The PPR78 model is a predictive cubic equation of state relying on the group-contribution concept. Our previous studies have highlightened its capacity to predict the phase behavior of mixtures containing a large variety of compounds: alkanes, alkenes, aromatic compounds, permanent gases, sulfur compounds, etc. In this paper, it is attempted for the first time to answer the question “can the PPR78 model be safely used in energy-rate balances?”. To do so, the largest possible number of enthalpy of mixing data and isobaric heat capacity of mixing data were collected in the open literature and predicted using the PPR78 model. It is shown that although certainly perfectible, this model generally provides from acceptable to accurate estimations of these properties depending on the nature of the mixtures and the conditions of temperature and pressure as well. Furthermore, this paper proposes some general reflections both on conceptual and practical issues: Is it always possible to claim that the excess enthalpy...

Enthalpy and Heat Capacity Changes on Mixing: Fundamental Aspects and Prediction by Means of the PPR78 Cubic Equation of State

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 (k ij) have been used to correlate the numerous data included in the proposed database, and its performance has been assessed following the proposed methodology.

https://hal.univ-lorraine.fr/hal-02921996/document

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

Thermodynamic study on binary mixtures of propyl ethanoate and an alkan-1-ol (C2–C4). Isobaric vapor–liquid equilibria and excess properties

Enthalpy of solvation correlations for gaseous solutes dissolved in dibutyl ether and ethyl acetate

Excess molar enthalpies and excess molar volumes of formamide + 1-propanol or 2-propanol and thermodynamic modeling by Prigogine–Flory–Patterson theory and Treszczanowicz–Benson association model

Molar excess enthalpies of ethyl acetate + alkanols at T = 298.15 K, p = 10.0 MPa

Excess enthalpies of seven binary liquid systems

The dilution enthalpies of formamide in aqueous methanol and ethanol solutions have been determined using a CSC-4400 isothermal calorimeter at 298.15 K. The homogeneous solution enthalpic interaction coefficients have been calculated over a range of alcohol concentrations according to the excess enthalpy concept. The results show that the enthalpic pair interaction coefficients h 2 of formamide are negative in aqueous alcohol solutions and pass through a minimum in mixed solvents, whereas the h 2 coefficients of formamide in aqueous ethanol solutions are more negative than those in aqueous methanol solutions. The results are discussed in terms of solute-solute and solute-solvent interactions.

Wei-dong Yan

Papers

Molar excess enthalpies of ethyl acetate + alkanols at T = 298.15 K, p = 10.0 MPa

Excess enthalpies of seven binary liquid systems

Enthalpic Interaction Coefficients of Formamide in Aqueous Methanol and Ethanol Solutions at 298.15 K