Inspired by the lack of characterization of natural eutectic and deep eutectic (DES) systems, we studied the solid-liquid equilibria (SLE) of binary and ternary mixtures involving choline chloride and sugars. The densities, viscosities and solvatochromic parameters for the binary systems containing choline chloride, [Ch]Cl, were measured at the eutectic composition, and the water impact on these properties was also investigated in order to address the tailoring of their properties using water. Mixtures of sugars are shown to present an ideal behavior, while their binary mixtures with choline chloride present negative deviations to the ideality, particularly in the sugar solubility curve. Aiming to develop a predictive model to design new sugar based DES, the [Ch]Cl + sugars phase diagrams were used to tune the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) parameters, which was after applied in the estimation of the eutectic points of new ternary DES. The predictions quality was checked experimentally, proving that COSMO-RS can be a useful tool for the design of deep eutectic solvents.

This work shows a new approach to the parameter-fitting problem useful in the solutions thermodynamic field, providing a more objective framework to obtain better empirical/semiempirical models for chemical engineering applications. A model based on the excess Gibbs energy function g E is used to represent the behavior of real solutions, together with its first derivative h E, using a combined modeling under the paradigm of multiobjective optimization. The problem is formulated as an MINLP methodology to simultaneously consider two aspects: the model complexity and the best parametrization to prevent the overfitting, controlling the trade-off between them by applying the Akaike Information Criterion to g E residuals. Two different solvers, one deterministic (SBB/CONOPT) and another evolutionary (GA), are used, and their ability to solve the problem is analyzed. The designed methodology is applied to three highlighted VLE cases in chemical engineering, and the results obtained show the ability of the method to get the best model in each case. The proposed methodology proved useful for modulating the number of parameters considering the imposed requirements, which decrease as the accuracy requirements for h E are relaxed. The efficient-fronts obtained show a small trade-off region, noting that the proposed framework provides the simplest models with the minimum completeness uncertainty.

In this work, a methodology is established to manage and use, in a more rigorous way, the experimental information that reflects the thermodynamic–mathematical behavior of dissolutions. The management of experimental information is carried out with an application on binaries of esters and alkanes which is useful in any other case. Specifically, for this work a new real database (of several properties under different conditions) is generated for eight binaries formed by four alkanoates, with a carbon number number ≥ 4, and two alkanes C6 and C8. A sequence of operations is proposed, ranging from experimentation to simulation, with two highly relevant intermediate stages, modeling↔verification of the quality of data, whose impact on the simulation is evaluated. The experimental contribution of some properties v E, c P E, h E, g E, gives rise to two very important operations, such as the combined modeling of the properties, taking into account the thermodynamic formalism, and the verification of the vapor–liquid equilibrium (VLE) data. For the latter process, the methodology designed in a previous work (J. Chem. Thermodyn.2017105385) is put into practice, as well as a new method, rigorous under a thermodynamic–mathematical point of view, in which the modeling of properties is considered. The binomial model-consistency test is generated as a strategic stage to define the quality of the data. To achieve an accurate modeling in the multifunctional correlation that is proposed, two procedures are adopted: (a), step-by-step (SSO), according to the inverse order of the derivation of the Gibbs function, and another (b), by multiobjective optimization (MOO). The parametrization obtained by the latter is implemented in the commercial software of Aspen-Plus to design a rectification operation to purify the compounds of one of the studied systems, comparing the results with those that the simulator emits with the information estimated by UNIFAC.

This study examines the influence of saturation gradients on pressure falloff data by rigorously accounting for the relative permeability characteristics of the porous medium. The study examines the significance of the various straight-line segments that appear when results are analyzed on semilogarithmic paper as a function of the relative permeability characteristics of the porous medium, injection rate, injection time, and distance to the external boundary. Conditions necessary to obtain the mobilities of the completely flooded region, the transitional (oil/water) zone, and the undamaged region are prescribed. The applicability of the methods suggested in the literature to locate the radii of fluid banks was investigated.

This work shows a practical experience involving the following sequence of tasks on eight binary solutions of alkyl (propyl, butyl) propanoate with four alkanes (hexane to nonane): experimentation → modeling ↔ verification → simulation. Thermodynamic properties related to dilution processes are determined, in addition to vapor−liquid equilibria at 101.32 kPa (iso-p VLE), providing a vast database. Some improvements are proposed for the aforementioned tasks: (a) density values at high temperature and pressure for the pure compounds and their modeling to improve the calculation of activity coefficients, (b) the procedure of multiproperty modeling using an ϵ-constraint multiobjective procedure combined with a genetic algorithm for mixed integer nonlinear problem (MINLP) problems, obtaining a {data + model} set, which is subjected to the third task of thermodynamic validation, and (c) with the methodology established in Wisniak, J. et al. A Fresh Look at the Thermodynamic Consistency of Vapour-Liquid Equilibria Data. J. Chem. Thermodyn. 2017, 105, 385 395, the consistency of iso-p VLE data was confirmed, and the process was assisted by a modification of our own method to guarantee the {model-checking} binomial, increasing the reliability of the experimental data provided and the model obtained. The systems propyl propanoate−octane and butyl propanoate−nonane are azeotropic with coordinates, respectively, at (x az = 0.650; T az /K = 392.4) and (x az = 0.633; T az /K = 417.1). The model obtained for the first system is used to simulate the separation process of that binary with a commercial simulator. After implementing the model, comparison of the results generated by the software produced values close to real ones obtained in a batch distillation in the laboratory, improving the values estimated by the simulator software.