Mass Transfer Thermodynamics through a Gas-Liquid Interface

Molecular level information about thermodynamic variations (enthalpy, entropy, and free energy) of a gas molecule as it crosses a gas-liquid interface is strongly lacking from an experimental perspective under equilibrium conditions. Herein, we perform in situ measurements of water interacting with the ionic liquid (IL) 1-butyl-3-methylimidazolium acetate, [C(4)mim] [Ace], using ambient pressure X-ray photoelectron spectroscopy in order to assess the interfacial uptake of water quantitatively as a function of temperature, pressure, and water mole fraction (x(w)). The surface spectroscopy results are compared to existing bulk water absorption experiments, showing that the amount of water in the interfacial region is consistently greater than that in the bulk. The enthalpy and entropy of water sorption vary significantly between the gas-liquid interface and the bulk as a function of x(w), with a crossover that occurs near x(w) = 0.6 where the water-IL mixture converts from being homogeneous (x(w) < 0.6) to nanostructured (x(w) > 0.6). Free energy results reveal that water at the gas-IL interface is thermodynamically more favorable than that in the bulk, consistent with the enhanced water concentration in the interfacial region. The results herein show that the efficacy for an ionic liquid to absorb a gas phase molecule is not merely a function of bulk solvation parameters but also is significantly influenced by the thermodynamics occurring across the gas-IL interface during the mass transfer process.