Solubility of CO₂ in Aqueous Formic Acid Solutions and the Effect of NaCl Addition: A Molecular Simulation Study

There is a growing interest in the development of routes to produce formic acid from CO₂, such as the electrochemical reduction of CO₂ to formic acid. The solubility of CO₂ in the electrolyte influences the production rate of formic acid. Here, the dependence of the CO₂ solubility in aqueous HCOOH solutions with electrolytes on the composition and the NaCl concentration was studied by Continuous Fractional Component Monte Carlo simulations at 298.15 K and 1 bar. The chemical potentials of CO₂, H₂O, and HCOOH were obtained directly from single simulations, enabling the calculation of Henry coefficients and subsequently considering salting in or salting out effects. As the force fields for HCOOH and H₂O may not be compatible due to the presence of strong hydrogen bonds, the Gibbs-Duhem integration test was used to test this compatibility. The combination of the OPLS/AA force field with a new set of parameters, in combination with the SPC/E force field for water, was selected. It was found that the solubility of CO₂ decreases with increasing NaCl concentration in the solution and increases with the increase of HCOOH concentration. This continues up to a certain concentration of HCOOH in the solution, after which the CO₂ solubility is high and the NaCl concentration has no significant effect.