A Simple Method for Estimating the Absolute Solvation Free Energy of Monovalent Ions in Different Solvents

Abstract

The solvation Gibbs free energies (SGFE) of 39 ions were estimated in protic and aprotic solvents including methanol, ethanol, N,N-dimethylformamide (DMF) and acetonitrile (ACN) using a proposed approach. In this method, the error of the applied computational method, used for estimating the SGFE of a specific ion in water and dimethyl sulfoxide (DMSO) solvents, was used as a reference value to correct the calculated SGFE of the ion in other protic and aprotic solvents, respectively. The estimated values of SGFE of ions, obtained in this work, show good agreement with those obtained using the other methods reported in literature. New correlation equations were also proposed for correlating the estimated values of SGFE of ions in a specific solvent to the corresponding values in water and DMSO for protic and aprotic solvent. By using the proposed method in this work, it is possible to estimate the values of SGFE of ions in the solvents that there are no experimental and theoretical reports on them in literature provided that the appropriate and correct reference solvent is selected. Typically, this method was applied on two most popular solvents in organic chemistry including acetone and 1-propanol to estimate the SGFE of the considered ions in them for the first time.

Absolute proton hydration free energy, surface potential of water, and redox potential of the hydrogen electrode from first principles: QM/MM MD free-energy simulations of sodium and potassium hydration

“…Clearly, the formulation of a consistent single-ion solvation thermodynamics also involves analogous determinations pertaining to other solvents, 151,322 relevant in particular in the context of transfer free energies, 323,324 and charge-asymmetric solvation effects. 17,325 Furthermore, not only the values of these quantities are of relevance, but also that of their P-or/and T -derivatives, related to the partial molar enthalpies, entropies, compressibilities, and expansivities.…”

Anion-Responsive Thiourea-Based Gel Actuator

“…When we compared the solvation energies of anions in DMSO, the solvation energy of F − (−82.6 kcal/mol) was significantly higher than that of CN − (−58.0 kcal/mol). 29,30 Thus, we can conclude that Type IIIa anions have a high solvation energy; therefore, they salt out the "deprotonated" gels and increase solvent−phobic interactions, resulting in the shrinking of the gels. In contrast, Type IIIb anions have a low solvation energy; thus, they increase the solubility of the deprotonated gels and the osmotic pressure inside, resulting in a larger swelling of the gels.…”

Promoting Amine-Activated Electrochemical CO2 Conversion with Alkali Salts

“…Geometry minimization was calculated at the B3LYP/6-311++G(d, p) level of theory. 29 All simulations used the Solvation Model Based on Density (SMD) to account for the solvent dielectric constant (ϵDMSO). 30 Optimized structures were confirmed by vibration frequency calculations at the B3LPY/6-311++G(d, p) level of theory.…”

“…For each individual species (RNH 2 , alkali-metal cation, DMSO, carbamic acid, carbamate, and ammonium), structure optimizations were conducted separately to obtain stable equilibrium configurations. Geometry minimization was calculated at the B3LYP/6-311++G­(d,p) level of theory . All simulations used the solvation model based on density (SMD) to account for the solvent dielectric constant (ε DMSO ) .…”