How sensitive are physical properties of choline chloride–urea mixtures to composition changes: Molecular dynamics simulations and Kirkwood–Buff theory

Deep eutectic solvents (DESs) have emerged as a cheaper and greener alternative to conventional organic solvents. Choline chloride (ChCl) mixed with urea at a molar ratio of 1:2 is one of the most common DESs for a wide range of applications such as electrochemistry, material science, and biochemistry. In this study, molecular dynamics simulations are performed to study the effect of urea content on the thermodynamic and transport properties of ChCl and urea mixtures. With increased mole fraction of urea, the number of hydrogen bonds (HBs) between cation–anion and ion–urea decreases, while the number of HBs between urea–urea increases. Radial distribution functions (RDFs) for ChCl–urea and ChCl–ChCl pairs shows a significant decrease as the mole fraction of urea increases. Using the computed RDFs, Kirkwood–Buff Integrals (KBIs) are computed. KBIs show that interactions of urea–urea become stronger, while interactions of urea–ChCl and ChCl–ChCl pairs become slightly weaker with increasing mole fraction of urea. All thermodynamic factors are found larger than one, indicating a non-ideal mixture. Our results also show that self- and collective diffusivities increase, while viscosities decrease with increasing urea content. This is mainly due to the weaker interactions between ions and urea, resulting in enhanced mobilities. Ionic conductivities exhibit a non-monotonic behavior. Up to a mole fraction of 0.5, the ionic conductivities increase with increasing urea content and then reach a plateau.