Phase equilibrium data regression is an unavoidable task necessary to obtain the appropriate values for any model to be used in separation equipment design for chemical process simulation and optimization. The accuracy of this process depends on different factors such as the experimental data quality, the selected model and the calculation algorithm. The present paper summarizes the results and conclusions achieved in our research on the capabilities and limitations of the existing G E models and about strategies that can be included in the correlation algorithms to improve the convergence and avoid inconsistencies. The NRTL model has been selected as a representative local composition model. New capabilities of this model, but also several relevant limitations, have been identified and some examples of the application of a modified NRTL equation have been discussed. Furthermore, a regression algorithm has been developed that allows for the advisable simultaneous regression of all the condensed phase equilibrium regions that are present in ternary systems at constant T and P. It includes specific strategies designed to avoid some of the pitfalls frequently found in commercial regression tools for phase equilibrium calculations. Most of the proposed strategies are based on the geometrical interpretation of the lowest common tangent plane equilibrium criterion, which allows an unambiguous comprehension of the behavior of the mixtures. The paper aims to show all the work as a whole in order to reveal the necessary efforts that must be devoted to overcome the difficulties that still exist in the phase equilibrium data regression problem.

/pdf/ge-models-and-algorithms-for-condensed-phase-equilibrium-2ktjoclgeo.pdf

GE models and algorithms for condensed phase equilibrium data regression in ternary systems: limitations and proposals

. This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic–water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model–measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

/pdf/improved-aiomfac-model-parameterisation-of-the-temperature-46pbr9xbyq.pdf

Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

(Liquid + liquid) equilibria for the ternary (water + acetic acid + toluene) system at different temperatures: Experimental data and correlation

The salting-out effect of NaCl and KCl on the liquid–liquid equilibrium (LLE) of the ternary system of {water (1) + 2-methylpropanoic acid (2) + (1-methylethyl)-benzene (3)}, a recommended system for liquid–liquid extraction investigations, was studied at temperatures of (288.15, 298.15, and 313.15) K. The generated data for salt-free system have been used to estimate the binary molecular interaction parameters for the nonrandom two-liquid (NRTL) activity coefficient model. Results show that this model reproduces very good tie lines by estimated binary molecular interaction coefficients. The distribution coefficient of 2-methylpropanoic acid between organic/aqueous phases increases with its concentration, both in salt-free and in the presence of salt cases; however, it decreases moderately with temperature, within the range used. Adding a 0.05 mass fraction (based on mass of initial water) NaCl leads to an average enhancement of about 4 4% in distribution coefficient, and hence, it reaches to about 124 % ...

Salting-Out Effect of NaCl and KCl on the Liquid–Liquid Equilibrium of Water + 2-Methylpropanoic Acid + (1-Methylethyl)-benzene System at Several Temperatures

Phase equilibria of (water + propionic acid or butyric acid + 2-methoxy-2-methylpropane) ternary systems at 298.2 K and 323.2 K

Liquid−liquid equilibria of the ternary system water + acetic acid + methyl tert-butyl ether were studied from 293.15 K to 318.15 K at atmospheric pressure. Distribution coefficients and separation factors were evaluated for the immiscibility region. The reliability of the experimental tie-line data was ascertained by applying the Othmer−Tobias correlation. The experimental results were also correlated with the NRTL and UNIQUAC models successfully.

Liquid−Liquid Equilibria of the Ternary System Water + Acetic Acid + Methyl tert-Butyl Ether

Energetic compounds, as a type of special material, are widely used in the fields of national defense, aerospace and exploration. Their research and production have received growing attention. Thermal stability is a crucial factor for the safety of energetic materials. Azole-rich energetic compounds have emerged as a research hotspot in recent years owing to their excellent properties. Due to the aromaticity of unsaturated azoles, many azole-rich energetic compounds have significant thermal stability, which is one of the properties that researchers focus on. This review presents a comprehensive summary of the physicochemical and energetic properties of various energetic materials, highlighting the relationship between thermal stability and the structural, physicochemical, and energetic properties of azole-rich energetic compounds. To improve the thermal stability of compounds, five aspects can be considered, including functional group modification, bridging, preparation of energetic salts, energetic metal-organic frameworks (EMOFs) and co-crystals. It was demonstrated that increasing the strength and number of hydrogen bonds of azoles and expanding the π-π stacking area are the key factors to improve thermal stability, which provides a valuable way to develop energetic materials with higher energy and thermal stability.

Xiangyang Miao

Papers

Liquid−Liquid Equilibria of the Ternary System Water + Acetic Acid + Methyl tert-Butyl Ether

Thermal stability of azole-rich energetic compounds: their structure, density, enthalpy of formation and energetic properties.