In
the recent years, the need to improve the thermodynamic models,
particularly making them more precise and predictable for complex
systems, has increased [Industrial Requirements
for Thermodynamics and Transport PropertiesHendriksE.
Hendriks, E.
Ind. Eng. Chem. Res.2010491113111141
Industrial Requirements for Thermodynamic and Transport PropertiesKontogeorgisG.
Kontogeorgis, G.
Ind. Eng. Chem. Res.20216049875013 The complexity of electrolyte systems is due to the strong interactions
between ions, the hydration forces that take place during salt dissociation,
and the physical forces at high concentrations of solute. Consequently,
the existing thermodynamic electrolyte models show some limitations
and are far from being completely optimized for industrial simulations.
Thermodynamics based on electrolyte mixtures and mixed solvents requires
further development and research [PolingB. E.
Poling, B. E.
The
Properties of Gases and LiquidsMcGraw-Hill Education2001The EleTher Joint Industrial Project (JIP) aims at promoting research
in this field. A practical workflow is under development where the
first stage consists in analyzing the data. The present work is part
of this larger scope and presents a strategy to analyze the internal
and external consistency of experimental data for electrolyte mixtures.
The focus is on alkali halide salts in water. Internal consistency
allows testing the quality of data by confronting them to each other
and using the thermodynamic relationships between these data. For
that purpose, the data are confronted with a model that was initially
optimized and the deviations are analyzed. For this purpose, the electrolyte
non-random two-liquid (eNRTL) thermodynamic model was selected. Some
deviations are attributed to the model inadequacy (high temperature
or high molalities). Others are to be attributed to data inconsistencies.
On the other hand, the objective of external consistency is to evaluate
the consistency between different systems of the same family. The
Bromley model is used for this purpose, as it contains a single adjustable
parameter. Investigating the trend of this parameter with type of
compound or with temperature may provide valuable information regarding
the underlying physics, in addition to identifying outliers.
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