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Systematic investigations on the liquid–liquid phase behavior of binary mixtures of ionic liquids (IL) of the type 1-alkyl-3-methylimidazolium bis­((trifluoromethyl)­sulfonyl)­amide (C x mimNTf2, x = 2, 4, 6, 8, and 10) with n-heptanol and its branched isomers 3-ethyl-3-pentanol and 2,4-dimethyl-3-pentanol have been performed. The phase diagrams were determined at atmospheric pressure in the temperature range (T) of 263–448 K by applying the cloud point method. The phase diagrams are analyzed in terms of well-established numerical concepts based on Ising criticality. The results are discussed, and trends and explanations for the shifts of the range of solubility are given. The systems show partial miscibility with upper critical solution temperatures. Comparing the solutions in branched alcohols with those in the linear isomer, the critical solution points are found to be remarkably shifted toward higher temperatures and lower IL contents. The trend becomes more pronounced for ILs with shorter alkyl side chains where also a change of the shape of the phase diagrams is observed.

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