Development of the modified quasichemical model in the distinguishable-pair approximation for multiple compositions of short-range ordering

TL;DR

This paper introduces the MQMDPA, an improved thermodynamic model that efficiently describes multiple short-range orderings in binary solutions with fewer parameters than previous models.

Contribution

The paper develops the MQMDPA, a novel model that accounts for multiple SROs using distinguishable pairs, reducing the number of parameters needed compared to the MQMPA.

Findings

Successfully modeled liquids with multiple SROs

Reduced model parameters for complex solutions

Demonstrated effectiveness and reliability of the new model

Abstract

A binary solution with short-range ordering (SRO) exhibits characteristic solution thermodynamics. The Modified Quasichemical Model in the Pair Approximation (MQMPA) can effectively capture the thermodynamic features of a binary solution with a onefold SRO. However, once the SRO occurs at multiple compositions in a binary solution, the MQMPA is in principle inconvenient to treat the solution thermodynamics. It usually requires a large number of model parameters to fit the thermodynamic data of such a solution. The present work proposes the Modified Quasichemical Model in the Distinguishable-Pair Approximation (MQMDPA), which is a further improvement of the MQMPA. The MQMDPA can more realistically describe the solution thermodynamics with manifold SROs using fewer model parameters. It benefits from grouping the ordered pairs, which were assumed to be indistinguishable within the MQMPA, into several distinguishable types. Each kind of ordered pair has unique coordination numbers and pair energy, which is responsible for describing one of the SROs at the desired composition and strength. Interestingly, the MQMDPA can be completely transformed into the MQMPA when all kinds of ordered pairs are assigned the same pair energy and coordination numbers. The distinguishable pairs have thus become indistinguishable. Several real liquids with at least two observed SROs were successfully treated by the MQMDPA to demonstrate its effectiveness and reliability.