1H and 13C NMR and FTIR Spectroscopic Analysis of Formic Acid Dissociation Dynamics in Water

Abstract

The formation and transport of ionic charges in formic acid-water (HCOOH-H₂O) mixtures with initial water mole fractions ranging from X_H2Oⁱ = 0 to 1 were investigated using ¹³C and ¹H NMR, FTIR spectroscopy, viscosity, conductivity, and pH measurements. The maximum molar concentration of ions (H₃O⁺ and HCOO^-), along with the relative differences between theoretical and experimental densities, spin-lattice relaxation times (T₁), activation energies (E_a), viscosity (η), and conductivity (σ), were identified within the range of X_H2Oⁱ ≈ 0.5-0.7. These results indicate that pure formic acid (FA) solutions predominantly consist of cyclic dimers at room temperature. As the water mole fraction increases up to 0.6, a structural shift occurs from cyclic dimers to a mixture of linear and cyclic dimers, driven by the formation of strong hydrogen bonds. Beyond a water mole fraction of 0.6, the structure transitions to linear dimers, with FA molecules behaving as free entities in the water. Furthermore, the acidity was found to increase approximately 2-fold with every 0.1 increment in water mole fraction. These findings are critical for understanding the kinetics of formic acid anions in body fluids, the structure of the hydrogen bonding network, and ionization energies.