Estimation of Solvation Quantities from Experimental Thermodynamic Data: Development of the Comprehensive CompSol Databank for Pure and Mixed Solutes

Abstract

The Gibbs energy of solvation measures the affinity of a solute for its solvent and is thus a key property for the selection of an appropriate solvent for a chemical synthesis or a separation process. More fundamentally, Gibbs energies of solvation are choice data for developing and benchmarking molecular models predicting solvation effects. The Comprehensive Solvation-CompSol-database was developed with the ambition to propose very large sets of new experimental solvation chemical-potential, solvation entropy, and solvation enthalpy data of pure and mixed components, covering extended temperature ranges. For mixed compounds, the solvation quantities were generated in infinite-dilution conditions by combining experimental values of pure-component and binary-mixture thermodynamic properties. Three types of binary-mixture properties were considered: partition coefficients, activity coefficients at infinite dilution, and Henry's-law constants. A rigorous methodology was implemented with the aim to select data at appropriate conditions of temperature, pressure, and concentration for the estimation of solvation data. Finally, our comprehensive CompSol database contains 21 671 data associated with 1969 pure species and 70 062 data associated with 14 102 binary mixtures (including 760 solvation data related to the ionic-liquid class of solvents). On the basis of the very large amount of experimental data contained in the CompSol database, it is finally discussed how solvation energies are influenced by hydrogen-bonding association effects.

Umbrella sampling and double decoupling data for methanol binding to Candida antarctica lipase B

“…2 ). Comparison with experimental estimates for the hydration free energy of methanol at C ( ) [3] and the methanol self-solvation free energy at ( ) [11] shows reasonable agreement and confirms the observed independence of the methanol concentration. The decoupling free energies in the protein binding pocket in contrast, revealed a considerable dependence on the methanol concentration.…”

Group Contribution and Machine Learning Approaches to Predict Abraham Solute Parameters, Solvation Free Energy, and Solvation Enthalpy

“…The A summary and analysis of the compiled solvation free energy and enthalpy data sets are given in Table 2. The solvation free energy data are acquired from the Minnesota solvation database (MNSol), 38 CompSol database, 46 FreeSolv database, 35 and published work by Abraham, Acree and coworkers and compiled together as a dGsolvDB1 data set. Additionally, we have nearly 4000 gas-water partition coefficient data (log K w ) from the in-house database.…”

“…Solvation enthalpy data are collected from Acree Enthalpy of Solvation data set 83 and Comp-Sol database. 46 Self-solvation data (solvation of a compound in itself) are included in both solvation energy and enthalpy data sets. It can be seen from Table 2 that the majority of the solvents in the data sets only have a single entry that corresponds to the self-solvation datum in the final database.…”

Atomistic modeling of electrocatalysis: Are we there yet?

“…(190) (iii) All of these models reside on more or less extensive parametrization. The existence of comprehensive tables for solvation free energies in bulk solution (191) makes this parametrization rather unproblematic for solvated molecules and ions, even though the crude approximations in implicit solvent models prohibits the development of truly universal models, spurring the continuous development in the field. (192,193,184,194,186,195) Such experimental benchmark data is much more sparse and less diverse for the (electrified) surfaces, so that the current parametrizations are only based on bulk solvation properties of organic molecules and ions.…”

“…(c) All of these models reside on more or less extensive parametrization. The existence of comprehensive tables for solvation free energies in bulk solution 191 makes this parametrization rather unproblematic for solvated molecules and ions, even though the crude approximations in implicit solvent models prohibits the development of truly universal models, spurring the continuous development in the field 184,186,192,193,194,195 …”