As part of the Workshop on Computational Chemistry as Strategical Tool for the Development of Functional Materials, I will deliver two plenary talks. The first talk is on Tuesday, November 26. Originally, Professor Zaworotko was scheduled to deliver the talk, however, he had to cancel his travel plans at the last minute. My talk will supplement the material in my workshop "Calculation and Application of Solvation Free Energies Using Modern Computational Tools." My talk is titled "Some Non-Conventional Uses of Solvation Free Energies," in which I will discuss two specific examples in which I have used solvation free energies in... well non-conventional ways. In the first example, I will show how solvation free energies can be used to interpret and predict the formation of azeotropes in binary systems. In order to predict whether a binary system will for a minimum or maximum boiling azeotrope, one need only perform four conventional solvation free energy calculations. When a system exhibits an azeotrope, special separation techniques are necessary to separate the mixture. One such technique is extractive distillation, wherein a third component is introduced to increase the relative volatility of the most volatile component. The ability to predict the formation of an azeotrope and understand the underlying intermolecular interactions is the first step in designing efficient separation processes. Details of this work can be found in the following publication, which I link to here:
A Simple Method to Predict and Interpret the Formation of Azeotropes in Binary Systems Using Conventional Solvation Free Energy Calculations
Sydnee N. Roese, Griffin V. Margulis, Alexa J. Schmidt, Cole B. Uzat, Justin D. Heintz, and Andrew S. Paluch
Industrial & Engineering Chemistry Research, DOI: 10.1021/acs.iecr.9b03694
Upon request, I can additionally send you a copy via e-mail (PaluchAS@MiamiOH.edu). This is part of a major effort of my MS student Sydnee Roese to assess the ability of the SMx universal solvents models to predict phase equilibria (vapor/liquid and liquid/liquid).
The second application demonstrates the application of the "dilute solution approximation" to extrapolate solvation free energy calculations at infinite dilution to finite concentrations. Two applications that I have found useful for this is predicting the solubility of non-electrolyte solids, and for predicting the solubility of gases beyond the Henry's law limit. In the talk, I will specifically demonstrate the application for predicting the solubility of non-electrolyte solids in super critical carbon dioxide. In this method, we assume that the solute is dilute where we can neglect solute-solute interactions. For this case, we can account for the composition dependence of the solvation free energy using a simple, analytic athermal solution theory, such as the Flory-Huggins equation. For details related to the discussion in the presentation, you are referred to the following publication, which I link to here:
Microscopic Structure and Solubility Predictions of Multifunctional Solids in Supercritical Carbon Dioxide: A Molecular Simulation Study
Javad Noroozi and Andrew S. Paluch
The Journal of Physical Chemistry B 2017 121 (7), 1660-1674
Historically, my work on the development of the dilute solution approximation began with two early publications while I was a PhD student:
Predicting the Solubility of Solid Phenanthrene: A Combined Molecular Simulation and Group Contribution Approach
Andrew S. Paluch and Edward J. Maginn
AIChE J 2013 59, 2647-2661
Efficient Estimation of the Equilibrium Solution-Phase Fugacity of Soluble Nonelectrolyte Solids in Binary Solvents by Molecular Simulation
Andrew S. Paluch and Edward J. Maginn
Industrial & Engineering Chemistry Research 2013 52 (38), 13743-13760
Upon request, I can additionally send you copies via e-mail (PaluchAS@MiamiOH.edu).
A PDF of my presentation is provided below, and when I have time, I will record a screen cast of the presentation:
PDF of "Some Non-Conventional Uses of Solvation Free Energies"
Screen cast of "Some Non-Conventional Uses of Solvation Free Energies"
If you have any questions, please do not hesitate to ask. If you would like any help applying either of the methods described in the presentation, please let me know.
My second talk was delivered on Thursday, November 28 and was titled: "Predicting Phase Behavior and Intuitive Solvent Selection Using MOSCED." In this work I will introduce you to the solubility parameter based method MOSCED (modified separation of cohesive energy density.) What makes MOSCED special is its treatment of association; namely, it separates the effect of hydrogen bond basicity and acidity. I will demonstrate the use of MOSCED for predicting and understanding the formation of azeotropes, and how it can be used to intuitively select an entrainer for extractive distillation. Additionally, I will demonstrate the use of MOSCED to predict and interpret solubility enhancement.
A PDF of my presentation is provided below. Additionally, this is based on a presentation I delivered at the 2019 AIChE Spring Meeting, for which a screen cast is provided below.
If you are interested in MOSCED, you might also have a look at my MOSCED playlist on YouTube. At the time of writing, this includes a simple example of performing MOSCED calculations with MATLAB or GNU Octave, with provided code.
During either my first or second seminar, I hope to have a chance to mention the graduate program in my home depart, the Department of Chemical, Paper, and Biomedical Engineering at Miami University. Currently, we offer a Master of Science in Chemical and Biomedical Engineering at Miami University. Our director of graduate studies, Professor Justin Saul, provided the slides below with additional information. You can reach out to Professor Saul at sauljm@miamioh.edu. You are also welcome to send me any questions. I would be very happy to talk to you further here at the workshop, and would love to welcome you to Miami University.