Abstract
We examine the role of water and urea in cellulose solubility in tetrabutylammonium hydroxide (TBAH). Molecular dynamics simulations were performed for several different solvent compositions with a fixed cellulose fraction. For each composition, two simulations were carried out with cellulose fixed in each of the crystalline and the dissolved states. From the enthalpy and the entropy of the two states, the difference in Gibbs free energy (ΔG) and hence the spontaneity is determined. A comparison with solubility experiments showed a strong correlation between the calculated ΔG and the experimental measurements. A breakdown of the enthalpic and entropic contributions reveals the roles of water and urea in solubility. At high water concentration, a drop in solubility is attributed to both increased enthalpy and decreased entropy of dissolution. Water displaces strong IL-cellulose interactions for weaker water-cellulose interactions, resulting in an overall enthalpy increase. This is accompanied by a strong decrease in entropy, which is primarily attributed to both water and the entropy of mixing. Adding urea to TBAH(aq) increases solubility by an addition to the mixing term and by reducing losses in solvent entropy upon dissolution. In the absence of urea, the flexible [TBA](+) ions lose substantial degrees of freedom when they interact with cellulose. When urea is present, it partially replaces [TBA](+) and to a lesser extent OH(-) near cellulose, losing less entropy because of its rigid structure. This suggests that one way to boost the dissolving power of an ionic liquid is to limit the number of degrees of freedom from the outset.