The second virial coefficient of the ionic liquid (IL) microemulsion was obtained for the first time using microcalorimetry. The heat of dilution of the microemulsion solutions was measured by isothermal titration microcalorimetry (ITC), and the second virial coefficient was derived from the heat of dilution and the number density of the IL microemulsion solutions on the basis of a hard-sphere interaction potential assumption and as a function of the second-order polynomial. The validity of the second virial coefficient was confirmed by the percolation behavior of different ionic liquid microemulsion solutions of Triton X-100 in cyclohexane with or without added salts. The information obtained from the second virial coefficient shows that the interactions between ionic liquid microemulsion droplets are much stronger than those for traditional microemulsions, which may be attributed to the relatively larger size of the microemulsion droplets.
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