Modeling Solvation in Supercritical CO₂

Abstract

This work is in memory of Professor Branka M. Ladanyi,w hose contribution in the field of computationalm odeling allowed important steps forward in understanding supercritical solvation.

Ultra-fast single-crystal polymerization of large-sized covalent organic frameworks

“…Considering the inertness, sc-CO 2 functions as an inert solvent in the reactions 34 , and the reaction thermodynamics is similar to that in liquid mediums. The difference is that the supercritical fluid combines gas-like viscosity and surface tension with liquid-like density and solvating properties 35 . The viscosity of sc-CO 2 is about 0.02 cp (80 °C, 8 MPa), while the surface tension is near zero 36 .…”

Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2

“…Even though there are several models that attempt to explain the solvation mechanism of scCO 2 (acid–base Lewis, π–π interactions), 63,64 it is generally accepted that quadrupole–polar interactions play a significant role. To probe how the solvent influences the control of the polymerisation, pair distribution or radial distribution functions (RDF) were computed from molecular dynamics simulations.…”

Green extraction processes, biorefineries and sustainability: Recovery of high added-value products from natural sources

“…In the published literature in the last two years there has been an increase in the contributions related to "green solvents AND supercrit*" (based on Scopus search, September 2017) with around 400 manuscripts, from which half correspond to "green solvents AND supercrit* AND design". This large increase has to do not only with the applications of green solvents in different high pressure conditions but also on new tools for solvent modelling; for instance using molecular dynamics (MD) simulations [8] and Monte Carlo simulations it has been possible to investigate, among others, the phase equilibria in CO2-expanded systems and to predict their physicochemical properties as media for engineering processes [9]. On the other hand, new solvents, with interesting properties have been studied with the goal of improving the coverage of supercritical CO2 for the solubilization of "insoluble" substances: for example, Ingrosso et al [9,10] synthesized and characterized a supramolecular complex in scCO2 to act as "solubilizer" (systems able to transport insoluble substances into the solvent owing to their emulsifying or dispersion properties) based on a polar aromatic molecule (benzoic acid) and peracetylated β-cyclodextrin, which is soluble in the supercritical medium.…”