Benchmark Database Containing Binary-System-High-Quality-Certified Data for Cross-Comparing Thermodynamic Models and Assessing Their Accuracy

In the last two centuries, equations
of state (EoSs) have become
a key tool for the correlation and prediction of thermodynamic properties
of fluids. They not only can be applied to pure substances as well as to mixtures but
also constitute the heart of commercially available computer-aided-process-design
software. In the last 20 years, thousands of publications have been
devoted to the development of sophisticated models or to the improvement
of already existing EoSs. Chemical engineering thermodynamics is thus
a field under steady development, and to assess the accuracy of a
thermodynamic model or to cross-compare two models, it is necessary
to confront model predictions with experimental data. In this context,
the importance of a reliable free-to-access benchmark database is
pivotal and becomes absolutely necessary. The goal of this paper is
thus to present a database, specifically designed to assess the accuracy
of a thermodynamic model or cross-compare models, to explain how it
was developed and to enlighten how to use it. A total of 200 nonelectrolytic
binary systems have been selected and divided into nine groups according
to the associating character of the components, i.e., their ability
to be involved in a hydrogen bond (the nature and strength of the
association phenomena are indeed considered a measure of the complexity
to model the thermodynamic properties of mixtures). The methodology
for assessing the performance of a given model is then described.
As an illustration, the Peng–Robinson EoS with classical van
der Waals mixing rules and a temperature-dependent binary interaction
parameter (kij) have been used to correlate
the numerous data included in the proposed database, and its performance
has been assessed following the proposed methodology.

在过去两个世纪中，状态方程（EoSs）已成为关联和预测流体热力学性质的关键工具。它们不仅适用于纯净物质和混合物，而且构成商业可用的计算机辅助工艺设计软件的核心。在过去的二十年里，数千篇出版物致力于开发复杂的模型或改进现有的EoSs。化学工程热力学因此成为一个持续发展的领域，为了评估热力学模型的准确性或进行模型间的交叉比较，将模型预测与实验数据进行对比是必要的。在此背景下，一个可靠且免费可用的基准数据库的重要性至关重要，变得绝对必要。因此，本文旨在提出一个专门设计的数据库，用于评估热力学模型的准确性或进行模型间的交叉比较，解释其开发过程，并阐明其使用方法。总共选取了200个非电解质二元系统，并根据组分的关联特性（即它们参与氢键的能力，即关联现象的性质和强度被视为模拟混合物热力学性质复杂性的一个度量）将其分为九组。随后，描述了评估给定模型性能的方法。作为示例，使用具有经典范德华混合规则和温度依赖性二元相互作用参数（kij）的Peng-Robinson EoS来关联所提出数据库中包含的大量数据，并按照提出的方法对其性能进行了评估。