS/SAC – is shown. This expression is equivalent to equations that had to be assumed or postulated in previous works. More interestingly, it allows to unravel order (or non-randomness) in pure compounds and mixtures in a very detailed way. It is possible to investigate the entropic contribution of every possible pair of molecular surface segments, without relying on any lattice or coordination number. Different types of mixtures are very well explained by modern quasi-chemical models, including polar, apolar, and associating compounds showing positive, negative, and s-shaped excess entropy. Finally, it is shown that these models are unable to precisely represent some aqueous mixtures — the assumption of pairwise additive interactions is apparently too limited in those cases.