![]() A similar comparison for dielectric constant predictions gave s(est) as 2.5 units. A comparison of the predicted vs experimental melting points for nine of the ILs (excluding those where no melting transition was observed and two outliers that were not well described by the model) gave a standard error of the estimate (s(est)) of 8 degrees C. This model can be used to predict the melting temperatures and dielectric constants of ILs with good accuracy. Thus, these ILs are liquid under standard ambient conditions because the liquid state is thermodynamically favorable, due to the large size and conformational flexibility of the ions involved, which leads to small lattice enthalpies and large entropy changes that favor melting. Under standard ambient conditions (298.15 K and 10(5) Pa) Delta(fus)G degrees was found to be negative for all the ILs studied, as expected for liquid samples. Free energies of solvation (Delta(solv)G) of each ion in the bulk molten salt were calculated using the COSMO solvation model and the experimental dielectric constants. Lattice free energies (Delta(latt)G) were estimated using a combination of Volume Based Thermodynamics (VBT) and quantum chemical calculations. As part of this project we synthesized and determined accurate melting points (by DSC) and dielectric constants (by dielectric spectroscopy) for 14 ionic liquids based on four common anions and nine common cations. This was done using a suitable Born-Fajans-Haber cycle that was closed by the lattice (i.e., IL(s) -> IL(g)) Gibbs energy and the solvation (i.e., IL(g) -> IL(l)) Gibbs energies of the constituent ions in the molten salt. The basic concept was to assess the Gibbs free energy of fusion (Delta(fus)G) for the process IL(s) -> IL(l), which relates to the melting point of the IL. We have developed a simple and quantitative explanation for the relatively low melting temperatures of ionic liquids (ILs).
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