| Abstract: | The solubilities of 1alkyl‐3‐methylimidazolium chloride, [Cnmim][Cl], where n=4, 8, 10, and 12, in 1octanol and water have been measured by a dynamic method in the temperature range from 270 to 370 K. The solubility data was used to calculate the 1octanol/water partition coefficients as a function of temperature and alkyl substituent. The melting point, enthalpies of fusion, and enthalpies of solid–solid phase transitions were determined by differential scanning calorimetry, DSC. The solubility of [Cnmim][Cl], where n=10 or 12 in 1octanol is comparable and higher than that of [C4mim][Cl] in 1octanol. Liquid 1n‐octyl‐3‐methylimidazolium chloride, [C8mim][Cl], is not miscible with 1octanol and water, consequently, the liquid–liquid equilibrium, LLE was measured in this system. The differences between the solubilities in water for n=4 and 12 are shown only in α1 and γ1 solid crystalline phases. Additionally, the immiscibility region was observed for the higher concentration of [C10mim][Cl] in water. The intermolecular solute–solvent interaction of 1butyl‐3‐methylimidazolium chloride with water is higher than for other 1alkyl‐3‐methylimidazolium chlorides. The data was correlated by means of the UNIQUAC ASM and two modified NRTL equations utilizing parameters derived from the solid–liquid equilibrium, SLE. The root‐mean‐square deviations of the solubility temperatures for all calculated data are from 1.8 to 7 K and depend on the particular equation used. In the calculations, the existence of two solid–solid first‐order phase transitions in [C12mim][Cl] has also been taken into consideration. Experimental partition coefficients (log P) are negative at three temperatures; this is evidence for the possible use of these ionic liquids as green solvents. |
